Diclofenac Potassium Transdermal Patches Using Natural Rubber Latex Biomembranes as Carrier

Directory of Open Access Journals (Sweden)

Natan Roberto de Barros

2015-01-01

Full Text Available The aim of this study was to design a compound transdermal patch containing diclofenac potassium (Dic-K using natural rubber latex (NRL biomembrane. The NRL from Hevea brasiliensis is easily manipulated and low cost and presents high mechanical resistance. It is a biocompatible material which can stimulate natural angiogenesis and is capable of adhering cells on its surface. Recent researches have used the NRL for Transdermal Drug Delivery Systems (TDDSs. Dic-K is used for the treatment of rheumatoid arthritis and osteoarthritis and pain relief for postoperative and posttraumatic cases, as well as inflammation and edema. Results showed that the biomembrane can release Dic-K for up to 216 hours. The kinetics of the Dic-K release could be fitted with double exponential function. X-ray diffraction and Fourier Transform Infrared (FTIR spectroscopy show some interaction by hydrogen bound. The results indicated the potential of the compound patch.

Influence of ionizing radiation on the regulatory function of biomembranes

Energy Technology Data Exchange (ETDEWEB)

Burlakova, E B; Archipova, G V; Shishkina, L N; Goloshchapov, A N; Zaslavskij, Yu A [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1975-01-01

Changes of the antioxidative activity in lipids of mitochondria and nuclei as well as the phospholipid content of all organelles from BaIb strain mouse liver are studies at early stages after irradiation. It is supposed that the lipid composition and the structural rearrangements of the biomembrane cause changes in the enzyme activity of irradiated cells.

Clusters of proteins in bio-membranes: insights into the roles of interaction potential shapes and of protein diversity

OpenAIRE

Meilhac, Nicolas; Destainville, Nicolas

2011-01-01

It has recently been proposed that proteins embedded in lipidic bio-membranes can spontaneously self-organize into stable small clusters, or membrane nano-domains, due to the competition between short-range attractive and longer-range repulsive forces between proteins, specific to these systems. In this paper, we carry on our investigation, by Monte Carlo simulations, of different aspects of cluster phases of proteins in bio-membranes. First, we compare different long-range potentials (includ...

Expression of VEGF and collagen using a latex biomembrane as bladder replacement in rabbits

Directory of Open Access Journals (Sweden)

André Luís Alonso Domingos

2012-08-01

Full Text Available OBJECTIVE: To investigate the VEGF expression and collagen deposition using a latex biomembrane as bladder replacement in rabbits. MATERIALS AND METHODS: After partial cystectomy, a patch of a non-vulcanized latex biomembrane (2 x 2 cm was sewn to the bladder of rabbits with 5/0 monofilament polydioxanone sulfate sutures in a watertight manner. Groups of 5 animals were killed at 15, 45 and 90 days after surgery and the bladder was removed. Sections of 5µm were cut and stained with picrosirius-red in order to estimate the amount of extracellular matrix in the graft. To confirm the presence of VEGF in tissues, protein expression was determined by immunohistochemistry. RESULTS: No death, urinary leakage or graft extrusion occurred in any group. All bladders showed a spherical shape. A progressive reduction in the amount of collagen occurred in the graft area and was negatively and linearly correlated with time (p < 0.001. VEGF expression was higher in grafted areas when compared to controls at 15 and 45 days after surgery and decreased with time (p < 0.001. CONCLUSION: The latex biomembrane as a matrix for partial bladder replacement in rabbits promotes temporary collagen deposition and stimulates the angiogenic process.

Novel NMR tools to study structure and dynamics of biomembranes.

Science.gov (United States)

Gawrisch, Klaus; Eldho, Nadukkudy V; Polozov, Ivan V

2002-06-01

Nuclear magnetic resonance (NMR) studies on biomembranes have benefited greatly from introduction of magic angle spinning (MAS) NMR techniques. Improvements in MAS probe technology, combined with the higher magnetic field strength of modern instruments, enables almost liquid-like resolution of lipid resonances. The cross-relaxation rates measured by nuclear Overhauser enhancement spectroscopy (NOESY) provide new insights into conformation and dynamics of lipids with atomic-scale resolution. The data reflect the tremendous motional disorder in the lipid matrix. Transfer of magnetization by spin diffusion along the proton network of lipids is of secondary relevance, even at a long NOESY mixing time of 300 ms. MAS experiments with re-coupling of anisotropic interactions, like the 13C-(1)H dipolar couplings, benefit from the excellent resolution of 13C shifts that enables assignment of the couplings to specific carbon atoms. The traditional 2H NMR experiments on deuterated lipids have higher sensitivity when conducted on oriented samples at higher magnetic field strength. A very large number of NMR parameters from lipid bilayers is now accessible, providing information about conformation and dynamics for every lipid segment. The NMR methods have the sensitivity and resolution to study lipid-protein interaction, lateral lipid organization, and the location of solvents and drugs in the lipid matrix.

Morphological and Physical Analysis of Natural Phospholipids-Based Biomembranes

OpenAIRE

Jacquot, Adrien; Francius, Grégory; Razafitianamaharavo, Angelina; Dehghani, Fariba; Tamayol, Ali; Linder, Michel; Arab-Tehrany, Elmira

2014-01-01

International audience; Background: Liposomes are currently an important part of biological, pharmaceutical, medical and nutritional research, as they are considered to be among the most effective carriers for the introduction of various types of bioactive agents into target cells.Scope of Review: In this work, we study the lipid organization and mechanical properties of biomembranes made of marine and plant phospholipids. Membranes based on phospholipids extracted from rapeseed and salmon ar...

Development of zwitterionic chromophores for electro-optic applications

Science.gov (United States)

Xiong, Ying

In order to unlock the full potential of the zwitterionic NLO chromophores for electro-optic (EO) applications, a new series of PeQDM chromophores with large first hyperpolarizabilities (beta0 ˜ 600 x 10-30 esu) have been designed and synthesized. A large EO coefficient (r33) of 110 pm/V at 1550 nm has been realized with a 5 wt% (corresponding to 3.8 wt% core content) chromophore doped polymer. The EO study of guest-host polymers reveals that dipolar dye aggregation in a less polar medium is responsible for a low chromophore loading and low EO activity. Modification of NLO chromophore by attaching large dendrons can effectively increase the chromophore loading in a host and improve the poling efficiency. Crosslinkable NLO polymers have also been prepared to improve the temporal stability of the poled noncentrosymmetric order. The following are some important highlights from this thesis work. (1) A series of thermally stable zwitterionic chromophores (PeQDM) with large first hyperpolarizabilities (beta up to -1797 x 10-30 esu) are synthesized in good yields (˜ 50%). The charge-separated ground state is evident by a negative solvatochromism. X-ray crystallographic data further confirms the zwitterionic nature and demonstrates a face-to-face anti-parallel H-aggregation of two monomers due to strong electrostatic interactions between the dipoles. (2) PeQDM chromophores are also NIR fluorescent (lambdaPL ˜ 840-870 nm in solution) and labile to acid, making them potential candidates for NIR pH sensor applications. (3) The hydroxyl-containing PeQDM chromophores are modified with ES-dendron, which exhibit good solubility in solvents and polymers. Self-forming films can be prepared by direct casting or spin-coating of two dendrons modified chromophores (ES-PeQDM-2 and ES-PeQDM-3), in which the chromophore core contents reach 14.9 and 16.9 wt%, respectively. Compared to ES-PeQDM-2 with two dendrons only at the donor part (r33 = 0 pm/V), ES-PeQDM-3 with the bulky ES

Room-Temperature Ionic Liquids and Biomembranes: Setting the Stage for Applications in Pharmacology, Biomedicine, and Bionanotechnology.

Science.gov (United States)

Benedetto, Antonio; Ballone, Pietro

2018-03-21

Empirical evidence and conceptual elaboration reveal and rationalize the remarkable affinity of organic ionic liquids for biomembranes. Cations of the so-called room-temperature ionic liquids (RTILs), in particular, are readily absorbed into the lipid fraction of biomembranes, causing a variety of observable biological effects, including generic cytotoxicity, broad antibacterial potential, and anticancer activity. Chemical physics analysis of model systems made of phospholipid bilayers, RTIL ions, and water confirm and partially explain this evidence, quantifying the mild destabilizing effect of RTILs on the structural, dynamic, and thermodynamic properties of lipids in biomembranes. Our Feature Article presents a brief introduction to these systems and to their roles in biophysics and biotechnology, summarizing recent experimental and computational results on their properties. More importantly, it highlights the many developments in pharmacology, biomedicine, and bionanotechnology expected from the current research effort on this topic. To anticipate future developments, we speculate on (i) potential applications of (magnetic) RTILs to affect and control the rheology of cells and biological tissues, of great relevance for diagnostics and (ii) the use of RTILs to improve the durability, reliability, and output of biomimetic photovoltaic devices.

Synthesis and properties of the para-trimethylammonium analogues of green fluorescence protein (GFP) chromophore: The mimic of protonated GFP chromophore.

Science.gov (United States)

Fanjiang, Ming-Wei; Li, Ming-Ju; Sung, Robert; Sung, Kuangsen

2018-04-01

At low pH, protons from the external, bulk solution can protonate the phenoxide group of the p-HBDI chromophore in wild-type green fluorescent protein (wtGFP) and its mutants, and likely continue to tentatively protonate the phenol hydroxyl group of the same chromophores. Because the protonated GFP chromophore is a transient, we prepare the stable p-trimethylammonium analogues (2a and 2b) of the GFP chromophore to mimic it and explore their properties. What we found is that the p-trimethylammonium analogues of the GFP chromophore have the highly electrophilic amidine carbon, blue-shifted electronic absorption, smaller molar absorptivity, smaller fluorescent quantum yield, and faster E-Z thermoisomerization rate. The amidine carbon of the p-trimethylammonium analogue (2b) of the GFP chromophore is the only site that is attacked by very weak nucleophile of water, resulting in ring-opening of the imidazolinone moiety. The half-life of its decay rate in D 2 O is around 33 days. Actually, acid-catalyzed hydrolysis of p-HBDI also results in ring-opening of the imidazolinone moiety. The ratio of the acid-catalyzed hydrolysis rate constants [k obs (p-HBDI)/k obs (1b)] between p-HBDI and 1b (p-dimethylammonium analogue of the GFP chromophore) is dramatically increased from 0.30 at pH = 2 to 0.63 at pH = 0. This is the evidence that more and more phenol hydroxyl groups of p-HBDI are tentatively protonated in a low-pH aqueous solution and that accelerates hydrolysis of p-HBDI in the way similar to the quaternary ammonium derivatives 2a and 2b in water. With this view point, 2a and 2b still can partially mimic the cationic p-HBDI with the protonated phenol hydroxyl group. Implication of the experiment is that the amidine carbon of the chromophore in wtGFP and its mutants at very low pH should be highly electrophilic. Whether ring-opening of the imidazolinone moiety of the GFP chromophore would occur or not depends on if water molecules can reach the amidine carbon of

Use of a latex biomembrane for bladder augmentation in a rabbit model: biocompatibility, clinical and histological outcomes

Directory of Open Access Journals (Sweden)

Andre L. A. Domingos

2009-04-01

Full Text Available PURPOSE: To investigate histological features and biocompatibility of a latex biomembrane for bladder augmentation using a rabbit model. MATERIAL AND METHODS: After a partial cystectomy, a patch of a non-vulcanized latex biomembrane (2x4 cm was sewn to the bladder with 5/0 monofilament polydioxanone sulfate in a watertight manner. Groups of 5 animals were sacrificed at 15, 45 and 90 days after surgery and the bladder was removed. The 5-µm preparations obtained from grafted area and normal bladder were stained with hematoxylin-eosin. Immunohistochemical staining was performed with a primary antibody against alpha-actin to assess muscle regeneration. RESULTS: No death, urinary leakage or graft extrusion occurred in any group. All bladders showed a spherical shape. Macroscopically, after 90 days, the latex biomembrane was not identifiable and the patch was indistinguishable from normal bladder. A bladder stone was found in one animal (6.6%. On the 90th day, histology revealed continuity of transitional epithelium of host bladder tissue on the patch area. At this time, the muscle layers were well organized in a similar fashion to native bladder muscle layers. The inflammatory process was higher on grafted areas when compared to controls: 15 days - p < 0.0001, 45 days - p < 0.001, and 90 days - p < 0.01. The anti alpha-actin immunoexpression peaked at 45 days, when the graft was observed covered by muscle cells. CONCLUSION: The latex biomembrane is biocompatible and can be used in models for bladder augmentation in rabbits. It promotes epithelium and muscle regeneration without urinary leakage.

BFPTool: a software tool for analysis of Biomembrane Force Probe experiments

Czech Academy of Sciences Publication Activity Database

Šmít, Daniel; Fouquet, C.; Doulazmi, M.; Pincet, F.; Trembleau, A.; Zápotocký, Martin

2017-01-01

Roč. 10, Feb (2017), č. článku 2. ISSN 2046-1682 R&D Projects: GA ČR(CZ) GA14-16755S; GA MŠk(CZ) 7AMB12FR002 Institutional support: RVO:67985823 Keywords : Biomembrane Force Probe * motion tracking * image analysis * force spectroscopy * cell mechanics Subject RIV: BO - Biophysics OBOR OECD: Biophysics Impact factor: 2.292, year: 2016

Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

KAUST Repository

Cekli, Seda; Winkel, Russell W.; Alarousu, Erkki; Mohammed, Omar F.; Schanze, Kirk S.

2016-01-01

A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

Triplet excited state properties in variable gap π-conjugated donor–acceptor–donor chromophores

KAUST Repository

Cekli, Seda

2016-02-12

A series of variable band-gap donor–acceptor–donor (DAD) chromophores capped with platinum(II) acetylide units has been synthesized and fully characterized by electrochemical and photophysical methods, with particular emphasis placed on probing triplet excited state properties. A counter-intuitive trend of increasing fluorescence quantum efficiency and lifetime with decreasing excited state energy (optical gap) is observed across the series of DAD chromophores. Careful study of the excited state dynamics, including triplet yields (as inferred from singlet oxygen sensitization), reveals that the underlying origin of the unusual trend in the fluorescence parameters is that the singlet–triplet intersystem crossing rate and yield decrease with decreasing optical gap. It is concluded that the rate of intersystem crossing decreases as the LUMO is increasingly localized on the acceptor unit in the DAD chromophore, and this result is interpreted as arising because the extent of spin–orbit coupling induced by the platinum heavy metal centers decreases as the LUMO is more localized on the acceptor. In addition to the trend in intersystem crossing, the results show that the triplet decay rates follow the Energy Gap Law correlation over a 1.8 eV range of triplet energy and 1000-fold range of triplet decay rates. Finally, femtosecond transient absorption studies for the DAD chromophores reveals a strong absorption in the near-infrared region which is attributed to the singlet excited state. This spectral band appears to be general for DAD chromophores, and may be a signature of the charge transfer (CT) singlet excited state.

Dicarboxylic phospholipids and irradiated biomembranes

International Nuclear Information System (INIS)

Dousset, Nicole.

1977-01-01

It was decided to study the effects of ionizing radiations on biomembranes, with special reference to erythrocytes and liver microsomes representing two kinds of membrane very common in nature. Diacid phospholipids were observed at these membranes and the results are reported in part one of this work. It appeared essential to examine as far as possible the metabolism, in vitro and in animals, of these diacids and to find out whether certain harmful effects of radiations on the proteins (membrane permeability changes and enzyme inactivation) could be due to the action of these newly formed compounds. The study of acid compounds formed under irradiation was limited to nonanal-9-oic acid and azelaic acid. Part two deals with the incorporation of acid and diacid compounds into lipids and the effects of diacid phospholipids on the membrane permeability. A chapter is devoted to the changes in certain enzyme activities brought about by diacid phospholipids [fr

Action of the multifunctional peptide BP100 on native biomembranes examined by solid-state NMR

Energy Technology Data Exchange (ETDEWEB)

Misiewicz, Julia [Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (Germany); Afonin, Sergii; Grage, Stephan L.; Berg, Jonas van den; Strandberg, Erik; Wadhwani, Parvesh [Karlsruhe Institute of Technology (KIT), Institute of Biological Interfaces (IBG-2) (Germany); Ulrich, Anne S., E-mail: anne.ulrich@kit.edu [Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (Germany)

2015-04-15

Membrane composition is a key factor that regulates the destructive activity of antimicrobial peptides and the non-leaky permeation of cell penetrating peptides in vivo. Hence, the choice of model membrane is a crucial aspect in NMR studies and should reflect the biological situation as closely as possible. Here, we explore the structure and dynamics of the short multifunctional peptide BP100 using a multinuclear solid-state NMR approach. The membrane alignment and mobility of this 11 amino acid peptide was studied in various synthetic lipid bilayers with different net charge, fluidity, and thickness, as well as in native biomembranes harvested from prokaryotic and eukaryotic cells. {sup 19}F-NMR provided the high sensitivity and lack of natural abundance background that are necessary to observe a labelled peptide even in protoplast membranes from Micrococcus luteus and in erythrocyte ghosts. Six selectively {sup 19}F-labeled BP100 analogues gave remarkably similar spectra in all of the macroscopically oriented membrane systems, which were studied under quasi-native conditions of ambient temperature and full hydration. This similarity suggests that BP100 has the same surface-bound helical structure and high mobility in the different biomembranes and model membranes alike, independent of charge, thickness or cholesterol content of the system. {sup 31}P-NMR spectra of the phospholipid components did not indicate any bilayer perturbation, so the formation of toroidal wormholes or micellarization can be excluded as a mechanism of its antimicrobial or cell penetrating action. However, {sup 2}H-NMR analysis of the acyl chain order parameter profiles showed that BP100 leads to considerable membrane thinning and thereby local destabilization.

Insight into the effects of modifying chromophores on the performance of quinoline-based dye-sensitized solar cells

Science.gov (United States)

Mao, Mao; Wang, Jian-Bo; Liu, Xiu-Lin; Wu, Guo-Hua; Fang, Xia-Qin; Song, Qin-Hua

2018-02-01

A series of organic dyes based on quinoline as an electron-deficient π-linker, were designed and synthesized for dye sensitized solar cells (DSSC) application. These push-pull conjugated dyes, sharing same anchoring group with distinctive electron-rich donating groups such as N,N-diethyl (DEA-Q), 3,6-dimethoxy carbazole (CBZ-Q), bis(4-butoxyphenyl)amine (BPA-Q), were synthesized by Riley oxidation of sbnd CH3 followed by Knoevenagel condensation of the corresponding aldehyde precursors 2a-c with cyanoacrylic acid. The optical, electrochemical, theoretical calculation and photovoltaic properties with these three dyes were systematically investigated. Compared to DEA-Q and CBZ-Q, BPA-Q possesses better light harvesting properties with regard to extended conjugate length, red-shifted intramolecular charge transfer band absorption and broaden light-responsive IPCE spectrum, resulting in a greater short circuit photocurrent density output. BPA-Q also has improved open-circuit voltage due to the apparent large charge recombination resistance. Consequently, assembled with iodine redox electrolytes, the device with BPA-Q achieved the best overall conversion efficiency value of 3.07% among three dyes under AM 1.5G standard conditions. This present investigation demonstrates the importance of various N-substituent chromophores in the prevalent D-π-A type organic sensitizers for tuning the photovoltaic performance of their DSSCs.

Photoionization of oxidized coenzyme Q in microemulsion: laser flash photolysis study in biomembrane-like system.

Science.gov (United States)

Li, Kun; Wang, Mei; Wang, Jin; Zhu, Rongrong; Sun, Dongmei; Sun, Xiaoyu; Wang, Shi-Long

2013-01-01

Photoexcitation to generate triplet state has been proved to be the main photoreaction in homogeneous system for many benzoquinone derivatives, including oxidized coenzyme Q (CoQ) and its analogs. In the present study, microemulsion of CoQ, a heterogeneous system, is employed to mimic the distribution of CoQ in biomembrane. The photochemistry of CoQ(10) in microemulsion and cyclohexane is investigated and compared using laser flash photolysis and results show that CoQ(10) undergoes photoionization via a monophotonic process to generate radical cation of CoQ(10) in microemulsion and photoexcitation to generate excited triplet state in cyclohexane. Meanwhile, photoreactions of duroquinone (DQ) and CoQ(0) in microemulsion are also investigated to analyze the influence of molecular structure on the photochemistry of benzoquinone derivatives in microemulsion. Results suggest that photoexcitation, which is followed by excited state-involved hydrogen-abstraction reaction, is the main photoreaction for DQ and CoQ(0) in microemulsion. However, photoexcited CoQ(0) also leads to the formation of hydrated electrons. The isoprenoid side chain-involved high resonance stabilization is proposed to explain the difference in photoreactions of CoQ(0) and CoQ(10) in microemulsion. Considering that microemulsion is close to biomembrane system, its photoionization in microemulsion may be helpful to understand the real photochemistry of biological quinones in biomembrane system. © 2012 Tongji University. Photochemistry and Photobiology © 2012 The American Society of Photobiology.

LDRD final report : energy conversion using chromophore-functionalized carbon nanotubes.

Energy Technology Data Exchange (ETDEWEB)

Vance, Andrew L.; Zifer, Thomas; Zhou, Xinjian; Leonard, Francois Leonard; Wong, Bryan Matthew; Kane, Alexander; Katzenmeyer, Aaron Michael; Krafcik, Karen Lee

2010-09-01

With the goal of studying the conversion of optical energy to electrical energy at the nanoscale, we developed and tested devices based on single-walled carbon nanotubes functionalized with azobenzene chromophores, where the chromophores serve as photoabsorbers and the nanotube as the electronic read-out. By synthesizing chromophores with specific absorption windows in the visible spectrum and anchoring them to the nanotube surface, we demonstrated the controlled detection of visible light of low intensity in narrow ranges of wavelengths. Our measurements suggested that upon photoabsorption, the chromophores isomerize to give a large change in dipole moment, changing the electrostatic environment of the nanotube. All-electron ab initio calculations were used to study the chromophore-nanotube hybrids, and show that the chromophores bind strongly to the nanotubes without disturbing the electronic structure of either species. Calculated values of the dipole moments supported the notion of dipole changes as the optical detection mechanism.

Spectroscopic and thermal characterization of alternative model biomembranes from shed skins of Bothrops jararaca and Spilotis pullatus

Directory of Open Access Journals (Sweden)

André Rolim Baby

2009-09-01

Full Text Available Recently, there has been an interest in the use of shed snake skin as alternative model biomembrane for human stratum corneum. This research work presented as objective the qualitative characterization of alternative model biomembranes from Bothrops jararaca and Spilotis pullatus by FT-Raman, PAS-FTIR and DSC. The employed biophysical techniques permitted the characterization of the biomembranes from shed snake skin of B. jararaca and S. pullatus by the identification of vibrational frequencies and endothermic transitions that are similar to those of the human stratum corneum.Existe atualmente interesse no uso da muda de pele de cobra como modelos alternativos de biomembranas da pele humana. O presente trabalho apresentou como objetivo a caracterização qualitativa de modelos alternativos de biomembranas provenientes de mudas de pele de cobra da Bothrops jararaca e Spilotis pullatus por espectroscopia Raman (FT-Raman, espectroscopia fotoacústica no infravermelho (PAS-FTIR e calorimetria exploratória diferencial (DSC. As técnicas biofísicas FT-Raman, PAS-FTIR e DSC permitiram caracterizar qualitativamente os modelos alternativos de biomembranas provenientes das mudas de pele de cobra da B. jararaca e S. pullatus e identificar freqüências vibracionais e transições endotérmicas similares ao estrato córneo humano.

Molecular recognition of chromophore molecules to amine terminated surfaces

International Nuclear Information System (INIS)

Flores-Perez, Rosangelly; Ivanisevic, Albena

2007-01-01

We report the design and characterization of quartz surfaces that can bind to three retinal based chromophores. The amine terminated surfaces were engineered in order to mimic the environment of the opsin protein that accommodates binding of chromophore molecules in the human eye. Each surface coupling step was characterized by water contact angle measurements, ellipsometry, atomic force microscopy, X-ray photoelectron spectroscopy, and transmission infrared spectroscopy. The spectroscopic techniques confirmed that the three chromophore molecules can bind to the surface using a Schiff base mode. Our data suggests that the availability of the amine groups on the surface is critical in the accommodation of the binding of different chromophores

Effect of some colloid surfactants on spectrophotometric characteristics of metal chelates with chromophore organic reagents

International Nuclear Information System (INIS)

Chernova, R.K.

1977-01-01

Theoretical regularities and prospects of using surface active substances (SAS) in spectrophotometric determination of metal ions (including ions of rare-earth elements, transition metals, Be(3)) with chromophore chelating reagents were investigated. The chromophore reagents investigated were pyrocatechol violet, phenolcarboxylic acids of the triarylmethane series, fluorones, phthalexones and azo-compounds. As SAS certain long-chain quaternary ammonium and pyridinium salts (LQAS) were employed. From the results reported it follows that the introduction of LQAS in the system of Mesup(n+)-chromophore reagent is a rather effective method of enhancing the contrast rendition and, in some cases, the sensitivity and selectivity of the reagents. Explanations are suggested as to the factors which cause the changes observed in the contrast of the reactions in the presence of SAS; the underlying phenomena are the ligand-ligand interactions between the organic reagents and SAS and solubilization processes of the reaction products by the micelles of SAS

Evaluation of peptides release using a natural rubber latex biomembrane as a carrier.

Science.gov (United States)

Miranda, M C R; Borges, F A; Barros, N R; Santos Filho, N A; Mendonça, R J; Herculano, R D; Cilli, E M

2018-05-01

The biomembrane natural (NRL-Natural Rubber Latex), manipulated from the latex obtained from the rubber tree Hevea brasiliensis, has shown great potential for application in biomedicine and biomaterials. Reflecting the biocompatibility and low bounce rate of this material, NRL has been used as a physical barrier to infectious agents and for the controlled release of drugs and extracts. The aim of the present study was to evaluate the incorporation and release of peptides using a latex biomembrane carrier. After incorporation, the release of material from the membrane was observed using spectrophotometry. Analyses using HPLC and mass spectroscopy did not confirm the release of the antimicrobial peptide [W 6 ]Hylin a1 after 24 h. In addition, analysis of the release solution showed new compounds, indicating the degradation of the peptide by enzymes contained in the latex. Additionally, the release of a peptide with a shorter sequence (Ac-WAAAA) was evaluated, and degradation was not observed. These results showed that the use of NRL as solid matrices as delivery systems of peptide are sequence dependent and could to be evaluated for each sequence.

Search for Singlet Fission Chromophores

Energy Technology Data Exchange (ETDEWEB)

Havlas, Z.; Akdag, A.; Smith, M. B.; Dron, P.; Johnson, J. C.; Nozik, A. J.; Michl, J.

2012-01-01

Singlet fission, in which a singlet excited chromophore shares its energy with a ground-state neighbor and both end up in their triplet states, is of potential interest for solar cells. Only a handful of compounds, mostly alternant hydrocarbons, are known to perform efficiently. In view of the large number of conditions that a successful candidate for a practical cell has to meet, it appears desirable to extend the present list of high performers to additional classes of compounds. We have (i) identified design rules for new singlet fission chromophores and for their coupling to covalent dimers, (ii) synthesized them, and (iii) evaluated their performance as neat solids or covalent dimers.

Photoresponse of the protonated Schiff-base retinal chromophore in the gas phase

DEFF Research Database (Denmark)

Toker, Jonathan; Rahbek, Dennis Bo; Kiefer, H V

2013-01-01

The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The sel......The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse...... modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary...

Intelligent biomembranes and biochips by radiation

International Nuclear Information System (INIS)

Nakayama, H.; Sutani, K.; Sakata, S.; Kita, Y.; Kaetsu, I.; Uchida, K.; Matsubara, Y.

2002-01-01

Complete text of publication follows. The authors have studied stimuli-responsive polyelectrolyte and polyampholyte hydrogels. Thermo-responsive copolymer hydrogels also have been studied. Recently, the authors have applied those hydrogels to radiation curable intelligent coatings for the gating of drug release channel. One way of this application is the coating on a drug including membrane to initiate and stop the drug release by on-off switching of stimulations. Some practical intelligent biomembranes such as glucose responsive insulin release membrane, glucose responsive nicotine release membrane and temperature responsive perfume release membrane were investigated and proved the function. On the other hand, the stimuli-responsive coating was applied to the porous biochip to cover the multi-drug reservoirs in the chip and computer programmed drug release from the biochip was investigated. Some results of primary studies proved the possibility of techniques for the application to biochip systems such as multi-signals responsive multi-drug release systems

The study of the use of a latex biomembrane and conjunctival autograft in rabbit conjunctiva wound healing.

Science.gov (United States)

Pinho, Erika Christina Canarim Martha de; Chahud, Fernando; Lachat, João-José; Coutinho-Netto, Joaquim José; Sousa, Sidney Julio Faria E

2018-04-01

RESUMO Objetivo: Estudar o uso da biomembrana de látex e o transplante conjuntival autólogo na cicatrização conjuntival em coelhos. Métodos: Em nove coelhos albinos, neo-zelandeses, machos foram removidas áreas retangulares idênticas, do quadrante supero nasal, adjacente ao limbo, de ambos os olhos. As áreas desnudas da camada esclerótica nos olhos direitos foram recobertas com biomembrana de látex e a dos olhos esquerdos com enxerto conjuntival autólogo. Os animais foram sacrificados em grupos de três, aos 7, 14 e 21 dias após a cirurgia. Os tecidos do local cirúrgico, incluindo a córnea, foram fixados em formaldeído, antes de serem processados em parafina e corados com hematoxilina e eosina. A natureza e a intensidade da resposta inflamatória e o padrão de epitelização da superfície conjuntival foram avaliados sob microscopia óptica, em seções histológicas longitudinais, passando pelo centro dos espécimes anatômicos. Resultados: Até o décimo quarto dia pós-operatório, o grupo que recebeu a biomembrana apresentou reação inflamatória mais intensa do que o grupo com auto enxerto conjuntival. Aos 14 dias, os olhos com biomembrana apresentavam-se menos inflamados e com estroma mais espesso do que aos 7 dias. Aos 21 dias, a reparação conjuntival de ambos os grupos apresentavam características semelhantes. Conclusão: Apesar de apresentar uma cicatrização mais lenta, a biomembrana de látex se mostrou tão eficaz quanto o auto enxerto conjuntival na reconstrução da superfície ocular após três semanas de cicatrização pós-operatória. Devido as suas baixas toxicidade e alergenicidade, este material parece ser uma opção terapêutica promissora na reconstrução da conjuntiva.ABSTRACT Purpose: To study a latex biomembrane and conjunctival autograft with regard to the promotion of conjunctival healing in rabbits. The study included nine male albino rabbits. In these rabbits, a rectangular area of the conjunctiva was surgically

Molecular Selectivity of Brown Carbon Chromophores

Energy Technology Data Exchange (ETDEWEB)

Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey; Roach, Patrick J.; Eckert, Peter A.; Gilles, Mary K.; Wang, Bingbing; Lee, Hyun Ji; Hu, Qichi

2014-10-21

Complementary methods of high-resolution mass spectrometry and micro-spectroscopy were utilized for molecular analysis of secondary organic aerosol (SOA) generated from ozonolysis of two structural monoterpene isomers: D-limonene (LSOA) and a-pinene (PSOA). Laboratory simulated aging of LSOA and PSOA, through conversion of carbonyls into imines mediated by NH3 vapors in humid air, resulted in selective browning of the LSOA sample, while the PSOA sample remained white. Comparative analysis of the reaction products in the aged LSOA and PSOA samples provided insights into chemistry relevant to formation of brown carbon chromophores. A significant fraction of carbonyl-imine conversion products with identical molecular formulas were detected in both samples. This reflects the high level of similarity in the molecular composition of these two closely related SOA materials. Several highly conjugated products were detected exclusively in the brown LSOA sample and were identified as potential chromophores responsible for the observed color change. The majority of the unique products in the aged LSOA sample with the highest number of double bonds contain two nitrogen atoms. We conclude that chromophores characteristic of the carbonyl- imine chemistry in LSOA are highly conjugated oligomers of secondary imines (Schiff bases) present at relatively low concentrations. Formation of this type of conjugated compounds in PSOA is hindered by the structural rigidity of the a-pinene oxidation products. Our results suggest that the overall light-absorbing properties of SOA may be determined by trace amounts of strong brown carbon chromophores.

Element-specific density profiles in interacting biomembrane models

International Nuclear Information System (INIS)

Schneck, Emanuel; Rodriguez-Loureiro, Ignacio; Bertinetti, Luca; Gochev, Georgi; Marin, Egor; Novikov, Dmitri; Konovalov, Oleg

2017-01-01

Surface interactions involving biomembranes, such as cell–cell interactions or membrane contacts inside cells play important roles in numerous biological processes. Structural insight into the interacting surfaces is a prerequisite to understand the interaction characteristics as well as the underlying physical mechanisms. Here, we work with simplified planar experimental models of membrane surfaces, composed of lipids and lipopolymers. Their interaction is quantified in terms of pressure–distance curves using ellipsometry at controlled dehydrating (interaction) pressures. For selected pressures, their internal structure is investigated by standing-wave x-ray fluorescence (SWXF). This technique yields specific density profiles of the chemical elements P and S belonging to lipid headgroups and polymer chains, as well as counter-ion profiles for charged surfaces. (paper)

Structural control of side-chain chromophores to achieve highly efficient electro-optic activity.

Science.gov (United States)

Yang, Yuhui; Chen, Zhuo; Liu, Jialei; Xiao, Hongyan; Zhen, Zhen; Liu, Xinhou; Jiang, Guohua

2017-05-10

A series of chromophores J1-J4 have been synthesized based on julolidine donors modified with different rigid steric hindrance groups. Compared with the chromophore (J1) without the isolation group, chromophores J2, J3 and J4 show better stability. Structural analysis and photophysical property measurements were carried out to compare the molecular mobility and steric hindrance effect of the different donor-modified chromophores. All of these chromophores with isolation groups showed superb thermal stabilities with high thermal decomposition temperatures above 250 °C. Furthermore, with rigid steric hindrance, chromophores J3 and J4 showed more enhanced thermal stabilities with thermal decomposition temperatures of 269 °C and 275 °C, respectively. Density functional theory was used to calculate the hyperpolarizability (β), and the high molecular hyperpolarizability of these chromophores can be effectively translated into large electro-optic coefficients. The electro-optic coefficients of poled films containing 20 wt% of these new chromophores doped in amorphous polycarbonate were 127, 266 and 209 pm V -1 at 1310 nm for chromophores J1-J3, respectively, while the film containing chromophore J4 showed the largest r 33 value of only 97 pm V -1 at 25 wt%. These results indicated that the introduced isolation group can reduce intermolecular electrostatic interactions, thus enhancing the macroscopic electro-optic activity, while the size of the isolation group should be suitable.

Maxillary Bone Regeneration Based on Nanoreservoirs Functionalized ε-Polycaprolactone Biomembranes in a Mouse Model of Jaw Bone Lesion

Directory of Open Access Journals (Sweden)

Marion Strub

2018-01-01

Full Text Available Current approaches of regenerative therapies constitute strategies for bone tissue reparation and engineering, especially in the context of genetical diseases with skeletal defects. Bone regeneration using electrospun nanofibers’ implant has the following objectives: bone neoformation induction with rapid healing, reduced postoperative complications, and improvement of bone tissue quality. In vivo implantation of polycaprolactone (PCL biomembrane functionalized with BMP-2/Ibuprofen in mouse maxillary defects was followed by bone neoformation kinetics evaluation using microcomputed tomography. Wild-Type (WT and Tabby (Ta mice were used to compare effects on a normal phenotype and on a mutant model of ectodermal dysplasia (ED. After 21 days, no effect on bone neoformation was observed in Ta treated lesion (4% neoformation compared to 13% in the control lesion. Between the 21st and the 30th days, the use of biomembrane functionalized with BMP-2/Ibuprofen in maxillary bone lesions allowed a significant increase in bone neoformation peaks (resp., +8% in mutant Ta and +13% in WT. Histological analyses revealed a neoformed bone with regular trabecular structure, areas of mineralized bone inside the membrane, and an improved neovascularization in the treated lesion with bifunctionalized membrane. In conclusion, PCL functionalized biomembrane promoted bone neoformation, this effect being modulated by the Ta bone phenotype responsible for an alteration of bone response.

Novel multi-chromophor light absorber concepts for DSSCs for efficient electron injection

Energy Technology Data Exchange (ETDEWEB)

Schuetz, Robert; Strothkaemper, Christian; Bartelt, Andreas; Hannappel, Thomas; Eichberger, Rainer [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Fasting, Carlo [Institut fuer Organische Chemie, Freie Universitaet Berlin, Takustrasse 3, 14195 Berlin (Germany); Thomas, Inara [Helmholtz-Zentrum Berlin fuer Materialien und Energie, Hahn-Meitner-Platz 1, 14109 Berlin (Germany); Institut fuer Organische Chemie, Freie Universitaet Berlin, Takustrasse 3, 14195 Berlin (Germany)

2011-07-01

Dye sensitized solar cells (DSSCs) operate by injecting electrons from the excited state of a light-harvesting dye into the continuum of conduction band states of a wide bandgap semiconductor. The light harvesting efficiency of pure organic dyes is limited by a narrow spectral electronic transition. A beneficial broad ground state absorption in the VIS region can be achieved by applying a single molecular dye system with multiple chromophors involving a Foerster resonance energy transfer (FRET) mechanism for an efficient electron injection. A model donor acceptor dye system capable for FRET chemically linked to colloidal TiO{sub 2} and ZnO nanorod surfaces was investigated in UHV environment. We used VIS/NIR femtosecond transient absorption spectroscopy and optical pump terahertz probe spectroscopy to study the charge injection dynamics of the antenna system. Different chromophors attached to a novel scaffold/anchor system connecting the organic absorber unit to the metal oxide semiconductor were probed.

Benzimidazole acrylonitriles as multifunctional push-pull chromophores: Spectral characterisation, protonation equilibria and nanoaggregation in aqueous solutions

Science.gov (United States)

Horak, Ema; Vianello, Robert; Hranjec, Marijana; Krištafor, Svjetlana; Zamola, Grace Karminski; Steinberg, Ivana Murković

2017-05-01

Heterocyclic donor-π-acceptor molecular systems based on an N,N-dimethylamino phenylacrylonitrile benzimidazole skeleton have been characterised and are proposed for potential use in sensing applications. The benzimidazole moiety introduces a broad spectrum of useful multifunctional properties to the system including electron accepting ability, pH sensitivity and compatibility with biomolecules. The photophysical characterisation of the prototropic forms of these chromophores has been carried out in both solution and on immobilisation in polymer films. The experimental results are further supported by computational determination of pKa values. It is noticed that compound 3 forms nanoaggregates in aqueous solutions with aggregation-induced emission (AIE) at 600 nm. All the systems demonstrate spectral pH sensitivity in acidic media which shifts towards near-neutral values upon immobilisation in polymer films or upon aggregation in an aqueous environment (compound 3). The structure-property relationships of these functional chromophores, involving their spectral characteristics, acid-base equilibria, pKa values and aggregation effects have been determined. Potential applications of the molecules as pH and biomolecular sensors are proposed based on their pH sensitivity and AIE properties.

Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

KAUST Repository

Goswami, Subhadip; Winkel, Russell W.; Alarousu, Erkki; Ghiviriga, Ion; Mohammed, Omar F.; Schanze, Kirk S.

2014-01-01

A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

Photophysics of organometallic platinum(II) derivatives of the diketopyrrolopyrrole chromophore

KAUST Repository

Goswami, Subhadip

2014-12-18

A pair of diketopyrrolopyrrole (DPP) chromophores that are end-functionalized with platinum containing "auxochromes" were subjected to electrochemical and photophysical study. The chromophores contain either platinum acetylide or ortho-metalated 2-thienylpyridinyl(platinum) end-groups (DPP-Pt(CC) and DPP-Pt(acac), respectively). The ground state redox potentials of the chromophores were determined by solution electrochemistry, and the HOMO and LUMO levels were estimated. The chromophores\\' photophysical properties were characterized by absorption, photoluminescence, and time-resolved absorption spectroscopy on time scales from sub-picoseconds to microseconds. Density functional theory (DFT) computations were performed to understand the molecular orbitals involved in both the singlet and triplet excited state photophysics. The results reveal that in both platinum DPP derivatives the organometallic auxochromes have a significant effect on the chromophores\\' photophysics. The most profound effect is a reduction in the fluorescence yields accompanied by enhanced triplet yields due to spin-orbit coupling induced by the metal centers. The effects are most pronounced in DPP-Pt(acac), indicating that the orthometalated platinum auxochrome is able to induce spin-orbital coupling to a greater extent compared to the platinum acetylide units. (Figure Presented).

Branched charge-transfer chromophores featuring a 4,5-dicyanoimidazole unit

Czech Academy of Sciences Publication Activity Database

Bureš, F.; Kulhánek, J.; Mikysek, T.; Ludvík, Jiří; Lokaj, J.

2010-01-01

Roč. 51, č. 15 (2010), s. 2055-2058 ISSN 0040-4039 Institutional research plan: CEZ:AV0Z40400503 Keywords : non-linear optical chromophores * 2-photon absorption * imidazole chromophores Subject RIV: CG - Electrochemistry Impact factor: 2.618, year: 2010

Single oligomer spectra probe chromophore nanoenvironments of tetrameric fluorescent proteins

NARCIS (Netherlands)

Blum, Christian; Meixner, Alfred J; Subramaniam, Vinod

2006-01-01

When analyzing the emission of a large number of individual chromophores embedded in a matrix, the spread of the observed parameters is a characteristic property for the particular chromophore-matrix system. To quantitatively assess the influence of the matrix on the single molecule emission

The gecko visual pigment: the chromophore dark exchange reaction.

Science.gov (United States)

Crescitelli, F

1988-02-01

This study confirms the occurrence of a dark-exchange reaction in the extracted 521-pigment of the Tokay gecko (G. gekko). The present study involved the exchange, in the dark, of the natural 11-cis-chromophore by the 9-cis-10-F-retinal analog. This analog is able to combine with the 521-opsin to regenerate a photopigment at 492 nm. In addition to this shift in absorbance from 521 to 492 nm, the analog photopigment has a photosensitivity some 2.4% that of the native 521-system in the chloride-sufficient state. These two properties of the regenerated analog pigment have simplified the demonstration of a dark exchange of chromophores. At 15 degrees C the 9-cis-10-F-analog replaces the 11-cis-chromophore by at least 30% (density-wise) in about 15 hr. This exchange occurs with the system in the chloride-deficient state. The presence of chloride during the period in the dark significantly reduces the magnitude of the exchange. Apparently, the protein has a more open structure at the chromophoric binding site, allowing this interchange of chromophores. The addition of chloride induces a conformational change at this site, 'burying' the Schiff base and reducing the exchange reaction. The biological implication of this mobile property of the gecko opsin is that it is similar to the behavior of the cone pigment iodopsin but is unlike that of rhodopsins. This supports the idea that the gecko visual cells, despite their appearance as rods, are phylogenetically related to ancestral photopic receptors.

On the ability of PAMAM dendrimers and dendrimer/DNA aggregates to penetrate POPC model biomembranes.

Science.gov (United States)

Ainalem, Marie-Louise; Campbell, Richard A; Khalid, Syma; Gillams, Richard J; Rennie, Adrian R; Nylander, Tommy

2010-06-03

Poly(amido amine) (PAMAM) dendrimers have previously been shown, as cationic condensing agents of DNA, to have high potential for nonviral gene delivery. This study addresses two key issues for gene delivery: the interaction of the biomembrane with (i) the condensing agent (the cationic PAMAM dendrimer) and (ii) the corresponding dendrimer/DNA aggregate. Using in situ null ellipsometry and neutron reflection, parallel experiments were carried out involving dendrimers of generations 2 (G2), 4 (G4), and 6 (G6). The study demonstrates that free dendrimers of all three generations were able to traverse supported palmitoyloleoylphosphatidylcholine (POPC) bilayers deposited on silica surfaces. The model biomembranes were elevated from the solid surfaces upon dendrimer penetration, which offers a promising new way to generate more realistic model biomembranes where the contact with the supporting surface is reduced and where aqueous cavities are present beneath the bilayer. The largest dendrimer (G6) induced partial bilayer destruction directly upon penetration, whereas the smaller dendrimers (G2 and G4) leave the bilayer intact, so we propose that lower generation dendrimers have greater potential as transfection mediators. In addition to the experimental observations, coarse-grained simulations on the interaction between generation 3 (G3) dendrimers and POPC bilayers were performed in the absence and presence of a bilayer-supporting negatively charged surface that emulates the support. The simulations demonstrate that G3 is transported across free-standing POPC bilayers by direct penetration and not by endocytosis. The penetrability was, however, reduced in the presence of a surface, indicating that the membrane transport observed experimentally was not driven solely by the surface. The experimental reflection techniques were also applied to dendrimer/DNA aggregates of charge ratio = 0.5, and while G2/DNA and G4/DNA aggregates interact with POPC bilayers, G6/DNA

Direct Measurement of the Isomerization Barrier of the Isolated Retinal Chromophore

DEFF Research Database (Denmark)

Dilger, Jonathan; Musbat, Lihi; Sheves, Mordechai

2015-01-01

Isomerizations of the retinal chromophore were investigated using the IMS-IMS technique. Four different structural features of the chromophore were observed, isolated, excited collisionally, and the resulting isomer and fragment distributions were measured. By establishing the threshold activatio...

Adsorption and desorption behaviors of cationic liposome-DNA complexes upon lipofection in inside and outside biomembrane models using a dynamic quasi-elastic laser scattering method.

Science.gov (United States)

Uchiyama, Yoshiko; Yui, Hiroharu; Sawada, Tsuguo

2004-11-01

The dynamic behaviors of cationic liposome-DNA complexes in inside and outside biomembrane models upon lipofection were investigated using the time-resolved quasi-elastic laser scattering (QELS) method. Inside and outside biomembrane models with similar phospholipid compositions to those in living cells were formed at a tetradecane/phosphate buffered saline (TD/PBS) interface. Cationic liposome-DNA complexes were injected into the buffer subphase, and their adsorption/desorption behaviors at the biomembrane models were monitored through changes in the interfacial tension. We found that the adsorption rate of the complexes increased 2.6 times more in the outside model than in the inside one. The adsorption rate of DNA alone did not show a remarkable difference from one side to the other; however, the adsorption rate of the cationic liposome alone showed a similar tendency to that of the liposome-DNA complex. These results indicated that the difference in lipid composition induced a different dynamic behavior of exogenous biomolecules and that the cationic liposomes played an important role in the faster incorporation of DNA into cells upon lipofection.

Theoretical study of chromophores for biological sensing: Understanding the mechanism of rhodol based multi-chromophoric systems

Science.gov (United States)

Rivera-Jacquez, Hector J.; Masunov, Artëm E.

2018-06-01

Development of two-photon fluorescent probes can aid in visualizing the cellular environment. Multi-chromophore systems display complex manifolds of electronic transitions, enabling their use for optical sensing applications. Time-Dependent Density Functional Theory (TDDFT) methods allow for accurate predictions of the optical properties. These properties are related to the electronic transitions in the molecules, which include two-photon absorption cross-sections. Here we use TDDFT to understand the mechanism of aza-crown based fluorescent probes for metals sensing applications. Our findings suggest changes in local excitation in the rhodol chromophore between unbound form and when bound to the metal analyte. These changes are caused by a charge transfer from the aza-crown group and pyrazol units toward the rhodol unit. Understanding this mechanism leads to an optimized design with higher two-photon excited fluorescence to be used in medical applications.

Engineering and validation of a novel lipid thin film for biomembrane modeling in lipophilicity determination of drugs and xenobiotics

Directory of Open Access Journals (Sweden)

Ogbonna Udochi

2009-09-01

Full Text Available Abstract Background Determination of lipophilicity as a tool for predicting pharmacokinetic molecular behavior is limited by the predictive power of available experimental models of the biomembrane. There is current interest, therefore, in models that accurately simulate the biomembrane structure and function. A novel bio-device; a lipid thin film, was engineered as an alternative approach to the previous use of hydrocarbon thin films in biomembrane modeling. Results Retention behavior of four structurally diverse model compounds; 4-amino-3,5-dinitrobenzoic acid (ADBA, naproxen (NPX, nabumetone (NBT and halofantrine (HF, representing 4 broad classes of varying molecular polarities and aqueous solubility behavior, was investigated on the lipid film, liquid paraffin, and octadecylsilane layers. Computational, thermodynamic and image analysis confirms the peculiar amphiphilic configuration of the lipid film. Effect of solute-type, layer-type and variables interactions on retention behavior was delineated by 2-way analysis of variance (ANOVA and quantitative structure property relationships (QSPR. Validation of the lipid film was implemented by statistical correlation of a unique chromatographic metric with Log P (octanol/water and several calculated molecular descriptors of bulk and solubility properties. Conclusion The lipid film signifies a biomimetic artificial biological interface capable of both hydrophobic and specific electrostatic interactions. It captures the hydrophilic-lipophilic balance (HLB in the determination of lipophilicity of molecules unlike the pure hydrocarbon film of the prior art. The potentials and performance of the bio-device gives the promise of its utility as a predictive analytic tool for early-stage drug discovery science.

Evaluation of the mechanism of skin enhancing surfactants on the biomembrane of shed snake skin.

Science.gov (United States)

Wonglertnirant, Nanthida; Ngawhirunpat, Tanasait; Kumpugdee-Vollrath, Mont

2012-01-01

The aim of the present work was to investigate the effects of different surfactants at various concentrations as a skin penetration enhancer through the biomembrane of the shed skin of Naja kaouthia. Additionally, the enhancer mechanism(s) of each class of surfactants were evaluated using physical characterization techniques, such as scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, and small and wide angle X-ray scattering (SWAXS). Our results showed that skin permeability increased with increasing concentrations of surfactants and the degree of increase was higher for the model hydrophilic permeant, deuterium dioxide (D(2)O), than the lipophilic permeant, ketoprofen (KP). Ionic surfactants, sodium lauryl sulfate (SLS) and cetyl trimethyl ammonium bromide (CTAB), demonstrated higher enhancement ability than the polyoxyethylene (20) sorbitan mono-oleate (Tween 80) non-ionic surfactant, which was consistent with the results from physical characterization studies. Increasing amounts of permeated drug resulted in an increase in membrane interactions. From our observations, it can be assumed that SLS and CTAB can be localized inside the biomembrane and thereby enhance drug permeation mainly through interactions with intercellular lipids in the stratum corneum (SC) and the creation of a perturbed microenvironment among lipid alkyl chains and polar head groups.

Tautomeric forms of PPI dendrimers functionalized with 4-(4′-ethoxybenzoyloxy)salicylaldehyde chromophores

International Nuclear Information System (INIS)

Franckevičius, M.; Vaišnoras, R.; Marcos, M.; Serrano, J.L.; Gruodis, A.; Galikova, N.; Gulbinas, V.

2012-01-01

Highlights: ► SA chromophore groups are formed by bonding terminal groups to PPI dendrimers. ► SA chromophore groups reveal four most stable tautomeric forms. ► Tautomeric properties of SA groups depend on the dendrimer generation and solvent. ► Aggregation of SA chromophores facilitates formation of the trans-keto tautomers. ► Fluorescence of PPI SA dendrimers is attributed to nπ ∗ states of keto tautomers. -- Abstract: Bonding of the promesogenic unit derived from 4-(4′-ethoxybenzoyloxy)salicylaldehyde to the amino terminated PPI dendrimer chains results in formation of the salicylidenimine chromophore groups. Absorption and fluorescence investigations of the dendrimer solutions supported by the quantum chemistry calculations revealed that the chromophore groups may exist in enol and keto tautomeric forms with relative concentrations depending on the dendrimer generation and solvent. The dendrimer fluorescence is attributed to nπ ∗ states of keto tautomers which may also be formed from excited enol tautomers.

Nanoplasmonic sensing and capillary electrophoresis for fast screening of interactions between phosphatidylcholine biomembranes and surfactants

Czech Academy of Sciences Publication Activity Database

Duša, Filip; Chen, W.; Witos, J.; Wiedmer, S. K.

2018-01-01

Roč. 34, č. 20 (2018), s. 5889-5900 ISSN 0743-7463 Grant - others:AV ČR(CZ) MSM200311602 Program:Program na podporu mezinárodní spolupráce začínajících výzkumných pracovníků Institutional support: RVO:68081715 Keywords : biomembrane * surfactant * nanoplasmon Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 3.833, year: 2016

Skin image illumination modeling and chromophore identification for melanoma diagnosis

Science.gov (United States)

Liu, Zhao; Zerubia, Josiane

2015-05-01

The presence of illumination variation in dermatological images has a negative impact on the automatic detection and analysis of cutaneous lesions. This paper proposes a new illumination modeling and chromophore identification method to correct lighting variation in skin lesion images, as well as to extract melanin and hemoglobin concentrations of human skin, based on an adaptive bilateral decomposition and a weighted polynomial curve fitting, with the knowledge of a multi-layered skin model. Different from state-of-the-art approaches based on the Lambert law, the proposed method, considering both specular reflection and diffuse reflection of the skin, enables us to address highlight and strong shading effects usually existing in skin color images captured in an uncontrolled environment. The derived melanin and hemoglobin indices, directly relating to the pathological tissue conditions, tend to be less influenced by external imaging factors and are more efficient in describing pigmentation distributions. Experiments show that the proposed method gave better visual results and superior lesion segmentation, when compared to two other illumination correction algorithms, both designed specifically for dermatological images. For computer-aided diagnosis of melanoma, sensitivity achieves 85.52% when using our chromophore descriptors, which is 8~20% higher than those derived from other color descriptors. This demonstrates the benefit of the proposed method for automatic skin disease analysis.

Lake and sea populations of Mysis relicta (Crustacea, Mysida with different visual-pigment absorbance spectra use the same A1 chromophore.

Directory of Open Access Journals (Sweden)

Nikolai Belikov

Full Text Available Glacial-relict species of the genus Mysis (opossum shrimps inhabiting both fresh-water lakes and brackish sea waters in northern Europe show a consistent lake/sea dichotomy in eye spectral sensitivity. The absorbance peak (λmax recorded by microspectrophotometry in isolated rhabdoms is invariably 20-30 nm red-shifted in "lake" compared with "sea" populations. The dichotomy holds across species, major opsin lineages and light environments. Chromophore exchange from A1 to A2 (retinal → 3,4-didehydroretinal is a well-known mechanism for red-shifting visual pigments depending on environmental conditions or stages of life history, present not only in fishes and amphibians, but in some crustaceans as well. We tested the hypothesis that the lake/sea dichotomy in Mysis is due to the use of different chromophores, focussing on two populations of M. relicta from, respectively, a Finnish lake and the Baltic Sea. They are genetically very similar, having been separated for less than 10 kyr, and their rhabdoms show a typical lake/sea difference in λmax (554 nm vs. 529 nm. Gene sequencing has revealed no differences translating into amino acid substitutions in the transmembrane parts of their opsins. We determined the chromophore identity (A1 or A2 in the eyes of these two populations by HPLC, using as standards pure chromophores A1 and A2 as well as extracts from bovine (A1 and goldfish (A2 retinas. We found that the visual-pigment chromophore in both populations is A1 exclusively. Thus the spectral difference between these two populations of M. relicta is not due to the use of different chromophores. We argue that this conclusion is likely to hold for all populations of M. relicta as well as its European sibling species.

Chromophore Structure of Photochromic Fluorescent Protein Dronpa: Acid-Base Equilibrium of Two Cis Configurations.

Science.gov (United States)

Higashino, Asuka; Mizuno, Misao; Mizutani, Yasuhisa

2016-04-07

Dronpa is a novel photochromic fluorescent protein that exhibits fast response to light. The present article is the first report of the resonance and preresonance Raman spectra of Dronpa. We used the intensity and frequency of Raman bands to determine the structure of the Dronpa chromophore in two thermally stable photochromic states. The acid-base equilibrium in one photochromic state was observed by spectroscopic pH titration. The Raman spectra revealed that the chromophore in this state shows a protonation/deprotonation transition with a pKa of 5.2 ± 0.3 and maintains the cis configuration. The observed resonance Raman bands showed that the other photochromic state of the chromophore is in a trans configuration. The results demonstrate that Raman bands selectively enhanced for the chromophore yield valuable information on the molecular structure of the chromophore in photochromic fluorescent proteins after careful elimination of the fluorescence background.

Dielectric Properties of Azo Polymers: Effect of the Push-Pull Azo Chromophores

Directory of Open Access Journals (Sweden)

Xuan Zhang

2018-01-01

Full Text Available The relationship between the structure and the dielectric properties of the azo polymers was studied. Four azo polymers were synthesized through the azo-coupling reaction between the same precursor (PAZ and diazonium salts of 4-aminobenzoic acid ethyl ester, 4-aminobenzonitrile, 4-nitroaniline, and 2-amino-5-nitrothiazole, respectively. The precursor and azo polymers were characterized by 1H NMR, FT-IR, UV-vis, GPC, and DSC. The dielectric constant and dielectric loss of the samples were measured in the frequency range of 100 Hz–200 kHz. Due to the existence of the azo chromophores, the dielectric constant of the azo polymers increases compared with that of the precursor. In addition, the dielectric constant of the azo polymers increases with the increase of the polarity of the azo chromophores. A random copolymer (PAZ-NT-PAZ composed of the azo polymer PAZ-NT and the precursor PAZ was also prepared to investigate the content of the azo chromophores on the dielectric properties of the azo polymers. It showed that the dielectric constant increases with the increase of the azo chromophores. The results show that the dielectric constant of this kind of azo polymers can be controlled by changing the structures and contents of azo chromophores during the preparation process.

Synthesis and Properties of the p-Sulfonamide Analogue of the Green Fluorescent Protein (GFP) Chromophore: The Mimic of GFP Chromophore with Very Strong N-H Photoacid Strength.

Science.gov (United States)

Chen, Yi-Hui; Sung, Robert; Sung, Kuangsen

2018-04-06

The para-sulfonamide analogue ( p-TsABDI) of a green fluorescent protein (GFP) chromophore was synthesized to mimic the GFP chromophore. Its S 1 excited-state p K a * value in dimethylsulfoxide (DMSO) is -1.5, which is strong enough to partially protonate dipolar aprotic solvents and causes excited-state proton transfer (ESPT), so it can partially mimic the GFP chromophore to further study the ESPT-related photophysics and the blinking phenomenon of GFP. In comparison with 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) (p K a = 7.4, p K a * = 1.3 in water), p-TsABDI (p K a = 6.7, p K a * = -1.5 in DMSO) is a better photoacid for pH-jump studies.

Photo-fragmentation and electron-detachment studies of gas-phase chromophore ions

DEFF Research Database (Denmark)

Rahbek, Dennis Bo

. Depending on the function of the protein, this may result in human vision, emission of light at a higher wavelength, fluorescence, or harvesting of energy used as an energy source by bacteria, algae or plants. The interaction between these chromophores and the surrounding protein is crucial for fine...... in terms of oscillator strength and excitation energies. Interestingly, the effects are similar for both of the chromophore families....

Ultraviolet-resonance femtosecond stimulated Raman study of the initial events in photoreceptor chromophore

Directory of Open Access Journals (Sweden)

Tahara T.

2013-03-01

Full Text Available Newly-developed ultraviolet-resonance femtosecond stimulated-Raman spectroscopy was utilized to study the initial structural evolution of photoactive yellow protein chromophore in solution. The obtained spectra changed drastically within 1 ps, demonstrating rapid in-plane deformations of the chromophore.

Engineering a genetically-encoded SHG chromophore by electrostatic targeting to the membrane

Directory of Open Access Journals (Sweden)

Yuka eJinno

2014-11-01

Full Text Available Although second harmonic generation (SHG microscopy provides unique imaging advantages for voltage imaging and other biological applications, genetically-encoded SHG chromophores remain relatively unexplored. SHG only arises from non-centrosymmetric media, so an anisotropic arrangement of chromophores is essential to provide strong SHG signals. Here, inspired by the mechanism by which K-Ras4B associates with plasma membranes, we sought to achieve asymmetric arrangements of chromophores at the membrane-cytoplasm interface using the fluorescent protein mVenus. After adding a farnesylation motif to the C-terminus of mVenus, nine amino acids composing its -barrel surface were replaced by lysine, forming an electrostatic patch. This protein (mVe9Knus-CVIM was efficiently targeted to the plasma membrane in a geometrically defined manner and exhibited SHG in HEK293 cells. In agreement with its design, mVe9Knus-CVIM hyperpolarizability was oriented at a small angle (~7.3º from the membrane normal. Genetically-encoded SHG chromophores could serve as a molecular platform for imaging membrane potential.

Resonance raman spectroscopy of an ultraviolet-sensitive insect rhodopsin

International Nuclear Information System (INIS)

Pande, C.; Deng, H.; Rath, P.; Callender, R.H.; Schwemer, J.

1987-01-01

The authors present the first visual pigment resonance Raman spectra from the UV-sensitive eyes of an insect, Ascalaphus macaronius (owlfly). This pigment contains 11-cis-retinal as the chromophore. Raman data have been obtained for the acid metarhodopsin at 10 0 C in both H 2 O and D 2 O. The C=N stretching mode at 1660 cm -1 in H 2 O shifts to 1631 cm -1 upon deuteriation of the sample, clearly showing a protonated Schiff base linkage between the chromophore and the protein. The structure-sensitive fingerprint region shows similarities to the all-trans-protonated Schiff base of model retinal chromophores, as well as to the octopus acid metarhodopsin and bovine metarhodopsin I. Although spectra measured at -100 0 C with 406.7-nm excitation, to enhance scattering from rhodopsin (λ/sub max/ 345 nm), contain a significant contribution from a small amount of contaminants [cytochrome(s) and/or accessory pigment] in the sample, the C=N stretch at 1664 cm -1 suggests a protonated Schiff base linkage between the chromophore and the protein in rhodopsin as well. For comparison, this mode also appears at ∼ 1660 cm -1 in both the vertebrate (bovine) and the invertebrate (octopus) rhodopsins. These data are particularly interesting since the absorption maximum of 345 nm for rhodopsin might be expected to originate from an unprotonated Schiff base linkage. That the Schiff base linkage in the owlfly rhodopsin, like in bovine and in octopus, is protonated suggests that a charged chromophore is essential to visual transduction

Preparation and optical characteristics of layered perovskite-type lead-bromide-incorporated azobenzene chromophores

Science.gov (United States)

Sasai, Ryo; Shinomura, Hisashi

2013-02-01

Lead bromide-based layered perovskite powders with azobenzene derivatives were prepared by a homogeneous precipitation method. From the diffuse reflectance (DR) and photoluminescence (PL) spectra of the hybrid powder materials, the present hybrids exhibited sharp absorption and PL peaks originating from excitons produced in the PbBr42- layer. When the present hybrid powder was irradiated with UV light at 350 nm, the absorption band from the trans-azobenzene chromophore, observed around 350 nm, decreased, while the absorption band from the cis-azobenzene chromophore, observed around 450 nm, increased. These results indicate that azobenzene chromophores in the present hybrid materials exhibit reversible photoisomerization. Moreover, it was found that the PL intensity from the exciton also varied due to photoisomerization of the azobenzene chromophores in the present hybrid. Thus, for the first time we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation.

Interaction of cholesterol-conjugated ionizable amino lipids with biomembranes: lipid polymorphism, structure-activity relationship, and implications for siRNA delivery.

Science.gov (United States)

Zhang, Jingtao; Fan, Haihong; Levorse, Dorothy A; Crocker, Louis S

2011-08-02

Delivery of siRNA is a major obstacle to the advancement of RNAi as a novel therapeutic modality. Lipid nanoparticles (LNP) consisting of ionizable amino lipids are being developed as an important delivery platform for siRNAs, and significant efforts are being made to understand the structure-activity relationship (SAR) of the lipids. This article uses a combination of small-angle X-ray scattering (SAXS) and differential scanning calorimetry (DSC) to evaluate the interaction between cholesterol-conjugated ionizable amino lipids and biomembranes, focusing on an important area of lipid SAR--the ability of lipids to destabilize membrane bilayer structures and facilitate endosomal escape. In this study, cholesterol-conjugated amino lipids were found to be effective in increasing the order of biomembranes and also highly effective in inducing phase changes in biological membranes in vitro (i.e., the lamellar to inverted hexagonal phase transition). The phase transition temperatures, determined using SAXS and DSC, serve as an indicator for ranking the potency of lipids to destabilize endosomal membranes. It was found that the bilayer disruption ability of amino lipids depends strongly on the amino lipid concentration in membranes. Amino lipids with systematic variations in headgroups, the extent of ionization, tail length, the degree of unsaturation, and tail asymmetry were evaluated for their bilayer disruption ability to establish SAR. Overall, it was found that the impact of these lipid structure changes on their bilayer disruption ability agrees well with the results from a conceptual molecular "shape" analysis. Implications of the findings from this study for siRNA delivery are discussed. The methods reported here can be used to support the SAR screening of cationic lipids for siRNA delivery, and the information revealed through the study of the interaction between cationic lipids and biomembranes will contribute significantly to the design of more efficient si

A possibly universal red chromophore for modeling color variations on Jupiter

Science.gov (United States)

Sromovsky, L. A.; Baines, K. H.; Fry, P. M.; Carlson, R. W.

2017-07-01

A new laboratory-generated chemical compound made from photodissociated ammonia (NH3) molecules reacting with acetylene (C2H2) was suggested as a possible coloring agent for Jupiter's Great Red Spot (GRS) by Carlson et al. (2016, Icarus 274, 106-115). Baines et al. (2016, Icarus, submitted) showed that the GRS spectrum measured by the visual channels of the Cassini VIMS instrument in 2000 could be accurately fit by a cloud model in which the chromophore appeared as a physically thin layer of small particles immediately above the main cloud layer of the GRS. Here we show that the same chromophore and same layer location can also provide close matches to the short wavelength spectra of many other cloud features on Jupiter, suggesting this material may be a nearly universal chromophore that could explain the various degrees of red coloration on Jupiter. This is a robust conclusion, even for 12% changes in VIMS calibration and large uncertainties in the refractive index of the main cloud layer due to uncertain fractions of NH4SH and NH3 in its cloud particles. The chromophore layer can account for color variations among north and south equatorial belts, equatorial zone, and the Great Red Spot, by varying particle size from 0.12 μm to 0.29 μm and 1-μm optical depth from 0.06 to 0.76. The total mass of the chromophore layer is much less variable, ranging from 18 to 30 μg/cm2, except in the equatorial zone, where it is only 10-13 μg/cm2. We also found a depression of the ammonia volume mixing ratio in the two belt regions, which averaged 0.4 - 0.5 ×10-4 immediately below the ammonia condensation level, while the other regions averaged twice that value.

Ultrafast dual photoresponse of isolated biological chromophores: link to the photoinduced mode-specific non-adiabatic dynamics in proteins

DEFF Research Database (Denmark)

Bochenkova, Anastasia; Andersen, Lars Henrik

2013-01-01

The anionic wild-type Green Fluorescent Protein (GFP) chromophore defines the entire class of naturally occurring chromophores, which are based on the oxydized tyrosine side chain. The GFP chromophore exhibits an enriched photoinduced non-adiabatic dynamics in the multiple excited-state decay cha...

Highly fluorescent benzofuran derivatives of the GFP chromophore

DEFF Research Database (Denmark)

Christensen, Mikkel Andreas; Jennum, Karsten Stein; Abrahamsen, Peter Bæch

2012-01-01

Intramolecular cyclization reactions of Green Fluorescent Protein chromophores (GFPc) containing an arylethynyl ortho-substituent at the phenol ring provide new aryl-substituted benzofuran derivatives of the GFPc. Some of these heteroaromatic compounds exhibit significantly enhanced fluorescence...

Absorption tuning of the green fluorescent protein chromophore: synthesis and studies of model compounds

DEFF Research Database (Denmark)

Brøndsted Nielsen, Mogens; Andersen, Lars Henrik; Rinza, Tomás Rocha

2011-01-01

The green fluorescent protein (GFP) chromophore is a heterocyclic compound containing a p-hydroxybenzylidine attached to an imidazol-5(4H)-one ring. This review covers the synthesis of a variety of model systems for elucidating the intrinsic optical properties of the chromophore in the gas phase ...

Highly sensitive measurement in two-photon absorption cross section and investigation of the mechanism of two-photon-induced polymerization

Energy Technology Data Exchange (ETDEWEB)

Lu Youmei E-mail: luym19@cc.tuat.ac.jp; Hasegawa, Fuyuki; Goto, Takamichi; Ohkuma, Satoshi; Fukuhara, Setsuko; Kawazu, Yukie; Totani, Kenro; Yamashita, Takashi; Watanabe, Toshiyuki E-mail: toshi@cc.tuat.ac.jp

2004-10-01

A novel two-photon initiator, 4,4'-bis[4-(di-n-butylamino)styryl]-benzene with the side-group methyl (Me) (abbreviated as Chromophore 1), was synthesized in comparison with the chromophore with the side group methoxy (MeO) (abbreviated as Chromophore 2). Femtosecond laser-induced fluorescence intensity was used to evaluate two-photon absorption (TPA) cross section, {delta}, by means of a charge-coupled device, USB-2000 (abbreviated as CCD). Results showed that changing the side group from Me to MeO led to a significant red-shift of the two-photon absorption ({sup 2}{lambda}{sub max}). However, the microstructures obtained by two-photon-induced polymerization (TPIP) demonstrated that the sensitivities of Chromophore 1 increased despite a two-fold decrease in the two-photon cross section {delta}{sub max,} relative to Chromophore 2. Correlated with the appearance that the long-lived charge transfer emission of the chromophore in the monomer bulk, we suggest that the intramolecular charge transfer (intra-CT) takes place within the excited dye. Then intermolecular charge transfer was successive as a result of the formation of an exciplex between the dye and the monomer. The Me group was favorable for the intra-CT, relative to MeO, which contributed to the enhancement of the sensitivity of TPIP.

Synthesis and electro-optic properties of the chromophore-containing NLO polyarylate polymers

Science.gov (United States)

Ren, Haohui; Peng, Chengcheng; Bo, Shuhui; Fan, Guofang; Xu, Guangming; Zhao, Hui; Zhen, Zhen; Liu, Xinhou

2014-03-01

Base on the same two monomers, diphenolic acid (DPA) and isophthaloyl chloride (IPC), three chromophore-containing nonlinear optical (NLO) polyarylate polymers were prepared. A tricyanofuran (TCF)-acceptor type chromophore group was in main-chain (mPAR-chr1), side-chain (sPAR-chr1) and side-chain with a 1,1-bis(4-hydroxyphenyl)-1-phenyl-2,2,2-trifluoroethane (BPAPF) group (sPAR-F-chr1), respectively. The obtained polymers were characterized and evaluated by UV-Vis, 1H NMR, DSC and TGA. All the polymers exhibited good electro-optic (EO) activity. The relationship between EO coefficients (r33) and the chromophore concentration of the three polymers were also characterized and discussed. There were no obvious differences found in EO activity between mPAR-chr1 and sPAR-chr1 polyarylates with the same chromophore. The fluorinated block polyarylate sPAR-F-chr1 has the largest r33 value in these three polyarylates which is 52 pm/V at the wavelength of 1310 nm (which is almost twice the r33 value of normal polymers contained the same chormophore at the same content), when the concentration of chromophore 1 is 18wt.%. 85% of the r33 value was retained in the sPAR-F-chr1 after being heated at 85°C for 600 hours. The polymer sPAR-F-chr1, with good solubility, high Tg (above 200 °C) and side functional group at the same time, may probably be a practical NLO material. These properties make the new polyarylates have potential applications in EO devices such as EO modulators and switches.

Quantitative analysis of valence photoemission spectra and quasiparticle excitations at chromophore-semiconductor interfaces.

Science.gov (United States)

Patrick, Christopher E; Giustino, Feliciano

2012-09-14

Investigating quasiparticle excitations of molecules on surfaces through photoemission spectroscopy forms a major part of nanotechnology research. Resolving spectral features at these interfaces requires a comprehensive theory of electron removal and addition processes in molecules and solids which captures the complex interplay of image charges, thermal effects, and configurational disorder. Here, we develop such a theory and calculate the quasiparticle energy-level alignment and the valence photoemission spectrum for the prototype biomimetic solar cell interface between anatase TiO(2) and the N3 chromophore. By directly matching our calculated photoemission spectrum to experimental data, we clarify the atomistic origin of the chromophore peak at low binding energy. This case study sets a new standard in the interpretation of photoemission spectroscopy at complex chromophore-semiconductor interfaces.

Facile attachment of nonlinear optical chromophores to polycarbonates

NARCIS (Netherlands)

Faccini, M.; Balakrishnan, M.; Torosantucci, Riccardo; Driessen, A.; Reinhoudt, David; Verboom, Willem

2008-01-01

A versatile, generally applicable synthetic methodology for side-chain NLO polycarbonates was developed. This represents the first example of covalent incorporation of NLO chromophores to a prepolymerized polycarbonate backbone. This methodology allows to adjust the polymer backbone structure and to

BFPTool: a software tool for analysis of Biomembrane Force Probe experiments.

Science.gov (United States)

Šmít, Daniel; Fouquet, Coralie; Doulazmi, Mohamed; Pincet, Frédéric; Trembleau, Alain; Zapotocky, Martin

2017-01-01

The Biomembrane Force Probe is an approachable experimental technique commonly used for single-molecule force spectroscopy and experiments on biological interfaces. The technique operates in the range of forces from 0.1 pN to 1000 pN. Experiments are typically repeated many times, conditions are often not optimal, the captured video can be unstable and lose focus; this makes efficient analysis challenging, while out-of-the-box non-proprietary solutions are not freely available. This dedicated tool was developed to integrate and simplify the image processing and analysis of videomicroscopy recordings from BFP experiments. A novel processing feature, allowing the tracking of the pipette, was incorporated to address a limitation of preceding methods. Emphasis was placed on versatility and comprehensible user interface implemented in a graphical form. An integrated analytical tool was implemented to provide a faster, simpler and more convenient way to process and analyse BFP experiments.

Contrasting the excited-state dynamics of the photoactive yellow protein chromophore: Protein versus solvent environments

NARCIS (Netherlands)

Vengris, M.; Horst, M.A.; Zgrablic, G.; van Stokkum, I.H.M.; Haacke, S.; Chergui, M.; Hellingwerf, K.J.; van Grondelle, R.; Larsen, D.S.

2004-01-01

Wavelength- and time-resolved fluorescence experiments have been performed on the photoactive yellow protein, the E46Q mutant, the hybrids of these proteins containing a nonisomerizing "locked" chromophore, and the native and locked chromophores in aqueous solution. The ultrafast dynamics of these

An adaptive meshfree method for phase-field models of biomembranes. Part I: Approximation with maximum-entropy basis functions

OpenAIRE

Rosolen, A.; Peco, C.; Arroyo, M.

2013-01-01

We present an adaptive meshfree method to approximate phase-field models of biomembranes. In such models, the Helfrich curvature elastic energy, the surface area, and the enclosed volume of a vesicle are written as functionals of a continuous phase-field, which describes the interface in a smeared manner. Such functionals involve up to second-order spatial derivatives of the phase-field, leading to fourth-order Euler–Lagrange partial differential equations (PDE). The solutions develop sharp i...

Enhancement of biomembrane functions under phase-separated conditions: A self-organized criticality phenomenon?

International Nuclear Information System (INIS)

Eze, M.O.; Chela Flores, J.

1993-12-01

Self-organized criticality (SOC) is hereby proposed as a possible physical basis for explaining observations in the temperature-dependence of the rates of biological membrane-associated events. The biomembrane undergoes a reversible, cooperative, thermotropic gel-to-liquid crystalline phase transition which is broad, and involves lateral phase separation. The lateral phase separated (rather than the totally gel-, or the totally liquid crystalline-) membrane state has been observed to be the state in which vital membrane functions are facilitated. The membrane in this unique state is viewed, for our purposes here, as a dynamical, extended dissipative system with spatial and temporal degrees of freedom, exhibiting power law behaviour, typical of the self-organized critical state. Experiments are suggested for verifying this hypothesis. (author). 30 refs

Stabilization of structure in near-infrared fluorescent proteins by binding of biliverdin chromophore

Science.gov (United States)

Stepanenko, Olesya V.; Stepanenko, Olga V.; Bublikov, G. S.; Kuznetsova, I. M.; Verkhusha, V. V.; Turoverov, K. K.

2017-07-01

Near-infrared fluorescent proteins (NIR FPs) engineered from bacterial phytochromes and their mutants with different location of Cys residues, which able to bind a biliverdin chromophore, or without these Cys residues were studied using intrinsic tryptophan fluorescence, NIR fluorescence and circular dichroism. It was shown that a covalent binding of the biliverdin chromophore to a Cys residue via thioether group substantially stabilizes the spatial structure of NIR FPs. The stability of the protein structure and the chromophore association strength strongly depends on the location of Cys residues and decreases in the following order: a protein with Cys residues in both domains, a protein with Cys in PAS domains, and a protein with Cys in GAF domains. NIR FPs without Cys residues capable to covalently attach biliverdin have the lowest stability, comparable to NIR FP apoforms.

Dual Mechanism Nonlinear Response of Selected Metal Organic Chromophores

National Research Council Canada - National Science Library

Peak, John D

2007-01-01

13 The goal for the research described herein is the development of a series of transition metal based metal organic chromophores that display both two-photon and excited state absorption (TPA/ESA) character...

Fabrication of biomembrane-like films on carbon electrodes using alkanethiol and diazonium salt and their application for direct electrochemistry of myoglobin.

Science.gov (United States)

Anjum, Saima; Qi, Wenjing; Gao, Wenyue; Zhao, Jianming; Hanif, Saima; Aziz-Ur-Rehman; Xu, Guobao

2015-03-15

Alkanethiols generally form self-assembled monolayers on gold electrodes and the electrochemical reduction of aromatic diazonium salts is a popular method for the covalent modification of carbon. Based on the reaction of alkanethiol with aldehyde groups covalently bound on carbon surface by the electrochemical reduction of aromatic diazonium salts, a new strategy for the modification of carbon electrodes with alkanethiols has been developed. The modification of carbon surface with aldehyde groups is achieved by the electrochemical reduction of aromatic diazonium salts in situ electrogenerated from a nitro precursor, p-nitrophenylaldehyde, in the presence of nitrous acid. By this way, in situ electrogenerated p-aminophenyl aldehyde from p-nitrophenylaldehyde immediately reacts with nitrous acid, effectively minimizing the side reaction of amine groups and aldehyde groups. The as-prepared alkanethiol-modified glassy carbon electrode was further used to make biomembrane-like films by casting didodecyldimethylammonium bromide on its surface. The biomembrane-like films enable the direct electrochemistry of immobilized myoglobin for the detection of hydrogen peroxide. The response is linear over the range of 1-600μM with a detection limit of 0.3μM. Copyright © 2014 Elsevier B.V. All rights reserved.

Performance of Popular XC-Functionals for the Description of Excitation Energies in GFP-Like Chromophore Models

DEFF Research Database (Denmark)

List, Nanna Holmgaard; Olsen, Jógvan Magnus Haugaard; Rocha-Rinza, Tomás

2012-01-01

this task. We present an evaluation of the performance of commonly used XC-functionals for the prediction of excitation energies of GFP-like chromophores. In particular, we have considered the TD-DFT vertical excitation energies of chromophores displaying different charge states. We compare the quality...

Smartphone snapshot mapping of skin chromophores under triple-wavelength laser illumination

Science.gov (United States)

Spigulis, Janis; Oshina, Ilze; Berzina, Anna; Bykov, Alexander

2017-09-01

Chromophore distribution maps are useful tools for skin malformation severity assessment and for monitoring of skin recovery after burns, surgeries, and other interactions. The chromophore maps can be obtained by processing several spectral images of skin, e.g., captured by hyperspectral or multispectral cameras during seconds or even minutes. To avoid motion artifacts and simplify the procedure, a single-snapshot technique for mapping melanin, oxyhemoglobin, and deoxyhemoglobin of in-vivo skin by a smartphone under simultaneous three-wavelength (448-532-659 nm) laser illumination is proposed and examined. Three monochromatic spectral images related to the illumination wavelengths were extracted from the smartphone camera RGB image data set with respect to crosstalk between the RGB detection bands. Spectral images were further processed accordingly to Beer's law in a three chromophore approximation. Photon absorption path lengths in skin at the exploited wavelengths were estimated by means of Monte Carlo simulations. The technique was validated clinically on three kinds of skin lesions: nevi, hemangiomas, and seborrheic keratosis. Design of the developed add-on laser illumination system, image-processing details, and the results of clinical measurements are presented and discussed.

Theoretical description of protein field effects on electronic excitations of biological chromophores

International Nuclear Information System (INIS)

Varsano, Daniele; Caprasecca, Stefano; Coccia, Emanuele

2017-01-01

Photoinitiated phenomena play a crucial role in many living organisms. Plants, algae, and bacteria absorb sunlight to perform photosynthesis, and convert water and carbon dioxide into molecular oxygen and carbohydrates, thus forming the basis for life on Earth. The vision of vertebrates is accomplished in the eye by a protein called rhodopsin, which upon photon absorption performs an ultrafast isomerisation of the retinal chromophore, triggering the signal cascade. Many other biological functions start with the photoexcitation of a protein-embedded pigment, followed by complex processes comprising, for example, electron or excitation energy transfer in photosynthetic complexes. The optical properties of chromophores in living systems are strongly dependent on the interaction with the surrounding environment (nearby protein residues, membrane, water), and the complexity of such interplay is, in most cases, at the origin of the functional diversity of the photoactive proteins. The specific interactions with the environment often lead to a significant shift of the chromophore excitation energies, compared with their absorption in solution or gas phase. The investigation of the optical response of chromophores is generally not straightforward, from both experimental and theoretical standpoints; this is due to the difficulty in understanding diverse behaviours and effects, occurring at different scales, with a single technique. In particular, the role played by ab initio calculations in assisting and guiding experiments, as well as in understanding the physics of photoactive proteins, is fundamental. At the same time, owing to the large size of the systems, more approximate strategies which take into account the environmental effects on the absorption spectra are also of paramount importance. Here we review the recent advances in the first-principle description of electronic and optical properties of biological chromophores embedded in a protein environment. We show

Theoretical description of protein field effects on electronic excitations of biological chromophores

Science.gov (United States)

Varsano, Daniele; Caprasecca, Stefano; Coccia, Emanuele

2017-01-01

Photoinitiated phenomena play a crucial role in many living organisms. Plants, algae, and bacteria absorb sunlight to perform photosynthesis, and convert water and carbon dioxide into molecular oxygen and carbohydrates, thus forming the basis for life on Earth. The vision of vertebrates is accomplished in the eye by a protein called rhodopsin, which upon photon absorption performs an ultrafast isomerisation of the retinal chromophore, triggering the signal cascade. Many other biological functions start with the photoexcitation of a protein-embedded pigment, followed by complex processes comprising, for example, electron or excitation energy transfer in photosynthetic complexes. The optical properties of chromophores in living systems are strongly dependent on the interaction with the surrounding environment (nearby protein residues, membrane, water), and the complexity of such interplay is, in most cases, at the origin of the functional diversity of the photoactive proteins. The specific interactions with the environment often lead to a significant shift of the chromophore excitation energies, compared with their absorption in solution or gas phase. The investigation of the optical response of chromophores is generally not straightforward, from both experimental and theoretical standpoints; this is due to the difficulty in understanding diverse behaviours and effects, occurring at different scales, with a single technique. In particular, the role played by ab initio calculations in assisting and guiding experiments, as well as in understanding the physics of photoactive proteins, is fundamental. At the same time, owing to the large size of the systems, more approximate strategies which take into account the environmental effects on the absorption spectra are also of paramount importance. Here we review the recent advances in the first-principle description of electronic and optical properties of biological chromophores embedded in a protein environment. We show

Simultaneous control of emission localization and two-photon absorption efficiency in dissymmetrical chromophores

International Nuclear Information System (INIS)

Tretiak, Sergei

2009-01-01

The aim of the present work is to demonstrate that combined spectral tuning of fluorescence and two-photon absorption (TPA) properties of multipolar chromophores can be achieved by introduction of slight electronic chemical dissymmetry. In that perspective, two novel series of structurally related chromophores have been designed and studied: a first series based on rod-like quadrupolar chromophores bearing different electron-donating (D) end groups and a second series based on three-branched octupolar chromophores built from a trigonal donating moiety and bearing various acceptor (A) peripheral groups. The influence of the electronic dissymmetry is investigated by combined experimental and theoretical studies of the linear and nonlinear optical properties of dissymmetric chromophores compared to their symmetrical counterparts. In both types of systems (i.e. quadrupoles and octupoles) experiments and theory reveal that excitation is essentially delocalized and that excitation involves synchronized charge redistribution between the different D and A moieties within the multipolar structure (i.e. concerted intramolecular charge transfer). In contrast, the emission stems only from a particular dipolar subunit bearing the strongest D or A moieties due to fast excitation localization after excitation prior to emission. Hence control of emission characteristics (polarization and emission spectrum) in addition to localization can be achieved by controlled introduction of electronic dissymmetry (i.e. replacement of one of the D or A end-groups by a slightly stronger D(prime) or A(prime) units). Interestingly dissymmetrical functionalization of both quadrupolar and octupolar compounds does not lead to significant loss in TPA responses and can even be beneficial due to the spectral broadening and peak position tuning that it allows. This study thus reveals an original molecular engineering route strategy allowing major TPA enhancement in multipolar structures due to concerted

Gas phase absorption studies of photoactive yellow protein chromophore derivatives.

Science.gov (United States)

Rocha-Rinza, Toms; Christiansen, Ove; Rajput, Jyoti; Gopalan, Aravind; Rahbek, Dennis B; Andersen, Lars H; Bochenkova, Anastasia V; Granovsky, Alexander A; Bravaya, Ksenia B; Nemukhin, Alexander V; Christiansen, Kasper Lincke; Nielsen, Mogens Brøndsted

2009-08-27

Photoabsorption spectra of deprotonated trans p-coumaric acid and two of its methyl substituted derivatives have been studied in gas phase both experimentally and theoretically. We have focused on the spectroscopic effect of the location of the two possible deprotonation sites on the trans p-coumaric acid which originate to either a phenoxide or a carboxylate. Surprisingly, the three chromophores were found to have the same absorption maximum at 430 nm, in spite of having different deprotonation positions. However, the absorption of the chromophore in polar solution is substantially different for the distinct deprotonation locations. We also report on the time scales and pathways of relaxation after photoexcitation for the three photoactive yellow protein chromophore derivatives. As a result of these experiments, we could detect the phenoxide isomer within the deprotonated trans p-coumaric acid in gas phase; however, the occurrence of the carboxylate is uncertain. Several computational methods were used simultaneously to provide insights and assistance in the interpretation of our experimental results. The calculated excitation energies S(0)-S(1) are in good agreement with experiment for those systems having a negative charge on a phenoxide moiety. Although our augmented multiconfigurational quasidegenerate perturbation theory calculations agree with experiment in the description of the absorption spectrum of anions with a carboxylate functional group, there are some puzzling disagreements between experiment and some calculational methods in the description of these systems.

Fractal analysis of lateral movement in biomembranes.

Science.gov (United States)

Gmachowski, Lech

2018-04-01

Lateral movement of a molecule in a biomembrane containing small compartments (0.23-μm diameter) and large ones (0.75 μm) is analyzed using a fractal description of its walk. The early time dependence of the mean square displacement varies from linear due to the contribution of ballistic motion. In small compartments, walking molecules do not have sufficient time or space to develop an asymptotic relation and the diffusion coefficient deduced from the experimental records is lower than that measured without restrictions. The model makes it possible to deduce the molecule step parameters, namely the step length and time, from data concerning confined and unrestricted diffusion coefficients. This is also possible using experimental results for sub-diffusive transport. The transition from normal to anomalous diffusion does not affect the molecule step parameters. The experimental literature data on molecular trajectories recorded at a high time resolution appear to confirm the modeled value of the mean free path length of DOPE for Brownian and anomalous diffusion. Although the step length and time give the proper values of diffusion coefficient, the DOPE speed calculated as their quotient is several orders of magnitude lower than the thermal speed. This is interpreted as a result of intermolecular interactions, as confirmed by lateral diffusion of other molecules in different membranes. The molecule step parameters are then utilized to analyze the problem of multiple visits in small compartments. The modeling of the diffusion exponent results in a smooth transition to normal diffusion on entering a large compartment, as observed in experiments.

Electron transport through supported biomembranes at the nanoscale by conductive atomic force microscopy

International Nuclear Information System (INIS)

Casuso, I; Fumagalli, L; Samitier, J; Padros, E; Reggiani, L; Akimov, V; Gomila, G

2007-01-01

We present a reliable methodology to perform electron transport measurements at the nanoscale on supported biomembranes by conductive atomic force microscopy (C-AFM). It allows measurement of both (a) non-destructive conductive maps and (b) force controlled current-voltage characteristics in wide voltage bias range in a reproducible way. Tests experiments were performed on purple membrane monolayers, a two-dimensional (2D) crystal lattice of the transmembrane protein bacteriorhodopsin. Non-destructive conductive images show uniform conductivity of the membrane with isolated nanometric conduction defects. Current-voltage characteristics under different compression conditions show non-resonant tunneling electron transport properties, with two different conduction regimes as a function of the applied bias, in excellent agreement with theoretical predictions. This methodology opens the possibility for a detailed study of electron transport properties of supported biological membranes, and of soft materials in general

Electron transport through supported biomembranes at the nanoscale by conductive atomic force microscopy

Energy Technology Data Exchange (ETDEWEB)

Casuso, I [Department Electronica, Universitat de Barcelona and Laboratori de Nanobioenginyeria-IBEC, Parc CientIfic de Barcelona, Barcelona (Spain); Fumagalli, L [Department Electronica, Universitat de Barcelona and Laboratori de Nanobioenginyeria-IBEC, Parc CientIfic de Barcelona, Barcelona (Spain); Samitier, J [Department Electronica, Universitat de Barcelona and Laboratori de Nanobioenginyeria-IBEC, Parc CientIfic de Barcelona, Barcelona (Spain); Padros, E [Unitat de BiofIsica, Departamento de BioquImica i de Biologia Molecular, Facultat de Medicina i Centre d' Estudis en BiofIsica, Universitat Autonoma de Barcelona, Barcelona (Spain); Reggiani, L [CNR-INFM National Nanotechnology Laboratory, Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, Lecce (Italy); Akimov, V [CNR-INFM National Nanotechnology Laboratory, Dipartimento di Ingegneria dell' Innovazione, Universita di Lecce, Lecce (Italy); Gomila, G [Department Electronica, Universitat de Barcelona and Laboratori de Nanobioenginyeria-IBEC, Parc CientIfic de Barcelona, Barcelona (Spain)

2007-11-21

We present a reliable methodology to perform electron transport measurements at the nanoscale on supported biomembranes by conductive atomic force microscopy (C-AFM). It allows measurement of both (a) non-destructive conductive maps and (b) force controlled current-voltage characteristics in wide voltage bias range in a reproducible way. Tests experiments were performed on purple membrane monolayers, a two-dimensional (2D) crystal lattice of the transmembrane protein bacteriorhodopsin. Non-destructive conductive images show uniform conductivity of the membrane with isolated nanometric conduction defects. Current-voltage characteristics under different compression conditions show non-resonant tunneling electron transport properties, with two different conduction regimes as a function of the applied bias, in excellent agreement with theoretical predictions. This methodology opens the possibility for a detailed study of electron transport properties of supported biological membranes, and of soft materials in general.

Orientation phenomena in chromophore DR1-containing polymer films and their non-linear optical response

International Nuclear Information System (INIS)

Moencke, Doris; Mountrichas, Grigoris; Pispas, Stergios; Kamitsos, Efstratios I.

2011-01-01

The effectiveness of chromophore alignment in polymer films following corona poling can be assessed by the generated second harmonic signal. Optimization of the stability and strength of this nonlinear optical response may improve with a better understanding of the underlying principal order phenomena. Structural analysis by vibrational, optical, and 1 H NMR spectroscopy reveals side chain tacticity, aggregation effects, and changes in orientation as a function of temperature. Co-polymers with the functionalized chromophore Disperse Red 1 methacrylate (MDR1) were prepared for three different methacrylate types. High side chain polarity and short side chain length increase generally chromophore aggregation in films, whereas the very long poly-ether side chains in PMEO based co-polymers are wrapped separately around the DR1 entities. Side chain tacticity depends on space requirements, but also on the capacity of side groups to form OH-bridges. Side chain tacticity might present an additional parameter for the assessment of chromophore aggregation and poling induced alignments. Stepwise heating of co-polymer films causes an increase in the number of random over ordered side chain arrangements. Cross-linking by anhydride formation is observed after heating the methacrylic acid based co-polymer.

Preparation and optical characteristics of layered perovskite-type lead-bromide-incorporated azobenzene chromophores

International Nuclear Information System (INIS)

Sasai, Ryo; Shinomura, Hisashi

2013-01-01

Lead bromide-based layered perovskite powders with azobenzene derivatives were prepared by a homogeneous precipitation method. From the diffuse reflectance (DR) and photoluminescence (PL) spectra of the hybrid powder materials, the present hybrids exhibited sharp absorption and PL peaks originating from excitons produced in the PbBr 4 2− layer. When the present hybrid powder was irradiated with UV light at 350 nm, the absorption band from the trans-azobenzene chromophore, observed around 350 nm, decreased, while the absorption band from the cis-azobenzene chromophore, observed around 450 nm, increased. These results indicate that azobenzene chromophores in the present hybrid materials exhibit reversible photoisomerization. Moreover, it was found that the PL intensity from the exciton also varied due to photoisomerization of the azobenzene chromophores in the present hybrid. Thus, for the first time we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation. - Graphical abstract: For the first time, we succeeded in preparing the azobenzene derivative lead-bromide-based layered perovskite with photochromism before and after UV light irradiation. Highlights: ► PbBr-based layered perovskite with azobenezene derivatives could be synthesized by a homogeneous precipitation method. ► Azobenzene derivatives incorporated the present hybrid that exhibited reversible photoisomerization under UV and/or visible light irradiation. ► PL property of the present hybrid could also be varied by photoisomerization.

Solid state supramolecular structure of diketopyrrolopyrrole chromophores: correlating stacking geometry with visible light absorption

OpenAIRE

Pop, Flavia; Lewis, William; Amabilino, David B.

2016-01-01

Mono- and di-alkylated 1,4-diketo-3,6-dithiophenylpyrrolo[3-4-c]pyrrole derivatives (TDPPs) have been synthesised and their solid state packing and absorption properties have been correlated. In this library of compounds the bulkier substituents distort the geometry of the chromophores and shift the lowest energy absorption band as a consequence of reduced π–π stacking and inter-chromophore overlap. Longitudinal displacement of the conjugated core is affected by donor–acceptor intermolecular ...

A sensitive fluorescent sensor of lanthanide ions

CERN Document Server

Bekiari, V; Lianos, P

2003-01-01

A fluorescent probe bearing a diazostilbene chromophore and a benzo-15-crown-5 ether moiety is a very efficient sensor of lanthanide ions. The ligand emits strong fluorescence only in the presence of specific ions, namely lanthanide ions, while the emission wavelength is associated with a particular ion providing high sensitivity and resolution.

Red-light absorption and fluorescence of phytochrome chromophores: A comparative theoretical study

Energy Technology Data Exchange (ETDEWEB)

Falklöf, Olle; Durbeej, Bo, E-mail: bodur@ifm.liu.se

2013-11-08

Highlights: • Calculation of red-light absorption and emission of phytochrome chromophores. • Comparison of TD-DFT and ab initio methods. • Pure functionals show better accuracy than hybrid functionals. - Abstract: Currently, much experimental effort is being invested in the engineering of phytochromes, a large superfamily of photoreceptor proteins, into fluorescent proteins suitable for bioimaging in the near-infrared regime. In this work, we gain insight into the potential of computational methods to contribute to this development by investigating how well representative quantum chemical methods reproduce recently recorded red-light absorption and emission maxima of synthetic derivatives of the bilin chromophores of phytochromes. Focusing on the performance of time-dependent density functional theory but using also the ab initio CIS(D), CC2 and CASPT2 methods, we explore how various methodological considerations influence computed spectra and find, somewhat surprisingly, that density functionals lacking exact exchange reproduce the experimental measurements with smaller errors than functionals that include exact exchange. Thus, for the important class of chromophores that bilins constitute, the widely established trend that hybrid functionals give more accurate excitation energies than pure functionals does not apply.

Artificial biomembrane morphology: a dissipative particle dynamics study.

Science.gov (United States)

Becton, Matthew; Averett, Rodney; Wang, Xianqiao

2017-09-18

Artificial membranes mimicking biological structures are rapidly breaking new ground in the areas of medicine and soft-matter physics. In this endeavor, we use dissipative particle dynamics simulation to investigate the morphology and behavior of lipid-based biomembranes under conditions of varied lipid density and self-interaction. Our results show that a less-than-normal initial lipid density does not create the traditional membrane; but instead results in the formation of a 'net', or at very low densities, a series of disparate 'clumps' similar to the micelles formed by lipids in nature. When the initial lipid density is high, a membrane forms, but due to the large number of lipids, the naturally formed membrane would be larger than the simulation box, leading to 'rippling' behavior as the excess repulsive force of the membrane interior overcomes the bending energy of the membrane. Once the density reaches a certain point however, 'bubbles' appear inside the membrane, reducing the rippling behavior and eventually generating a relatively flat, but thick, structure with micelles of water inside the membrane itself. Our simulations also demonstrate that the interaction parameter between individual lipids plays a significant role in the formation and behavior of lipid membrane assemblies, creating similar structures as the initial lipid density distribution. This work provides a comprehensive approach to the intricacies of lipid membranes, and offers a guideline to design biological or polymeric membranes through self-assembly processes as well as develop novel cellular manipulation and destruction techniques.

Gas-phase infrared spectrum of the anionic GFP-chromophore

NARCIS (Netherlands)

Almasian, M.; Grzetic, J.; G. Berden,; Bakker, B.; Buma, W. J.; Oomens, J.

2012-01-01

The gas-phase IR spectrum of the anionic chromophore of the green fluorescent protein (p-hydroxy-benzylidene-2,3-dimethylimidazolidinone, HBDI) is recorded in the 800–1800 cm−1 frequency range using the free electron laser FELIX in combination with an electrospray ionization (ESI) Fourier

An adaptive meshfree method for phase-field models of biomembranes. Part II: A Lagrangian approach for membranes in viscous fluids

OpenAIRE

Peco, C.; Rosolen, A.; Arroyo, M.

2013-01-01

We present a Lagrangian phase-field method to study the low Reynolds number dynamics of vesicles embedded in a viscous fluid. In contrast to previous approaches, where the field variables are the phase-field and the fluid velocity, here we exploit the fact that the phasefield tracks a material interface to reformulate the problem in terms of the Lagrangian motion of a background medium, containing both the biomembrane and the fluid. We discretize the equations in space with maximum-entr...

CHROMOPHORIC DISSOLVED ORGANIC MATTER (CDOM) SOURCE CHARACTERIZATION IN THE LOUISIANA BIGHT

Science.gov (United States)

Chromophoric dissolved organic matter (CDOM) in the Mississippi plume region may have several distinct sources: riverine (terrestrial soils), wetland (terrestrial plants), biological production (phytoplankton, zooplankton, microbial), and sediments. Complex mixing, photodegradati...

Chemical modification of glass surface with a monolayer of nonchromophoric and chromophoric methacrylate terpolymer

Energy Technology Data Exchange (ETDEWEB)

Janik, Ryszard [Department of Polymer Engineering and Technology, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Kucharski, Stanislaw, E-mail: stanislaw.kucharski@pwr.wroc.pl [Department of Polymer Engineering and Technology, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Sobolewska, Anna [Institute of Physical and Theoretical Chemistry, Wroclaw University of Technology, 50-370 Wroclaw (Poland); Barille, Regis [Institut des Sciences et Techniques Moleculaires d' Angers ' Moltech Anjou' , CNRS UMR 6200, 49045 Angers (France)

2010-11-15

The methacrylate terpolymers, a nonchromophoric and chromophoric one, containing 2-hydroxyethyl groups were reacted with 3-isocyanatopropyltriethoxysilane to obtain reactive polymers able to form covalent bonding with -SiOH groups of the glass surface via triethoxysilane group condensation. Chemical modification of the Corning 2949 glass plates treated in this way resulted in increase of wetting angle from 11{sup o} to ca. 70-73{sup o}. Determination of ellipsometric parameters revealed low value of the substrate refractive index as compared with that of bulk Corning 2949 glass suggesting roughness of the surface. The AFM image of the bare glass surface and that modified with terpolymer monolayer confirmed this phenomenon. Modification of the glass with the terpolymer monolayer made it possible to create the substrate surface well suited for deposition of familiar chromophore film by spin-coating. The chromophore polymer film deposited onto the modified glass surface was found to be resistant to come unstuck in aqueous solution.

Fiber optic-based fluorescence detection system for in vivo studies of exogenous chromophore pharmacokinetics

Science.gov (United States)

Doiron, Daniel R.; Dunn, J. B.; Mitchell, W. L.; Dalton, Brian K.; Garbo, Greta M.; Warner, Jon A.

1995-05-01

The detection and quantification of the concentration of exogenous chromophores in-vivo by their fluorescence is complicated by many physical and geometrical parameters. Measurement of such signals is advantageous in determining the pharmacokinetics of photosensitizers such as those used in photodynamic therapy (PDT) or to assist in the diagnosis of tissue histological state. To overcome these difficulties a ratio based fiber optic contact fluorometer has been developed. This fluorescence detection system (FDS) uses the ratio of the fluorescence emission peak of the exogenous chromophore to that of endogenous chromophores, i.e. autofluorescence, to correct for a variety of parameters affecting the magnitude of the measured signals. By doing so it also minimizes the range of baseline measurements prior to exogenous drug injection, for various tissue types. Design of the FDS and results of its testing in animals and patients using the second generation photosensitizer Tin ethyletiopurpurin (SnET2) are presented. These results support the feasibility and usefulness of the Ratio FDS system.

Minimal domain of bacterial phytochrome required for chromophore binding and fluorescence

Science.gov (United States)

Rumyantsev, Konstantin A.; Shcherbakova, Daria M.; Zakharova, Natalia I.; Emelyanov, Alexander V.; Turoverov, Konstantin K.; Verkhusha, Vladislav V.

2015-12-01

Fluorescent proteins (FP) are used to study various biological processes. Recently, a series of near-infrared (NIR) FPs based on bacterial phytochromes was developed. Finding ways to improve NIR FPs is becoming progressively important. By applying rational design and molecular evolution we have engineered R. palustris bacterial phytochrome into a single-domain NIR FP of 19.6 kDa, termed GAF-FP, which is 2-fold and 1.4-fold smaller than bacterial phytochrome-based NIR FPs and GFP-like proteins, respectively. Engineering of GAF-FP involved a substitution of 15% of its amino acids and a deletion of the knot structure. GAF-FP covalently binds two tetrapyrrole chromophores, biliverdin (BV) and phycocyanobilin (PCB). With the BV chromophore GAF-FP absorbs at 635 nm and fluoresces at 670 nm. With the PCB chromophore GAF-FP becomes blue-shifted and absorbs at 625 nm and fluoresces at 657 nm. The GAF-FP structure has a high tolerance to small peptide insertions. The small size of GAF-FP and its additional absorbance band in the violet range has allowed for designing a chimeric protein with Renilla luciferase. The chimera exhibits efficient non-radiative energy transfer from luciferase to GAF-FP, resulting in NIR bioluminescence. This study opens the way for engineering of small NIR FPs and NIR luciferases from bacterial phytochromes.

Effect of Solvation on Electron Detachment and Excitation Energies of a Green Fluorescent Protein Chromophore Variant.

Science.gov (United States)

Bose, Samik; Chakrabarty, Suman; Ghosh, Debashree

2016-05-19

Hybrid quantum mechanics/molecular mechanics (QM/MM) is applied to the fluorinated green fluorescent protein (GFP) chromophore (DFHBDI) in its deprotonated form to understand the solvatochromic shifts in its vertical detachment energy (VDE) and vertical excitation energy (VEE). This variant of the GFP chromophore becomes fluorescent in an RNA environment and has a wide range of applications in biomedical and biochemical fields. From microsolvation studies, we benchmark (with respect to full QM) the accuracy of our QM/MM calculations with effective fragment potential (EFP) as the MM method of choice. We show that while the solvatochromic shift in the VEE is minimal (0.1 eV blue shift) and its polarization component is only 0.03 eV, the effect of the solvent on the VDE is quite large (3.85 eV). We also show by accurate calculations on the solvatochromic shift of the VDE that polarization accounts for ∼0.23 eV and therefore cannot be neglected. The effect of the counterions on the VDE of the deprotonated chromophore in solvation is studied in detail, and a charge-smearing scheme is suggested for charged chromophores.

Uso da biomembrana de látex em cavidade exenterada: relato de caso The use of latex biomembrane in exenteration: case report

Directory of Open Access Journals (Sweden)

Fernando Fugimoto

2007-10-01

Full Text Available A membrana de látex é um material extraído da Hevea brasiliensis, e devido às suas propriedades neoangiogênicas, de adesão celular e formação de matriz extracelular, é utilizada em recobrimentos de úlceras, meringoplastias e outras feridas, com sucesso. Neste caso descrevemos seu uso, inédito, na ferida pós-exenteração orbitária por carcinoma basocelular em paciente do sexo masculino, 72 anos, procedente da Bahia com lesão na pálpebra do olho esquerdo há dois anos com prurido, sangramento, lacrimejamento, e dor. Ao exame oftalmológico do olho esquerdo evidenciou-se lesão ulcerada de pálpebra superior e canto medial, hiperemia conjuntival, afilamento corneano, catarata, perfuração ocular. Sem alterações significativas à direita. A tomografia de órbitas revelou lesão expansiva palpebral com invasão pré-septal, osso frontal e lâmina papirácea à esquerda. Realizada exenteração total com curativo de biomembrana de látex; troca a cada 24 horas nos primeiros sete dias e a cada 48 horas nos outros sete dias. Retirou-se a biomembrana de látex por não ter sido evidenciada granulação, o que só ocorreu após um mês e quinze dias. A exenteração orbitária consiste na retirada de todo o conteúdo da órbita, incluindo olho e partes moles. É considerada total quando as pálpebras são incluídas, e subtotal quando as mesmas são preservadas. Existem várias técnicas de reconstrução da cavidade exenterada: como granulação espontânea, enxerto de pele, retalho frontal, retalho miocutâneo, entre outros. Neste caso utilizamos curativo com biomembrana de látex, material que se mostrou eficaz no recobrimento de outros tecidos cruentos como úlceras, mas sem o mesmo sucesso em nossa experiência. Mais estudos são necessários para que possamos concluir as vantagens e desvantagens do uso da biomembrana de látex na área da oftalmologia.The latex biomembrane is a material from Hevea brasiliensis and has angiogenic

Organic small molecule semiconducting chromophores for use in organic electronic devices

Energy Technology Data Exchange (ETDEWEB)

Welch, Gregory C.; Hoven, Corey V.; Nguyen, Thuc-Quyen

2018-02-13

Small organic molecule semi-conducting chromophores containing a pyridalthiadiazole, pyridaloxadiazole, or pyridaltriazole core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

Band-engineering of TiO2 as a wide-band gap semiconductor using organic chromophore dyes

Science.gov (United States)

Wahyuningsih, S.; Kartini, I.; Ramelan, A. H.; Saputri, L. N. M. Z.; Munawaroh, H.

2017-07-01

Bond-engineering as applied to semiconductor materials refers to the manipulation of the energy bands in order to control charge transfer processes in a device. When the device in question is a photoelectrochemical cell, the charges affected by drift become the focus of the study. The ideal band gap of semiconductors for enhancement of photocatalyst activity can be lowered to match with visible light absorption and the location of conduction Band (CB) should be raised to meet the reducing capacity. Otherwise, by the addition of the chromofor organic dyes, the wide-band gab can be influences by interacation resulting between TiO2 surface and the dyes. We have done the impruvisation wide-band gap of TiO2 by the addition of organic chromophore dye, and the addition of transition metal dopand. The TiO2 morphology influence the light absorption as well as the surface modification. The organic chromophore dye was syntesized by formation complexes compound of Co(PAR)(SiPA)(PAR)= 4-(2-piridylazoresorcinol), SiPA = Silyl propil amine). The result showed that the chromophore groups adsorbed onto TiO2 surface can increase the visible light absorption of wide-band gab semiconductor. Initial absorption of a chromophore will affect light penetration into the material surfaces. The use of photonic material as a solar cell shows this phenomenon clearly from the IPCE (incident photon to current conversion efficiency) measurement data. Organic chromophore dyes of Co(PAR)(SiPA) exhibited the long wavelength absorption character compared to the N719 dye (from Dyesol).

Single Oligomer Spectra Probe Chromophore Nanoenvironments of Tetrameric Fluorescent Proteins

NARCIS (Netherlands)

Blum, Christian; Meixner, Alfred J.; Subramaniam, Vinod

2006-01-01

When analyzing the emission of a large number of individual chromophores embedded in a matrix, the spread of the observed parameters is a characteristic property for the particular chromophore−matrix system. To quantitatively assess the influence of the matrix on the single molecule emission

Depth distributions of light action spectra for skin chromophores

Science.gov (United States)

Barun, V. V.; Ivanov, A. P.

2010-03-01

Light action spectra over wavelengths of 300-1000 nm are calculated for components of the human cutaneous covering: melanin, basal (bloodless) tissue, and blood oxy- and deoxyhemoglobin. The transformation of the spectra with depth in biological tissue results from two factors. The first is the wavelength dependence of the absorption coefficient corresponding to a particular skin chromophore and the second is the spectral selectivity of the radiation flux in biological tissue. This factor is related to the optical properties of all chromophores. A significant change is found to take place in the spectral distribution of absorbed radiant power with increasing depth. The action spectrum of light for the molecular oxygen contained in all components of biological tissue is also studied in the 625-645 nm range. The spectra are found to change with both the volume fraction of blood vessels and the degree of oxygenation of the blood. These results are useful for analyzing processes associated with optical absorption that are possible mechanisms for the interaction of light with biological tissues: photodissociation of oxyhemoglobin and the light-oxygen effect.

Electrochemical screening of biomembrane-active compounds in water

Energy Technology Data Exchange (ETDEWEB)

Mohamadi, Shahrzad, E-mail: cmsm@leeds.ac.uk; Tate, Daniel J.; Vakurov, Alexander; Nelson, Andrew

2014-02-01

Graphical abstract: - Highlights: • Analytical technology application with improvement allowing for on-line high-throughput water toxin screening is presented. • Compound classes of related structure and shape interact with DOPC coated Pt/Hg with a class specific response. • Predecessor membrane system proved as fragile, complex and for environmental application incompatible. - Abstract: Interactions of biomembrane-active compounds with phospholipid monolayers on microfabricated Pt/Hg electrodes in an on-line high throughput flow system are demonstrated by recording capacitance current peak changes as rapid cyclic voltammograms (RCV). Detection limits of the compounds’ effects on the layer have been estimated from the data. Compounds studied include steroids, polycyclic aromatic hydrocarbons, tricyclic antidepressants and tricyclic phenothiazines. The results show that the extent and type of interaction depends on the—(a) presence and number of aromatic rings and substituents, (b) presence and composition of side chains and, (c) molecular shape. Interaction is only indirectly related to compound hydrophobicity. For a selection of tricyclic antidepressants and tricyclic phenothiazines the detection limit in water is related to their therapeutic normal threshold. The sensing assay has been tested in the presence of humic acid as a potential interferent and in a tap water matrix. The system can be applied to the screening of putative hazardous substances and pharmaceuticals allowing for early detection thereof in the water supply. The measurements are made in real time which means that potentially toxic compounds are detected rapidly within <10 min per assay. This technology will contribute greatly to environment safety and health.

Electrochemical screening of biomembrane-active compounds in water

International Nuclear Information System (INIS)

Mohamadi, Shahrzad; Tate, Daniel J.; Vakurov, Alexander; Nelson, Andrew

2014-01-01

Graphical abstract: - Highlights: • Analytical technology application with improvement allowing for on-line high-throughput water toxin screening is presented. • Compound classes of related structure and shape interact with DOPC coated Pt/Hg with a class specific response. • Predecessor membrane system proved as fragile, complex and for environmental application incompatible. - Abstract: Interactions of biomembrane-active compounds with phospholipid monolayers on microfabricated Pt/Hg electrodes in an on-line high throughput flow system are demonstrated by recording capacitance current peak changes as rapid cyclic voltammograms (RCV). Detection limits of the compounds’ effects on the layer have been estimated from the data. Compounds studied include steroids, polycyclic aromatic hydrocarbons, tricyclic antidepressants and tricyclic phenothiazines. The results show that the extent and type of interaction depends on the—(a) presence and number of aromatic rings and substituents, (b) presence and composition of side chains and, (c) molecular shape. Interaction is only indirectly related to compound hydrophobicity. For a selection of tricyclic antidepressants and tricyclic phenothiazines the detection limit in water is related to their therapeutic normal threshold. The sensing assay has been tested in the presence of humic acid as a potential interferent and in a tap water matrix. The system can be applied to the screening of putative hazardous substances and pharmaceuticals allowing for early detection thereof in the water supply. The measurements are made in real time which means that potentially toxic compounds are detected rapidly within <10 min per assay. This technology will contribute greatly to environment safety and health

Optomechanical Control of Quantum Yield in Trans-Cis Ultrafast Photoisomerization of a Retinal Chromophore Model.

Science.gov (United States)

Valentini, Alessio; Rivero, Daniel; Zapata, Felipe; García-Iriepa, Cristina; Marazzi, Marco; Palmeiro, Raúl; Fdez Galván, Ignacio; Sampedro, Diego; Olivucci, Massimo; Frutos, Luis Manuel

2017-03-27

The quantum yield of a photochemical reaction is one of the most fundamental quantities in photochemistry, as it measures the efficiency of the transduction of light energy into chemical energy. Nature has evolved photoreceptors in which the reactivity of a chromophore is enhanced by its molecular environment to achieve high quantum yields. The retinal chromophore sterically constrained inside rhodopsin proteins represents an outstanding example of such a control. In a more general framework, mechanical forces acting on a molecular system can strongly modify its reactivity. Herein, we show that the exertion of tensile forces on a simplified retinal chromophore model provokes a substantial and regular increase in the trans-to-cis photoisomerization quantum yield in a counterintuitive way, as these extension forces facilitate the formation of the more compressed cis photoisomer. A rationale for the mechanochemical effect on this photoisomerization mechanism is also proposed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

New closed-form approximation for skin chromophore mapping.

Science.gov (United States)

Välisuo, Petri; Kaartinen, Ilkka; Tuchin, Valery; Alander, Jarmo

2011-04-01

The concentrations of blood and melanin in skin can be estimated based on the reflectance of light. Many models for this estimation have been built, such as Monte Carlo simulation, diffusion models, and the differential modified Beer-Lambert law. The optimization-based methods are too slow for chromophore mapping of high-resolution spectral images, and the differential modified Beer-Lambert is not often accurate enough. Optimal coefficients for the differential Beer-Lambert model are calculated by differentiating the diffusion model, optimized to the normal skin spectrum. The derivatives are then used in predicting the difference in chromophore concentrations from the difference in absorption spectra. The accuracy of the method is tested both computationally and experimentally using a Monte Carlo multilayer simulation model, and the data are measured from the palm of a hand during an Allen's test, which modulates the blood content of skin. The correlations of the given and predicted blood, melanin, and oxygen saturation levels are correspondingly r = 0.94, r = 0.99, and r = 0.73. The prediction of the concentrations for all pixels in a 1-megapixel image would take ∼ 20 min, which is orders of magnitude faster than the methods based on optimization during the prediction.

Active and silent chromophore isoforms for phytochrome Pr photoisomerization: An alternative evolutionary strategy to optimize photoreaction quantum yields

Directory of Open Access Journals (Sweden)

Yang Yang

2014-01-01

Full Text Available Photoisomerization of a protein bound chromophore is the basis of light sensing of many photoreceptors. We tracked Z-to-E photoisomerization of Cph1 phytochrome chromophore PCB in the Pr form in real-time. Two different phycocyanobilin (PCB ground state geometries with different ring D orientations have been identified. The pre-twisted and hydrogen bonded PCBa geometry exhibits a time constant of 30 ps and a quantum yield of photoproduct formation of 29%, about six times slower and ten times higher than that for the non-hydrogen bonded PCBb geometry. This new mechanism of pre-twisting the chromophore by protein-cofactor interaction optimizes yields of slow photoreactions and provides a scaffold for photoreceptor engineering.

Morphological and physical analysis of natural phospholipids-based biomembranes.

Directory of Open Access Journals (Sweden)

Adrien Jacquot

Full Text Available BACKGROUND: Liposomes are currently an important part of biological, pharmaceutical, medical and nutritional research, as they are considered to be among the most effective carriers for the introduction of various types of bioactive agents into target cells. SCOPE OF REVIEW: In this work, we study the lipid organization and mechanical properties of biomembranes made of marine and plant phospholipids. Membranes based on phospholipids extracted from rapeseed and salmon are studied in the form of liposome and as supported lipid bilayer. Dioleylphosphatidylcholine (DOPC and dipalmitoylphosphatidylcholine (DPPC are used as references to determine the lipid organization of marine and plant phospholipid based membranes. Atomic force microscopy (AFM imaging and force spectroscopy measurements are performed to investigate the membranes' topography at the micrometer scale and to determine their mechanical properties. MAJOR CONCLUSIONS: The mechanical properties of the membranes are correlated to the fatty acid composition, the morphology, the electrophoretic mobility and the membrane fluidity. Thus, soft and homogeneous mechanical properties are evidenced for salmon phospholipids membrane containing various polyunsaturated fatty acids. Besides, phase segregation in rapeseed membrane and more important mechanical properties were emphasized for this type of membranes by contrast to the marine phospholipids based membranes. GENERAL SIGNIFICANCE: This paper provides new information on the nanomechanical and morphological properties of membrane in form of liposome by AFM. The originality of this work is to characterize the physico-chemical properties of the nanoliposome from the natural sources containing various fatty acids and polar head.

Associated depression in pseudophakic patients with intraocular lens with and without chromophore

Directory of Open Access Journals (Sweden)

Mendoza-Mendieta ME

2016-03-01

Full Text Available María Elena Mendoza-Mendieta, Ana Aurora Lorenzo-Mejía Association to Prevent Blindness in Mexico (APEC, Hospital “Dr Luis Sánchez Bulnes”, Mexico City, Mexico Background: With aging, the crystalline lens turns yellowish, which increases the absorption of wavelengths in the blue electromagnetic spectrum, reducing their photoreception in the retina. Since these wavelengths are the main stimulus in the regulation of the circadian rhythm, progressive reduction in their transmission is associated with chronic sleep disturbances and depression in elderly patients. Cataract extraction improves circadian photoreception at any age. However, lenses that block blue waves have 27% to 38% less melatonin suppression than lenses that block only ultraviolet (UV rays. Purpose: To assess the depression symptoms in subjects who have had bilateral phacoemulsification and intraocular lens (IOL implants, one group with yellow chromophore IOLs and the other group with transparent IOLs were compared. Setting: Association to Prevent Blindness in Mexico (APEC, Hospital “Dr Luis Sánchez Bulnes”. Design: This was an observational, cross-sectional, and single-center study. Materials and methods: Twenty-six subjects between 60 and 80 years of age, with a history of bilateral phacoemulsification and placement of the same type of IOL in both eyes from 4 to 12 months prior to the study, who attended the follow-up visits and agreed to participate in this study, and provided signed informed consent were included in the study. They were asked to answer the short version of the 15-item Geriatric Depression Scale. Results: The average age of the study participants was 72.5±5.94 years. The group without chromophore included 46.1% (n=12 of the patients and the group with chromophore included 53.9% (n=14 of the patients (P=0.088. Conclusion: In the group of patients with IOLs that block the passage of blue light, the depression rate was 21.4%, a rate similar to that

Water-Soluble Triarylborane Chromophores for One- and Two-Photon Excited Fluorescence Imaging of Mitochondria in Cells.

Science.gov (United States)

Griesbeck, Stefanie; Zhang, Zuolun; Gutmann, Marcus; Lühmann, Tessa; Edkins, Robert M; Clermont, Guillaume; Lazar, Adina N; Haehnel, Martin; Edkins, Katharina; Eichhorn, Antonius; Blanchard-Desce, Mireille; Meinel, Lorenz; Marder, Todd B

2016-10-04

Three water-soluble tetracationic quadrupolar chromophores comprising two three-coordinate boron π-acceptor groups bridged by thiophene-containing moieties were synthesised for biological imaging applications. Compound 3 containing the bulkier 5-(3,5-Me2 C6 H2 )-2,2'-(C4 H2 S)2 -5'-(3,5-Me2 C6 H2 ) bridge is stable over a long period of time, exhibits a high fluorescence quantum yield and strong one- and two-photon absorption (TPA), and has a TPA cross section of 268 GM at 800 nm in water. Confocal laser scanning fluorescence microscopy studies in live cells indicated localisation of the chromophore at the mitochondria; moreover, cytotoxicity measurements proved biocompatibility. Thus, chromophore 3 has excellent potential for one- and two-photon-excited fluorescence imaging of mitochondrial function in cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Heterocyclic Nonlinear Optical Chromophores Composed of Phenothiazine or Carbazole Donor and 2-Cyanomethylene-3-cyano-4,5,5- trimethyl-2,5-dihydrofuran Acceptor

International Nuclear Information System (INIS)

Cho, Min Ju; Kim, Ja Youn; Kim, Jae Hong; Lee, Seung Hwan; Choi, Dong Hoon; Dalton, Larry R.

2005-01-01

We prepared the new nonlinear optical chromophores that show fairly high microscopic nonlinearity through intramolecular charge transfer. Phenothiazine and carbazole units played an important role to contribute high electron donability and connect the resonance pathway via conjugative effect in the cyclized ring beside the aromatic ring. Theoretical calculation, electrochemical analysis, and absorption spectroscopic study gave us useful information about the energy states and microscopic nonlinearities of two serial chromophores. We compared the microscopic nonlinearities of four chromophores with the conjugation length and electron donability in the push-pull type NLO chromophores. The effect of gradient donability and lengthening the conjugation were investigated on the electronic state and microscopic nonlinearity

Chromophore photophysics and dynamics in fluorescent proteins of the GFP family

International Nuclear Information System (INIS)

Nienhaus, Karin; Nienhaus, G Ulrich

2016-01-01

Proteins of the green fluorescent protein (GFP) family are indispensable for fluorescence imaging experiments in the life sciences, particularly of living specimens. Their essential role as genetically encoded fluorescence markers has motivated many researchers over the last 20 years to further advance and optimize these proteins by using protein engineering. Amino acids can be exchanged by site-specific mutagenesis, starting with naturally occurring proteins as templates. Optical properties of the fluorescent chromophore are strongly tuned by the surrounding protein environment, and a targeted modification of chromophore-protein interactions requires a profound knowledge of the underlying photophysics and photochemistry, which has by now been well established from a large number of structural and spectroscopic experiments and molecular-mechanical and quantum-mechanical computations on many variants of fluorescent proteins. Nevertheless, such rational engineering often does not meet with success and thus is complemented by random mutagenesis and selection based on the optical properties. In this topical review, we present an overview of the key structural and spectroscopic properties of fluorescent proteins. We address protein-chromophore interactions that govern ground state optical properties as well as processes occurring in the electronically excited state. Special emphasis is placed on photoactivation of fluorescent proteins. These light-induced reactions result in large structural changes that drastically alter the fluorescence properties of the protein, which enables some of the most exciting applications, including single particle tracking, pulse chase imaging and super-resolution imaging. We also present a few examples of fluorescent protein application in live-cell imaging experiments. (topical review)

Chromophore photophysics and dynamics in fluorescent proteins of the GFP family

Science.gov (United States)

Nienhaus, Karin; Nienhaus, G. Ulrich

2016-11-01

Proteins of the green fluorescent protein (GFP) family are indispensable for fluorescence imaging experiments in the life sciences, particularly of living specimens. Their essential role as genetically encoded fluorescence markers has motivated many researchers over the last 20 years to further advance and optimize these proteins by using protein engineering. Amino acids can be exchanged by site-specific mutagenesis, starting with naturally occurring proteins as templates. Optical properties of the fluorescent chromophore are strongly tuned by the surrounding protein environment, and a targeted modification of chromophore-protein interactions requires a profound knowledge of the underlying photophysics and photochemistry, which has by now been well established from a large number of structural and spectroscopic experiments and molecular-mechanical and quantum-mechanical computations on many variants of fluorescent proteins. Nevertheless, such rational engineering often does not meet with success and thus is complemented by random mutagenesis and selection based on the optical properties. In this topical review, we present an overview of the key structural and spectroscopic properties of fluorescent proteins. We address protein-chromophore interactions that govern ground state optical properties as well as processes occurring in the electronically excited state. Special emphasis is placed on photoactivation of fluorescent proteins. These light-induced reactions result in large structural changes that drastically alter the fluorescence properties of the protein, which enables some of the most exciting applications, including single particle tracking, pulse chase imaging and super-resolution imaging. We also present a few examples of fluorescent protein application in live-cell imaging experiments.

Chromophoric Dissolved Organic Material, Aqua MODIS, NPP, 0.125 degrees, East US

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National Oceanic and Atmospheric Administration, Department of Commerce — MODIS data is used to develop an index of the amount of chromophoric dissolved organic material (CDOM) in the surface waters. CDOM absorbs heavily in the blue...

Chromophoric Dissolved Organic Material, Aqua MODIS, NPP, 0.125 degrees, West US

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — MODIS data is used to develop an index of the amount of chromophoric dissolved organic material (CDOM) in the surface waters. CDOM absorbs heavily in the blue...

Photoabsorption of green and red fluorescent protein chromophore anions in vacuo.

Science.gov (United States)

Wan, Songbo; Liu, Shasha; Zhao, Guangjiu; Chen, Maodu; Han, Keli; Sun, Mengtao

2007-09-01

Photoabsorption properties of green and red fluorescent protein chromophore anions in vacuo were investigated theoretically, based on the experimental results in gas phase [Phys. Rev. Lett. 2001, 87, 228102; Phys. Rev. Lett. 2003, 90, 118103]. Their calculated transition energies in absorption with TD-DFT and ZINDO methods are directly compared to the experimental reports in gas phase, and the calculations with ZINDO method can correctly reproduce the absorption spectra. The orientation and strength of their transition dipole moments were revealed with transition density. We also showed the orientation and result of their intramolecular charge transfer with transition difference density. The calculated results show that with the increase of the extended conjugated system, the orientation of transition dipole moments and the orientation of charge transfer can be reversed. They are the linear responds with the external electric fields. These theoretical results reveal the insight understanding of the photoinduced dynamics of green and red fluorescent protein chromophore anions and cations in vacuo.

THE ROLE OF NITROGEN IN CHROMOPHORIC AND FLUORESCENT DISSOLVED ORGANIC MATTER FORMATION

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Microbial and photochemical processes affect chromophoric dissolved organic matter (CDOM) dynamics in the ocean. Some evidence suggests that dissolved nitrogen plays a role in CDOM formation, although this has received little systematic attention in marine ecosystems. Coastal sea...

Structure of the red fluorescent protein from a lancelet (Branchiostoma lanceolatum): a novel GYG chromophore covalently bound to a nearby tyrosine

Energy Technology Data Exchange (ETDEWEB)

Pletnev, Vladimir Z., E-mail: vzpletnev@gmail.com; Pletneva, Nadya V.; Lukyanov, Konstantin A.; Souslova, Ekaterina A.; Fradkov, Arkady F.; Chudakov, Dmitry M.; Chepurnykh, Tatyana; Yampolsky, Ilia V. [Russian Academy of Sciences, Moscow (Russian Federation); Wlodawer, Alexander [National Cancer Institute, Frederick, MD 21702 (United States); Dauter, Zbigniew [National Cancer Institute, Argonne, IL 60439 (United States); Pletnev, Sergei, E-mail: vzpletnev@gmail.com [National Cancer Institute, Argonne, IL 60439 (United States); SAIC-Frederick, Argonne, IL 60439 (United States); Russian Academy of Sciences, Moscow (Russian Federation)

2013-09-01

The crystal structure of the novel red emitting fluorescent protein from lancelet Branchiostoma lanceolatum (Chordata) revealed an unusual five residues cyclic unit comprising Gly58-Tyr59-Gly60 chromophore, the following Phe61 and Tyr62 covalently bound to chromophore Tyr59. A key property of proteins of the green fluorescent protein (GFP) family is their ability to form a chromophore group by post-translational modifications of internal amino acids, e.g. Ser65-Tyr66-Gly67 in GFP from the jellyfish Aequorea victoria (Cnidaria). Numerous structural studies have demonstrated that the green GFP-like chromophore represents the ‘core’ structure, which can be extended in red-shifted proteins owing to modifications of the protein backbone at the first chromophore-forming position. Here, the three-dimensional structures of green laGFP (λ{sub ex}/λ{sub em} = 502/511 nm) and red laRFP (λ{sub ex}/λ{sub em} ≃ 521/592 nm), which are fluorescent proteins (FPs) from the lancelet Branchiostoma lanceolatum (Chordata), were determined together with the structure of a red variant laRFP-ΔS83 (deletion of Ser83) with improved folding. Lancelet FPs are evolutionarily distant and share only ∼20% sequence identity with cnidarian FPs, which have been extensively characterized and widely used as genetically encoded probes. The structure of red-emitting laRFP revealed three exceptional features that have not been observed in wild-type fluorescent proteins from Cnidaria reported to date: (i) an unusual chromophore-forming sequence Gly58-Tyr59-Gly60, (ii) the presence of Gln211 at the position of the conserved catalytic Glu (Glu222 in Aequorea GFP), which proved to be crucial for chromophore formation, and (iii) the absence of modifications typical of known red chromophores and the presence of an extremely unusual covalent bond between the Tyr59 C{sup β} atom and the hydroxyl of the proximal Tyr62. The impact of this covalent bond on the red emission and the large Stokes shift (�

A Light-Induced Reaction with Oxygen Leads to Chromophore Decomposition and Irreversible Photobleaching in GFP-Type Proteins.

Science.gov (United States)

Grigorenko, Bella L; Nemukhin, Alexander V; Polyakov, Igor V; Khrenova, Maria G; Krylov, Anna I

2015-04-30

Photobleaching and photostability of proteins of the green fluorescent protein (GFP) family are crucially important for practical applications of these widely used biomarkers. On the basis of simulations, we propose a mechanism for irreversible bleaching in GFP-type proteins under intense light illumination. The key feature of the mechanism is a photoinduced reaction of the chromophore with molecular oxygen (O2) inside the protein barrel leading to the chromophore's decomposition. Using quantum mechanics/molecular mechanics (QM/MM) modeling we show that a model system comprising the protein-bound Chro(-) and O2 can be excited to an electronic state of the intermolecular charge-transfer (CT) character (Chro(•)···O2(-•)). Once in the CT state, the system undergoes a series of chemical reactions with low activation barriers resulting in the cleavage of the bridging bond between the phenolic and imidazolinone rings and disintegration of the chromophore.

Chromophores from photolyzed ammonia reacting with acetylene: Application to Jupiters Great Red Spot

Science.gov (United States)

Carlson, Robert W.; Baines, Kevin H.; Anderson, M. S.; Filacchione, G.; Simon, A. A.

2016-01-01

The high altitude of Jupiter's Great Red Spot (GRS) may enhance the upward flux of gaseous ammonia (NH3 ) into the high troposphere, where NH3 molecules can be photodissociated and initiate a chain of chemical reactions with downwelling acetylene molecules (C2H2 ). These reactions, experimentally studied earlier by (Ferris and Ishikawa [1987] Nature 326, 777-778) and (Ferris and Ishikawa [1988] J. Amer. Chem. Soc. 110, 4306-4312), produce chromophores that absorb in the visible and ultraviolet regions. In this work we photolyzed mixtures of NH3 and C2H2 using ultraviolet radiation with a wavelength of 214 nm and measured the spectral transmission of the deposited films in the visible region (400-740 nm). From these transmission data we estimated the imaginary indices of refraction. Assuming that ammonia grains at the top of the GRS clouds are coated with this material, we performed layered sphere and radiative transfer calculations to predict GRS reflection spectra. Comparison of those results with observed and previously unreported Cassini visible spectra and with true-color images of the GRS show that the unknown GRS chromophore is spectrally consistent with the coupled NH3-C2H2 photochemical products produced in our laboratory experiments. Using high-resolution mass spectrometry and infrared spectroscopy we infer that the chromophore-containing residue is composed of aliphatic azine, azo, and diazo compounds.

Determination of retinal chromophore structure in bacteriorhodopsin with resonance Raman spectroscopy.

Science.gov (United States)

Smith, S O; Lugtenburg, J; Mathies, R A

1985-01-01

The analysis of the vibrational spectrum of the retinal chromophore in bacteriorhodopsin with isotopic derivatives provides a powerful "structural dictionary" for the translation of vibrational frequencies and intensities into structural information. Of importance for the proton-pumping mechanism is the unambiguous determination of the configuration about the C13=C14 and C=N bonds, and the protonation state of the Schiff base nitrogen. Vibrational studies have shown that in light-adapted BR568 the Schiff base nitrogen is protonated and both the C13=C14 and C=N bonds are in a trans geometry. The formation of K625 involves the photochemical isomerization about only the C13=C14 bond which displaces the Schiff base proton into a different protein environment. Subsequent Schiff base deprotonation produces the M412 intermediate. Thermal reisomerization of the C13=C14 bond and reprotonation of the Schiff base occur in the M412------O640 transition, resetting the proton-pumping mechanism. The vibrational spectra can also be used to examine the conformation about the C--C single bonds. The frequency of the C14--C15 stretching vibration in BR568, K625, L550 and O640 argues that the C14--C15 conformation in these intermediates is s-trans. Conformational distortions of the chromophore have been identified in K625 and O640 through the observation of intense hydrogen out-of-plane wagging vibrations in the Raman spectra (see Fig. 2). These two intermediates are the direct products of chromophore isomerization. Thus it appears that following isomerization in a tight protein binding pocket, the chromophore cannot easily relax to a planar geometry. The analogous observation of intense hydrogen out-of-plane modes in the primary photoproduct in vision (Eyring et al., 1982) suggests that this may be a general phenomenon in protein-bound isomerizations. Future resonance Raman studies should provide even more details on how bacterio-opsin and retinal act in concert to produce an

The importance of charge-transfer interactions in determining chromophoric dissolved organic matter (CDOM) optical and photochemical properties.

Science.gov (United States)

Sharpless, Charles M; Blough, Neil V

2014-04-01

Absorption of sunlight by chromophoric dissolved natural organic matter (CDOM) is environmentally significant because it controls photic zone depth and causes photochemistry that affects elemental cycling and contaminant fate. Both the optics (absorbance and fluorescence) and photochemistry of CDOM display unusual properties that cannot easily be ascribed to a superposition of individual chromophores. These include (i) broad, unstructured absorbance that decreases monotonically well into the visible and near IR, (ii) fluorescence emission spectra that all fall into a single envelope regardless of the excitation wavelength, and (iii) photobleaching and photochemical quantum yields that decrease monotonically with increasing wavelength. In contrast to a simple superposition model, these phenomena and others can be reasonably well explained by a physical model in which charge-transfer interactions between electron donating and accepting chromophores within the CDOM control the optical and photophysical properties. This review summarizes current understanding of the processes underlying CDOM photophysics and photochemistry as well as their physical basis.

Chromophoric Dissolved Organic Material, Aqua MODIS, NPP, 0.125 degrees, Gulf of Mexico

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — MODIS data is used to develop an index of the amount of chromophoric dissolved organic material (CDOM) in the surface waters. CDOM absorbs heavily in the blue...

Chromophoric Dissolved Organic Material, Aqua MODIS, NPP, 0.05 degrees, Global, Science Quality

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — MODIS data is used to develop an index of the amount of chromophoric dissolved organic material (CDOM) in the surface waters. CDOM absorbs heavily in the blue...

Chromophore-protein coupling beyond nonpolarizable models: understanding absorption in green fluorescent protein

NARCIS (Netherlands)

Daday, C.; Curutchet, C.; Sinicropi, A.; Mennucci, B.; Filippi, Claudia

2015-01-01

The nature of the coupling of the photoexcited chromophore with the environment in a prototypical system like green fluorescent protein (GFP) is to date not understood, and its description still defies state-of-the-art multiscale approaches. To identify which theoretical framework of the

Photoresponsive Block Copolymers Containing Azobenzenes and Other Chromophores

Directory of Open Access Journals (Sweden)

Takaomi Kobayashi

2010-01-01

Full Text Available Photoresponsive block copolymers (PRBCs containing azobenzenes and other chromophores can be easily prepared by controlled polymerization. Their photoresponsive behaviors are generally based on photoisomerization, photocrosslinking, photoalignment and photoinduced cooperative motions. When the photoactive block forms mesogenic phases upon microphase separation of PRBCs, supramolecular cooperative motion in liquid-crystalline PRBCs enables them to self-organize into hierarchical structures with photoresponsive features. This offers novel opportunities to photocontrol microphase-separated nanostructures of well-defined PRBCs and extends their diverse applications in holograms, nanotemplates, photodeformed devices and microporous films.

Phase sensitive control of vibronic guest-host interaction: Br2 in Ar matrix.

Science.gov (United States)

Ibrahim, Heide; Héjjas, Mónika; Fushitani, Mizuho; Schwentner, Nikolaus

2009-07-02

Vibronic progressions are programmed into a pulse shaper which converts them via the inherent Fourier transformation into a train of femtosecond pulses in time domain for chromophore excitation. Double pulse results agree with phase-sensitive wave packet superposition from a Michelson interferometer which delivers coherence times with high reliability. Spectral resolution of 1 nm and a spacing of around 4 nm within the 20 nm envelope centered at 590 nm delivers a train of seven phase-controlled 40 fs subpulses separated by 250 fs. Combs adjusted to the zero phonon lines (ZPL) and phonon sidebands (PSB) of the B state vibronic progression are reproduced in the chromophore for a coherent subpulse accumulation. B state ZPL wave packet dynamics dominates in pump-probe spectra due to its coherence despite an overwhelming but incoherent A state contribution in absorption. PSB comb accumulation is also phase sensitive and demonstrates coherence within several 100 matrix degrees of freedom in the vicinity.

Lab on a Biomembrane: Rapid prototyping and manipulation of 2D fluidic lipid bilayers circuits

Science.gov (United States)

Ainla, Alar; Gözen, Irep; Hakonen, Bodil; Jesorka, Aldo

2013-01-01

Lipid bilayer membranes are among the most ubiquitous structures in the living world, with intricate structural features and a multitude of biological functions. It is attractive to recreate these structures in the laboratory, as this allows mimicking and studying the properties of biomembranes and their constituents, and to specifically exploit the intrinsic two-dimensional fluidity. Even though diverse strategies for membrane fabrication have been reported, the development of related applications and technologies has been hindered by the unavailability of both versatile and simple methods. Here we report a rapid prototyping technology for two-dimensional fluidic devices, based on in-situ generated circuits of phospholipid films. In this “lab on a molecularly thin membrane”, various chemical and physical operations, such as writing, erasing, functionalization, and molecular transport, can be applied to user-defined regions of a membrane circuit. This concept is an enabling technology for research on molecular membranes and their technological use. PMID:24067786

Importance of Force Decomposition for Local Stress Calculations in Biomembrane Molecular Simulations.

Science.gov (United States)

Vanegas, Juan M; Torres-Sánchez, Alejandro; Arroyo, Marino

2014-02-11

Local stress fields are routinely computed from molecular dynamics trajectories to understand the structure and mechanical properties of lipid bilayers. These calculations can be systematically understood with the Irving-Kirkwood-Noll theory. In identifying the stress tensor, a crucial step is the decomposition of the forces on the particles into pairwise contributions. However, such a decomposition is not unique in general, leading to an ambiguity in the definition of the stress tensor, particularly for multibody potentials. Furthermore, a theoretical treatment of constraints in local stress calculations has been lacking. Here, we present a new implementation of local stress calculations that systematically treats constraints and considers a privileged decomposition, the central force decomposition, that leads to a symmetric stress tensor by construction. We focus on biomembranes, although the methodology presented here is widely applicable. Our results show that some unphysical behavior obtained with previous implementations (e.g. nonconstant normal stress profiles along an isotropic bilayer in equilibrium) is a consequence of an improper treatment of constraints. Furthermore, other valid force decompositions produce significantly different stress profiles, particularly in the presence of dihedral potentials. Our methodology reveals the striking effect of unsaturations on the bilayer mechanics, missed by previous stress calculation implementations.

The crystal structure of human protein α1M reveals a chromophore-binding site and two putative protein–protein interfaces

International Nuclear Information System (INIS)

Zhang, Yangli; Gao, Zengqiang; Guo, Zhen; Zhang, Hongpeng; Zhang, Zhenzhen; Luo, Miao; Hou, Haifeng; Huang, Ailong; Dong, Yuhui; Wang, Deqiang

2013-01-01

Highlights: •We determined the first structure of human α1M with heavy electron density of the chromophore. •We proposed a new structural model of the chromophore. •We first revealed that the two conserved surface regions of α1M are proposed as putative protein–protein interface sites. -- Abstract: Lipocalin α1-microglobulin (α1M) is a conserved glycoprotein present in plasma and in the interstitial fluids of all tissues. α1M is linked to a heterogeneous yellow–brown chromophore of unknown structure, and interacts with several target proteins, including α1-inhibitor-3, fibronectin, prothrombin and albumin. To date, there is little knowledge about the interaction sites between α1M and its partners. Here, we report the crystal structure of the human α1M. Due to the crystallization occurring in a low ionic strength solution, the unidentified chromophore with heavy electron density is observed at a hydrophobic inner tube of α1M. In addition, two conserved surface regions of α1M are proposed as putative protein–protein interface sites. Further study is needed to unravel the detailed information about the interaction between α1M and its partners

Synthesis and Properties of Novel T-Type Polyurethanes Containing 2,5-Dioxynitrostilbenyl Group as a Nonlinear Optical Chromophore

International Nuclear Information System (INIS)

Lee, Ju Yeon; Lee, Won Jung; Park, Eun Ju; Bang, Han Bae; Rhee, Bum Ku; Jung, Chang Soo; Lee, Seung Mook; Lee, Jin Hyun

2003-01-01

Two approaches to minimize the randomization have been proposed. One is to use crosslinking method and the other is to use high T g polymers such as polyimides. Polyurethane matrix forms extensive hydrogen bond between urethane linkage and increases rigidity preventing the relaxation of induced dipoles. In this work we prepared new T-type polyurethanes containing dioxynitrostilbenyl group as a NLO-chromophore. We selected 2,5-dioxynitrostilbenyl group as NLO-chromophore because it will have a large dipole moment and is rather easy to synthesize. Furthermore 2,5-dioxynitrostilbenyl group constitutes a novel T-type NLO polyurthanes, in which the NLO chromophores are parts of polymer backbones. These T-type NLO polyurethanes are not shown in the literature. After confirming the structure of the resulting polymers we investigated the properties such as T g and second harmonic generation (SHG) activity (d 33 ). We now report the results of the initial phase of the work

Structure and dynamics of biomembranes in room-temperature ionic liquid water solutions studied by neutron scattering and by molecular dynamics simulations

Science.gov (United States)

Benedetto, Antonio; Ballone, Pietro

2018-05-01

Increasing attention is being devoted to the interaction of a new class of organic ionic liquids known as room-temperature ionic liquids (RTILs) with biomolecules, partly because of health and environment concerns, and, even more, for the prospect of exciting new applications in biomedicine, sensing and energy technologies. Here we focus on the interaction between RTILs and phospholipid bilayers that are well-accepted models for bio-membranes. We discuss how neutron scattering has been used to probe both the structure and the dynamics of these systems, and how its integration with molecular dynamics simulation has allowed the determination of the microscopic details of their interaction.

Bioinspired synthesis of pentalene-based chromophores from an oligoketone chain.

Science.gov (United States)

Saito, Yuki; Higuchi, Masayuki; Yoshioka, Shota; Senboku, Hisanori; Inokuma, Yasuhide

2018-04-24

We report a bioinspired synthesis of 2,5-dihydropentalene-based chromophores from an aliphatic oligoketone bearing 1,3- and 1,4-diketone subunits. Unlike the natural polyketone sequence, fused five-membered rings were formed via an intramolecular aldol condensation. A subsequent Knoevenagel condensation reaction with malononitrile furnished a multiply cross-conjugated π-system with low-lying LUMO levels. Furthermore, pentalenes obtained from a non-conjugated aliphatic chain exhibited visible absorption and solid-state fluorescence.

Refractive index modulation in the polyurethane films containing diazo sulfonamide chromophores

Energy Technology Data Exchange (ETDEWEB)

Ortyl, E. [Insitute of Organic and Polymer Technology, WrocIaw University of Technology, 50-384 WrocIaw (Poland); Kucharski, S. [Insitute of Organic and Polymer Technology, WrocIaw University of Technology, 50-384 WrocIaw (Poland)]. E-mail: stanislaw.kucharski@pwr.wroc.pl; Gotszalk, T. [Faculty of Microsystem Electronics and Photonics, WrocIaw University of Technology, 50-384 WrocIaw (Poland)

2005-05-23

The series of photochromic polyurethanes was obtained by modification of precursor polymers prepared from 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene 1,6-diisocyanate (HDI) or toluene 2,4-diisocyanate (TDI) and N,N'-di-(2-hydroxyethyl) aniline. The precursor polymers were functionalized by an azo-coupling reaction to form the polymers with different degrees of functionalization and various heterocyclic sulfonamide groups. Ellipsometric measurements showed a decrease of the refractive index during illumination of thin polymer films with white light. The change of real part of the refractive index was in the range of 0.0033-0.0296 depending on the polymer kind and chromophore content. It was found that photocurrent was generated in the polymer films deposited onto indium tin oxide (ITO) glass plates. For the polyurethanes containing sulfathiazole groups in side chains the current density was up to 180 nA/cm{sup 2}. The formation of diffraction grating in the polymer films was easily achieved using linearly polarized laser light (532 nm) in a standard two beam coupling (TBC) system. The diffraction efficiency of the first diffraction beam was dependent on the chromophore content reaching ca. 12% for the derivatives of sulfamethoxazole.

Ionically conducting Er3+-doped DNA-based biomembranes for electrochromic devices

International Nuclear Information System (INIS)

Leones, R.; Fernandes, M.; Sentanin, F.; Cesarino, I.; Lima, J.F.; Zea Bermudez, V. de; Pawlicka, A.; Magon, C.J.; Donoso, J.P.; Silva, M.M.

2014-01-01

Biopolymer-based membranes have particular interest due to their biocompatibility, Biodegradability, easy extraction from natural resources and low cost. The incorporation of Er 3+ ions into natural macromolecule hosts with the purpose of producing highly efficient emitting phosphors is of widespread interest in materials science, due to their important roles in display devices. Thus, biomembranes may be viewed as innovative materials for the area of optics. This paper describes studies of luminescent material DNA-based membranes doped with erbium triflate and demonstrates that their potential technological applications may be expanded to electrochromic devices. The sample that exhibits the highest ionic conductivity is DNA 10 Er, (1.17 × 10 −5 and 7.76 × 10 −4 S.cm −1 at 30 and 100 °C, respectively). DSC, XRD and POM showed that the inclusion of the guest salt into DNA does not change significantly its amorphous nature. The overall redox stability was ca. 2.0 V indicating that these materials have an acceptable stability window for applications in solid state electrochemical devices. The EPR analysis suggested that the Er 3+ ions are distributed in various environments. A small ECD comprising a Er 3+ -doped DNA-based membrane was assembled and tested by cyclic voltammetry and chronoamperometry. These electrochemical analyses revealed a pale blue color to transparent color change and a decrease of the charge density from -4.0 to -1.2 mC.cm −2 during 4000 color/bleaching cycles

On the mechanism of non-radiative decay of blue fluorescent protein chromophore: New insight from the excited-state molecular dynamics simulations and potential energy calculations

Science.gov (United States)

Zhao, Li; Liu, Jian-Yong; Zhou, Pan-Wang

2017-11-01

A detailed theoretical investigation based on the ab initio on-the-fly surface hopping dynamics simulations and potential energy surfaces calculations has been performed to unveil the mechanism of the photoinduced non-adiabatic relaxation process of the isolated blue fluorescent protein (BFP) chromophore in gas phase. The data analysis presents that the dominant reaction coordinate of the BFP chromophore is driven by a rotation motion around the CC double bridging bond, which is in remarkable difference with a previous result which supports a Hula-Twist rotation pattern. Such behavior is consistent with the double bond rotation pattern of the GFP neutral chromophore. In addition, the dynamics simulations give an estimated decay time of 1.1 ps for the S1 state, which is agrees well with the experimental values measured in proteins. The present work offers a straightforward understanding for the decay mechanism of the BFP chromophore and suggestions of the photochemical properties of analogous protein chromophores. We hope the current work would be helpful for further exploration of the BFP photochemical and photophysical properties in various environments, and can provide guidance and prediction for rational design of the fluorescent proteins catering for different demands.

Ultrafast excited and ground-state dynamics of the green fluorescent protein chromophore in solution

NARCIS (Netherlands)

Vengris, M.; van Stokkum, I.H.M.; He, X.; Bell, A.F.; Tonge, P.J.; van Grondelle, R.; Larsen, D.S.

2004-01-01

Ultrafast dispersed pump-dump-probe spectroscopy was applied to HBDI (4′-hydroxybenzylidene-2,3-dimethylimidazolinone), a model green fluorescent protein (GFP) chromophore in solution with different protonation states. The measured three-dimensional data was analyzed using a global analysis method

Accessible protocol for practice classroom about physical and chemical factors that affect the biomembranes integrity

Directory of Open Access Journals (Sweden)

Thiago Barros Galvão

2012-12-01

Full Text Available The aim of the current work is to review a protocol used in practical classes to demonstrate some factors that affect biomembrane integrity. Sugar-beet fragments were utilized as the experimental model as membrane damage could be visualized by leakage of betacyanins, hydrophilic pigments accumulated in the cell vacuoles. The tests were carried out as discrete experiments utilizing physical agents and chemical products present in the student daily routine. To test the effect of temperature, sugar-beet fragments were submitted to heat, cold or both at different times of exposition. When chemical products were tested, sugar-beet fragments were exposed to organic solvents (common alcohol and acetone or polar and amphipathic substances (disinfectant, detergent, hydrogen peroxide, and sodium hypochlorite. The obtained results were discussed in terms of the capacity of the physical and chemical factors to cause membrane damage. The review of this protocol using reagents that are present in the student daily routine were able to demonstrate clearly the effect of the different tested factors, allowing the utilization of this practical class under limited conditions.

DNA-Conjugated Organic Chromophores in DNA Stacking Interactions

DEFF Research Database (Denmark)

Filichev, Vyacheslav V.; Pedersen, Erik Bjerregaard

2009-01-01

Since the discovery of the intercalation of acridine derivatives into DNA (1961), chemists have synthesized many intercalators tethered to DNA. Advances in the chemical synthesis of modified nucleosides along with progress in oligonucleotide synthesis have made it possible to introduce organic ch...... review presents those efforts in the design of intercalators/organic chromophores as oligonucleotide conjugates that form a foundation for the generation of novel nucleic acid architectures......Since the discovery of the intercalation of acridine derivatives into DNA (1961), chemists have synthesized many intercalators tethered to DNA. Advances in the chemical synthesis of modified nucleosides along with progress in oligonucleotide synthesis have made it possible to introduce organic...

Dynamic Electron Correlation Effects on the Ground State Potential Energy Surface of a Retinal Chromophore Model.

Science.gov (United States)

Gozem, Samer; Huntress, Mark; Schapiro, Igor; Lindh, Roland; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

2012-11-13

The ground state potential energy surface of the retinal chromophore of visual pigments (e.g., bovine rhodopsin) features a low-lying conical intersection surrounded by regions with variable charge-transfer and diradical electronic structures. This implies that dynamic electron correlation may have a large effect on the shape of the force fields driving its reactivity. To investigate this effect, we focus on mapping the potential energy for three paths located along the ground state CASSCF potential energy surface of the penta-2,4-dieniminium cation taken as a minimal model of the retinal chromophore. The first path spans the bond length alternation coordinate and intercepts a conical intersection point. The other two are minimum energy paths along two distinct but kinetically competitive thermal isomerization coordinates. We show that the effect of introducing the missing dynamic electron correlation variationally (with MRCISD) and perturbatively (with the CASPT2, NEVPT2, and XMCQDPT2 methods) leads, invariably, to a stabilization of the regions with charge transfer character and to a significant reshaping of the reference CASSCF potential energy surface and suggesting a change in the dominating isomerization mechanism. The possible impact of such a correction on the photoisomerization of the retinal chromophore is discussed.

Mechanism of ascorbic acid interference in biochemical tests that use peroxide and peroxidase to generate chromophore.

Science.gov (United States)

Martinello, Flávia; Luiz da Silva, Edson

2006-11-01

Ascorbic acid interferes negatively in peroxidase-based tests (Trinder method). However, the precise mechanism remains unclear for tests that use peroxide, a phenolic compound and 4-aminophenazone (4-AP). We determined the chemical mechanism of this interference, by examining the effects of ascorbic acid in the reaction kinetics of the production and reduction of the oxidized chromophore in urate, cholesterol, triglyceride and glucose tests. Reaction of ascorbic acid with the Trinder method constituents was also verified. Ascorbic acid interfered stoichiometrically with all tests studied. However, it had two distinct effects on the reaction rate. In the urate test, ascorbic acid decreased the chromophore formation with no change in its production kinetics. In contrast, in cholesterol, triglyceride and glucose tests, an increase in the lag phase of color development occurred. Of all the Trinder constituents, only peroxide reverted the interference. In addition, ascorbic acid did not interfere with oxidase activity nor reduce significantly the chromophore formed. Peroxide depletion was the predominant chemical mechanism of ascorbic acid interference in the Trinder method with phenolics and 4-AP. Distinctive effects of ascorbic acid on the reaction kinetics of urate, cholesterol, glucose and triglyceride might be due to the rate of peroxide production by oxidases.

Probing microhydration effect on the electronic structure of the GFP chromophore anion: Photoelectron spectroscopy and theoretical investigations

Energy Technology Data Exchange (ETDEWEB)

Bhaskaran-Nair, Kiran; Shelton, William A. [Cain Department of Chemical Engineering, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Center for Computation and Technology, Louisiana State University, Baton Rouge, Louisiana 70803 (United States); Valiev, Marat; Kowalski, Karol, E-mail: karol.kowalski@pnnl.gov [William R. Wiley Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, K8-91, P.O. Box 999, Richland, Washington 99352 (United States); Deng, S. H. M.; Wang, Xue-Bin, E-mail: xuebin.wang@pnnl.gov [Physical Sciences Division, Pacific Northwest National Laboratory, K8-88, P.O. Box 999, Richland, Washington 99352 (United States)

2015-12-14

The photophysics of the Green Fluorescent Protein (GFP) chromophore is critically dependent on its local structure and on its environment. Despite extensive experimental and computational studies, there remain many open questions regarding the key fundamental variables that govern this process. One outstanding problem is the role of autoionization as a possible relaxation pathway of the excited state under different environmental conditions. This issue is considered in our work through combined experimental and theoretical studies of microsolvated clusters of the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI{sup −}), an analog of the GFP chromophore. Through selective generation of microsolvated structures of predetermined size and subsequent analysis of experimental photoelectron spectra by high level ab initio methods, we are able to precisely identify the structure of the system, establish the accuracy of theoretical data, and provide reliable description of auto-ionization process as a function of hydrogen-bonding environment. Our study clearly illustrates the first few water molecules progressively stabilize the excited state of the chromophore anion against the autodetached neutral state, which should be an important trait for crystallographic water molecules in GFPs that has not been fully explored to date.

Acentric 2-D ensembles of D-br-A electron-transfer chromophores via vectorial orientation within amphiphilic n-helix bundle peptides for photovoltaic device applications.

Science.gov (United States)

Koo, Jaseung; Park, Jaehong; Tronin, Andrey; Zhang, Ruili; Krishnan, Venkata; Strzalka, Joseph; Kuzmenko, Ivan; Fry, H Christopher; Therien, Michael J; Blasie, J Kent

2012-02-14

We show that simply designed amphiphilic 4-helix bundle peptides can be utilized to vectorially orient a linearly extended donor-bridge-acceptor (D-br-A) electron transfer (ET) chromophore within its core. The bundle's interior is shown to provide a unique solvation environment for the D-br-A assembly not accessible in conventional solvents and thereby control the magnitudes of both light-induced ET and thermal charge recombination rate constants. The amphiphilicity of the bundle's exterior was employed to vectorially orient the peptide-chromophore complex at a liquid-gas interface, and its ends were tailored for subsequent covalent attachment to an inorganic surface, via a "directed assembly" approach. Structural data, combined with evaluation of the excited state dynamics exhibited by these peptide-chromophore complexes, demonstrate that densely packed, acentrically ordered 2-D monolayer ensembles of such complexes at high in-plane chromophore densities approaching 1/200 Å(2) offer unique potential as active layers in binary heterojunction photovoltaic devices.

Production of Chromophoric Dissolved Organic Matter from Mangrove Leaf Litter and Floating Sargassum Colonies

Science.gov (United States)

Chromophoric dissolved organic matter (CDOM) strongly absorbs solar radiation in the blue-green and serves as the primary attenuator of water column ultraviolet radiation (UV-R). CDOM interferes with remote sensing of ocean chlorophyll and can control UV-R-induced damage to light...

Extension of Light-Harvesting Ability of Photosynthetic Light-Harvesting Complex 2 (LH2) through Ultrafast Energy Transfer from Covalently Attached Artificial Chromophores.

Science.gov (United States)

Yoneda, Yusuke; Noji, Tomoyasu; Katayama, Tetsuro; Mizutani, Naoto; Komori, Daisuke; Nango, Mamoru; Miyasaka, Hiroshi; Itoh, Shigeru; Nagasawa, Yutaka; Dewa, Takehisa

2015-10-14

Introducing appropriate artificial components into natural biological systems could enrich the original functionality. To expand the available wavelength range of photosynthetic bacterial light-harvesting complex 2 (LH2 from Rhodopseudomonas acidophila 10050), artificial fluorescent dye (Alexa Fluor 647: A647) was covalently attached to N- and C-terminal Lys residues in LH2 α-polypeptides with a molar ratio of A647/LH2 ≃ 9/1. Fluorescence and transient absorption spectroscopies revealed that intracomplex energy transfer from A647 to intrinsic chromophores of LH2 (B850) occurs in a multiexponential manner, with time constants varying from 440 fs to 23 ps through direct and B800-mediated indirect pathways. Kinetic analyses suggested that B800 chromophores mediate faster energy transfer, and the mechanism was interpretable in terms of Förster theory. This study demonstrates that a simple attachment of external chromophores with a flexible linkage can enhance the light harvesting activity of LH2 without affecting inherent functions of energy transfer, and can achieve energy transfer in the subpicosecond range. Addition of external chromophores, thus, represents a useful methodology for construction of advanced hybrid light-harvesting systems that afford solar energy in the broad spectrum.

Resolving Electronic Transitions in Synthetic Fluorescent Protein Chromophores by Magnetic Circular Dichroism

Czech Academy of Sciences Publication Activity Database

Štěpánek, P.; Cowie, T. Y.; Šafařík, Martin; Šebestík, Jaroslav; Pohl, Radek; Bouř, Petr

2016-01-01

Roč. 17, č. 15 (2016), s. 2348-2354 ISSN 1439-4235 R&D Projects: GA ČR GA13-03978S; GA ČR(CZ) GA16-05935S Institutional support: RVO:61388963 Keywords : density functional calculations * fluorescence protein chromophores * magnetic circular dichroism * organic synthesis * spectral simulations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.075, year: 2016

Free volume modifications in chalcone chromophore doped PMMA films by electron irradiation: Positron annihilation study

Science.gov (United States)

Ismayil; Ravindrachary, V.; Praveena, S. D.; Mahesha, M. G.

2018-03-01

The free volume related fluorescence behaviour in electron beam irradiated chalcone chromophore doped Poly(methyl methacrylate) (PMMA) composite films have been studied using FTIR, UV-Visible, XRD and Positron Annihilation techniques. From the FTIR spectral study it is found that the formation of polarons and bipolaron takes place due to cross linking as well as chain scission processes at lower and higher doses respectively. It reveals that the formation of various polaronic defect levels upon irradiation is responsible for the creation of three optical energy band gaps within the polymer films as obtained from UV-Visible spectra. The crosslinking process at lower doses increases the distance between the pendant groups to reduce the interchain distance and chain scission process at higher doses decreases interchain separation to enhance the number of polarons in the polymer composites as suggested by XRD studies. The fluorescence studies show the enhancement of fluorescence emission at lower doses and reduction at higher doses under electron irradiation. The positron annihilation study suggests that the low radiation doses induce crosslinking which affect the free volume properties and in turn hinders the chalcone molecular rotation within the polymer composite. At higher doses chain scission process support polymer matrix relaxation and facilitates non-radiative transition of the chromophore upon excitation. This study shows that fluorescence enhancement and mobility of chromophore within the polymer matrix is directly related to the free volume around it.

Imidazole as a parent π-conjugated backbone in charge-transfer chromophores

Directory of Open Access Journals (Sweden)

Jiří Kulhánek

2012-01-01

Full Text Available Research activities in the field of imidazole-derived push–pull systems featuring intramolecular charge transfer (ICT are reviewed. Design, synthetic pathways, linear and nonlinear optical properties, electrochemistry, structure–property relationships, and the prospective application of such D-π-A organic materials are described. This review focuses on Y-shaped imidazoles, bi- and diimidazoles, benzimidazoles, bis(benzimidazoles, imidazole-4,5-dicarbonitriles, and imidazole-derived chromophores chemically bound to a polymer chain.

Design, Structure, and Optical Properties of Organic-Inorganic Perovskites Containing an Oligothiophene Chromophore.

Science.gov (United States)

Mitzi, David B.; Chondroudis, Konstantinos; Kagan, Cherie R.

1999-12-27

A quaterthiophene derivative, 5,5' "-bis(aminoethyl)-2,2':5',2' ':5' ',2' "-quaterthiophene (AEQT), has been selected for incorporation within the layered organic-inorganic perovskite structure. In addition to having an appropriate molecular shape and two tethering aminoethyl groups to bond to the inorganic framework, AEQT is also a dye and can influence the optical properties of lead(II) halide-based perovskites. Crystals of C(20)H(22)S(4)N(2)PbBr(4) were grown from a slowly cooled aqueous solution containing lead(II) bromide and quaterthiophene derivative (AEQT.2HBr) salts. The new layered perovskite adopts a monoclinic (C2/c) subcell with the lattice parameters a = 39.741(2) Å, b = 5.8420(3) Å, c = 11.5734(6) Å, beta = 92.360(1) degrees, and Z = 4. Broad superstructure peaks are observed in the X-ray diffraction data, indicative of a poorly ordered, doubled supercell along both the a and b axes. The quaterthiophene segment of AEQT(2+) is nearly planar, with a syn-anti-syn relationship between adjacent thiophene rings. Each quaterthiophene chromophore is ordered between nearest-neighbor lead(II) bromide sheets in a herringbone arrangement with respect to neighboring quaterthiophenes. Room temperature optical absorption spectra for thermally ablated films of the perovskites (AEQT)PbX(4) (X = Cl, Br, I) exhibit an exciton peak arising from the lead(II) halide sheets, along with absorption from the quaterthiophene moiety. No evidence of the inorganic sheet excitonic transition is observed in the photoluminescence spectra for any of the chromophore-containing perovskites. However, strong quaterthiophene photoluminescence is observed for X = Cl, with an emission peak at approximately lambda(max) = 532 nm. Similar photoluminescence is observed for the X = Br and I materials, but with substantial quenching, as the inorganic layer band gap decreases relative to the chromophore HOMO-LUMO gap.

CHROMOPHORIC DISSOLVED ORGANIC MATTER (CDOM) DERIVED FROM DECOMPOSITION OF VARIOUS VASCULAR PLANT AND ALGAL SOURCES

Science.gov (United States)

Chromophoric dissolved organic (CDOM) in aquatic environments is derived from the microbial decomposition of terrestrial and microbial organic matter. Here we present results of studies of the spectral properties and photoreactivity of the CDOM derived from several organic matter...

D-π-A-A-π-D prototype 2,2'-bipyridine dyads exhibiting large structure and environment-sensitive fluorescence: synthesis, photophysics, and computation.

Science.gov (United States)

Sarma, Monima; Chatterjee, Tanmay; Ghanta, Susanta; Das, Samar K

2012-01-06

A series of 4,4'-π-conjugated-2,2'-bipyridine chromophores (MS 1-8) were synthesized, and their photophysical and thermal properties were investigated. The title "push-pull' chromophores", except MS 1, were integrated with both alkoxy and alkylamino donor functionalities that differ in their donation capabilities. The oligophenylenevinylene (OPV) chromophores MS 4-8 are associated with a π-extended backbone in which the position and the number of alkoxy donors were systematically varied. All of the studied systems possess a D-π-A-A-π-D dyad archetype in which the A-A is the central 2,2'-bipyridine acceptor core that is electronically attached with the donor termini through π-linkers. The fluorescence quantum yields of the synthesized chromophores are found to be sensitive to the molecular archetype and the solvent medium. Out of the eight fluorescent compounds reported in this article, the compound MS 5 exhibits fluorescence in the solid state also. The modulating effect of the nature, position, and number of donor functionalities on the optical properties of these classes of compounds has further been comprehended on the basis of DFT and TD-DFT computation in a solvent reaction field.

New hyperbranched polytriazoles containing isolation chromophore moieties derived from AB4 monomers through click chemistry under copper(I) catalysis: improved optical transparency and enhanced NLO effects.

Science.gov (United States)

Wu, Wenbo; Ye, Cheng; Yu, Gui; Liu, Yunqi; Qin, Jingui; Li, Zhen

2012-04-02

By modifying a synthetic procedure, two new hyperbranched polytriazoles (HP1 and HP2) containing isolation chromophores were synthesized successfully through click chemistry reactions under copper(I) catalysis. For the first time, these two polymers were derived from an AB(4)-type monomer, although they contain different end-capping chromophores. They are soluble in normal polar organic solvents and are well characterized. Thanks to the presence of the isolation chromophore, the two polymers demonstrate good nonlinear optical (NLO) properties and optical transparency, making them promising candidates for practical applications. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast dynamics of isolated model photoactive yellow protein chromophores: "Chemical perturbation theory" in the laboratory

NARCIS (Netherlands)

Vengris, M.; Larsen, D.S.; van der Horst, M.A.; Larsen, O.F.A.; Hellingwerf, K.J.; van Grondelle, R.

2005-01-01

Pump-probe and pump-dump probe experiments have been performed on several isolated model chromophores of the photoactive yellow protein (PYP). The observed transient absorption spectra are discussed in terms of the spectral signatures ascribed to solvation, excited-state twisting, and vibrational

How far can a single hydrogen bond tune the spectral properties of the GFP chromophore?

DEFF Research Database (Denmark)

Kiefer, Hjalte; Lattouf, Elie; Persen, Natascha Wardinghus

2015-01-01

Photoabsorption of the hydrogen-bonded complex of a neutral and an anionic Green Fluorescent Protein chromophore has been studied using a new dual-detection approach to action-absorption spectroscopy. Following absorption of one photon, dissociation through a single channel ensures that the full ...

Direct and Indirect Electron Emission from the Green Fluorescent Protein Chromophore

Science.gov (United States)

Toker, Y.; Rahbek, D. B.; Klærke, B.; Bochenkova, A. V.; Andersen, L. H.

2012-09-01

Photoelectron spectra of the deprotonated green fluorescent protein chromophore have been measured in the gas phase at several wavelengths within and beyond the S0-S1 photoabsorption band of the molecule. The vertical detachment energy (VDE) was determined to be 2.68±0.1eV. The data show that the first electronically excited state is bound in the Franck-Condon region, and that electron emission proceeds through an indirect (resonant) electron-emission channel within the corresponding absorption band.

Luminescent Lanthanide Reporters for High-Sensitivity Novel Bioassays

Energy Technology Data Exchange (ETDEWEB)

Anstey, Mitchell R. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Fruetel, Julia A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Foster, Michael E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Hayden, Carl C. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Buckley, Heather L. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Arnold, John [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

2013-09-01

Biological imaging and assay technologies rely on fluorescent organic dyes as reporters for a number of interesting targets and processes. However, limitations of organic dyes such as small Stokes shifts, spectral overlap of emission signals with native biological fluorescence background, and photobleaching have all inhibited the development of highly sensitive assays. To overcome the limitations of organic dyes for bioassays, we propose to develop lanthanide-based luminescent dyes and demonstrate them for molecular reporting applications. This relatively new family of dyes was selected for their attractive spectral and chemical properties. Luminescence is imparted by the lanthanide atom and allows for relatively simple chemical structures that can be tailored to the application. The photophysical properties offer unique features such as narrow and non-overlapping emission bands, long luminescent lifetimes, and long wavelength emission, which enable significant sensitivity improvements over organic dyes through spectral and temporal gating of the luminescent signal.Growth in this field has been hindered due to the necessary advanced synthetic chemistry techniques and access to experts in biological assay development. Our strategy for the development of a new lanthanide-based fluorescent reporter system is based on chelation of the lanthanide metal center using absorbing chromophores. Our first strategy involves "Click" chemistry to develop 3-fold symmetric chelators and the other involves use of a new class of tetrapyrrole ligands called corroles. This two-pronged approach is geared towards the optimization of chromophores to enhance light output.

Photobleaching Kinetics of Chromophoric Dissolved Organic Matter Derived from Mangrove Leaf Litter and Floating Sargassum Colonies

Science.gov (United States)

We examined the photoreactivity of chromophoric dissolved organic matter (CDOM) derived from Rhizophora mangle (red mangrove) leaf litter and floating Sargassum colonies as these marine plants can be important contributors to coastal and open ocean CDOM pools, respectively. Mangr...

Preparation and third-order nonlinear optical property of poly(urethane-imide containing dispersed red chromophore

Directory of Open Access Journals (Sweden)

2008-11-01

Full Text Available A novel poly(urethane-imide (PUI containing dispersed red chromophore was synthesized. The PUI was characterized by FT-IR, UV-Vis, DSC and TGA. The results of DSC and TGA indicated that the PUI exhibited high thermal stability up to its glass-transition temperature (Tg of 196°C and 5% heat weight loss temperature of 229°C. According to UV-Vis spectrum and working curve, the maximum molar absorption coefficient and absorption wavelength were measured. They were used to calculate the third-order nonlinear optical coefficient χ(3. At the same time, the chromophore density of PUI, nonlinear refractive index coefficient and molecular hyperpolarizability of PUI were obtained. The fluorescence spectra of PUI and model compound DR-19 were determined at excitation wavelength 300 nm. The electron donor and acceptor in polymer formed the exciplex through the transfer of the electric charges. The results show that the poly(urethane-imide is a promising candidate for application in optical devices.

Exploiting quantum interference in dye sensitized solar cells

DEFF Research Database (Denmark)

Maggio, Emanuele; Solomon, Gemma C.; Troisi, Alessandro

2014-01-01

A strategy to hinder the charge recombination process in dye sensitized solar cells is developed in analogy with similar approaches to modulate charge transport across nanostructures. The system studied is a TiO2 (anatase)-chromophore interface, with an unsaturated carbon bridge connecting the two...... of the possible tunnelling path. Calculations carried out on realistic molecules at the DFT level of theory show how the recombination lifetime can be modulated by changes in the electron-withdrawing (donating) character of the groups connected to the cross-conjugated bridge. Tight binding calculations...

Photochemical degradation of chromophoric-dissolved organic matter exposed to simulated UV-B and natural solar radiation

NARCIS (Netherlands)

Zhang, Y.; Liu, M.; Qin, B.; Feng, S.

2009-01-01

Photochemical degradation of chromophoric-dissolved organic matter (CDOM) by UV-B radiation decreases CDOM absorption in the UV region and fluorescence intensity, and alters CDOM composition. CDOM absorption, fluorescence, and the spectral slope indicating the CDOM composition were studied using

Structural communication between the chromophore-binding pocket and the N-terminal extension in plant phytochrome phyB.

Science.gov (United States)

Velázquez Escobar, Francisco; Buhrke, David; Fernandez Lopez, Maria; Shenkutie, Sintayehu Manaye; von Horsten, Silke; Essen, Lars-Oliver; Hughes, Jon; Hildebrandt, Peter

2017-05-01

The N-terminal extension (NTE) of plant phytochromes has been suggested to play a functional role in signaling photoinduced structural changes. Here, we use resonance Raman spectroscopy to study the effect of the NTE on the chromophore structure of B-type phytochromes from two evolutionarily distant plants. NTE deletion seems to have no effect on the chromophore in the inactive Pr state, but alters the torsion of the C-D ring methine bridge and the surrounding hydrogen bonding network in the physiologically active Pfr state. These changes are accompanied by a shift of the conformational equilibrium between two Pfr substates, which might affect the thermal isomerization rate of the C-D double bond and, thus, account for the effect of the NTE on the dark reversion kinetics. © 2017 Federation of European Biochemical Societies.

Sea cucumbers reduce chromophoric dissolved organic matter in aquaculture tanks.

Science.gov (United States)

Sadeghi-Nassaj, Seyed Mohammad; Catalá, Teresa S; Álvarez, Pedro A; Reche, Isabel

2018-01-01

Mono-specific aquaculture effluents contain high concentrations of nutrients and organic matter, which affect negatively the water quality of the recipient ecosystems. A fundamental feature of water quality is its transparency. The fraction of dissolved organic matter that absorbs light is named chromophoric dissolved organic matter (CDOM). A sustainable alternative to mono-specific aquaculture is the multitrophic aquaculture that includes species trophically complementary named "extractive" species that uptake the waste byproducts. Sea cucumbers are recognized as efficient extractive species due to the consumption of particulate organic matter (POM). However, the effects of sea cucumbers on CDOM are still unknown. During more than one year, we monitored CDOM in two big-volume tanks with different trophic structure. One of the tanks (-holothurian) only contained around 810 individuals of Anemonia sulcata , whereas the other tank (+holothurian) also included 90 individuals of Holothuria tubulosa and Holothuria forskali . We routinely analyzed CDOM absorption spectra and determined quantitative (absorption coefficients at 325 nm) and qualitative (spectral slopes) optical parameters in the inlet waters, within the tanks, and in their corresponding effluents. To confirm the time-series results, we also performed three experiments. Each experiment consisted of two treatments: +holothurians (+H) and -holothurians (-H). We set up three +H tanks with 80 individuals of A. sulcata and 10 individuals of H. tubulosa in each tank and four -H tanks that contained only 80 individuals of A. sulcata . In the time-series, absorption coefficients at 325 nm ( a 325 ) and spectral slopes from 275 to 295 nm ( S 275-295 ) were significantly lower in the effluent of the +holothurian tank (average: 0.33 m -1 and 16 µm -1 , respectively) than in the effluent of the -holothurian tank (average: 0.69 m -1 and 34 µm -1 , respectively), the former being similar to those found in the inlet

Influences of excluded volume of molecules on signaling processes on the biomembrane.

Directory of Open Access Journals (Sweden)

Masashi Fujii

Full Text Available We investigate the influences of the excluded volume of molecules on biochemical reaction processes on 2-dimensional surfaces using a model of signal transduction processes on biomembranes. We perform simulations of the 2-dimensional cell-based model, which describes the reactions and diffusion of the receptors, signaling proteins, target proteins, and crowders on the cell membrane. The signaling proteins are activated by receptors, and these activated signaling proteins activate target proteins that bind autonomously from the cytoplasm to the membrane, and unbind from the membrane if activated. If the target proteins bind frequently, the volume fraction of molecules on the membrane becomes so large that the excluded volume of the molecules for the reaction and diffusion dynamics cannot be negligible. We find that such excluded volume effects of the molecules induce non-trivial variations of the signal flow, defined as the activation frequency of target proteins, as follows. With an increase in the binding rate of target proteins, the signal flow varies by i monotonically increasing; ii increasing then decreasing in a bell-shaped curve; or iii increasing, decreasing, then increasing in an S-shaped curve. We further demonstrate that the excluded volume of molecules influences the hierarchical molecular distributions throughout the reaction processes. In particular, when the system exhibits a large signal flow, the signaling proteins tend to surround the receptors to form receptor-signaling protein clusters, and the target proteins tend to become distributed around such clusters. To explain these phenomena, we analyze the stochastic model of the local motions of molecules around the receptor.

Characteristics of Chromophoric and Fluorescent Dissolved Organic Matter in the Nordic Seas

OpenAIRE

Makarewicz, Anna; Kowalczuk, Piotr; Sagan, Sławomir; Granskog, Mats A.; Pavlov, Alexey K.; Zdun, Agnieszka; Borzycka, Karolina; Zabłocka, Monika

2018-01-01

Optical properties of Chromophoric (CDOM) and Fluorescent Dissolved Organic Matter (FDOM) were characterized in the Nordic Seas including the West Spitsbergen Shelf during June–July of 2013, 2014 and 2015. The CDOM absorption coefficient at 350 nm, aCDOM(350) showed significant interannual variation. In 2013, the highest average aCDOM(350) values (aCDOM = 0.30 ± 0.12 m−1) were observed due to the influence of cold and low–saline wat...

Electrostatic Effects in Phase Transitions of Biomembranes between Cubic Phases and Lamellar Liquid-Crystalline (Lα) phase

Science.gov (United States)

Masum, Shah Md.; Li, Shu Jie; Tamba, Yukihiro; Yamashita, Yuko; Yamazaki, Masahito

2004-04-01

Elucidation of the mechanisms of transitions between cubic phase and liquid-crystalline (Lα) phase, and between different IPMS cubic phases, are essential for understanding of dynamics of biomembranes and topological transformation of lipid membranes. Recently, we found that electrostatic interactions due to surface charges of lipid membranes induce transition between cubic phase and Lα phase, and between different IPMS cubic phases. As electrostatic interactions increase, the most stable phase of a monoolein (MO) membrane changes: Q224 ⇒ Q229 ⇒ Lα. We also found that a de novo designed peptide partitioning into electrically neutral lipid membrane changed the phase stability of the MO membranes. As peptide-1 concentration increased, the most stable phase of a MO membrane changes: Q224 ⇒ Q229 ⇒Lα. In both cases, the increase in the electrostatic repulsive interaction greatly reduced the absolute value of spontaneous curvature of the MO monolayer membrane. We also investigated factors such as poly (L-lysine) and osmotic stress to control structure and phase stability of DOPA/MO membranes. Based on these results, we discuss the mechanism of the effect of electrostatic interactions on the stability of cubic phase.

Natural lipid extracts and biomembrane-mimicking lipid compositions are disposed to form nonlamellar phases, and they release DNA from lipoplexes most efficiently

Energy Technology Data Exchange (ETDEWEB)

Koynova, Rumiana; MacDonald, Robert C. (NWU)

2010-01-18

A viewpoint now emerging is that a critical factor in lipid-mediated transfection (lipofection) is the structural evolution of lipoplexes upon interacting and mixing with cellular lipids. Here we report our finding that lipid mixtures mimicking biomembrane lipid compositions are superior to pure anionic liposomes in their ability to release DNA from lipoplexes (cationic lipid/DNA complexes), even though they have a much lower negative charge density (and thus lower capacity to neutralize the positive charge of the lipoplex lipids). Flow fluorometry revealed that the portion of DNA released after a 30-min incubation of the cationic O-ethylphosphatidylcholine lipoplexes with the anionic phosphatidylserine or phosphatidylglycerol was 19% and 37%, respectively, whereas a mixture mimicking biomembranes (MM: phosphatidylcholine/phosphatidylethanolamine/phosphatidylserine /cholesterol 45:20:20:15 w/w) and polar lipid extract from bovine liver released 62% and 74%, respectively, of the DNA content. A possible reason for this superior power in releasing DNA by the natural lipid mixtures was suggested by structural experiments: while pure anionic lipids typically form lamellae, the natural lipid mixtures exhibited a surprising predilection to form nonlamellar phases. Thus, the MM mixture arranged into lamellar arrays at physiological temperature, but began to convert to the hexagonal phase at a slightly higher temperature, {approx} 40-45 C. A propensity to form nonlamellar phases (hexagonal, cubic, micellar) at close to physiological temperatures was also found with the lipid extracts from natural tissues (from bovine liver, brain, and heart). This result reveals that electrostatic interactions are only one of the factors involved in lipid-mediated DNA delivery. The tendency of lipid bilayers to form nonlamellar phases has been described in terms of bilayer 'frustration' which imposes a nonzero intrinsic curvature of the two opposing monolayers. Because the stored

Light transmission through intraocular lenses with or without yellow chromophore (blue light filter) and its potential influence on functional vision in everyday environmental conditions.

Science.gov (United States)

Owczarek, Grzegorz; Gralewicz, Grzegorz; Skuza, Natalia; Jurowski, Piotr

2016-01-01

In this research the factors used to evaluate the light transmission through two types of acrylic hydrophobic intraocular lenses, one that contained yellow chromophore that blocks blue light transmission and the other which did not contain that filter, were defined according to various light condition, e.g., daylight and at night. The potential influence of light transmission trough intraocular lenses with or without yellow chromophore on functional vision in everyday environmental conditions was analysed.

Synthesis and solution aggregation studies of a suite of mixed neutral and zwitterionic chromophores for second-order nonlinear optics.

Science.gov (United States)

Peddie, Victoria; Anderson, Jack; Harvey, Joanne E; Smith, Gerald J; Kay, Andrew

2014-11-07

We report details of the synthesis of a series of bi- and trichromophores. These compounds contain mixtures of chromophores that have zwitterionic (ZWI) and neutral ground state (NGS) components covalently attached to each other. The neutral ground state moieties are based on dyes with aniline donors--such as Disperse Red 1--whereas the zwitterionic components are derived from chromophores with pro-aromatic donors such as 1,4-dihydropyridinylidene. By combining both ZWI and NGS components, we aim to develop novel compounds for nonlinear optics in which there is an enhancement of the overall hyperpolarizability coupled with a decrease in the net dipole moment. Thus, this approach should eliminate the electrostatic effects that result when only one type of chromophore is used, and so reduce the likelihood of undesirable aggregation occurring. This, in turn, should enable us to realize organic materials with large macroscopic optical nonlinearities. An analysis of the UV-vis results suggests that there is a strong dependence on solvent polarity that determines whether the embedded constituents should be treated as discrete elements; in low polarity solvents, there appear to be strong intramolecular interactions occurring, particularly when a 1,4-quinolinylidene-based donor is used in the ZWI component.

A Successful Attempt to Obtain the Linear Dependence Between One-Photon and Two-Photon Spectral Properties and Hammett Parameters of Various Aromatic Substituents in New π-Extended Asymmetric Organic Chromophores.

Science.gov (United States)

Hu, Nvdan; Gong, Yulong; Wang, Xinchao; Lu, Yao; Peng, Guangyue; Yang, Long; Zhang, Shengtao; Luo, Ziping; Li, Hongru; Gao, Fang

2015-11-01

A series of new asymmetric chromophores containing aromatic substituents and possessing the excellent π-extension in space were prepared through multi-steps routes. One-photon and two-photon spectral properties of these new chromophores could be tuned by these substituents finely and simultaneously. The linear correlation of the wave numbers of the one-photon absorption and emission maxima to Hammett parameters of these substituents was presented. Near infrared two-photon absorption emission integrated areas of the target chromophores were correlated linearly to Hammett constants of these substituted groups.

PHOTOREACTIVITY OF CHROMOPHORIC DISSOLVED ORGANIC MATTER (CDOM) DERIVED FROM DECOMPOSITION OF VARIOUS VASCULAR PLANT AND ALGAL SOURCES

Science.gov (United States)

Chromophoric dissolved organic matter (CDOM) in aquatic environments is derived from the microbial decomposition of terrestrial and microbial organic matter. Here we present results of studies of the spectral properties and photoreactivity of the CDOM derived from several organi...

Unmixing chromophores in human skin with a 3D multispectral optoacoustic mesoscopy system

Science.gov (United States)

Schwarz, Mathias; Aguirre, Juan; Soliman, Dominik; Buehler, Andreas; Ntziachristos, Vasilis

2016-03-01

The absorption of visible light by human skin is governed by a number of natural chromophores: Eumelanin, pheomelanin, oxyhemoglobin, and deoxyhemoglobin are the major absorbers in the visible range in cutaneous tissue. Label-free quantification of these tissue chromophores is an important step of optoacoustic (photoacoustic) imaging towards clinical application, since it provides relevant information in diseases. In tumor cells, for instance, there are metabolic changes (Warburg effect) compared to healthy cells, leading to changes in oxygenation in the environment of tumors. In malignant melanoma changes in the absorption spectrum have been observed compared to the spectrum of nonmalignant nevi. So far, optoacoustic imaging has been applied to human skin mostly in single-wavelength mode, providing anatomical information but no functional information. In this work, we excited the tissue by a tunable laser source in the spectral range from 413-680 nm with a repetition rate of 50 Hz. The laser was operated in wavelengthsweep mode emitting consecutive pulses at various wavelengths that allowed for automatic co-registration of the multispectral datasets. The multispectral raster-scan optoacoustic mesoscopy (MSOM) system provides a lateral resolution of melanin, oxyhemoglobin, and deoxyhemoglobin, three-dimensional absorption maps of all three absorbers were calculated from the multispectral dataset.

2,4,5-trihydroxy-3-methylacetophenone: A cellulosic chromophore as a case study of aromaticity

Science.gov (United States)

Nele Sophie Zwirchmayr; Thomas Elder; Markus Bacher; Andreas Hofinger-Horvath; Paul Kosma; Thomas. Rosenau

2017-01-01

The title compound (2,4,5-trihydroxy-3-methylacetophenone, 1) was isolated as chromophore from aged cellulosic pulps. The peculiar feature of the compound is its weak aromatic system that can be converted into nonaromatic (quinoid or cyclic aliphatic) tautomers, depending on the conditions and reaction partners. In alkaline media, the participation of quinoid canonic...

Sea cucumbers reduce chromophoric dissolved organic matter in aquaculture tanks

Directory of Open Access Journals (Sweden)

Seyed Mohammad Sadeghi-Nassaj

2018-02-01

Full Text Available Background Mono-specific aquaculture effluents contain high concentrations of nutrients and organic matter, which affect negatively the water quality of the recipient ecosystems. A fundamental feature of water quality is its transparency. The fraction of dissolved organic matter that absorbs light is named chromophoric dissolved organic matter (CDOM. A sustainable alternative to mono-specific aquaculture is the multitrophic aquaculture that includes species trophically complementary named “extractive” species that uptake the waste byproducts. Sea cucumbers are recognized as efficient extractive species due to the consumption of particulate organic matter (POM. However, the effects of sea cucumbers on CDOM are still unknown. Methods During more than one year, we monitored CDOM in two big-volume tanks with different trophic structure. One of the tanks (−holothurian only contained around 810 individuals of Anemonia sulcata, whereas the other tank (+holothurian also included 90 individuals of Holothuria tubulosa and Holothuria forskali. We routinely analyzed CDOM absorption spectra and determined quantitative (absorption coefficients at 325 nm and qualitative (spectral slopes optical parameters in the inlet waters, within the tanks, and in their corresponding effluents. To confirm the time-series results, we also performed three experiments. Each experiment consisted of two treatments: +holothurians (+H and –holothurians (−H. We set up three +H tanks with 80 individuals of A. sulcata and 10 individuals of H. tubulosa in each tank and four –H tanks that contained only 80 individuals of A. sulcata. Results In the time-series, absorption coefficients at 325 nm (a325 and spectral slopes from 275 to 295 nm (S275−295 were significantly lower in the effluent of the +holothurian tank (average: 0.33 m−1 and 16 µm−1, respectively than in the effluent of the −holothurian tank (average: 0.69 m−1 and 34 µm−1, respectively, the former

Preparation, property of the complex of carboxymethyl chitosan grafted copolymer with iodine and application of it in cervical antibacterial biomembrane

Energy Technology Data Exchange (ETDEWEB)

Chen, Yu [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Yang, Yumin; Liao, Qingping [Zhejiang Sanchuang Biological Technology Co., Ltd., Jiaxing, Zhejiang Province 314031 (China); Yang, Wei [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Ma, Wanfeng [Zhejiang Sanchuang Biological Technology Co., Ltd., Jiaxing, Zhejiang Province 314031 (China); Zhao, Jian [Department of Gynaecology and Obstetrics, The First Hospital of Peking University, Beijing 100034 (China); Zheng, Xionggao [School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081 (China); Yang, Yang [Zhejiang Sanchuang Biological Technology Co., Ltd., Jiaxing, Zhejiang Province 314031 (China); Chen, Rui [Department of Gynaecology and Obstetrics, The First Hospital of Peking University, Beijing 100034 (China)

2016-10-01

Cervical erosion is one of the common diseases of women. The loop electrosurgical excisional procedure (LEEP) has been used widely in the treatment of the cervical diseases. However, there are no effective wound dressings for the postoperative care to protect the wound area from further infection, leading to increased secretion and longer healing time. Iodine is a widely used inorganic antibacterial agent with many advantages. However, the carrier for stable iodine complex antibacterial agents is lack. In the present study, a novel iodine carrier, Carboxymethyl chitosan-g-(poly(sodium acrylate)-co-polyvinylpyrrolidone) (CMCTS-g-(PAANa-co-PVP), was prepared by graft copolymerization of sodium acrylate (AANa) and N-vinylpyrrolidone (NVP) to a carboxymethyl chitosan (CMCTS) skeleton. The obtained structure could combine prominent property of poly(sodium acrylate) (PAANa) anionic polyelectrolyte segment and good complex property of polyvinylpyrrolidone (PVP) segment to iodine. The bioactivity of CMCTS could also be kept. The properties of the complex, CMCTS-g-(PAANa-co-PVP)-I{sub 2}, were studied. The in vitro experiment shows that it has broad-spectrum bactericidal effects to virus, fungus, gram-positive bacteria and gram-negative bacteria. A CMCTS-g-(PAANa-co-PVP)-I{sub 2} complex contained cervical antibacterial biomembrane (CABM) was prepared. The iodine release from the CABM is pH-dependent. The clinic trial results indicate that CABM has better treatment effectiveness than the conventional treatment in the postoperative care of the LEEP operation. - Highlights: • The multifunctional iodine complexing carrier CMCTS-g-(PAANa-co-PVP) was prepared. • CMCTS-g-(PAANa-co-PVP)-I{sub 2} with high antibacterial property and bio-safety was studied. • By compositing it with CMCTS and gelatin further, CABM with multifunction was deduced. • The releasing properties of the activated iodine from CABM showed pH sensitivity. • CABM showed good treating effect for

Chromophore dynamics in the PYP photocycle from femtosecond stimulated Raman spectroscopy.

Science.gov (United States)

Creelman, Mark; Kumauchi, Masato; Hoff, Wouter D; Mathies, Richard A

2014-01-23

Femtosecond stimulated Raman spectroscopy (FSRS) is used to examine the structural dynamics of the para-hydroxycinnamic acid (HCA) chromophore during the first 300 ps of the photoactive yellow protein (PYP) photocycle, as the system transitions from its vertically excited state to the early ground state cis intermediate, I0. A downshift in both the C7═C8 and C1═O stretches upon photoexcitation reveals that the chromophore has shifted to an increasingly quinonic form in the excited state, indicating a charge shift from the phenolate moiety toward the C9═O carbonyl, which continues to increase for 170 fs. In addition, there is a downshift in the C9═O carbonyl out-of-plane vibration on an 800 fs time scale as PYP transitions from its excited state to I0, indicating that weakening of the hydrogen bond with Cys69 and out-of-plane rotation of the C9═O carbonyl are key steps leading to photoproduct formation. HOOP intensity increases on a 3 ps time scale during the formation of I0, signifying distortion about the C7═C8 bond. Once on the I0 surface, the C7═C8 and C1═O stretches blue shift, indicating recovery of charge to the phenolate, while persistent intensity in the HOOP and carbonyl out-of-plane modes reveal HCA to be a cissoid structure with significant distortion about the C7═C8 bond and of C9═O out of the molecular plane.

The Major Chromophore Arising from Glucose Degradation and Oxidative Stress Occurrence during Lens Proteins Glycation Induced by Glucose

Directory of Open Access Journals (Sweden)

Felipe Ávila

2017-12-01

Full Text Available Glucose autoxidation has been proposed as a key reaction associated with deleterious effects induced by hyperglycemia in the eye lens. Little is known about chromophores generated during glucose autoxidation. In this study, we analyzed the effect of oxidative and dicarbonyl stress in the generation of a major chromophore arising from glucose degradation (GDC and its association with oxidative damage in lens proteins. Glucose (5 mM was incubated with H2O2 (0.5–5 mM, Cu2+ (5–50 μM, glyoxal (0.5–5 mM or methylglyoxal (0.5–5 mM at pH 7.4, 5% O2, 37 °C, from 0 to 30 days. GDC concentration increased with incubation time, as well as when incubated in the presence of H2O2 and/or Cu2+, which were effective even at the lowest concentrations. Dicarbonylic compounds did not increase the levels of GDC during incubations. 1H, 13C and FT-IR spectra from the purified fraction containing the chromophore (detected by UV/vis spectroscopy showed oxidation products of glucose, including gluconic acid. Lens proteins solutions (10 mg/mL incubated with glucose (30 mM presented increased levels of carboxymethyl-lysine and hydrogen peroxide that were associated with GDC increase. Our results suggest a possible use of GDC as a marker of autoxidative reactions occurring during lens proteins glycation induced by glucose.

Increased light harvesting in dye-sensitized solar cells with energy relay dyes

KAUST Repository

Hardin, Brian E.

2009-06-21

Conventional dye-sensitized solar cells have excellent charge collection efficiencies, high open-circuit voltages and good fill factors. However, dye-sensitized solar cells do not completely absorb all of the photons from the visible and near-infrared domain and consequently have lower short-circuit photocurrent densities than inorganic photovoltaic devices. Here, we present a new design where high-energy photons are absorbed by highly photoluminescent chromophores unattached to the titania and undergo Förster resonant energy transfer to the sensitizing dye. This novel architecture allows for broader spectral absorption, an increase in dye loading, and relaxes the design requirements for the sensitizing dye. We demonstrate a 26% increase in power conversion efficiency when using an energy relay dye (PTCDI) with an organic sensitizing dye (TT1). We estimate the average excitation transfer efficiency in this system to be at least 47%. This system offers a viable pathway to develop more efficient dye-sensitized solar cells.

Biogeneration of chromophoric dissolved organic matter by bacteria and krill in the southern ocean

OpenAIRE

Ortega-Retuerta, E.; Frazer, Thomas K.; Duarte, Carlos M.; Ruiz-Halpern, Sergio; Tovar-Sánchez, Antonio; Arrieta López de Uralde, Jesús M.; Reche, Isabel

2009-01-01

Chromophoric dissolved organic matter (CDOM), the optically active fraction of dissolved organic matter, is primarily generated by pelagic organisms in the open ocean. In this study, we experimentally determined the quantity and spectral quality of CDOM generated by bacterioplankton using two different substrates (with and without photoproducts) and by Antarctic krill Euphausia superba and evaluated their potential contributions to CDOM dynamics in the peninsular region of the Southern Ocean....

Electron transfer in silicon-bridged adjacent chromophores: the source for blue-green emission.

Science.gov (United States)

Bayda, Malgorzata; Angulo, Gonzalo; Hug, Gordon L; Ludwiczak, Monika; Karolczak, Jerzy; Koput, Jacek; Dobkowski, Jacek; Marciniak, Bronislaw

2017-05-10

Si-Bridged chromophores have been proposed as sources for blue-green emission in several technological applications. The origin of this dual emission is to be found in an internal charge transfer reaction. The current work is an attempt to describe the details of these processes in these kinds of substances, and to design a molecular architecture to improve their performance. Nuclear motions essential for intramolecular charge transfer (ICT) can involve processes from twisted internal moieties to dielectric relaxation of the solvent. To address these issues, we studied ICT between adjacent chromophores in a molecular compound containing N-isopropylcarbazole (CBL) and 1,4-divinylbenzene (DVB) linked by a dimethylsilylene bridge. In nonpolar solvents emission arises from the local excited state (LE) of carbazole whereas in solvents of higher polarity dual emission was detected (LE + ICT). The CT character of the additional emission band was concluded from the linear dependence of the fluorescence maxima on solvent polarity. Electron transfer from CBL to DVB resulted in a large excited-state dipole moment (37.3 D) as determined from a solvatochromic plot and DFT calculations. Steady-state and picosecond time-resolved fluorescence experiments in butyronitrile (293-173 K) showed that the ICT excited state arises from the LE state of carbazole. These results were analyzed and found to be in accordance with an adiabatic version of Marcus theory including solvent relaxation.

Correlation of surface pressure and hue of planarizable push–pull chromophores at the air/water interface

Directory of Open Access Journals (Sweden)

Frederik Neuhaus

2017-06-01

Full Text Available It is currently not possible to directly measure the lateral pressure of a biomembrane. Mechanoresponsive fluorescent probes are an elegant solution to this problem but it requires first the establishment of a direct correlation between the membrane surface pressure and the induced color change of the probe. Here, we analyze planarizable dithienothiophene push–pull probes in a monolayer at the air/water interface using fluorescence microscopy, grazing-incidence angle X-ray diffraction, and infrared reflection–absorption spectroscopy. An increase of the lateral membrane pressure leads to a well-packed layer of the ‘flipper’ mechanophores and a clear change in hue above 18 mN/m. The fluorescent probes had no influence on the measured isotherm of the natural phospholipid DPPC suggesting that the flippers probe the lateral membrane pressure without physically changing it. This makes the flipper probes a truly useful addition to the membrane probe toolbox.

Phospholipid monolayer coated microfabricated electrodes to model the interaction of molecules with biomembranes

International Nuclear Information System (INIS)

Coldrick, Zachary; Steenson, Paul; Millner, Paul; Davies, Matthew; Nelson, Andrew

2009-01-01

The hanging mercury (Hg) drop electrode (HMDE) has a classical application as a tool to study adsorption and desorption processes of surface organic films due to its: (a) atomically smooth surface and, (b) hydrophobicity at its potential of zero charge. In this study we report on a replacement of the HMDE for studying supported organic layers in the form of platinum (Pt) working electrodes fabricated using lithography techniques on which a thin film of Hg is electrodeposited. These wafer-based Pt/Hg electrodes are characterised and compared to the HMDE using rapid cyclic voltammetry (RCV) and show similar capacitance-potential profiles while being far more mechanically stable and consuming considerably less Hg over their lifetime of several months. The electrodes have been used to support self-assembled phospholipid monolayers which are dynamic surface coatings with unique dielectric properties. The issue of surface contamination has been solved by regenerating the electrode surface prior to phospholipid coating by application of extreme cathodic potentials more negative than -2.6 V (vs. Ag/AgCl). The phospholipid coated electrodes presented in this paper mimic one half of a phospholipid bilayer and exhibit interactions with the biomembrane active drug molecules chlorpromazine, and quinidine. The magnitudes of these interactions have been assessed by recording changes in the capacitance-potential profiles in real time using RCV at 40 V s -1 over potential ranges >1 V. A method for electrode coating with phospholipids with the electrodes fitted in a flow cell device has been developed. This has enabled sequential rapid cleaning/coating/interaction cycles for the purposes of drug screening and/or on-line monitoring for molecules of interest.

Phospholipid monolayer coated microfabricated electrodes to model the interaction of molecules with biomembranes

Energy Technology Data Exchange (ETDEWEB)

Coldrick, Zachary [Centre for Self-Organising Molecular Systems (SOMS), School of Chemistry, University of Leeds, Leeds, LS2 9JT (United Kingdom)], E-mail: eenzc@leeds.ac.uk; Steenson, Paul [School of Electronic Engineering, University of Leeds, Leeds, LS2 9JT (United Kingdom); Millner, Paul [Institute of Membrane and Systems Biology, University of Leeds, Leeds, LS2 9JT (United Kingdom); Davies, Matthew [Health and Safety Laboratories, Buxton, SK17 9JN (United Kingdom); Nelson, Andrew [Centre for Self-Organising Molecular Systems (SOMS), School of Chemistry, University of Leeds, Leeds, LS2 9JT (United Kingdom)

2009-09-01

The hanging mercury (Hg) drop electrode (HMDE) has a classical application as a tool to study adsorption and desorption processes of surface organic films due to its: (a) atomically smooth surface and, (b) hydrophobicity at its potential of zero charge. In this study we report on a replacement of the HMDE for studying supported organic layers in the form of platinum (Pt) working electrodes fabricated using lithography techniques on which a thin film of Hg is electrodeposited. These wafer-based Pt/Hg electrodes are characterised and compared to the HMDE using rapid cyclic voltammetry (RCV) and show similar capacitance-potential profiles while being far more mechanically stable and consuming considerably less Hg over their lifetime of several months. The electrodes have been used to support self-assembled phospholipid monolayers which are dynamic surface coatings with unique dielectric properties. The issue of surface contamination has been solved by regenerating the electrode surface prior to phospholipid coating by application of extreme cathodic potentials more negative than -2.6 V (vs. Ag/AgCl). The phospholipid coated electrodes presented in this paper mimic one half of a phospholipid bilayer and exhibit interactions with the biomembrane active drug molecules chlorpromazine, and quinidine. The magnitudes of these interactions have been assessed by recording changes in the capacitance-potential profiles in real time using RCV at 40 V s{sup -1} over potential ranges >1 V. A method for electrode coating with phospholipids with the electrodes fitted in a flow cell device has been developed. This has enabled sequential rapid cleaning/coating/interaction cycles for the purposes of drug screening and/or on-line monitoring for molecules of interest.

Winter to spring variations of chromophoric dissolved organic matter in a temperate estuary (Po River, northern Adriatic Sea).

Science.gov (United States)

Berto, D; Giani, M; Savelli, F; Centanni, E; Ferrari, C R; Pavoni, B

2010-07-01

The light absorbing fraction of dissolved organic carbon (DOC), known as chromophoric dissolved organic matter (CDOM) showed wide seasonal variations in the temperate estuarine zone in front of the Po River mouth. DOC concentrations increased from winter through spring mainly as a seasonal response to increasing phytoplankton production and thermohaline stratification. The monthly dependence of the CDOM light absorption by salinity and chlorophyll a concentrations was explored. In 2003, neither DOC nor CDOM were linearly correlated with salinity, due to an exceptionally low Po river inflow. Though the CDOM absorbance coefficients showed a higher content of chromophoric dissolved organic matter in 2004 with respect to 2003, the spectroscopic features confirmed that the qualitative nature of CDOM was quite similar in both years. CDOM and DOC underwent a conservative mixing, only after relevant Po river freshets, and a change in optical features with an increase of the specific absorption coefficient was observed, suggesting a prevailing terrestrial origin of dissolved organic matter. Published by Elsevier Ltd.

The role of biomembrane lipids in the molecular mechanism of ion transport radiation damage

International Nuclear Information System (INIS)

Medvedev, B.I.; Evtodienko, Yu.V.; Yaguzhinsky, L.S.; Kuzin, A.M.

1977-01-01

Increase in the rate of ATP synthesis (I.4-I.6 times), Ca 2+ -capacity (I.4-I.8 times), membrane potential (by 20-50 mv) and decrease in K - -conductivity (2.5-3 times) in rat liver mitochondria was observed three hours after γ-irradiation at a dose of 1000r. The process of oxidative phosphorylation was normalized 24 hours later, whereas damages of Ca 2+ -accumulation and K + -conductivity remain. The molecular mechanism of reduction in K + -permeability of mitochondrial membranes has been studied. The endogenous regulators of ionic transport in the lipid phase of mitochondrial biomembranes were investigated before and after γ-irradiation. It was revealed that K + -conductivity of the artificial phospholipid membranes (APM) formed of the phospholipids from irradiated mitochondria was substantially lower than that in the control. Using thin-layer chromatography the minor phospholipid fraction which increases K + -conductivity of APM was isolated from the lipids of unirradiated mitochondria. In the lipid preparations of irradiated mitochondria the minor phospholipid fraction content is sharply lowered (or absent at all). Besides the content of lysoforms of phosphatidylcholine and phosphatidylethanolamine as well as that of fatty acids and cholesterol esters were reduced 24 hours after irradiation. Three compounds with different capability to increase the APM conductivity for monovalent ions were revealed in the composition of the minor fraction. One of these components was shown to be lysopolyglycerophosphatide (lysodiphosphatidylglycerol). The role of the enzyme systems involved in radiational changes of the membrane lipid components and the importance of these phenomena for cell radiosensitivity will be discussed

Dimeric fluorescent energy transfer dyes comprising asymmetric cyanine azole-indolenine chromophores

Science.gov (United States)

Glazer, Alexander N.; Benson, Scott C.

1998-01-01

Novel fluorescent heterodimeric DNA-staining energy transfer dyes are provided combining asymmetric cyanine azole-indolenine dyes, which provide for strong DNA affinity, large Stokes shifts and emission in the red region of the spectrum. The dyes find particular application in gel electrophoresis and for labels which may be bound to a variety of compositions in a variety of contexts. Kits and individual compounds are provided, where the kits find use for simultaneous detection of a variety of moieties, particularly using a single narrow wavelength irradiation source. The individual compounds are characterized by high donor quenching and high affinity to dsDNA as a result of optimizing the length of the linking group separating the two chromophores.

Anti-inflammatory and Antibacterial Effects of Covalently Attached Biomembrane-Mimic Polymer Grafts on Gore-Tex Implants.

Science.gov (United States)

Jin, Young Ju; Kang, Sunah; Park, Pona; Choi, Dongkil; Kim, Dae Woo; Jung, Dongwook; Koh, Jaemoon; Jeon, Joohee; Lee, Myoungjin; Ham, Jiyeon; Seo, Ji-Hun; Jin, Hong-Ryul; Lee, Yan

2017-06-07

Expanded polytetrafluoroethylene (ePTFE), also known as Gore-Tex, is widely used as an implantable biomaterial in biomedical applications because of its favorable mechanical properties and biochemical inertness. However, infection and inflammation are two major complications with ePTFE implantations, because pathogenic bacteria can inhabit the microsized pores, without clearance by host immune cells, and the limited biocompatibility can induce foreign body reactions. To minimize these complications, we covalently grafted a biomembrane-mimic polymer, poly(2-methacryloyloxylethyl phosphorylcholine) (PMPC), by partial defluorination followed by UV-induced polymerization with cross-linkers on the ePTFE surface. PMPC grafting greatly reduced serum protein adsorption as well as fibroblast adhesion on the ePTFE surface. Moreover, the PMPC-grafted ePTFE surface exhibited a dramatic inhibition of the adhesion and growth of Staphylococcus aureus, a typical pathogenic bacterium in ePTFE implants, in the porous network. On the basis of an analysis of immune cells and inflammation-related factors, i.e., transforming growth factor-β (TGF-β) and myeloperoxidase (MPO), we confirmed that inflammation was efficiently alleviated in tissues around PMPC-grafted ePTFE plates implanted in the backs of rats. Covalent PMPC may be an effective strategy for promoting anti-inflammatory and antibacterial functions in ePTFE implants and to reduce side effects in biomedical applications of ePTFE.

Chromophoric dissolved organic matter in experimental mesocosms maintained under different pCO2 levels

OpenAIRE

Rochelle-Newall, E.; Delille, B.; Frankignoulle, M.; Gattuso, J.-P.; Jacquet, S.; Riebesell, Ulf; Terbrüggen, A.; Zondervan, I.

2004-01-01

Chromophoric dissolved organic matter (CDOM) represents the optically active fraction of the bulk dissolved organic matter (DOM) pool. Recent evidence pointed towards a microbial source of CDOM in the aquatic environment and led to the proposal that phytoplankton is not a direct source of CDOM, but that heterotrophic bacteria, through reprocessing of DOM of algal origin, are an important source of CDOM. In a recent experiment designed at looking at the effects of elevated pCO2 on blooms of th...

Effect of intercalation and chromophore arrangement on the linear and nonlinear optical properties of model aminopyridine push–pull molecules

Czech Academy of Sciences Publication Activity Database

Bureš, F.; Cvejn, D.; Melánová, Klára; Beneš, L.; Svoboda, Jan; Zima, Vítězslav; Pytela, O.; Mikysek, T.; Růžičková, Z.; Kityk, I. V.; Wojciechowski, A.; AlZayed, N.

2016-01-01

Roč. 4, č. 3 (2016), s. 468-478 ISSN 2050-7526 R&D Projects: GA ČR(CZ) GA13-01061S Institutional support: RVO:61389013 Keywords : push-pull chromophore * intercalation * layered phosphates Subject RIV: CA - Inorganic Chemistry Impact factor: 5.256, year: 2016

Quantitative spatially resolved measurement of tissue chromophore concentrations using photoacoustic spectroscopy: application to the measurement of blood oxygenation and haemoglobin concentration

Science.gov (United States)

Laufer, Jan; Delpy, Dave; Elwell, Clare; Beard, Paul

2007-01-01

A new approach based on pulsed photoacoustic spectroscopy for non-invasively quantifying tissue chromophore concentrations with high spatial resolution has been developed. The technique is applicable to the quantification of tissue chromophores such as oxyhaemoglobin (HbO2) and deoxyhaemoglobin (HHb) for the measurement of physiological parameters such as blood oxygen saturation (SO2) and total haemoglobin concentration. It can also be used to quantify the local accumulation of targeted contrast agents used in photoacoustic molecular imaging. The technique employs a model-based inversion scheme to recover the chromophore concentrations from photoacoustic measurements. This comprises a numerical forward model of the detected time-dependent photoacoustic signal that incorporates a multiwavelength diffusion-based finite element light propagation model to describe the light transport and a time-domain acoustic model to describe the generation, propagation and detection of the photoacoustic wave. The forward model is then inverted by iteratively fitting it to measurements of photoacoustic signals acquired at different wavelengths to recover the chromophore concentrations. To validate this approach, photoacoustic signals were generated in a tissue phantom using nanosecond laser pulses between 740 nm and 1040 nm. The tissue phantom comprised a suspension of intralipid, blood and a near-infrared dye in which three tubes were immersed. Blood at physiological haemoglobin concentrations and oxygen saturation levels ranging from 2% to 100% was circulated through the tubes. The signal amplitude from different temporal sections of the detected photoacoustic waveforms was plotted as a function of wavelength and the forward model fitted to these data to recover the concentrations of HbO2 and HHb, total haemoglobin concentration and SO2. The performance was found to compare favourably to that of a laboratory CO-oximeter with measurement resolutions of ±3.8 g l-1 (±58 µM) and ±4

Quantitative spatially resolved measurement of tissue chromophore concentrations using photoacoustic spectroscopy: application to the measurement of blood oxygenation and haemoglobin concentration

Energy Technology Data Exchange (ETDEWEB)

Laufer, Jan; Delpy, Dave; Elwell, Clare; Beard, Paul [Department of Medical Physics and Bioengineering, University College London, Malet Place Engineering Building, London WC1E 6BT (United Kingdom)

2007-01-07

A new approach based on pulsed photoacoustic spectroscopy for non-invasively quantifying tissue chromophore concentrations with high spatial resolution has been developed. The technique is applicable to the quantification of tissue chromophores such as oxyhaemoglobin (HbO{sub 2}) and deoxyhaemoglobin (HHb) for the measurement of physiological parameters such as blood oxygen saturation (SO{sub 2}) and total haemoglobin concentration. It can also be used to quantify the local accumulation of targeted contrast agents used in photoacoustic molecular imaging. The technique employs a model-based inversion scheme to recover the chromophore concentrations from photoacoustic measurements. This comprises a numerical forward model of the detected time-dependent photoacoustic signal that incorporates a multiwavelength diffusion-based finite element light propagation model to describe the light transport and a time-domain acoustic model to describe the generation, propagation and detection of the photoacoustic wave. The forward model is then inverted by iteratively fitting it to measurements of photoacoustic signals acquired at different wavelengths to recover the chromophore concentrations. To validate this approach, photoacoustic signals were generated in a tissue phantom using nanosecond laser pulses between 740 nm and 1040 nm. The tissue phantom comprised a suspension of intralipid, blood and a near-infrared dye in which three tubes were immersed. Blood at physiological haemoglobin concentrations and oxygen saturation levels ranging from 2% to 100% was circulated through the tubes. The signal amplitude from different temporal sections of the detected photoacoustic waveforms was plotted as a function of wavelength and the forward model fitted to these data to recover the concentrations of HbO{sub 2} and HHb, total haemoglobin concentration and SO{sub 2}. The performance was found to compare favourably to that of a laboratory CO-oximeter with measurement resolutions of {+-}3

Quantitative spatially resolved measurement of tissue chromophore concentrations using photoacoustic spectroscopy: application to the measurement of blood oxygenation and haemoglobin concentration

International Nuclear Information System (INIS)

Laufer, Jan; Delpy, Dave; Elwell, Clare; Beard, Paul

2007-01-01

A new approach based on pulsed photoacoustic spectroscopy for non-invasively quantifying tissue chromophore concentrations with high spatial resolution has been developed. The technique is applicable to the quantification of tissue chromophores such as oxyhaemoglobin (HbO 2 ) and deoxyhaemoglobin (HHb) for the measurement of physiological parameters such as blood oxygen saturation (SO 2 ) and total haemoglobin concentration. It can also be used to quantify the local accumulation of targeted contrast agents used in photoacoustic molecular imaging. The technique employs a model-based inversion scheme to recover the chromophore concentrations from photoacoustic measurements. This comprises a numerical forward model of the detected time-dependent photoacoustic signal that incorporates a multiwavelength diffusion-based finite element light propagation model to describe the light transport and a time-domain acoustic model to describe the generation, propagation and detection of the photoacoustic wave. The forward model is then inverted by iteratively fitting it to measurements of photoacoustic signals acquired at different wavelengths to recover the chromophore concentrations. To validate this approach, photoacoustic signals were generated in a tissue phantom using nanosecond laser pulses between 740 nm and 1040 nm. The tissue phantom comprised a suspension of intralipid, blood and a near-infrared dye in which three tubes were immersed. Blood at physiological haemoglobin concentrations and oxygen saturation levels ranging from 2% to 100% was circulated through the tubes. The signal amplitude from different temporal sections of the detected photoacoustic waveforms was plotted as a function of wavelength and the forward model fitted to these data to recover the concentrations of HbO 2 and HHb, total haemoglobin concentration and SO 2 . The performance was found to compare favourably to that of a laboratory CO-oximeter with measurement resolutions of ±3.8 g l -1 (±58 �

New organic photorefractive material composed of a charge-transporting dendrimer and a stilbene chromophore

Science.gov (United States)

Bai, Jaeil; Ducharme, Stephen; Leonov, Alexei G.; Lu, Liu; Takacs, James M.

1999-10-01

In this report, we introduce new organic photorefractive composites consisting of charge transporting den-drimers highly doped with a stilbene nonlinear optic chromophore, The purpose of making these composites is to improve charge transport, by reducing inhomogeneity when compared to ordinary polymer-based systems. Because the structure of this material gives us freedom to control the orientation of charge transport agents synthetically, we can study the charge transport mechanism more systematically than in polymers. We discuss this point and present the characterization results for this material.

Phosphorescence parameters for platinum (II) organometallic chromophores: A study at the non-collinear four-component Kohn–Sham level of theory

DEFF Research Database (Denmark)

Norman, Patrick; Jensen, Hans Jørgen Aagaard

2012-01-01

A theoretical characterization of the phosphorescence decay traces of a prototypical platinum (II) organic chromophore has been conducted. The phosphorescence wavelength and radiative lifetime are predicted to equal 544 nm and 160 μs, respectively. The third triplet state is assigned as participa...

Investigating the sensitivity of PMMA optical fibres for use as an evanescent field absorption sensor in aqueous solutions

International Nuclear Information System (INIS)

Lye, P G; Boerkamp, M; Ernest, A; Lamb, D W

2005-01-01

Polymethylmethacrylate (PMMA) optical fibres are low-cost polymer fibres that are generally more physically robust than silica fibres, are more flexible, yet like silica fibres have the potential to be used for practical evanescent field absorption sensors in aqueous solutions. However, evanescent field absorption in aqueous solutions is influenced by more than just the specific absorptivity of the solution in question. The physical configuration of the optical fibre itself, as well as surface charge interactions between the fibre and the chromophore in the solution also significantly affects the sensitivity of the fibre to evanescent field absorption. This paper reports on an investigation of numerous physical phenomena that influence evanescent field absorption for PMMA fibres using an aqueous solution of the dye Amidoblack. Parameters investigated included fibre coiling configuration and bend radius, fibre interaction length, and effect of solution pH. Coiled fibres were found to be more sensitive to evanescent field absorption than straight (uncoiled) lengths, and sensitivity was found to increase with a further reduction in bend radius. At high solution pH, the absorption versus solution concentration proved to be linear whereas at low pH the absorption versus concentration relationship exhibited a clear deviation from linearity. The observed nonlinearity at low pH points to the importance of accounting for electrostatic interactions between chromophore and fibre surface when designing a PMMA sensor for evanescent field absorption measurements in aqueous solutions

Gamma ray induced chromophore modification of softwood thermomechanical pulp

International Nuclear Information System (INIS)

Robert, S.; Daneault, C.; Viel, C.; Lepine, F.

1992-01-01

This study focuses on bleaching a softwood (black spruce, balsam fur) thermomechanical pulp with gamma rays. Gamma rays are known for their enormous penetrating power, along with their ionizing properties. They can generate highly energetic radicals capable of oxidizing lignin chromophores. The authors studied the influence of isopropyl alcohol, sodium borohydride, oxygen, hydrogen peroxide, nitrogen dioxide and water along with gamma ray irradiation of the pulps. The authors measured the optimal dose and dose rate, along with the influence of the radical scavengers like oxygen on the bleaching effect of gamma irradiated pulps. They observe various degrees of bleaching of these pulps. Evidence relates this bleaching to the generation of perhydroxyl anions upon irradiation of water. Also, they were able to pinpoint the influence of the dose rate on the rate of formation and disappearance of these perhydroxyl anions and their influence on bleaching kinetics. Stability toward photoyellowing, and photoyellowing's kinetic of papers from these pulps was also studied

Photoelectrochemical characteristics of dye-sensitized solar cells incorporating innovative and inexpensive materials

Science.gov (United States)

Harlow, Lisa Jean

The use of energy is going to continue to increase rapidly due to population and economic advances occurring throughout the world. The most widely used energies produce carbon dioxide during their combustion and have finite limits on how much of these resources are available. A strong push to utilizing renewable energy is necessary to keep up with the demand. The only renewable energy that has unlimited supply is solar. Our goal is to find cost-effective alternatives to historically the most extensively used materials in dye-sensitized solar cells. In order to rely on efficiency changes coinciding with the introduction of a new component, a standard baseline of performance is necessary to establish. A reproducible fabrication procedure composed of standard materials was instituted; the efficiency parameters exhibited a less than 10% standard deviation for any set of solar cells. Any modifications to the cell components would be apparent in the change in efficiency. Our cell modifications focused on economical alternatives to the electrolyte, the counter electrode and the chromophore. Solution-based electrolytes were replaced with a non-volatile ionic liquid, 1-methyl-3-propylimidazolium iodide, and then a poly(imidazole-functionalized) silica nanoparticle. Solid-state electrolytes reduce or prevent leakage and could ease manufacturing in large-scale devices. Platinum has been the counter electrode catalyst primarily used with the iodide/triiodide redox couple, but is a rare metal making it rather costly. We reduce platinum loading by introducing a novel counter electrode that employs platinum nanoparticles embedded on a graphene nanoplatelet paper. The highly conductive carbon base also negates the use of the expensive conductive substrate necessary for the platinum catalyst, further reducing cost. We also study the differences in transitioning from ruthenium polypyridyls to iron-based chromophores in dye-sensitized solar cells. Iron introduces low-lying ligand

Spatiotemporal Characterization of Chromophoric Dissolved Organic Matter (CDOM) and CDOM-DOC Relationships for Highly Polluted Rivers

OpenAIRE

Sijia Li; Jiquan Zhang; Guangyi Mu; Hanyu Ju; Rui Wang; Danjun Li; Ali Hassan Shabbir

2016-01-01

Spectral characteristics of CDOM (Chromophoric dissolved organic matter) in water columns are a key parameter for bio-optical modeling. Knowledge of CDOM optical properties and spatial discrepancy based on the relationship between water quality and spectral parameters in the Yinma River watershed with in situ data collected from highly polluted waters are exhibited in this study. Based on the comprehensive index method, the riverine waters showed serious contamination; especially the chemical...

Second harmonic generation and photochromic grating in polyurethane films containing diazo isoxazole chromophore

Science.gov (United States)

Marański, Krzysztof; Kucharski, Stanisław; Ortyl, Ewelina; Nunzi, Jean-Michel; Ahmadi-Kandjani, Sohrab; Dabos-Seignon, Sylvie; Chan, Siu-Wai; Barille, Regis

2008-08-01

The chromophoric intermediate: 2,2'-({4-[( E)-(5-methylisoxazol-3-yl)diazenyl]phenyl}-imino)diethanol was used in polyaddition reaction with di-isocyanate to obtain a new polyurethane polymeric material showing nonlinear optical and photochromic properties. The maximum absorption band of the polymer film was at 418 nm. The illumination of the film with crossed beams of the 488 nm Ar + laser yielded surface relief grating of regular structure. Measurement of the frequency doubling signal with 1064 nm laser indicated the polymer as interesting material for photooptical applications. The measured nonlinear optical coefficient, d33, reached 90.2 pm/V.

Enhanced Indirect Photochemical Transformation of Histidine and Histamine through Association with Chromophoric Dissolved Organic Matter.

Science.gov (United States)

Chu, Chiheng; Lundeen, Rachel A; Remucal, Christina K; Sander, Michael; McNeill, Kristopher

2015-05-05

Photochemical transformations greatly affect the stability and fate of amino acids (AAs) in sunlit aquatic ecosystems. Whereas the direct phototransformation of dissolved AAs is well investigated, their indirect photolysis in the presence of chromophoric dissolved organic matter (CDOM) is poorly understood. In aquatic systems, CDOM may act both as sorbent for AAs and as photosensitizer, creating microenvironments with high concentrations of photochemically produced reactive intermediates, such as singlet oxygen (1O2). This study provides a systematic investigation of the indirect photochemical transformation of histidine (His) and histamine by 1O2 in solutions containing CDOM as a function of solution pH. Both His and histamine showed pH-dependent enhanced phototransformation in the CDOM systems as compared to systems in which model, low-molecular-weight 1O2 sensitizers were used. Enhanced reactivity resulted from sorption of His and histamine to CDOM and thus exposure to elevated 1O2 concentrations in the CDOM microenvironment. The extent of reactivity enhancement depended on solution pH via its effects on the protonation state of His, histamine, and CDOM. Sorption-enhanced reactivity was independently supported by depressed rate enhancements in the presence of a cosorbate that competitively displaced His and histamine from CDOM. Incorporating sorption and photochemical transformation processes into a reaction rate prediction model improved the description of the abiotic photochemical transformation rates of His in the presence of CDOM.

Wide-range tuning of polymer microring resonators by the photobleaching of CLD-1 chromophores

Science.gov (United States)

Poon, Joyce K. S.; Huang, Yanyi; Paloczi, George T.; Yariv, Amnon; Zhang, Cheng; Dalton, Larry R.

2004-11-01

We present a simple and effective method for the postfabrication trimming of optical microresonators. We photobleach CLD-1 chromophores to tune the resonance wavelengths of polymer microring resonator optical notch filters. A maximum wavelength shift of -8.73 nm is observed. The resonators are fabricated with a soft-lithography molding technique and have an intrinsic Q value of 2.6×10^4 and a finesse of 9.3. The maximum extinction ratio of the resonator filters is -34 dB, indicating that the critical coupling condition has been satisfied.

Substitution of Ethynyl-Thiophene Chromophores on Ruthenium Sensitizers: Influence on Thermal and Photovoltaic Performance of Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Malapaka Chandrasekharam

2012-01-01

Full Text Available A new high molar extinction coefficient ruthenium(II bipyridyl complex, “Ru(2,2-bipyridine-4,4′-dicarboxylic acid(4,4′-bis((3-hexylthiophen-2-ylethynyl-2,2′-bipyridine(NCS2 (N(C4H94, MC101” was synthesized and fully characterized by 1H-NMR, ESI-MASS, FT-IR, UV-Vis., and fluorescence spectroscopes. The dye showed relatively high molar extinction coefficient of 25.0 × 103 M-1 cm-1 at λ maximum of 544 nm, while the reference C101 has shown 15.8 × 103 M-1cm-1 at λ maximum 528 nm. The monochromatic incident photon-to-collected electron conversion efficiency of 44.1% was obtained for MC101 over the entire visible range, while the C101 sensitized solar cell fabricated and evaluated under identical conditions exhibited 40.1%. The DSSCs fabricated with 0.54 cm2 active area TiO2 electrodes and high efficient electrolyte (E01, from the sensitizers MC101 and C101 exhibited energy conversion efficiencies of 3.25% (short-circuit current density (JSC = 7.32 mA/cm2, VOC = 610 mV, ff = 0.725 and 2.94% (JSC = 6.60 mA/cm2; VOC = 630 mV; ff = 0.709, respectively, under air mass of 1.5 sunlight.

Ferrocene-quinoxaline Y-shaped chromophores as fascinating second-order NLO building blocks for long lasting highly active SHG polymeric films.

Science.gov (United States)

Senthilkumar, Kabali; Thirumoorthy, Krishnan; Dragonetti, Claudia; Marinotto, Daniele; Righetto, Stefania; Colombo, Alessia; Haukka, Matti; Palanisami, Nallasamy

2016-07-26

The first example of a Y-shaped ferrocene quinoxaline derivative with a surprisingly high and stable second harmonic generation (SHG) response in composite polymeric films is reported. The interesting quadratic hyperpolarizability values of different substituted Y-shaped chromophores are also investigated in solution by the EFISH technique.

Photorefractive performance of polymer composite sensitized by CdSe nanoparticles passivated by 1-hexadecylamine

Science.gov (United States)

Aslam, Farzana; Binks, David J.; Rahn, Mark D.; West, David P.; O'Brien, Paul; Pickett, Nigel

2005-07-01

The performance of a photorefractive polymer composite sensitized by 1-hexadecylamine capped CdSe nanoparticles is reported. The polymer composite also comprises the charge transporting matrix poly(N-vinylcarbazole) and the electro-optic chromophore 1-(2-ethylhexyloxy)-2,5-dimethyl-4-(4-nitrophenylazo) benzene. At an applied field of 70?V?µ m-1 two beam coupling gain of 13.2?cm-1 was observed, confirming the photorefractive nature of the induced grating. At the same field, a holographic contrast of 9.12×10-4±6×10-6, a photorefractive sensitivity of 5.1×10-4 ±0.2×10-4?cm3?J-1 and a space-charge field rise time of 13±1?s were obtained.

Characteristics and sources of chromophoric dissolved organic matter in lakes of the Yungui Plateau, China, differing in trophic state and altitude

NARCIS (Netherlands)

Zhang, Y.; Zhang, E.; Yin, Y.; Van Dijk, M.A.; Feng, L.; Shi, Z.; Liu, M.; Qina, B.

2010-01-01

The high-mountain lakes on the Yungui Plateau in China are exposed to high-intensity ultraviolet radiation, and contain low concentrations of chromophoric dissolved organic matter (CDOM). We determined CDOM absorption, fluorescence, composition, and source in 38 lakes on the Yungui Plateau at

Symmetry Breaking in Platinum Acetylide Chromophores Studied by Femtosecond Two-Photon Absorption Spectroscopy

Science.gov (United States)

2014-02-01

used hyper- Raman and hyper-Rayleigh scattering to show that in some nominally centrosymmetric metal- free chromophores the inversion symmetry could be...67 618 320 1300 654 1300 NH2 742 18 53 590 30 160 782 93 51 602 160 650 644 420 OCH3 722 16 16 560 57 120 774 57 66 604 190 660 646 300 t-butyl 714...420 644 220 F 706 5.9 1.6 560 85 85 772 53 89 600 60 340 644 170 CF3 714 6.4 22 586 31 110 792 120 210 602 87 440 650 250 CN 732 29 28 590 32 120 814

The importance of nuclear quantum effects in spectral line broadening of optical spectra and electrostatic properties in aromatic chromophores

Science.gov (United States)

Law, Y. K.; Hassanali, A. A.

2018-03-01

In this work, we examine the importance of nuclear quantum effects on capturing the line broadening and vibronic structure of optical spectra. We determine the absorption spectra of three aromatic molecules indole, pyridine, and benzene using time dependent density functional theory with several molecular dynamics sampling protocols: force-field based empirical potentials, ab initio simulations, and finally path-integrals for the inclusion of nuclear quantum effects. We show that the absorption spectrum for all these chromophores are similarly broadened in the presence of nuclear quantum effects regardless of the presence of hydrogen bond donor or acceptor groups. We also show that simulations incorporating nuclear quantum effects are able to reproduce the heterogeneous broadening of the absorption spectra even with empirical force fields. The spectral broadening associated with nuclear quantum effects can be accounted for by the broadened distribution of chromophore size as revealed by a particle in the box model. We also highlight the role that nuclear quantum effects have on the underlying electronic structure of aromatic molecules as probed by various electrostatic properties.

[Photodegradation of chromophoric dissolved organic matter from Jiulong River Estuary under natural solar radiation].

Science.gov (United States)

Guo, Wei-dong; Cheng, Yuan-yue

2008-06-01

Low salinity water sample collected from Jiulong River Estuary filtered using 0.2 microm Millipore filter was exposed to natural solar radiation from 10:00 to 16:00 each day during one week period in early and late May, 2005. Photodegradation of fluorescence and absorption properties of CDOM (chromophoric dissolved organic matter) was observed. The results showed that humic-like fluorescence (lambda Ex/lambda Em = 350/450 nm), tryptophan-like fluorescence (lambda Ex/lambda Em = 225/350 nm) and absorption coefficient of CDOM can be significantly photodegraded during short-term solar exposure in early summer. These photodegradation processes followed the first-order dynamic equation. The degradation half time of humic-like fluorescence, tryptophan-like fluorescence and a (280) were calculated as 3.5-5.1 d, 3.0-4.5 d and 6.3 d. The absorption loss spectra of CDOM indicated that the solar UV radiation was responsible for the photochemical degradation of CDOM. The loss of humic-like fluorescence (70%) was obviously higher than loss of a (280) (about 40%), suggesting that photobleaching ability of CDOM fluorophores were much stronger than CDOM chromophores. However, the correlation relationship between humic-like fluorescence and absorption coefficient are still kept. A250/A350 of CDOM increased till the end of radiation experiment compared with the control group, suggesting photodegradation may decrease the average molecular size of CDOM. These findings show that terrestrial CDOM can be transformed and removed by photochemical decomposition after transport into the sea, and photodegradation might be an important sink for terrestrial CDOM.

Chromophoric dissolved organic matter export from U.S. rivers

Science.gov (United States)

Spencer, Robert G. M.; Aiken, George R.; Dornblaser, Mark M.; Butler, Kenna D.; Holmes, R. Max; Fiske, Greg; Mann, Paul J.; Stubbins, Aron

2013-04-01

Chromophoric dissolved organic matter (CDOM) fluxes and yields from 15 major U.S. rivers draining an assortment of terrestrial biomes are presented. A robust relationship between CDOM and dissolved organic carbon (DOC) loads is established (e.g., a350 versus DOC; r2 = 0.96, p CDOM yields are also correlated to watershed percent wetland (e.g. a350; r2 = 0.81, p CDOM export from ungauged watersheds. A large variation in CDOM yields was found across the rivers. The two rivers in the north-eastern U.S. (Androscoggin and Penobscot), the Edisto draining into the South Atlantic Bight, and some rivers draining into the Gulf of Mexico (Atchafalaya and Mobile) exhibit the highest CDOM yields, linked to extensive wetlands in these watersheds. If the Edisto CDOM yield is representative of other rivers draining into the South Atlantic Bight, this would result in a CDOM load equivalent to that of the Mississippi from a region of approximately 10% of the Mississippi watershed, indicating the importance of certain regions with respect to the role of terrigenous CDOM in ocean color budgets.

Predicting dissolved lignin phenol concentrations in the coastal ocean from chromophoric dissolved organic matter (CDOM absorption coefficients

Directory of Open Access Journals (Sweden)

Cédric G. Fichot

2016-02-01

Full Text Available Dissolved lignin is a well-established biomarker of terrigenous dissolved organic matter (DOM in the ocean, and a chromophoric component of DOM. Although evidence suggests there is a strong linkage between lignin concentrations and chromophoric DOM (CDOM absorption coefficients in coastal waters, the characteristics of this linkage and the existence of a relationship that is applicable across coastal oceans remain unclear. Here, 421 paired measurements of dissolved lignin concentrations (sum of 9 lignin phenols and CDOM absorption coefficients (ag(λ were used to examine their relationship along the river-ocean continuum (0-37 salinity and across contrasting coastal oceans (sub-tropical, temperate, high-latitude. Overall, lignin concentrations spanned four orders of magnitude and revealed a strong, non-linear relationship with ag(λ. The characteristics of the relationship (shape, wavelength dependency, lignin-composition dependency and evidence from degradation indicators were all consistent with lignin being an important driver of CDOM variability in coastal oceans, and suggested physical mixing and long-term photodegradation were important in shaping the relationship. These observations were used to develop two simple empirical models for estimating lignin concentrations from ag(λ with a +/- 20% error relative to measured values. The models are expected to be applicable in most coastal oceans influenced by terrigenous inputs.

Synthesis, photophysical properties of triazolyl-donor/acceptor chromophores decorated unnatural amino acids: Incorporation of a pair into Leu-enkephalin peptide and application of triazolylperylene amino acid in sensing BSA.

Science.gov (United States)

Bag, Subhendu Sekhar; Jana, Subhashis; Pradhan, Manoj Kumar

2016-08-15

The research in the field of design and synthesis of unnatural amino acids is growing at a fast space for the increasing demand of proteins of potential therapeutics and many other diversified novel functional applications. Thus, we report herein the design and synthesis of microenvironment sensitive fluorescent triazolyl unnatural amino acids (UNAA) decorated with donor and/or acceptor aromatic chromophores via click chemistry. The synthesized fluorescent amino acids show interesting solvatochromic characteristic and/or intramolecular charge transfer (ICT) feature as is revealed from the UV-visible, fluorescence photophysical properties and DFT/TDDFT calculation. HOMO-LUMO distribution shows that the emissive states of some of the amino acids are characterized with more significant electron redistribution between the triazolyl moiety and the aromatic chromophores linked to it leading to modulated emission property. A pair of donor-acceptor amino acid shows interesting photophysical interaction property indicating a FRET quenching event. Furthermore, one of the amino acid, triazolyl-perylene amino acid, has been exploited for studying interaction with BSA and found that it is able to sense BSA with an enhancement of fluorescence intensity. Finally, we incorporated a pair of donor/acceptor amino acids into a Leu-enkephalin analogue pentapeptide which was found to adopt predominantly type II β-turn conformation. We envisage that our investigation is of importance for the development of new fluorescent donor-acceptor unnatural amino acids a pair of which can be exploited for generating fluorescent peptidomimetic probe of interesting photophysical property for applications in studying peptide-protein interaction. Copyright © 2016 Elsevier Ltd. All rights reserved.

[Effect of Charge-Transfer Complex on Ultraviolet-Visible (UV-Vis) Absorption Property of Chromophoric Dissolved Organic Matter (CDOM) in Waters of Typical Water-Level Fluctuation Zones of the Three Gorges Reservoir Areas].

Science.gov (United States)

Jiang, Tao; Liang, Jian; Zhang, Mu-xue; Wang, Ding-yong; Wei, Shi-qiang; Lu, Song

2016-02-15

As an important fraction of dissolved organic matter (DOM), chromophoric dissolved organic matter (CDOM) plays a key role in decision of the optical properties and photogeochemistry of DOM, and further affects pollutant fate and global carbon cycle. These optical properties are ascribed to two chromophoric systems including superposition of individual chromophores and charge-transfer (CT) complexation between electron donor (e.g., phenols and indoles) and acceptor (e.g., quinones and other oxidized aromatics) in DOM structures. Thus in this study, based on the "double-chromophoric system" model, DOM samples from four typical water-level fluctuation zones of Three Gorges Reservoir (TGR) areas were selected, to investigate the effect and contribution of charge-transfer complex to ultraviolet-visible (UV-Vis) absorption property of CDOM. Using NaBH, reduction method, original featureless absorption curve was classified into two independent curves caused by individual chromophoric group, which were derived from a simple superposition of independent chromophore and charge-transfer complex, respectively. Also, the changes in curve properties and specific parameters before and after NaBH4 reduction were compared. The results showed that in all DOM samples from the four sites of TGR, more than 35% of absorption was attributed from CT complex. Shibaozhai of Zhongxian and Zhenxi of Fuling showed the highest proportion ( > 50%). It suggested that the role of CT complex in CDOM property could not be neglected. After removal of CT complex, absorption curve showed blue-shift and CDOM concentration [a (355)] decreased significantly. Meanwhile, because of deforming of bonds by reduction, DOM structures became more dispersive and the molecular size was decreased, resulting in the lower spectral slope (S) observed, which evidentially supported that the supermolecular association structure of DOM was self-assembled through CT complex. Meanwhile, deceasing hydrophobic components led

UVA photolysis using the protein-bound sensitizers present in human lens

International Nuclear Information System (INIS)

Ortwerth, B.J.; Olesen, P.R.

1994-01-01

This research was undertaken to demonstrate that the protein-bound chromophores in aged human lens can act as sensitizers for protein damage by UVA light. The water-insoluble (WI) proteins from pooled human and bovine lenses were solubilized by sonication in water and illuminated with UV light similar in output to that transmitted by the cornea. Analysis of the irradiated proteins showed a linear decrease in sulfhydryl groups with a 30% loss after 2 h. No loss was seen when native α-crystallin was irradiated under the same conditions. A 25% loss of histidine residues was also observed with the human lens WI fraction, and sodium dodecyl sulfate polyacrylamide gels indicated considerable protein cross-linking. Similar photodamage was seen with a WI fraction from old bovine lenses. While the data show the presence of UVA sensitizers, some histidine destruction and protein cross-linking were also obtained with α-crystallin and with lysozyme which argue that part of the histidine loss in the human WISS was likely due to tryptophan acting as a sensitizer. (Author)

Sulfates as chromophores for multiwavelength photoacoustic imaging phantoms

Science.gov (United States)

Fonseca, Martina; An, Lu; Beard, Paul; Cox, Ben

2017-12-01

As multiwavelength photoacoustic imaging becomes increasingly widely used to obtain quantitative estimates, the need for validation studies conducted on well-characterized experimental phantoms becomes ever more pressing. One challenge that such studies face is the design of stable, well-characterized phantoms and absorbers with properties in a physiologically realistic range. This paper performs a full experimental characterization of aqueous solutions of copper and nickel sulfate, whose properties make them close to ideal as chromophores in multiwavelength photoacoustic imaging phantoms. Their absorption varies linearly with concentration, and they mix linearly. The concentrations needed to yield absorption values within the physiological range are below the saturation limit. The shape of their absorption spectra makes them useful analogs for oxy- and deoxyhemoglobin. They display long-term photostability (no indication of bleaching) as well as resistance to transient effects (no saturable absorption phenomena), and are therefore suitable for exposure to typical pulsed photoacoustic light sources, even when exposed to the high number of pulses required in scanning photoacoustic imaging systems. In addition, solutions with tissue-realistic, predictable, and stable scattering can be prepared by mixing sulfates and Intralipid, as long as an appropriate emulsifier is used. Finally, the Grüneisen parameter of the sulfates was found to be larger than that of water and increased linearly with concentration.

Ethyne-linked push-pull chromophores: implications of crystal structure and molecular electronics on the quadric nonlinear activity

Czech Academy of Sciences Publication Activity Database

Kautny, P.; Kriegner, H.; Bader, D.; Dušek, Michal; Reider, G.A.; Froehlich, J.; Stoeger, B.

2017-01-01

Roč. 17, č. 8 (2017), s. 4124-4136 ISSN 1528-7483 R&D Projects: GA ČR(CZ) GA15-12653S; GA MŠk LO1603 EU Projects: European Commission(XE) CZ.2.16/3.1.00/24510 Institutional support: RVO:68378271 Keywords : ethyne-linked materials * nonlinear optical chromophores * molecular structure * optical activity Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics, supercond.) Impact factor: 4.055, year: 2016

Interaction of Local Anesthetics with Biomembranes Consisting of Phospholipids and Cholesterol: Mechanistic and Clinical Implications for Anesthetic and Cardiotoxic Effects

Directory of Open Access Journals (Sweden)

Hironori Tsuchiya

2013-01-01

Full Text Available Despite a long history in medical and dental application, the molecular mechanism and precise site of action are still arguable for local anesthetics. Their effects are considered to be induced by acting on functional proteins, on membrane lipids, or on both. Local anesthetics primarily interact with sodium channels embedded in cell membranes to reduce the excitability of nerve cells and cardiomyocytes or produce a malfunction of the cardiovascular system. However, the membrane protein-interacting theory cannot explain all of the pharmacological and toxicological features of local anesthetics. The administered drug molecules must diffuse through the lipid barriers of nerve sheaths and penetrate into or across the lipid bilayers of cell membranes to reach the acting site on transmembrane proteins. Amphiphilic local anesthetics interact hydrophobically and electrostatically with lipid bilayers and modify their physicochemical property, with the direct inhibition of membrane functions, and with the resultant alteration of the membrane lipid environments surrounding transmembrane proteins and the subsequent protein conformational change, leading to the inhibition of channel functions. We review recent studies on the interaction of local anesthetics with biomembranes consisting of phospholipids and cholesterol. Understanding the membrane interactivity of local anesthetics would provide novel insights into their anesthetic and cardiotoxic effects.

Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM)

International Nuclear Information System (INIS)

Clark, Catherine D.; Bruyn, Warren de; Jones, Joshua G.

2014-01-01

Highlights: • CDOM produces hydrogen peroxide in sunlit surface waters. • Quinone moieties have been proposed as the photo-active chromophore in CDOM. • Hydrogen peroxide is produced in irradiated aqueous quinone solutions. • Concentrations and production rates are comparable to humic and fulvic acids. • Optical properties post-irradiation were similar to CDOM. - Abstract: To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H 2 O 2 ) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H 2 O 2 with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h −1 ); values ranged from 6.99 to 0.137 mM h −1 for quinones. Apparent quantum yields (Θ app ; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation–emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM

Occlusion of chromophore oxides by Sol-Gel methods: Application to the synthesis of hematite-silica red pigments

Directory of Open Access Journals (Sweden)

Vicent, J. B.

2000-02-01

Full Text Available Heteromorphic pigments present the chromophore particle occluded in an encapsulating matrix which is thermally stable and insoluble in glazes. The occluded chromophore compound is also insoluble in the host matrix. In this work the mechanisms of formation of this type of pigments are analyzed and the occlusion of hematite into silica matrix is discussed. The formation of this hematite-silica red pigment follows a sintering-coarsening mechanism, and, consequently, the control of both hematite particles nucleation and their crystal growth results to be decisive to obtain a good coloring effectiveness.

En los pigmentos heteromórficos la partícula de cromóforo es ocluida en una matriz encapsuladora estable tanto termicamente como frente a los vidriados. El compuesto cromóforo ocluido y la matriz no coloreada son insolubles. En este trabajo se analiza los diferentes mecanismos de formación de estos pigmentos heteromórficos y se estudia la oclusión de hematita en sílice mediante métodos sol-gel acuoso. El pigmento sigue un mecanismo de sinterización-crecimiento cristalino por lo que es muy importante controlar el momento de nucleación y la velocidad de crecimiento de las partículas de hematita en el seno de la matriz.

Acceptor number-dependent ultrafast photo-physical properties of push-pull chromophores using time-resolved methods

Science.gov (United States)

Chi, Xiao-Chun; Wang, Ying-Hui; Gao, Yu; Sui, Ning; Zhang, Li-Quan; Wang, Wen-Yan; Lu, Ran; Ji, Wen-Yu; Yang, Yan-Qiang; Zhang, Han-Zhuang

2018-04-01

Three push-pull chromophores comprising a triphenylamine (TPA) as electron-donating moiety and functionalized β-diketones as electron acceptor units are studied by various spectroscopic techniques. The time-correlated single-photon counting data shows that increasing the number of electron acceptor units accelerates photoluminescence relaxation rate of compounds. Transient spectra data shows that intramolecular charge transfer (ICT) takes place from TPA units to β-diketones units after photo-excitation. Increasing the number of electron acceptor units would prolong the generation process of ICT state, and accelerate the excited molecule reorganization process and the relaxation process of ICT state.

Chromophoric dissolved organic matter export from U.S. rivers

Science.gov (United States)

Spencer, Robert G. M.; Aiken, George R.; Dornblaser, Mark M.; Butler, Kenna D.; Holmes, R. Max; Fiske, Greg; Mann, Paul J.; Stubbins, Aron

2013-01-01

Chromophoric dissolved organic matter (CDOM) fluxes and yields from 15 major U.S. rivers draining an assortment of terrestrial biomes are presented. A robust relationship between CDOM and dissolved organic carbon (DOC) loads is established (e.g., a350 versus DOC; r2 = 0.96, p CDOM yields are also correlated to watershed percent wetland (e.g. a350; r2 = 0.81, p CDOM export from ungauged watersheds. A large variation in CDOM yields was found across the rivers. The two rivers in the north-eastern U.S. (Androscoggin and Penobscot), the Edisto draining into the South Atlantic Bight, and some rivers draining into the Gulf of Mexico (Atchafalaya and Mobile) exhibit the highest CDOM yields, linked to extensive wetlands in these watersheds. If the Edisto CDOM yield is representative of other rivers draining into the South Atlantic Bight, this would result in a CDOM load equivalent to that of the Mississippi from a region of approximately 10% of the Mississippi watershed, indicating the importance of certain regions with respect to the role of terrigenous CDOM in ocean color budgets.

Chiral 1,2- and 1,3-diol-functionalized chromophores as Lego building blocks for coupled structures.

Science.gov (United States)

Spange, Stefan; Hofmann, Katja; Walfort, Bernhard; Rüffer, Tobias; Lang, Heinrich

2005-10-14

Chiral nitroanilines containing 1,2- or 1,3-diol functionalities have been synthesized by nucleophilic aromatic substitution of fluoronitroanilines with 1-aminopropane-2,3-diols and 2-aminopropane-1,3-diol in the melt. X-ray structure analyses confirm retention of the configuration of the chiral center. The novel chromophores are suitable to link reversibly to various substituted arylboronic acids which allows the construction of new solvatochromic sensor molecules suitable to response to solvent and anion coordination by fluoride. The solvatochromism of the new compounds has been studied using the Kamlet-Taft LSE relationship.

Mapping the Excited State Potential Energy Surface of a Retinal Chromophore Model with Multireference and Equation-of-Motion Coupled-Cluster Methods.

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Gozem, Samer; Melaccio, Federico; Lindh, Roland; Krylov, Anna I; Granovsky, Alexander A; Angeli, Celestino; Olivucci, Massimo

2013-10-08

The photoisomerization of the retinal chromophore of visual pigments proceeds along a complex reaction coordinate on a multidimensional surface that comprises a hydrogen-out-of-plane (HOOP) coordinate, a bond length alternation (BLA) coordinate, a single bond torsion and, finally, the reactive double bond torsion. These degrees of freedom are coupled with changes in the electronic structure of the chromophore and, therefore, the computational investigation of the photochemistry of such systems requires the use of a methodology capable of describing electronic structure changes along all those coordinates. Here, we employ the penta-2,4-dieniminium (PSB3) cation as a minimal model of the retinal chromophore of visual pigments and compare its excited state isomerization paths at the CASSCF and CASPT2 levels of theory. These paths connect the cis isomer and the trans isomer of PSB3 with two structurally and energetically distinct conical intersections (CIs) that belong to the same intersection space. MRCISD+Q energy profiles along these paths provide benchmark values against which other ab initio methods are validated. Accordingly, we compare the energy profiles of MRPT2 methods (CASPT2, QD-NEVPT2, and XMCQDPT2) and EOM-SF-CC methods (EOM-SF-CCSD and EOM-SF-CCSD(dT)) to the MRCISD+Q reference profiles. We find that the paths produced with CASSCF and CASPT2 are topologically and energetically different, partially due to the existence of a "locally excited" region on the CASPT2 excited state near the Franck-Condon point that is absent in CASSCF and that involves a single bond, rather than double bond, torsion. We also find that MRPT2 methods as well as EOM-SF-CCSD(dT) are capable of quantitatively describing the processes involved in the photoisomerization of systems like PSB3.

Structure effect on the interaction of phenylurea herbicides with model biomembrane as an environmental mobility parameter.

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Librando, Vito; Forte, Stefano; Sarpietro, Maria G

2004-01-15

During recent years, intensive use of herbicides has raised increasing concern mainly due to their massive pollution of the environment. As these herbicides are directly or indirectly toxic to a wide range of organisms, their potential for contaminating soil, surface water, and groundwater makes these xenobiotics of special interest from a health and environmental point of view. Knowledge of the mechanisms by which they exert their toxic effects is becoming a need. Because of the herbicides' lipophilicity, a possible site of interaction in the cell is represented by biomembranes. The interaction of four herbicides, difenoxuron, diuron, linuron, and metoxuron, with model membranes constituted of dimyristoylphosphatidylcholine multilamellar vesicles was investigated by the differential scanning calorimetry technique. The aim was to study the effects exerted by an increasing amount of the examined compounds on thermotropic behavior of the model phospholipid membranes and to correlate the obtained results with structural features of the herbicides due to their environmental mobility. Among the herbicides studied, linuron is the most effective in perturbing the ordinate structure of vesicles forming phospholipids, whereas metoxuron is the least effective and the others exert an intermediate effect. Linuron exerts its effect both on the transition temperature of the gel to the liquid crystalline phase and on the enthalpy change. Difenoxuron, diuron, and metoxuron cause a change in the transition temperature but have an insignificant effect on the enthalpy change. The calorimetric results, correlated with the structural features of the herbicides, are consistent with their partition coefficient, log K(ow), suggesting that the more hydrophobic compound character causes a greater liposolubility and consequential cellular absorption with more effectiveness on the membrane order.

Synthesis and Properties of Novel Polyurethane Containing Nitrophenylazocatecholic Group as NLO Chromophore

International Nuclear Information System (INIS)

Song, Mi Young; Kim, Mi Sung; Lee, Ju Yeon

2012-01-01

The promise of NLO polymers lies in their higher nonlinear optical activity, faster response time, and easy fabrication into electro-optic devices. In the developments of NLO polymers for electrooptic device applications, stabilization of electrically induced dipole alignment is one of important considerations; in this context, two approaches to minimize the randomization have been proposed, namely the use of cross-linked systems and the utilization of polymers with high glass transition temperature (T g ) such as polyimides. A polyurethane matrix forms extensive hydrogen bonding between urethane linkages, with increased rigidity preventing the relaxation of induced dipoles. Polyurethanes functionalized with hemicyanine and thiophene ring in side chain show an enhanced thermal stability of aligned dipoles. Polyurethanes with NLO chromophores, whose dipole moments are aligned transverse to the main chains, show large second-order nonlinearity with good thermal stability

Picosecond absorption studies of photoinduced charge separation in polyelectrolyte bound aromatic chromophores

Science.gov (United States)

Shand, M. A.; Rodgers, M. A. J.; Webber, S. E.

1991-02-01

Picosecond absorption studies of photoinduced electron transfer between aromatic chromophores bound to polymethacrylic acid (P) and methylviologen (MV 2+ have been carried out in aqueous solution. The diphenylanthracene copolymer/viologen system at pH 2.8 shows the corresponding redox products DPA + rad and MV + rad arising from the singlet state of DPA with a forward rate constant of electron transfer of 2.6 × 10 9 s -1. At pH 9.0 the quenching of the S 1 state of DPA occurs with no charge separated products being observed. The pyrene copolymer shows no evidence of charge separated products at any pH in the range 2.8-9.0. It is proposed that the differences in the radical pair kinetics arise from differences in the degree of binding of the ground state complexes formed by the donor and acceptor species.

UV-Vis spectroscopy of tyrosine side-groups in studies of protein structure. Part 1: basic principles and properties of tyrosine chromophore.

Science.gov (United States)

Antosiewicz, Jan M; Shugar, David

2016-06-01

Spectroscopic properties of tyrosine residues may be employed in structural studies of proteins. Here we discuss several different types of UV-Vis spectroscopy, like normal, difference and second-derivative UV absorption spectroscopy, fluorescence spectroscopy, linear and circular dichroism spectroscopy, and Raman spectroscopy, and corresponding optical properties of the tyrosine chromophore, phenol, which are used to study protein structure.

Delineating the relationship between chromophoric dissolved organic matter (CDOM) variability and biogeochemical parameters in a shallow continental shelf

OpenAIRE

Sourav Das; Sugata Hazra; Aneesh A. Lotlikar; Isha Das; Sandip Giri; Abhra Chanda; Anirban Akhand; Sourav Maity; T. Srinivasa Kumar

2016-01-01

Absorption coefficient of chromophoric dissolved organic matter (CDOM) at 440 nm [aCDOM (440)], sea surface salinity (SSS), total suspended matter (TSM) and chlorophyll-a (chl-a) were measured during October, 2014 to March, 2015 in the shallow continental shelf waters of the Hugli Estuary, adjacent to West Bengal coast, India. The primary objective of the study was to characterize the relationship between aCDOM (440) and the above mentioned biogeochemical parameters. Upon analyzing the result...

Photoconversion changes bilin chromophore conjugation and protein secondary structure in the violet/orange cyanobacteriochrome NpF2164g3' [corrected].

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Lim, Sunghyuk; Rockwell, Nathan C; Martin, Shelley S; Dallas, Jerry L; Lagarias, J Clark; Ames, James B

2014-06-01

Cyanobacteriochromes (CBCRs) are cyanobacterial photoreceptors distantly related to phytochromes. All CBCRs examined to date utilize a conserved Cys residue to form a covalent thioether linkage to the bilin chromophore. In the insert-Cys CBCR subfamily, a second conserved Cys can covalently link to the bilin C10 methine bridge, allowing detection of near-UV to blue light. The best understood insert-Cys CBCR is the violet/orange CBCR NpF2164g3 from Nostoc punctiforme, which has a stable second linkage in the violet-absorbing dark state. Photoconversion of NpF2164g3 leads to elimination of the second linkage and formation of an orange-absorbing photoproduct. We recently reported NMR chemical shift assignments for the orange-absorbing photoproduct state of NpF2164g3. We here present equivalent information for its violet-absorbing dark state. In both photostates, NpF2164g3 is monomeric in solution and regions containing the two conserved Cys residues essential for photoconversion are structurally disordered. In contrast to blue light receptors such as phototropin, NpF2164g3 is less structurally ordered in the dark state than in the photoproduct. The insert-Cys insertion loop and C-terminal helix exhibit light-dependent structural changes. Moreover, a motif containing an Asp residue also found in other CBCRs and in phytochromes adopts a random-coil structure in the dark state but a stable α-helix structure in the photoproduct. NMR analysis of the chromophore is consistent with a less ordered dark state, with A-ring resonances only resolved in the photoproduct. The C10 atom of the bilin chromophore exhibits a drastic change in chemical shift upon photoconversion, changing from 34.5 ppm (methylene) in the dark state to 115 ppm (methine) in the light-activated state. Our results provide structural insight into the two-Cys photocycle of NpF2164g3 and the structurally diverse mechanisms used for light perception by the larger phytochrome superfamily.

Synthesis and photochemical properties of a novel iron-sulfur-nitrosyl cluster derivatized with the pendant chromophore protoporphyrin IX.

Science.gov (United States)

Conrado, Christa L; Wecksler, Stephen; Egler, Christian; Magde, Douglas; Ford, Peter C

2004-09-06

The novel Roussin red-salt ester (PPIX-RSE) with a pendant porphyrin chromophore was prepared and investigated as a precursor for the photochemical generation of nitric oxide. PPIX-RSE has the general formula Fe(2)(NO)(4)[(mu-S,mu-S')P] (where (S,S')P is the bis(2-thiolatoethyl) diester of protoporphyrin IX. The photoexcitation of PPIX-RSE with 436- or 546-nm light in an aerated chloroform solution led to the photodecomposition of the cluster with the respective quantum yields (5.2 +/- 0.7) x 10(-4) and (2.5 +/- 0.5 x 10(-4)) and the concomitant release of NO. PPIX-RSE is a significantly more effective NO generator at longer wavelength excitation than are other Fe(2)(mu-SR)(2)(NO)(4) esters for which R is a simple alkyl group such as CH(3)CH(2)- because of the much higher absorptivity of the pendant PPIX chromophore at these wavelengths and a modestly higher quantum yield. Fluorescence intensity and lifetime data indicate that the photoexcited porphyrin of PPIX-RSE is largely quenched by the energy transfer to the Fe(2)S(2)(NO)(4) cluster's core. However, a small fraction of this emission is not quenched, and it is proposed that PPIX-RSE may exist in solution as two conformers.

Tracing global biogeochemical cycles and meridional overturning circulation using chromophoric dissolved organic matter

Science.gov (United States)

Nelson, Norman B.; Siegel, David A.; Carlson, Craig A.; Swan, Chantal M.

2010-02-01

Basin-scale distributions of light absorption by chromophoric dissolved organic matter (CDOM) are positively correlated (R2 > 0.8) with apparent oxygen utilization (AOU) within the top kilometer of the Pacific and Indian Oceans. However, a much weaker correspondence is found for the Atlantic (R2 organic matter from sinking particles. The observed meridional-depth sections of CDOM result from a balance between biogeochemical processes (autochthonous production and solar bleaching) and the meridional overturning circulation. Rapid mixing in the Atlantic dilutes CDOM in the interior and implies that the time scale for CDOM accumulation is greater than ˜50 years. CDOM emerges as a unique tracer for diagnosing changes in biogeochemistry and the overturning circulation, similar to dissolved oxygen, with the additional feature that it can be quantified from satellite observation.

The role of the [CpM(CO)2](-) chromophore in the optical properties of the [Cp2ThMCp(CO)2](+) complexes, where M = Fe, Ru and Os. A theoretical view.

Science.gov (United States)

Cantero-López, Plinio; Le Bras, Laura; Páez-Hernández, Dayán; Arratia-Pérez, Ramiro

2015-12-14

The chemical bond between actinide and the transition metal unsupported by bridging ligands is not well characterized. In this paper we study the electronic properties, bonding nature and optical spectra in a family of [Cp2ThMCp(CO)2](+) complexes where M = Fe, Ru, Os, based on the relativistic two component density functional theory calculations. The Morokuma-Ziegler energy decomposition analysis shows an important ionic contribution in the Th-M interaction with around 25% of covalent character. Clearly, charge transfer occurs on Th-M bond formation, however the orbital term most likely represents a strong charge rearrangement in the fragments due to the interaction. Finally the spin-orbit-ZORA calculation shows the possible NIR emission induced by the [FeCp(CO)2](-) chromophore accomplishing the antenna effect that justifies the sensitization of the actinide complexes.

Absorption features of chromophoric dissolved organic matter (CDOM) and tracing implication for dissolved organic carbon (DOC) in Changjiang Estuary, China

OpenAIRE

Zhang, X. Y.; Chen, X.; Deng, H.; Du, Y.; Jin, H. Y.

2013-01-01

Chromophoric dissolved organic matter (CDOM) represents the light absorbing fraction of dissolved organic carbon (DOC). Studies have shown that the optical properties of CDOM can be used to infer the distribution and diffusion characteristics of DOC in the estuary and coastal zone. The inversion of DOC concentrations from remote sensing has been implemented in certain regions. In this study we investigate the potential of tracing DOC from CDOM by the measure...

Evaluation of light scattering properties and chromophore concentrations in skin tissue based on diffuse reflectance signals at isosbestic wavelengths of hemoglobin

Science.gov (United States)

Yokokawa, Takumi; Nishidate, Izumi

2016-04-01

We investigate a method to evaluate light-scattering properties and chromophore concentrations in human skin tissue through diffuse reflectance spectroscopy using the reflectance signals acquired at isosbestic wavelengths of hemoglobin (420, 450, 500, and 585 nm). In the proposed method, Monte Carlo simulation-based empirical formulas are used to specify the scattering parameters of skin tissue, such as the scattering amplitude a and the scattering power b, as well as the concentration of melanin C m and the total blood concentration C tb. The use of isosbestic wavelengths of hemoglobin enables the values of C m, C tb, a, and b to be estimated independently of the oxygenation of hemoglobin. The spectrum of the reduced scattering coefficient is reconstructed from the scattering parameters. Experiments using in vivo human skin tissues were performed to confirm the feasibility of the proposed method for evaluating the changes in scattering properties and chromophore concentrations in skin tissue. The experimental results revealed that light scattering is significantly reduced by the application of a glycerol solution, which indicates an optical clearing effect due to osmotic dehydration and the matching of the refractive indices of scatterers in the epidermis.

Synthesis of Dendrimer Containing Dialkylated-fluorene Unit as a Core Chromophore via Click Chemistry

International Nuclear Information System (INIS)

Han, Seung Choul; Lee, Jae Wook; Jin, Sung Ho

2012-01-01

The convergent synthetic strategy for the emissive dendrimers having the chromophore at core via the coppercatalyzed 1,3-dipolar cycloaddition reaction between alkyne and azide was described. 2,7-Diazido-9,9-dioctyl- 9H-fluorene, designed to serve as the core in dendrimer, was stitched with the alkyne-functionalized Frechettype and PAMAM dendrons by the click chemistry leading to the formation of the corresponding fluorescent dendrimers in high yields. The preliminary photoluminescence studies indicated that 2,7-diazido-9,9-dioctyl- 9H-fluorene showed no fluorescence due to the quenching effect from the electron-rich α-nitrogen of the azido group but the dendrimers fluoresced due to the elimination of the quenching through the formation of the triazole ring

[1]Benzothieno[3,2-b]benzothiophene-Based Organic Dyes for Dye-Sensitized Solar Cells.

Science.gov (United States)

Capodilupo, Agostina L; Fabiano, Eduardo; De Marco, Luisa; Ciccarella, Giuseppe; Gigli, Giuseppe; Martinelli, Carmela; Cardone, Antonio

2016-04-15

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

Evolution of dissolved and particulate chromophoric materials during the VAHINE mesocosm experiment in the New Caledonian coral lagoon (South West Pacific)

Science.gov (United States)

Tedetti, M.; Marie, L.; Röttgers, R.; Rodier, M.; Van Wambeke, F.; Helias, S.; Caffin, M.; Cornet-Barthaux, V.; Dupouy, C.

2015-10-01

In the framework of the VAHINE project, we investigated the spectral characteristics and the variability of dissolved and particulate chromophoric materials throughout a 23 day mesocosm experiment conducted in the South West Pacific at the exit of the New Caledonian coral lagoon (22°29.073 S-166°26.905 E) from 13 January to 4 February 2013. Samples were collected in a mesocosm fertilized with phosphorus at 1, 6 and 12 m depth and in the surrounding waters. Light absorption coefficients of chromophoric dissolved organic matter (CDOM) (ag(λ)), particulate matter (ap(λ)) and CDOM + particulate matter (ag+p(λ)) were measured using a point-source integrating-cavity absorption meter (PSICAM), while fluorescent DOM (FDOM) components were determined from excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC). The evolutions of ag(λ), ap(λ) and ag+p(λ) in the mesocosm were similar to those of total chlorophyll a concentration, Synechococcus spp. and picoeukaryote abundances, bacterial production, particulate organic nitrogen and total organic carbon concentrations, with roughly a decrease from the beginning of the experiment to days 9-10, and an increase from days 9-10 to the end of the experiment. In the surrounding waters, the same trend was observed but the increase was much less pronounced, emphasizing the effect of the phosphorus fertilization on the mesocosm's plankton community. Correlations suggested that both Synechococcus cyanobacteria and heterotrophic bacteria were strongly involved in the production of CDOM and absorption of particulate matter. The increase in phytoplankton activities during the second part of the experiment led to a higher contribution of particulate material in the absorption budget at 442 nm. The three FDOM components identified (tryptophan-, tyrosine- and UVC humic-like fluorophores) did not follow the evolution of CDOM and particulate matter, proving that these were driven by different production

Depth profiling of laser-heated chromophores in biological tissues by pulsed photothermal radiometry

International Nuclear Information System (INIS)

Milner, T.E.; Goodman, D.M.; Tanenbaum, B.S.; Nelson, J.S.

1995-01-01

A solution method is proposed to the inverse problem of determining the unknown initial temperature distribution in a laser-exposed test material from measurements provided by infrared radiometry. A Fredholm integral equation of the first kind is derived that relates the temporal evolution of the infrared signal amplitude to the unknown initial temperature distribution in the exposed test material. The singular-value decomposition is used to demonstrate the severely ill-posed nature of the derived inverse problem. Three inversion methods are used to estimate solutions for the initial temperature distribution. A nonnegatively constrained conjugate-gradient algorithm using early termination is found superior to unconstrained inversion methods and is applied to image the depth of laser-heated chromophores in human skin. Key words: constrained conjugate gradients, ill-posed problem, infrared radiometry, laser surgery, nonnegative, singular-value decomposition

DFT calculations on spectroscopic and structural properties of a NLO chromophore

Science.gov (United States)

Altürk, Sümeyye; Avci, Davut; Tamer, Ömer; Atalay, Yusuf

2016-03-01

The molecular geometry optimization, vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C NMR chemical shift values of 2-(1'-(4'''-Methoxyphenyl)-5'-(thien-2″-yl)pyrrol-2'-yl)-1,3-benzothiazole as potential nonlinear optical (NLO) material were calculated using density functional theory (DFT) HSEh1PBE method with 6-311G(d,p) basis set. The best of our knowledge, this study have not been reported to date. Additionally, a detailed vibrational study was performed on the basis of potential energy distribution (PED) using VEDA program. It is noteworthy that NMR chemical shifts are quite useful for understanding the relationship between the molecular structure and electronic properties of molecules. The computed IR and NMR spectra were used to determine the types of the experimental bands observed. Predicted values of structural and spectroscopic parameters of the chromophore were compared with each other so as to display the effects of the different substituents on the spectroscopic and structural properties. Obtained data showed that there is an agreement between the predicted and experimental data.

Characterization of chromophoric dissolved organic matter (CDOM) in rainwater using fluorescence spectrophotometry.

Science.gov (United States)

Salve, P R; Lohkare, H; Gobre, T; Bodhe, G; Krupadam, R J; Ramteke, D S; Wate, S R

2012-02-01

The fluorescence excitation-emission matrix of Chromophoric dissolved organic matter (CDOM) samples from rainwater collected at Rameswaram, Tamilnadu, India are analysed. Total five peaks were observed for humic/marine and protein likes substances respectively. The peak A and C intensities varies form 1.98 ± 0.28 and 0.97 ± 0.11 QSU respectively represents humic like substances. The peak B and T intensities varies from 3.94 ± 0.75 and 7.42 ± 1.43 QSU showed association of protein like substances whereas peak M intensities varies from 1.92 ± 0.37 QSU indicates marine contribution. Among the fluorophores, the following sequence were observed as T > B > A > M > C which indicates dominance of Tryptophan like substances in rainwater. The average peak T/C ratios was observed as 7.88 ± 2.2 indicates microbial contamination by Tryptophan-like substances with the high biological activity and low volatility.

Direct two-photon excitation of Sm3+, Eu3+, Tb3+, Tb.DOTA-, and Tb.propargylDO3A in solution

Science.gov (United States)

Sørensen, Thomas Just; Blackburn, Octavia A.; Tropiano, Manuel; Faulkner, Stephen

2012-07-01

We have observed direct two-photon excitation of samarium, europium and terbium ions in solution upon near IR excitation using a tuneable pulsed light source, and have also studied two-photon processes in a pair of related terbium complexes, namely [Tb.DOTA]- and Tb.propargylDO3A. Direct two-photon excitation of lanthanides is observed in simple systems in the absence of sensitizing chromophores. Where even simple chromophores such as a triple bond are present in the complex, then single and two-photon excitation of chromophore excited states competes with direct two-photon excitation of the ions and is the dominant pathway for sensitizing formation of the lanthanide excited state.

Mobile Phone Ratiometric Imaging Enables Highly Sensitive Fluorescence Lateral Flow Immunoassays without External Optical Filters.

Science.gov (United States)

Shah, Kamal G; Singh, Vidhi; Kauffman, Peter C; Abe, Koji; Yager, Paul

2018-05-14

Paper-based diagnostic tests based on the lateral flow immunoassay concept promise low-cost, point-of-care detection of infectious diseases, but such assays suffer from poor limits of detection. One factor that contributes to poor analytical performance is a reliance on low-contrast chromophoric optical labels such as gold nanoparticles. Previous attempts to improve the sensitivity of paper-based diagnostics include replacing chromophoric labels with enzymes, fluorophores, or phosphors at the expense of increased fluidic complexity or the need for device readers with costly optoelectronics. Several groups, including our own, have proposed mobile phones as suitable point-of-care readers due to their low cost, ease of use, and ubiquity. However, extant mobile phone fluorescence readers require costly optical filters and were typically validated with only one camera sensor module, which is inappropriate for potential point-of-care use. In response, we propose to couple low-cost ultraviolet light-emitting diodes with long Stokes-shift quantum dots to enable ratiometric mobile phone fluorescence measurements without optical filters. Ratiometric imaging with unmodified smartphone cameras improves the contrast and attenuates the impact of excitation intensity variability by 15×. Practical application was shown with a lateral flow immunoassay for influenza A with nucleoproteins spiked into simulated nasal matrix. Limits of detection of 1.5 and 2.6 fmol were attained on two mobile phones, which are comparable to a gel imager (1.9 fmol), 10× better than imaging gold nanoparticles on a scanner (18 fmol), and >2 orders of magnitude better than gold nanoparticle-labeled assays imaged with mobile phones. Use of the proposed filter-free mobile phone imaging scheme is a first step toward enabling a new generation of highly sensitive, point-of-care fluorescence assays.

Dynamics and ecological risk assessment of chromophoric dissolved organic matter in the Yinma River Watershed: Rivers, reservoirs, and urban waters.

Science.gov (United States)

Li, Sijia; Zhang, Jiquan; Guo, Enliang; Zhang, Feng; Ma, Qiyun; Mu, Guangyi

2017-10-01

The extensive use of a geographic information system (GIS) and remote sensing in ecological risk assessment from a spatiotemporal perspective complements ecological environment management. Chromophoric dissolved organic matter (CDOM), which is a complex mixture of organic matter that can be estimated via remote sensing, carries and produces carcinogenic disinfection by-products and organic pollutants in various aquatic environments. This paper reports the first ecological risk assessment, which was conducted in 2016, of CDOM in the Yinma River watershed including riverine waters, reservoir waters, and urban waters. Referring to the risk formation theory of natural disaster, the entropy evaluation method and DPSIR (driving force-pressure-state-impact-response) framework were coupled to establish a hazard and vulnerability index with multisource data, i.e., meteorological, remote sensing, experimental, and socioeconomic data, of this watershed. This ecological vulnerability assessment indicator system contains 23 indicators with respect to ecological sensitivity, ecological pressure, and self-resilience. The characteristics of CDOM absorption parameters from different waters showed higher aromatic content and molecular weights in May because of increased terrestrial inputs. The assessment results indicated that the overall ecosystem risk in the study area was focused in the extremely, heavily, and moderately vulnerable regions. The ecological risk assessment results objectively reflect the regional ecological environment and demonstrate the potential of ecological risk assessment of pollutants over traditional chemical measurements. Copyright © 2017. Published by Elsevier Inc.

Cyclometalated N-heterocyclic carbene iridium(iii) complexes with naphthalimide chromophores: a novel class of phosphorescent heteroleptic compounds.

Science.gov (United States)

Lanoë, Pierre-Henri; Chan, Jonny; Groué, Antoine; Gontard, Geoffrey; Jutand, Anny; Rager, Marie-Noelle; Armaroli, Nicola; Monti, Filippo; Barbieri, Andrea; Amouri, Hani

2018-03-06

A series of cyclometalated N-heterocyclic carbene complexes of the general formula [Ir(C^N) 2 (C^C:)] has been prepared. Two sets of compounds were designed, those where (C^C:) represents a bidentate naphthalimide-substituted imidazolylidene ligand and (C^N) = ppy (3a), F2ppy (4a), bzq (5a) and those where (C^C:) represents a naphthalimide-substituted benzimidazolylidene ligand and (C^N) = ppy (3b), F2ppy (4b), bzq (5b). The naphthalimide-imidazole and naphthalimide-benzimidazole ligands 1a,b and the related imidazolium and benzimidazolium salts 2a,b were also prepared and fully characterized. The N-heterocyclic carbene Ir(iii) complexes have been characterized by NMR spectroscopy, cyclic voltammetry and elemental analysis. Moreover, the molecular structures of one imidazolium salt and four Ir(iii) complexes were determined by single-crystal X-ray diffraction. The structures provide us with valuable information, most notably the orientation of the naphthalimide chromophore with respect to the N-heterocyclic carbene moiety. All compounds are luminescent at room temperature and in a frozen solvent at 77 K, exhibiting a broad emission band that extends beyond 700 nm. The presence of the naphthalimide moiety changes the character of the lowest excited state from 3 MLCT to 3 LC, as corroborated by DFT and TD-DFT calculations. Remarkably, replacing imidazole with a benzimidazole unit improves the quantum yields of these compounds by decreasing the k nr values which is an important feature for optimized emission performance. These studies provide valuable insights about a novel class of N-heterocyclic carbene-based luminescent complexes containing organic chromophores and affording metal complexes emitting across the red-NIR range.

Effective photo-enhancement of cellular activity of fluorophore-octaarginine antisense PNA conjugates correlates with singlet oxygen formation, endosomal escape and chromophore lipophilicity

DEFF Research Database (Denmark)

Yarani, Reza; Shiraishi, Takehiko; Nielsen, Peter E.

2018-01-01

Photochemical internalization (PCI) is a cellular drug delivery method based on the generation of light-induced reactive oxygen species (ROS) causing damage to the endosomal membrane and thereby resulting in drug release to the cytoplasm. In our study a series of antisense fluorophore octaarginin...... indicate that efficient photodynamic endosomal escape is strongly dependent on the quantum yield for photochemical singlet oxygen formation, photostability as well as the lipophilicity of the chromophore....

Resonance Raman spectra of the copper-sulfur chromophores in Achromobacter cycloclastes nitrite reductase.

Science.gov (United States)

Dooley, D M; Moog, R S; Liu, M Y; Payne, W J; LeGall, J

1988-10-15

Resonance Raman spectroscopy at ambient temperature and 77 K has been used to probe the structures of the copper sites in Achromobacter cycloclastes nitrite reductase. This enzyme contains three copper ions per protein molecule and has two principal electronic absorption bands with lambda max values of 458 and 585 nm. Comparisons between the resonance Raman spectra of nitrite reductase and blue copper proteins establish that both the 458 and 585 nm bands are associated with Cu(II)-S(Cys) chromophores. A histidine ligand probably is also present. Different sets of vibrational frequencies are observed with 457.9 nm (ambient) or 476.1 nm (77 K) excitation as compared with 590 nm (ambient) or 593 nm (77 K) excitation. Excitation profiles indicate that the 458 and 585 nm absorption bands are associated with separate [Cu(II)-S(Cys)N(His)] sites or with inequivalent and uncoupled cysteine ligands in the same site. The former possibility is considered to be more likely.

Tuning pentacene based dye-sensitized solar cells.

Science.gov (United States)

Kunzmann, Andreas; Gruber, Marco; Casillas, Rubén; Tykwinski, Rik R; Costa, Rubén D; Guldi, Dirk M

2018-05-10

We report on the synthesis, as well as photophysical and electrochemical characterization of a new family of pentacene derivatives, which are applied in n-type dye-sensitized solar cells (DSSCs). As far as the molecular structure of the pentacene is concerned, the synthetic design focuses on cyano acrylic tethered at the 13-position of the pentacene chromophore. The electrolyte composition features increasing amounts of Li+ ions as an additive. In general, the increase of Li+ concentrations extrinsically reduces the quasi Fermi level of the photoanode and as such facilitates the electron injection process. We demonstrate that pentacene derivatives give rise to a unique charge injection process, which is controlled by the positioning of the quasi Fermi level energies as a function of the Li+ concentration. As a result of the enhanced charge injection, device efficiencies as high as 1.5% are achieved, representing a 3-fold increase from previously reported efficiencies in pentacene-based DSSCs. These findings are supported by device analysis in combination with transient absorption and electrochemical impedance spectroscopy assays.

Rhenium complexes of chromophore-appended dipicolylamine ligands: syntheses, spectroscopic properties, DNA binding and X-ray crystal structure

International Nuclear Information System (INIS)

Mullice, L.A.; Buurma, N.J.; Pope, S.J.A.; Laye, R.H.; Harding, L.P.

2008-01-01

The syntheses of two chromophore-appended dipicolylamine-derived ligands and their reactivity with penta-carbonyl-chloro-rhenium have been studied. The resultant complexes each possess the fac-Re(CO) 3 core. The ligands L 1 1-[bis(pyridine-2-yl-methyl)amino]methyl-pyrene and L 2 2-[bis(pyridine-2-yl-methyl)amino]methyl-quinoxaline were isolated via a one-pot reductive amination in moderate yield. The corresponding rhenium complexes were isolated in good yields and characterised by 1 H NMR, MS, IR and UV-Vis studies. X-Ray crystallographic data were obtained for fac-{Re(CO) 3 (L 1 )}(BF 4 ), C 34 H 26 BF 4 N 4 O 3 Re: monoclinic, P2(1)/c, a 18.327(2) Angstroms, α = 90.00 degrees, b 14.1537(14) Angstroms, β96.263(6) degrees, c = 23.511(3) Angstroms, γ 90.00 Angstroms, 6062.4(11) (Angstroms) 3 , Z=8. The luminescence properties of the ligands and complexes were also investigated, with the emission attributed to the appended chromophore in each case. Isothermal titration calorimetry suggests that fac-{Re(CO) 3 (L 1 )}(BF 4 ) self-aggregates cooperatively in aqueous solution, probably forming micelle-like aggregates with a cmc of 0.18 mM. Investigations into the DNA-binding properties of fac-{Re(CO) 3 (L 1 )}(BF 4 ) were undertaken and revealed that fac-{Re(CO) 3 (L 1 )}(BF 4 ) binding to fish sperm DNA (binding constant 1.5 ± 0.2 * 10 5 M -1 , binding site size 3.2 ± 0.3 base pairs) is accompanied by changes in the UV-Vis spectrum as typically observed for pyrene-based intercalators while the calorimetrically determined binding enthalpy (-14 ± 2 kcal mol -1 ) also agrees favourably with values as typically found for intercalators. (authors)

Removal of Chromophore-proximal Polar Atoms Decreases Water Content and Increases Fluorescence in a Near Infrared Phytofluor

Directory of Open Access Journals (Sweden)

Heli eLehtivuori

2015-11-01

Full Text Available Genetically encoded fluorescent markers have revolutionized cell and molecular biology due to their biological compatibility, controllable spatiotemporal expression, and photostability. To achieve in vivo imaging in whole animals, longer excitation wavelength probes are needed due to the superior ability of near infrared light to penetrate tissues unimpeded by absorbance from biomolecules or autofluorescence of water. Derived from near infrared-absorbing bacteriophytochromes, phytofluors are engineered to fluoresce in this region of the electromagnetic spectrum, although high quantum yield remains an elusive goal. An invariant aspartate residue is of utmost importance for photoconversion in native phytochromes, presumably due to the proximity of its backbone carbonyl to the pyrrole ring nitrogens of the biliverdin (BV chromophore as well as the size and charge of the side chain. We hypothesized that the polar interaction network formed by the charged side chain may contribute to the decay of the excited state via proton transfer. Thus, we chose to further probe the role of this amino acid by removing all possibility for polar interactions with its carboxylate side chain by incorporating leucine instead. The resultant fluorescent protein, WiPhy2, maintains BV binding, monomeric status, and long maximum excitation wavelength while minimizing undesirable protoporphyrin IXα binding in cells. A crystal structure and time-resolved fluorescence spectroscopy reveal that water near the BV chromophore is excluded and thus validate our hypothesis that removal of polar interactions leads to enhanced fluorescence by increasing the lifetime of the excited state. This new phytofluor maintains its fluorescent properties over a broad pH range and does not suffer from photobleaching. WiPhy2 achieves the best compromise to date between high fluorescence quantum yield and long illumination wavelength in this class of fluorescent proteins.

The global distribution and dynamics of chromophoric dissolved organic matter.

Science.gov (United States)

Nelson, Norman B; Siegel, David A

2013-01-01

Chromophoric dissolved organic matter (CDOM) is a ubiquitous component of the open ocean dissolved matter pool, and is important owing to its influence on the optical properties of the water column, its role in photochemistry and photobiology, and its utility as a tracer of deep ocean biogeochemical processes and circulation. In this review, we discuss the global distribution and dynamics of CDOM in the ocean, concentrating on developments in the past 10 years and restricting our discussion to open ocean and deep ocean (below the main thermocline) environments. CDOM has been demonstrated to exert primary control on ocean color by its absorption of light energy, which matches or exceeds that of phytoplankton pigments in most cases. This has important implications for assessing the ocean biosphere via ocean color-based remote sensing and the evaluation of ocean photochemical and photobiological processes. The general distribution of CDOM in the global ocean is controlled by a balance between production (primarily microbial remineralization of organic matter) and photolysis, with vertical ventilation circulation playing an important role in transporting CDOM to and from intermediate water masses. Significant decadal-scale fluctuations in the abundance of global surface ocean CDOM have been observed using remote sensing, indicating a potentially important role for CDOM in ocean-climate connections through its impact on photochemistry and photobiology.

An Unprecedented Blue Chromophore Found in Nature using a "Chemistry First" and Molecular Networking Approach: Discovery of Dactylocyanines A-H.

Science.gov (United States)

Bonneau, Natacha; Chen, Guanming; Lachkar, David; Boufridi, Asmaa; Gallard, Jean-François; Retailleau, Pascal; Petek, Sylvain; Debitus, Cécile; Evanno, Laurent; Beniddir, Mehdi A; Poupon, Erwan

2017-10-17

Guided by a "chemistry first" approach using molecular networking, eight new bright-blue colored natural compounds, namely dactylocyanines A-H (3-10), were isolated from the Polynesian marine sponge Dactylospongia metachromia. Starting from ilimaquinone (1), an hemisynthetic phishing probe (2) was prepared for annotating and matching structurally related natural substances in D. metachromia crude extract network. This strategy allowed characterizing for the first time in Nature the blue zwitterionic quinonoid chromophore. The solvatochromic properties of the latter are reported. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorescence and absorption properties of chromophoric dissolved organic matter (CDOM) in coastal surface waters of the Northwestern Mediterranean Sea (Bay of Marseilles, France)

OpenAIRE

J. Para; P. G. Coble; B. Charrière; M. Tedetti; C. Fontana; R. Sempéré

2010-01-01

Seawater samples were collected in surface waters (2 and 5 m depths) of the Bay of Marseilles (Northwestern Mediterranean Sea; 5°17′30′′ E, 43°14′30′′ N) during one year from November 2007 to December 2008 and studied for total organic carbon (TOC) as well as chromophoric dissolved organic matter (CDOM) optical properties (absorbance and fluorescence). The annual mean value of surface CDOM absorption coefficient ...

Computational design and elaboration of a de novo heterotetrameric alpha-helical protein that selectively binds an emissive abiological (porphinato)zinc chromophore.

Science.gov (United States)

Fry, H Christopher; Lehmann, Andreas; Saven, Jeffery G; DeGrado, William F; Therien, Michael J

2010-03-24

The first example of a computationally de novo designed protein that binds an emissive abiological chromophore is presented, in which a sophisticated level of cofactor discrimination is pre-engineered. This heterotetrameric, C(2)-symmetric bundle, A(His):B(Thr), uniquely binds (5,15-di[(4-carboxymethyleneoxy)phenyl]porphinato)zinc [(DPP)Zn] via histidine coordination and complementary noncovalent interactions. The A(2)B(2) heterotetrameric protein reflects ligand-directed elements of both positive and negative design, including hydrogen bonds to second-shell ligands. Experimental support for the appropriate formulation of [(DPP)Zn:A(His):B(Thr)](2) is provided by UV/visible and circular dichroism spectroscopies, size exclusion chromatography, and analytical ultracentrifugation. Time-resolved transient absorption and fluorescence spectroscopic data reveal classic excited-state singlet and triplet PZn photophysics for the A(His):B(Thr):(DPP)Zn protein (k(fluorescence) = 4 x 10(8) s(-1); tau(triplet) = 5 ms). The A(2)B(2) apoprotein has immeasurably low binding affinities for related [porphinato]metal chromophores that include a (DPP)Fe(III) cofactor and the zinc metal ion hemin derivative [(PPIX)Zn], underscoring the exquisite active-site binding discrimination realized in this computationally designed protein. Importantly, elements of design in the A(His):B(Thr) protein ensure that interactions within the tetra-alpha-helical bundle are such that only the heterotetramer is stable in solution; corresponding homomeric bundles present unfavorable ligand-binding environments and thus preclude protein structural rearrangements that could lead to binding of (porphinato)iron cofactors.

Image analysis of skin color heterogeneity focusing on skin chromophores and the age-related changes in facial skin.

Science.gov (United States)

Kikuchi, Kumiko; Masuda, Yuji; Yamashita, Toyonobu; Kawai, Eriko; Hirao, Tetsuji

2015-05-01

Heterogeneity with respect to skin color tone is one of the key factors in visual perception of facial attractiveness and age. However, there have been few studies on quantitative analyses of the color heterogeneity of facial skin. The purpose of this study was to develop image evaluation methods for skin color heterogeneity focusing on skin chromophores and then characterize ethnic differences and age-related changes. A facial imaging system equipped with an illumination unit and a high-resolution digital camera was used to develop image evaluation methods for skin color heterogeneity. First, melanin and/or hemoglobin images were obtained using pigment-specific image-processing techniques, which involved conversion from Commission Internationale de l'Eclairage XYZ color values to melanin and/or hemoglobin indexes as measures of their contents. Second, a spatial frequency analysis with threshold settings was applied to the individual images. Cheek skin images of 194 healthy Asian and Caucasian female subjects were acquired using the imaging system. Applying this methodology, the skin color heterogeneity of Asian and Caucasian faces was characterized. The proposed pigment-specific image-processing techniques allowed visual discrimination of skin redness from skin pigmentation. In the heterogeneity analyses of cheek skin color, age-related changes in melanin were clearly detected in Asian and Caucasian skin. Furthermore, it was found that the heterogeneity indexes of hemoglobin were significantly higher in Caucasian skin than in Asian skin. We have developed evaluation methods for skin color heterogeneity by image analyses based on the major chromophores, melanin and hemoglobin, with special reference to their size. This methodology focusing on skin color heterogeneity should be useful for better understanding of aging and ethnic differences. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

[Study on optical characteristics of chromophoric dissolved organic matter (CDOM) in rainwater by fluorescence excitation-emission matrix and absorbance spectroscopy].

Science.gov (United States)

Cheng, Yuan-yue; Guo, Wei-dong; Long, Ai-min; Chen, Shao-yong

2010-09-01

The optical characteristics of chromophoric dissolved organic matter (CDOM) were determined in rain samples collected in Xiamen Island, during a rainy season in 2007, using fluorescence excitation-emission matrix spectroscopy associated with UV-Vis absorbance spectra. Results showed that the absorbance spectra of CDOM in rain samples decreased exponentially with wavelength. The absorbance coefficient at 300 nm [a(300)] ranged from 0.27 to 3.45 m(-1), which would be used as an index of CDOM abundance, and the mean value was 1.08 m(-1). The content of earlier stage of precipitation events was higher than that of later stage of precipitation events, which implied that anthropogenic sources or atmospheric pollution or air mass types were important contributors to CDOM levels in precipitation. EEMs spectra showed 4 types of fluorescence signals (2 humic-like fluorescence peaks and 2 protein-like fluorescence peaks) in rainwater samples, and there were significant positive correlations of peak A with C and peak B with S, showing their same sources or some relationship of the two humic-like substance and the two protein-like substance. The strong positive correlations of the two humic-like fluorescence peaks with a(300), suggested that the chromophores responsible for absorbance might be the same as fluorophores responsible for fluorescence. Results showed that the presence of highly absorbing and fluorescing CDOM in rainwater is of significant importance in atmospheric chemistry and might play a previously unrecognized role in the wavelength dependent spectral attenuation of solar radiation by atmospheric waters.

Electrospun Nanofibers from a Tricyanofuran-Based Molecular Switch for Colorimetric Recognition of Ammonia Gas.

Science.gov (United States)

Khattab, Tawfik A; Abdelmoez, Sherif; Klapötke, Thomas M

2016-03-14

A chromophore based on tricyanofuran (TCF) with a hydrazone (H) recognition moiety was developed. Its molecular-switching performance is reversible and has differential sensitivity towards aqueous ammonia at comparable concentrations. Nanofibers were fabricated from the TCF-H chromophore by electrospinning. The film fabricated from these nanofibers functions as a solid-state optical chemosensor for probing ammonia vapor. Recognition of ammonia vapor occurs by proton transfer from the hydrazone fragment of the chromophore to the ammonia nitrogen atom and is facilitated by the strongly electron withdrawing TCF fragment. The TCF-H chromophore was added to a solution of poly(acrylic acid), which was electrospun to obtain a nanofibrous sensor device. The morphology of the nanofibrous sensor was determined by SEM, which showed that nanofibers with a diameter range of 200-450 nm formed a nonwoven mat. The resultant nanofibrous sensor showed very good sensitivity in ammonia-vapor detection. Furthermore, very good reversibility and short response time were also observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Potential Applications of Real-Time Monitoring of Water Quality in a Large Shallow Lake (Lake Taihu, China) Using a Chromophoric Dissolved Organic Matter Fluorescence Sensor

OpenAIRE

Niu, Cheng; Zhang, Yunlin; Zhou, Yongqiang; Shi, Kun; Liu, Xiaohan; Qin, Boqiang

2014-01-01

This study presents results from field surveys performed over various seasons in a large, eutrophic, shallow lake (Lake Taihu, China) using an in situ chromophoric dissolved organic matter (CDOM) fluorescence sensor as a surrogate for other water quality parameters. These measurements identified highly significant empirical relationships between CDOM concentration measured using the in situ fluorescence sensor and CDOM absorption, fluorescence, dissolved organic carbon (DOC), chemical oxygen ...

Light harvesting via energy transfer in the dye solar cell

Energy Technology Data Exchange (ETDEWEB)

Siegers, Conrad

2007-11-09

The PhD-thesis ''Light Harvesting via Energy Transfer in the Dye Solar Cell'' (University of Freiburg, July 2007) describes the conceptual design, synthesis and testing of energy donor acceptor sensitizers for the dye solar cell (DSC). Under monochromatic illumination solar cells sensitized with the novel donor acceptor systems revealed a higher power conversion efficiency than cells containing exclusively the acceptor component. The following approach led to this conclusion: (i) the choice of suitable chromophores as energy donor and acceptor moieties according to the Foerster-theory, (ii) the synthesis of different donor acceptor systems, (iii) the development of a methodology allowing the quantification of energy transfer within dye solar cells, and (iv) the evaluation of characteristics of DSCs that were sensitized with the different donor acceptor systems. The acceptor chromophores used in this work were derived from [Ru(dcbpy)2acac]Cl (dcbpy = 4,4'-dicarboxy-2,2'-bipyridin, acac = acetylacetonato). This complex offered the opportunity to introduce substituents at the acac-ligand's terminal CH3 groups without significantly affecting its excellent photoelectrochemical properties. Alkylated 4-amino-1,8-naphthalimides (termed Fluorols in the following) were used as energy donor chromophores. This class of compounds fulfils the requirements for efficient energy transfer to [Ru(dcbpy)2acac]Cl. Covalently linking donor and acceptor chromophores to one another was achieved by two different concepts. A dyad comprising one donor and one acceptor chromophore was synthesized by subsequent hydrosilylation steps of an olefin-bearing donor and an acceptor precursor to the dihydrosilane HSiMe2-CH2CH2-SiMe2H. A series of polymers comprising multiple donor and acceptor units was made by the addition of alkyne-bearing chromophores to hyperbranched polyglycerol azide (''Click-chemistry''). In this series the donor acceptor

Photobleaching of chromophoric dissolved organic matter (CDOM) in the Yangtze River estuary: kinetics and effects of temperature, pH, and salinity.

Science.gov (United States)

Song, Guisheng; Li, Yijie; Hu, Suzheng; Li, Guiju; Zhao, Ruihua; Sun, Xin; Xie, Huixiang

2017-06-21

The kinetics and temperature-, pH- and salinity-dependences of photobleaching of chromophoric dissolved organic matter (CDOM) in the Yangtze River estuary (YRE) were evaluated using laboratory solar-simulated irradiation and compared to those of Suwannee River humic substances (SRHSs). Nearly all CDOM in water at the head of the estuary (headwater herein) was photobleachable in both summer and winter, while significant fractions of CDOM (13-29%) were resistant to photobleaching in saltier waters. The photobleaching rate constant in the headwater was 25% higher in summer than that in winter. The absorbed photon-based photobleaching efficiency (PE) increased with temperature following the linear Arrhenius equation. For a 20 °C increase in temperature, PE increased by ∼45% in the headwater and by 70-81% in the saltier waters. PE for YRE samples exhibited minima at pH from 6 to 7 and increased with both lower and higher pH values, contrasting the consistent increase in PE with pH shown by SRHSs. No consistent effect of salinity on PE was observed for both SRHSs and YRE samples. Photobleaching increased the spectral slope coefficient between 275 nm and 295 nm in summer, consistent with the behavior of SRHSs, but decreased it in winter, implying a difference in the molecular composition of chromophores between the two seasons. Temperature, salinity, and pH modified the photoalteration of the spectral shape but their effects varied spatially and seasonally. This study demonstrates that CDOM quality, temperature, and pH should be incorporated into models involving quantification of photobleaching.

Molecular Polygons Probe the Role of Intramolecular Strain in the Photophysics of π-Conjugated Chromophores.

Science.gov (United States)

Wilhelm, Philipp; Vogelsang, Jan; Poluektov, Georgiy; Schönfelder, Nina; Keller, Tristan J; Jester, Stefan-Sven; Höger, Sigurd; Lupton, John M

2017-01-24

π-Conjugated segments, chromophores, are the electronically active units of polymer materials used in organic electronics. To elucidate the effect of the bending of these linear moieties on elementary electronic properties, such as luminescence color and radiative rate, we introduce a series of molecular polygons. The π-system in these molecules becomes so distorted in bichromophores (digons) that these absorb and emit light of arbitrary polarization: any part of the chain absorbs and emits radiation with equal probability. Bending leads to a cancellation of transition dipole moment (TDM), increasing excited-state lifetime. Simultaneously, fluorescence shifts to the red as radiative transitions require mixing of the excited state with vibrational modes. However, strain can become so large that excited-state localization on shorter units of the chain occurs, compensating TDM cancellation. The underlying correlations between shape and photophysics can only be resolved in single molecules. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixing behavior of chromophoric dissolved organic matter in the Pearl River Estuary in spring

Science.gov (United States)

Lei, Xia; Pan, Jiayi; Devlin, Adam T.

2018-02-01

Mixing behavior of chromophoric dissolved organic matter (CDOM) in the Pearl River Estuary (PRE) and relevant hydrodynamic parameters such as horizontal transport and vertical mixing are identified and discussed based on a set of sampling data obtained during a cruise in May 2014. Using a theoretical conservative mixing model, the surface CDOM in the PRE in spring is classified into two groups by the CDOM absorption-spectral slope relationship (a(300) vs S(275-295)): First, terrigenous CDOM under a non-conservative mixing condition, and removal processes such as photobleaching are suggested to happen; second, marine CDOM behaves conservatively during mixing. The mixing of CDOM at the bottom is shown to be conservative. Controlled by the two-layer gravitational circulation in the PRE, the northern and western estuary shows higher CDOM absorption and lower spectral slope than the southern and eastern estuary, and the surface CDOM presents higher absorption and lower spectral slope than the bottom. Horizontal transport is hypothesized to be the dominant hydrodynamic mechanism affecting CDOM variation and mixing behavior in the PRE, while the vertical mixing has less influence.

Determination of the absorption coefficient of chromophoric dissolved organic matter from underway spectrophotometry.

Science.gov (United States)

Dall'Olmo, Giorgio; Brewin, Robert J W; Nencioli, Francesco; Organelli, Emanuele; Lefering, Ina; McKee, David; Röttgers, Rüdiger; Mitchell, Catherine; Boss, Emmanuel; Bricaud, Annick; Tilstone, Gavin

2017-11-27

Measurements of the absorption coefficient of chromophoric dissolved organic matter (ay) are needed to validate existing ocean-color algorithms. In the surface open ocean, these measurements are challenging because of low ay values. Yet, existing global datasets demonstrate that ay could contribute between 30% to 50% of the total absorption budget in the 400-450 nm spectral range, thus making accurate measurement of ay essential to constrain these uncertainties. In this study, we present a simple way of determining ay using a commercially-available in-situ spectrophotometer operated in underway mode. The obtained ay values were validated using independent collocated measurements. The method is simple to implement, can provide measurements with very high spatio-temporal resolution, and has an accuracy of about 0.0004 m -1 and a precision of about 0.0025 m -1 when compared to independent data (at 440 nm). The only limitation for using this method at sea is that it relies on the availability of relatively large volumes of ultrapure water. Despite this limitation, the method can deliver the ay data needed for validating and assessing uncertainties in ocean-colour algorithms.

Molecular hyperpolarizabilities of push–pull chromophores: A comparison between theoretical and experimental results

Energy Technology Data Exchange (ETDEWEB)

Capobianco, A. [Dipartimento di Fisica E.R. Caianiello, Università di Salerno, via ponte don Melillo, I-84084 Fisciano (Italy); Centore, R. [Dipartimento di Chimica P. Corradini, Università di Napoli, via Cintia, I-80126 Napoli (Italy); Noce, C. [Dipartimento di Fisica E.R. Caianiello, Università di Salerno, via ponte don Melillo, I-84084 Fisciano (Italy); Peluso, A., E-mail: apeluso@unisa.it [Dipartimento di Chimica e Biologia, Università di Salerno, via ponte don Melillo, I-84084 Fisciano (Italy)

2013-01-16

Highlights: ► Electro-optical determined and MP2/DFT computed NLO properties have been compared. ► Significant dependence of dipole moments of elongated NLO chromophores on conformations has been found. ► A thorough comparison between MP2 and DFT/TD-DFT computational approaches has been carried out. ► The two-state model overestimates hyperpolarizability. - Abstract: Electric dipole moments and static first order hyperpolarizabilities of two push–pull molecules with an extended π electron systems have been evaluated at different computational levels and compared with the results of electro-optical absorption measurements, based on the two state model. Calculations show that: (i) the dipole moments of such elongated systems depend significantly on conformation, a thorough conformational search is necessary for a meaningful comparison between theoretical and experimental results; (ii) DFT methods, in particular CAM-B3LYP and M05-2X, yield dipole moments which compare well with those obtained by post Hartree–Fock methods (MP2) and by EOA measurements; (iii) theoretical first order hyperpolarizabilities are largely underestimated, both by MP2 and DFT methods, possibly because of the failure of two state model used in electro-optical measurements.

Spectral Properties and Orientation of Voltage-Sensitive Dyes in Lipid Membranes

KAUST Repository

Matson, Maria

2012-07-24

Voltage-sensitive dyes are frequently used for probing variations in the electric potential across cell membranes. The dyes respond by changing their spectral properties: measured as shifts of wavelength of absorption or emission maxima or as changes of absorption or fluorescence intensity. Although such probes have been studied and used for decades, the mechanism behind their voltage sensitivity is still obscure. We ask whether the voltage response is due to electrochromism as a result of direct field interaction on the chromophore or to solvatochromism, which is the focus of this study, as result of changed environment or molecular alignment in the membrane. The spectral properties of three styryl dyes, di-4-ANEPPS, di-8-ANEPPS, and RH421, were investigated in solvents of varying polarity and in model membranes using spectroscopy. Using quantum mechanical calculations, the spectral dependence of monomer and dimer ANEPPS on solvent properties was modeled. Also, the kinetics of binding to lipid membranes and the binding geometry of the probe molecules were found relevant to address. The spectral properties of all three probes were found to be highly sensitive to the local environment, and the probes are oriented nearly parallel with the membrane normal. Slow binding kinetics and scattering in absorption spectra indicate, especially for di-8-ANEPPS, involvement of aggregation. On the basis of the experimental spectra and time-dependent density functional theory calculations, we find that aggregate formation may contribute to the blue-shifts seen for the dyes in decanol and when bound to membrane models. In conclusion, solvatochromic and other intermolecular interactions effects also need to be included when considering electrochromic response voltage-sensitive dyes. © 2012 American Chemical Society.

Recent Advances in Stimuli-Responsive Photofunctional Materials Based on Accommodation of Chromophore into Layered Double Hydroxide Nanogallery

Directory of Open Access Journals (Sweden)

Wu Li

2013-01-01

Full Text Available The assembly of photofunctional molecules into host matrices has become an important strategy to achieve tunable fluorescence and to develop intelligent materials. The stimuli-responsive photofunctional materials based on chromophores-assembled layered double hydroxides (LDHs have received much attention from both academic and industry fields as a result of their advantages, such as high photo/thermal stability, easy processing, and well reversibility, which can construct new types of smart luminescent nanomaterials (e.g., ultrathin film and nanocomposite for sensor and switch applications. In this paper, external environmental stimuli have mainly involved physical (such as temperature, pressure, light, and electricity and chemical factors (such as pH and metal ion; recent progress on the LDH-based organic-inorganic stimuli-responsive materials has been summarized. Moreover, perspectives on further development of these materials are also discussed.

The role of many-body effects in describing low-lying excited states of pi-conjugated chromophores: high-level equation-of-motion coupled-cluster studies of fused porphyrin systems

Energy Technology Data Exchange (ETDEWEB)

Kowalski, Karol [Pacific Northwest National Laboratory (PNNL); Olson, Ryan M [Cray, Inc.; Krishnamoorthy, Sriram [Pacific Northwest National Laboratory (PNNL); Tipparaju, Vinod [ORNL; Apra, Edoardo [ORNL

2011-01-01

The unusual photophysical properties of the {pi}-conjugated chromophores make them potential building blocks of various molecular devices. In particular, significant narrowing of the HOMO-LUMO gaps can be observed as an effect of functionalization chromophores with polycyclic aromatic hydrocarbons (PAHs). In this paper we present equation-of-motion coupled cluster (EOMCC) calculations for vertical excitation energies of several functionalized forms of porphyrins. The results for free-base porphyrin (FBP) clearly demonstrate significant differences between functionalization of FBP with one- (anthracene) and two-dimensional (coronene) structures. We also compare the EOMCC results with the experimentally available results for anthracene fused zinc-porphyrin. The impact of various types of correlation effects is illustrated on several benchmark models, where the comparison with the experiment is possible. In particular, we demonstrate that for all excited states considered in this paper, all of them being dominated by single excitations, the inclusion of triply excited configurations is crucial for attaining qualitative agreement with experiment. We also demonstrate the parallel performance of the most computationally intensive part of the completely renormalized EOMCCSD(T) approach (CR-EOMCCSD(T)) across 120000 cores.

Vibrational Spectroscopy on Photoexcited Dye-Sensitized Films via Pump-Degenerate Four-Wave Mixing.

Science.gov (United States)

Abraham, Baxter; Fan, Hao; Galoppini, Elena; Gundlach, Lars

2018-03-01

Molecular sensitization of semiconductor films is an important technology for energy and environmental applications including solar energy conversion, photocatalytic hydrogen production, and water purification. Dye-sensitized films are also scientifically complex and interesting systems with a long history of research. In most applications, photoinduced heterogeneous electron transfer (HET) at the molecule/semiconductor interface is of critical importance, and while great progress has been made in understanding HET, many open questions remain. Of particular interest is the role of combined electronic and vibrational effects and coherence of the dye during HET. The ultrafast nature of the process, the rapid intramolecular vibrational energy redistribution, and vibrational cooling present complications in the study of vibronic coupling in HET. We present the application of a time domain vibrational spectroscopy-pump-degenerate four-wave mixing (pump-DFWM)-to dye-sensitized solid-state semiconductor films. Pump-DFWM can measure Raman-active vibrational modes that are triggered by excitation of the sample with an actinic pump pulse. Modifications to the instrument for solid-state samples and its application to an anatase TiO 2 film sensitized by a Zn-porphyrin dye are discussed. We show an effective combination of experimental techniques to overcome typical challenges in measuring solid-state samples with laser spectroscopy and observe molecular vibrations following HET in a picosecond time window. The cation spectrum of the dye shows modes that can be assigned to the linker group and a mode that is localized on the Zn-phorphyrin chromophore and that is connected to photoexcitation.

Action spectra and chromophores for lethal photosensitization of Candida albicans by DNA monoadducts formed by 8-methoxypsoralen and monofunctional furocoumarins

International Nuclear Information System (INIS)

Baydoun, S.; Gibbs, N.K.; Young, A.R.

1992-01-01

The red-shift furocoumarin action spectra, compared with their absorption spectra, has been investigated. An action spectrum for 8-methoxypsoralen (8-Mop) monoadduct formation in the yeast Candida albicans has been determined. The yeast cells were initially exposed to sublethal doses of monochromatic UV A at different wavelengths. Monoadduct formation was monitored by growth inhibition induced, after washing out any unbound 8-Mop, by re-irradiation with a constant second (non-lethal) dose of 330 nm radiation. A comparison between this action spectrum and the absorption spectrum of the dark complex of 8-Mop and DNA was made. In addition, the action spectra of monoadduct formation of five monofunctional compounds including a coumarin derivative have been determined. These action spectra were compared with their respective DNA dark complex absorption spectra. In general, the peaks of the furocoumarin DNA dark complexes show a red-shift when compared with the free furocoumarin molecule and the action spectra show peaks which correspond with the peaks of the dark complexes. Such data indicate that the DNA dark complex is the chromophore for growth inhibition in yeast rather than the free furocoumarin. The similarity of the 8-Mop monoadduct formation spectrum and 8-Mop action spectra suggests that spectral dependence for the photobiological effects (including the red-shift) is dependent on monoadduct formation rather than, as previously suggested by several authors, crosslink formation. The action spectrum for the coumarin derivative 4-methyl N-ethylpyrrolo (3,2-g) coumarin (PCNEt) correlated well with the free molecule absorption spectrum rather than DNA dark complex indicating that the free molecule is the chromophore. This was supported by studies which showed that PCNEt photosensitization is oxygen dependent. (author). 38 refs., 3 tabs., 7 figs

Peripheral Hole Acceptor Moieties on an Organic Dye Improve Dye‐Sensitized Solar Cell Performance

Science.gov (United States)

Hao, Yan; Gabrielsson, Erik; Lohse, Peter William; Yang, Wenxing; Johansson, Erik M. J.; Hagfeldt, Anders

2015-01-01

Investigation of charge transfer dynamics in dye‐sensitized solar cells is of fundamental interest and the control of these dynamics is a key factor for developing more efficient solar cell devices. One possibility for attenuating losses through recombination between injected electrons and oxidized dye molecules is to move the positive charge further away from the metal oxide surface. For this purpose, a metal‐free dye named E6 is developed, in which the chromophore core is tethered to two external triphenylamine (TPA) units. After photoinduced electron injection into TiO2, the remaining hole is rapidly transferred to a peripheral TPA unit. Electron–hole recombination is slowed down by 30% compared to a reference dye without peripheral TPA units. Furthermore, it is found that the added TPA moieties improve the electron blocking effect of the dye, retarding recombination of electrons from TiO2 to the cobalt‐based electrolyte. PMID:27722076

Response of biomembrane domains to external stimuli

Science.gov (United States)

Urbancic, Iztok

To enrich our knowledge about membrane domains, new measurement techniques with extended spatial and temporal windows are being vigorously developed by combining various approaches. Following such efforts of the scientific community, we set up fluorescence microspectroscopy (FMS), bridging two well established methods: fluorescence microscopy, which enables imaging of the samples with spatial resolution down to 200 nm, and fluorescence spectroscopy that provides molecular information of the environment at nanometer and nanosecond scale. The combined method therefore allows us to localize this type of information with the precision suitable for studying various cellular structures. Faced with weak available fluorescence signals, we have put considerable efforts into optimization of measurement processes and analysis of the data. By introducing a novel acquisition scheme and by fitting the data with a mathematical model, we preserved the spectral resolution, characteristic for spectroscopic measurements of bulk samples, also at microscopic level. We have at the same time overcome the effects of photobleaching, which had previously considerably distorted the measured spectral lineshape of photosensitive dyes and consequently hindered the reliability of FMS. Our new approach has therefore greatly extended the range of applicable environmentally sensitive probes, which can now be designed to better accommodate the needs of each particular experiment. Moreover, photobleaching of fluorescence signal can now even be exploited to obtain new valuable information about molecular environment of the probes, as bleaching rates of certain probes also depend on physical and chemical properties of the local surroundings. In this manner we increased the number of available spatially localized spectral parameters, which becomes invaluable when investigating complex biological systems that can only be adequately characterized by several independent variables. Applying the developed

Dynamic bio-adhesion of polymer nanoparticles on MDCK epithelial cells and its impact on bio-membranes, endocytosis and paracytosis.

Science.gov (United States)

He, Bing; Yuan, Lan; Dai, Wenbing; Gao, Wei; Zhang, Hua; Wang, Xueqing; Fang, Weigang; Zhang, Qiang

2016-03-21

Nowadays, concern about the use of nanotechnology for biomedical application is unprecedentedly increasing. In fact, nanosystems applied for various potential clinical uses always have to cross the primary biological barrier consisting of epithelial cells. However, little is really known currently in terms of the influence of the dynamic bio-adhesion of nanosystems on bio-membranes as well as on endocytosis and transcytosis. This was investigated here using polymer nanoparticles (PNs) and MDCK epithelial cells as the models. Firstly, the adhesion of PNs on cell membranes was found to be time-dependent with a shift of both location and dispersion pattern, from the lateral adhesion of mainly mono-dispersed PNs initially to the apical coverage of the PN aggregate later. Then, it was interesting to observe in this study that the dynamic bio-adhesion of PNs only affected their endocytosis but not their transcytosis. It was important to find that the endocytosis of PNs was not a constant process. A GM1 dependent CDE (caveolae dependent endocytosis) pathway was dominant in the preliminary stage, followed by the co-existence of a CME (clathrin-mediated endocytosis) pathway for the PN aggregate at a later stage, in accordance with the adhesion features of PNs, suggesting the modification of PN adhesion patterns on the endocytosis pathways. Next, the PN adhesion was noticed to affect the structure of cell junctions, via altering the extra- and intra-cellular calcium levels, leading to the enhanced paracellular transport of small molecules, but not favorably enough for the obviously increased passing of PNs themselves. Finally, FRAP and other techniques all demonstrated the obvious impact of PN adhesion on the membrane confirmation, independent of the adhesion location and time, which might lower the threshold for the internalization of PNs, even their aggregates. Generally, these findings confirm that the transport pathway mechanism of PNs through epithelial cells is rather

Dynamic bio-adhesion of polymer nanoparticles on MDCK epithelial cells and its impact on bio-membranes, endocytosis and paracytosis

Science.gov (United States)

He, Bing; Yuan, Lan; Dai, Wenbing; Gao, Wei; Zhang, Hua; Wang, Xueqing; Fang, Weigang; Zhang, Qiang

2016-03-01

Nowadays, concern about the use of nanotechnology for biomedical application is unprecedentedly increasing. In fact, nanosystems applied for various potential clinical uses always have to cross the primary biological barrier consisting of epithelial cells. However, little is really known currently in terms of the influence of the dynamic bio-adhesion of nanosystems on bio-membranes as well as on endocytosis and transcytosis. This was investigated here using polymer nanoparticles (PNs) and MDCK epithelial cells as the models. Firstly, the adhesion of PNs on cell membranes was found to be time-dependent with a shift of both location and dispersion pattern, from the lateral adhesion of mainly mono-dispersed PNs initially to the apical coverage of the PN aggregate later. Then, it was interesting to observe in this study that the dynamic bio-adhesion of PNs only affected their endocytosis but not their transcytosis. It was important to find that the endocytosis of PNs was not a constant process. A GM1 dependent CDE (caveolae dependent endocytosis) pathway was dominant in the preliminary stage, followed by the co-existence of a CME (clathrin-mediated endocytosis) pathway for the PN aggregate at a later stage, in accordance with the adhesion features of PNs, suggesting the modification of PN adhesion patterns on the endocytosis pathways. Next, the PN adhesion was noticed to affect the structure of cell junctions, via altering the extra- and intra-cellular calcium levels, leading to the enhanced paracellular transport of small molecules, but not favorably enough for the obviously increased passing of PNs themselves. Finally, FRAP and other techniques all demonstrated the obvious impact of PN adhesion on the membrane confirmation, independent of the adhesion location and time, which might lower the threshold for the internalization of PNs, even their aggregates. Generally, these findings confirm that the transport pathway mechanism of PNs through epithelial cells is rather

Photochemical solar cells based on dye-sensitization of nanocrystalline TiO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Deb, S.K.; Ellingson, R.; Ferrere, S.; Frank, A.J.; Gregg, B.A.; Nozik, A.J.; Park, N.; Schlichthoerl, G. [National Renewable Energy Lab., Golden, CO (United States)

1998-09-01

A photoelectrochemical solar cell that is based on the dye-sensitization of thin nanocrystalline films of TiO{sub 2} (anatase) nanoparticles in contact with a non-aqueous liquid electrolyte is described. The cell, fabricated at NREL, shows a conversion efficiency of {approximately} 9.2% at AM1.5, which approaches the best reported value of 10--11% by Graetzel at EPFL in Lausanne, Switzerland. The femtosecond (fs) pump-probe spectroscopy has been used to time resolve the injection of electrons into the conduction band of nanocrystalline TiO{sub 2} films under ambient conditions following photoexcitation of the adsorbed Ru(II)-complex dye. The measurement indicates an instrument-limited {minus}50 fs upper limit on the electron injection time. The authors also report the sensitization of nanocrystalline TiO{sub 2} by a novel iron-based dye, CIS-[Fe{sup II}(2,2{prime}-bipyridine-4,4,{prime}-dicarboxylic acid){sub 2}(CN){sub 2}], a chromophore with an extremely short-lived, nonemissive excited state. The dye also exhibits a unique band selective sensitization through one of its two absorption bands. The operational principle of the device has been studied through the measurement of electric field distribution within the device structure and studies on the pH dependence of dye-redox potential. The incorporation of WO{sub 3}-based electrochromic layer into this device has led to a novel photoelectrochromic device structure for smart window application.

Absorption and fluorescence characteristics of chromophoric dissolved organic matter in the Yangtze Estuary.

Science.gov (United States)

Sun, Qiyuan; Wang, Chao; Wang, Peifang; Hou, Jun; Ao, Yanhui

2014-03-01

The Yangtze Estuary is heavily influenced by coast-continent geochemical processes and anthropogenic activity; thus, the source and distribution of chromophoric dissolved organic matter (CDOM) in the estuary are strongly impacted by these processes. Here, a series of samples were collected from across the Yangtze Estuary to investigate the source and spatial dynamics of CDOM and its components throughout the system. Three indices (a(355), spectral slope, and fluorescence) were then calculated and interpreted. The results indicated that the distribution of CDOM was dominated by allochthonous input, conservative mixing, and phase transfer. The contribution of biogenic CDOM to total CDOM increased with salinity, and three individual CDOM components were identified upon fluorescence excitation emission matrix spectroscopy and parallel factor analysis of the water samples: C1, corresponding to humic substance-like CDOM, C2, corresponding to tryptophan-like CDOM, and C3, corresponding to tyrosine-like CDOM. C1 primarily originated from a terrestrial source, C2 had widespread origins, none of which played a dominant role, and C3 mainly originated from allochthonous input in the medium salinity area. Unexpectedly, no marine humic-like component was found in the surface water of the Yangtze Estuary, possibly because turbidity decreased the depth of sunlight penetration, limiting production of this component.

Fluorescence and absorption properties of chromophoric dissolved organic matter (CDOM) in coastal surface waters of the northwestern Mediterranean Sea, influence of the Rhône River

OpenAIRE

J. Para; P. G. Coble; B. Charrière; M. Tedetti; C. Fontana; R. Sempéré

2010-01-01

Seawater samples were collected monthly in surface waters (2 and 5 m depths) of the Bay of Marseilles (northwestern Mediterranean Sea; 5°17'30" E, 43°14'30" N) during one year from November 2007 to December 2008 and studied for total organic carbon (TOC) as well as chromophoric dissolved organic matter (CDOM) optical properties (absorbance and fluorescence). The annual mean value of surface CDOM absorption coefficient at 350 nm [a_CDOM(350)] was very l...

Estimation of chromophoric dissolved organic matter in the Mississippi and Atchafalaya river plume regions using above-surface hyperspectral remote sensing

Science.gov (United States)

Zhu, Weining; Yu, Qian; Tian, Yong Q.; Chen, Robert F.; Gardner, G. Bernard

2011-02-01

A method for the inversion of hyperspectral remote sensing was developed to determine the absorption coefficient for chromophoric dissolved organic matter (CDOM) in the Mississippi and Atchafalaya river plume regions and the northern Gulf of Mexico, where water types vary from Case 1 to turbid Case 2. Above-surface hyperspectral remote sensing data were measured by a ship-mounted spectroradiometer and then used to estimate CDOM. Simultaneously, water absorption and attenuation coefficients, CDOM and chlorophyll fluorescence, turbidities, and other related water properties were also measured at very high resolution (0.5-2 m) using in situ, underwater, and flow-through (shipboard, pumped) optical sensors. We separate ag, the absorption coefficient a of CDOM, from adg (a of CDOM and nonalgal particles) based on two absorption-backscattering relationships. The first is between ad (a of nonalgal particles) and bbp (total particulate backscattering coefficient), and the second is between ap (a of total particles) and bbp. These two relationships are referred as ad-based and ap-based methods, respectively. Consequently, based on Lee's quasi-analytical algorithm (QAA), we developed the so-called Extended Quasi-Analytical Algorithm (QAA-E) to decompose adg, using both ad-based and ap-based methods. The absorption-backscattering relationships and the QAA-E were tested using synthetic and in situ data from the International Ocean-Colour Coordinating Group (IOCCG) as well as our own field data. The results indicate the ad-based method is relatively better than the ap-based method. The accuracy of CDOM estimation is significantly improved by separating ag from adg (R2 = 0.81 and 0.65 for synthetic and in situ data, respectively). The sensitivities of the newly introduced coefficients were also analyzed to ensure QAA-E is robust.

Glycine Insertion Makes Yellow Fluorescent Protein Sensitive to Hydrostatic Pressure

Science.gov (United States)

Watanabe, Tomonobu M.; Imada, Katsumi; Yoshizawa, Keiko; Nishiyama, Masayoshi; Kato, Chiaki; Abe, Fumiyoshi; Morikawa, Takamitsu J.; Kinoshita, Miki; Fujita, Hideaki; Yanagida, Toshio

2013-01-01

Fluorescent protein-based indicators for intracellular environment conditions such as pH and ion concentrations are commonly used to study the status and dynamics of living cells. Despite being an important factor in many biological processes, the development of an indicator for the physicochemical state of water, such as pressure, viscosity and temperature, however, has been neglected. We here found a novel mutation that dramatically enhances the pressure dependency of the yellow fluorescent protein (YFP) by inserting several glycines into it. The crystal structure of the mutant showed that the tyrosine near the chromophore flipped toward the outside of the β-can structure, resulting in the entry of a few water molecules near the chromophore. In response to changes in hydrostatic pressure, a spectrum shift and an intensity change of the fluorescence were observed. By measuring the fluorescence of the YFP mutant, we succeeded in measuring the intracellular pressure change in living cell. This study shows a new strategy of design to engineer fluorescent protein indicators to sense hydrostatic pressure. PMID:24014139

New Homogeneous Chromophore/Catalyst Concepts for the Solar-Driven Reduction of Carbon Dioxide

Energy Technology Data Exchange (ETDEWEB)

Hopkins, Michael D. [The University of Chicago, Chicago, IL (United States)

2015-06-22

One of the major scientific and technical challenges of this century is to develop chemical means to store solar energy in the form of fuels. This can be accomplished by developing light-absorbing and catalytic compounds that function cooperatively to rearrange the chemical bonds of feedstocks in a way that allows solar energy to be stored and released on demand. The research conducted during this project was directed toward addressing fundamental questions that underlie the conversion of CO₂ to a solar fuel using homogeneous molecular systems. The research focused particularly on developing methods for extracting the reducing equivalents for these photochemical conversions from H₂, which is a renewable molecule sourced to water. The research followed two main lines. One effort focused on understanding the general principles that govern how light-absorbing molecules interact with independent H₂ oxidation and CO₂ reduction catalysts to produce a functional cycle for driving the energy-storing reverse water-gas-shift reaction with light. The second effort centered on developing the excited-state properties and H₂ activation chemistry of tungsten–alkylidyne complexes. These chromophores were found to be powerful excited-state reducing agents, which could be incorporated into light-light-harvesting assemblies, and to hold the potential to be regenerated using H₂.

Crystallographic Structure of Xanthorhodopsin, the Light-Driven Proton Pump With a Dual Chromophore

International Nuclear Information System (INIS)

Luecke, H.; Schobert, B.; Stagno, J.; Imasheva, E.S.; Wang, J.M.; Balashov, S.P.; Lanyi, J.K

2008-01-01

Homologous to bacteriorhodopsin and even more to proteorhodopsin, xanthorhodopsin is a light-driven proton pump that, in addition to retinal, contains a noncovalently bound carotenoid with a function of a light-harvesting antenna. We determined the structure of this eubacterial membrane protein-carotenoid complex by X-ray diffraction, to 1.9-(angstrom) resolution. Although it contains 7 transmembrane helices like bacteriorhodopsin and archaerhodopsin, the structure of xanthorhodopsin is considerably different from the 2 archaeal proteins. The crystallographic model for this rhodopsin introduces structural motifs for proton transfer during the reaction cycle, particularly for proton release, that are dramatically different from those in other retinal-based transmembrane pumps. Further, it contains a histidine-aspartate complex for regulating the pK a of the primary proton acceptor not present in archaeal pumps but apparently conserved in eubacterial pumps. In addition to aiding elucidation of a more general proton transfer mechanism for light-driven energy transducers, the structure defines also the geometry of the carotenoid and the retinal. The close approach of the 2 polyenes at their ring ends explains why the efficiency of the excited-state energy transfer is as high as ∼45%, and the 46 o angle between them suggests that the chromophore location is a compromise between optimal capture of light of all polarization angles and excited-state energy transfer

Conformational heterogeneity of the Pfr chromophore in plant and cyanobacterial phytochromes

Directory of Open Access Journals (Sweden)

Francisco eVelazquez Escobar

2015-07-01

Full Text Available Phytochromes are biological photoreceptors that can be reversibly photoconverted between a dark and photoactivated state. The underlying reaction sequences are initiated by the photoisomerisation of the tetrapyrrole cofactor, which in plant and cyanobacterial phytochromes are a phytochromobilin (PB and a phycocyanobilin (PCB, respectively. The transition between the two states represents an on/off-switch of the output module activating or deactivating downstream physiological processes. In addition, the photoactivated state, i.e. Pfr in canonical phytochromes, can be thermally reverted to the dark state (Pr. The present study aimed to improve our understanding of the specific reactivity of various PB- and PCB-binding phytochromes in the Pfr state by analyzing the cofactor structure by vibrational spectroscopic techniques. Resonance Raman (RR spectroscopy revealed two Pfr conformers (Pfr-I and Pfr-II forming a temperature-dependent conformational equilibrium. The two sub-states - found in all phytochromes studied, albeit with different relative contributions - differ in structural details of the C-D and A-B methine bridges. In the Pfr-I sub-state the torsion between the rings C and D is larger by ca. 10o compared to Pfr-II. This structural difference is presumably related to different hydrogen bonding interactions of ring D as revealed by time-resolved IR spectroscopic studies of the cyanobacterial phytochrome Cph1. The transitions between the two sub-states are evidently too fast (i.e., nanosecond time scale to be resolved by NMR spectroscopy which could not detect a structural heterogeneity of the chromophore in Pfr. The implications of the present findings for the dark reversion of the Pfr state are discussed.

Theory and Applications of Solid-State NMR Spectroscopy to Biomembrane Structure and Dynamics

Science.gov (United States)

Xu, Xiaolin

Solid-state Nuclear Magnetic Resonance (NMR) is one of the premiere biophysical methods that can be applied for addressing the structure and dynamics of biomolecules, including proteins, lipids, and nucleic acids. It illustrates the general problem of determining the average biomolecular structure, including the motional mean-square amplitudes and rates of the fluctuations. Lineshape and relaxtion studies give us a view into the molecular properties under different environments. To help the understanding of NMR theory, both lineshape and relaxation experiments are conducted with hexamethylbezene (HMB). This chemical compound with a simple structure serves as a perfect test molecule. Because of its highly symmetric structure, its motions are not very difficult to understand. The results for HMB set benchmarks for other more complicated systems like membrane proteins. After accumulating a large data set on HMB, we also proceed to develop a completely new method of data analysis, which yields the spectral densities in a body-fixed frame revealing internal motions of the system. Among the possible applications of solid-state NMR spectroscopy, we study the light activation mechanism of visual rhodopsin in lipid membranes. As a prototype of G-protein-coupled receptors, which are a large class of membrane proteins, the cofactor isomerization is triggered by photon absorption, and the local structural change is then propagated to a large-scale conformational change of the protein. Facilitation of the binding of transducin then passes along the visual signal to downstream effector proteins like transducin. To study this process, we introduce 2H labels into the rhodopsin chromophore retinal and the C-terminal peptide of transducin to probe the local structure and dynamics of these two hotspots of the rhodopsin activation process. In addition to the examination of local sites with solid-state 2H NMR spectroscopy, wide angle X-ray scattering (WAXS) provides us the chance of

Michler’s Hydrol Blue: A Sensitive Probe for Amyloid Fibril Detection

KAUST Repository

Kitts, Catherine C.

2011-05-03

Michler\\'s hydrol blue (MHB) is investigated with respect to photophysical properties in varied solvent environment and when bound to insulin and lysozyme fibrils. The MHB chromophore is shown to act like a molecular rotor and bind well to amyloid fibrils, where it exhibits a characteristic red-shift in its excitation spectrum and an increase in the emission quantum yield upon binding. MHB is more sensitive to environmental changes than Thioflavin T (ThT) and furthermore, in contrast to the latter amyloid probe, can differentiate between insulin and lysozyme fibrils by a more red-shifted excitation spectrum for insulin fibrils. To support the experimental observations, time-dependent density functional theory (TDDFT) calculations were performed on MHB at several levels of theory. The predicted changes of spectral properties as a function of the environment are in good agreement with the experimental results. Linear dichroism (LD) is used to determine the orientation of the MHB within the fibrils. It was shown through LD and molecular modeling that MHB aligns itself preferentially parallel with the amyloid fiber at an angle of 14°-22° to the fibril axis and along the grooves of the β-sheet. © 2011 American Chemical Society.

An organic dye with very large Stokes-shift and broad tunability of fluorescence: Potential two-photon probe for bioimaging and ultra-sensitive solid-state gas sensor

Energy Technology Data Exchange (ETDEWEB)

He, Tingchao; Tian, Xiaoqing; Lin, Xiaodong, E-mail: linxd@szu.edu.cn, E-mail: hdsun@ntu.edu.sg [College of Physics Science and Technology, Shenzhen University, Shenzhen 518060 (China); Wang, Yue; Zhao, Xin; Sun, Handong, E-mail: linxd@szu.edu.cn, E-mail: hdsun@ntu.edu.sg [Division of Physics and Applied Physics, and Centre for Disruptive Photonic Technologies (CDPT), School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Gao, Yang; Grimsdale, Andrew C. [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore)

2016-01-04

Light-emitting nonlinear optical molecules, especially those with large Stokes shifts and broad tunability of their emission wavelength, have attracted considerable attention for various applications including biomedical imaging and fluorescent sensors. However, most fluorescent chromophores have only limited potential for such applications due to small Stokes shifts, narrow tunability of fluorescence emissions, and small optical nonlinearity in highly polar solvents. In this work, we demonstrate that a two-photon absorbing stilbene chromophore exhibits a large two-photon absorption action cross-section (ηδ = 320 GM) in dimethylsulfoxide (DMSO) and shows broad fluorescence tunability (125 nm) by manipulating the polarity of the surrounding medium. Importantly, a very large Stokes shift of up to 227 nm is achieved in DMSO. Thanks to these features, this chromophore can be utilized as a two-photon probe for bioimaging applications and in an ultrasensitive solid-state gas detector.

Synthesis of Dendrimer Containing Carbazole Unit as a Core Chromophore

International Nuclear Information System (INIS)

Han, Seung Choul; Lee, Jae Wook; Jin, Sungho

2012-01-01

Dendrimers, which are prepared by repetition of a given set of reactions using either divergent or convergent strategies, are highly branched and regular macromolecules with well-defined structures and have served as functional objects in nanotechnology and nano-materials science. Following conventional organic small molecules and polymers, dendrimers are now regarded as the third class of materials for use in organic light-emitting diodes (OLEDs) and have attracted much attention due to their distinguished properties. Dendrimers contain three distinct structural parts that are the core, end-groups, and branched units connecting core and periphery. For light-emitting dendrimers, the core is usually selected as the luminescent chromophore, and the dendrons and their periphery are charge transporting units and can also tune the solubility. In contrast to linear polymers, dendrimers are sphere-like with dimensions of the order of nanometers depending on the generation number. By careful structural design, dendrimers combine the potential advantages of both small molecules and polymers. Therefore, the innovative strategy different from conventional convergent and divergent routes has been required to simplify dendrimer synthesis. Recent solid chemistry is the click chemistry which is the copper-catalyzed 1,3-dipolar cycloaddition reaction between alkyne and azide developed by Sharpless and Tornφe. This reaction has many advantages: very high yields, mild and simple reaction conditions, oxygen and water tolerance, and easy isolation of product. This reaction is clearly a breakthrough in the synthesis of dendrimers and dendritic and polymer materials. We have developed the fusion and stitching methods for the synthesis of various dendrimers using click chemistry between an alkyne and an azide. Overall, this method was found to be a straightforward strategy for the synthesis of triazole-based dendrimers. Taking advantage of this fact, herein we report a feasible route

Chromophoric dissolved organic matter and microbial enzymatic activity. A biophysical approach to understand the marine carbon cycle.

Science.gov (United States)

Gonnelli, Margherita; Vestri, Stefano; Santinelli, Chiara

2013-12-01

This study reports the first information on extracellular enzymatic activity (EEA) combined with a study of DOM dynamics at the Arno River mouth. DOM dynamics was investigated from both a quantitative (dissolved organic carbon, DOC) and a qualitative (absorption and fluorescence of chromophoric DOM, CDOM) perspective. The data here reported highlight that the Arno River was an important source of both DOC and CDOM for this coastal area. CDOM optical properties suggested that terrestrial DOM did not undergo simple dilution at the river mouth but, other physical-chemical and biological processes were probably at work to change its molecular characteristics. This observation was further supported by the "potential" enzymatic activity of β-glucosidase (BG) and leucine aminopeptidase (LAP). Their Vmax values were markedly higher in the river water than in the seawater and their ratio suggested that most of the DOM used by microbes in the Arno River was polysaccharide-like, while in the seawater it was mainly protein-like. © 2013. Published by Elsevier B.V. All rights reserved.

Light-harvesting dendrimer zinc-phthalocyanines chromophores labeled single-wall carbon nanotube nanoensembles: Synthesis and photoinduced electron transfer

Energy Technology Data Exchange (ETDEWEB)

Yang, Hongqin [Key Laboratory of Optoelectronic Science and Technology for Medicine, Ministry of Education and Fujian Provincial Key Laboratory for Photonics Technology, Fujian Normal University, Fuzhou 350007 (China); Pan, Sujuan; Ma, Dongdong; He, Dandan; Wang, Yuhua [College of Chemistry & Engineering, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou 350007 (China); Xie, Shusen [Key Laboratory of Optoelectronic Science and Technology for Medicine, Ministry of Education and Fujian Provincial Key Laboratory for Photonics Technology, Fujian Normal University, Fuzhou 350007 (China); Peng, Yiru, E-mail: yirupeng@fjnu.edu.cn [College of Chemistry & Engineering, Fujian Provincial Key Laboratory of Polymer Materials, Fujian Normal University, Fuzhou 350007 (China)

2016-11-15

A novel series of light-harvesting dendrimer zinc-phthalocyanines chromophores labeled-single-wall carbon nanotubes (SWNTs) nanoparticles, in which 0–2 generations dendrimer zinc phthalocyanines covalently linked with SWNTs using either ethylenediamine or hexamethylenediamine as the space linkers were prepared. The structures and morphologies of these nanoconjugates were comprehensively characterized by Raman spectroscopy, transmission electron microscopy and thermal gravimetric analysis methods. Their photophysical properties were investigated by fluorescence and time-resolved spectroscopic methods. The photoinduced intramolecular electron transfer occurred from phthalocyanines (donors) to SWNTs (acceptors). Besides, the electron transfer exchange rates and exchange efficacies between the dendritic phthalocyanines and single-wall carbon nanotubes increased as the length of spacer linker decreased, or as the dendritic generation increased. Cyclic voltammetry (CV) method further confirmed thermodynamics possibility of the electron transfer from phthalocyanines to single-wall carbon nanotubes. These new nanoconjugates are fundamentally important due to the synergy effects of both carbon nanotubes and dendrimer phthalocyanines, which may find potential applications in the fields of drug delivery, biological labeling, or others.

Efficiency and stability of spectral sensitization of boron-doped-diamond electrodes through covalent anchoring of a donor–acceptor organic chromophore (P1)

Czech Academy of Sciences Publication Activity Database

Krýsová, Hana; Bartoň, Jan; Petrák, Václav; Jurok, R.; Kuchař, M.; Cígler, Petr; Kavan, Ladislav

2016-01-01

Roč. 18, č. 24 (2016), s. 16444-16450 ISSN 1463-9076 R&D Projects: GA ČR GA13-31783S Institutional support: RVO:61388955 ; RVO:61388963 ; RVO:68378271 Keywords : dye-sensitized solar cells * boron-doped diamond * nanoscale Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.123, year: 2016

Aminothiols linked to quinoline and acridine chromophores efficiently decrease 7,8-dihydro-8-oxo-2'-deoxyguanosine formation in γ-irradiated DNA

International Nuclear Information System (INIS)

Laayoun, A.; Coulombeau, C.; Constant, J.F.; Lhomme, J.; Berger, M.; Cadet, J.

1994-01-01

In a search for more active radioprotective compounds, we have prepared and examined a series of model molecules in which the radioprotective β-aminothiol unit (free or derivatized as acetate or phosphorothioate) is tethered to the DNA-binding chromophores quinoline and acridine through links of variable length. The modifying activity of these 'hybrid' molecules was estimated by measuring the formation of 8-oxo-2'-deoxyguanosine (8-oxodGuo) in double-strand DNA upon exposure to γ-rays in oxygen-free solution in the presence of the drugs. We show that all hybrid molecules protect the guanine moiety from oxidation more efficiently than the parent β-aminothiol units. The degree of protection is the highest for the molecules in which the thiol is linked to the strong binding intercalator acridine through a long polyaminochain. (author)

Distinguishing the Effects of Bond-Length Alternation versus Bond-Order Alternation on the Nonlinear Optical Properties of π-Conjugated Chromophores

KAUST Repository

Gieseking, Rebecca L.; Risko, Chad; Bredas, Jean-Luc

2015-01-01

Understanding the relationships between the molecular nonlinear optical (NLO) properties and the bond-length alternation (BLA) or π-bond-order alternation (BOA) along the molecular backbone of linear π-conjugated systems has proven widely useful in the development of NLO organic chromophores and materials. Here, we examine model polymethines to elucidate the reliability of these relationships. While BLA is solely a measure of molecular geometric structure, BOA includes information pertaining to the electronic structure. As a result, BLA is found to be a good predictor of NLO properties only when optimized geometries are considered, whereas BOA is more broadly applicable. Proper understanding of the distinction between BLA and BOA is critical when designing computational studies of NLO properties, especially for molecules in complex environments or in nonequilibrium geometries. © 2015 American Chemical Society.

Distinguishing the Effects of Bond-Length Alternation versus Bond-Order Alternation on the Nonlinear Optical Properties of π-Conjugated Chromophores

KAUST Repository

Gieseking, Rebecca L.

2015-06-18

Understanding the relationships between the molecular nonlinear optical (NLO) properties and the bond-length alternation (BLA) or π-bond-order alternation (BOA) along the molecular backbone of linear π-conjugated systems has proven widely useful in the development of NLO organic chromophores and materials. Here, we examine model polymethines to elucidate the reliability of these relationships. While BLA is solely a measure of molecular geometric structure, BOA includes information pertaining to the electronic structure. As a result, BLA is found to be a good predictor of NLO properties only when optimized geometries are considered, whereas BOA is more broadly applicable. Proper understanding of the distinction between BLA and BOA is critical when designing computational studies of NLO properties, especially for molecules in complex environments or in nonequilibrium geometries. © 2015 American Chemical Society.

Fluorescence characteristics of chromophoric dissolved organic matter in shallow water along the Zhejiang coasts, southeast China.

Science.gov (United States)

Gao, Lei; Fan, Daidu; Li, Daoji; Cai, Jingong

2010-04-01

Twenty-eight surface water samples from rivers, muddy intertidal flats, sand shores, and bedrock coasts were collected along the Zhejiang coastline in southeast China. In addition, three samples from the Changjiang (Yangtze River) were collected for comparison. CDOM (chromophoric dissolved organic matter) absorption and fluorescence excitation-emission matrix (EEM) spectroscopy, as well as nutrients and DOC were measured in these samples. According to salinity, nutrient, and DOC constituents, the 28 Zhejiang samples were categorized into four groups, i.e. highly-polluted, river derived, muddy-flat derived, and saltwater dominated ones. Among the six parameters (two humic-like and two protein-like peak intensities in fluorescence EEM contours, absorption at 300 nm, and DOC concentration) for the Zhejiang samples, any two of them were positively correlated. The submarine groundwater discharge, rather than local rivers, might have provided most of the freshwater that interacted with the saltwater during the mixing process. The high protein-like EEM peaks in samples from muddy salt marshes and rivers were probably caused by terrestrial inputs, land-based pollution, and local biological activities in combination. Copyright 2009. Published by Elsevier Ltd.

Fluorescent sensors for selective detection of thiols: expanding the intramolecular displacement based mechanism to new chromophores.

Science.gov (United States)

Niu, Li-Ya; Zheng, Hai-Rong; Chen, Yu-Zhe; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

2014-03-21

Biological thiols, including cysteine (Cys), homocystein (Hcy) and glutathione (GSH), play crucial roles in maintaining the appropriate redox status of biological systems. An abnormal level of biothiols is associated with different diseases, therefore, the discrimination between them is of great importance. Herein, we present two fluorescent sensors for selective detection of biothiols based on our recently reported intramolecular displacement mechanism. We expanded this mechanism to commercially available chromophores, 4-chloro-7-nitro-2,1,3-benzoxadiazole (NBD-Cl) and heptamethine cyanine dye IR-780. The sensors operate by undergoing displacement of chloride by thiolate. The amino groups of Cys/Hcy further replace the thiolate to form amino-substituted products, which exhibit dramatically different photophysical properties compared to sulfur-substituted products from the reaction with GSH. NBD-Cl is highly selective towards Cys/Hcy and exhibits significant fluorescence enhancement. IR-780 showed a variation in its fluorescence ratio towards Cys over other thiols. Both of the sensors can be used for live-cell imaging of Cys. The wide applicability of the mechanism may provide a powerful tool for developing novel fluorescent sensors for selective detection of biothiols.

Photoproduction of hydrogen peroxide in aqueous solution from model compounds for chromophoric dissolved organic matter (CDOM).

Science.gov (United States)

Clark, Catherine D; de Bruyn, Warren; Jones, Joshua G

2014-02-15

To explore whether quinone moieties are important in chromophoric dissolved organic matter (CDOM) photochemistry in natural waters, hydrogen peroxide (H2O2) production and associated optical property changes were measured in aqueous solutions irradiated with a Xenon lamp for CDOM model compounds (dihydroquinone, benzoquinone, anthraquinone, napthoquinone, ubiquinone, humic acid HA, fulvic acid FA). All compounds produced H2O2 with concentrations ranging from 15 to 500 μM. Production rates were higher for HA vs. FA (1.32 vs. 0.176 mM h(-1)); values ranged from 6.99 to 0.137 mM h(-1) for quinones. Apparent quantum yields (Θ app; measure of photochemical production efficiency) were higher for HA vs. FA (0.113 vs. 0.016) and ranged from 0.0018 to 0.083 for quinones. Dihydroquinone, the reduced form of benzoquinone, had a higher production rate and efficiency than its oxidized form. Post-irradiation, quinone compounds had absorption spectra similar to HA and FA and 3D-excitation-emission matrix fluorescence spectra (EEMs) with fluorescent peaks in regions associated with CDOM. Copyright © 2014 Elsevier Ltd. All rights reserved.

Can time-dependent density functional theory predict intersystem crossing in organic chromophores? A case study on benzo(bis)-X-diazole based donor-acceptor-donor type molecules.

Science.gov (United States)

Tam, Teck Lip Dexter; Lin, Ting Ting; Chua, Ming Hui

2017-06-21

Here we utilized new diagnostic tools in time-dependent density functional theory to explain the trend of intersystem crossing in benzo(bis)-X-diazole based donor-acceptor-donor type molecules. These molecules display a wide range of fluorescence quantum yields and triplet yields, making them excellent candidates for testing the validity of these diagnostic tools. We believe that these tools are cost-effective and can be applied to structurally similar organic chromophores to predict/explain the trends of intersystem crossing, and thus fluorescence quantum yields and triplet yields without the use of complex and expensive multireference configuration interaction or multireference pertubation theory methods.

Efficient {pi} electrons delocalization in prospective push-pull non-linear optical chromophore 4-[N,N-dimethylamino]-4'-nitro stilbene (DANS): A vibrational spectroscopic study

Energy Technology Data Exchange (ETDEWEB)

Vijayakumar, T.; Hubert Joe, I. [Centre for Molecular and Biophysics Research, Department of Physics, Mar Ivanios College, Thiruvananthapuram 695 015, Kerala (India); Reghunadhan Nair, C.P. [Polymers and Special Chemicals Division, Vikram Sarabhai Space Centre, Thiruvananthapuram 695 022, Kerala (India); Jayakumar, V.S. [Centre for Molecular and Biophysics Research, Department of Physics, Mar Ivanios College, Thiruvananthapuram 695 015, Kerala (India)], E-mail: vsjk@vsnl.net

2008-01-22

A comprehensive investigation on the intramolecular charge transfer (ICT) of an efficient {pi}-conjugated potential push-pull NLO chromophore, 4-[N,N-dimethylamino]-4'-nitro stilbene (DANS), from a strong electron-donor group (dimethylamino-N(CH{sub 3}){sub 2}) to a strong electron-acceptor group (nitro-NO{sub 2}) through the {pi}-conjugated bridge (trans-stilbene) has been carried out from their vibrational spectra. The NIR FT-Raman and FT-IR spectra supported by the density functional theory (DFT) quantum chemical computations have been employed to analyze the effects of intramolecular charge transfer on the geometries and the vibrational modes contributing to the linear electro-optic effect of the organic NLO material. It has been observed that the changes in the endocyclic and exocyclic angles result from the charge-transfer interaction of the phenyl ring and the amino group in the electron-donor side of the NLO chromophore. The strongest vibrational modes contributing to the electro-optic effect have been identified and examined from the concurrent IR and Raman activation of {nu}(C=C/C-C) mode, ring C=C stretching modes, in-plane deformation modes, nitro modes and the umbrella mode of methyl groups. Furthermore, the splitting of the vinyl stretching modes and the electronic effects such as hyperconjugation and backdonation on the methyl hydrogen atoms causing the decrease of stretching frequencies and infrared intensities have also been analyzed in detail. The effect of frontier orbitals transition of electron density transfer and the influence of planarity between the phenyl rings of the stilbene moiety on the first hyperpolarizability have also been discussed.

Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska

Science.gov (United States)

Spencer, R.G.M.; Aiken, G.R.; Butler, K.D.; Dornblaser, M.M.; Striegl, Robert G.; Hernes, P.J.

2009-01-01

The quality and quantity of dissolved organic matter (DOM) exported by Arctic rivers is known to vary with hydrology and this exported material plays a fundamental role in the biogeochemical cycling of carbon at high latitudes. We highlight the potential of optical measurements to examine DOM quality across the hydrograph in Arctic rivers. Furthermore, we establish chromophoric DOM (CDOM) relationships to dissolved organic carbon (DOC) and lignin phenols in the Yukon River and model DOC and lignin loads from CDOM measurements, the former in excellent agreement with long-term DOC monitoring data. Intensive sampling across the historically under-sampled spring flush period highlights the importance of this time for total export of DOC and particularly lignin. Calculated riverine DOC loads to the Arctic Ocean show an increase from previous estimates, especially when new higher discharge data are incorporated. Increased DOC loads indicate decreased residence times for terrigenous DOM in the Arctic Ocean with important implications for the reactivity and export of this material to the Atlantic Ocean. Citation: Spencer, R. G. M., G. R. Aiken, K. D. Butler, M. M. Dornblaser, R. G. Striegl, and P. J. Hernes (2009), Utilizing chromophoric dissolved organic matter measurements to derive export and reactivity of dissolved organic carbon exported to the Arctic Ocean: A case study of the Yukon River, Alaska, Geophys. Res. Lett., 36, L06401, doi:10.1029/ 2008GL036831. Copyright 2009 by the American Geophysical Union.

Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

KAUST Repository

Li, Jingrui

2015-07-29

The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

Electronic Structure of the Perylene / Zinc Oxide Interface: A Computational Study of Photoinduced Electron Transfer and Impact of Surface Defects

KAUST Repository

Li, Jingrui; Li, Hong; Winget, Paul; Bredas, Jean-Luc

2015-01-01

The electronic properties of dye-sensitized semiconductor surfaces consisting of pery- lene chromophores chemisorbed on zinc oxide via different spacer-anchor groups, have been studied at the density-functional-theory level. The energy distributions of the donor states and the rates of photoinduced electron transfer from dye to surface are predicted. We evaluate in particular the impact of saturated versus unsaturated aliphatic spacer groups inserted between the perylene chromophore and the semiconductor as well as the influence of surface defects on the electron-injection rates.

X-ray absorption spectroscopy of ultramarine pigments: A new analytical method for the polysulfide radical anion S3- chromophore

International Nuclear Information System (INIS)

Fleet, Michael E.; Liu, Xi

2010-01-01

Blue and mauve ultramarine artists' pigments and their heat-treated products have been investigated by sulfur K-edge X-ray absorption. X-ray absorption near-edge structure spectra are dominated by features of reduced sulfur and sulfate species. There is also a pre-peak at about 2468.0 eV which reflects the presence of the unpaired electron on the polysulfide radical anion (S 3 - ). Pre-peak intensity is directly proportional to the depth of blue coloration, and provides a new, independent method for estimating the proportion of ultramarine cage sites occupied by the blue chromophore. The occupancy of the polysulfide radical anion S 3 - is estimated to be 33% in an intense ultramarine blue pigment, 22% in a dark blue ultramarine pigment, and 1% in deep royal blue lazurite from Afghanistan. The more efficient development of color in lazurite is attributed to extensive annealing of the mineral structure in the natural environment.

Absorption properties of chromophoric dissolved organic matter (CDOM) in the East China Sea and the waters off eastern Taiwan

Science.gov (United States)

Zhou, Fengxia; Gao, Xuelu; Song, Jinming; Chen, Chen-Tung Arthur; Yuan, Huamao; Xing, Qianguo

2018-05-01

The absorption properties of chromophoric dissolved organic matter (CDOM) in the East China Sea (ECS) and the waters off eastern Taiwan (WET) were studied during May 2014. CDOM absorption coefficient (a280) and spectral slope (S275-295) revealed considerable spatial variations. In the ECS, the values of a280 and S275-295 presented a reverse distribution pattern. In the WET, a280 values were generally low while S275-295 values were generally high. Vertical distributions of a280 and S275-295 also varied in different regions. Terrestrial input, phytoplankton production, sediment release or photobleaching may be responsible for the dynamics of CDOM. Relationships among CDOM related parameters could partly support this conclusion. a280 were also used to trace different water masses and the result showed that the influence of Changjiang Diluted Water could reach the outer shelf of the northern ECS, and that the Kuroshio Current had a strong influence on the middle shelf of the southern ECS.

Asymmetrically Substituted and π-Conjugated 2,2'-Bipyridine Derivatives: Synthesis, Spectroscopy, Computation, and Crystallography.

Science.gov (United States)

Bodapati, Ramakrishna; Sarma, Monima; Kanakati, Arunkumar; Das, Samar K

2015-12-18

A new series of monosubstituted styryl- and bistyryl-2,2'-bipyridine luminophores (compounds 16-23) have been synthesized via Horner-Wadsworth-Emmons reaction involving a monophosphonate and donor aromatic aldehydes. In the title chromophores, the amino donors are varied between acyclic and cyclic while the alkoxy donors are varied in terms of their number and position. The absorption maxima of these chromophores shift predominantly due to intramolecular charge transfer (ICT) between different donor and acceptor moieties. The title donor-acceptor molecules exhibit intense fluorescence in solution at room temperature, and their emissive behavior has been found to be highly sensitive to solvent polarity. The fluorescence spectra and quantum yields of all the chromophores were recorded in four different solvent media, and the chromophores 16, 17, 19, and 21 exhibit fluorescence in the solid state too. The influence of the nature and position of the donor functionalities in the conjugated backbone of the bipyridine moiety on the electronic absorption properties of the title chromophores (16-23) has been demonstrated, which has further been corroborated by DFT and TD-DFT computation both in gas phase and in solution phase. The crystal structure of compound 18 has been described as a representative member of the family (16-23).

Daily changes of structure, function and rhodopsin content in the compound eye of the crab Hemigrapsus sanguineus.

Science.gov (United States)

Arikawa, K; Kawamata, K; Suzuki, T; Eguchi, E

1987-08-01

The compound eye of the crab hemigrapsus sanguineus undergoes daily changes in morphology as determined by light and electron microscopy, both in the quantity of chromophore substances studied by HPLC and in visual sensitivity as shown by electrophysiological techniques. 1. At a temperature of 20 degrees C, the rhabdom occupation ratio (ROR) of an ommatidial retinula was 11.6% (maximum) at midnight, 8.0 times larger than the minimum value at midday (1.4%). 2. Observations by freeze-fracture revealed that the densities of intra-membranous particles (9-11 nm in diameter) of rhabdomeric membrane were ca. 2000/microns 2 and ca. 3000/microns 2 for night and daytime compound eyes, respectively. 3. Screening pigment granules migrated longitudinally and aggregated at night, but dispersed during the day. Reflecting pigment granules migrate transversally in the proximal half of the reticula layer i.e. cytoplasmic extensions containing reflecting pigment granules squeeze between neighbouring retinula cells causing optical isolation (Fig. 4). Thus the screening pigment granules within the retinula cells show longitudinal migration and radial movement so that the daytime rhabdoms are closely surrounded by the pigment granules. 4. At 20 degrees C, the total amount of chromophore of the visual pigment (11-cis and all-trans-retinal) was 1.4 times larger at night than during the day i.e. 46.6 pmol/eye at midnight and 33.2 pmol/eye at midday. Calculations of the total surface area of rhabdomeric membrane, total number of intra-membranous particles in rhabdomeric membrane and the total number of chromophore molecules in a compound eye, indicate that a considerable amount of chromophore-protein complex exists outside the rhabdom during the day. 5. The change in rhabdom size and quantity of chromophore were highly dependent on temperature. At 10 degrees C both rhabdom size and amount of chromophore stayed close to daytime levels throughout the 24 hours. 6. The intracellularly

From Dark to Light to Fluorescence Resonance Energy Transfer (FRET): Polarity-Sensitive Aggregation-Induced Emission (AIE)-Active Tetraphenylethene-Fused BODIPY Dyes with a Very Large Pseudo-Stokes Shift.

Science.gov (United States)

Şen, Esra; Meral, Kadem; Atılgan, Serdar

2016-01-11

The work presented herein is devoted to the fabrication of large Stokes shift dyes in both organic and aqueous media by combining dark resonance energy transfer (DRET) and fluorescence resonance energy transfer (FRET) in one donor-acceptor system. In this respect, a series of donor-acceptor architectures of 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) dyes substituted by one, two, or three tetraphenylethene (TPE) luminogens were designed and synthesised. The photophysical properties of these three chromophore systems were studied to provide insight into the nature of donor-acceptor interactions in both THF and aqueous media. Because the generation of emissive TPE donor(s) is strongly polarity dependent, due to its aggregation-induced emission (AIE) feature, one might expect the formation of appreciable fluorescence emission intensity with a very large pseudo-Stokes shift in aqueous media when considering FRET process. Interestingly, similar results were also recorded in THF for the chromophore systems, although the TPE fragment(s) of the dyes are non-emissive. The explanation for this photophysical behaviour lies in the DRET. This is the first report on combining two energy-transfer processes, namely, FRET and DRET, in one polarity-sensitive donor-acceptor pair system. The accuracy of the dark-emissive donor property of the TPE luminogen is also presented for the first time as a new feature for AIE phenomena. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical properties and composition changes in chromophoric dissolved organic matter along trophic gradients: Implications for monitoring and assessing lake eutrophication.

Science.gov (United States)

Zhang, Yunlin; Zhou, Yongqiang; Shi, Kun; Qin, Boqiang; Yao, Xiaolong; Zhang, Yibo

2017-12-26

Chromophoric dissolved organic matter (CDOM) is an important optically active substance in aquatic environments and plays a key role in light attenuation and in the carbon, nitrogen and phosphorus biogeochemical cycles. Although the optical properties, abundance, sources, cycles, compositions and remote sensing estimations of CDOM have been widely reported in different aquatic environments, little is known about the optical properties and composition changes in CDOM along trophic gradients. Therefore, we collected 821 samples from 22 lakes along a trophic gradient (oligotrophic to eutrophic) in China from 2004 to 2015 and determined the CDOM spectral absorption and nutrient concentrations. The total nitrogen (TN), total phosphorus (TP), and chlorophyll a (Chla) concentrations and the Secchi disk depth (SDD) ranged from 0.02 to 24.75 mg/L, 0.002-3.471 mg/L, 0.03-882.66 μg/L, and 0.05-17.30 m, respectively. The trophic state index (TSI) ranged from 1.55 to 98.91 and covered different trophic states, from oligotrophic to hyper-eutrophic. The CDOM absorption coefficient at 254 nm (a(254)) ranged from 1.68 to 92.65 m -1 . Additionally, the CDOM sources and composition parameters, including the spectral slope and relative molecular size value, exhibited a substantial variability from the oligotrophic level to other trophic levels. The natural logarithm value of the CDOM absorption, lna(254), is highly linearly correlated with the TSI (r 2  = 0.92, p 10 m -1 , respectively. The results suggested that the CDOM absorption coefficient a(254) might be a more sensitive single indicator of the trophic state than TN, TP, Chla and SDD. Therefore, we proposed a CDOM absorption coefficient and determined the threshold for defining the trophic state of a lake. Several advantages of measuring and estimating CDOM, including rapid experimental measurements, potential in situ optical sensor measurements and large-spatial-scale remote sensing estimations, make it

Vectorial photoinduced energy transfer between boron-dipyrromethene (Bodipy) chromophores across a fluorene bridge.

Science.gov (United States)

Puntoriero, Fausto; Nastasi, Francesco; Campagna, Sebastiano; Bura, Thomas; Ziessel, Raymond

2010-08-02

A series of novel multichromophoric, luminescent compounds has been prepared, and their absorption spectra, luminescence properties (both at 77 K in rigid matrix and at 298 K in fluid solution), and photoinduced intercomponent energy-transfer processes have been studied. The series contains two new multichromophoric systems 1 and 2, each one containing two different boron-dipyrromethene (Bodipy) subunits and one bridging fluorene species, and two fluorene-Bodipy bichromophoric species, 6 and 7. Three monochromophoric compounds, 3, 4, and 5, used as precursors in the synthetic process, were also fully characterized. The absorption spectra of the multichromophoric compounds are roughly the summation of the absorption spectra of their individual components, thus demonstrating the supramolecular nature of the assemblies. Luminescence studies show that quantitative energy transfer occurs in 6 and 7 from the fluorene chromophore to the Bodipy dyes. Luminescence studies, complemented by transient-absorption spectroscopy studies, also indicate that efficient inter-Bodipy energy transfer across the rigid fluorene spacer takes place in 1 and 2, with rate constants, evaluated by several experimental methods, between 2.0 and 7.0 x 10(9) s(-1). Such an inter-Bodipy energy transfer appears to be governed by the Förster mechanism. By taking advantage of the presence of various protonable sites in the substituents of the lower-energy Bodipy subunit of 1 and 2, the effect of protonation on the energy-transfer rates has also been investigated. The results suggest that control of energy-transfer rate and efficiency of inter-Bodipy energy transfer in this type of systems can be achieved by an external, reversible input.

Molecular characterization of brown carbon (BrC) chromophores in secondary organic aerosol generated from photo-oxidation of toluene.

Science.gov (United States)

Lin, Peng; Liu, Jiumeng; Shilling, John E; Kathmann, Shawn M; Laskin, Julia; Laskin, Alexander

2015-09-28

Atmospheric brown carbon (BrC) is a significant contributor to light absorption and climate forcing. However, little is known about a fundamental relationship between the chemical composition of BrC and its optical properties. In this work, light-absorbing secondary organic aerosol (SOA) was generated in the PNNL chamber from toluene photo-oxidation in the presence of NOx (Tol-SOA). Molecular structures of BrC components were examined using nanospray desorption electrospray ionization (nano-DESI) and liquid chromatography (LC) combined with UV/Vis spectroscopy and electrospray ionization (ESI) high-resolution mass spectrometry (HRMS). The chemical composition of BrC chromophores and the light absorption properties of toluene SOA (Tol-SOA) depend strongly on the initial NOx concentration. Specifically, Tol-SOA generated under high-NOx conditions (defined here as initial NOx/toluene of 5/1) appears yellow and mass absorption coefficient of the bulk sample (MACbulk@365 nm = 0.78 m(2) g(-1)) is nearly 80 fold higher than that measured for the Tol-SOA sample generated under low-NOx conditions (NOx/toluene atmosphere.

Chromophoric dissolved organic matter of black waters in a highly eutrophic Chinese lake: Freshly produced from algal scums?

Science.gov (United States)

Zhou, Yongqiang; Jeppesen, Erik; Zhang, Yunlin; Niu, Cheng; Shi, Kun; Liu, Xiaohan; Zhu, Guangwei; Qin, Boqiang

2015-12-15

Field campaigns and an incubation experiment were conducted to evaluate the sources of chromophoric dissolved organic matter (CDOM) in black water spots in highly polluted regions of the Chinese Lake Taihu. A significant positive correlation (pCDOM absorption coefficient a(350), indicating that algae degradation was likely the primary source of CDOM in black waters. This is supported by our field results that Chl-a, a(350) and the spectral slope ratio (SR) were significantly higher in the black water samples than in the regular samples (pCDOM source where a(350) increased with decreasing Chl-a concentrations. After seven days' incubation, a 72.2% decrease and a 74.9% increase were recorded for Chl-a and a(350), respectively, relative to the initial values. Parallel factor analysis identified five fluorescent components. The maximal fluorescence intensity (Fmax) of tryptophan-like C1 and microbial humic-like C3 of black water samples was significantly higher than in the regular water samples (pCDOM source in black water spots. Copyright © 2015 Elsevier B.V. All rights reserved.

[Spectral characteristics variations of chromophoric dissolved organic matter during growth of filamentous green macroalgae].

Science.gov (United States)

Jiang, De-gang; Huang, Qing-hui; Li, Jian-hua

2010-07-01

As an important component of dissolved organic matter (DOM), chromophoric dissolved organic matter (CDOM) plays a central role in the global biogeochemical carbon cycle. Macroalgae are essential producers in aquatic ecosystems. They can release a considerable part of photosynthetic products as CDOM. So changes in optical properties of CDOM are studied on filamentous green macroalgae-Chadophorasle found in tidal flats of a brackish Lake Beihu in natural field condition by using spectrometry. Humic-like fluorescence peaks and protein-like fluorescence peaks detected by fluorescence excitation-emission matrix spectrum (EEMS) change little in control experiment but increase dramatically in incubation experiment. Applying parallel factor analysis (PARAFAC) together with fluorescence excitation-emission matrix can get four components of CDOM (C1, C2, C3 and C4) which are relative to humic-like fluorescence peak A(C), M and protein-like fluorescence peak B, T respectively. In incubation experiment four components increase by 211.5%, 255.8%, 75.3% and 129.3% respectively while in control experiment components have little changes except C1 decreasing by 34.3%. Absorption coefficient alpha (355) increases by 92.9% and has positive significant correlation (P CDOM molecular weight and composition, M and S values in incubation experiment are smaller than in control experiment, which illustrate that aromatic and macromolecular CDOM is produced in growth of Chadophorasle. All results indicate that growth of Chadophorasle can change the content and composition of CDOM.

Watching individual molecules flex within lipid membranes using SERS

Science.gov (United States)

Taylor, Richard W.; Benz, Felix; Sigle, Daniel O.; Bowman, Richard W.; Bao, Peng; Roth, Johannes S.; Heath, George R.; Evans, Stephen D.; Baumberg, Jeremy J.

2014-08-01

Interrogating individual molecules within bio-membranes is key to deepening our understanding of biological processes essential for life. Using Raman spectroscopy to map molecular vibrations is ideal to non-destructively `fingerprint' biomolecules for dynamic information on their molecular structure, composition and conformation. Such tag-free tracking of molecules within lipid bio-membranes can directly connect structure and function. In this paper, stable co-assembly with gold nano-components in a `nanoparticle-on-mirror' geometry strongly enhances the local optical field and reduces the volume probed to a few nm3, enabling repeated measurements for many tens of minutes on the same molecules. The intense gap plasmons are assembled around model bio-membranes providing molecular identification of the diffusing lipids. Our experiments clearly evidence measurement of individual lipids flexing through telltale rapid correlated vibrational shifts and intensity fluctuations in the Raman spectrum. These track molecules that undergo bending and conformational changes within the probe volume, through their interactions with the environment. This technique allows for in situ high-speed single-molecule investigations of the molecules embedded within lipid bio-membranes. It thus offers a new way to investigate the hidden dynamics of cell membranes important to a myriad of life processes.

Polymorphism of lipid self-assembly systems

International Nuclear Information System (INIS)

Takahashi, Hiroshi

2002-01-01

When lipid molecules are dispersed into an aqueous medium, various self-organized structures are formed, depending on conditions (temperature, concentration, etc), in consequence of the amphipathic nature of the molecules. In addition, lipid self-assembly systems exhibit polymorphic phase transition behavior. Since lipids are one of main components of biomembranes, studies on the structure and thermodynamic properties of lipid self-assembly systems are fundamentally important for the consideration of the stability of biomembranes. (author)

Ultrafast relaxation dynamics of a biologically relevant probe dansyl at the micellar surface.

Science.gov (United States)

Sarkar, Rupa; Ghosh, Manoranjan; Pal, Samir Kumar

2005-02-01

We report picosecond-resolved measurement of the fluorescence of a well-known biologically relevant probe, dansyl chromophore at the surface of a cationic micelle (cetyltrimethylammonium bromide, CTAB). The dansyl chromophore has environmentally sensitive fluorescence quantum yields and emission maxima, along with large Stokes shift. In order to study the solvation dynamics of the micellar environment, we measured the fluorescence of dansyl chromophore attached to the micellar surface. The fluorescence transients were observed to decay (with time constant approximately 350 ps) in the blue end and rise with similar timescale in the red end, indicative of solvation dynamics of the environment. The solvation correlation function is measured to decay with time constant 338 ps, which is much slower than that of ordinary bulk water. Time-resolved anisotropy of the dansyl chromophore shows a bi-exponential decay with time constants 413 ps (23%) and 1.3 ns (77%), which is considerably slower than that in free solvents revealing the rigidity of the dansyl-micelle complex. Time-resolved area-normalized emission spectroscopic (TRANES) analysis of the time dependent emission spectra of the dansyl chromophore in the micellar environment shows an isoemissive point at 21066 cm-1. This indicates the fluorescence of the chromophore contains emission from two kinds of excited states namely locally excited state (prior to charge transfer) and charge transfer state. The nature of the solvation dynamics in the micellar environments is therefore explored from the time-resolved anisotropy measurement coupled with the TRANES analysis of the fluorescence transients. The time scale of the solvation is important for the mechanism of molecular recognition.

Design, Synthesis, Structural and Spectroscopic Studies of Push-Pull Two-Photon Absorbing Chromophores with Acceptor Groups of Varying Strength

Science.gov (United States)

Morales, Alma R.; Frazer, Andrew; Woodward, Adam W.; Ahn-White, Hyo-Yang; Fonari, Alexandr; Tongwa, Paul; Timofeeva, Tatiana; Belfield, Kevin D.

2013-01-01

A new series of unsymmetrical diphenylaminofluorene-based chromophores with various strong π-electron acceptors were synthesized and fully characterized. The systematic alteration of the structural design facilitated the investigation of effects such as molecular symmetry and strength of electron-donating and/or withdrawing termini have on optical nonlinearity. In order to determine the electronic and geometrical properties of the novel compounds, a thorough investigation was carried out by a combination of linear and nonlinear spectroscopic techniques, single crystal X-ray diffraction, and quantum chemical calculations. Finally, on the basis of two-photon absorption (2PA) cross sections, the general trend for π -electron accepting ability, i.e., ability to accept charge transfer from diphenylamine was: 2-pyran-4-ylidene malononitrile (pyranone) > dicyanovinyl > bis(dicyanomethylidene)indane > 1-(thiophen-2-yl)propenone > dicyanoethylenyl > 3-(thiophen-2-yl)propenone. An analog with the 2-pyran-4-ylidene malononitrile acceptor group exhibited a nearly three-fold enhancement of the 2PA< δ (1650 GM at 840 nm), relative to other members of the series. PMID:23305555

Characteristics and sources analysis of riverine chromophoric dissolved organic matter in Liaohe River, China.

Science.gov (United States)

Shao, Tiantian; Song, Kaishan; Jacinthe, Pierre-Andre; Du, Jia; Zhao, Ying; Ding, Zhi; Guan, Ying; Bai, Zhang

2016-12-01

Chromophoric dissolved organic matter (CDOM) in riverine systems can be affected by environmental conditions and land-use, and thus could provide important information regarding human activities in surrounding landscapes. The optical properties of water samples collected at 42 locations across the Liaohe River (LHR, China) watershed were examined using UV-Vis and fluorescence spectroscopy to determine CDOM characteristics, composition and sources. Total nitrogen (TN) and total phosphorus (TP) concentrations at all sampling sites exceeded the GB3838-2002 (national quality standards for surface waters, China) standard for Class V waters of 2.0 mg N/L and 0.4 mg P/L respectively, while trophic state index (TSI M ) indicated that all the sites investigated were mesotrophic, 64% of which were eutrophic at the same time. Redundancy analysis showed that total suspended matter (TSM), dissolved organic carbon (DOC), and turbidity had a strong correlation with CDOM, while the other parameters (Chl a, TN, TP and TSI M ) exhibited weak correlations with CDOM absorption. High spectral slope values and low SUVA254 (the specific UV absorption) values indicated that CDOM in the LHR was primarily comprised of low molecular weight organic substances. Analysis of excitation-emission matrices contour plots showed that CDOM in water samples collected from upstream locations exhibited fulvic-acid-like characteristics whereas protein-like substances were most likely predominant in samples collected in estuarine areas and downstream from large cities. These patterns were interpreted as indicative of water pollution from urban and industrial activities in several downstream sections of the LHR watershed.

Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA

Science.gov (United States)

Spencer, Robert G. M.; Butler, Kenna D.; Aiken, George R.

2012-09-01

Dissolved organic carbon (DOC) concentration and chromophoric dissolved organic matter (CDOM) parameters were measured over a range of discharge in 30 U.S. rivers, covering a diverse assortment of fluvial ecosystems in terms of watershed size and landscape drained. Relationships between CDOM absorption at a range of wavelengths (a254, a350, a440) and DOC in the 30 watersheds were found to correlate strongly and positively for the majority of U.S. rivers. However, four rivers (Colorado, Colombia, Rio Grande and St. Lawrence) exhibited statistically weak relationships between CDOM absorption and DOC. These four rivers are atypical, as they either drain from the Great Lakes or experience significant impoundment of water within their watersheds, and they exhibited values for dissolved organic matter (DOM) parameters indicative of autochthonous or anthropogenic sources or photochemically degraded allochthonous DOM and thus a decoupling between CDOM and DOC. CDOM quality parameters in the 30 rivers were found to be strongly correlated to DOM compositional metrics derived via XAD fractionation, highlighting the potential for examining DOM biochemical quality from CDOM measurements. This study establishes the ability to derive DOC concentration from CDOM absorption for the majority of U.S. rivers, describes characteristics of riverine systems where such an approach is not valid, and emphasizes the possibility of examining DOM composition and thus biogeochemical function via CDOM parameters. Therefore, the usefulness of CDOM measurements, both laboratory-based analyses and in situ instrumentation, for improving spatial and temporal resolution of DOC fluxes and DOM dynamics in future studies is considerable in a range of biogeochemical studies.

Dissolved organic carbon and chromophoric dissolved organic matter properties of rivers in the USA

Science.gov (United States)

Spencer, Robert G.M.; Butler, Kenna D.; Aiken, George R.

2012-01-01

Dissolved organic carbon (DOC) concentration and chromophoric dissolved organic matter (CDOM) parameters were measured over a range of discharge in 30 U.S. rivers, covering a diverse assortment of fluvial ecosystems in terms of watershed size and landscape drained. Relationships between CDOM absorption at a range of wavelengths (a254, a350, a440) and DOC in the 30 watersheds were found to correlate strongly and positively for the majority of U.S. rivers. However, four rivers (Colorado, Colombia, Rio Grande and St. Lawrence) exhibited statistically weak relationships between CDOM absorption and DOC. These four rivers are atypical, as they either drain from the Great Lakes or experience significant impoundment of water within their watersheds, and they exhibited values for dissolved organic matter (DOM) parameters indicative of autochthonous or anthropogenic sources or photochemically degraded allochthonous DOM and thus a decoupling between CDOM and DOC. CDOM quality parameters in the 30 rivers were found to be strongly correlated to DOM compositional metrics derived via XAD fractionation, highlighting the potential for examining DOM biochemical quality from CDOM measurements. This study establishes the ability to derive DOC concentration from CDOM absorption for the majority of U.S. rivers, describes characteristics of riverine systems where such an approach is not valid, and emphasizes the possibility of examining DOM composition and thus biogeochemical function via CDOM parameters. Therefore, the usefulness of CDOM measurements, both laboratory-based analyses and in situ instrumentation, for improving spatial and temporal resolution of DOC fluxes and DOM dynamics in future studies is considerable in a range of biogeochemical studies.

Design and synthesis of bipyridine platinum(II) bisalkynyl fullerene donor-chromophore-acceptor triads with ultrafast charge separation.

Science.gov (United States)

Lee, Sai-Ho; Chan, Chris Tsz-Leung; Wong, Keith Man-Chung; Lam, Wai Han; Kwok, Wai-Ming; Yam, Vivian Wing-Wah

2014-07-16

Donor-chromophore-acceptor triads, (PTZ)2-Pt(bpy)-C60 and ((t)BuPTZ)2-Pt(bpy)-C60, along with their model compound, (Ph)2-Pt(bpy)-C60, have been synthesized and characterized; their photophysical and electrochemical properties have been studied, and the origin of the absorption and emission properties has been supported by computational studies. The photoinduced electron transfer reactions have been investigated using the femtosecond and nanosecond transient absorption spectroscopy. In dichloromethane, (Ph)2-Pt(bpy)-C60 shows ultrafast triplet-triplet energy transfer from the (3)MLCT/LLCT excited state within 4 ps to give the (3)C60* state, while in (PTZ)2-Pt(bpy)-C60 and ((t)BuPTZ)2-Pt(bpy)-C60, charge-separated state forms within 400 fs from the (3)MLCT/LLCT excited state with efficiency of over 0.90, and the total efficiency with the contribution of (3)C60* is estimated to be 0.99. Although the forward electron transfer reactions are very rapid, the charge-separated state recombines to the singlet ground state at a time of hundreds of nanoseconds because of the difference in spin multiplicity between the charge-separated state and the ground state.

Selective elimination of chromophoric and fluorescent dissolved organic matter in a full-scale municipal wastewater treatment plant.

Science.gov (United States)

Yang, Xiaofang; Zhou, Zhongbo; Raju, Maddela Naga; Cai, Xiaoxuan; Meng, Fangang

2017-07-01

Effluent organic matter (EfOM) from municipal wastewater treatment plants potentially has a detrimental effect on both aquatic organisms and humans. This study evaluated the removal and transformation of chromophoric dissolved organic matter (CDOM) and fluorescent dissolved organic matter (FDOM) in a full-scale wastewater treatment plant under different seasons. The results showed that bio-treatment was found to be more efficient in removing bulk DOM (in term of dissolved organic carbon, DOC) than CDOM and FDOM, which was contrary to the disinfection process. CDOM and FDOM were selectively removed at various stages during the treatment. Typically, the low molecular weight fractions of CDOM and protein-like FDOM were more efficiently removed during bio-treatment process, whereas the humic-like FDOM exhibited comparable decreases in both bio-treatment and disinfection processes. Overall, the performance of the WWTP was weak in terms of CDOM and FDOM removal, resulting in enrichment of CDOM and FDOM in effluent. Moreover, the total removal of the bulk DOM (PCDOM and the humic-like FDOM showed little differences between summer and winter. In all, the results provide useful information for understanding the fate and transformation of DOM, illustrating that sub-fractions of DOM could be selectively removed depending on treatment processes and seasonality. Copyright © 2016. Published by Elsevier B.V.

Formation of Chromophoric Dissolved Organic Matter by Bacterial Degradation of Phytoplankton-Derived Aggregates

Directory of Open Access Journals (Sweden)

Joanna D. Kinsey

2018-01-01

Full Text Available Organic matter produced and released by phytoplankton during growth is processed by heterotrophic bacterial communities that transform dissolved organic matter into biomass and recycle inorganic nutrients, fueling microbial food web interactions. Bacterial transformation of phytoplankton-derived organic matter also plays a poorly known role in the formation of chromophoric dissolved organic matter (CDOM which is ubiquitous in the ocean. Despite the importance of organic matter cycling, growth of phytoplankton and activities of heterotrophic bacterial communities are rarely measured in concert. To investigate CDOM formation mediated by microbial processing of phytoplankton-derived aggregates, we conducted growth experiments with non-axenic monocultures of three diatoms (Skeletonema grethae, Leptocylindrus hargravesii, Coscinodiscus sp. and one haptophyte (Phaeocystis globosa. Phytoplankton biomass, carbon concentrations, CDOM and base-extracted particulate organic matter (BEPOM fluorescence, along with bacterial abundance and hydrolytic enzyme activities (α-glucosidase, β-glucosidase, leucine-aminopeptidase were measured during exponential growth and stationary phase (~3–6 weeks and following 6 weeks of degradation. Incubations were performed in rotating glass bottles to keep cells suspended, promoting cell coagulation and, thus, formation of macroscopic aggregates (marine snow, more similar to surface ocean processes. Maximum carbon concentrations, enzyme activities, and BEPOM fluorescence occurred during stationary phase. Net DOC concentrations (0.19–0.46 mg C L−1 increased on the same order as open ocean concentrations. CDOM fluorescence was dominated by protein-like signals that increased throughout growth and degradation becoming increasingly humic-like, implying the production of more complex molecules from planktonic-precursors mediated by microbial processing. Our experimental results suggest that at least a portion of open

Coupling of lipid membrane elasticity and in-plane dynamics

Science.gov (United States)

Tsang, Kuan-Yu; Lai, Yei-Chen; Chiang, Yun-Wei; Chen, Yi-Fan

2017-07-01

Biomembranes exhibit liquid and solid features concomitantly with their in-plane fluidity and elasticity tightly regulated by cells. Here, we present experimental evidence supporting the existence of the dynamics-elasticity correlations for lipid membranes and propose a mechanism involving molecular packing densities to explain them. This paper thereby unifies, at the molecular level, the aspects of the continuum mechanics long used to model the two membrane features. This ultimately may elucidate the universal physical principles governing the cellular phenomena involving biomembranes.

Monitoring of Au(iii) species in plants using a selective fluorescent probe.

Science.gov (United States)

Li, Zhen; Xu, Yuqing; Fu, Jie; Zhu, Hailiang; Qian, Yong

2018-01-23

A colorimetric and ratiometric probe with a push-pull chromophore dicyanoisophorone system, AuP, has been developed for the detection of Au(iii) species with highly sensitive and selective response to real-water samples and living tissues of Arabidopsis thaliana.

Role of microgel formation in scavenging of chromophoric dissolved organic matter and heavy metals in a river-sea system.

Science.gov (United States)

Shiu, Ruei-Feng; Lee, Chon-Lin

2017-04-15

We use riverine and marine dissolved organic carbon (DOC) polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit very much difference in size and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of hazardous materials. Copyright © 2017 Elsevier B.V. All rights reserved.

Looking at the Green Fluorescent Protein (GFP) chromophore from a different perspective: A computational insight

Science.gov (United States)

Paul, Bijan Kumar; Guchhait, Nikhil

2013-02-01

In the present contribution Density Functional Theory (DFT) has been applied to explore molecular dipole moment, frontier molecular orbital (FMO) features, chemical hardness, and the molecular electrostatic potential surface (MEPS) characteristics for optimized molecular geometry of the Green Fluorescent Protein (GFP) chromophore p-hydroxybenzylideneimidazolinone (HBDI) both in its protonated (neutral) and deprotonated (anion) forms. The distribution of atomic charges over the entire molecular framework as obtained from Natural Bond Orbital (NBO) analysis is found to faithfully replicate the predictions from the MEP map in respect of reactivity map of HBDI (neutral and anion) and possible sites for hydrogen bonding interactions etc. The three dimensional MEP map encompassing the entire molecule yields a reliable reactivity map of HBDI molecule also displaying the most probable regions for non-covalent interactions. The differential distribution of the electrostatic potential over the neutral and anionic species of HBDI is authentically reflected on MEP map and NBO charge distribution analysis. Thermodynamic properties such as heat capacity, thermal energy, enthalpy, entropy have been calculated and the correlation of the various thermodynamic functions with temperature has been established for neutral molecule. More importantly, however, the computational approach has been employed to unveil the nonlinear optical (NLO) properties of protonated (neutral) and deprotonated (anion) HBDI. Also in an endeavor to achieve a fuller understanding on this aspect the effect of basis set on the NLO properties of the title molecule has been investigated. Our computations delineate the discernible differences in NLO properties between the neutral and anionic species of HBDI whereby indicating the possibility of development of photoswitchable NLO device.

Chromophore-assisted light inactivation of pKi-67 leads to inhibition of ribosomal RNA synthesis.

Science.gov (United States)

Rahmanzadeh, R; Hüttmann, G; Gerdes, J; Scholzen, T

2007-06-01

Expression of the nuclear Ki-67 protein (pKi-67) is strongly associated with cell proliferation. For this reason, antibodies against this protein are widely used as prognostic tools for the assessment of cell proliferation in biopsies from cancer patients. Despite this broad application in histopathology, functional evidence for the physiological role of pKi-67 is still missing. Recently, we proposed a function of pKi-67 in the early steps of ribosomal RNA (rRNA) synthesis. Here, we have examined the involvement of pKi-67 in this process by photochemical inhibition using chromophore-assisted light inactivation (CALI). Anti-pKi-67 antibodies were labelled with the fluorochrome fluorescein 5(6)-isothiocyanate and were irradiated after binding to their target protein. Performing CALI in vitro on cell lysates led to specific cross-linking of pKi-67. Moreover, the upstream binding factor (UBF) necessary for rRNA transcription was also partly subjected to cross-link formation, indicating a close spatial proximity of UBF and pKi-67. CALI in living cells, using micro-injected antibody, caused a striking relocalization of UBF from foci within the nucleoli to spots located at the nucleolar rim or within the nucleoplasm. pKi-67-CALI resulted in dramatic inhibition of RNA polymerase I-dependent nucleolar rRNA synthesis, whereas RNA polymerase II-dependent nucleoplasmic RNA synthesis remained almost unaltered. Our data presented here argue for a crucial role of pKi-67 in RNA polymerase I-dependent nucleolar rRNA synthesis.

Study on mechanism of decreased lipid peroxide by low dose radiation

International Nuclear Information System (INIS)

Yamaoka, Kiyonori; Okazoe, Yoko; Akimaru, Kunihiro; Sato, E.F.; Utsumi, Kozo.

1991-01-01

We examined the effect of SOD on lipid peroxidation in biomembrane from V.E-deficient rats, in order to study the mechanism of increased SOD activities and decreased lipid peroxide by low dose irradiation. The following results were obtained. i. Active oxygen (O 2 - ) strongly enhances lipid peroxidations in biomembrane with the Fe 3+ as catalyst. ii. SOD evidently inhibits lipid peroxidations under above conditions. iii. We suggested that the effect of SOD enhanced by low dose irradiation results in inhibition of lipid peroxidation. (author)

Effects of conjugation length and resonance enhancement on two-photon absorption in phenylene–vinylene oligomers

DEFF Research Database (Denmark)

Johnsen, Mette; Paterson, M.J.; Arnbjerg, J.

2008-01-01

. This phenomenon of the so-called resonance enhancement allows for greater control in obtaining an optimal response when using existing two-photon chromophores, and provides a much-needed guide for the systematic development and efficient use of two-photon singlet oxygen sensitizers....

A cure for the blues: opsin duplication and subfunctionalization for short-wavelength sensitivity in jewel beetles (Coleoptera: Buprestidae).

Science.gov (United States)

Lord, Nathan P; Plimpton, Rebecca L; Sharkey, Camilla R; Suvorov, Anton; Lelito, Jonathan P; Willardson, Barry M; Bybee, Seth M

2016-05-18

. Through structural comparisons of known insect opsins, we suggest that opsin duplication and amino acid variation within the chromophore binding pocket explains sensitivity in the short-wavelength portion of the visible light spectrum in these species. These findings are the first to reveal molecular complexity of the color vision system within beetles.

Alteration of chromophoric dissolved organic matter by solar UV radiation causes rapid changes in bacterial community composition†

Science.gov (United States)

Piccini, Claudia; Conde, Daniel; Pernthaler, Jakob; Sommaruga, Ruben

2010-01-01

We evaluated the effect of photochemical alterations of chromophoric dissolved organic matter (CDOM) on bacterial abundance, activity and community composition in a coastal lagoon of the Atlantic Ocean with high dissolved organic carbon concentration. On two occasions during the austral summer, bacteria-free water of the lagoon was exposed to different regions of the solar spectrum (full solar radiation, UV-A + PAR, PAR) or kept in the dark. Subsequently, dilution cultures were established with bacterioplankton from the lagoon that were incubated in the pre-exposed water for 5 h in the dark. Cell abundance, activity, and community composition of bacterioplankton were assessed before and after incubation in the different treatments. Changes in absorption, fluorescence, and DOC concentration were used as proxies for CDOM photoalteration. We found a significant CDOM photobleaching signal, DOC loss, as well as a stimulation of bacterial activity in the treatments pre-exposed to UV radiation, suggesting increased bioavailability of DOM. Bacterial community analysis by fluorescence in situ hybridization revealed that this stimulation was mainly accompanied by the specific enrichment of Alpha- and Betaproteobacteria. Thus, our results suggest that CDOM photoalteration not only stimulates bacterioplankton growth, but also induces rapid changes in bacterioplankton composition, which can be of relevance for ecosystem functioning, particularly considering present and future changes in the input of terrestrial CDOM to aquatic systems. PMID:19707620

Alteration of chromophoric dissolved organic matter by solar UV radiation causes rapid changes in bacterial community composition.

Science.gov (United States)

Piccini, Claudia; Conde, Daniel; Pernthaler, Jakob; Sommaruga, Ruben

2009-09-01

We evaluated the effect of photochemical alterations of chromophoric dissolved organic matter (CDOM) on bacterial abundance, activity and community composition in a coastal lagoon of the Atlantic Ocean with high dissolved organic carbon concentration. On two occasions during the austral summer, bacteria-free water of the lagoon was exposed to different regions of the solar spectrum (full solar radiation, UV-A+PAR, PAR) or kept in the dark. Subsequently, dilution cultures were established with bacterioplankton from the lagoon that were incubated in the pre-exposed water for 5 h in the dark. Cell abundance, activity, and community composition of bacterioplankton were assessed before and after incubation in the different treatments. Changes in absorption, fluorescence, and DOC concentration were used as proxies for CDOM photoalteration. We found a significant CDOM photobleaching signal, DOC loss, as well as a stimulation of bacterial activity in the treatments pre-exposed to UV radiation, suggesting increased bioavailability of DOM. Bacterial community analysis by fluorescence in situ hybridization revealed that this stimulation was mainly accompanied by the specific enrichment of Alpha- and Betaproteobacteria. Thus, our results suggest that CDOM photoalteration not only stimulates bacterioplankton growth, but also induces rapid changes in bacterioplankton composition, which can be of relevance for ecosystem functioning, particularly considering present and future changes in the input of terrestrial CDOM to aquatic systems.

[Near ultraviolet absorption spectral properties of chromophoric dissolved organic matter in the north area of Yellow Sea].

Science.gov (United States)

Wang, Lin; Zhao, Dong-Zhi; Yang, Jian-Hong; Chen, Yan-Long

2010-12-01

Chromophoric dissolved organic matter (CDOM) near ultraviolet absorption spectra contains CDOM molecular structure, composition and other important physical and chemical information. Based on the measured data of CDOM absorption coefficient in March 2009 in the north area of Yellow Sea, the present paper analyzed near ultraviolet absorption spectral properties of CDOM. The results showed that due to the impact of near-shore terrigenous input, the composition of CDOM is quite different in the north area of Yellow Sea, and this area is a typical case II water; fitted slope with specific range of spectral band and absorption coefficient at specific band can indicate the relative size of CDOM molecular weight, correlation between spectral slope of the Sg,275-300), Sg,300-350, Sg,350-400 and Sg,250-275 and the relative size of CDOM molecular weight indicative parameter M increases in turn and the highest is up to 0.95. Correlation between a(g)(lambda) and M value increases gradually with the increase in wavelength, and the highest is up to 0.92 at 400 nm; being correlated or not between spectral slope and absorption coefficient is decided by the fitting-band wavelength range for the spectra slope and the wavelength for absorption coefficient. Correlation between Sg,275-300 and a(g)(400) is the largest, up to 0.87.

UV-Vis reflection spectroscopy under variable angle incidence at the air-liquid interface.

Science.gov (United States)

Roldán-Carmona, Cristina; Rubia-Payá, Carlos; Pérez-Morales, Marta; Martín-Romero, María T; Giner-Casares, Juan J; Camacho, Luis

2014-03-07

The UV-Vis reflection spectroscopy (UV-Vis-RS) in situ at the air-liquid interface provides information about tilt and aggregation of chromophores in Langmuir monolayers. This information is particularly important given in most cases the chromophore is located at the polar region of the Langmuir monolayer. This region of the Langmuir monolayers has been hardly accessible by other experimental techniques. In spite of its enormous potential, the application of UV-Vis-RS has been limited mainly to reflection measurements under light normal incidence or at lower incidence angles than the Brewster angle. Remarkably, this technique is quite sensitive to the tilt of the chromophores at values of incidence angles close to or larger than the Brewster angle. Therefore, a novel method to obtain the order parameter of the chromophores at the air-liquid interface by using s- and p-polarized radiation at different incidence angles is proposed. This method allowed for the first time the experimental observation of the two components with different polarization properties of a single UV-Vis band at the air-liquid interface. The method of UV-Vis spectroscopy under variable angle incidence is presented as a new tool for obtaining rich detailed information on Langmuir monolayers.

Structural-functional analysis of the oligomeric protein R-phycoerythrin

Directory of Open Access Journals (Sweden)

JOSÉ MARTÍNEZ-OYANEDEL

2004-01-01

Full Text Available The structure of phycobiliproteins and their spatial organization in the phycobilisome provide the environment for high efficiency in light harvesting and conduction towards photosystem II. This article focuses on the analysis of R-phycoerythrin, a light harvesting hexameric phycobiliprotein that is part of the phycobilisomes. The interaction surfaces and the environment of the chromophores of R-phycoerythrin were studied in order to explain its structural stability and spectroscopic sensitivity, properties revealed by perturbation experiments. Three interaction surfaces are described (ab, (ab3 and (ab6. The analysis shows the importance of a subunits in the interaction between trimers, the homodimeric nature of the monomer (ab and also the presence of anchor points in every interaction surface studied: a18Phe and b18Tyr for (ab, b76Asn for (ab3 and a25Asn for (ab6 . Side chains of arginine, lysine or glutamine residues are located in the proximity of the chromophores providing the correct stabilization of their carboxylates. Aspartic acids residues are associated through H-bonds to the N atom of the two central rings of the tetrapyrrolic chromophores. Changes in the spectroscopic properties are observed in perturbation experiments, confirming the spatial requirement for an efficient resonance energy transfer among chromophores and through the phycobilisome

An artificial light-harvesting array constructed from multiple Bodipy dyes.

Science.gov (United States)

Ziessel, Raymond; Ulrich, Gilles; Haefele, Alexandre; Harriman, Anthony

2013-07-31

An artificial light-harvesting array, comprising 21 discrete chromophores arranged in a rational manner, has been synthesized and characterized fully. The design strategy follows a convergent approach that leads to a molecular-scale funnel, having an effective chromophore concentration of 0.6 M condensed into ca. 55 nm(3), able to direct the excitation energy to a focal point. A cascade of electronic energy-transfer steps occurs from the rim to the focal point, with the rate slowing down as the exciton moves toward its ultimate target. Situated midway along each branch of the V-shaped array, two chromophoric relays differ only slightly in terms of their excitation energies, and this situation facilitates reverse energy transfer. Thus, the excitation energy becomes spread around the array, a situation reminiscent of a giant holding pattern for the photon that can sample many different chromophores before being trapped by the terminal acceptor. At high photon flux under conditions of relatively slow off-load to a device, such as a solar cell, electronic energy transfer encounters one or more barriers that hinder forward progress of the exciton and thereby delays arrival of the second photon. Preliminary studies have addressed the ability of the array to function as a sensitizer for amorphous silicon solar cells.

Spatial frequency domain imaging using a snap-shot filter mosaic camera with multi-wavelength sensitive pixels

Science.gov (United States)

Strömberg, Tomas; Saager, Rolf B.; Kennedy, Gordon T.; Fredriksson, Ingemar; Salerud, Göran; Durkin, Anthony J.; Larsson, Marcus

2018-02-01

Spatial frequency domain imaging (SFDI) utilizes a digital light processing (DLP) projector for illuminating turbid media with sinusoidal patterns. The tissue absorption (μa) and reduced scattering coefficient (μ,s) are calculated by analyzing the modulation transfer function for at least two spatial frequencies. We evaluated different illumination strategies with a red, green and blue light emitting diodes (LED) in the DLP, while imaging with a filter mosaic camera, XiSpec, with 16 different multi-wavelength sensitive pixels in the 470-630 nm wavelength range. Data were compared to SFDI by a multispectral camera setup (MSI) consisting of four cameras with bandpass filters centered at 475, 560, 580 and 650 nm. A pointwise system for comprehensive microcirculation analysis was used (EPOS) for comparison. A 5-min arterial occlusion and release protocol on the forearm of a Caucasian male with fair skin was analyzed by fitting the absorption spectra of the chromophores HbO2, Hb and melanin to the estimatedμa. The tissue fractions of red blood cells (fRBC), melanin (/mel) and the Hb oxygenation (S02 ) were calculated at baseline, end of occlusion, early after release and late after release. EPOS results showed a decrease in S02 during the occlusion and hyperemia during release (S02 = 40%, 5%, 80% and 51%). The fRBC showed an increase during occlusion and release phases. The best MSI resemblance to the EPOS was for green LED illumination (S02 = 53%, 9%, 82%, 65%). Several illumination and analysis strategies using the XiSpec gave un-physiological results (e.g. negative S02 ). XiSpec with green LED illumination gave the expected change in /RBC , while the dynamics in S02 were less than those for EPOS. These results may be explained by the calculation of modulation using an illumination and detector setup with a broad spectral transmission bandwidth, with considerable variation in μa of included chromophores. Approaches for either reducing the effective bandwidth of

Integrated photoacoustic/ultrasound imaging: applications and new techniques

NARCIS (Netherlands)

van den Berg, P.J.

2017-01-01

Photoacoustic imaging (PAI) is a unique combination of optical sensitivity to tissue chromophores like hemoglobin, and ultrasonic resolution. Research in this PhD thesis is made possible by the development of a probe that combines PAI with regular ultrasound imaging. This probe is handheld and

"In situ" observation of the role of chloride ion binding to monkey green sensitive visual pigment by ATR-FTIR spectroscopy.

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Katayama, Kota; Furutani, Yuji; Iwaki, Masayo; Fukuda, Tetsuya; Imai, Hiroo; Kandori, Hideki

2018-01-31

Long-wavelength-sensitive (LWS) pigment possesses a chloride binding site in its protein moiety. The binding of chloride alters the absorption spectra of LWS; this is known as the chloride effect. Although the two amino acid substitutions of His197 and Lys200 influence the chloride effect, the molecular mechanism of chloride binding, which underlies the spectral tuning, has yet to be clarified. In this study, we applied ATR-FTIR spectroscopy to monkey green (MG) pigment to gain structural information of the chloride binding site. The results suggest that chloride binding stabilizes the β-sheet structure on the extracellular side loop with perturbation of the retinal polyene chain, promotes a hydrogen bonding exchange with the hydroxyl group of Tyr, and alters the protonation state of carboxylate. Combining with the results of the binding analyses of various anions (Br - , I - and NO 3 - ), our findings suggest that the anion binding pocket is organized for only Cl - (or Br - ) to stabilize conformation around the retinal chromophore, which is functionally relevant with absorbing long wavelength light.

Application of biohydrometallurgy to uranium ore processing

International Nuclear Information System (INIS)

Zhang Jiantang

1989-01-01

The development on application of biohydrometallargy to uranium ore processing is briefly introduced. The device designed for oxidizing ferrous ions in solution by using biomembrane, several bacterial leaching methods and the experimental results are given in this paper. The presented biohydrometallurgical process for recovering uranium includes bacterial leaching following by adsorption using tertiary amine resin 351 and oxidation of ferrous ions in the device with biomembranes. This process brings more economical benefits for treating silicate type original ores. The prospects on application of biogydrometallyurgy to solution mining is also discussed

Structure and properties of cell membranes. Volume 3: Methodology and properties of membranes

International Nuclear Information System (INIS)

Benga, G.

1985-01-01

This book covers the topics: Quantum chemical approach to study the mechanisms of proton translocation across membranes through protein molecules; monomolecular films as biomembrane models; planar lipid bilayers in relation to biomembranes; relation of liposomes to cell membranes; reconstitution of membrane transport systems; structure-function relationships in cell membranes as revealed by X-ray techniques; structure-function relationships in cell membranes as revealed by spin labeling ESR; structure and dynamics of cell membranes as revealed by NMR techniques; the effect of dietary lipids on the composition and properties of biological membranes and index

Characterization and spacial distribution variability of chromophoric dissolved organic matter (CDOM) in the Yangtze Estuary.

Science.gov (United States)

Wang, Ying; Zhang, Di; Shen, Zhenyao; Chen, Jing; Feng, Chenghong

2014-01-01

The spatial characteristics and the quantity and quality of the chromophoric dissolved organic matter (CDOM) in the Yangtze Estuary, based on the abundance, degree of humification and sources, were studied using 3D fluorescence excitation emission matrix spectra (F-EEMs) with parallel factor and principal component analysis (PARAFAC-PCA). The results indicated that the CDOM abundance decreased and the aromaticity increased from the upstream to the downstream areas of the estuary. Higher CDOM abundance and degrees of humification were observed in the pore water than that in the surface and bottom waters. Two humic-like components (C1 and C3) and one tryptophan-like component (C2) were identified using the PARAFAC model. The separation of the samples by PCA highlighted the differences in the DOM properties. Components C1 and C3 concurrently displayed positive factor 1 loadings with nearly zero factor 2 loadings, while C2 showed highly positive factor 2 loadings. The C1 and C3 were very similar and exhibited a direct relationship with A355 and DOC. The CDOM in the pore water increased along the river to the coastal area, which was mainly influenced by C1 and C3 and was significantly derived from sediment remineralization and deposition from the inflow of the Yangtze River. The CDOM in the surface and bottom waters was dominated by C2, especially in the inflows of multiple tributaries that were affected by intensive anthropogenic activities. The microbial degradation of exogenous wastes from the tributary inputs and shoreside discharges were dominant sources of the CDOM in the surface and bottom waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

Morphologic evaluation of the use of a latex prosthesis in videolaparoscopic inguinoplasty: an experimental study in dogs Avaliação morfológica da utilização de prótese de latex na inguinoplastia videolaparoscópica: estudo experimental em cães

Directory of Open Access Journals (Sweden)

Luiz Henrique de Sousa

2011-01-01

Full Text Available PURPOSE: To evaluate the morphological aspects of the behavior of 4 types of latex biomembranes implanted in preperitoneal videolaparoscopic inguinoplasty. METHODS: Sixteen inguinoplasties were performed in 12 dogs: group 1 received an impermeable latex biomembrane in the right inguinal region and a prolene prosthesis, as control, in the contralateral inguinal region; groups 2, 3 and 4 received latex biomembranes respectively containing impermeable polyamide, 1-mm thick porous polyamide and 0.5-mm thick porous polyamide. Macro- and microscopic evaluations of the inguinal region and of the removed implants were made on the 7th, 14th, 21st and 28th days in group 1 and on the 28th postoperative day in the other groups. RESULTS: We observed absence of hematoma, seroma and infection; presence of tortuosities; induction of vascular neoformation, inflammatory reaction and collagen deposition, and full encystment of the latex biomembranes, except that with fine porous polyamide, which was partially incorporated, with the formation of microcysts. No latex biomembrane induced fibrosis as observed in the prolene control group. CONCLUSIONS: The biomembranes maintain induction of the healing process without fibrosis, are fully encysted and, except for the one with fine porous polyamide, are not incorporated into adjacent tissues. The latex biomembrane, with or without polyamide, is not recommended as a separate material for preperitoneal inguinoplasty.OBJETIVO: Avaliar aspectos morfológicos do comportamento de 4 tipos de biomembranas de latex, colocadas pré-peritonealmente em cães, por inguinoplastia videolaparoscópica. MÉTODOS: Dezesseis inguinoplastias em 12 cães: grupo 1, com biomembrana de latex impermeável inguinal direita em quatro cães e prótese de prolene, como controle, contra-lateral; grupos 2, 3 e 4, com biomembrana de latex respectivamente de poliamida impermeável, poliamida porosa com 1mm de espessura e poliamida porosa com 0,5mm de

Distribution and spectral characteristics of chromophoric dissolved organic matter in a coastal bay in northern China.

Science.gov (United States)

Li, Guiju; Liu, Jing; Ma, Yulan; Zhao, Ruihua; Hu, Suzheng; Li, Yijie; Wei, Hao; Xie, Huixiang

2014-08-01

The absorption spectra of chromophoric dissolved organic matter (CDOM), along with general physical, chemical and biological variables, were determined in the Bohai Bay, China, in the springs of 2011 and 2012. The absorption coefficient of CDOM at 350 nm (a350) in surface water ranged from 1.00 to 1.83 m⁻¹ (mean: 1.35 m⁻¹) in May 2011 and from 0.78 to 1.92 m⁻¹ (mean: 1.19 m⁻¹) in April 2012. Little surface-bottom difference was observed due to strong vertical mixing. The a350 was weakly anti-correlated to salinity but positively correlated to chlorophyll a (Chl-a) concentration. A shoulder over 260-290 nm, suggestive of biogenic molecules, superimposed the overall pattern of exponentially decreasing CDOM absorption with wavelength. The wavelength distribution of the absorption spectral slope manifested a pronounced peak at ca. 300 nm characteristic of algal-derived CDOM. All a250/a365 ratios exceeded 6, corresponding to CDOM molecular weights (Mw) of less than 1 kDa. Spectroscopically, CDOM in the Bohai Bay differed substantively from that in the Haihe River, the bay's dominant source of land runoff; photobleaching of the riverine CDOM enlarged the difference. Results point to marine biological production being the principal source of CDOM in the Bohai Bay during the sampling seasons. Relatively low runoff, fast dilution, and selective photodegradation are postulated to be among the overarching elements responsible for the lack of terrigenous CDOM signature in the bay water. Copyright © 2014. Published by Elsevier B.V.

Chromophore-Dependent Intramolecular Exciton-Vibrational Coupling in the FMO Complex: Quantification and Importance for Exciton Dynamics.

Science.gov (United States)

Padula, Daniele; Lee, Myeong H; Claridge, Kirsten; Troisi, Alessandro

2017-11-02

In this paper, we adopt an approach suitable for monitoring the time evolution of the intramolecular contribution to the spectral density of a set of identical chromophores embedded in their respective environments. We apply the proposed method to the Fenna-Matthews-Olson (FMO) complex, with the objective to quantify the differences among site-dependent spectral densities and the impact of such differences on the exciton dynamics of the system. Our approach takes advantage of the vertical gradient approximation to reduce the computational demands of the normal modes analysis. We show that the region of the spectral density that is believed to strongly influence the exciton dynamics changes significantly in the timescale of tens of nanoseconds. We then studied the impact of the intramolecular vibrations on the exciton dynamics by considering a model of FMO in a vibronic basis and neglecting the interaction with the environment to isolate the role of the intramolecular exciton-vibration coupling. In agreement with the assumptions in the literature, we demonstrate that high frequency modes at energy much larger than the excitonic energy splitting have negligible influence on exciton dynamics despite the large exciton-vibration coupling. We also find that the impact of including the site-dependent spectral densities on exciton dynamics is not very significant, indicating that it may be acceptable to apply the same spectral density on all sites. However, care needs to be taken for the description of the exciton-vibrational coupling in the low frequency part of intramolecular modes because exciton dynamics is more susceptible to low frequency modes despite their small Huang-Rhys factors.

From Antenna to Assay: Lessons Learned in Lanthanide Luminescence

Energy Technology Data Exchange (ETDEWEB)

Moore, Evan; Samuel, Amanda; Raymond, Kenneth

2008-09-25

Ligand-sensitized luminescent lanthanide(III) complexes are of considerable current interest due to their unique photophysical properties (micro- to millisecond lifetimes, characteristic and narrow emission bands, and large Stokes shifts), which make them well suited to serve as labels in fluorescence-based bioassays. The long-lived Ln(III) emission can be temporally resolved from scattered light and background fluorescence, resulting in vastly enhanced measurement sensitivity. One of the challenges in this field is the design of sensitizing ligands that provide highly emissive Ln(III) complexes that also possess sufficient stability and aqueous solubility required for practical applications. In this account we give an overview of some of the general properties of the trivalent lanthanides and follow with a summary of advances made in our laboratory in the development of highly luminescent Tb(III) and Eu(III) complexes for applications in biotechnology. A focus of our research has been the optimization of these compounds as potential commercial agents for use in Homogeneous Time Resolved Fluorescence (HTRF) technology, the requirements and current use of which will be briefly discussed. Our approach involves developing high-stability octadentate Tb(III) and Eu(III) complexes that rely on all-oxygen donor atoms as well as using multi-chromophore chelates to increase molar absorptivity compared to earlier examples that utilize a single pendant antenna chromophore. We have found that ligands based on 2-hydroxyisophthalamide (IAM) provide exceptionally emissive Tb(III) complexes with quantum yield values up to ca. 60%. Solution thermodynamic studies have indicated that these complexes are stable at the nanomolar concentrations required for commercial assays. Through synthetic modification of the IAM-chromophore, in conjunction with time-dependent density functional theory (TD-DFT) calculations, we have developed a method to predict absorption and emission properties of

Optical properties of chromophoric dissolved organic matter (CDOM) in surface and pore waters adjacent to an oil well in a southern California salt marsh.

Science.gov (United States)

Bowen, Jennifer C; Clark, Catherine D; Keller, Jason K; De Bruyn, Warren J

2017-01-15

Chromophoric dissolved organic matter (CDOM) optical properties were measured in surface and pore waters as a function of depth and distance from an oil well in a southern California salt marsh. Higher fluorescence and absorbances in pore vs. surface waters suggest soil pore water is a reservoir of CDOM in the marsh. Protein-like fluorophores in pore waters at distinct depths corresponded to variations in sulfate depletion and Fe(II) concentrations from anaerobic microbial activity. These variations were supported by fluorescence indexes and are consistent with differences in optical molecular weight and aromaticity indicators. Fluorescence indices were consistent with autochthonous material of aquatic origin in surface waters, with more terrestrial, humified allochthonous material in deeper pore waters. CDOM optical properties were consistent with significantly enhanced microbial activity in regions closest to the oil well, along with a three-dimensional excitation/emission matrix fluorescence spectrum peak attributable to oil, suggesting anaerobic microbial degradation of oil. Copyright © 2016 Elsevier Ltd. All rights reserved.

Strategy to Identify and Test Putative Light-Sensitive Non-Opsin G-Protein-Coupled Receptors: A Case Study.

Science.gov (United States)

Faggionato, Davide; Serb, Jeanne M

2017-08-01

The rise of high-throughput RNA sequencing (RNA-seq) and de novo transcriptome assembly has had a transformative impact on how we identify and study genes in the phototransduction cascade of non-model organisms. But the advantage provided by the nearly automated annotation of RNA-seq transcriptomes may at the same time hinder the possibility for gene discovery and the discovery of new gene functions. For example, standard functional annotation based on domain homology to known protein families can only confirm group membership, not identify the emergence of new biochemical function. In this study, we show the importance of developing a strategy that circumvents the limitations of semiautomated annotation and apply this workflow to photosensitivity as a means to discover non-opsin photoreceptors. We hypothesize that non-opsin G-protein-coupled receptor (GPCR) proteins may have chromophore-binding lysines in locations that differ from opsin. Here, we provide the first case study describing non-opsin light-sensitive GPCRs based on tissue-specific RNA-seq data of the common bay scallop Argopecten irradians (Lamarck, 1819). Using a combination of sequence analysis and three-dimensional protein modeling, we identified two candidate proteins. We tested their photochemical properties and provide evidence showing that these two proteins incorporate 11-cis and/or all-trans retinal and react to light photochemically. Based on this case study, we demonstrate that there is potential for the discovery of new light-sensitive GPCRs, and we have developed a workflow that starts from RNA-seq assemblies to the discovery of new non-opsin, GPCR-based photopigments.

The Design of Dual-Emissive Composite Material [Zn2(HL)3]+@MOF-5 as Self-Calibrating Luminescent Sensors of Al3+ Ions and Monoethanolamine.

Science.gov (United States)

Wu, Meng-Meng; Wang, Jiao-Yang; Sun, Rui; Zhao, Cui; Zhao, Jiong-Peng; Che, Guang-Bo; Liu, Fu-Chen

2017-08-21

Introducing another chromophore into a luminescent MOF is a potential way to assembling novel dual-emissive luminescent materials. Putting the chromophore, for which luminescence can be enhanced by Zn 2+ ion, into MOF-5 by the "bottle around ship" strategy is a simple but efficient synthesis method to realize such dual-emissive materials. According to this strategy, a novel dual-emissive luminescent composite material [Zn 2 (HL) 3 ] + @MOF-5 was constructed by loading the [La 3 (HL) 2 L 2 (NO 3 ) 3 H 2 O] (1) (H 2 L = 7,7'-(ethane-1,1'-diyl)8-hydro-quinoline) into MOF-5, in which the [Zn 2 (HL) 3 ] + anions were transformed from 1 with the existence of Zn 2+ . The dual-emissive composite materials show excellent luminescence with two emissions of MOF-5 at 410 nm and [Zn 2 (HL) 3 ] + at 524 nm. Furthermore, by combining characteristics of MOF-5 and the guest chromophore, the composite material is highly selectively sensitive toward Al 3+ and monoethanolamine, which makes [Zn 2 (HL) 3 ] + @MOF-5 a potential self-calibrated fluorescence sensor.

Observation of undulation motion of lipid bilayers by neutron spin echo

International Nuclear Information System (INIS)

Yamada, Norifumi L.; Seto, Hideki; Hishida, Mafumi

2010-01-01

Aqueous solutions of synthesized phospholipids have been well investigated as model biomembranes. These lipids usually self-assemble into regular stacks of bilayers with a characteristic repeat distance on the order of nm, whereas real biomembrane exist as single bilayers. The key phenomenon in understanding the formation of single isolated bilayers in 'unbinding' of lipid bilayers, in which the inter-bilayer distance of lipid bilayers diverges by the steric interaction due to the membrane undulation. In this paper, we show some results of neutron spin-echo (NSE) experiments to investigate the effect of the steric interaction on unbinding and related phenomena. (author)

Chromophoric Dissolved Organic Matter across a Marine Distributed Biological Observatory in the Pacific Arctic Region

Science.gov (United States)

Berman, S. L.; Frey, K. E.; Shake, K. L.; Cooper, L. W.; Grebmeier, J. M.

2014-12-01

Dissolved organic matter (DOM) plays an important role in marine ecosystems as both a carbon source for the microbial food web (and thus a source of CO2 to the atmosphere) and as a light inhibitor in marine environments. The presence of chromophoric dissolved organic matter (CDOM; the optically active portion of total DOM) can have significant controlling effects on transmittance of sunlight through the water column and therefore on primary production as well as the heat balance of the upper ocean. However, CDOM is also susceptible to photochemical degradation, which decreases the flux of solar radiation that is absorbed. Knowledge of the current spatial and temporal distribution of CDOM in marine environments is thus critical for understanding how ongoing and future changes in climate may impact these biological, biogeochemical, and physical processes. We describe the quantity and quality of CDOM along five key productive transects across a developing Distributed Biological Observatory (DBO) in the Pacific Arctic region. The samples were collected onboard the CCGS Sir Wilfred Laurier in July 2013 and 2014. Monitoring of the variability of CDOM along transects of high productivity can provide important insights into biological and biogeochemical cycling across the region. Our analyses include overall concentrations of CDOM, as well as proxy information such as molecular weight, lability, and source (i.e., autochthonous vs. allochthonous) of organic matter. We utilize these field observations to compare with satellite-derived CDOM concentrations determined from the Aqua MODIS satellite platform, which ultimately provides a spatially and temporally continuous synoptic view of CDOM concentrations throughout the region. Examining the current relationships among CDOM, sea ice variability, biological productivity, and biogeochemical cycling in the Pacific Arctic region will likely provide key insights for how ecosystems throughout the region will respond in future

Biomembrane models and drug-biomembrane interaction studies: Involvement in drug design and development

Directory of Open Access Journals (Sweden)

R Pignatello

2011-01-01

Full Text Available Contact with many different biological membranes goes along the destiny of a drug after its systemic administration. From the circulating macrophage cells to the vessel endothelium, to more complex absorption barriers, the interaction of a biomolecule with these membranes largely affects its rate and time of biodistribution in the body and at the target sites. Therefore, investigating the phenomena occurring on the cell membranes, as well as their different interaction with drugs in the physiological or pathological conditions, is important to exploit the molecular basis of many diseases and to identify new potential therapeutic strategies. Of course, the complexity of the structure and functions of biological and cell membranes, has pushed researchers toward the proposition and validation of simpler two- and three-dimensional membrane models, whose utility and drawbacks will be discussed. This review also describes the analytical methods used to look at the interactions among bioactive compounds with biological membrane models, with a particular accent on the calorimetric techniques. These studies can be considered as a powerful tool for medicinal chemistry and pharmaceutical technology, in the steps of designing new drugs and optimizing the activity and safety profile of compounds already used in the therapy.

Estimation of chromophoric dissolved organic matter (CDOM) and photosynthetic activity of estuarine phytoplankton using a multiple-fixed-wavelength spectral fluorometer.

Science.gov (United States)

Goldman, Emily A; Smith, Erik M; Richardson, Tammi L

2013-03-15

The utility of a multiple-fixed-wavelength spectral fluorometer, the Algae Online Analyser (AOA), as a means of quantifying chromophoric dissolved organic matter (CDOM) and phytoplankton photosynthetic activity was tested using algal cultures and natural communities from North Inlet estuary, South Carolina. Comparisons of AOA measurements of CDOM to those by spectrophotometry showed a significant linear relationship, but increasing amounts of background CDOM resulted in progressively higher over-estimates of chromophyte contributions to a simulated mixed algal community. Estimates of photosynthetic activity by the AOA at low irradiance (≈ 80 μmol quanta m(-2) s(-1)) agreed well with analogous values from the literature for the chlorophyte, Dunaliella tertiolecta, but were substantially lower than previous measurements of the maximum quantum efficiency of photosystem II (F(v)/F(m)) in Thalassiosira weissflogii (a diatom) and Rhodomonas salina (a cryptophyte). When cells were exposed to high irradiance (1500 μmol quanta m(-2) s(-1)), declines in photosynthetic activity with time measured by the AOA mirrored estimates of cellular fluorescence capacity using the herbicide 3'-(3, 4-dichlorophenyl)-1',1'-dimethyl urea (DCMU). The AOA shows promise as a tool for the continuous monitoring of phytoplankton community composition, CDOM, and the group-specific photosynthetic activity of aquatic ecosystems. Copyright © 2012 Elsevier Ltd. All rights reserved.

Highly sensitive optical sensor that detects Hg"2"+ and Cu"2"+ by immobilizing dicarboxylate 1,5-diphenyl-3-thiocarbazone on surface functionalized PVA microspheres

International Nuclear Information System (INIS)

Bai, Xue; Gu, Haixin; Hua, Zulin; Dai, Zhangyan; Yang, Bei; Li, Yulong

2015-01-01

Highlights: • PVA microspheres were chosen as carrier and DDT groups were chosen as chromophores. • The DDT–PVA microspheres could detect Hg"2"+ and Cu"2"+ simultaneously within 120 s. • The DDT–PVA microspheres had excellent detection for Hg"2"+ and Cu"2"+ ions. • The DDT–PVA microspheres had preeminent selectivity and reusability. - Abstract: A novel optical sensor to detect Hg"2"+ and Cu"2"+ is prepared by immobilizing a synthesized dicarboxylate 1,5-diphenyl-3-thiocarbazone (DDT) group on functionalized polyvinyl alcohol (PVA) microspheres. This optical sensor is successfully fabricated by extensive characterization with Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Its colorimetric properties, selectivity, sensitivity, and reversibility are investigated as well. In this sensing system, DDT–PVA selectively recognized multiple heavy metal ions, as indicated by the changes in color from orange to scarlet for Hg"2"+ and from orange to gray for Cu"2"+. In particular, this optical sensor exhibits the most apparent color changes at pH levels of 12 and 2. Hence, Hg"2"+ and Cu"2"+ can be detected in aqueous solution at minimum detection limits of 0.053 and 0.132 μM, respectively, with a UV-vis spectrometer. Furthermore, the sensor can be regenerated by ethylene diamine tetraacetic acid and reused several times. Therefore, the optical sensor can detect Hg"2"+ because of its selectivity, sensitivity, and reversibility.

Constructing polyatomic potential energy surfaces by interpolating diabatic Hamiltonian matrices with demonstration on green fluorescent protein chromophore

Energy Technology Data Exchange (ETDEWEB)

Park, Jae Woo; Rhee, Young Min, E-mail: ymrhee@postech.ac.kr [Center for Self-assembly and Complexity, Institute for Basic Science (IBS), Pohang 790-784 (Korea, Republic of); Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 790-784 (Korea, Republic of)

2014-04-28

Simulating molecular dynamics directly on quantum chemically obtained potential energy surfaces is generally time consuming. The cost becomes overwhelming especially when excited state dynamics is aimed with multiple electronic states. The interpolated potential has been suggested as a remedy for the cost issue in various simulation settings ranging from fast gas phase reactions of small molecules to relatively slow condensed phase dynamics with complex surrounding. Here, we present a scheme for interpolating multiple electronic surfaces of a relatively large molecule, with an intention of applying it to studying nonadiabatic behaviors. The scheme starts with adiabatic potential information and its diabatic transformation, both of which can be readily obtained, in principle, with quantum chemical calculations. The adiabatic energies and their derivatives on each interpolation center are combined with the derivative coupling vectors to generate the corresponding diabatic Hamiltonian and its derivatives, and they are subsequently adopted in producing a globally defined diabatic Hamiltonian function. As a demonstration, we employ the scheme to build an interpolated Hamiltonian of a relatively large chromophore, para-hydroxybenzylidene imidazolinone, in reference to its all-atom analytical surface model. We show that the interpolation is indeed reliable enough to reproduce important features of the reference surface model, such as its adiabatic energies and derivative couplings. In addition, nonadiabatic surface hopping simulations with interpolation yield population transfer dynamics that is well in accord with the result generated with the reference analytic surface. With these, we conclude by suggesting that the interpolation of diabatic Hamiltonians will be applicable for studying nonadiabatic behaviors of sizeable molecules.

Absorption and Fluorescence Properties of Chromophoric Dissolved Organic Matter Produced by Algae.

Science.gov (United States)

Peng, Tong; Lu, Xiao-lan; Su, Rong-guo; Zhang, Dong-mei

2015-09-01

Four kinds of diatom (Chaetoceros curvisetus, Phaeodactylum tricornutum, Nitzschia closterium f. minutissima and Navicula halophile) and two kinds of dinoflagellates (Prorocentrum donghaiense and Gymnodinium) were cultured under laboratory conditions. Variations of optical properties of chromophoric dissolved organic matter (CDOM) were studied with absorption and fluorescence excitation-emission matrix spectroscopy(EEM) during growth of marine microalgae in incubation experiment. Absorption spectrum revealed absorption coefficient a(355) (CDOM absorption coefficients at 355 nm) of 6 kinds of marine microalgae above increased by 64.8%, 242.3%, 535.1%, 903.2%, 836% and 196.4%, respectively. Simultaneously, the absorption spectral slope (Sg), determined between 270 and 350 nm, representing the size of molecular weight of CDOM and humic-like composition, decreased by 8.7%, 34.6%, 39.4%, 53.1%, 46.7%, and 35.7%, respectively. Applying parallel factor analysis (PARAFAC) together with EEM got four components of CDOM: C1(Ex/Em=350(260) nm/450 nm), C2 (Ex/Em=260(430) nm/525 nm), C3 (Ex/Em=325 nm/400 nm) and C4(Ex/Em=275 nm/325 nm), which were relative to three humic-like and one protein-like fluorescent components of Nitzschia closterium f. minutissima and Navicula halophile. In incubation experiment, fluorescence intensity of these four components during growth of Nitzschia closterium f. minutissima increased by, respectively, 8.68, 24.9, 7.19 and 39.8 times, and those of Navicula halophile increased by 2.64, 0.07, 4.39 and 12.4 times, respectively. Significant relationships were found between the fluorescence intensity of four components of CDOM, a(355) and Sg. All results demonstrated that both content and molecular weight of CDOM produced by diatom and dinoflagellate studied in incubation experiment increased, but these two parameters changed more obviously of the diatom than those of dinoflagellate; the proportion of humic-like components in the composition of CDOM

Influence of environmental factors on spectral characteristic of chromophoric dissolved organic matter (CDOM) in Inner Mongolia Plateau, China

Science.gov (United States)

Wen, Z. D.; Song, K. S.; Zhao, Y.; Du, J.; Ma, J. H.

2015-06-01

Spectral characteristics of chromophoric dissolved organic matter (CDOM) were examined in conjunction with environmental factors in the waters of 22 rivers and 26 terminal waters in Hulun Buir plateau, northeast China. Dissolved organic carbon (DOC), total nitrogen (TN), and total phosphorous (TP) were significantly higher in terminal waters than rivers waters (p CDOM absorption in river waters was significantly lower than terminal waters (p CDOM in river waters had higher aromaticity, molecular weight, and vascular plant contribution than in terminal waters. Furthermore, results showed that DOC concentration, CDOM light absorption, and the proportion of autochthonous sources of CDOM in plateau waters were all higher than in other freshwater rivers reported in the literature. The strong evapoconcentration, intense ultraviolet irradiance and landscape features of Hulun Buir plateau may be responsible for the above phenomenon. Redundancy analysis (RDA) indicated that the environmental variables TSM, TN, and EC had a strong correlation with light absorption characteristics, followed by TDS and chlorophyll a. In most sampling locations, CDOM was the dominant non-water light-absorbing substance. Light absorption by non-algal particles often exceeded that by phytoplankton in the plateau waters. Study of these optical-physicochemical correlations is helpful in the evaluation of the potential influence of water quality factors on non-water light absorption in cold plateau water environments. And the study on organic carbon in plateau lakes had a vital contribution to global carbon balance estimation.

Characterization of chromophoric dissolved organic matter and relationships among PARAFAC components and water quality parameters in Heilongjiang, China.

Science.gov (United States)

Cui, Hongyang; Shi, Jianhong; Qiu, Linlin; Zhao, Yue; Wei, Zimin; Wang, Xinglei; Jia, Liming; Li, Jiming

2016-05-01

Chromophoric dissolved organic matter (CDOM) is an important optically active substance that can transports nutrients and pollutants from terrestrial to aquatic systems. Additionally, it is used as a measure of water quality. To investigate the source and composition of CDOM, we used chemical and fluorescent analyses to characterize CDOM in Heilongjiang. The composition of CDOM can be investigated by excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC). PARAFAC identified four individual components that were attributed to microbial humic-like (C1) and terrestrial humic-like (C2-4) in water samples collected from the Heilongjiang River. The relationships between the maximum fluorescence intensities of the four PARAFAC components and the water quality parameters indicate that the dynamic of the four components is related to nutrients in the Heilongjiang River. The relationships between the fluorescence component C3 and the biochemical oxygen demand (BOD5) indicates that component C3 makes a great contribution to BOD5 and it can be used as a carbon source for microbes in the Heilongjiang River. Furthermore, the relationships between component C3, the particulate organic carbon (POC), and the chemical oxygen demand (CODMn) show that component C3 and POC make great contributions to BOD5 and CODMn. The use of these indexes along with PARAFAC results would be of help to characterize the co-variation between the CDOM and water quality parameters in the Heilongjiang River.

Drug-model membrane interactions

International Nuclear Information System (INIS)

Deniz, Usha K.

1994-01-01

In the present day world, drugs play a very important role in medicine and it is necessary to understand their mode of action at the molecular level, in order to optimise their use. Studies of drug-biomembrane interactions are essential for gaining such as understanding. However, it would be prohibitively difficult to carry out such studies, since biomembranes are highly complex systems. Hence, model membranes (made up of these lipids which are important components of biomembranes) of varying degrees of complexity are used to investigate drug-membrane interactions. Bio- as well as model-membranes undergo a chain melting transition when heated, the chains being in a disordered state above the transition point, T CM . This transition is of physiological importance since biomembranes select their components such that T CM is less than the ambient temperature but not very much so, so that membrane flexibility is ensured and porosity, avoided. The influence of drugs on the transition gives valuable clues about various parameters such as the location of the drug in the membrane. Deep insights into drug-membrane interactions are obtained by observing the effect of drugs on membrane structure and the mobilities of the various groups in lipids, near T CM . Investigation of such changes have been carried out with several drugs, using techniques such as DSC, XRD and NMR. The results indicate that the drug-membrane interaction not only depends on the nature of drug and lipids but also on the form of the model membrane - stacked bilayer or vesicles. The light that these results shed on the nature of drug-membrane interactions is discussed. (author). 13 refs., 13 figs., 1 tab

Waste water biological purification plants of dairy products industry and energy management

Science.gov (United States)

Stepanov, Sergey; Solkina, Olga; Stepanov, Alexander; Zhukova, Maria

2017-10-01

The paper presents results of engineering and economical comparison of waste water biological purification plants of dairy products industry. Three methods of purification are compared: traditional biological purification with the use of secondary clarifiers and afterpurification through granular-bed filters, biomembrane technology and physical-and-chemical treatment together with biomembrane technology for new construction conditions. The improvement of the biological purification technology using nitro-denitrification and membrane un-mixing of sludge mixture is a promising trend in this area. In these calculations, an energy management which is widely applied abroad was used. The descriptions of the three methods are illustrated with structural schemes. Costs of equipment and production areas are taken from manufacturers’ data. The research is aimed at an engineering and economical comparison of new constructions of waste water purification of dairy products industry. The experiment demonstrates advantages of biomembrane technology in waste water purification. This technology offers prospects of 122 million rubles cost saving during 25 years of operation when compared with of the technology of preparatory reagent flotation and of 13.7 million rubles cost saving compared to the option of traditional biological purification.

Coupled sensitizer-catalyst dyads: electron-transfer reactions in a perylene-polyoxometalate conjugate.

Science.gov (United States)

Odobel, Fabrice; Séverac, Marjorie; Pellegrin, Yann; Blart, Errol; Fosse, Céline; Cannizzo, Caroline; Mayer, Cédric R; Elliott, Kristopher J; Harriman, Anthony

2009-01-01

Ultrafast discharge of a single-electron capacitor: A variety of intramolecular electron-transfer reactions are apparent for polyoxometalates functionalized with covalently attached perylene monoimide chromophores, but these are restricted to single-electron events. (et=electron transfer, cr=charge recombination, csr=charge-shift reaction, PER=perylene, POM=polyoxometalate).A new strategy is introduced that permits covalent attachment of an organic chromophore to a polyoxometalate (POM) cluster. Two examples are reported that differ according to the nature of the anchoring group and the flexibility of the linker. Both POMs are functionalized with perylene monoimide units, which function as photon collectors and form a relatively long-lived charge-transfer state under illumination. They are reduced to a stable pi-radical anion by electrolysis or to a protonated dianion under photolysis in the presence of aqueous triethanolamine. The presence of the POM opens up an intramolecular electron-transfer route by which the charge-transfer state reduces the POM. The rate of this process depends on the molecular conformation and appears to involve through-space interactions. Prior reduction of the POM leads to efficient fluorescence quenching, again due to intramolecular electron transfer. In most cases, it is difficult to resolve the electron-transfer products because of relatively fast reverse charge shift that occurs within a closed conformer. Although the POM can store multiple electrons, it has not proved possible to use these systems as molecular-scale capacitors because of efficient electron transfer from the one-electron-reduced POM to the excited singlet state of the perylene monoimide.

Second-order nonlinear optical properties of composite material of an azo-chromophore with a tricyanodiphenyl acceptor in a poly(styrene-co-methyl methacrylate) matrix

Science.gov (United States)

Shelkovnikov, Vladimir; Selivanova, Galina; Lyubas, Gleb; Korotaev, Sergey; Shundrina, Inna; Tretyakov, Evgeny; Zueva, Ekaterina; Plekhanov, Alexander; Mikerin, Sergey; Simanchuk, Andrey

2017-07-01

The composite material of new synthesized 4-((4-(N,N-n-dibutylamino) phenyl)diazenyl)-biphenyl-2,3,4-tricarbonitrile (GAS dye) in commercial poly(styrene-co-methyl methacrylate) (PSMMA) was prepared, poled and its nonlinear optical properties compared with DR1 dye were studied. High thermal stability of the composite material was revealed, and the maximal concentration of the chromophore was found to reach ∼20 wt%. The dipole moment, polarizability tensor, and first hyperpolarizability tensor of the investigated dyes were calculated by within the framework of the coupled perturbed density functional theory. A nanosecond second-harmonic generation Maker fringes technique was used which is capable of providing the magnitude of the second-order nonlinearity of optical materials at a wavelength of 1064 nm. For the tested GAS-PSMMA composite material, maximal coefficient d33 was found to be 50 pm/V. The nonlinear optical response, which was achieved here, shows possible usefulness of the GAS dye as a component for molecular design of nonlinear-optical materials with advanced characteristics.

The potential applications of real-time monitoring of water quality in a large shallow lake (Lake Taihu, China) using a chromophoric dissolved organic matter fluorescence sensor.

Science.gov (United States)

Niu, Cheng; Zhang, Yunlin; Zhou, Yongqiang; Shi, Kun; Liu, Xiaohan; Qin, Boqiang

2014-06-30

This study presents results from field surveys performed over various seasons in a large, eutrophic, shallow lake (Lake Taihu, China) using an in situ chromophoric dissolved organic matter (CDOM) fluorescence sensor as a surrogate for other water quality parameters. These measurements identified highly significant empirical relationships between CDOM concentration measured using the in situ fluorescence sensor and CDOM absorption, fluorescence, dissolved organic carbon (DOC), chemical oxygen demand (COD) and total phosphorus (TP) concentrations. CDOM concentration expressed in quinine sulfate equivalent units, was highly correlated with the CDOM absorption coefficient (r(2) = 0.80, p CDOM concentration measured using the in situ fluorescence sensor could act as a substitute for the CDOM absorption coefficient and fluorescence measured in the laboratory. Similarly, CDOM concentration was highly correlated with DOC concentration (r(2) = 0.68, p CDOM fluorescence sensor measurements could be a proxy for DOC concentration. In addition, significant positive correlations were found between laboratory CDOM absorption coefficients and COD (r(2) = 0.83, p CDOM fluorescence sensor.

Why is the Great Red Spot Red? The Exogenic, Photolytic Origin of the UV/Blue-Absorbing Chromophores of Jupiter’s Great Red Spot as Determined by Spectral Analysis of Cassini/VIMS Observations using New Laboratory Optical Coefficients

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Baines, Kevin H.; Carlson, Robert W.; Momary, Thomas W.

2014-11-01

For centuries, a major question for Jupiter has been: Why is the Great Red Spot red? In particular, two major theories have been proposed: (1) that the coloring is due to photolytic processes in the upper cloud layer, or (2) it is due to the upwellimg of red materials processed relatively deep within the troposphere. Utilizing indices of refraction for red choromophores generated by the photolysis of ammonia and acetylene in the laboratory, we present results of a spectral analysis of the core of Jupiter’s Great Red Spot (GRS) as observed by the visual channel of the Cassini/Visual Infrared Mapping Spectrometer (VIMS). Consistent with the physical origin of such laboratory-generated chromophores in Jupiter - i.e., by solar-driven UV photolysis within the upper levels of the GRS structure near ~ 0.3 bar - our spectral modeling yields satisfactory results for such Mie scattering chromophores only when they are confined to the upper ~ 100 mbar of the GRS. Beneath this reddish upper cloud layer, our models indicate that the remainder of the GRS cloud - assumed to extend down to at least the ammonia condensation level near 0.6 bar - must be relatively spectrally bright throughout the UV-red spectrum; that is, they must be predominantly a whitish or grey color at depth. Thus, our 0.35-1.0 micron spectral models of the GRS are inconsistent with an endogenic origin of the reddish coloring originating in the depths of Jupiter, but are consistent with a photolytic origin due to the photolysis of ammonia and acetylene in the upper troposphere.

Development of a near-infrared spectroscopy instrument for applications in urology.

Science.gov (United States)

Macnab, Andrew J; Stothers, Lynn

2008-10-01

Near infrared spectroscopy (NIRS) is an established technology using photons of light in the near infrared spectrum to monitor changes in tissue of naturally occurring chromophores, including oxygenated and deoxygenated hemoglobin. Technology and methodology have been validated for measurement of a range of physiologic parameters. NIRS has been applied successfully in urology research; however current instruments are designed principally for brain and muscle study. To describe development of a NIRS instrument specifically designed for monitoring changes in chromophore concentration in the bladder detrusor in real time, to facilitate research to establish the role of this non-invasive technology in the evaluation of patients with voiding dysfunction The portable continuous wave NIRS instrument has a 3 laser diode light source (785, 808 and 830 nanometers), fiber optic cables for light transmission, a self adhesive patient interface patch with an emitter and sensor, and software to detect the difference between the light transmitted and received by the instrument. Software incorporated auto-attenuates the optical signals and converts raw optical data into chromophore concentrations displayed graphically. The prototype was designed, tested, and iteratively developed to achieve optimal suprapubic transcutaneous monitoring of the detrusor in human subjects during bladder filling and emptying. Evaluation with simultaneous invasive urodynamic measurement in men and women indicates good specificity and sensitivity of NIRS chromophore concentration changes by receiver operator curve analysis, and correlation between NIRS data and urodynamic pressures. Urological monitoring with this NIRS instrument is feasible and generates data of potential diagnostic value.

Sources and transformations of dissolved lignin phenols and chromophoric dissolved organic matter in Otsuchi Bay, Japan

Directory of Open Access Journals (Sweden)

Chia-Jung eLu

2016-06-01

Full Text Available Dissolved lignin phenols and optical properties of dissolved organic matter (DOM were measured to investigate the sources and transformations of terrigenous DOM (tDOM in Otsuchi Bay, Japan. Three rivers discharge into the bay, and relatively high values of syringyl:vanillyl phenols (0.73 ± 0.07 and cinnamyl:vanillyl phenols (0.33 ± 0.10 indicated large contributions of non-woody angiosperm tissues to lignin and tDOM. The physical mixing of river and seawater played an important role in controlling the concentrations and distributions of lignin phenols and chromophoric DOM (CDOM optical properties in the bay. Lignin phenol concentrations and the CDOM absorption coefficient at 350 nm, a(350, were strongly correlated in river and bay waters. Measurements of lignin phenols and CDOM in bay waters indicated a variety of photochemical and biological transformations of tDOM, including oxidation reactions, photobleaching and a decrease in molecular weight. Photodegradation and biodegradation of lignin and CDOM were investigated in decomposition experiments with river water and native microbial assemblages exposed to natural sunlight or kept in the dark. There was a rapid and substantial removal of lignin phenols and CDOM during the first few days in the light treatment, indicating transformations of tDOM and CDOM can occur soon after discharge of buoyant river water into the bay. The removal of lignin phenols was slightly greater in the dark (34% than in the light (30% during the remaining 59 days of the incubation. Comparison of the light and dark treatments indicated biodegradation was responsible for 67% of total lignin phenol removal during the 62-day incubation exposed to natural sunlight, indicating biodegradation is a dominant removal process in Otsuchi Bay.

The relationship of chromophoric dissolved organic matter parallel factor analysis fluorescence and polycyclic aromatic hydrocarbons in natural surface waters.

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Li, Sijia; Chen, Ya'nan; Zhang, Jiquan; Song, Kaishan; Mu, Guangyi; Sun, Caiyun; Ju, Hanyu; Ji, Meichen

2018-01-01

Polycyclic aromatic hydrocarbons (PAHs), a large group of persistent organic pollutants (POPs), have caused wide environmental pollution and ecological effects. Chromophoric dissolved organic matter (CDOM), which consists of complex compounds, was seen as a proxy of water quality. An attempt was made to understand the relationships of CDOM absorption parameters and parallel factor analysis (PARAFAC) components with PAHs under seasonal variation in the riverine, reservoir, and urban waters of the Yinma River watershed in 2016. These different types of water bodies provided wide CDOM and PAHs concentration ranges with CDOM absorption coefficients at a wavelength of 350 nm (a CDOM (350)) of 1.17-20.74 m -1 and total PAHs of 0-1829 ng/L. CDOM excitation-emission matrix (EEM) presented two fluorescent components, e.g., terrestrial humic-like (C1) and tryptophan-like (C2) were identified using PARAFAC. Tryptophan-like associated protein-like fluorescence often dominates the EEM signatures of sewage samples. Our finding is that seasonal CDOM EEM-PARAFAC and PAHs concentration showed consistent tendency indicated that PAHs were un-ignorable pollutants. However, the disparities in seasonal CDOM-PAH relationships relate to the similar sources of CDOM and PAHs, and the proportion of PAHs in CDOM. Overlooked and poorly appreciated, quantifying the relationship between CDOM and PAHs has important implications, because these results simplify ecological and health-based risk assessment of pollutants compared to the traditional chemical measurements.

Characterization of light absorption by chromophoric dissolved organic matter (CDOM) in the upper layer of the Red Sea

Science.gov (United States)

Kheireddine, Malika; Ouhssain, Mustapha; Calleja, Maria Ll.; Morán, Xosé Anxelu G.; Sarma, Y. V. B.; Tiwari, Surya P.; Jones, Burton H.

2018-03-01

The absorption coefficient of chromophoric dissolved organic matter (CDOM) is a major variable used in developing robust bio-optical models and understanding biogeochemical processes. Over the last decade, the optical properties of CDOM in the open sea have been intensely studied. However, their variations in clear water are poorly documented, particularly in the Red Sea, owing to the absence of in situ measurements. We performed several cruises in the Red Sea to investigate the spatial distribution of the absorption coefficient of CDOM. The spectral absorption coefficients were determined from 400 nm to 740 nm using a WETLabs ac-s hyper-spectral spectrophotometer. In general, we found a latitudinal gradient in the CDOM absorption coefficient at 443 nm (aCDOM(443)) from south to north that is likely influenced by the exchange of water through the strait of Bab-el-Mandeb and the thermohaline circulation of the Red Sea. However, high aCDOM(443) values were observed in the northern Red Sea due to the existence of a sub-mesoscale feature that may induce an increase in phytoplankton production and lead to CDOM production. The aCDOM(443) covaried with the chlorophyll a concentration ([Chl a],) despite a high scatter. Furthermore, the aCDOM(443) for a given [Chl a] concentration was higher than those predicted by global ocean bio-optical models. This study advances our understanding of CDOM concentration in the Red Sea and may help improve the accuracy of the algorithms used to obtain CDOM absorption from ocean color.

Characterization of light absorption by chromophoric dissolved organic matter (CDOM) in the upper layer of the Red Sea

KAUST Repository

Kheireddine, Malika

2018-02-07

The absorption coefficient of chromophoric dissolved organic matter (CDOM) is a major variable used in developing robust bio‐optical models and understanding biogeochemical processes. Over the last decade, the optical properties of CDOM in the open sea have been intensely studied. However, their variations in clear water are poorly documented, particularly in the Red Sea, owing to the absence of in situ measurements. We performed several cruises in the Red Sea to investigate the spatial distribution of the absorption coefficient of CDOM. The spectral absorption coefficients were determined from 400nm to 740nm using a WETLabs ac-s hyper-spectral spectrophotometer. In general, we found a latitudinal gradient in the CDOM absorption coefficient at 443nm (aCDOM(443)) from south to north that is likely influenced by the exchange of water through the strait of Bab-el-Mandeb and the thermohaline circulation of the Red Sea. However, high aCDOM(443) values were observed in the northern Red Sea due to the existence of a sub-mesoscale feature that may induce an increase in phytoplankton production and lead to CDOM production. The aCDOM(443) covaried with the chlorophyll a concentration ([Chl a],) despite a high scatter. Furthermore, the aCDOM(443) for a given [Chl a] concentration was higher than those predicted by global ocean bio-optical models. This study advances our understanding of CDOM concentration in the Red Sea and may help improve the accuracy of the algorithms used to obtain CDOM absorption from ocean color.

Seasonal dynamics of light absorption by chromophoric dissolved organic matter (CDOM) in the NW Mediterranean Sea (BOUSSOLE site)

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Organelli, Emanuele; Bricaud, Annick; Antoine, David; Matsuoka, Atsushi

2014-09-01

We analyze a two-year time-series of chromophoric dissolved organic matter (CDOM) light absorption measurements in the upper 400 m of the water column at the BOUSSOLE site in the NW Mediterranean Sea. The seasonal dynamics of the CDOM light absorption coefficients at 440 nm (acdom(440)) is essentially characterized by (i) subsurface maxima forming in spring and progressively reinforcing throughout summer, (ii) impoverishment in the surface layer throughout summer and (iii) vertical homogeneity in winter. Seasonal variations of the spectral dependence of CDOM absorption, as described by the exponential slope value (Scdom), are characterized by highest values in summer and autumn at the surface and low values at the depths of acdom(440) subsurface maxima or just below them. Variations of acdom(440) are likely controlled by microbial digestion of phytoplankton cells, which leads to CDOM production, and by photochemical destruction (photobleaching), which leads to CDOM degradation. Photobleaching is also the main driver of Scdom variations. Consistently with previous observations, acdom(440) for a given chlorophyll a concentration is higher than expected from Case I waters bio-optical models. The total non-water light absorption budget shows that surface waters at the BOUSSOLE site are largely dominated by CDOM during all seasons but the algal bloom in March and April. These results improve the knowledge of CDOM absorption dynamics in the Mediterranean Sea, which is scarcely documented. In addition, they open the way to improved algorithms for the retrieval of CDOM absorption from field or satellite radiometric measurements.

Antifungal activity of fluconazole-loaded natural rubber latex against Candida albicans.

Science.gov (United States)

Yonashiro Marcelino, Mônica; Azevedo Borges, Felipe; Martins Costa, Ana Flávia; de Lacorte Singulani, Junya; Ribeiro, Nathan Vinícius; Barcelos Costa-Orlandi, Caroline; Garms, Bruna Cambraia; Soares Mendes-Giannini, Maria José; Herculano, Rondinelli Donizetti; Fusco-Almeida, Ana Marisa

2018-03-01

This work aimed to produce a membrane based on fluconazole-loaded natural rubber latex (NRL), and study their interaction, drug release and antifungal susceptibility against Candida albicans. Fluconazole-loaded NRL membrane was obtained by casting method. The Fourier Transform Infrared Spectroscopy showed no modifications either in NRL or fluconazole after the incorporation. Mechanical test presented low Young's modulus and high strain, indicating the membranes have sufficient elasticity for biomedical application. The bio-membrane was able to release the drug and inhibit the growth of C. albicans as demonstrated by disk diffusion and macrodilution assays. The biomembrane was able to release fluconazole and inhibit the growth of C. albicans, representing a promising biomaterial for skin application.

Spatial and seasonal changes in optical properties of autochthonous and allochthonous chromophoric dissolved organic matter in a stratified mountain lake.

Science.gov (United States)

Bracchini, Luca; Dattilo, Arduino Massimo; Hull, Vincent; Loiselle, Steven Arthur; Nannicini, Luciano; Picchi, Maria Pia; Ricci, Maso; Santinelli, Chiara; Seritti, Alfredo; Tognazzi, Antonio; Rossi, Claudio

2010-03-01

In this study, we present results on seasonal and spatial changes in CDOM absorption and fluorescence (fCDOM) in a deep mountain lake (Salto Lake, Italy). A novel approach was used to describe the shape of CDOM absorption between 250-700 nm (distribution of the spectral slope, S(lambda)) and a new fluorescence ratio is used to distinguish between humic and amino acid-like components. Solar ultraviolet irradiance, dissolved organic carbon (DOC), DOM fluorescence and absorption measurements were analysed and compared to other physicochemical parameters. We show that in the UV-exposed mixed layer: (i) fluorescence by autochthonous amino acid-like CDOM, (ii) values of S(lambda) across UV-C and UV-B wavebands increased during the summer months, whereas (i) average molar absorption coefficient and (ii) fluorescence by allochthonous humic CDOM decreased. In the unexposed deep layer of the water column (and in the entire water column in winter), humic-like CDOM presented high values of molar absorption coefficients and low values of S(lambda). UV attenuation coefficients correlated with both chlorophyll a concentrations and CDOM absorption. In agreement with changes in CDOM, minimal values in UV attenuation were found in summer. The S(lambda) curve was used as a signature of the mixture between photobleached and algal-derived CDOM with respect to the unexposed chromophoric dissolved compounds in this thermal stratified lake. Furthermore, S(lambda) curves were useful to distinguish between low and high molecular weight CDOM.

Influence of environmental factors on spectral characteristics of chromophoric dissolved organic matter (CDOM) in Inner Mongolia Plateau, China

Science.gov (United States)

Wen, Z. D.; Song, K. S.; Zhao, Y.; Du, J.; Ma, J. H.

2016-02-01

Spectral characteristics of chromophoric dissolved organic matter (CDOM) were examined in conjunction with environmental factors in the waters of rivers and terminal lakes within the Hulun Buir plateau, northeast China. Dissolved organic carbon (DOC), total nitrogen (TN), and total phosphorous (TP) were significantly higher in terminal lakes than rivers waters (p CDOM absorption in river waters was significantly lower than terminal lakes. Analysis of the ratio of absorption at 250 to 365 nm (E250 : 365), specific ultraviolet (UV) absorbance (SUVA254), and the spectral slope ratio (Sr) indicated that CDOM in river waters had higher aromaticity, molecular weight, and vascular plant contribution than in terminal lakes. Furthermore, results showed that DOC concentration, CDOM light absorption, and the proportion of autochthonous sources of CDOM in plateau waters were all higher than in other freshwater rivers reported in the literature. The strong evapoconcentration, intense ultraviolet irradiance, and landscape features of the Hulun Buir plateau may be responsible for the above phenomenon. Redundancy analysis (RDA) indicated that the environmental variables total suspended matter (TSM), TN, and electrical conductivity (EC) had a strong correlation with light absorption characteristics, followed by total dissolved solid (TDS) and chlorophyll a. In most sampling locations, CDOM was the dominant non-water light-absorbing substance. Light absorption by non-algal particles often exceeded that by phytoplankton in the plateau waters. Study of these optical-physicochemical correlations is helpful in the evaluation of the potential influence of water quality factors on non-water light absorption in cold plateau water environments. The construction of a correlation between DOC concentration and water quality factors may help contribute to regional estimates of carbon sources and fate for catchment carbon budget assessments.

The Potential Applications of Real-Time Monitoring of Water Quality in a Large Shallow Lake (Lake Taihu, China) Using a Chromophoric Dissolved Organic Matter Fluorescence Sensor

Science.gov (United States)

Niu, Cheng; Zhang, Yunlin; Zhou, Yongqiang; Shi, Kun; Liu, Xiaohan; Qin, Boqiang

2014-01-01

This study presents results from field surveys performed over various seasons in a large, eutrophic, shallow lake (Lake Taihu, China) using an in situ chromophoric dissolved organic matter (CDOM) fluorescence sensor as a surrogate for other water quality parameters. These measurements identified highly significant empirical relationships between CDOM concentration measured using the in situ fluorescence sensor and CDOM absorption, fluorescence, dissolved organic carbon (DOC), chemical oxygen demand (COD) and total phosphorus (TP) concentrations. CDOM concentration expressed in quinine sulfate equivalent units, was highly correlated with the CDOM absorption coefficient (r2 = 0.80, p CDOM concentration measured using the in situ fluorescence sensor could act as a substitute for the CDOM absorption coefficient and fluorescence measured in the laboratory. Similarly, CDOM concentration was highly correlated with DOC concentration (r2 = 0.68, p CDOM fluorescence sensor measurements could be a proxy for DOC concentration. In addition, significant positive correlations were found between laboratory CDOM absorption coefficients and COD (r2 = 0.83, p CDOM fluorescence sensor. PMID:24984060

Study of influencing factors to chromophoric dissolved organic matter absorption properties from fluorescence features in Taihu lake in autumn

Directory of Open Access Journals (Sweden)

Chuang-Chun Huang

2013-04-01

Full Text Available In order to identify the components of chromophoric dissolved organic matter (CDOM, confirm the influence of components to the absorption coefficient of CDOM (aCDOM, and estimate aCDOM from fluorescence spectra, fluorescence and optical measurements of CDOM were carried out in November 2008. The results indicate that, the primary component of CDOM is humic-like. The secondary component is tryptophan-like, which is the product of phytoplankton and aquatic debris rather than the wastewater treatment drainaged from city. In this study, six fluorophores with multiple excitation-emission matrices (EEMs peaks (A, B, C, N, M, T were identified according to the parallel factor analysis (PARAFAC. The average contribution of each component to the CDOM is 19.93, 18.82, 16.88, 16.39, 12.26, and 15.72%, respectively. Red Shifted phenomenon will happen with the increase of fluorescence intensity for ultraviolet and terrestrially humic-like. Conversely, marine humic-like will appear Reverse Red Shifted with the increase of fluorescence intensity. The primary contributor to the shoulder value of CDOM’s absorption coefficient at 275 nm is phytoplankton productivity, followed by marine humic-like. The main contributors to the shoulder shape are UV humic-like and phytoplankton productivity, followed by marine humic-like and tryptophan-like. A strong correlation between CDOM absorption and fluorescence intensity at emission wavelength of 424 nm and excitation wavelength ranging from 280 to 360 nm was found. The absorption coefficient can be retrieved successfully from the same excitation wavelength’s fluorescence intensity by an exponential model.

Role of microgel formation in scavenging of chromophoric dissolved organic matter and heavy metals in a river-sea system

International Nuclear Information System (INIS)

Shiu, Ruei-Feng; Lee, Chon-Lin

2017-01-01

Highlights: • Different types of DOC polymers forming microgel were compared. • The assembly effectiveness of marine DOC was much higher than riverine DOC. • Types and sources of DOC polymers may control the aquatic microgel abundance. • An alternative route for CDOM and heavy metals removal is presented. • Ecological risk and fate assessments of pollutants may consider the microgel phase. - Abstract: We use riverine and marine dissolved organic carbon (DOC) polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit very much difference in size and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of hazardous materials.

Role of microgel formation in scavenging of chromophoric dissolved organic matter and heavy metals in a river-sea system

Energy Technology Data Exchange (ETDEWEB)

Shiu, Ruei-Feng [Department of Marine Environment and Engineering, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Lee, Chon-Lin, E-mail: linnohc@fac.nsysu.edu.tw [Department of Marine Environment and Engineering, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Department of Public Health, College of Health Science, Kaohsiung Medical University, Kaohsiung, Taiwan (China); Asia-Pacific Ocean Research Center, National Sun Yat-sen University, Kaohsiung, Taiwan (China); Research Center for Environmental Medicine, Kaohsiung Medical University, Kaohsiung, Taiwan (China)

2017-04-15

Highlights: • Different types of DOC polymers forming microgel were compared. • The assembly effectiveness of marine DOC was much higher than riverine DOC. • Types and sources of DOC polymers may control the aquatic microgel abundance. • An alternative route for CDOM and heavy metals removal is presented. • Ecological risk and fate assessments of pollutants may consider the microgel phase. - Abstract: We use riverine and marine dissolved organic carbon (DOC) polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit very much difference in size and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of hazardous materials.

Highly sensitive optical sensor that detects Hg{sup 2+} and Cu{sup 2+} by immobilizing dicarboxylate 1,5-diphenyl-3-thiocarbazone on surface functionalized PVA microspheres

Energy Technology Data Exchange (ETDEWEB)

Bai, Xue, E-mail: baixue@hhu.edu.cn; Gu, Haixin; Hua, Zulin; Dai, Zhangyan; Yang, Bei; Li, Yulong

2015-11-15

Highlights: • PVA microspheres were chosen as carrier and DDT groups were chosen as chromophores. • The DDT–PVA microspheres could detect Hg{sup 2+} and Cu{sup 2+} simultaneously within 120 s. • The DDT–PVA microspheres had excellent detection for Hg{sup 2+} and Cu{sup 2+} ions. • The DDT–PVA microspheres had preeminent selectivity and reusability. - Abstract: A novel optical sensor to detect Hg{sup 2+} and Cu{sup 2+} is prepared by immobilizing a synthesized dicarboxylate 1,5-diphenyl-3-thiocarbazone (DDT) group on functionalized polyvinyl alcohol (PVA) microspheres. This optical sensor is successfully fabricated by extensive characterization with Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Its colorimetric properties, selectivity, sensitivity, and reversibility are investigated as well. In this sensing system, DDT–PVA selectively recognized multiple heavy metal ions, as indicated by the changes in color from orange to scarlet for Hg{sup 2+} and from orange to gray for Cu{sup 2+}. In particular, this optical sensor exhibits the most apparent color changes at pH levels of 12 and 2. Hence, Hg{sup 2+} and Cu{sup 2+} can be detected in aqueous solution at minimum detection limits of 0.053 and 0.132 μM, respectively, with a UV-vis spectrometer. Furthermore, the sensor can be regenerated by ethylene diamine tetraacetic acid and reused several times. Therefore, the optical sensor can detect Hg{sup 2+} because of its selectivity, sensitivity, and reversibility.

New technology of bio-heap leaching uranium ore and its industrial application in Ganzhou uranium mine

International Nuclear Information System (INIS)

Fan Baotuan; Meng Yunsheng; Liu Jian; Meng Jin; Li Weicai; Xiao Jinfeng; Chen Sencai; Du Yuhai; Huang Bin

2006-10-01

Bioleaching mechanism of uranium ore is discussed. Incubation and selection of new strain, biomembrane oxidizing tank--a kind of new equipment for bacteria culture and oxidation regeneration of leaching agent are also introduced. The results of industrial experiment and industrial production are summarized. Compared with conventional heap leaching, bioleaching period and acid amount are reduced, oxidant and leaching agent are saved, and uranium concentration in leaching solution is increased. It is the first time to realize industrial production by bio-heap leaching in Chinese uranium mine. New equipment-biomembrane oxidizing tank give the basis of bio-heap leaching industrial application. Bio-heap leaching process is an effective technique to reform technique of uranium mine and extract massive low-content uranium ore in China. (authors)

Identification of quenchers of photoexcited States as novel agents for skin photoprotection.

Science.gov (United States)

Wondrak, Georg T; Jacobson, Myron K; Jacobson, Elaine L

2005-02-01

Photooxidative stress is a key mechanism in UVA-induced skin photodamage. Photoexcited states of endogenous UVA chromophores such as porphyrins, melanin precursors, and cross-link-fluorophores of skin collagen exert skin photodamage by direct reaction with substrate molecules (type I photosensitization) or molecular oxygen (type II), leading to formation of reactive oxygen species. Based on our previous research on the role of photoexcited states of endogenous skin chromophores as sensitizers of photooxidative stress, we describe here the identification of a novel class of chemopreventive agents for topical skin photoprotection: quenchers of photoexcited states (QPES). QPES compounds antagonize the harmful excited state chemistry of endogenous sensitizers by physical quenching, facilitating the harmless return of the sensitizer excited state to the electronic ground state by energy dissipation. To identify QPES compounds suitable for development, we designed a primary screening assay based on QPES suppression of photosensitized plasmid cleavage using conditions that exclude antioxidants. This screen is followed with a screen to test for nonsacrificial quenching of dye-sensitized singlet oxygen ((1)O(2)) formation by electron paramagnetic resonance detection of 2,2,6,6-tetramethyl-piperidine-1-oxyl, a stable free radical indicative of (1)O(2) formation. These initial screens identified a pyrrolidine pharmacophore with pronounced QPES activity, and l-proline and other noncytotoxic proline derivatives containing this pharmacophore were then screened for efficacy in cellular models of sensitized photodamage. These compounds showed QPES protection against dye-sensitized and psoralen-UVA-induced apoptosis and suppression of proliferation in cultured human skin keratinocytes and fibroblasts. Furthermore, QPES photoprotection of reconstructed full thickness human skin exposed to solar simulated light has been demonstrated.

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African Journals Online (AJOL)

"Laboratories for Biomembrane Research and Biotechnology, Biochemistry Department, College of Medicine, Univer- sity of Ibadan ... stable structures called advanced glycated end-prod- ... in a population of normal red cells is covalently.

Journal of Biosciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

2007-03-22

Mar 22, 2007 ... Adaptation; Arabidopsis; molecular response to stress; stressors: cold, forst, ... only the biomembranes in ripening seeds (late embryogenesis abundant ... and roots during cold adaptation, especially in drought tolerant plants.

Generalized tolerance sensitivity and DEA metric sensitivity

OpenAIRE

Neralić, Luka; E. Wendell, Richard

2015-01-01

This paper considers the relationship between Tolerance sensitivity analysis in optimization and metric sensitivity analysis in Data Envelopment Analysis (DEA). Herein, we extend the results on the generalized Tolerance framework proposed by Wendell and Chen and show how this framework includes DEA metric sensitivity as a special case. Further, we note how recent results in Tolerance sensitivity suggest some possible extensions of the results in DEA metric sensitivity.

Generalized tolerance sensitivity and DEA metric sensitivity

Directory of Open Access Journals (Sweden)

Luka Neralić

2015-03-01

Full Text Available This paper considers the relationship between Tolerance sensitivity analysis in optimization and metric sensitivity analysis in Data Envelopment Analysis (DEA. Herein, we extend the results on the generalized Tolerance framework proposed by Wendell and Chen and show how this framework includes DEA metric sensitivity as a special case. Further, we note how recent results in Tolerance sensitivity suggest some possible extensions of the results in DEA metric sensitivity.

Molecular insight into the inclusion of the dietary plant flavonol fisetin and its chromophore within a chemically modified γ-cyclodextrin: Multi-spectroscopic, molecular docking and solubility studies.

Science.gov (United States)

Pahari, Biswapathik; Chakraborty, Sandipan; Sengupta, Pradeep K

2018-09-15

We explored the encapsulation of dietary plant flavonols fisetin and its chromophore 3-hydroxyflavone, within 2-hydroxypropyl-γ-cyclodextrin (HPγ-CDx) nano-cavity in aqueous solution using multi-spectroscopic approaches and molecular docking. Upon addition of HPγ-CDx, dramatic changes occur in the intrinsic 'two color' fluorescence behavior of the fluorophores. This is manifested by significant increase in the steady state fluorescence intensities, anisotropies, average fluorescence lifetimes and rotational correlation times. Furthermore, in the CDx environment, intrinsically achiral flavonols exhibit prominent induced circular dichroism bands. These findings indicate that the flavonol molecules spontaneously enter the relatively hydrophobic, chiral environment of the HPγ-CDx nano-cavities. Molecular docking computations corroborate the spectroscopic findings, and predict selectivity in orientation of the encapsulated flavonols. HPγ-CDx inclusion increases the aqueous solubility of individual flavonols ∼100-1000 times. The present study demonstrates that the hydroxypropyl substituent in γ-CDx controls the inclusion mode of the flavonols, leading to their enhanced solubilization and altered spectral signatures. Copyright © 2018 Elsevier Ltd. All rights reserved.

Spin labels. Applications in biology

International Nuclear Information System (INIS)

Frangopol, T.P.; Frangopol, M.; Ionescu, S.M.; Pop, I.V.; Benga, G.

1980-11-01

The main applications of spin labels in the study of biomembranes, enzymes, nucleic acids, in pharmacology, spin immunoassay are reviewed along with the fundamentals of the spin label method. 137 references. (author)

tracts of Cnestis ferruginea

African Journals Online (AJOL)

“Laboratories for Biomembrane Research and Biotechnology, Biochemistry Department, College of Medicine, Univer- sity of Ibadan ... stable structures called advanced glycated end-prod- ... in a population of normal red cells is covalently.

Spectral dynamics in the B800 band of LH2 from Rhodospirillum molischianum: a single-molecule study

International Nuclear Information System (INIS)

Hofmann, Clemens; Aartsma, Thijs J; Michel, Hartmut; Koehler, Juergen

2004-01-01

The BChl a absorptions in the B800 spectrum of individual LH2 complexes from Rhodospirillum molischianum show sudden, reversible spectral jumps between a finite number of spectral positions. From our data, we conclude that these fluctuations result from conformational changes of the protein backbone in close vicinity of the chromophores which provides a sensitive tool to monitor local modulations of the pigment-protein interaction

High pressure near infrared study of the mutated light-harvesting complex LH2

Directory of Open Access Journals (Sweden)

Braun P.

2005-01-01

Full Text Available The pressure sensitivities of the near infrared spectra of the light-harvesting (LH2 complex and a mutant complex with a simplified BChl-B850 binding pocket were compared. In the mutant an abrupt change in the spectral properties occurred at 250 MPa, which was not observed with the native sample. Increased disorder due to collapse of the chromophore pocket is suggested.

Variations in Spectral Absorption Properties of Phytoplankton, Non-algal Particles and Chromophoric Dissolved Organic Matter in Lake Qiandaohu

Directory of Open Access Journals (Sweden)

Liangliang Shi

2017-05-01

Full Text Available Light absorption by phytoplankton, non-algal particles (NAP and chromophoric dissolved organic matter (CDOM was investigated at 90 sites of a clear, deep artificial lake (Lake Qiandaohu to study natural variability of absorption coefficients. Our study shows that CDOM absorption is a major contributor to the total absorption signal in Lake Qiandaohu during all seasons, except autumn when it has an equivalent contribution as total particle absorption. The exponential slope of CDOM absorption varies within a narrow range around a mean value of 0.0164 nm−1 ( s d = 0.00176 nm−1. Our study finds some evidence for thIS autochthonous production of CDOM in winter and spring. Absorption by phytoplankton, and therefore its contribution to total absorption, is generally greatest in spring, suggesting that phytoplankton growth in Lake Qiandaohu occurs predominantly in the spring. Phytoplankton absorption in freshwater lakes generally has a direct relationship with chlorophyll-a concentration, similar to the one established for open ocean waters. The NAP absorption, whose relative contribution to total absorption is highest in summer, has a spectral shape that can be well fitted by an exponential function with an average slope of 0.0065 nm−1 ( s d = 0.00076 nm−1. There is significant spatial variability present in the summer of Lake Qiandaohu, especially in the northwestern and southwestern extremes where the optical properties of the water column are strongly affected by the presence of allochthonous matter. Variations in the properties of the particle absorption spectra with depths provides evidence that the water column was vertically inhomogeneous and can be monitored with an optical measurement program. Moreover, the optical inhomogeneity in winter is less obvious. Our study will support the parameterization of the Bio-optical model for Lake Qiandaohu from in situ or remotely sensing aquatic color signals.

Removal of Chromophoric Dissolved Organic Matter and Heavy Metals in a River-Sea System: Role of Aquatic Microgel Formation

Science.gov (United States)

Shiu, R. F.; Lee, C. L.

2016-12-01

Dissolved organic carbon (DOC) polymers are complex and poorly understood mixture of organic macromolecules in environment system. Portions of these polymers spontaneously form microgels that play key roles in many biogeochemical reactions, including mediating aggregation processes, element cycling, and pollutant mobility. However, the detailed interaction of microgels-heterogeneous materials in aquatic systems is still lacking. Insight into the interaction between surrounding materials and microgels from different types of aquatic DOC polymers are extremely important, as it is crucial in determining the fate and transport of these materials. Here, we use riverine and marine DOC polymers to examine their aggregation behavior, and to evaluate the roles of microgel formation in scavenging of chromophoric dissolved organic matter (CDOM) and heavy metals in a river-sea system. Our results indicate that riverine and marine microgels did not exhibit too much difference in size ( 3-5 μm) and self-assembly curve; however, the assembly effectiveness ([microgel]/DOC) of marine samples was much higher than riverine. Instead of concentration of DOC, other factors such as types and sources of DOC polymers may control the microgel abundance in aquatic environments. After filtering water samples (microgels removed), the CDOM and selected metals (Cu, Ni, Mn) in the filtrate were quantified. CDOM and metals were concurrently removed to an extent via DOC polymer re-aggregation, which also suggested that the microgels had the sequestering capability in CDOM and metals. This finding provides an alternative route for CDOM and heavy metals removal from the water column. As such the process of re-aggregation into microgels should then be considered besides traditional phase partitioning in the assessment of the ecological risk and fate of pollutant.

Characterizing spatiotemporal variations of chromophoric dissolved organic matter in headwater catchment of a key drinking water source in China.

Science.gov (United States)

Chen, Yihan; Yu, Kaifeng; Zhou, Yongqiang; Ren, Longfei; Kirumba, George; Zhang, Bo; He, Yiliang

2017-12-01

Natural surface drinking water sources with the increasing chromophoric dissolved organic matter (CDOM) have profound influences on the aquatic environment and drinking water safety. Here, this study investigated the spatiotemporal variations of CDOM in Fengshuba Reservoir and its catchments in China. Twenty-four surface water samples, 45 water samples (including surface water, middle water, and bottom water), and 15 pore water samples were collected from rivers, reservoir, and sediment of the reservoir, respectively. Then, three fluorescent components, namely two humic-like components (C1 and C2) and a tryptophan-like component (C3), were identified from the excitation-emission matrix coupled with parallel factor analysis (EEM-PARAFAC) for all samples. For spatial distributions, the levels of CDOM and two humic-like components in the reservoir were significantly lower than those in the upstream rivers (p CDOM and humic-like matters from the surrounding catchment. For temporal variations, the mean levels of CDOM and three fluorescent components did not significantly change in rivers, suggesting that perennial anthropic activity maybe an important factor impacting the concentration and composition of river CDOM but not the precipitation and runoff. However, these mean values of CDOM for the bulk waters of the reservoir changed markedly along with seasonal variations, indicating that the hydrological processes in the reservoir could control the quality and quantity of CDOM. The different correlations between the fluorescent components and primary water parameters in the river, reservoir, and pore water samples further suggest that the reservoir is an important factor regulating the migration and transformation of FDOM along with the variations of different environmental gradients.

X-ray specular reflection and fluorescence study of nano-films

International Nuclear Information System (INIS)

Zheludeva, S.; Novikova, N.

2001-01-01

The techniques that combine the advantages of high-resolution structure sensitive x-ray methods with spectroscopic selectivity of data obtained are shown to be extremely promising for characterization of organic and inorganic nano films and nano structures. Fluorescence yield angular dependences exited by complicated evanescent wave / x-ray standing wave pattern at total reflection and glancing incidence can be used to detect structure position of different ions in organic systems and alien interfacial layers in inorganic multilayers;, to get information about interdiffusion at the interfaces of Langmuir- Blodgett (L-B) films and artificial inorganic - x-ray mirrors; to study ion permeation through L-B nano structures - models of biomembrans; to obtain nano - film thickness and density; to get precisely the parameters of small d-space multilayer mirrors, ets

Estabilidade e estudo de penetração cutânea in vitro da rutina veiculada em uma emulsão cosmética através de um modelo de biomembrana alternativo Stability and in vitro penetration study of rutin incorporated in a cosmetic emulsion through an alternative model biomembrane

Directory of Open Access Journals (Sweden)

André Rolim Baby

2008-06-01

employed as antioxidant and to prevent the capillary fragility and, when incorporated in cosmetic emulsions, it must target the action site. In vitro cutaneous penetration studies through human skin is the ideal situation, however, there are difficulties to obtain and to maintain this tissue viability. Among the membrane models, shed snake skin presents itself as pure stratum corneum, providing barrier function similar to human and it is obtained without the animal sacrifice. The objectives of this research were the development and stability evaluation of a cosmetic emulsion containing rutin and propylene glycol (penetration enhancer and the evaluation of rutin in vitro cutaneous penetration and retention from the emulsion, employing an alternative model biomembrane. Emulsion was developed with rutin and propylene glycol, both at 5.0% w/w. Active substance presented on the formulation was quantified by a validated spectrophotometric method at 361.0 nm. Rutin cutaneous penetration and retention was performed in vertical diffusion cells with shed snake skin of Crotalus durissus, as alternative model biomembrane, and distilled water and ethanol 99.5% (1:1, as receptor fluid. The experiment was conducted for six hours, at 37.0 ± 0.5 ºC with constant stirring of 300 rpm. Spectrophotometry at 410.0 nm, previously validated, determined the active substance after cutaneous penetration/retention. Emulsion did not promote rutin cutaneous penetration through C. durissus skin, retaining 0.931 ± 0.0391 mg rutin/mg shed snake skin. The referred formulation was chemically stable for 30 days after stored at 25.0 ± 2.0 ºC, 5.0 ± 0.5 ºC and 45.0 ± 0.5 ºC. In conclusion, it has not been verified the active cutaneous penetration through the model biomembrane, but only its retention on the Crotalus durissus stratum corneum, condition considered stable for 30 days.

Positive selection of a duplicated UV-sensitive visual pigment coincides with wing pigment evolution in Heliconius butterflies

OpenAIRE

Briscoe, Adriana D.; Bybee, Seth M.; Bernard, Gary D.; Yuan, Furong; Sison-Mangus, Marilou P.; Reed, Robert D.; Warren, Andrew D.; Llorente-Bousquets, Jorge; Chiao, Chuan-Chin

2010-01-01

The butterfly Heliconius erato can see from the UV to the red part of the light spectrum with color vision proven from 440 to 640 nm. Its eye is known to contain three visual pigments, rhodopsins, produced by an 11-cis-3-hydroxyretinal chromophore together with long wavelength (LWRh), blue (BRh) and UV (UVRh1) opsins. We now find that H. erato has a second UV opsin mRNA (UVRh2)—a previously undescribed duplication of this gene among Lepidoptera. To investigate its evolutionary origin, we scre...

Positive selection of a duplicated UV-sensitive visual pigment coincides with wing pigment evolution in Heliconius butterflies

Science.gov (United States)

Briscoe, Adriana D.; Bybee, Seth M.; Bernard, Gary D.; Yuan, Furong; Sison-Mangus, Marilou P.; Reed, Robert D.; Warren, Andrew D.; Llorente-Bousquets, Jorge; Chiao, Chuan-Chin

2010-01-01

The butterfly Heliconius erato can see from the UV to the red part of the light spectrum with color vision proven from 440 to 640 nm. Its eye is known to contain three visual pigments, rhodopsins, produced by an 11-cis-3-hydroxyretinal chromophore together with long wavelength (LWRh), blue (BRh) and UV (UVRh1) opsins. We now find that H. erato has a second UV opsin mRNA (UVRh2)—a previously undescribed duplication of this gene among Lepidoptera. To investigate its evolutionary origin, we screened eye cDNAs from 14 butterfly species in the subfamily Heliconiinae and found both copies only among Heliconius. Phylogeny-based tests of selection indicate positive selection of UVRh2 following duplication, and some of the positively selected sites correspond to vertebrate visual pigment spectral tuning residues. Epi-microspectrophotometry reveals two UV-absorbing rhodopsins in the H. erato eye with λmax = 355 nm and 398 nm. Along with the additional UV opsin, Heliconius have also evolved 3-hydroxy-DL-kynurenine (3-OHK)-based yellow wing pigments not found in close relatives. Visual models of how butterflies perceive wing color variation indicate this has resulted in an expansion of the number of distinguishable yellow colors on Heliconius wings. Functional diversification of the UV-sensitive visual pigments may help explain why the yellow wing pigments of Heliconius are so colorful in the UV range compared to the yellow pigments of close relatives lacking the UV opsin duplicate. PMID:20133601

Probing Photosensitization by Functionalized Carbon Nanotubes

Science.gov (United States)

Carbon nanotubes (CNTs) photosensitize the production of reactive oxygen species that can damage organisms by biomembrane oxidation or mediate CNTs' environmental transformations. The photosensitized nature of derivatized carbon nanotubes from various synthetic methods, and thus ...

Spatio-seasonal variability of chromophoric dissolved organic matter absorption and responses to photobleaching in a large shallow temperate lake

Science.gov (United States)

Encina Aulló-Maestro, María; Hunter, Peter; Spyrakos, Evangelos; Mercatoris, Pierre; Kovács, Attila; Horváth, Hajnalka; Preston, Tom; Présing, Mátyás; Torres Palenzuela, Jesús; Tyler, Andrew

2017-03-01

The development and validation of remote-sensing-based approaches for the retrieval of chromophoric dissolved organic matter (CDOM) concentrations requires a comprehensive understanding of the sources and magnitude of variability in the optical properties of dissolved material within lakes. In this study, spatial and seasonal variability in concentration and composition of CDOM and the origin of its variation was studied in Lake Balaton (Hungary), a large temperate shallow lake in central Europe. In addition, we investigated the effect of photobleaching on the optical properties of CDOM through in-lake incubation experiments. There was marked variability throughout the year in CDOM absorption in Lake Balaton (aCDOM(440) = 0. 06-9.01 m-1). The highest values were consistently observed at the mouth of the main inflow (Zala River), which drains humic-rich material from the adjoining Kis-Balaton wetland, but CDOM absorption decreased rapidly towards the east where it was consistently lower and less variable than in the westernmost lake basins. The spectral slope parameter for the interval of 350-500 nm (SCDOM(350-500)) was more variable with increasing distance from the inflow (observed range 0.0161-0.0181 nm-1 for the mouth of the main inflow and 0.0158-0.0300 nm-1 for waters closer to the outflow). However, spatial variation in SCDOM was more constant exhibiting a negative correlation with aCDOM(440). Dissolved organic carbon (DOC) was strongly positively correlated with aCDOM(440) and followed a similar seasonal trend but it demonstrated more variability than either aCDOM or SCDOM with distance through the system. Photobleaching resulting from a 7-day exposure to natural solar UV radiation resulted in a marked decrease in allochthonous CDOM absorption (7.04 to 3.36 m-1, 42 % decrease). Photodegradation also resulted in an increase in the spectral slope coefficient of dissolved material.

Photocatalytic degradation of different chromophoric dyes in aqueous phase using La and Mo doped TiO{sub 2} hybrid carbon spheres

Energy Technology Data Exchange (ETDEWEB)

Raza, Waseem; Haque, M.M. [Department of Chemistry, Aligarh Muslim University, Aligarh 202002 (India); Muneer, M., E-mail: m.muneer.ch@amu.ac.in [Department of Chemistry, Aligarh Muslim University, Aligarh 202002 (India); Fleisch, M.; Hakki, A.; Bahnemann, D. [Institut fuer Technische Chemie, Leibniz Universität Hannover, Callinstrasse 3, D-30167 Hannover (Germany)

2015-05-25

Highlights: • La and Mo doped TiO{sub 2} hybrid carbon spheres have been synthesized using hydrothermal method. • The characterization of La and Mo doped TiO{sub 2} hybrid carbon spheres uniform morphology having anatase phase and good structural stability. • TiO{sub 2} hybrid carbon spheres with dopant concentration of 2.0% (La) and 1.5% (Mo) showed the highest photocatalytic activity as compared to the other dopant concentrations for the degradation of all the dyes under investigation. - Abstract: La and Mo-doped TiO{sub 2} coated carbon spheres have been synthesized using the hydrothermal method. The prepared materials were characterized by standard analytical techniques, X-ray diffraction (XRD), UV–Vis spectrophotometry, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and Raman spectroscopy. The XRD and Raman spectroscopic analysis showed that the particles are in anatase phase. The EDX and SEM images showed that La/Mo-doped TiO{sub 2} are present on the surface of the carbon spheres. The photocatalytic activity of the synthesized particles were tested by studying the degradation of three different chromophoric dyes, i.e., Acid Yellow 29 (azo dye), Coomassie Brilliant Blue G250 (triphenylmethane dye) and Acid Green 25 (anthraquinone dye) as a function of time on irradiation in aqueous suspension. TiO{sub 2} particle with dopant concentration of 2.0% La and 1.5% Mo showed the highest photocatalytic activity as compared to the other dopant concentrations for the degradation of all the dyes under investigation.

Role of Many-Body Effects in Describing Low-Lying Excited States of pi-Conjugated Chromophores: High-Level Equation-of-Motion Coupled-Cluster Studies of Fused Porphyrin Systems

Energy Technology Data Exchange (ETDEWEB)

Kowalski, Karol; Olson, Ryan M.; Krishnamoorthy, Sriram; Tipparaju, Vinod; Apra, Edoardo

2011-07-12

The unusual photophysical properties of the pi-conjugated chrompohores makes them potential building blocks of various molecular devices. In particular, significant narrowing of the HOMO-LUMO gaps can be observed as an effect of functionalization chromophores with polycyclic aromatic hydrocabrons (PAHs). In this paper we present equation-of-motion coupled cluster calculations for vertical excitation energies of several functionalized forms of porphyrins. The results of free-base porphyrin (FBP) clearly demonstrate significant differences between functionalization of FBP with one- (anthracene) and two-dimensional (coronene) structures. We also compare the EOMCC results with the experimentally available results for the anthracene fused zinc porphyrin. The impact of various-type correlation effects is illustrated on several benchmark models where the comparison with the experiment is possible. In particular, we demonstrate that for all excited states considered in this paper, all of them being dominated by single excitations, the inclusion of triply excited configurations is crucial for attaining qualitative agreement with the experiment. We also demonstrate the parallel performance of the most computationally intensive part of the completely renormalized EOMCCSD(T) approach (CR-EOMCCSD(T)) across 120,000 cores.

Modification of indole by electron-rich atoms and their application in novel electron donor materials

Science.gov (United States)

Zhang, Maolin; Qin, Guangjiong; Liu, Jialei; Zhen, Zhen; Fedorchuk, A. A.; Lakshminarayana, G.; Albassam, A. A.; El-Naggar, A. M.; Ozga, Katarzyna; Kityk, I. V.

2017-08-01

Novel nonlinear optical (NLO) chromophore based on 6-(pyrrolidin-1-yl)-1H-indole as the electron donor group was designed and synthesized. The molecular structure of this chromophore was characterized by 1H NMR spectra, 13C NMR spectra, and MS spectra. The delocalized energy level was estimated by UV-Vis. spectra. The thermal property was studied by thermogravimetric analysis (TGA). The poled films containing chromophores ZML-1 with a loading density of 10 wt% in amorphous polycarbonate (APC) afford an average electro-optic (EO) coefficient (r33) of 19 pm/V at 1310 nm. Compared to the reported aniline-based chromophore (r33 = 12 pm/V) analogues, chromophore ZML-1 exhibits enhanced electro-optical activity.

Effects of Crystal Morphology on Singlet Exciton Fission in Diketopyrrolopyrrole Thin Films.

Science.gov (United States)

Hartnett, Patrick E; Margulies, Eric A; Mauck, Catherine M; Miller, Stephen A; Wu, Yilei; Wu, Yi-Lin; Marks, Tobin J; Wasielewski, Michael R

2016-02-25

Singlet exciton fission (SF) is a promising strategy for increasing photovoltaic efficiency, but in order for SF to be useful in solar cells, it should take place in a chromophore that is air-stable, highly absorptive, solution processable, and inexpensive. Unlike many SF chromophores, diketopyrrolopyrrole (DPP) conforms to these criteria, and here we investigate SF in DPP for the first time. SF yields in thin films of DPP derivatives, which are widely used in organic electronics and photovoltaics, are shown to depend critically on crystal morphology. Time-resolved spectroscopy of three DPP derivatives with phenyl (3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, PhDPP), thienyl (3,6-di(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, TDPP), and phenylthienyl (3,6-di(5-phenylthiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione, PhTDPP) aromatic substituents in 100-200 nm thin films reveals that efficient SF occurs only in TDPP and PhTDPP (τSF = 220 ± 20 ps), despite the fact that SF is most exoergic in PhDPP. This result correlates well with the greater degree of π-overlap and closer π-stacking in TDPP (3.50 Å) and PhTDPP (3.59 Å) relative to PhDPP (3.90 Å) and demonstrates that SF in DPP is highly sensitive to the electronic coupling between adjacent chromophores. The triplet yield in PhTDPP films is determined to be 210 ± 35% by the singlet depletion method and 165 ± 30% by the energy transfer method, showing that SF is nearly quantitative in these films and that DPP derivatives are a promising class of SF chromophores for enhancing photovoltaic performance.

Developing a structure-function model for the cryptophyte phycoerythrin 545 using ultrahigh resolution crystallography and ultrafast laser spectroscopy.

Science.gov (United States)

Doust, Alexander B; Marai, Christopher N J; Harrop, Stephen J; Wilk, Krystyna E; Curmi, Paul M G; Scholes, Gregory D

2004-11-12

Cryptophyte algae differ from cyanobacteria and red algae in the architecture of their photosynthetic light harvesting systems, even though all three are evolutionarily related. Central to cryptophyte light harvesting is the soluble antenna protein phycoerythrin 545 (PE545). The ultrahigh resolution crystal structure of PE545, isolated from a unicellular cryptophyte Rhodomonas CS24, is reported at both 1.1A and 0.97A resolution, revealing details of the conformation and environments of the chromophores. Absorption, emission and polarized steady state spectroscopy (298K, 77K), as well as ultrafast (20fs time resolution) measurements of population dynamics are reported. Coupled with complementary quantum chemical calculations of electronic transitions of the bilins, these enable assignment of spectral absorption characteristics to each chromophore in the structure. Spectral differences between the tetrapyrrole pigments due to chemical differences between bilins, as well as their binding and interaction with the local protein environment are described. Based on these assignments, and considering customized optical properties such as strong coupling, a model for light harvesting by PE545 is developed which explains the fast, directional harvesting of excitation energy. The excitation energy is funnelled from four peripheral pigments (beta158,beta82) into a central chromophore dimer (beta50/beta61) in approximately 1ps. Those chromophores, in turn, transfer the excitation energy to the red absorbing molecules located at the periphery of the complex in approximately 4ps. A final resonance energy transfer step sensitizes just one of the alpha19 bilins on a time scale of 22ps. Furthermore, it is concluded that binding of PE545 to the thylakoid membrane is not essential for efficient energy transfer to the integral membrane chlorophyll a-containing complexes associated with PS-II.

Strongly oxidizing perylene-3,4-dicarboximides for use in water oxidation photoelectrochemical cells

Energy Technology Data Exchange (ETDEWEB)

Lindquist, Rebecca J.; Phelan, Brian T.; Reynal, Anna; Margulies, Eric A.; Shoer, Leah E.; Durrant, James R.; Wasielewski, Michael R.

2016-01-01

Perylene-3,4-dicarboximide (PMI) based chromophores have demonstrated the ability to inject electrons into TiO2 for dye-sensitized solar cell applications and to accept electrons from metal complexes relevant to water oxidation, but they are nearly unexplored for use in photoelectrochemical cells (PECs) for solar fuels generation. A series of related PMIs with high oxidation potentials and carboxylate binding groups was synthesized and investigated for this purpose. Charge injection and recombination dynamics were measured using transient absorption (TA) spectroscopy on the picosecond to second timescales. The dynamics and electron injection yields were correlated with the PMI energetics and structures. Injection began in less than 1 ps for the dye with the best performance and a significant charge-separated state yield remained at long times. Finally, this chromophore was used to oxidize a covalently bound water oxidation precatalyst following electron injection into TiO2 to demonstrate the utility of the dyes for use in PECs.

Planar integrated optical waveguide used as a transducer to yield chemical information: detection of the activity of proteolytic enzymes e.g. serine-proteases

Science.gov (United States)

Zhylyak, Gleb; Ramoz-Perez, Victor; Linnhoff, Michael; Hug, Thomas; Citterio, Daniel; Spichiger-Keller, Ursula E.

2005-03-01

The paper shows the very first results of a feasibility study where the activity of proteolytic enzymes towards dye-labelled artificial substrates immobilized on the surface of planar optical Ta2O5 waveguide was investigated. Within this project, a chromophore label was developed, synthesized and attached to the carboxy-terminus of specific tripeptides. The goal was to develop a highly sensitive optical assay in order to monitor the activity of serine-proteases by cleavage of the amide bond between peptide and chromophore. On the one hand, a strategy was developed to immobilize the labeled tripeptide unto integrated planar waveguides. On the other hand, an instrument, the so-called "chip-reader" was developed to detect the biological process on the surface of the integrated planar optical waveguide. Surface characteristics were analyzed by XPS, TOF-SIMS and contact angle measurements. A comparison between the effectivity of ATR-photometry on chip using TE0 mode and photometry in transmission mode is discussed.

Molecular Tuning of Phenylene-Vinylene Derivatives for Two-Photon Photosensitized Singlet Oxygen Production

DEFF Research Database (Denmark)

Nielsen, Christian B.; Arnbjerg, Jacob; Johnsen, Mette

2009-01-01

Substituent-dependent features and properties of the sensitizer play an important role in the photosensitized production of singlet oxygen, O2(a1Δg). In this work, we systematically examine the effect of molecular changes in the sensitizer on the efficiency of singlet oxygen production using......, as the sensitizer, oligophenylene-vinylene derivatives designed to optimally absorb light in a nonlinear two-photon process. We demonstrate that one cannot always rely on rule-of-thumb guidelines when attempting to construct efficient two-photon singlet oxygen sensitizers. Rather, as a consequence of behavior...... that can deviate from the norm, a full investigation of the photophysical properties of the system is generally required. For example, it is acknowledged that the introduction of a ketone moiety to the sensitizer chromophore often results in more efficient production of singlet oxygen. However, we show...

Aggregation properties of levofloxacin in water and ethanol and its ...

Indian Academy of Sciences (India)

and can be used as alternative to biomembranes to study. ∗For correspondence ... effective against both gram positive and gram negative bacteria.8 It is found to have ... tion which makes it a very popular medicine. Solubility of levofloxacin is ...

Electromechanical properties of biomembranes and nerves

International Nuclear Information System (INIS)

Heimburg, T; Blicher, A; Mosgaard, L D; Zecchi, K

2014-01-01

Lipid membranes are insulators and capacitors, which can be charged by an external electric field. This phenomenon plays an important role in the field of electrophysiology, for instance when describing nerve pulse conduction. Membranes are also made of polar molecules meaning that they contain molecules with permanent electrical dipole moments. Therefore, the properties of membranes are subject to changes in trans-membrane voltage. Vice versa, mechanical forces on membranes lead to changes in the membrane potential. Associated effects are flexoelectricity, piezoelectricity, and electrostriction. Lipid membranes can melt from an ordered to a disordered state. Due to the change of membrane dimensions associated with lipid membrane melting, electrical properties are linked to the melting transition. Melting of the membrane can induce changes in trans-membrane potential, and application of voltage can lead to a shift of the melting transition. Further, close to transitions membranes are very susceptible to piezoelectric phenomena. We discuss these phenomena in relation with the occurrence of lipid ion channels. Close to melting transitions, lipid membranes display step-wise ion conduction events, which are indistinguishable from protein ion channels. These channels display a voltage-dependent open probability. One finds asymmetric current-voltage relations of the pure membrane very similar to those found for various protein channels. This asymmetry falsely has been considered a criterion to distinguish lipid channels from protein channels. However, we show that the asymmetry can arise from the electromechanical properties of the lipid membrane itself. Finally, we discuss electromechanical behavior in connection with the electromechanical theory of nerve pulse transduction. It has been found experimentally that nerve pulses are related to changes in nerve thickness. Thus, during the nerve pulse a solitary mechanical pulse travels along the nerve. Due to electromechanical coupling it is unavoidable that this pulse generates a trans-membrane voltage. In the past, we have proposed that this electromechanical pulse is the origin of the action potential in nerves

Electromechanical properties of biomembranes and nerves

Science.gov (United States)

Heimburg, T.; Blicher, A.; Mosgaard, L. D.; Zecchi, K.

2014-12-01

Lipid membranes are insulators and capacitors, which can be charged by an external electric field. This phenomenon plays an important role in the field of electrophysiology, for instance when describing nerve pulse conduction. Membranes are also made of polar molecules meaning that they contain molecules with permanent electrical dipole moments. Therefore, the properties of membranes are subject to changes in trans-membrane voltage. Vice versa, mechanical forces on membranes lead to changes in the membrane potential. Associated effects are flexoelectricity, piezoelectricity, and electrostriction. Lipid membranes can melt from an ordered to a disordered state. Due to the change of membrane dimensions associated with lipid membrane melting, electrical properties are linked to the melting transition. Melting of the membrane can induce changes in trans-membrane potential, and application of voltage can lead to a shift of the melting transition. Further, close to transitions membranes are very susceptible to piezoelectric phenomena. We discuss these phenomena in relation with the occurrence of lipid ion channels. Close to melting transitions, lipid membranes display step-wise ion conduction events, which are indistinguishable from protein ion channels. These channels display a voltage-dependent open probability. One finds asymmetric current-voltage relations of the pure membrane very similar to those found for various protein channels. This asymmetry falsely has been considered a criterion to distinguish lipid channels from protein channels. However, we show that the asymmetry can arise from the electromechanical properties of the lipid membrane itself. Finally, we discuss electromechanical behavior in connection with the electromechanical theory of nerve pulse transduction. It has been found experimentally that nerve pulses are related to changes in nerve thickness. Thus, during the nerve pulse a solitary mechanical pulse travels along the nerve. Due to electromechanical coupling it is unavoidable that this pulse generates a trans-membrane voltage. In the past, we have proposed that this electromechanical pulse is the origin of the action potential in nerves.

Chromophoric dissolved organic matter (CDOM) variability in Barataria Basin using excitation-emission matrix (EEM) fluorescence and parallel factor analysis (PARAFAC).

Science.gov (United States)

Singh, Shatrughan; D'Sa, Eurico J; Swenson, Erick M

2010-07-15

Chromophoric dissolved organic matter (CDOM) variability in Barataria Basin, Louisiana, USA,was examined by excitation emission matrix (EEM) fluorescence combined with parallel factor analysis (PARAFAC). CDOM optical properties of absorption and fluorescence at 355nm along an axial transect (36 stations) during March, April, and May 2008 showed an increasing trend from the marine end member to the upper basin with mean CDOM absorption of 11.06 + or - 5.01, 10.05 + or - 4.23, 11.67 + or - 6.03 (m(-)(1)) and fluorescence 0.80 + or - 0.37, 0.78 + or - 0.39, 0.75 + or - 0.51 (RU), respectively. PARAFAC analysis identified two terrestrial humic-like (component 1 and 2), one non-humic like (component 3), and one soil derived humic acid like (component 4) components. The spatial variation of the components showed an increasing trend from station 1 (near the mouth of basin) to station 36 (end member of bay; upper basin). Deviations from this increasing trend were observed at a bayou channel with very high chlorophyll-a concentrations especially for component 3 in May 2008 that suggested autochthonous production of CDOM. The variability of components with salinity indicated conservative mixing along the middle part of the transect. Component 1 and 4 were found to be relatively constant, while components 2 and 3 revealed an inverse relationship for the sampling period. Total organic carbon showed increasing trend for each of the components. An increase in humification and a decrease in fluorescence indices along the transect indicated an increase in terrestrial derived organic matter and reduced microbial activity from lower to upper basin. The use of these indices along with PARAFAC results improved dissolved organic matter characterization in the Barataria Basin. Copyright 2010 Elsevier B.V. All rights reserved.

Absorption and fluorescence properties of chromophoric dissolved organic matter: implications for the monitoring of water quality in a large subtropical reservoir.

Science.gov (United States)

Liu, Xiaohan; Zhang, Yunlin; Shi, Kun; Zhu, Guangwei; Xu, Hai; Zhu, Mengyuan

2014-12-01

The development of techniques for real-time monitoring of water quality is of great importance for effectively managing inland water resources. In this study, we first analyzed the absorption and fluorescence properties in a large subtropical reservoir and then used a chromophoric dissolved organic matter (CDOM) fluorescence monitoring sensor to predict several water quality parameters including the total nitrogen (TN), total phosphorus (TP), chemical oxygen demand (COD), dissolved organic carbon (DOC), and CDOM fluorescence parallel factor analysis (PARAFAC) components in the reservoir. The CDOM absorption coefficient at 254 nm (a(254)), the humic-like component (C1), and the tryptophan-like component (C3) decreased significantly along a gradient from the northwest to the lake center, northeast, southwest, and southeast region in the reservoir. However, no significant spatial difference was found for the tyrosine-like component (C2), which contributed only four marked peaks. A highly significant linear correlation was found between the a(254) and CDOM concentration measured using the CDOM fluorescence sensor (r(2) = 0.865, n = 76, p CDOM concentrations could act as a proxy for the CDOM absorption coefficient measured in the laboratory. Significant correlations were also found between the CDOM concentration and TN, TP, COD, DOC, and the maximum fluorescence intensity of C1, suggesting that the real-time monitoring of CDOM concentrations could be used to predict these water quality parameters and trace the humic-like fluorescence substance in clear aquatic ecosystems with DOC CDOM fluorescence sensor is a useful tool for on-line water quality monitoring if the empirical relationship between the CDOM concentration measured using the CDOM fluorescence sensor and the water quality parameters is calibrated and validated.

Function and structure of GFP-like proteins in the protein data bank.

Science.gov (United States)

Ong, Wayne J-H; Alvarez, Samuel; Leroux, Ivan E; Shahid, Ramza S; Samma, Alex A; Peshkepija, Paola; Morgan, Alicia L; Mulcahy, Shawn; Zimmer, Marc

2011-04-01

The RCSB protein databank contains 266 crystal structures of green fluorescent proteins (GFP) and GFP-like proteins. This is the first systematic analysis of all the GFP-like structures in the pdb. We have used the pdb to examine the function of fluorescent proteins (FP) in nature, aspects of excited state proton transfer (ESPT) in FPs, deformation from planarity of the chromophore and chromophore maturation. The conclusions reached in this review are that (1) The lid residues are highly conserved, particularly those on the "top" of the β-barrel. They are important to the function of GFP-like proteins, perhaps in protecting the chromophore or in β-barrel formation. (2) The primary/ancestral function of GFP-like proteins may well be to aid in light induced electron transfer. (3) The structural prerequisites for light activated proton pumps exist in many structures and it's possible that like bioluminescence, proton pumps are secondary functions of GFP-like proteins. (4) In most GFP-like proteins the protein matrix exerts a significant strain on planar chromophores forcing most GFP-like proteins to adopt non-planar chromophores. These chromophoric deviations from planarity play an important role in determining the fluorescence quantum yield. (5) The chemospatial characteristics of the chromophore cavity determine the isomerization state of the chromophore. The cavities of highlighter proteins that can undergo cis/trans isomerization have chemospatial properties that are common to both cis and trans GFP-like proteins.

Chemical kinetic functional sensitivity analysis: Elementary sensitivities

International Nuclear Information System (INIS)

Demiralp, M.; Rabitz, H.

1981-01-01

Sensitivity analysis is considered for kinetics problems defined in the space--time domain. This extends an earlier temporal Green's function method to handle calculations of elementary functional sensitivities deltau/sub i//deltaα/sub j/ where u/sub i/ is the ith species concentration and α/sub j/ is the jth system parameter. The system parameters include rate constants, diffusion coefficients, initial conditions, boundary conditions, or any other well-defined variables in the kinetic equations. These parameters are generally considered to be functions of position and/or time. Derivation of the governing equations for the sensitivities and the Green's funciton are presented. The physical interpretation of the Green's function and sensitivities is given along with a discussion of the relation of this work to earlier research

Measuring sensitivity in pharmacoeconomic studies. Refining point sensitivity and range sensitivity by incorporating probability distributions.

Science.gov (United States)

Nuijten, M J

1999-07-01

The aim of the present study is to describe a refinement of a previously presented method, based on the concept of point sensitivity, to deal with uncertainty in economic studies. The original method was refined by the incorporation of probability distributions which allow a more accurate assessment of the level of uncertainty in the model. In addition, a bootstrap method was used to create a probability distribution for a fixed input variable based on a limited number of data points. The original method was limited in that the sensitivity measurement was based on a uniform distribution of the variables and that the overall sensitivity measure was based on a subjectively chosen range which excludes the impact of values outside the range on the overall sensitivity. The concepts of the refined method were illustrated using a Markov model of depression. The application of the refined method substantially changed the ranking of the most sensitive variables compared with the original method. The response rate became the most sensitive variable instead of the 'per diem' for hospitalisation. The refinement of the original method yields sensitivity outcomes, which greater reflect the real uncertainty in economic studies.

Partitioning of resveratrol between pentane and DMSO

DEFF Research Database (Denmark)

Shen, Chen; Stein, Paul C.; Klösgen-Buchkremer, Beate Maria

2015-01-01

Partitioning of trans-3,5,4′-trihydroxy-stilbene (resveratrol) between n-pentane and DMSO was investigated as a contribution to understand the interaction between resveratrol and biomembranes. In order to determine the partition coefficient P* of resveratrol between pentane and DMSO, resveratrol ...

European Science Notes Information Bulletin Reports on Current European/ Middle Eastern Science

Science.gov (United States)

1991-12-01

outstanding in biology research. The Centro de Biologia ° Biomembranes Molecular (Center for Molecular Biology) has been ° Cell reproduction operating...Centro de Biologia Molecular o Mechanisms of action of neuropeptides • Structure, function and regulation of plasma The Centro de Biologia Molecular

Cholesterol Depletion from a Ceramide/Cholesterol Mixed Monolayer: A Brewster Angle Microscope Study

KAUST Repository

Mandal, Pritam; Noutsi, Bakiza Kamal; Chaieb, Saharoui

2016-01-01

to deplete cholesterol (Chol) from biomembranes. Here, we focus on the depletion of cholesterol from a C16 ceramide/cholesterol (C16-Cer/Chol) mixed monolayer using MβCD. While the removal of cholesterol by MβCD depends on the cholesterol concentration

Ruthenium Sensitizers and Their Applications in Dye-Sensitized Solar Cells

Directory of Open Access Journals (Sweden)

Yuancheng Qin

2012-01-01

Full Text Available Dye-sensitized solar cells (DSSCs have attracted considerable attention in recent years due to the possibility of low-cost conversion of photovoltaic energy. The DSSCs-based ruthenium complexes as sensitizers show high efficiency and excellent stability, implying potential practical applications. This review focuses on recent advances in design and preparation of efficient ruthenium sensitizers and their applications in DSSCs, including thiocyanate ruthenium sensitizers and thiocyanate-free ruthenium sensitizers.

Dark states and delocalization: Competing effects of quantum coherence on the efficiency of light harvesting systems.

Science.gov (United States)

Hu, Zixuan; Engel, Gregory S; Alharbi, Fahhad H; Kais, Sabre

2018-02-14

Natural light harvesting systems exploit electronic coupling of identical chromophores to generate efficient and robust excitation transfer and conversion. Dark states created by strong coupling between chromophores in the antenna structure can significantly reduce radiative recombination and enhance energy conversion efficiency. Increasing the number of the chromophores increases the number of dark states and the associated enhanced energy conversion efficiency yet also delocalizes excitations away from the trapping center and reduces the energy conversion rate. Therefore, a competition between dark state protection and delocalization must be considered when designing the optimal size of a light harvesting system. In this study, we explore the two competing mechanisms in a chain-structured antenna and show that dark state protection is the dominant mechanism, with an intriguing dependence on the parity of the number of chromophores. This dependence is linked to the exciton distribution among eigenstates, which is strongly affected by the coupling strength between chromophores and the temperature. Combining these findings, we propose that increasing the coupling strength between the chromophores can significantly increase the power output of the light harvesting system.

The selectively bred high alcohol sensitivity (HAS) and low alcohol sensitivity (LAS) rats differ in sensitivity to nicotine.

Science.gov (United States)

de Fiebre, NancyEllen C; Dawson, Ralph; de Fiebre, Christopher M

2002-06-01

Studies in rodents selectively bred to differ in alcohol sensitivity have suggested that nicotine and ethanol sensitivities may cosegregate during selective breeding. This suggests that ethanol and nicotine sensitivities may in part be genetically correlated. Male and female high alcohol sensitivity (HAS), control alcohol sensitivity, and low alcohol sensitivity (LAS) rats were tested for nicotine-induced alterations in locomotor activity, body temperature, and seizure activity. Plasma and brain levels of nicotine and its primary metabolite, cotinine, were measured in these animals, as was the binding of [3H]cytisine, [3H]epibatidine, and [125I]alpha-bungarotoxin in eight brain regions. Both replicate HAS lines were more sensitive to nicotine-induced locomotor activity depression than the replicate LAS lines. No consistent HAS/LAS differences were seen on other measures of nicotine sensitivity; however, females were more susceptible to nicotine-induced seizures than males. No HAS/LAS differences in nicotine or cotinine levels were seen, nor were differences seen in the binding of nicotinic ligands. Females had higher levels of plasma cotinine and brain nicotine than males but had lower brain cotinine levels than males. Sensitivity to a specific action of nicotine cosegregates during selective breeding for differential sensitivity to a specific action of ethanol. The differential sensitivity of the HAS/LAS rats is due to differences in central nervous system sensitivity and not to pharmacokinetic differences. The differential central nervous system sensitivity cannot be explained by differences in the numbers of nicotinic receptors labeled in ligand-binding experiments. The apparent genetic correlation between ethanol and nicotine sensitivities suggests that common genes modulate, in part, the actions of both ethanol and nicotine and may explain the frequent coabuse of these agents.

Comparison of optical properties of chromophoric dissolved organic matter (CDOM) in alpine lakes above or below the tree line: insights into sources of CDOM.

Science.gov (United States)

Su, Yaling; Chen, Feizhou; Liu, Zhengwen

2015-05-01

Here we investigated absorption and fluorescence properties of chromophoric dissolved organic matter (CDOM) in 15 alpine lakes located below or above the tree line to determine its source and composition. The results indicate that the concentrations of CDOM in below-tree-line lakes are significantly higher than in above-tree-line lakes, as evidenced from the absorption coefficients of a250 and a365. The intensities of the protein-like and humic-like fluorescence in below-tree-line lakes are higher than in above-tree-line lakes as well. Three fluorescent components were identified using parallel factor analysis (PARAFAC) modelling. Component 1 is probably associated with biological degradation of terrestrial humic component. The terrestrial humic-like component 2 is only found in below-tree-line lakes. The protein-like or phenolic component 3 is dominant in above-tree-line lakes, which is probably more derived from autochthonous origin. In this study, (1) higher a250/a365 and S275-295 values indicate smaller molecular weights of CDOM in above-tree-line lakes than in below-tree-line lakes, and smaller molecular weights at the surface than at 2.0 m depth; (2) SUVA254 and FI255 results provide evidence of lower percent aromaticity of CDOM in above-tree-line lakes; and (3) FI310 and FI370 suggest a strong allochthonous origin at the surface in below-tree-line lakes, and more contribution from autochthonous biological and aquatic bacterial origin in above-tree-line lakes.

Luminescence Properties of Self-Aggregating TbIII-DOTA-Functionalized Calix[4]arenes

Science.gov (United States)

Mayer, Florian; Tiruvadi Krishnan, Sriram; Schühle, Daniel T.; Eliseeva, Svetlana V.; Petoud, Stéphane; Tóth, Éva; Djanashvili, Kristina

2018-01-01

Self-aggregating calix[4]arenes carrying four DOTA ligands on the upper rim for stable complexation of paramagnetic GdIII-ions have already been proposed as MRI probes. In this work, we investigate the luminescence properties of TbIII-DOTA-calix[4]arene-4OPr containing four propyl-groups and compare them with those of the analogue substituted with a phthalimide chromophore (TbIII-DOTA-calix[4]arene-3OPr-OPhth). We show that, given its four aromatic rings, the calix[4]arene core acts as an effective sensitizer of Tb-centered luminescence. Substituents on the lower rim can modulate the aggregation behavior, which in turn determines the luminescence properties of the compounds. In solid state, the quantum yield of the phthalimide derivative is almost three times as high as that of the propyl-functionalized analogue demonstrating a beneficial role of the chromophore on Tb-luminescence. In solution, however, the effect of the phthalimide group vanishes, which we attribute to the large distance between the chromophore and the lanthanide, situated on the opposite rims of the calix[4]arene. Both quantum yields and luminescence lifetimes show clear concentration dependence in solution, related to the strong impact of aggregation on the luminescence behaviour. We also evidence the variability in the values of the critical micelle concentration depending on the experimental technique. Such luminescent calix[4]arene platforms accommodating stable lanthanide complexes can be considered valuable building blocks for the design of dual MR/optical imaging probes.

Influence of Nitrogen Doping on Device Operation for TiO2-Based Solid-State Dye-Sensitized Solar Cells: Photo-Physics from Materials to Devices

Directory of Open Access Journals (Sweden)

Jin Wang

2016-02-01

Full Text Available Solid-state dye-sensitized solar cells (ssDSSC constitute a major approach to photovoltaic energy conversion with efficiencies over 8% reported thanks to the rational design of efficient porous metal oxide electrodes, organic chromophores, and hole transporters. Among the various strategies used to push the performance ahead, doping of the nanocrystalline titanium dioxide (TiO2 electrode is regularly proposed to extend the photo-activity of the materials into the visible range. However, although various beneficial effects for device performance have been observed in the literature, they remain strongly dependent on the method used for the production of the metal oxide, and the influence of nitrogen atoms on charge kinetics remains unclear. To shed light on this open question, we synthesized a set of N-doped TiO2 nanopowders with various nitrogen contents, and exploited them for the fabrication of ssDSSC. Particularly, we carefully analyzed the localization of the dopants using X-ray photo-electron spectroscopy (XPS and monitored their influence on the photo-induced charge kinetics probed both at the material and device levels. We demonstrate a strong correlation between the kinetics of photo-induced charge carriers probed both at the level of the nanopowders and at the level of working solar cells, illustrating a direct transposition of the photo-physic properties from materials to devices.

An extended study of the phase separation between phospholipids and grafted polymers on a bilayer biomembrane

Energy Technology Data Exchange (ETDEWEB)

Benhamou, M; Joudar, I; Kaidi, H; Elhasnaoui, K; Ridouane, H; Qamar, H, E-mail: benhamou.mabrouk@gmail.com [Laboratoire de Physique des Polymeres et Phenomenes Critiques, Faculte des Sciences, Ben M' sik, PO Box 7955, Casablanca (Morocco)

2011-06-01

We re-examine here the phase separation between phospholipids and adsorbed polymer chains on a fluid membrane with a change in some suitable parameter (temperature). Our purpose is to quantify the significant effects of the solvent quality and of the polydispersity of adsorbed loops formed by grafted polymer chains on the segregation phenomenon. To this end, we elaborate on a theoretical model that allows us to derive the expression for the mixing free energy. From this, we extract the phase diagram shape in the composition-temperature plane. Our main conclusion is that the polymer chain condensation is very sensitive to the solvent quality and to the polydispersity of loops of adsorbed chains.

Local induction of inflammation affects bone formation

NARCIS (Netherlands)

Croes, M; Kruyt, M C; Loozen, L; Kragten, A H; Yuan, H; Dhert, W J; Öner, F C; Alblas, J

2017-01-01

To explore the influence of inflammatory processes on bone formation, we applied a new in vivo screening model. Confined biological pockets were first created in rabbits as a response to implanted bone cement discs. These biomembrane pockets were subsequently used to study the effects of

SENSIT: a cross-section and design sensitivity and uncertainty analysis code

International Nuclear Information System (INIS)

Gerstl, S.A.W.

1980-01-01

SENSIT computes the sensitivity and uncertainty of a calculated integral response (such as a dose rate) due to input cross sections and their uncertainties. Sensitivity profiles are computed for neutron and gamma-ray reaction cross sections of standard multigroup cross section sets and for secondary energy distributions (SEDs) of multigroup scattering matrices. In the design sensitivity mode, SENSIT computes changes in an integral response due to design changes and gives the appropriate sensitivity coefficients. Cross section uncertainty analyses are performed for three types of input data uncertainties: cross-section covariance matrices for pairs of multigroup reaction cross sections, spectral shape uncertainty parameters for secondary energy distributions (integral SED uncertainties), and covariance matrices for energy-dependent response functions. For all three types of data uncertainties SENSIT computes the resulting variance and estimated standard deviation in an integral response of interest, on the basis of generalized perturbation theory. SENSIT attempts to be more comprehensive than earlier sensitivity analysis codes, such as SWANLAKE

Hydraulic connectivity and evaporation control the water quality and sources of chromophoric dissolved organic matter in Lake Bosten in arid northwest China.

Science.gov (United States)

Zhou, Lei; Zhou, Yongqiang; Hu, Yang; Cai, Jian; Bai, Chengrong; Shao, Keqiang; Gao, Guang; Zhang, Yunlin; Jeppesen, Erik; Tang, Xiangming

2017-12-01

Lake Bosten is the largest oligosaline lake in arid northwestern China, and water from its tributaries and evaporation control the water balance of the lake. In this study, water quality and chromophoric dissolved organic matter (CDOM) absorption and fluorescence were investigated in different seasons to elucidate how hydraulic connectivity and evaporation may affect the water quality and variability of CDOM in the lake. Mean suspended solids and turbidity were significantly higher in the upstream tributaries than in the lake, the difference being notably more pronounced in the wet than in the dry season. A markedly higher mean first principal component (PC1) score, which was significantly positively related to protein-like components, and a considerably lower fluorescence peak integration ratio - I C :I T , indicative of the terrestrial humic-like CDOM contribution percentage, were observed in the lake than in the upstream tributaries. Correspondingly, notably higher contribution percentages of terrestrial humic-like components were observed in the river mouth areas than in the remaining lake regions. Furthermore, significantly higher mean turbidity, and notably lower mean conductivity and salinity, were recorded in the southwestern Kaidu river mouth than in the remaining lake regions in the wet season. Notably higher mean salinity is recorded in Lake Bosten than in upstream tributaries. Autochthonous protein-like associated amino-acids and also PC1 scores increased significantly with increasing salinity. We conclude that the dynamics of water quality and CDOM composition in remote arid Lake Bosten are strongly driven by evaporation and also the hydraulic connectivity between the upstream tributaries and the downstream lake. Copyright © 2017 Elsevier Ltd. All rights reserved.

Mo, Mn and La doped TiO{sub 2}: Synthesis, characterization and photocatalytic activity for the decolourization of three different chromophoric dyes

Energy Technology Data Exchange (ETDEWEB)

Umar, K.; Haque, M.M. [Department of Chemistry, Aligarh Muslim University, Aligarh 202 002 (India); Muneer, M., E-mail: readermuneer@gmail.com [Department of Chemistry, Aligarh Muslim University, Aligarh 202 002 (India); Harada, T.; Matsumura, M. [Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka 560-8531 (Japan)

2013-11-25

Highlights: •Detail study on synthesis, characterization and photocatalytic activity of doped-TiO{sub 2}. •SEM images indicates partial crystalline nature with rough surfaces. •The XRD analysis shows the partial crystalline nature and anatase phase. •The UV–Vis absorption spectra showed λ{sub max} shift towards longer wavelength. •TiO{sub 2} with dopant 0.75% (Mo), 1.0% (Mn, La) showed best photocatalytic efficiency. -- Abstract: Nanocrystalline TiO{sub 2} particles doped with different concentrations of Molybdenum (Mo), Manganese (Mn) and Lanthanum (La) (0.25–1.0%) were synthesized using sol–gel method and characterized by standard analytical techniques such as X-ray diffraction (XRD), UV–Vis spectroscopy and Scanning Electron Microscopy (SEM). The XRD analysis shows the partial crystalline nature and anatase phase. The SEM images of undoped and doped TiO{sub 2} at different magnifications also show the partial crystalline nature with rough surfaces. The photocatalytic activity of the synthesized particles (TiO{sub 2} doped with Mo, Mn and La) was tested by studying the decolourization of three different chromophoric dyes such as Acid Red 88 (azo dye), Gentian Violet (triphenylmethane dye) and Remazol Brilliant Blue R (anthraquinone dye) as a function of time on irradiation in aqueous suspension in an immersion well photochemical reactor with a 500 W halogen linear lamp in the presence of atmospheric oxygen. The results indicate that TiO{sub 2} with dopant concentration of 0.75% (Mo) and 1.0% (Mn, La) showed the highest photocatalytic activity as compared to the other dopant concentrations for the decolourization of all the dyes.

Context Sensitive Modeling of Cancer Drug Sensitivity.

Directory of Open Access Journals (Sweden)

Bo-Juen Chen

Full Text Available Recent screening of drug sensitivity in large panels of cancer cell lines provides a valuable resource towards developing algorithms that predict drug response. Since more samples provide increased statistical power, most approaches to prediction of drug sensitivity pool multiple cancer types together without distinction. However, pan-cancer results can be misleading due to the confounding effects of tissues or cancer subtypes. On the other hand, independent analysis for each cancer-type is hampered by small sample size. To balance this trade-off, we present CHER (Contextual Heterogeneity Enabled Regression, an algorithm that builds predictive models for drug sensitivity by selecting predictive genomic features and deciding which ones should-and should not-be shared across different cancers, tissues and drugs. CHER provides significantly more accurate models of drug sensitivity than comparable elastic-net-based models. Moreover, CHER provides better insight into the underlying biological processes by finding a sparse set of shared and type-specific genomic features.

Characterizing chromophoric dissolved organic matter in Lake Tianmuhu and its catchment basin using excitation-emission matrix fluorescence and parallel factor analysis.

Science.gov (United States)

Zhang, Yunlin; Yin, Yan; Feng, Longqing; Zhu, Guangwei; Shi, Zhiqiang; Liu, Xiaohan; Zhang, Yuanzhi

2011-10-15

Chromophoric dissolved organic matter (CDOM) is an important optically active substance that transports nutrients, heavy metals, and other pollutants from terrestrial to aquatic systems and is used as a measure of water quality. To investigate how the source and composition of CDOM changes in both space and time, we used chemical, spectroscopic, and fluorescence analyses to characterize CDOM in Lake Tianmuhu (a drinking water source) and its catchment in China. Parallel factor analysis (PARAFAC) identified three individual fluorophore moieties that were attributed to humic-like and protein-like materials in 224 water samples collected between December 2008 and September 2009. The upstream rivers contained significantly higher concentrations of CDOM than did the lake water (a(350) of 4.27±2.51 and 2.32±0.59 m(-1), respectively), indicating that the rivers carried a substantial load of organic matter to the lake. Of the three main rivers that flow into Lake Tianmuhu, the Pingqiao River brought in the most CDOM from the catchment to the lake. CDOM absorption and the microbial and terrestrial humic-like components, but not the protein-like component, were significantly higher in the wet season than in other seasons, indicating that the frequency of rainfall and runoff could significantly impact the quantity and quality of CDOM collected from the catchment. The different relationships between the maximum fluorescence intensities of the three PARAFAC components, CDOM absorption, and chemical oxygen demand (COD) concentration in riverine and lake water indicated the difference in the composition of CDOM between Lake Tianmuhu and the rivers that feed it. This study demonstrates the utility of combining excitation-emission matrix fluorescence and PARAFAC to study CDOM dynamics in inland waters. Copyright © 2011 Elsevier Ltd. All rights reserved.

The tryptophan-derived endogenous arylhydrocarbon receptor ligand 6-formylindolo[3,2-b]carbazole (FICZ) is a nanomolar UVA-photosensitizer in epidermal keratinocytes

Science.gov (United States)

Williams, Joshua D.; Cabello, Christopher M.; Qiao, Shuxi; Wondrak, Georg T.

2014-01-01

Endogenous UVA-chromophores may act as sensitizers of oxidative stress underlying cutaneous photoaging and photocarcinogenesis, but the molecular identity of non-DNA key chromophores displaying UVA-driven photodyamic activity in human skin remains largely undefined. Here we report that 6-formylindolo[3,2-b]carbazole (FICZ), a tryptophan photoproduct and endogenous high affinity aryl hydrocarbon receptor (AhR) agonist, acts as a nanomolar photosensitizer potentiating UVA-induced oxidative stress irrespective of AhR ligand activity. In human HaCaT and primary epidermal keratinocytes, photodynamic induction of apoptosis was elicited by the combined action of solar simulated UVA and FICZ, whereas exposure to the isolated action of UVA or FICZ did not impair viability. In a human epidermal tissue reconstruct, FICZ/UVA-cotreatment caused pronounced phototoxicity inducing keratinocyte cell death, and FICZ photodynamic activity was also substantiated in a murine skin exposure model. Array analysis revealed pronounced potentiation of cellular heat shock, ER stress, and oxidative stress response gene expression observed only upon FICZ/UVA-cotreatment. FICZ photosensitization caused intracellular oxidative stress, and comet analysis revealed introduction of formamidopyrimidine-DNA glycosylase (FPG)-sensitive oxidative DNA lesions suppressible by antioxidant cotreatment. Taken together, our data demonstrate that the endogenous AhR ligand FICZ displays nanomolar photodynamic activity representing a molecular mechanism of UVA-induced photooxidative stress potentially operative in human skin. PMID:25431849

One-Dimensional Multichromophor Arrays Based on DNA: From Self-Assembly to Light-Harvesting.

Science.gov (United States)

Ensslen, Philipp; Wagenknecht, Hans-Achim

2015-10-20

Light-harvesting complexes collect light energy and deliver it by a cascade of energy and electron transfer processes to the reaction center where charge separation leads to storage as chemical energy. The design of artificial light-harvesting assemblies faces enormous challenges because several antenna chromophores need to be kept in close proximity but self-quenching needs to be avoided. Double stranded DNA as a supramolecular scaffold plays a promising role due to its characteristic structural properties. Automated DNA synthesis allows incorporation of artificial chromophore-modified building blocks, and sequence design allows precise control of the distances and orientations between the chromophores. The helical twist between the chromophores, which is induced by the DNA framework, controls energy and electron transfer and thereby reduces the self-quenching that is typically observed in chromophore aggregates. This Account summarizes covalently multichromophore-modified DNA and describes how such multichromophore arrays were achieved by Watson-Crick-specific and DNA-templated self-assembly. The covalent DNA systems were prepared by incorporation of chromophores as DNA base substitutions (either as C-nucleosides or with acyclic linkers as substitutes for the 2'-deoxyribofuranoside) and as DNA base modifications. Studies with DNA base substitutions revealed that distances but more importantly relative orientations of the chromophores govern the energy transfer efficiencies and thereby the light-harvesting properties. With DNA base substitutions, duplex stabilization was faced and could be overcome, for instance, by zipper-like placement of the chromophores in both strands. For both principal structural approaches, DNA-based light-harvesting antenna could be realized. The major disadvantages, however, for covalent multichromophore DNA conjugates are the poor yields of synthesis and the solubility issues for oligonucleotides with more than 5-10 chromophore

Altered membrane permeability in multidrug resistant Escherichia ...

African Journals Online (AJOL)

The study was conducted with the objective of examining the outer membrane proteins and their involvement during the transport of β - lactams in multidrug resistant Escherichia coli isolated from extra-intestinal infections. Also, the response of gram negative bacterial biomembrane alteration was studied using extended ...

Optical Characteristics and Distribution of Chromophoric Dissolved Organic Matter in Onega Bay (White Sea) during the Summer Season (Findings from an Expedition from June 22 to 26, 2015)

Science.gov (United States)

Zaitseva, A. F.; Konyukhov, I. V.; Kazimirko, Yu. V.; Pogosyan, S. I.

2018-03-01

Onega Bay waters are characterized by a high content of chromophoric dissolved organic matter (CDOM). The absorbance spectra and fluorescence intensity (excitation wavelength 455 nm, emission wavelength >680 nm) were used to assess the distribution of CDOM content in water filtered through a GF/F filter. The CDOM content at different points in Onega Bay showed more than a fourfold difference, as inferred from the measured values. The CDOM content in surface waters was, as a rule, higher than in the deeper horizons. A higher CDOM content was measured near the Onega River, near the middle part of the Onega shore, and near the Pomor shore opposite the town of Belomorsk. River runoff is the major source of CDOM in Onega Bay water. The CDOM chemical composition in Onega Bay waters was heterogeneous. The ratio of the fluorescence intensity to the absorbance value was higher near the mouths of rivers and in intensive mixing zones than in water characterized by high salinity. A highly significant linear correlation ( R 2 = 0.7825) between water salinity and CDOM fluorescence intensity was demonstrated. The contribution of fluorescent compounds to river runoff CDOM is substantially higher than the contribution to the composition marine CDOM.

ON THE ROLE OF BACTERIAL MICROFLORA IN ETIOLOGY OF CHRONIC ADENOIDITIS IN CHILDREN

Directory of Open Access Journals (Sweden)

D. A. Tulupov

2014-01-01

Full Text Available A review of the results of clinical studies on the role of pathogenic bacterial microflora in etiology of chronic adenoiditis in children is shown in this article. According to the literature data the main cause of the development of chronic diseases of the nasopharynx in children is viral infection. The role of the bacterial microflora is secondary, but nevertheless significant. The main bacterial pathogens isolated from the nasopharynx of children with chronic adenoiditis are Staphylococcus aureus, Haemophilus influenzae and Streptococcus pneumonia. However there is significant dissociation in the prevalence of these bacterial agents according to the data of different scientists. Ability of the bacteria to produce biomembranes plays significant role in formation of persistence of the above-mentioned pathogens in the nasopharynx in chronic adenoiditis. Bacterial biomembranes as well as the revealing of the large amounts of bacteria within the tissues of adenoids determines discussions on possibilities of systemic and topical antibacterial treatment. 

Microchemical device based on microscopic bilayer lipid membranes; Bisho 2 bunshimaku wo mochiiita maikuro kagaku debaisu

Energy Technology Data Exchange (ETDEWEB)

Yokoyama, H. [Electrotechnical Lab., Ibaraki (Japan)

1996-04-01

If an organism is regarded as a macromolecular system, the element device to construct the same is the molecular structure of nano meter scale formed by the functional protein existing in biomembranes. A lot of essential functions of organism such as the sense reception including vision, gustation, etc., photosynthesis, energy-substance production and so on are performed therein. In this paper, the structure, preparing process and the functions of the microchemical device using micro-bilipid membranes are described. The simulation of the sense receiving functions of organisms is tried by said microchemical device wherein, same as biomembranes, the base is bilayer lipid molecular membrane and the receptive protein for receiving signals from exterior and output molecules such as ion channels connected to said receptive protein and the like are incorporated in the membranes. Recently, it becomes possible to make a partial imaging of the bilayer lipid membranes fixed on porous membrane by the observation with scanning Maxwell-stress microscope. 4 refs., 3 figs.

Radioecological sensitivity

International Nuclear Information System (INIS)

Howard, Brenda J.; Strand, Per; Assimakopoulos, Panayotis

2003-01-01

After the release of radionuclide into the environment it is important to be able to readily identify major routes of radiation exposure, the most highly exposed individuals or populations and the geographical areas of most concern. Radioecological sensitivity can be broadly defined as the extent to which an ecosystem contributes to an enhanced radiation exposure to Man and biota. Radioecological sensitivity analysis integrates current knowledge on pathways, spatially attributes the underlying processes determining transfer and thereby identifies the most radioecologically sensitive areas leading to high radiation exposure. This identifies where high exposure may occur and why. A framework for the estimation of radioecological sensitivity with respect to humans is proposed and the various indicators by which it can be considered have been identified. These are (1) aggregated transfer coefficients (Tag), (2) action (and critical) loads, (3) fluxes and (4) individual exposure of humans. The importance of spatial and temporal consideration of all these outputs is emphasized. Information on the extent of radionuclide transfer and exposure to humans at different spatial scales is needed to reflect the spatial differences which can occur. Single values for large areas, such as countries, can often mask large variation within the country. Similarly, the relative importance of different pathways can change with time and therefore assessments of radiological sensitivity are needed over different time periods after contamination. Radioecological sensitivity analysis can be used in radiation protection, nuclear safety and emergency preparedness when there is a need to identify areas that have the potential of being of particular concern from a risk perspective. Prior identification of radioecologically sensitive areas and exposed individuals improve the focus of emergency preparedness and planning, and contribute to environmental impact assessment for future facilities. The

Sensitivity functions for uncertainty analysis: Sensitivity and uncertainty analysis of reactor performance parameters

International Nuclear Information System (INIS)

Greenspan, E.

1982-01-01

This chapter presents the mathematical basis for sensitivity functions, discusses their physical meaning and information they contain, and clarifies a number of issues concerning their application, including the definition of group sensitivities, the selection of sensitivity functions to be included in the analysis, and limitations of sensitivity theory. Examines the theoretical foundation; criticality reset sensitivities; group sensitivities and uncertainties; selection of sensitivities included in the analysis; and other uses and limitations of sensitivity functions. Gives the theoretical formulation of sensitivity functions pertaining to ''as-built'' designs for performance parameters of the form of ratios of linear flux functionals (such as reaction-rate ratios), linear adjoint functionals, bilinear functions (such as reactivity worth ratios), and for reactor reactivity. Offers a consistent procedure for reducing energy-dependent or fine-group sensitivities and uncertainties to broad group sensitivities and uncertainties. Provides illustrations of sensitivity functions as well as references to available compilations of such functions and of total sensitivities. Indicates limitations of sensitivity theory originating from the fact that this theory is based on a first-order perturbation theory

Identifying and selecting edible luminescent probes as sensors of food quality

Directory of Open Access Journals (Sweden)

Maria G. Corradini

2016-06-01

Full Text Available Foods contain a plethora of aromatic molecules—natural colors, synthetic dyes, flavors, vitamins, antioxidants, etc.—that are luminescent, exhibiting prompt fluorescence or delayed phosphorescence. Although food autofluorescence has been used to detect specific contaminants (e.g., aflatoxins or to authenticate specific foods (olive oil, much of the potential of using the optical luminescence of intrinsic molecules for sensing properties of foods is unrealized. We summarize here work characterizing the photophysical properties of some edible, and potentially GRAS (generally-recognized-as-safe, chromophores and especially their sensitivity to, and thus potential for sensing, various physical—viscosity, mobility/rigidity—or chemical—polarity, pH—properties of food known to reflect or be indicative of food quality, stability, and safety. A thorough-going characterization of and robust protocols for interpretation of the luminescent signals from edible chromophores can expand the repertoire of analytical techniques available to monitor quality, and even safety, of the food supply at various stages of production, distribution and storage or even at point of sale.

Photodriven hydrogen evolution by molecular catalysts using Al2O3-protected perylene-3,4-dicarboximide on NiO electrodes† †Electronic supplementary information (ESI) available: Experimental details; additional electrochemical and photoelectrochemical characterization, UV-Vis spectra, and fsTA results; quantification of evolved hydrogen; and DFT-computed ground state structure of PMI diester. See DOI: 10.1039/c6sc02477g Click here for additional data file.

Science.gov (United States)

Kamire, Rebecca J.; Majewski, Marek B.; Hoffeditz, William L.; Phelan, Brian T.; Farha, Omar K.; Hupp, Joseph T.

2017-01-01

The design of efficient hydrogen-evolving photocathodes for dye-sensitized photoelectrochemical cells (DSPECs) requires the incorporation of molecular light absorbing chromophores that are capable of delivering reducing equivalents to molecular proton reduction catalysts at rates exceeding those of charge recombination events. Here, we report the functionalization and kinetic analysis of a nanostructured NiO electrode with a modified perylene-3,4-dicarboximide chromophore (PMI) that is stabilized against degradation by atomic layer deposition (ALD) of thick insulating Al2O3 layers. Following photoinduced charge injection into NiO in high yield, films with Al2O3 layers demonstrate longer charge separated lifetimes as characterized via femtosecond transient absorption spectroscopy and photoelectrochemical techniques. The photoelectrochemical behavior of the electrodes in the presence of Co(ii) and Ni(ii) molecular proton reduction catalysts is examined, revealing reduction of both catalysts. Under prolonged irradiation, evolved H2 is directly observed by gas chromatography supporting the applicability of PMI embedded in Al2O3 as a photocathode architecture in DSPECs. PMID:28616134

Spatiotemporal Characterization of Chromophoric Dissolved Organic Matter (CDOM and CDOM-DOC Relationships for Highly Polluted Rivers

Directory of Open Access Journals (Sweden)

Sijia Li

2016-09-01

Full Text Available Spectral characteristics of CDOM (Chromophoric dissolved organic matter in water columns are a key parameter for bio-optical modeling. Knowledge of CDOM optical properties and spatial discrepancy based on the relationship between water quality and spectral parameters in the Yinma River watershed with in situ data collected from highly polluted waters are exhibited in this study. Based on the comprehensive index method, the riverine waters showed serious contamination; especially the chemical oxygen demand (COD, iron (Fe, manganese (Mn, mercury (Hg and dissolved oxygen (DO were out of range of the contamination warning. Dissolved organic carbon (DOC and total suspended matter (TSM with prominent non-homogenizing were significantly high in the riverine waters, but chlorophyll-a (Chl-a was the opposite. The ternary phase diagram showed that non-algal particle absorption played an important role in total non-water light absorption (>50% in most sampling locations, and mean contributions of CDOM were 13% and 22% in the summer and autumn, respectively. The analysis of the ratio of absorption at 250–365 nm (E250:365 and the spectral slope (S275–295 indicated that CDOM had higher aromaticity and molecular weight in autumn than in summer, which is consistent with the results of water quality and the CDOM relative contribution rate. Redundancy analysis (RDA indicated that the environmental variables OSM (Organic suspended matter had a strong correlation with CDOM absorption, followed by heavy metals, e.g., Mn, Hg and Cr6+. However, for the specific UV absorbance (SUVA254, the seasonal values showed opposite results compared with the reported literature. The potential reasons were that more UDOM (uncolored dissolved organic matter from human sources (wastewater effluent existed in the waters. Terrigenous inputs simultaneously are in relation to the aCDOM(440-DOC relationship with the correlation coefficient of 0.90 in the summer (two-tailed, p < 0

Regeneration of bovine and octopus opsins in situ with natural and artificial retinals

International Nuclear Information System (INIS)

Koutalos, Y.; Ebrey, T.G.; Tsuda, M.

1989-01-01

The authors consider the problem of color regulation in visual pigments for both bovine rhodopsin and octopus rhodopsin. Both pigments have 11-cis-retinal as their chromophore. These rhodopsins were bleached in their native membranes, and the opsins were regenerated with natural and artificial chromophores. Both bovine and octopus opsins were regenerated with the 9-cis- and 11-cis-retinal isomers, but the octopus opsin was additionally regenerated with the 13-cis and all-trans isomers. Titration of the octopus opsin with 11-cis-retinal gave an extinction coefficient for octopus rhodopsin of 27,000 ± 3,000 M -1 cm -1 at 475 nm. The absorption maxima of bovine artificial pigments formed by regenerating opsin with the 11-cis dihydro series of chromophores support a color regulation model for bovine rhodopsin in which the chromophore-binding site of the protein has two negative charges: one directly hydrogen bonded to the Schiff base nitrogen and another near carbon-13. Formation of octopus artificial pigments with both all-trans and 11-cis dihydro chromophores leads to a similar model for octopus rhodopsin and metarhodopsin: there are two negative charges in the chromophore-binding site, one directly hydrogen bonded to the Schiff base nitrogen and a second near carbon-13. The interaction of this second charge with the chromophore in octopus rhodopsin is weaker than in bovine, while in metarhodopsin it is as strong as in bovine

A review on radiation damage of erythrocyte membranes

International Nuclear Information System (INIS)

Wang Junling; Wang Weidong; Qin Guangyong

2007-01-01

Biomembrane has very important biological function. Its damage will seriously disturb the directivity, the orderly nature and coordination of cell metabolism, and finally causes the cell death. This paper reviewed the effects of radiation damage on erythrocyte membrane in membrane composition, membrane function and oxidation resistance system. (authors)

Effects of the antioxidant moieties of dissolved organic matter on triplet-sensitized phototransformation processes: Implications for the photochemical modeling of sulfadiazine.

Science.gov (United States)

Vione, Davide; Fabbri, Debora; Minella, Marco; Canonica, Silvio

2018-01-01

Previous studies have shown that the photodegradation of some pollutants, induced by the excited triplet states of chromophoric dissolved organic matter ( 3 CDOM*), can be inhibited by back-reduction processes carried out by phenolic antioxidants occurring in dissolved organic matter (DOM). Here, for the first time to our knowledge, we included such an inhibition effect into a photochemical model and applied the model predictions to sulfadiazine (SDZ), a sulfonamide antibiotic that occurs in surface waters in two forms, neutral HSDZ and anionic SDZ - (pK a  = 6.5). The input parameters of the photochemical model were obtained by means of dedicated experiments, which showed that the inhibition effect was more marked for SDZ - than for HSDZ. Compared to the behavior of 2,4,6-trimethylphenol, which does not undergo antioxidant inhibition when irradiated in natural water samples, the back-reduction effect on the degradation of SDZ was proportional to the electron-donating capacity of the DOM. According to the model results, direct photolysis and OH reaction would account for the majority of both HSDZ and SDZ - photodegradation in waters having low dissolved organic carbon (DOC DOC values (>3-4 mgC L -1 ) and despite the back-reduction processes, the 3 CDOM* reactions are expected to account for the majority of HSDZ phototransformation. In the case of SDZ - at high DOC, most of the photodegradation would be accounted for by direct photolysis. The relative importance of the triplet-sensitized phototransformation of both SDZ - and (most importantly) HSDZ is expected to increase with increasing DOC, even in the presence of back reduction. An increase in water pH, favoring the occurrence of SDZ - with respect to HSDZ, would enhance direct photolysis at the expense of triplet sensitization. SDZ should be fairly photolabile under summertime sunlight, with predicted half-lives ranging from a few days to a couple of months depending on water conditions. Copyright © 2017

Dye-Sensitized Approaches to Photovoltaics

Science.gov (United States)

Grätzel, Michael

2008-03-01

Sensitization of wide band-gap semiconductors to photons of energy less than the band-gap is a key step in two technically important processes - panchromatic photography and photoelectrochemical solar cells. In both cases the photosensitive species is not the semiconductor - silver halide or metal oxide - but rather an electrochemically active dye. The gap between the highest occupied molecular level (HOMO) and the lowest unoccupied molecular level (LUMO) is less than the band-gap of the semiconductor with which it is associated. It can therefore absorb light of a wavelength longer than that to which the semiconductor itself is sensitive. The electrochemical process is initiated when the dye molecule relaxes from its photoexcited level by electron injection into the semiconductor, which therefore acts as a photoanode. If the dye is in contact with a redox electrolyte, the negative charge represented by the lost electron can be recovered from the reduced state of the redox system, which in return is regenerated by charge transfer from a cathode. An external load completes the electrical circuit. The system therefore represents a conversion of the energy of absorbed photons into an electrical current by a regenerative device in every functional respect analogous to a solid-state photovoltaic cell. As in any engineering system, choice of materials, their optimization and their synergy are essential to efficient operation. While a semiconductor-electrolyte contact is analogous to a Schottky contact, in that a barrier is established between two materials of different conduction mechanism, with the possibility of optical absorption, charge carrier pair generation and separation, it should be remembered that the photogenerated valence band hole in the semiconductor represents a powerful oxidizing agent. Given that the band-gap is related to the strength and therefore the stability of chemical bonding within the semiconductor, for narrow-gap materials the most likely

Sensitivity analysis

Science.gov (United States)

... page: //medlineplus.gov/ency/article/003741.htm Sensitivity analysis To use the sharing features on this page, please enable JavaScript. Sensitivity analysis determines the effectiveness of antibiotics against microorganisms (germs) ...

Superior optical nonlinearity of an exceptional fluorescent stilbene dye

Energy Technology Data Exchange (ETDEWEB)

He, Tingchao [College of Physics Science and Technology, Shenzhen University, Shenzhen 518060 (China); Division of Physics and Applied Physics, Centre for Disruptive Photonic Technologies (CDPT), School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Sreejith, Sivaramapanicker; Zhao, Yanli [Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore); Gao, Yang; Grimsdale, Andrew C. [School of Materials Science and Engineering, Nanyang Technological University, Singapore, Singapore 639798 (Singapore); Lin, Xiaodong, E-mail: linxd@szu.edu.cn, E-mail: hdsun@ntu.edu.sg [College of Physics Science and Technology, Shenzhen University, Shenzhen 518060 (China); Sun, Handong, E-mail: linxd@szu.edu.cn, E-mail: hdsun@ntu.edu.sg [Division of Physics and Applied Physics, Centre for Disruptive Photonic Technologies (CDPT), School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 (Singapore)

2015-03-16

Strong multiphoton absorption and harmonic generation in organic fluorescent chromophores are, respectively, significant in many fields of research. However, most of fluorescent chromophores fall short of the full potential due to the absence of the combination of such different nonlinear upconversion behaviors. Here, we demonstrate that an exceptional fluorescent stilbene dye could exhibit efficient two- and three-photon absorption under the excitation of femtosecond pulses in solution phase. Benefiting from its biocompatibility and strong excited state absorption behavior, in vitro two-photon bioimaging and superior optical limiting have been exploited, respectively. Simultaneously, the chromophore could generate efficient three-photon excited fluorescence and third-harmonic generation (THG) when dispersed into PMMA film, circumventing the limitations of classical fluorescent chromophores. Such chromophore may find application in the production of coherent light sources of higher photon energy. Moreover, the combination of three-photon excited fluorescence and THG can be used in tandem to provide complementary information in biomedical studies.

Unique proteomic signature for radiation sensitive patients; a comparative study between normo-sensitive and radiation sensitive breast cancer patients

Energy Technology Data Exchange (ETDEWEB)

Skiöld, Sara [Center for Radiation Protection Research, Department of Molecular Biosciences, The Wernner-Gren Institute, Stockholm University, Stockholm (Sweden); Azimzadeh, Omid [Institute of Radiation Biology, German Research Center for Environmental Health, Helmholtz Zentrum München (Germany); Merl-Pham, Juliane [Research Unit Protein Science, German Research Center for Environmental Health, Helmholtz Zentrum München, Neuherberg (Germany); Naslund, Ingemar; Wersall, Peter; Lidbrink, Elisabet [Division of Radiotherapy, Radiumhemmet, Karolinska University Hospital, Stockholm (Sweden); Tapio, Soile [Institute of Radiation Biology, German Research Center for Environmental Health, Helmholtz Zentrum München (Germany); Harms-Ringdahl, Mats [Center for Radiation Protection Research, Department of Molecular Biosciences, The Wernner-Gren Institute, Stockholm University, Stockholm (Sweden); Haghdoost, Siamak, E-mail: Siamak.Haghdoost@su.se [Center for Radiation Protection Research, Department of Molecular Biosciences, The Wernner-Gren Institute, Stockholm University, Stockholm (Sweden)

2015-06-15

Highlights: • The unique protein expression profiles were found that separate radiosensitive from normal sensitive breast cancer patients. • The oxidative stress response, coagulation properties and acute phase response suggested to be the hallmarks of radiation sensitivity. - Abstract: Radiation therapy is a cornerstone of modern cancer treatment. Understanding the mechanisms behind normal tissue sensitivity is essential in order to minimize adverse side effects and yet to prevent local cancer reoccurrence. The aim of this study was to identify biomarkers of radiation sensitivity to enable personalized cancer treatment. To investigate the mechanisms behind radiation sensitivity a pilot study was made where eight radiation-sensitive and nine normo-sensitive patients were selected from a cohort of 2914 breast cancer patients, based on acute tissue reactions after radiation therapy. Whole blood was sampled and irradiated in vitro with 0, 1, or 150 mGy followed by 3 h incubation at 37 °C. The leukocytes of the two groups were isolated, pooled and protein expression profiles were investigated using isotope-coded protein labeling method (ICPL). First, leukocytes from the in vitro irradiated whole blood from normo-sensitive and extremely sensitive patients were compared to the non-irradiated controls. To validate this first study a second ICPL analysis comparing only the non-irradiated samples was conducted. Both approaches showed unique proteomic signatures separating the two groups at the basal level and after doses of 1 and 150 mGy. Pathway analyses of both proteomic approaches suggest that oxidative stress response, coagulation properties and acute phase response are hallmarks of radiation sensitivity supporting our previous study on oxidative stress response. This investigation provides unique characteristics of radiation sensitivity essential for individualized radiation therapy.

Unique proteomic signature for radiation sensitive patients; a comparative study between normo-sensitive and radiation sensitive breast cancer patients

International Nuclear Information System (INIS)

Skiöld, Sara; Azimzadeh, Omid; Merl-Pham, Juliane; Naslund, Ingemar; Wersall, Peter; Lidbrink, Elisabet; Tapio, Soile; Harms-Ringdahl, Mats; Haghdoost, Siamak

2015-01-01

Highlights: • The unique protein expression profiles were found that separate radiosensitive from normal sensitive breast cancer patients. • The oxidative stress response, coagulation properties and acute phase response suggested to be the hallmarks of radiation sensitivity. - Abstract: Radiation therapy is a cornerstone of modern cancer treatment. Understanding the mechanisms behind normal tissue sensitivity is essential in order to minimize adverse side effects and yet to prevent local cancer reoccurrence. The aim of this study was to identify biomarkers of radiation sensitivity to enable personalized cancer treatment. To investigate the mechanisms behind radiation sensitivity a pilot study was made where eight radiation-sensitive and nine normo-sensitive patients were selected from a cohort of 2914 breast cancer patients, based on acute tissue reactions after radiation therapy. Whole blood was sampled and irradiated in vitro with 0, 1, or 150 mGy followed by 3 h incubation at 37 °C. The leukocytes of the two groups were isolated, pooled and protein expression profiles were investigated using isotope-coded protein labeling method (ICPL). First, leukocytes from the in vitro irradiated whole blood from normo-sensitive and extremely sensitive patients were compared to the non-irradiated controls. To validate this first study a second ICPL analysis comparing only the non-irradiated samples was conducted. Both approaches showed unique proteomic signatures separating the two groups at the basal level and after doses of 1 and 150 mGy. Pathway analyses of both proteomic approaches suggest that oxidative stress response, coagulation properties and acute phase response are hallmarks of radiation sensitivity supporting our previous study on oxidative stress response. This investigation provides unique characteristics of radiation sensitivity essential for individualized radiation therapy

Easily Processed Host-Guest Polymer Systems with High-Tg Characteristics (First-year Report)

Science.gov (United States)

2012-05-01

manner such that the effective electro- optical coefficient is maximized. Unfortunately, relaxation of the chromophore in the host polymer leads to...polished stainless steel facing plates (0.25 in thickness, McMaster ) and window molds cut from aluminum stock (1 mm thickness, McMaster ). Both facing...plasticization from the chromophore. Both chromophores resulted in substantial red-shifted absorption compared to a sample prepared in virgin PMMA. We expect

Photophysics of the variable quantum yield of asymmetric bilirubin

International Nuclear Information System (INIS)

Troup, G.J.

1998-01-01

Full text: Bilirubin (BR), responsible for neonatal jaundice, is a molecule containing two pyrromethenone chromophores conjoined by a 'saturated' carbon CH 2 group. Because this disease is cured by phototherapy, BR has been extensively studied by laser means. When the chromophores in each half of the molecule are identical, we have symmetrical BR (SBR); when they are not, we have asymmetric BR (ASBR). The quantum yield of the photoproducts in simple organic solution from SBR is not wavelength-dependent, while that from ASBR is. Because of the proximity of the two chromophores, both the SBR and ASBR systems are subject to Davidoff (dynamic electric dipole) splitting of the chromophore excited states. A quantum mechanical calculation shows that when the two (ASBR) chromophore states are not degenerate, the higher Davidoff state is preferentially occupied by the chromophore with the 'original' higher energy, and the lower Davidoff state by the chromophore of 'original' lower energy. This is just what is required for the quantum yield to vary with wavelength. If the variation of the quantum yield of ASBR in the presence of human serum albumen is approximated by a square-wave (narrow line approximation), the deduced ratio of the short wavelength photoproduct yield with the long wavelength one is in agreement with accepted values for the 'original' energy difference of the chromophores, and the Davidoff splitting parameter. A previous explanation has involved variation of relaxation processes with wavelength, but only qualitatively. The quantum yields for SBRs bonded to HSA are not yet published, but show wavelength variation, possibly from asymmetric bonding. In 0.1% ammonia/methanol however, there is no such variation for the SBRs, while for ASBR, there is, and the photoproduct ratios for long and short wavelength are reciprocals of one another, as predicted by our theory

Robustness, efficiency, and optimality in the Fenna-Matthews-Olson photosynthetic pigment-protein complex

Energy Technology Data Exchange (ETDEWEB)

Baker, Lewis A.; Habershon, Scott, E-mail: S.Habershon@warwick.ac.uk [Department of Chemistry and Centre for Scientific Computing, University of Warwick, Coventry CV4 7AL (United Kingdom)

2015-09-14

Pigment-protein complexes (PPCs) play a central role in facilitating excitation energy transfer (EET) from light-harvesting antenna complexes to reaction centres in photosynthetic systems; understanding molecular organisation in these biological networks is key to developing better artificial light-harvesting systems. In this article, we combine quantum-mechanical simulations and a network-based picture of transport to investigate how chromophore organization and protein environment in PPCs impacts on EET efficiency and robustness. In a prototypical PPC model, the Fenna-Matthews-Olson (FMO) complex, we consider the impact on EET efficiency of both disrupting the chromophore network and changing the influence of (local and global) environmental dephasing. Surprisingly, we find a large degree of resilience to changes in both chromophore network and protein environmental dephasing, the extent of which is greater than previously observed; for example, FMO maintains EET when 50% of the constituent chromophores are removed, or when environmental dephasing fluctuations vary over two orders-of-magnitude relative to the in vivo system. We also highlight the fact that the influence of local dephasing can be strongly dependent on the characteristics of the EET network and the initial excitation; for example, initial excitations resulting in rapid coherent decay are generally insensitive to the environment, whereas the incoherent population decay observed following excitation at weakly coupled chromophores demonstrates a more pronounced dependence on dephasing rate as a result of the greater possibility of local exciton trapping. Finally, we show that the FMO electronic Hamiltonian is not particularly optimised for EET; instead, it is just one of many possible chromophore organisations which demonstrate a good level of EET transport efficiency following excitation at different chromophores. Overall, these robustness and efficiency characteristics are attributed to the highly

Robustness, efficiency, and optimality in the Fenna-Matthews-Olson photosynthetic pigment-protein complex

International Nuclear Information System (INIS)

Baker, Lewis A.; Habershon, Scott

2015-01-01

Pigment-protein complexes (PPCs) play a central role in facilitating excitation energy transfer (EET) from light-harvesting antenna complexes to reaction centres in photosynthetic systems; understanding molecular organisation in these biological networks is key to developing better artificial light-harvesting systems. In this article, we combine quantum-mechanical simulations and a network-based picture of transport to investigate how chromophore organization and protein environment in PPCs impacts on EET efficiency and robustness. In a prototypical PPC model, the Fenna-Matthews-Olson (FMO) complex, we consider the impact on EET efficiency of both disrupting the chromophore network and changing the influence of (local and global) environmental dephasing. Surprisingly, we find a large degree of resilience to changes in both chromophore network and protein environmental dephasing, the extent of which is greater than previously observed; for example, FMO maintains EET when 50% of the constituent chromophores are removed, or when environmental dephasing fluctuations vary over two orders-of-magnitude relative to the in vivo system. We also highlight the fact that the influence of local dephasing can be strongly dependent on the characteristics of the EET network and the initial excitation; for example, initial excitations resulting in rapid coherent decay are generally insensitive to the environment, whereas the incoherent population decay observed following excitation at weakly coupled chromophores demonstrates a more pronounced dependence on dephasing rate as a result of the greater possibility of local exciton trapping. Finally, we show that the FMO electronic Hamiltonian is not particularly optimised for EET; instead, it is just one of many possible chromophore organisations which demonstrate a good level of EET transport efficiency following excitation at different chromophores. Overall, these robustness and efficiency characteristics are attributed to the highly

The contribution of component variation and phytoplankton growth to the distribution variation of chromophoric dissolved organic matter content in a mid-latitude subtropical drinking water source reservoir for two different seasons.

Science.gov (United States)

Sun, Qiyuan; Jiang, Juan; Zheng, Yuyi; Wang, Feifeng; Wu, Chunshan; Xie, Rong-Rong

2017-07-01

The distribution variation in chromophoric dissolved organic matter (CDOM) content in mid-latitude subtropical drinking water source reservoirs (MDWSRs) has great significance in the security of aquatic environments and human health. CDOM distribution is heavily influenced by biogeochemical processes and anthropogenic activity. However, little is known regarding the impact of component variation and phytoplankton growth on CDOM distribution variation in MDWSR. Therefore, samples were collected from a representative MDWSR (the Shanzai Reservoir) for analysis. CDOM absorption and fluorescence coupling with parallel factor analysis were measured and calculated. The results indicated that only two CDOM components were found in the surface water of Shanzai Reservoir, fulvic acid, and high-excitation tryptophan, originating from terrestrial and autochthonous sources, respectively. The types of components did not change with the season. The average molecular weight of CDOM increased in proportion to its fulvic acid content. The distribution variation in CDOM content mainly resulted from the variation in two CDOM components in summer and from high-excitation tryptophan in winter. Phytoplankton growth strongly influenced the distribution variation of CDOM content in summer; the metabolic processes of Cyanobacteria and Bacillariophyta consumed fulvic acid, while that of Cryptophyta produced high-excitation tryptophan.

Effects of nitrate and phosphate supply on chromophoric and fluorescent dissolved organic matter in the Eastern Tropical North Atlantic: a mesocosm study

Science.gov (United States)

Loginova, A. N.; Borchard, C.; Meyer, J.; Hauss, H.; Kiko, R.; Engel, A.

2015-12-01

In open-ocean regions, as is the Eastern Tropical North Atlantic (ETNA), pelagic production is the main source of dissolved organic matter (DOM) and is affected by dissolved inorganic nitrogen (DIN) and phosphorus (DIP) concentrations. Changes in pelagic production under nutrient amendments were shown to also modify DOM quantity and quality. However, little information is available about the effects of nutrient variability on chromophoric (CDOM) and fluorescent (FDOM) DOM dynamics. Here we present results from two mesocosm experiments ("Varied P" and "Varied N") conducted with a natural plankton community from the ETNA, where the effects of DIP and DIN supply on DOM optical properties were studied. CDOM accumulated proportionally to phytoplankton biomass during the experiments. Spectral slope (S) decreased over time indicating accumulation of high molecular weight DOM. In Varied N, an additional CDOM portion, as a result of bacterial DOM reworking, was determined. It increased the CDOM fraction in DOC proportionally to the supplied DIN. The humic-like FDOM component (Comp.1) was produced by bacteria proportionally to DIN supply. The protein-like FDOM component (Comp.2) was released irrespectively to phytoplankton or bacterial biomass, but depended on DIP and DIN concentrations. Under high DIN supply, Comp.2 was removed by bacterial reworking, leading to an accumulation of humic-like Comp.1. No influence of nutrient availability on amino acid-like FDOM component in peptide form (Comp.3) was observed. Comp.3 potentially acted as an intermediate product during formation or degradation of Comp.2. Our findings suggest that changes in nutrient concentrations may lead to substantial responses in the quantity and quality of optically active DOM and, therefore, might bias results of the applied in situ optical techniques for an estimation of DOC concentrations in open-ocean regions.

Vibrational energy flow through the green fluorescent protein-water interface: communication maps and thermal boundary conductance.

Science.gov (United States)

Xu, Yao; Leitner, David M

2014-07-17

We calculate communication maps for green fluorescent protein (GFP) to elucidate energy transfer pathways between the chromophore and other parts of the protein in the ground and excited state. The approach locates energy transport channels from the chromophore to remote regions of the protein via residues and water molecules that hydrogen bond to the chromophore. We calculate the thermal boundary conductance between GFP and water over a wide range of temperature and find that the interface between the protein and the cluster of water molecules in the β-barrel poses negligible resistance to thermal flow, consistent with facile vibrational energy transfer from the chromophore to the β-barrel waters observed in the communication maps.

Noise sensitivity: symptoms, health status, illness behavior and co-occurring environmental sensitivities.

NARCIS (Netherlands)

Baliatsas, C.; Kamp, I. van; Swart, W.; Hooiveld, M.; Yzermans, J.

2016-01-01

Epidemiological evidence on the symptomatic profile, health status and illness behavior of people with subjective sensitivity to noise is still scarce. Also, it is unknown to what extent noise sensitivity co-occurs with other environmental sensitivities such as multi-chemical sensitivity and

Luminescence Properties of Self-Aggregating TbIII-DOTA-Functionalized Calix[4]arenes

Directory of Open Access Journals (Sweden)

Florian Mayer

2018-01-01

Full Text Available Self-aggregating calix[4]arenes carrying four DOTA ligands on the upper rim for stable complexation of paramagnetic GdIII-ions have already been proposed as MRI probes. In this work, we investigate the luminescence properties of TbIII-DOTA-calix[4]arene-4OPr containing four propyl-groups and compare them with those of the analog substituted with a phthalimide chromophore (TbIII-DOTA-calix[4]arene-3OPr-OPhth. We show that, given its four aromatic rings, the calix[4]arene core acts as an effective sensitizer of Tb-centered luminescence. Substituents on the lower rim can modulate the aggregation behavior, which in turn determines the luminescence properties of the compounds. In solid state, the quantum yield of the phthalimide derivative is almost three times as high as that of the propyl-functionalized analog demonstrating a beneficial role of the chromophore on Tb-luminescence. In solution, however, the effect of the phthalimide group vanishes, which we attribute to the large distance between the chromophore and the lanthanide, situated on the opposite rims of the calix[4]arene. Both quantum yields and luminescence lifetimes show clear concentration dependence in solution, related to the strong impact of aggregation on the luminescence behavior. We also evidence the variability in the values of the critical micelle concentration depending on the experimental technique. Such luminescent calix[4]arene platforms accommodating stable lanthanide complexes can be considered valuable building blocks for the design of dual MR/optical imaging probes.

The Potential Applications of Real-Time Monitoring of Water Quality in a Large Shallow Lake (Lake Taihu, China Using a Chromophoric Dissolved Organic Matter Fluorescence Sensor

Directory of Open Access Journals (Sweden)

Cheng Niu

2014-06-01

Full Text Available This study presents results from field surveys performed over various seasons in a large, eutrophic, shallow lake (Lake Taihu, China using an in situ chromophoric dissolved organic matter (CDOM fluorescence sensor as a surrogate for other water quality parameters. These measurements identified highly significant empirical relationships between CDOM concentration measured using the in situ fluorescence sensor and CDOM absorption, fluorescence, dissolved organic carbon (DOC, chemical oxygen demand (COD and total phosphorus (TP concentrations. CDOM concentration expressed in quinine sulfate equivalent units, was highly correlated with the CDOM absorption coefficient (r2 = 0.80, p < 0.001, fluorescence intensities (Ex./Em. 370/460 nm (r2 = 0.91, p < 0.001, the fluorescence index (r2 = 0.88, p < 0.001 and the humification index (r2 = 0.78, p < 0.001, suggesting that CDOM concentration measured using the in situ fluorescence sensor could act as a substitute for the CDOM absorption coefficient and fluorescence measured in the laboratory. Similarly, CDOM concentration was highly correlated with DOC concentration (r2 = 0.68, p < 0.001, indicating that in situ CDOM fluorescence sensor measurements could be a proxy for DOC concentration. In addition, significant positive correlations were found between laboratory CDOM absorption coefficients and COD (r2 = 0.83, p < 0.001, TP (r2 = 0.82, p < 0.001 concentrations, suggesting a potential further application for the real-time monitoring of water quality using an in situ CDOM fluorescence sensor.

Exciplex formation and energy transfer in a self-assembled metal-organic hybrid system.

Science.gov (United States)

Haldar, Ritesh; Rao, K Venkata; George, Subi J; Maji, Tapas Kumar

2012-05-07

Exciting assemblies: A metal-organic self-assembly of pyrenebutyric acid (PBA), 1,10-phenanthroline (o-phen), and Mg(II) shows solid-state fluorescence originating from a 1:1 PBA-o-phen exciplex. This exciplex fluorescence is sensitized by another residual PBA chromophore through an excited-state energy-transfer process. The solvent polarity modulates the self-assembly and the corresponding exciplex as well as the energy transfer, resulting in tunable emission of the hybrid (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Noise sensitivity: Symptoms, health status, illness behavior and co-occurring environmental sensitivities

Energy Technology Data Exchange (ETDEWEB)

Baliatsas, Christos, E-mail: c.baliatsas@nivel.nl [Netherlands Institute for Health Services Research (NIVEL), Utrecht (Netherlands); Kamp, Irene van, E-mail: irene.van.kamp@rivm.nl [National Institute for Public Health and the Environment (RIVM), Bilthoven (Netherlands); Swart, Wim, E-mail: wim.swart@rivm.nl [National Institute for Public Health and the Environment (RIVM), Bilthoven (Netherlands); Hooiveld, Mariëtte, E-mail: m.hooiveld@nivel.nl [Netherlands Institute for Health Services Research (NIVEL), Utrecht (Netherlands); Yzermans, Joris, E-mail: J.Yzermans@nivel.nl [Netherlands Institute for Health Services Research (NIVEL), Utrecht (Netherlands)

2016-10-15

Epidemiological evidence on the symptomatic profile, health status and illness behavior of people with subjective sensitivity to noise is still scarce. Also, it is unknown to what extent noise sensitivity co-occurs with other environmental sensitivities such as multi-chemical sensitivity and sensitivity to electromagnetic fields (EMF). A cross-sectional study performed in the Netherlands, combining self-administered questionnaires and electronic medical records of non-specific symptoms (NSS) registered by general practitioners (GP) allowed us to explore this further. The study sample consisted of 5806 participants, drawn from 21 general practices. Among participants, 722 (12.5%) responded “absolutely agree” to the statement “I am sensitive to noise”, comprising the high noise-sensitive (HNS) group. Compared to the rest of the sample, people in the HNS group reported significantly higher scores on number and duration of self-reported NSS, increased psychological distress, decreased sleep quality and general health, more negative symptom perceptions and higher prevalence of healthcare contacts, GP-registered NSS and prescriptions for antidepressants and benzodiazepines. These results remained robust after adjustment for demographic, residential and lifestyle characteristics, objectively measured nocturnal noise exposure from road-traffic and GP-registered morbidity. Co-occurrence rates with other environmental sensitivities varied between 9% and 50%. Individuals with self-declared sensitivity to noise are characterized by high prevalence of multiple NSS, poorer health status and increased illness behavior independently of noise exposure levels. Findings support the notion that different types of environmental sensitivities partly overlap. - Highlights: • People with self-reported noise sensitivity experience multiple non-specific symptoms. • They also report comparatively poorer health and increased illness behavior. • Co-occurrence with other

Noise sensitivity: Symptoms, health status, illness behavior and co-occurring environmental sensitivities

International Nuclear Information System (INIS)

Baliatsas, Christos; Kamp, Irene van; Swart, Wim; Hooiveld, Mariëtte; Yzermans, Joris

2016-01-01

Epidemiological evidence on the symptomatic profile, health status and illness behavior of people with subjective sensitivity to noise is still scarce. Also, it is unknown to what extent noise sensitivity co-occurs with other environmental sensitivities such as multi-chemical sensitivity and sensitivity to electromagnetic fields (EMF). A cross-sectional study performed in the Netherlands, combining self-administered questionnaires and electronic medical records of non-specific symptoms (NSS) registered by general practitioners (GP) allowed us to explore this further. The study sample consisted of 5806 participants, drawn from 21 general practices. Among participants, 722 (12.5%) responded “absolutely agree” to the statement “I am sensitive to noise”, comprising the high noise-sensitive (HNS) group. Compared to the rest of the sample, people in the HNS group reported significantly higher scores on number and duration of self-reported NSS, increased psychological distress, decreased sleep quality and general health, more negative symptom perceptions and higher prevalence of healthcare contacts, GP-registered NSS and prescriptions for antidepressants and benzodiazepines. These results remained robust after adjustment for demographic, residential and lifestyle characteristics, objectively measured nocturnal noise exposure from road-traffic and GP-registered morbidity. Co-occurrence rates with other environmental sensitivities varied between 9% and 50%. Individuals with self-declared sensitivity to noise are characterized by high prevalence of multiple NSS, poorer health status and increased illness behavior independently of noise exposure levels. Findings support the notion that different types of environmental sensitivities partly overlap. - Highlights: • People with self-reported noise sensitivity experience multiple non-specific symptoms. • They also report comparatively poorer health and increased illness behavior. • Co-occurrence with other

Tools for characterizing biomembranes : final LDRD report.

Energy Technology Data Exchange (ETDEWEB)

Alam, Todd Michael; Stevens, Mark; Holland, Gregory P.; McIntyre, Sarah K.

2007-10-01

A suite of experimental nuclear magnetic resonance (NMR) spectroscopy tools were developed to investigate lipid structure and dynamics in model membrane systems. By utilizing both multinuclear and multidimensional NMR experiments a range of different intra- and inter-molecular contacts were probed within the membranes. Examples on pure single component lipid membranes and on the canonical raft forming mixture of DOPC/SM/Chol are presented. A unique gel phase pretransition in SM was also identified and characterized using these NMR techniques. In addition molecular dynamics into the hydrogen bonding network unique to sphingomyelin containing membranes were evaluated as a function of temperature, and are discussed.

The Electrical and Dynamical Properties of Biomembranes

DEFF Research Database (Denmark)

Mosgaard, Lars Dalskov

of the coupling between the membrane and the electrical eld within a universal thermodynamic framework. Within this framework, known electrical phenomena associated with lipid membranes such as o set voltage, electrostriction, piezoelectricity and exoelectricity can be captured and viewed as special cases...... the functional behavior of membranes in biological systems. In order to do so we apply linear response theory and non-equilibrium thermodynamics to lipid membranes and propose a new approach: we investigate the relaxation behavior of lipid membranes in the vicinity of their lipid melting transition, taking...... into account the coupling between thermodynamical uctuations and the available heat reservoir. The next step is to combine the knowledge on lipid membranes subjected to an electrical eld with the knowledge on their relaxation behavior and use our understanding to attempt to re-evaluate the results of common...

Correlation of radiation sensitivity and nitrofurantoin sensitivity of Escherichia coli K-12

International Nuclear Information System (INIS)

Kloeck, K.

1981-01-01

The Uvr- and rec-mutants of E.coli K-12 have been tested with a view to their radiation- and nitrofuration sensitivity. The tests showed that all mutants tested were more radiation- and NF-sensitive than the wild type AB 1157. When the NF-sensitivity had been compared to the UV- and X-ray sensitivity it became obvious that the NF-sensitivity is correlated to the UV-sensitivity. Studies carried out with regard to the time dependence of the NF-effect on E.coli showed that the effect of NF on E. Coli became weaker after about 1 1/2 to 2 hours. That is possibly caused by the fact that the E. coli bacteria succeed in reducing the NF to an inactive form. By means of nitrosoguanidine mutants of E-coli AB 1157 had been induced and by means of the Replicite Plating Method, NF-sensible mutants had been isolated from the plutonium mixture. Among the mutants which had been isolated by this method, 74% had been more UV-sensitive than the wild type and 55% more X-ray sensitive. Thus NF-sensitive mutants have not necessarily to be considered as rec-mutants as there are also uvr-mutants in the mixture. (orig.) [de

Allergic sensitization

DEFF Research Database (Denmark)

van Ree, Ronald; Hummelshøj, Lone; Plantinga, Maud

2014-01-01

Allergic sensitization is the outcome of a complex interplay between the allergen and the host in a given environmental context. The first barrier encountered by an allergen on its way to sensitization is the mucosal epithelial layer. Allergic inflammatory diseases are accompanied by increased pe...

Electric Field-Controlled Ion Transport In TiO2 Nanochannel.

Science.gov (United States)

Li, Dan; Jing, Wenheng; Li, Shuaiqiang; Shen, Hao; Xing, Weihong

2015-06-03

On the basis of biological ion channels, we constructed TiO2 membranes with rigid channels of 2.3 nm to mimic biomembranes with flexible channels; an external electric field was employed to regulate ion transport in the confined channels at a high ionic strength in the absence of electrical double layer overlap. Results show that transport rates for both Na+ and Mg2+ were decreased irrespective of the direction of the electric field. Furthermore, a voltage-gated selective ion channel was formed, the Mg2+ channel closed at -2 V, and a reversed relative electric field gradient was at the same order of the concentration gradient, whereas the Na+ with smaller Stokes radius and lower valence was less sensitive to the electric field and thus preferentially occupied and passed the channel. Thus, when an external electric field is applied, membranes with larger nanochannels have promising applications in selective separation of mixture salts at a high concentration.

2369-IJBCS-Article-Jean-Marc Ategbo

African Journals Online (AJOL)

hp

Original Paper http://indexmedicus.afro.who.int. Etude Ethnobotanique des plantes médicinales utilisées dans le traitement traditionnel des hépatites virales B et C dans quelques départements du Bénin. F. D. Félix ... 2Département de Physiologie Animale, Laboratoire de Biomembrane et Signalisation Cellulaire,.

Effect of an ultraviolet-filtering intraocular lens on cystoid macular edema

Energy Technology Data Exchange (ETDEWEB)

Kraff, M.C.; Sanders, D.R.; Jampol, L.M.; Lieberman, H.L.

1985-03-01

A prospective double-masked study of 301 patients was undertaken to compare the effect of ultraviolet (UV) filtering in implant intraocular lenses (IOL) on the angiographic incidence of cystoid macular edema (CME) in patients undergoing extracapsular cataract extraction. Patients were randomized to receive either a posterior chamber IOL that contained UV-absorbing chromophore or an identical IOL which did not contain such a chromophore. All patients were scheduled for fluorescein angiography between three and six months after surgery; 228 angiograms were obtained that were readable for the presence or absence of angiographic CME. The mean interval following surgery was 4.3 months. The incidence of CME was 18.8% (21 of 112) in patients who received lenses without UV-filtering chromophore and 9.5% (11 of 116) in patients who received IOLs that contained UV-filtering chromophore. These findings show that UV-filtering-IOLs resulted in a statistically significant decrease in the incidence of CME. The presence or absence of the UV-filtering chromophore did not, however, significantly affect visual acuity in the early postoperative period.

Spatiotemporal variations in the abundance and composition of bulk and chromophoric dissolved organic matter in seasonally hypoxia-influenced Green Bay, Lake Michigan, USA.

Science.gov (United States)

DeVilbiss, Stephen E; Zhou, Zhengzhen; Klump, J Val; Guo, Laodong

2016-09-15

Green Bay, Lake Michigan, USA, is the largest freshwater estuary in the Laurentian Great Lakes and receives disproportional terrestrial inputs as a result of a high watershed to bay surface area ratio. While seasonal hypoxia and the formation of "dead zones" in Green Bay have received increasing attention, there are no systematic studies on the dynamics of dissolved organic matter (DOM) and its linkage to the development of hypoxia. During summer 2014, bulk dissolved organic carbon (DOC) analysis, UV-vis spectroscopy, and fluorescence excitation-emission matrices (EEMs) coupled with PARAFAC analysis were used to quantify the abundance, composition and source of DOM and their spatiotemporal variations in Green Bay, Lake Michigan. Concentrations of DOC ranged from 202 to 571μM-C (average=361±73μM-C) in June and from 279 to 610μM-C (average=349±64μM-C) in August. In both months, absorption coefficient at 254nm (a254) was strongly correlated to bulk DOC and was most abundant in the Fox River, attesting a dominant terrestrial input. Non-chromophoric DOC comprised, on average, ~32% of bulk DOC in June with higher terrestrial DOM and ~47% in August with higher aquagenic DOM, indicating that autochthonous and more degraded DOM is of lower optical activity. PARAFAC modeling on EEM data resulted in four major fluorescent DOM components, including two terrestrial humic-like, one aquagenic humic-like, and one protein-like component. Variations in the abundance of DOM components further supported changes in DOM sources. Mixing behavior of DOM components also indicated that while bulk DOM behaved quasi-conservatively, significant compositional changes occurred during transport from the Fox River to the open bay. Copyright © 2016 Elsevier B.V. All rights reserved.

Water quality monitoring in a bathing area of Civitavecchia (Latium, Italy) using Chromophoric Dissolved Organic Matter (CDOM) as a tracer of faecal contamination

Science.gov (United States)

Madonia, Alice; Bonamano, Simone; Caruso, Gabriella; Stefani', Chiara; Consalvi, Natalizia; Piermattei, Viviana; Zappalà, Giuseppe; Marcelli, Marco

2017-04-01

Coastal urban bathing areas are often affected by events of faecal contamination, caused by the discharge of untreated wastewaters during the bathing season that can increase the risk for public health. Monitoring the quality of recreational waters is still closely linked to time-consuming seawater sampling and laboratory analysis, not allowing promptly management interventions. To face this issue, the European environmental policies strongly promote the development of coastal observing systems, above all in the Southern European Seas (SES). Chromophoric Dissolved Organic Matter (CDOM) has been increasingly used as a tracer of bacterial loads, since wastewaters are characterized by a large amount of organic compounds. The aim of this work was to study the relation between CDOM and Escherichia coli abundance, giving relevance to bacterial physiological state detected using both the standard culture method and the innovative fluorescent antibody technique. Attention has been paid also on the expression of extracellular enzymatic activity by the total microbial community to explore the role of bacteria in the decomposition processes of dissolved organic matter. Data were collected during summer 2015 and 2016 in a bathing area of Civitavecchia at increasing distances from the discharge point. The results confirm the usefulness of CDOM measurements as a proxy of faecal pollution in bathing areas. In this perspective, the low-cost stand-alone systems equipped with CDOM fluorescence sensors developed by the Laboratory of Experimental Oceanology and Marine Ecology (Tuscia University) (Marcelli et al., 2014) could allow the continous monitoring of water quality, increasing the capabilities of the Civitavecchia Coastal Environmental Monitoring System (C-CEMS) in the analysis of pollution events. Thanks to the integration of in situ fixed stations, high-resolution satellites imagery and numerical models, C-CEMS provides a management tool to support the stakeholders for timely

Climate Sensitivity

Energy Technology Data Exchange (ETDEWEB)

Lindzen, Richard [M.I.T.

2011-11-09

Warming observed thus far is entirely consistent with low climate sensitivity. However, the result is ambiguous because the sources of climate change are numerous and poorly specified. Model predictions of substantial warming aredependent on positive feedbacks associated with upper level water vapor and clouds, but models are notably inadequate in dealing with clouds and the impacts of clouds and water vapor are intimately intertwined. Various approaches to measuring sensitivity based on the physics of the feedbacks will be described. The results thus far point to negative feedbacks. Problems with these approaches as well as problems with the concept of climate sensitivity will be described.

Photostable nonlinear optical polycarbonates

NARCIS (Netherlands)

Faccini, M.; Balakrishnan, M.; Diemeer, Mart; Torosantucci, Riccardo; Driessen, A.; Reinhoudt, David; Verboom, Willem

2008-01-01

Highly thermal and photostable nonlinear optical polymers were obtained by covalently incorporating the tricyanovinylidenediphenylaminobenzene (TCVDPA) chromophore to a polycarbonate backbone. NLO polycarbonates with different chromophore attachment modes and flexibilities were synthesized. In spite

Photophysics of conjugated polymers: interplay between Förster energy migration and defect concentration in shaping a photochemical funnel in PPV.

Science.gov (United States)

Saini, Sangeeta; Bagchi, Biman

2010-07-21

Recent single molecule experiments have suggested the existence of a photochemical funnel in the photophysics of conjugated polymers, like poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] (MEH-PPV). The funnel is believed to be a consequence of the presence of conformational or chemical defects along the polymer chain and efficient non-radiative energy transfer among different chromophore segments. Here we address the effect of the excitation energy dynamics on the photophysics of PPV. The PPV chain is modeled as a polymer with the length distribution of chromophores given either by a Gaussian or by a Poisson distribution. We observe that the Poisson distribution of the segment lengths explains the photophysics of PPV better than the Gaussian distribution. A recently proposed version of an extended 'particle-in-a-box' model is used to calculate the exciton energies and the transition dipole moments of the chromophores, and a master equation to describe the excitation energy transfer among different chromophores. The rate of energy transfer is assumed to be given here, as a first approximation, by the well-known Förster expression. The observed excitation population dynamics confirms the photochemical funneling of excitation energy from shorter to longer chromophores of the polymer chain. The time scale of spectral shift and energy transfer for our model polymer, with realistic values of optical parameters, is in the range of 200-300 ps. We find that the excitation energy may not always migrate towards the longest chromophore segments in the polymer chain as the efficiency of energy transfer between chromophores depends on the separation distance between the two and their relative orientation.

Report: GPU Based Massive Parallel Kawasaki Kinetics In Monte Carlo Modelling of Lipid Microdomains

OpenAIRE

Lis, M.; Pintal, L.

2013-01-01

This paper introduces novel method of simulation of lipid biomembranes based on Metropolis Hastings algorithm and Graphic Processing Unit computational power. Method gives up to 55 times computational boost in comparison to classical computations. Extensive study of algorithm correctness is provided. Analysis of simulation results and results obtained with classical simulation methodologies are presented.

Suppression of BRCA2 by Mutant Mitochondrial DNA in Prostate Cancer

Science.gov (United States)

2014-07-01

Columbia, Vancouver, British Columbia V6K 2P5, Canada 9Institute of Biomembranes and Bioenergetics, National Research Council (C.N.R.), Bari, Italy ...Jacquotte A, Polsky D, Ferrara J, Perez-Soler R, Cordon-Cardo C, Pagano M and Osman I. Altered expression of p27 and Skp2 proteins in prostate cancer of

Microring resonator based modulator made by direct photodefinition of an electro-optic polymer

Science.gov (United States)

Balakrishnan, M.; Faccini, M.; Diemeer, M. B. J.; Klein, E. J.; Sengo, G.; Driessen, A.; Verboom, W.; Reinhoudt, D. N.

2008-04-01

A laterally coupled microring resonator was fabricated by direct photodefinition of negative photoresist SU8, containing tricyanovinylidenediphenylaminobenzene chromophore, by exploiting the low ultraviolet absorption window of this chromophore. The ring resonator was first photodefined by slight cross-linking. Thereafter, poling (to align the chromophores) and further cross-linking (to increase the glass transition temperature) were simultaneously carried out. The material showed excellent photostability and the electro-optic modulation with an r33 of 11pm/V was demonstrated at 10MHz.

Atomistic absorption spectra and non-adiabatic dynamics of the LH2 complex with a GPU-accelerated ab initio exciton model

Science.gov (United States)

Glowacki, David

Recently, we outlined an efficient multi-tiered parallel excitonic framework that utilizes time dependent density functional theory (TDDFT) to calculate ground/excited state energies and gradients of large supramolecular complexes in atomistic detail. In this paper, we apply our ab initioexciton framework to the 27 coupled bacteriocholorophyll-a chromophores which make up the LH2 complex, using it to compute linear absorption spectra and short-time, on-the-fly nonadiabatic surface-hopping (SH) dynamics of electronically excited LH2. Our ab initio exciton model includes two key parameters whose values are determined by fitting to experiment: d, which is added to the diagonal elements, corrects for the error in TDDFT vertical excitation energies on a single chromophore; and e, which occurs on the off-diagonal matrix elements, describes the average dielectric screening of the inter-chromophore transition-dipole coupling. Using snapshots obtained from equilibrium molecular dynamics simulations (MD) of LH2, best-fit values of both d and e were obtained by fitting to the thermally broadened experimental absorption spectrum within the Frank-Condon approximation, providing a linear absorption spectrum that agrees reasonably well with the experimental observations. We follow the nonadiabatic dynamics using surface hopping to construct time-resolved visualizations of the EET dynamics in the sub-picosecond regime following photoexcitation. This provides some qualitative insight into the excitonic energy transfer (EET) that results from atomically resolved vibrational fluctuations of the chromophores. The dynamical picture that emerges is one of rapidly fluctuating eigenstates that are delocalized over multiple chromophores and undergo frequent crossing on a femtosecond timescale as a result of the underlying chromophore vibrational dynamics. The eigenstate fluctuations arise from disorder in both the diagonal chromophore site energies and the off-diagonal inter-chromophore

Effects of carotenoids on lipid bilayers.

Science.gov (United States)

Johnson, Quentin R; Mostofian, Barmak; Fuente Gomez, Gabriel; Smith, Jeremy C; Cheng, Xiaolin

2018-01-31

Carotenoids have been found to be important in improving the integrity of biomembranes in eukaryotes. However, the molecular details of how carotenoids modulate the physical properties of biomembranes are unknown. To this end, we have conducted a series of molecular dynamics simulations of different biologically-relevant membranes in the presence of carotenoids. The carotenoid effect on the membrane was found to be specific to the identity of the carotenoid and the composition of the membrane itself. Therefore, different classes of carotenoids produce a different effect on the membrane, and different membrane phases are affected differently by carotenoids. It is apparent from our data that carotenoids do trigger the bilayer to become thinner. The mechanism by which this occurs depends on two competing factors, the ability of the lipid tails of opposing monolayers to either (1) compress or (2) interdigitate as the bilayer condenses. Indeed, carotenoids directly influence the physical properties via these two mechanisms, thus compacting the bilayer. However, the degree to which these competing mechanisms are utilized depends on the bilayer phase and the carotenoid identity.

Comparison of the rate constants for energy transfer in the light-harvesting protein, C-phycocyanin, calculated from Foerster`s theory and experimentally measured by time-resolved fluorescence spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Debreczeny, Martin Paul [Univ. of California, Berkeley, CA (United States)

1994-05-01

We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.

Environmental Sensitivity in Children: Development of the Highly Sensitive Child Scale and Identification of Sensitivity Groups

Science.gov (United States)

Pluess, Michael; Assary, Elham; Lionetti, Francesca; Lester, Kathryn J.; Krapohl, Eva; Aron, Elaine N.; Aron, Arthur

2018-01-01

A large number of studies document that children differ in the degree they are shaped by their developmental context with some being more sensitive to environmental influences than others. Multiple theories suggest that "Environmental Sensitivity" is a common trait predicting the response to negative as well as positive exposures.…

The relationship between the anoxic sensitivity and the extent of sensitization by nitrous oxide

International Nuclear Information System (INIS)

Ewing, D.; Walton, H.L.; Guilfoil, D.S.; Ohm, M.B.

1991-01-01

Nitrous oxide reacts during irradiation to increase the yield of ·OH, a radical many believe to be a major cause of lethality. Logically, one would expect N 2 O to be a radiation sensitizer. In some instances it is, while in others it is not. In some cases we can explain why N 2 O fails to sensitize; factors such as dose rate, cell concentration, buffer composition and ionic strength all influence when N 2 O will sensitize and if it sensitizes, by what magnitude. Based on the results presented here with multiple strains of procaryotic and eucaryotic cells, we believe the anoxic sensitivity is another critical factor that governs whether N 2 O will sensitize. Our data, with data from the literature, show a relationship between the anoxic sensitivity and the N 2 O enhancement ratio. N 2 O does not sensitize in vitro unless the anoxic sensitivity (inactivation constant, K) is less than ∼ 0.2 daGy -1 . (author)

Microring resonator based modulator made by direct photodefinition of an electro-optic polymer

NARCIS (Netherlands)

Lam, Nghi Q.; Balakrishnan, M.; Faccini, M.; Diemeer, Mart; Klein, E.J.; Sengo, G.; Sengo, G.; Driessen, A.; Verboom, Willem; Reinhoudt, David

2008-01-01

A laterally coupled microring resonator was fabricated by direct photodefinition of negative photoresist SU8, containing tricyanovinylidenediphenylaminobenzene chromophore, by exploiting the low ultraviolet absorption window of this chromophore. The ring resonator was first photodefined by slight

Enhanced Measurements of Chromophoric Dissolved Organic Matter (CDOM) for Water Quality Analysis using a New Simultaneous Absorbance and Fluorescence Instrument

Science.gov (United States)

Gilmore, A. M.

2009-12-01

Water quality, with respect to suspended particles and dissolved organic and inorganic compounds, is now recognized as one of the top global environmental concerns. Contemporary research indicates fluorescence spectral analyses coupled with UV-VIS absorbance assays have the potential, especially when combined and coordinated, to facilitate rapid, robust quantification of a wide range of compounds, including interactions among them. Fluorescence excitation-emission matrices (EEMs) collected over the UV-VIS region provide a wealth of information on chromophoric dissolved organic matter (CDOM). CDOM includes humic and fulvic acid, chlorophyll, petroleum, protein, amino acid, quinone, fertilizer, pesticide, sewage and numerous other compound classes. Analysis of the EEMs using conventional and multivariate techniques, including primarily parallel factor analysis (PARAFAC), provides information about many types of CDOM relevant to carbon cycling and pollution of fresh, marine and drinking water sources. Of critical concern also are the CDOM interactions with, and optical activities of, dissolved inorganic compounds. Many of the inorganic compounds and oxygen demand parameters can be analyzed with a wide range of UV-VIS absorbance assays. The instrument is designed and optimized for high UV throughput and low stray light performance. The sampling optics are optimized for both fluorescence and absorbance detection with the same sample. Both EEM and absorbance measurements implement NIST traceable instrument correction and calibration routines. The fluorescence detection utilizes a high dynamic range CCD coupled to a high-resolution spectrograph while absorbance utilizes diode based detection with a high dynamic range and extremely low-stray light specifications. The CDOM analysis is facilitated by a transfer of the data and model information with the PARAFAC routine. The EEM analysis software package facilitates coordinated correction of and correlation with the

Dopamine mediated iron release from ferritin is enhanced at higher temperatures: Possible implications for fever-induced Parkinson's disease

International Nuclear Information System (INIS)

Babincova, Melania; Babinec, Peter

2005-01-01

A new molecular mechanism is proposed to explain the pathogenesis of fever-induced Parkinson's disease. This proposal is based on dopamine and 6-hydroxydopamine-mediated free iron release from ferritin magnetic nanoparticles, which is enhanced at higher temperatures, and which may lead to substantial peroxidation and injury of lipid biomembranes of the substantia nigra in the brain

Photoluminescence of self-organized perylene bisimide polymers

NARCIS (Netherlands)

Neuteboom, E.E.; Meskers, S.C.J.; Meijer, E.W.; Janssen, R.A.J.

2004-01-01

Three polymers consisting of alternating perylene bisimide chromophores and flexible polytetrahydrofuran segments of different length have been studied using absorption and (time-resolved) photoluminescence spectroscopy. In o-dichlorobenzene, the chromophores self organize to form H-like aggregates.

Synthetic incorporation of Nile Blue into DNA using 2′-deoxyriboside substitutes: Representative comparison of (R- and (S-aminopropanediol as an acyclic linker

Directory of Open Access Journals (Sweden)

Daniel Lachmann

2010-02-01

Full Text Available The Nile Blue chromophore was incorporated into oligonucleotides using “click” chemistry for the postsynthetic modification of oligonucleotides. These were synthesized using DNA building block 3 bearing an alkyne group and reacted with the azide 4. (R-3-amino-1,2-propanediol was applied as the linker between the phosphodiester bridges. Two sets of DNA duplexes were prepared. One set carried the chromophore in an A-T environment, the second set in a G-C environment. Both were characterized by optical spectroscopy. Sequence-dependent fluorescence quenching was applied as a sensitive tool to compare the stacking interactions with respect to the chirality of the acyclic linker attachment. The results were compared to recent results from duplexes that carried the Nile Blue label in a sequentially and structurally identical context, except for the opposite chirality of the linker ((S-3-amino-1,2-propandiol. Only minor, negligible differences were observed. Melting temperatures, UV–vis absorption spectra together with fluorescence quenching data indicate that Nile Blue stacks perfectly between the adjacent base pairs regardless of whether it has been attached via an S- or R-configured linker. This result was supported by geometrically optimized DNA models.

Developing cultural sensitivity

DEFF Research Database (Denmark)

Ruddock, Heidi; Turner, deSalle

2007-01-01

. Background. Many countries are becoming culturally diverse, but healthcare systems and nursing education often remain mono-cultural and focused on the norms and needs of the majority culture. To meet the needs of all members of multicultural societies, nurses need to develop cultural sensitivity......Title. Developing cultural sensitivity: nursing students’ experiences of a study abroad programme Aim. This paper is a report of a study to explore whether having an international learning experience as part of a nursing education programme promoted cultural sensitivity in nursing students...... and incorporate this into caregiving. Method. A Gadamerian hermeneutic phenomenological approach was adopted. Data were collected in 2004 by using in-depth conversational interviews and analysed using the Turner method. Findings. Developing cultural sensitivity involves a complex interplay between becoming...

The relationship between the anoxic sensitivity and the extent of sensitization by nitrous oxide

Energy Technology Data Exchange (ETDEWEB)

Ewing, D.; Walton, H.L.; Guilfoil, D.S.; Ohm, M.B. (Hahnemann Univ., Philadelphia, PA (USA). Dept. of Radiation Oncology and Nuclear Medicine)

1991-03-01

Nitrous oxide reacts during irradiation to increase the yield of center dotOH, a radical many believe to be a major cause of lethality. Logically, one would expect N{sub 2}O to be a radiation sensitizer. In some instances it is, while in others it is not. In some cases we can explain why N{sub 2}O fails to sensitize; factors such as dose rate, cell concentration, buffer composition and ionic strength all influence when N{sub 2}O will sensitize and if it sensitizes, by what magnitude. Based on the results presented here with multiple strains of procaryotic and eucaryotic cells, we believe the anoxic sensitivity is another critical factor that governs whether N{sub 2}O will sensitize. Our data, with data from the literature, show a relationship between the anoxic sensitivity and the N{sub 2}O enhancement ratio. N{sub 2}O does not sensitize in vitro unless the anoxic sensitivity (inactivation constant, K) is less than {similar to} 0.2 daGy{sup -1}. (author).

Beyond the Förster formulation for resonance energy transfer: the role of dark states.

Science.gov (United States)

Sissa, C; Manna, A K; Terenziani, F; Painelli, A; Pati, S K

2011-07-28

Resonance Energy Transfer (RET) is investigated in pairs of charge-transfer (CT) chromophores. CT chromophores are an interesting class of π conjugated chromophores decorated with one or more electron-donor and acceptor groups in polar (D-π-A), quadrupolar (D-π-A-π-D or A-π-D-π-A) or octupolar (D(-π-A)(3) or A(-π-D)(3)) structures. Essential-state models accurately describe low-energy linear and nonlinear spectra of CT-chromophores and proved very useful to describe spectroscopic effects of electrostatic interchromophore interactions in multichromophoric assemblies. Here we apply the same approach to describe RET between CT-chromophores. The results are quantitatively validated by an extensive comparison with time-dependent density functional theory (TDDFT) calculations, confirming that essential-state models offer a simple and reliable approach for the calculation of electrostatic interchromophore interactions. This is an important result since it sets the basis for more refined treatments of RET: essential-state models are in fact easily extended to account for molecular vibrations in truly non-adiabatic approaches and to account for inhomogeneous broadening effects due to polar solvation. Optically forbidden (dark) states of quadrupolar and octupolar chromophores offer an interesting opportunity to verify the reliability of the dipolar approximation. In striking contrast with the dipolar approximation that strictly forbids RET towards or from dark states, our results demonstrate that dark states can take an active role in RET with interaction energies that, depending on the relative orientation of the chromophores, can be even larger than those relevant to allowed states. Essential-state models, whose predictions are quantitatively confirmed by TDDFT results, allow us to relate RET interaction energies towards allowed and dark states to the supramolecular symmetry of the RET-pair, offering reliable design strategies to optimize RET-interactions. This