Rapid and selective derivatizatin method for the nitrogen-sensitive detection of carboxylic acids in biological fluids prior to gas chromatographic analysis

NARCIS (Netherlands)

Lingeman, H.; Haan, H.B.P.; Hulshoff, A.

1984-01-01

A rapid and selective derivatization procedure is described for the pre-column labelling of carboxylic acids with a nitrogen-containing label. The carboxylic acid function is activated with 2-bromo-1-methylpyridinium iodide and the activated carboxylic acid function reacts with a primary or a

Synthesis and Characterization of PEDOT Derivative with Carboxyl Group and Its Chemo/Bio Sensing Application as Nanocomposite, Immobilized Biological and Enhanced Optical Materials

International Nuclear Information System (INIS)

Zhang, Long; Wen, Yangping; Yao, Yuanyuan; Xu, Jingkun; Duan, Xuemin; Zhang, Ge

2014-01-01

Graphical abstract: Electropolymerization of C4-EDOT-COOH and corresponding polymer's sensing application for environmental, pharmaceutical, biology and food. -- Highlights: •C4-EDOT-COOH monomer with good solubility in water was synthesized by an efficient five-step route. •That acidic conditions were favorable for the electropolymerization of C4-EDOT-COOH. •The resulting high-quality polymer film can be employed for the fabrication of chemo/bio-sensors and optical sensors. •These as-prepared sensors can be applied to the simple, fast and sensitive detection of different analytes. -- Abstract: Various electrochemical chemo/bio-sensors and optical sensors are facilely explored for the sensitive determination of biomolecules, drug molecules, environmental pollutants, and metal ions using a carboxylic-functionalized poly(3,4-ethylenedioxythiophene) derivative (PC4), which is easily obtained by the direct electropolymerization of a water-soluble 4-((2,3-dihydrothieno[3,4-b][1,4] dioxin-2-yl) methoxy)-4-oxobutanoic acid (C4-EDOT-COOH) monomer in a microemulsion system. The effect of different pH values on the electropolymerization of C4-EDOT-COOH monomer is investigated, and the as-prepared PC4 film is characterized by electrochemical method, infrared spectrum, and scanning electron microscope. The resulting high-quality PC4 film as a sensing material not only can combine with various biologically active species via covalent linkage and inorganic materials via layer-by-layer self-assembly for the construction of electrochemical chemo/bio-sensors, but also excellent optical performance of PC4 can be employed for the fabrication of optical sensors. These as-prepared chemo/bio-sensors can be applied to the simple, fast and sensitive detection of environmental pollutants, pharmaceuticals, hazardous substances, and biological active substance and nutrients present in food by means of electrochemistry, ultraviolet and fluorescence spectroscopy. Satisfactory results

Synthesis and Biological Evaluation of Ru(II) and Pt(II) Complexes Bearing Carboxyl Groups as Potential Anticancer Targeted Drugs.

Science.gov (United States)

Martínez, Ma Ángeles; Carranza, M Pilar; Massaguer, Anna; Santos, Lucia; Organero, Juan A; Aliende, Cristina; de Llorens, Rafael; Ng-Choi, Iteng; Feliu, Lidia; Planas, Marta; Rodríguez, Ana M; Manzano, Blanca R; Espino, Gustavo; Jalón, Félix A

2017-11-20

The synthesis and characterization of Pt(II) (1 and 2) and Ru(II) arene (3 and 4) or polypyridine (5 and 6) complexes is described. With the aim of having a functional group to form bioconjugates, one uncoordinated carboxyl group has been introduced in all complexes. Some of the complexes were selected for their potential in photodynamic therapy (PDT). The molecular structures of complexes 2 and 5, as well as that of the sodium salt of the 4'-(4-carboxyphenyl)-2,2':6',2″-terpyridine ligand (cptpy), were determined by X-ray diffraction. Different techniques were used to evaluate the binding capacity to model DNA molecules, and MTT cytotoxicity assays were performed against four cell lines. Compounds 3, 4, and 5 showed little tendency to bind to DNA and exhibited poor biological activity. Compound 2 behaves as bonded to DNA probably through a covalent interaction, although its cytotoxicity was very low. Compound 1 and possibly 6, both of which contain a cptpy ligand, were able to intercalate with DNA, but toxicity was not observed for 6. However, compound 1 was active in all cell lines tested. Clonogenic assays and apoptosis induction studies were also performed on the PC-3 line for 1. The photodynamic behavior for complexes 1, 5, and 6 indicated that their nuclease activity was enhanced after irradiation at λ = 447 nm. The cell viability was significantly reduced only in the case of 5. The different behavior in the absence or presence of light makes complex 5 a potential prodrug of interest in PDT. Molecular docking studies followed by molecular dynamics simulations for 1 and the counterpart without the carboxyl group confirmed the experimental data that pointed to an intercalation mechanism. The cytotoxicity of 1 and the potential of 5 in PDT make them good candidates for subsequent conjugation, through the carboxyl group, to "selected peptides" which could facilitate the selective vectorization of the complex toward receptors that are overexpressed in

Giant regular polyhedra from calixarene carboxylates and uranyl

Science.gov (United States)

Pasquale, Sara; Sattin, Sara; Escudero-Adán, Eduardo C.; Martínez-Belmonte, Marta; de Mendoza, Javier

2012-01-01

Self-assembly of large multi-component systems is a common strategy for the bottom-up construction of discrete, well-defined, nanoscopic-sized cages. Icosahedral or pseudospherical viral capsids, built up from hundreds of identical proteins, constitute typical examples of the complexity attained by biological self-assembly. Chemical versions of the so-called 5 Platonic regular or 13 Archimedean semi-regular polyhedra are usually assembled combining molecular platforms with metals with commensurate coordination spheres. Here we report novel, self-assembled cages, using the conical-shaped carboxylic acid derivatives of calix[4]arene and calix[5]arene as ligands, and the uranyl cation UO22+ as a metallic counterpart, which coordinates with three carboxylates at the equatorial plane, giving rise to hexagonal bipyramidal architectures. As a result, octahedral and icosahedral anionic metallocages of nanoscopic dimensions are formed with an unusually small number of components. PMID:22510690

Biological roles and therapeutic potential of hydroxy-carboxylic acid receptors

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Kashan eAhmed

2011-10-01

Full Text Available In the recent past, deorphanization studies have described intermediates of energy metabolism to activate G protein-coupled receptors (GPCRs and to thereby regulate metabolic functions. GPR81, GPR109A and GPR109B, formerly known as the nicotinic acid receptor family, are encoded by clustered genes and share a high degree of sequence homology. Recently, hydroxy-carboxylic acids were identified as endogenous ligands of GPR81, GPR109A and GPR109B, and therefore these receptors have been placed into a novel receptor family of hydroxy-carboxylic acid (HCA receptors. The HCA1 receptor (GPR81 is activated by the glycolytic metabolite 2-hydroxy-propionic acid (lactate, the HCA2 receptor is activated by the ketone body 3-hydroxy-butyric acid and the HCA3 receptor (GPR109B is a receptor for the β-oxidation intermediate 3-hydroxy-octanoic acid. While HCA1 and HCA2 receptors are present in most mammalian species, the HCA3 receptor is exclusively found in humans and higher primates. HCA receptors are expressed in adipose tissue and mediate anti-lipolytic effects in adipocytes through Gi-type G-protein-dependent inhibition of adenylyl cyclase. HCA2 and HCA3 inhibit lipolysis during conditions of increased β-oxidation such as prolonged fasting, whereas HCA1 mediates the anti-lipolytic effects of insulin in the fed state. As HCA2 is a receptor for the established anti-dyslipidemic drug nicotinic acid, HCA1 and HCA3 also represent promising drug targets and several synthetic ligands for HCA receptors have been developed. In this article, we will summarize the deorphanization and pharmacological characterization of HCA receptors. Moreover, we will discuss recent progress in elucidating the physiological and pathophysiological role to further evaluate the therapeutic potential of the HCA receptor family for the treatment of metabolic disease.

Electro-induced reactions of biologically important molecules

International Nuclear Information System (INIS)

Kocisek, J.

2010-01-01

The thesis presents the results of research activities in the field of electron interactions with biologically relevant molecules which was carried out during my PhD studies at the Department of Experimental Physics, Comenius University in Bratislava. Electron induced interactions with biologically relevant molecules were experimentally studied using crossed electron-molecule beams experiment. The obtained results, were presented in four publications in international scientific journals. First study of deals with electron impact ionisation of furanose alcohols [see 1. in list of author publications on page 22]. It has been motivated by most important works in the field of electron induced damages of DNA bases [4]. Studied 3-hydroxytetrahydrofuran and tetrahydrofurfuryl alcohol, are important model molecules for more complex biological systems (e.g. deoxyribose).The influence of hydroxyl group on stabilisation of the positive ions of the molecules, together with the stability of furan ring in ionized form are main themes of the study. The studies of small amides and aminoacids are connected to scientific studies in the field of formation of the aminoacids and other biologically relevant molecules in space and works trying to explain electron induced processes in more complex molecules[12, 13, 24]. The most important results were obtained for aminoacid Serine [see 2. in list of author publications on page 22]. We have showed that additional OH group of Serine considerably lower the reaction enthalpy limit of reactions resulting to formation of neutral water molecules, in comparison to other amino acids. Also the study of (M-H)- reaction channel using the electron beam with FWHM under 100 meV is of high importance in the field. The last part of the thesis is focused on the electron interactions with organosilane compounds. Materials prepared from organosilane molecules in plasmas have wide range of applications in both biology and medicine. We have studied electron

An enantioselective approach toward 3,4-dihydroisocoumarin through the bromocyclization of styrene-type carboxylic acids.

Science.gov (United States)

Chen, Jie; Zhou, Ling; Tan, Chong Kiat; Yeung, Ying-Yeung

2012-01-20

A facile and enantioselective approach toward 3,4-dihydroisocoumarin was developed. The method involved an amino-thiocarbamate catalyzed enantioselective bromocyclization of styrene-type carboxylic acids, yielding 3-bromo-3,4-dihydroisocoumarins with good yields and ee's. 3-Bromo-3,4-dihydroisocoumarins are versatile building blocks for various dihydroisocoumarin derivatives in which the Br group can readily be modified to achieve biologically important 4-O-type and 4-N-type 3,4-dihydroisocoumarin systems. In addition, studies indicated that, by refining some parameters, the synthetically useful 5-exo phthalide products could be achieved with good yields and ee's.

Formation of biologically relevant carboxylic acids during the gamma irradiation of acetic acid

Science.gov (United States)

Negron-Mendoza, A.; Ponnamperuma, C.

1976-01-01

Irradiation of aqueous solutions of acetic acid with gamma rays produced several carboxylic acids in small yield. Their identification was based on the technique of gas chromatography combined with mass spectrometry. Some of these acids are Krebs Cycle intermediates. Their simultaneous formation in experiments simulating the primitive conditions on the earth suggests that metabolic pathways may have had their origin in prebiotic chemical processes.

Thiosemicarbazones: preparation methods, synthetic applications and biological importance

International Nuclear Information System (INIS)

Tenorio, Romulo P.; Goes, Alexandre J.S.; Lima, Jose G. de; Faria, Antonio R. de; Alves, Antonio J.; Aquino, Thiago M. de

2005-01-01

Thiosemicarbazones are a class of compounds known by their chemical and biological properties, such as antitumor, antibacterial, antiviral and antiprotozoal activity. Their ability to form chelates with metals has great importance in their biological activities. Their synthesis is very simple, versatile and clean, usually giving high yields. They are largely employed as intermediates, in the synthesis of others compounds. This article is a survey of some of these characteristics showing their great importance to organic and medicinal chemistry. (author)

Effects of Multiwalled Carbon Nanotube Surface Modification and Purification on Bovine Serum Albumin Binding and Biological Responses

Directory of Open Access Journals (Sweden)

Wei Bai

2016-01-01

Full Text Available Carboxylation of multiwalled carbon nanotubes (MWCNTs has been used to improve solubility in aqueous systems and for further functionalization with biologically active moieties for biomedical uses. An important consideration is that oxidation debris is generated during the process of carboxylation, which can be removed by base washing. We hypothesized that surface modification as well as purification by debris removal may alter physicochemical properties of MWCNTs and their ability to bind proteins. We utilized pristine MWCNT, carboxylated MWCNTs (F-MWCNTs, and base-washed carboxylated MWCNTs (BW-F-MWCNTs to examine formation of a bovine serum albumin (BSA protein corona and impact on biological responses. We found that carboxylation increased the capability of F-MWCNTs to bind BSA, and base washing further increased this binding. Functionalization increased cellular uptake by rat aortic endothelial cells (RAEC and mouse macrophages (RAW264.7, while base washing showed results similar to the functionalized analog. Interestingly, BSA binding downregulated mRNA levels of interleukin-6 (IL-6 and heme oxygenase 1 (Hmox1 in RAEC cells but upregulated the expression of IL-6 and Hmox1 in RAW264.7 cells. Overall, our study demonstrated that surface modification as well as further purification impacted the interaction of MWCNTs with proteins and subsequent cellular responses.

Stereospecific synthesis of syn-α-oximinoamides by a three-component reaction of isocyanides, syn-chlorooximes, and carboxylic acids.

Science.gov (United States)

Pirali, Tracey; Mossetti, Riccardo; Galli, Simona; Tron, Gian Cesare

2011-07-15

A stereospecific multicomponent reaction among isocyanides, syn-chlorooximes, and carboxylic acids provides an efficient synthesis of biologically relevant syn-α-oximinoamides. © 2011 American Chemical Society

Do carboximide–carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

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Ramanpreet Kaur

2015-05-01

Full Text Available Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular interactions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations.

Surface grafting of carboxylic groups onto thermoplastic polyurethanes to reduce cell adhesion

Energy Technology Data Exchange (ETDEWEB)

Alves, P., E-mail: palves@eq.uc.pt [CIEPQPF, Departamento de Engenharia Química, Universidade de Coimbra, Polo II, Pinhal de Marrocos, 3030-790 Coimbra (Portugal); Ferreira, P. [CIEPQPF, Departamento de Engenharia Química, Universidade de Coimbra, Polo II, Pinhal de Marrocos, 3030-790 Coimbra (Portugal); Kaiser, Jean-Pierre [EMPA, St. Gallen, Lerchenfeldstrasse 5, CH-9014 St. Gallen (Switzerland); Salk, Natalie [Mikrofertigung – Micro Engineering, Fraunhofer IFAM, Wiener Strasse 12, D-288359 Bremen (Germany); Bruinink, Arie [EMPA, St. Gallen, Lerchenfeldstrasse 5, CH-9014 St. Gallen (Switzerland); Sousa, Hermínio C. de; Gil, M.H. [CIEPQPF, Departamento de Engenharia Química, Universidade de Coimbra, Polo II, Pinhal de Marrocos, 3030-790 Coimbra (Portugal)

2013-10-15

The interaction of polymers with other materials is an important issue, being their surface properties clearly crucial. For some important polymer applications, their surfaces have to be modified. Surface modification aims to tailor the surface characteristics of a material for a specific application without affecting its bulk properties. Materials can be surface modified by using biological, chemical or physical methods. The aim of this work was to improve the reactivity of the thermoplastic polyurethane (TPU) material (Elastollan{sup ®}) surface and to make its surface cell repellent by grafting carboxylic groups onto its surface. Two TPU materials were studied: a polyether-based TPU and a polyester-based TPU. The grafting efficiency was evaluated by contact angle measurements and by analytical determination of the COOH groups. Scanning electron microscopy (SEM) of the membranes surface was performed as well as cell adhesion tests. It was proved that the surfaces of the TPUs membranes were successfully modified and that cell adhesion was remarkably reduced.

1-Azaniumylcyclobutane-1-carboxylate monohydrate

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Ray J. Butcher

2014-02-01

Full Text Available In the title compound, C5H9NO2·H2O, the amino acid is in the usual zwitterionic form involving the α-carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7 and 0.118 (7. In the crystal, N—H...O and O—H...O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+ and donor (through a single carboxylate O from two different aminocyclobutane carboxylate moities], resulting in a two-dimensional layered structure lying parallel to (100.

Correction: Synthesis of pyrrolidine-3-carboxylic acid derivatives via asymmetric Michael addition reactions of carboxylate-substituted enones.

Science.gov (United States)

Yin, Feng; Garifullina, Ainash; Tanaka, Fujie

2018-04-25

Correction for 'Synthesis of pyrrolidine-3-carboxylic acid derivatives via asymmetric Michael addition reactions of carboxylate-substituted enones' by Feng Yin et al., Org. Biomol. Chem., 2017, 15, 6089-6092.

Carboxylate ligands drastically enhance the rates of oxo exchange and hydrogen peroxide disproportionation by oxo manganese compounds of potential biological significance.

Science.gov (United States)

Dubois, Lionel; Pécaut, Jacques; Charlot, Marie-France; Baffert, Carole; Collomb, Marie-Noëlle; Deronzier, Alain; Latour, Jean-Marc

2008-01-01

To mimic the carboxylate-rich active site of the manganese catalases more closely we introduced carboxylate groups into dimanganese complexes in place of nitrogen ligands. The series of dimanganese(III,IV) complexes of tripodal ligands [Mn(2)(L)(2)(O)(2)](3+/+/-/3-) was extended from those of tpa (1) and H(bpg) (2) to those of H(2)(pda) (3) and H(3)(nta) (4) (tpa=tris-picolylamine, H(bpg)=bis-picolylglycylamine, H(2)(pda)=picolyldiglycylamine, H(3)(nta)=nitrilotriacetic acid). While 3 [Mn(2)(pda)(2)(O)(2)][Na(H(2)O)(3)] could be synthesized at -20 degrees C and characterized in the solid state, 4 [Mn(2)(nta)(2)(O)(2)](3-) could be obtained and studied only in solution at -60 degrees C. A new synthetic procedure for the dimanganese(III,III) complexes was devised, using stoichiometric reduction of the dimanganese(III,IV) precursor by the benzil radical with EPR monitoring. This enabled the preparation of the parent dimanganese(III,III) complex 5 [Mn(2)(tpa)(2)(O)(2)](ClO(4))(2), which was structurally characterized. The UV/visible, IR, EPR, magnetic, and electrochemical properties of complexes 1-3 and 5 were analyzed to assess the electronic changes brought about by the carboxylate replacement of pyridine ligands. The kinetics of the oxo ligand exchanges with labeled water was examined in acetonitrile solution. A dramatic effect of the number of carboxylates was evidenced. Interestingly, the influence of the second carboxylate substitution differs from that of the first one probably because this substitution occurs on an out-of-plane coordination while the former occurs in the plane of the [Mn(2)O(2)] core. Indeed, on going from 1 to 3 the exchange rate was increased by a factor of 50. Addition of triethylamine caused a rate increase for 1, but not for 3. The abilities of 1-3 to disproportionate H(2)O(2) were assessed volumetrically. The disproportionation exhibited a sensitivity corresponding to the carboxylate substitution. These observations strongly suggest that

Confinement effect of protonation/deprotonation of carboxylic group modified in nanochannel

International Nuclear Information System (INIS)

Gao, Hong-Li; Zhang, Hui; Li, Cheng-Yong; Xia, Xing-Hua

2013-01-01

Protonation and deprotonation processes are the key step of acid–base reaction and occur in many biological processes. Study on the deprotonation process of molecules and/or functional groups in confined conditions would help us understand the acid–base theory and confinement effect of biomolecules. In this paper, we use a recently established approach to the study of protonation and deprotonation processes of functional groups in porous anodic alumina array nanochannels by measuring the flux of electrochemical active probes (ferricyanide ions) using an Au film electrochemical detector sputtered at the end of nanochannels. The protonation and deprotonation processes of surface functional groups in nanochannels will change the surface charges and in turn modulate the transportation of charged electroactive probes through nanochannels. The titration curve for the deprotonation of carboxylic groups in nanochannel confined conditions is obtained by measuring the current signal of ferricyanide probe flowing through an carboxylic-anchored PAA nanochannels array at different solution pH. Results show that the deprotonation of carboxylic group in nanochannel occurs in one step with a pK 1/2 = 6.2. The present method provides an effective tool to study the deprotonation processes of various functional groups and biomolecules under confined conditions

CARBOXYLIC ACIDS ELECTROOXIDATION ON SHUNGITE ELECTRODE

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Oleksandr Davydenko

2017-03-01

Full Text Available Purpose: This article discusses the electrochemical method of directional conversion of carboxylic acids, which are the most aggressive hydrocarbons oxidation products back into the corresponding hydrocarbons. Existing methods for the regeneration of waste petroleum oils have significant drawbacks, which include the formation of new hard-reclaimed waste and loss of a significant part of the oil during regeneration. Methods: Electrooxidation processes of carboxylic acid on various electrode materials: platinum, graphite and shungite anodes were studied. Results: Potentiostatic polarization curves with simultaneous measurement of near-electrode solution pH showed differences in the process on these anode materials: dimer yield for Kolbe is decreased under the transition from platinum to shungite. At potentials higher than 2.0 v, carboxylic acid has a higher adsorbability compared to water. Therefore Faraday’s side-process of water oxidation doesn’t almost occur, which contributes to high yield of expected product according to current. Electrolysis of carboxylic acids solutions under controlled potential (2.0 and 2.4 V and chromatographic analysis of the formed products showed that along with the dimeric structures formation for Kolbe reaction, the occurrence of a hydrocarbons mixture takes place, which may be the result of disproportionation of hydrocarbon radicals (alkane and alkene and hydrocarbons of isomeric structure, by further oxidation of the hydrocarbon radical to carbocation and its subsequent transformation into the corresponding saturated and unsaturated isomers. Such statement is not supported by conception of the process of one- and two-electron carboxylic acid oxidation. Discussion: General carboxylic acid oxidation scheme according to one-electron mechanism (dimerization and disproportionation of the radical and two-electron mechanism (formation and carbocation rearrangement is proposed. The formation of hydrocarbons under

Li-Carboxylate Anode Structure-Property Relationships from Molecular Modeling

KAUST Repository

Burkhardt, Stephen E.

2013-01-22

The full realization of a renewable energy strategy hinges upon electrical energy storage (EES). EES devices play a key role in storing energy from renewable sources (which are inherently intermittent), to efficient transmission (e.g., grid load-leveling), and finally into the electrification of transportation. Organic materials represent a promising class of electrode active materials for Li-ion and post-Li-ion batteries. Organics consist of low-cost, lightweight, widely available materials, and their properties can be rationally tuned using the well-established principles of organic chemistry. Within the class of organic EES materials, carboxylates distinguish themselves for Li-ion anode materials based on their observed thermal stability, rate capability, and high cyclability. Further, many of the carboxylates studied to date can be synthesized from renewable or waste feedstocks. This report begins with a preliminary molecular density-functional theory (DFT) study, in which the calculated molecular properties of a set of 12 known Li-ion electrode materials based on carboxylate and carbonyl redox couples are compared to literature data. Based on the agreement between theoretical and experimental data, an expanded study was undertaken to identify promising materials and establish design principles for anodes based on Li-carboxylate salts. Predictive computational studies represent an important step forward for the identification of organic anode materials. © 2012 American Chemical Society.

Synthesis and bioactivities of Phenazine-1-carboxylic acid derivatives based on the modification of PCA carboxyl group.

Science.gov (United States)

Xiong, Zhipeng; Niu, Junfan; Liu, Hao; Xu, Zhihong; Li, Junkai; Wu, Qinglai

2017-05-01

Phenazine-1-carboxylic acid (PCA) as a natural product widely exists in microbial metabolites of Pseudomonads and Streptomycetes and has been registered for the fungicide against rice sheath blight in China. To find higher fungicidal activities compounds and study the effects on fungicidal activities after changing the carboxyl group of PCA, we synthesized a series of PCA derivatives by modifying the carboxyl group of PCA and their structures were confirmed by 1 H NMR and HRMS. Most compounds exhibited significant fungicidal activities in vitro. In particular, compound 6 exhibited inhibition effect against Rhizoctonia solani with EC 50 values of 4.35mg/L and compound 3b exhibited effect against Fusarium graminearum with EC 50 values of 8.30mg/L, compared to the positive control PCA with its EC 50 values of 7.88mg/L (Rhizoctonia solani) and 127.28mg/L (Fusarium graminearum), respectively. The results indicated that the carboxyl group of PCA could be modified to be amide group, acylhydrazine group, ester group, methyl, hydroxymethyl, chloromethyl and ether group etc. And appropriate modifications on carboxyl group of PCA were useful to extend the fungicidal scope. Copyright © 2017 Elsevier Ltd. All rights reserved.

Carboxylic acids in crystallization of macromolecules: learning from successful crystallization experiments.

Science.gov (United States)

Offermann, Lesa R; He, John Z; Mank, Nicholas J; Booth, William T; Chruszcz, Maksymilian

2014-03-01

The production of macromolecular crystals suitable for structural analysis is one of the most important and limiting steps in the structure determination process. Often, preliminary crystallization trials are performed using hundreds of empirically selected conditions. Carboxylic acids and/or their salts are one of the most popular components of these empirically derived crystallization conditions. Our findings indicate that almost 40 % of entries deposited to the Protein Data Bank (PDB) reporting crystallization conditions contain at least one carboxylic acid. In order to analyze the role of carboxylic acids in macromolecular crystallization, a large-scale analysis of the successful crystallization experiments reported to the PDB was performed. The PDB is currently the largest source of crystallization data, however it is not easily searchable. These complications are due to a combination of a free text format, which is used to capture information on the crystallization experiments, and the inconsistent naming of chemicals used in crystallization experiments. Despite these difficulties, our approach allows for the extraction of over 47,000 crystallization conditions from the PDB. Initially, the selected conditions were investigated to determine which carboxylic acids or their salts are most often present in crystallization solutions. From this group, selected sets of crystallization conditions were analyzed in detail, assessing parameters such as concentration, pH, and precipitant used. Our findings will lead to the design of new crystallization screens focused around carboxylic acids.

Carboxyl group reactivity in actin

Energy Technology Data Exchange (ETDEWEB)

Elzinga, M.

1986-01-01

While earlier work showed that the carboxyl groups of proteins could be quantitatively coupled to amino groups at pH 4.75 in the presence of EDC and a denaturing agent, the work presented here indicates that under milder conditions the modification of sidechain carboxyls is limited and somewhat specific. Most of the incorporated glycine ethyl ester (GEE) is apparently bound to five carboxyls. The total GEE incorporated was 3 to 4 moles/mole of protein as measured by an increase in Gly upon acid hydrolysis and amino acid analysis, as well as total radioactivity. 3.55 residues were found in peptides, 2.75 bound to residues 1 to 4, and 0.8 bound to Gly-100. 9 refs., 2 figs., 2 tabs.

Carboxyl group reactivity in actin

International Nuclear Information System (INIS)

Elzinga, M.

1986-01-01

While earlier work showed that the carboxyl groups of proteins could be quantitatively coupled to amino groups at pH 4.75 in the presence of EDC and a denaturing agent, the work presented here indicates that under milder conditions the modification of sidechain carboxyls is limited and somewhat specific. Most of the incorporated glycine ethyl ester (GEE) is apparently bound to five carboxyls. The total GEE incorporated was 3 to 4 moles/mole of protein as measured by an increase in Gly upon acid hydrolysis and amino acid analysis, as well as total radioactivity. 3.55 residues were found in peptides, 2.75 bound to residues 1 to 4, and 0.8 bound to Gly-100. 9 refs., 2 figs., 2 tabs

Identification of Key Residues for Enzymatic Carboxylate Reduction

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Holly Stolterfoht

2018-02-01

Full Text Available Carboxylate reductases (CARs, E.C. 1.2.1.30 generate aldehydes from their corresponding carboxylic acid with high selectivity. Little is known about the structure of CARs and their catalytically important amino acid residues. The identification of key residues for carboxylate reduction provides a starting point to gain deeper understanding of enzymatic carboxylate reduction. A multiple sequence alignment of CARs with confirmed activity recently identified in our lab and from the literature revealed a fingerprint of conserved amino acids. We studied the function of conserved residues by multiple sequence alignments and mutational replacements of these residues. In this study, single-site alanine variants of Neurospora crassa CAR were investigated to determine the contribution of conserved residues to the function, expressability or stability of the enzyme. The effect of amino acid replacements was investigated by analyzing enzymatic activity of the variants in vivo and in vitro. Supported by molecular modeling, we interpreted that five of these residues are essential for catalytic activity, or substrate and co-substrate binding. We identified amino acid residues having significant impact on CAR activity. Replacement of His 237, Glu 433, Ser 595, Tyr 844, and Lys 848 by Ala abolish CAR activity, indicating their key role in acid reduction. These results may assist in the functional annotation of CAR coding genes in genomic databases. While some other conserved residues decreased activity or had no significant impact, four residues increased the specific activity of NcCAR variants when replaced by alanine. Finally, we showed that NcCAR wild-type and mutants efficiently reduce aliphatic acids.

Production of carboxylic acid and salt co-products

Science.gov (United States)

Hanchar, Robert J.; Kleff, Susanne; Guettler, Michael V.

2014-09-09

This invention provide processes for producing carboxylic acid product, along with useful salts. The carboxylic acid product that is produced according to this invention is preferably a C.sub.2-C.sub.12 carboxylic acid. Among the salts produced in the process of the invention are ammonium salts.

Determination of the conformation of 2-hydroxy- and 2-aminobenzoic acid dimers using 13C NMR and density functional theory/natural bond order analysis: the central importance of the carboxylic acid carbon.

Science.gov (United States)

Burnette, Ronald R; Weinhold, Frank

2006-07-20

The 13C chemical shift for the carboxylic acid carbon provides a powerful diagnostic probe to determine the preferred isomeric dimer structures of benzoic acid derivatives undergoing intra- and intermolecular H-bonding in the gas, solution and crystalline phases. We have employed hybrid density functional calculations and natural bond orbital analysis to elucidate the electronic origins of the observed 13C shieldings and their relationship to isomeric stability. We find that delocalizing interactions from the carbonyl oxygen lone pairs (nO) into vicinal carbon-oxygen and carbon-carbon antibonds (sigmaCO*,sigmaCC*) make critical contributions to the 13C shieldings, and these nO --> sigmaCO*, nO --> sigmaCC* interactions are in turn sensitive to the intramolecular interactions that dictate dimer structure and stability. The carboxyl carbon atom can thus serve as a useful detector of subtle structural and conformational features in this pharmacologically important class of carboxylic acid interactions.

Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

KAUST Repository

Zhang, Tao; Croue, Jean-Philippe

2014-01-01

Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation

Synthesis of 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives

International Nuclear Information System (INIS)

Elhadi, S. A.

2004-09-01

Quinolin derivatives are a group of compounds known to possess a wide range of biological activities. The chemistry of quinolines together with their corresponding aldehydes were dealt with in chapter one of this study. Special emphasis was given to the chemistry of benzaldehyde. Twenty five 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives together with their corresponding intermediates were prepared in this work. Basically, the synthetic design of these compounds arise from the appropriate disconnections of the target 2-phenyl and 2,3-diphenyl-quinolin-4-carboxylic acids. The retro synthesis analysis of these compounds reveals pyruvic acid, aromatic amine and benzaldehyde or phenyl pyruvic acid, aromatic amine and benzaldehyde as possible logical precursors for 2-phenyl-and 2,3-diphenyl- quinoline-4-carboxylic acids respectively. The purity and identities of the synthesized compounds were elucidated through chromatographic and spectroscopic techniques. The compounds were heavily subjected to spectroscopic analysis (UV, IR, GC/MS, 1 H-and 13 C- NMR). The appropriate disconnections and the mechanisms of the corresponding reactions were given and discussed in chapter three. The spectral data were interpreted and correlated with the target structures. The prepared 2-phenyl- and 2,3-diphenyl-quinoline-4-carboxylic acid derivatives were screened for their antibacterial activity. The compounds were tested against the standard bacterial organisms B. subtilis, S. aureus, E. coli and P. vulgaris. Some of these compounds were devoid of antibacterial activity against S. aureus and P. vulgaris, while others showed moderate activity. All of the tested compounds showed an activity against B. subtilis and E. coli. 2,3-diphenyl -6-sulphanilamide-quinolin-4-carboxylic acid showed the highest activity against the four standard tested organisms.(Author)

Synthesis of 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives

Energy Technology Data Exchange (ETDEWEB)

Elhadi, S A [Department of Chemistry, Faculty of Education, University of Khartoum, Khartoum (Sudan)

2004-09-01

Quinolin derivatives are a group of compounds known to possess a wide range of biological activities. The chemistry of quinolines together with their corresponding aldehydes were dealt with in chapter one of this study. Special emphasis was given to the chemistry of benzaldehyde. Twenty five 2-phenyl- and 2,3-diphenyl-quinolin-4-carboxylic acid derivatives together with their corresponding intermediates were prepared in this work. Basically, the synthetic design of these compounds arise from the appropriate disconnections of the target 2-phenyl and 2,3-diphenyl-quinolin-4-carboxylic acids. The retro synthesis analysis of these compounds reveals pyruvic acid, aromatic amine and benzaldehyde or phenyl pyruvic acid, aromatic amine and benzaldehyde as possible logical precursors for 2-phenyl-and 2,3-diphenyl- quinoline-4-carboxylic acids respectively. The purity and identities of the synthesized compounds were elucidated through chromatographic and spectroscopic techniques. The compounds were heavily subjected to spectroscopic analysis (UV, IR, GC/MS, {sup 1}H-and {sup 13}C- NMR). The appropriate disconnections and the mechanisms of the corresponding reactions were given and discussed in chapter three. The spectral data were interpreted and correlated with the target structures. The prepared 2-phenyl- and 2,3-diphenyl-quinoline-4-carboxylic acid derivatives were screened for their antibacterial activity. The compounds were tested against the standard bacterial organisms B. subtilis, S. aureus, E. coli and P. vulgaris. Some of these compounds were devoid of antibacterial activity against S. aureus and P. vulgaris, while others showed moderate activity. All of the tested compounds showed an activity against B. subtilis and E. coli. 2,3-diphenyl -6-sulphanilamide-quinolin-4-carboxylic acid showed the highest activity against the four standard tested organisms.(Author)

Identification of important nodes in directed biological networks: a network motif approach.

Directory of Open Access Journals (Sweden)

Pei Wang

Full Text Available Identification of important nodes in complex networks has attracted an increasing attention over the last decade. Various measures have been proposed to characterize the importance of nodes in complex networks, such as the degree, betweenness and PageRank. Different measures consider different aspects of complex networks. Although there are numerous results reported on undirected complex networks, few results have been reported on directed biological networks. Based on network motifs and principal component analysis (PCA, this paper aims at introducing a new measure to characterize node importance in directed biological networks. Investigations on five real-world biological networks indicate that the proposed method can robustly identify actually important nodes in different networks, such as finding command interneurons, global regulators and non-hub but evolutionary conserved actually important nodes in biological networks. Receiver Operating Characteristic (ROC curves for the five networks indicate remarkable prediction accuracy of the proposed measure. The proposed index provides an alternative complex network metric. Potential implications of the related investigations include identifying network control and regulation targets, biological networks modeling and analysis, as well as networked medicine.

Effects of carboxylic acids on nC60 aggregate formation

International Nuclear Information System (INIS)

Chang Xiaojun; Vikesland, Peter J.

2009-01-01

The discovery that negatively charged aggregates of C 60 fullerene (nC 60 ) are stable in water has raised concerns regarding the potential environmental and health effects of these aggregates. In this work, we show that nC 60 aggregates produced by extended mixing in the presence of environmentally relevant carboxylic acids (acetic acid, tartaric acid, citric acid) have surface charge and morphologic properties that differ from those produced by extended mixing in water alone. In general, aggregates formed in the presence of these acids have a more negative surface charge and are more homogeneous than those produced in water alone. Carboxylic acid identity, solution pH, and sodium ion concentration, which are all intricately coupled, play an important role in setting the measured surface charge. Comparisons between particle sizes determined by analysis of TEM images and those obtained by dynamic light scattering (DLS) indicate that DLS results require careful evaluation when used to describe nC 60 aggregates. - The effects of carboxylic acids on the formation of nC 60 aggregates are discussed

Rhodium-catalyzed regioselective olefination directed by a carboxylic group.

Science.gov (United States)

Mochida, Satoshi; Hirano, Koji; Satoh, Tetsuya; Miura, Masahiro

2011-05-06

The ortho-olefination of benzoic acids can be achieved effectively through rhodium-catalyzed oxidative coupling with alkenes. The carboxylic group is readily removable to allow ortho-olefination/decarboxylation in one pot. α,β-Unsaturated carboxylic acids such as methacrylic acid also undergo the olefination at the β-position. Under the rhodium catalysis, the cine-olefination of heteroarene carboxylic acids such as thiophene-2-carboxylic acid proceeds smoothly accompanied by decarboxylation to selectively produce the corresponding vinylheteroarene derivatives. © 2011 American Chemical Society

Recovery and esterification of aqueous carboxylates by using CO

NARCIS (Netherlands)

Cabrera-Rodríguez, Carlos I.; Paltrinieri, Laura; Smet, De Louis C.P.M.; Wielen, Van Der Luuk A.M.; Straathof, Adrie J.J.

2017-01-01

The recovery of carboxylic acids from fermentation broth is one of the main bottlenecks for the industrial production of bio-based esters. This paper proposes an alternative for the recovery of carboxylates produced by fermentations at pH values above the pKa of the carboxylic acid. In this

Crystal and Molecular Structure Studies of Ethyl 4-(4-Hydroxyphenyl-6-(6-methoxy-2-naphthyl-2-oxocyclohex-3-ene-1-carboxylate and Ethyl 4-(3-Bromophenyl-6-(6-methoxy-2-naphthyl-2-oxocyclohex-3-ene-1-carboxylate

Directory of Open Access Journals (Sweden)

Badiadka Narayana

2012-08-01

Full Text Available The crystal and molecular structures of the title compounds, ethyl 4-(4-hydroxyphenyl-6-(6-methoxy-2-naphthyl-2-oxocyclohex-3-ene-1-carboxylate (I and ethyl 4-(3-bromophenyl-6-(6-methoxy-2-naphthyl-2-oxocyclohex-3-ene-1-carboxylate (II, are reported and confirmed by single crystal X-ray diffraction data. Compound (I, C26H24O5, crystallizes from a methanol solution in the monoclinic C2/c space group with eight molecules in the unit cell. The unit cell parameters are: a = 25.4114(5 Å, b = 8.47440(10 Å, c = 20.6921(4 Å, β = 108.328(2° and V = 4229.92(13 Å3. Disorder is observed throughout the entire molecule with an occupancy ratio 0.690(2:0.310(2. Compound (II, C26H23O4Br, crystallizes from an ethyl acetate solution in the monoclinic P21/c spacegroup with four molecules in the unit cell. The unit cell parameters are a = 17.8991(9 Å, b = 11.4369(6 Å, c = 10.8507(5 Å, β = 92.428(4° and V = 2219.25(19 Å3. Disorder is observed in the cyclohexenone ring and the carboxylate group with an occupancy ratio 0.830(6:0.170(6. Weak O–H...O (I or C–H...O (II intermolecular interactions are observed which influence crystal packing stability. These chalcone derivative types of molecules are important in their ability to act as activated unsaturated systems in conjugated addition reactions of carbanions in the presence of basic catalysts which exhibit a multitude of biological activities.

Enriched surface acidity for surfactant-free suspensions of carboxylated carbon nanotubes purified by centrifugation

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Elizabeth I. Braun

2016-06-01

Full Text Available It is well known that surfactant-suspended carbon nanotube (CNT samples can be purified by centrifugation to decrease agglomerates and increase individually-dispersed CNTs. However, centrifugation is not always part of protocols to prepare CNT samples used in biomedical applications. Herein, using carboxylated multi-walled CNTs (cMWCNTs suspended in water without a surfactant, we developed a Boehm titrimetric method for the analysis of centrifuged cMWCNT suspensions and used it to show that the surface acidity of oxidized carbon materials in aqueous cMWCNT suspensions was enriched by ∼40% by a single low-speed centrifugation step. This significant difference in surface acidity between un-centrifuged and centrifuged cMWCNT suspensions has not been previously appreciated and is important because the degree of surface acidity is known to affect the interactions of cMWCNTs with biological systems.

Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

Directory of Open Access Journals (Sweden)

H. F. Xie

2012-09-01

Full Text Available Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN. The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg, mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOHs nanocomposites were investigated by differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, universal test machine, thermogravimetric analysis and scanning electron microscopy (SEM. DSC kinetic studies showed that the addition of MWCNT–COOHs accelerated the curing reaction of the rubber-toughened epoxy resin. DMA results revealed that Tg of rubber-toughened epoxy nanocomposites lowered with MWCNT–COOH contents. The tensile strength, elongation at break, flexural strength and flexural modulus of DGEBA/CTBN/MWCNT-COOHs nanocomposites were increased at lower MWCNT-COOH concentration. A homogenous dispersion of nanocomposites at lower MWCNT–COOH concentration was observed by SEM.

Biologically Important Areas for Cetaceans within U.S. Waters

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — Biologically important areas (BIAs) for cetaceans were defined by compiling the best available information from scientific literature (including books, peer-reviewed...

Human Cells as Platform to Produce Gamma-Carboxylated Proteins.

Science.gov (United States)

de Sousa Bomfim, Aline; de Freitas, Marcela Cristina Corrêa; Covas, Dimas Tadeu; de Sousa Russo, Elisa Maria

2018-01-01

The gamma-carboxylated proteins belong to a family of proteins that depend on vitamin K for normal biosynthesis. The major representative gamma-carboxylated proteins are the coagulation system proteins, for example, factor VII, factor IX, factor X, prothrombin, and proteins C, S, and Z. These molecules have harbored posttranslational modifications, such as glycosylation and gamma-carboxylation, and for this reason they need to be produced in mammalian cell lines. Human cells lines have emerged as the most promising alternative to the production of gamma-carboxylated proteins. In this chapter, the methods to generate human cells as a platform to produce gamma-carboxylated proteins, for example the coagulation factors VII and IX, are presented. From the cell line modification up to the vitamin K adaptation of the produced cells is described in the protocols presented in this chapter.

A rapid and sensitive method for the simultaneous analysis of aliphatic and polar molecules containing free carboxyl groups in plant extracts by LC-MS/MS

Directory of Open Access Journals (Sweden)

Bonaventure Gustavo

2009-11-01

Full Text Available Abstract Background Aliphatic molecules containing free carboxyl groups are important intermediates in many metabolic and signalling reactions, however, they accumulate to low levels in tissues and are not efficiently ionized by electrospray ionization (ESI compared to more polar substances. Quantification of aliphatic molecules becomes therefore difficult when small amounts of tissue are available for analysis. Traditional methods for analysis of these molecules require purification or enrichment steps, which are onerous when multiple samples need to be analyzed. In contrast to aliphatic molecules, more polar substances containing free carboxyl groups such as some phytohormones are efficiently ionized by ESI and suitable for analysis by LC-MS/MS. Thus, the development of a method with which aliphatic and polar molecules -which their unmodified forms differ dramatically in their efficiencies of ionization by ESI- can be simultaneously detected with similar sensitivities would substantially simplify the analysis of complex biological matrices. Results A simple, rapid, specific and sensitive method for the simultaneous detection and quantification of free aliphatic molecules (e.g., free fatty acids (FFA and small polar molecules (e.g., jasmonic acid (JA, salicylic acid (SA containing free carboxyl groups by direct derivatization of leaf extracts with Picolinyl reagent followed by LC-MS/MS analysis is presented. The presence of the N atom in the esterified pyridine moiety allowed the efficient ionization of 25 compounds tested irrespective of their chemical structure. The method was validated by comparing the results obtained after analysis of Nicotiana attenuata leaf material with previously described analytical methods. Conclusion The method presented was used to detect 16 compounds in leaf extracts of N. attenuata plants. Importantly, the method can be adapted based on the specific analytes of interest with the only consideration that the

Biologically Important Areas for Cetaceans within U.S. Waters

Data.gov (United States)

National Oceanic and Atmospheric Administration, Department of Commerce — The Cetacean Density and Distribution Mapping Working Group identified Biologically Important Areas (BIAs) for 24 cetacean species, stocks, or populations in seven...

Novel Polymers with Carboxylic Acid Loading

DEFF Research Database (Denmark)

Thomsen, Anders Daugaard; Malmström, Eva; Hvilsted, Søren

2006-01-01

Click chemistry has been used to prepare a range of novel polymers with pendant carboxylic acid side groups. Four azido carboxylic acids, either mono- or difunctional and aliphatic or aromatic, have been prepared and thoroughly characterized. Extensive model reactions with 1-ethyl-4-hydroxybenzene......, the simplest model for poly(4-hydroxystyrene), and the four azido carboxylic acids have been conducted to establish the proper reaction conditions and provide an analytical frame for the corresponding polymers. Poly(4-hydroxystyrene) moieties in three different polymers—poly(4-hydroxystyrene), poly(4...... the polymers in general exhibit [when poly(4-hydroxystyrene) is a substantial part] significant changes in the glass-transition temperature from the polar poly(4-hydroxystyrene) (120–130 °C) to the much less polar alkyne polymers (46–60 °C). A direct correlation between the nature of the pendant groups...

Decarboxylative Trifluoromethylation of Aliphatic Carboxylic Acids.

Science.gov (United States)

Kautzky, Jacob A; Wang, Tao; Evans, Ryan W; MacMillan, David W C

2018-05-14

Herein we disclose an efficient method for the conversion of carboxylic acids to trifluoromethyl groups via the combination of photoredox and copper catalysis. This transformation tolerates a wide range of functionality including heterocycles, olefins, alcohols, and strained ring systems. To demonstrate the broad potential of this new methodology for late-stage functionalization, we successfully converted a diverse array of carboxylic acid-bearing natural products and medicinal agents to the corresponding trifluoromethyl analogues.

Preparation, characterization and biological evaluation of fac(M(CO)3)+ labeled amino carboxy ligands

International Nuclear Information System (INIS)

Baishya, Rinku; Halder, K.K.; Debnath, M.C.

2010-01-01

Full text: The objective of this study is to radiolabel various amino carboxy based chelating ligands with fac(M(CO) 3 )+ core, their physicochemical and biological characterization so that they can be used as bifunctional chelators and could be incorporated into biomolecules. Introduction: Amino acids as a class attract considerable physiological interest because of their participation in many vital processes associated with the living system. Some amino acids express in some particular organ like glutamic acid acts as excitatory neurotransmitter in mammalian brain. Histidine, methionine, tryptophan express in the tumor cell. Amino acids also play an important role for development of a new series of chelate complexes of 99m Tc that can direct the biodistribution of the radiotracer for purposes in diagnostic nuclear medicine. Various 99m Tc-amino acid chelates based on (Tc(V)O) 3 + core were reported from this laboratory some of which exhibited high renal specificity in animals. The structural requirements favouring this biological behaviour could be the oxotechnetium glycine sequence (TcO-NH-CH 2 -COOH) resembling the -CO-glycine sequence of hippurate. In recent years with the development of organometallic chemistry of technetium and rhenium for biological application intensive efforts have been executed on designing of the bifunctional chelator for effective coordination to (M(CO) 3 )+ core. The suitability and stability of the metal carbonyl core has given rise to a new platform for the preparation of the metal complexes of biologically active peptide in macroscopic quantity using the solid phase synthetic approach. Materials and Methods: We chelated different amino carboxy based ligands with ( 99m Tc(CO) 3 )+ and (Re(CO) 3 )+ core. The choice of amino acid was made by taking representative members from various groupings such as mono amino mono carboxylate, mono amino poly carboxylate, poly amino mono carboxylate and sulfur containing amino carboxylates. The

Determination of carboxyl groups in wood fibers by headspace gas chromatography

Science.gov (United States)

X.-S. Chai; Q.X. Hou; J.Y. Zhu; S.-L. Chen; S.F. Wang; L. Lucia

2003-01-01

The phase reaction conversion (PRC) headspace gas chromatographic (HSGC) technique was employed to develop a method for the determination of the content of carboxyl groups in wood fibers. Acid treatment of the wood fibers using hydrochloric was applied to convert carboxyl groups to carboxyl acids. Bicarbonate solution is then used to react with carboxyl acids on the...

40 CFR 721.4663 - Fluorinated carboxylic acid alkali metal salts.

Science.gov (United States)

2010-07-01

... Specific Chemical Substances § 721.4663 Fluorinated carboxylic acid alkali metal salts. (a) Chemical... fluorinated carboxylic acid alkali metal salts (PMNs P-95-979/980/981) are subject to reporting under this... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Fluorinated carboxylic acid alkali...

Floral Benzenoid Carboxyl Methyltransferases: From in Vitro to in Planta Function

Energy Technology Data Exchange (ETDEWEB)

Effmert,U.; Saschenbrecker, S.; Ross, J.; Negre, F.; Fraser, C.; Noel, J.; Dudareva, N.; Piechulla, B.

2005-01-01

Benzenoid carboxyl methyltransferases synthesize methyl esters (e.g., methyl benzoate and methyl salicylate), which are constituents of aromas and scents of many plant species and play important roles in plant communication with the surrounding environment. Within the past five years, eleven such carboxyl methyltransferases were isolated and most of them were comprehensively investigated at the biochemical, molecular and structural level. Two types of enzymes can be distinguished according to their substrate preferences: the SAMT-type enzymes isolated from Clarkia breweri, Stephanotis floribunda, Antirrhinum majus, Hoya carnosa, and Petunia hybrida, which have a higher catalytic efficiency and preference for salicylic acid, while BAMT-type enzymes from A. majus, Arabidopsis thaliana, Arabidopsis lyrata, and Nicotiana suaveolens prefer benzoic acid. The elucidation of C. breweri SAMT's three-dimensional structure allowed a detailed modelling of the active sites of the carboxyl methyltransferases and revealed that the SAM binding pocket is highly conserved among these enzymes while the methyl acceptor binding site exhibits some variability, allowing a classification into SAMT-type and BAMT-type enzymes. The analysis of expression patterns coupled with biochemical characterization showed that these carboxyl methyltransferases are involved either in floral scent biosynthesis or in plant defense responses. While the latter can be induced by biotic or abiotic stress, the genes responsible for floral scent synthesis exhibit developmental and rhythmic expression pattern. The nature of the product and efficiency of its formation in plants depend on the availability of substrates, the catalytic efficiency of the enzyme toward benzoic acid and/or salicylic acid, and the transcriptional, translational, and post-translational regulation at the enzyme level. The biochemical properties of benzenoid carboxyl methyltransferases suggest that the genes involved in plant defenses

Hydrated electron: a destroyer of perfluorinated carboxylates?

International Nuclear Information System (INIS)

Huang Li; Dong Wenbo; Hou Huiqi

2006-01-01

As a class, perfluorinated carboxylate (PFCA) was ranked among the most prominent organohalogen contaminants in environment with respect to thermal, chemical and biological inertness. Hydrated electron (e aq - ), a highly reactive and strongly reductive species, has been reported to readily decompose perfluoroaromatic compounds via intermolecular electron transfer process in aqueous solution. Question then arose: what would happen if perfluorinated carboxylates encountered with hydrated electron? Original laboratory trial on the interaction between F(CF 2 ) n COO - (n=1, 3, 7) and hydrated electron was attempted by using laser flash photolysis technique in this research work. Abundant hydrated electron (e aq - ) could be produced by photolysis of 1.25 x 10 -4 M K 4 Fe(CN) 6 in nitrogen saturated water. In the presence of F(CF 2 ) n COO - (n=1, 3, 7), the decay of e aq - was observed to enhance dramatically, indicating e aq - was able to attack PFCAs. On addition of perfluorinated carboxylates, the loss of e aq - was mainly due to the following channels. By mixing the solution of K 4 Fe(CN) 6 with excess K 3 Fe(CN) 6 and PFCAs, e aq - turned to decayed corresponding to mixed first- and second-order kinetics. Rate constants for the reactions of e aq - with PFCAs could be then easily determined by monitoring the decay of e aq - absorption at 690 nm. Since perfluorinated carboxylates were salts, the influence of ionic strength on k 3 was examined systematically by carrying out experiments of varying ionic strength ranging from 0.009 up to 0.102 M by adding NaClO 4 . In this manner, the second order rate constants for e-aq with CF 3 COO - , C 3 F 7 COO - , C 7 F 15 COO - were derived to be (1.9±0.2) x 10 6 M -1 S -1 (μ=0), (7.1±0.2) x 10 6 M -1 S -1 (μ=0) and (1.7±0.5) x10 7 M -1 S -1 (μ=0.009 M) respectively. Apparently, the length of F(CF 2 ) n group exerted substantial influence on the rate constant. Further study on byproducts analysis by ion chromatography

Carboxyl-terminated PAMAM dendrimer interaction with 1-palmitoyl-2-oleoyl phosphocholine bilayers

Science.gov (United States)

Polycationic polymers and liposomes have a great potential use as individual drug delivery systems and greater potential as a combined drug delivery system. Thus, it is important to better understand the interactions of polymers with phospholipid bilayers. A mechanistic study of carboxyl-terminate...

Cooperation of phosphates and carboxylates controls calcium oxalate crystallization in ultrafiltered urine.

Science.gov (United States)

Grohe, Bernd; Chan, Brian P H; Sørensen, Esben S; Lajoie, Gilles; Goldberg, Harvey A; Hunter, Graeme K

2011-10-01

Osteopontin (OPN) is one of a group of proteins found in urine that are believed to limit the formation of kidney stones. In the present study, we investigate the roles of phosphate and carboxylate groups in the OPN-mediated modulation of calcium oxalate (CaOx), the principal mineral phase found in kidney stones. To this end, crystallization was induced by addition of CaOx solution to ultrafiltered human urine containing either human kidney OPN (kOPN; 7 consecutive carboxylates, 8 phosphates) or synthesized peptides corresponding to residues 65-80 (pSHDHMDDDDDDDDDGD; pOPAR) or 220-235 (pSHEpSTEQSDAIDpSAEK; P3) of rat bone OPN. Sequence 65-80 was also synthesized without the phosphate group (OPAR). Effects on calcium oxalate monohydrate (COM) and dihydrate (COD) formation were studied by scanning electron microscopy. We found that controls form large, partly intergrown COM platelets; COD was never observed. Adding any of the polyelectrolytes was sufficient to prevent intergrowth of COM platelets entirely, inhibiting formation of these platelets strongly, and inducing formation of the COD phase. Strongest effects on COM formation were found for pOPAR and OPAR followed by kOPN and then P3, showing that acidity and hydrophilicity are crucial in polyelectrolyte-affected COM crystallization. At higher concentrations, OPAR also inhibited COD formation, while P3, kOPN and, in particular, pOPAR promoted COD, a difference explainable by the variations of carboxylate and phosphate groups present in the molecules. Thus, we conclude that carboxylate groups play a primary role in inhibiting COM formation, but phosphate and carboxylate groups are both important in initiating and promoting COD formation.

Carboxyl-terminal parathyroid hormone fragments: role in parathyroid hormone physiopathology.

Science.gov (United States)

D'Amour, Pierre; Brossard, Jean-Hugues

2005-07-01

Carboxyl-terminal parathyroid hormone (C-PTH) fragments constitute 80% of circulating PTH. Since the first 34 amino acids of the PTH structure are sufficient to explain PTH classical biological effects on the type I PTH/PTHrP receptor and since C-PTH fragments do not bind to this receptor, they have long been considered inactive. Recent data suggest the existence of a C-PTH receptor through which C-PTH fragments exert biological effects opposite to those of human PTH(1-84) on the type I PTH/PTHrP receptor. This is why a lot of attention has been paid to these fragments recently. In vivo, synthetic C-PTH fragments are able to decrease calcium concentration, to antagonize the calcemic response to human PTH(1-34) and human PTH(1-84) and to decrease the high bone turnover rate induced by human PTH(1-84). In vitro, they inhibit bone resorption, promote osteocyte apoptosis and exert a variety of effects on bone and cartilaginous cells. These effects are opposite to those of human PTH(1-84) on the PTH/PTHrP type I receptor. This suggests that the molecular forms of circulating PTH may control bone participation in calcium homeostasis via two different receptors. Clinically, the accumulation of C-PTH fragments in renal failure patients may cause PTH resistance and may be associated with adynamic bone disease. Rare parathyroid tumors, without a set point error, overproduce C-PTH fragments. The implication of C-PTH fragments in osteoporosis is still to be explored. C-PTH fragments represent a new field of investigation in PTH biology. More studies are necessary to disclose their real importance in calcium and bone homeostasis in health and disease.

Catalytic ozonation not relying on hydroxyl radical oxidation: A selective and competitive reaction process related to metal-carboxylate complexes

KAUST Repository

Zhang, Tao

2014-01-01

Catalytic ozonation following non-hydroxyl radical pathway is an important technique not only to degrade refractory carboxylic-containing organic compounds/matter but also to avoid catalyst deactivation caused by metal-carboxylate complexation. It is unknown whether this process is effective for all carboxylates or selective to special molecule structures. In this work, the selectivity was confirmed using O3/(CuO/CeO2) and six distinct ozone-resistant probe carboxylates (i.e., acetate, citrate, malonate, oxalate, pyruvate and succinate). Among these probe compounds, pyruvate, oxalate, and citrate were readily degraded following the rate order of oxalate>citrate>pyruvate, while the degradation of acetate, malonate, and succinate was not promoted. The selectivity was independent on carboxylate group number of the probe compounds and solution pH. Competitive degradation was observed for carboxylate mixtures following the preference order of citrate, oxalate, and finally pyruvate. The competitive degradation was ascribed to competitive adsorption on the catalyst surface. It was revealed that the catalytically degradable compounds formed bidentate chelating or bridging complexes with surface copper sites of the catalyst, i.e., the active sites. The catalytically undegradable carboxylates formed monodentate complexes with surface copper sites or just electrostatically adsorbed on the catalyst surface. The selectivity, relying on the structure of surface metal-carboxylate complex, should be considered in the design of catalytic ozonation process. © 2013 Elsevier B.V.

Mononuclear non-heme iron enzymes with the 2-His-1-carboxylate facial triad: recent developments in enzymology and modeling studies.

Science.gov (United States)

Bruijnincx, Pieter C A; van Koten, Gerard; Klein Gebbink, Robertus J M

2008-12-01

Iron-containing enzymes are one of Nature's main means of effecting key biological transformations. The mononuclear non-heme iron oxygenases and oxidases have received the most attention recently, primarily because of the recent availability of crystal structures of many different enzymes and the stunningly diverse oxidative transformations that these enzymes catalyze. The wealth of available structural data has furthermore established the so-called 2-His-1-carboxylate facial triad as a new common structural motif for the activation of dioxygen. This superfamily of mononuclear iron(ii) enzymes catalyzes a wide range of oxidative transformations, ranging from the cis-dihydroxylation of arenes to the biosynthesis of antibiotics such as isopenicillin and fosfomycin. The remarkable scope of oxidative transformations seems to be even broader than that associated with oxidative heme enzymes. Not only are many of these oxidative transformations of key biological importance, many of these selective oxidations are also unprecedented in synthetic organic chemistry. In this critical review, we wish to provide a concise background on the chemistry of the mononuclear non-heme iron enzymes characterized by the 2-His-1-carboxylate facial triad and to discuss the many recent developments in the field. New examples of enzymes with unique reactivities belonging to the superfamily have been reported. Furthermore, key insights into the intricate mechanistic details and reactive intermediates have been obtained from both enzyme and modeling studies. Sections of this review are devoted to each of these subjects, i.e. the enzymes, biomimetic models, and reactive intermediates (225 references).

Aromatic carboxylate effect on dimensionality of three bis(benzimidazole)-based cobalt(II) coordination polymers: Syntheses, structures and properties

International Nuclear Information System (INIS)

Zhang, Ju-Wen; Gong, Chun-Hua; Hou, Li-Li; Tian, Ai-Xiang; Wang, Xiu-Li

2013-01-01

Three new metal-organic coordination polymers [Co(4-bbc) 2 (bbbm)] (1), [Co(3,5-pdc)(bbbm)]·2H 2 O (2) and [Co(1,4-ndc)(bbbm)] (3) (4-Hbbc=4-bromobenzoic acid, 3,5-H 2 pdc=3,5-pyridinedicarboxylic acid, 1,4-H 2 ndc=1,4-naphthalenedicarboxylic acid and bbbm=1,1-(1,4-butanediyl)bis-1H-benzimidazole) were hydrothermally synthesized and structurally characterized. Polymer 1 is a 1D chain formed by the bbbm ligands and Co II ions. Polymer 2 exhibits a 2D network with a (3·4·5)(3 2 ·4·5·6 2 ·7 4 ) topology. Polymer 3 possesses a 3D three-fold interpenetrating framework. The versatile structures of title polymers indicate that the aromatic carboxylates have an important influence on the dimensionality of 1–3. Moreover, the thermal stability, electrochemical and luminescent properties of 1–3 were investigated. - graphical abstract: Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were hydrothermally synthesized and structurally characterized. The aromatic carboxylates play a key role in the dimensionality of three polymers. The electrochemical and luminescent properties of three polymers were investigated. Display Omitted - Highlights: • Three bis(benzimidazole)-based cobalt(II) coordination polymers tuned by aromatic carboxylates were obtained. • The aromatic carboxylates have an important influence on the dimensionality of three polymers. • The electrochemical and luminescent properties of three polymers were investigated

Synthesis and characterization of carboxylic acid functionalized silicon nanoparticles

Science.gov (United States)

Shaner, Ted V.

Silicon nanoparticles are of great interest in a great number of fields. Silicon nanoparticles show great promise particularly in the field of bioimaging. Carboxylic acid functionalized silicon nanoparticles have the ability to covalently bond to biomolecules through the conjugation of the carboxylic acid to an amine functionalized biomolecule. This thesis explores the synthesis of silicon nanoparticles functionalized by both carboxylic acids and alkenes and their carboxylic acid functionality. Also discussed is the characterization of the silicon nanoparticles by the use of x-ray spectroscopy. Finally, the nature of the Si-H bond that is observed on the surface of the silicon nanoparticles will be investigated using photoassisted exciton mediated hydrosilation reactions. The silicon nanoparticles are synthesized from both carboxylic acids and alkenes. However, the lack of solubility of diacids is a significant barrier to carboxylic acid functionalization by a mixture of monoacids and diacids. A synthesis route to overcome this obstacle is to synthesize silicon nanoparticles with terminal vinyl group. This terminal vinyl group is distal to the surface of the silicon nanoparticle. The conversion of the vinyl group to a carboxylic acid is accomplished by oxidative cleavage using ozonolysis. The carboxylic acid functionalized silicon nanoparticles were then successfully conjugated to amine functionalized DNA strand through an n-hydroxy succinimide ester activation step, which promotes the formation of the amide bond. Conjugation was characterized by TEM and polyacrylamide gel electrophoresis (PAGE). The PAGE results show that the silicon nanoparticle conjugates move slower through the polyacrylamide gel, resulting in a significant separation from the nonconjugated DNA. The silicon nanoparticles were then characterized by the use of x-ray absorption near edge spectroscopy (Xanes) and x-ray photoelectron spectroscopy (XPS) to investigate the bonding and chemical

Dynamic Biological Functioning Important for Simulating and Stabilizing Ocean Biogeochemistry

Science.gov (United States)

Buchanan, P. J.; Matear, R. J.; Chase, Z.; Phipps, S. J.; Bindoff, N. L.

2018-04-01

The biogeochemistry of the ocean exerts a strong influence on the climate by modulating atmospheric greenhouse gases. In turn, ocean biogeochemistry depends on numerous physical and biological processes that change over space and time. Accurately simulating these processes is fundamental for accurately simulating the ocean's role within the climate. However, our simulation of these processes is often simplistic, despite a growing understanding of underlying biological dynamics. Here we explore how new parameterizations of biological processes affect simulated biogeochemical properties in a global ocean model. We combine 6 different physical realizations with 6 different biogeochemical parameterizations (36 unique ocean states). The biogeochemical parameterizations, all previously published, aim to more accurately represent the response of ocean biology to changing physical conditions. We make three major findings. First, oxygen, carbon, alkalinity, and phosphate fields are more sensitive to changes in the ocean's physical state. Only nitrate is more sensitive to changes in biological processes, and we suggest that assessment protocols for ocean biogeochemical models formally include the marine nitrogen cycle to assess their performance. Second, we show that dynamic variations in the production, remineralization, and stoichiometry of organic matter in response to changing environmental conditions benefit the simulation of ocean biogeochemistry. Third, dynamic biological functioning reduces the sensitivity of biogeochemical properties to physical change. Carbon and nitrogen inventories were 50% and 20% less sensitive to physical changes, respectively, in simulations that incorporated dynamic biological functioning. These results highlight the importance of a dynamic biology for ocean properties and climate.

Synthesis of 1-indanones with a broad range of biological activity

Directory of Open Access Journals (Sweden)

Marika Turek

2017-03-01

Full Text Available This comprehensive review describes methods for the preparation of 1-indanones published in original and patent literature from 1926 to 2017. More than 100 synthetic methods utilizing carboxylic acids, esters, diesters, acid chlorides, ketones, alkynes, alcohols etc. as starting materials, have been performed. This review also covers the most important studies on the biological activity of 1-indanones and their derivatives which are potent antiviral, anti-inflammatory, analgesic, antimalarial, antibacterial and anticancer compounds. Moreover, they can be used in the treatment of neurodegenerative diseases and as effective insecticides, fungicides and herbicides.

Adsorption of UO2+2 by polyethylene adsorbents with amidoxime, carboxyl, and amidoxime/carboxyl group

International Nuclear Information System (INIS)

Choi, Seong-Ho; Nho, Young Chang

2000-01-01

The polyethylene (PE) adsorbents were prepared by a radiation-induced grafting of acrylonitrile (AN), acrylic acid (AA), and the mixture of AN/AA onto PE film, and by subsequent amidoximation of cyano groups of poly-AN graft chains. With an increase of AA composition in AN/AA monomer mixture, the water uptake of the grafted polyethylene film increased. In AN/AA mixture, the maximum adsorption of UO 2+ 2 was observed in the adsorbent with a ratio of AN/AA (50/50, mol%) in copolymer. The amidoxime, carboxyl, and amidoxime/carboxyl groups onto PE acted as a chelating site for the selected UO 2+ 2 . The complex structure of polyethylene with three functional groups and UO 2+ 2 was confirmed by Fourier Transform Infrared (FTIR) spectroscopy. (author)

Rational design of carboxyl groups perpendicularly attached to a graphene sheet: a platform for enhanced biosensing applications.

Science.gov (United States)

Bonanni, Alessandra; Chua, Chun Kiang; Pumera, Martin

2014-01-03

Graphene oxide (GO)-based materials offer great potential for biofunctionalization with applications ranging from biosensing to drug delivery. Such biofunctionalization utilizes specific functional groups, typically a carboxyl moiety, as anchoring points for biomolecule. However, due to the fact that the exact chemical structure of GO is still largely unknown and poorly defined (it was postulated to consist of various oxygen-containing groups, such as epoxy, hydroxyl, carboxyl, carbonyl, and peroxy in varying ratios), it is challenging to fabricate highly biofunctionalized GO surfaces. The predominant anchoring sites (i.e., carboxyl groups) are mainly present as terminal groups on the edges of GO sheets and thus account for only a fraction of the oxygen-containing groups on GO. Herein, we suggest a direct solution to the long-standing problem of limited abundance of carboxyl groups on GO; GO was first reduced to graphene and consequently modified with only carboxyl groups grafted perpendicularly to its surface by a rational synthesis using free-radical addition of isobutyronitrile with subsequent hydrolysis. Such grafted graphene oxide can contain a high amount of carboxyl groups for consequent biofunctionalization, at which the extent of grafting is limited only by the number of carbon atoms in the graphene plane; in contrast, the abundance of carboxyl groups on "classical" GO is limited by the amount of terminal carbon atoms. Such a graphene platform embedded with perpendicularly grafted carboxyl groups was characterized in detail by X-ray photoelectron spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy, and its application was exemplified with single-nucleotide polymorphism detection. It was found that the removal of oxygen functionalities after the chemical reduction enhanced the electron-transfer rate of the graphene. More importantly, the introduction of carboxyl groups promoted a more efficient immobilization of DNA probes on the

Uranium (IV) carboxylates - I

Energy Technology Data Exchange (ETDEWEB)

Satpathy, K C; Patnaik, A K [Sambalpur Univ. (India). Dept. of Chemistry

1975-11-01

A few uranium(IV) carboxylates with monochloro and trichloro acetic acid, glycine, malic, citric, adipic, o-toluic, anthranilic and salicylic acids have been prepared by photolytic methods. The I.R. spectra of these compounds are recorded and basing on the spectral data, structure of the compounds have been suggested.

Ru(II)-Catalyzed Oxidative Heck-Type Olefination of Aromatic Carboxylic Acids with Styrenes through Carboxylate-Assisted C-H Bond Activation.

Science.gov (United States)

Dana, Suman; Mandal, Anup; Sahoo, Harekrishna; Mallik, Sumitava; Grandhi, Gowri Sankar; Baidya, Mahiuddin

2018-02-02

A straightforward synthesis of 2-styrylbenzoic acids from aryl carboxylic acids is disclosed through a carboxylate-assisted coupling under Ru(II) catalysis. This protocol is simple and exhibits broad scope with high tolerance of common organic functional groups, providing good to excellent yields of diverse olefinated products. The efficacy of this protocol has been showcased through sequential syntheses of isochromanone, isocoumarin, and formal synthesis of anacardic acid derivative in good yields.

Pd(II)/Bipyridine-Catalyzed Conjugate Addition of Arylboronic Acids to α,β-Unsaturated Carboxylic Acids. Synthesis of β-Quaternary Carbons Substituted Carboxylic Acids.

Science.gov (United States)

Liu, Rui; Yang, Zhenyu; Ni, Yuxin; Song, Kaixuan; Shen, Kai; Lin, Shaohui; Pan, Qinmin

2017-08-04

Pd(II)/bipyridine-catalyzed conjugate addition of arylboronic acids to α,β-unsaturated carboxylic acids (including β,β-disubstituted acrylic acids) was developed and optimized, which provided a mild and convenient method for the highly challenging synthesis of β-quaternary carbons substituted carboxylic acids.

Model calculations of nuclear data for biologically-important elements

International Nuclear Information System (INIS)

Chadwick, M.B.; Blann, M.; Reffo, G.; Young, P.G.

1994-05-01

We describe calculations of neutron-induced reactions on carbon and oxygen for incident energies up to 70 MeV, the relevant clinical energy in radiation neutron therapy. Our calculations using the FKK-GNASH, GNASH, and ALICE codes are compared with experimental measurements, and their usefulness for modeling reactions on biologically-important elements is assessed

Photodecarboxylative Cyclizations of ω-Phthalimido-para-phenoxy Carboxylates

Energy Technology Data Exchange (ETDEWEB)

Kim, Ae Rhan; Lee, Younsik; Yoo, Dong Jin [Chonbuk National Univ., Jeonju (Korea, Republic of); Cho, Hyunseung [Seonam Univ., Namwon (Korea, Republic of)

2012-10-15

The chemistry of electronically-excited phthalimides is dictated by electron and/or hydrogen transfer reactions. The photochemistry of phthalimides has been intensively studied, and numerous synthetically useful transformations with high chemical and quantum yields have been developed. 3 Among the synthetic applications, intra- and intermolecular photodecarboxylation (PDC) of ω-phthalimidoalkyl carboxylates has been developed by Griesbeck and coworkers as a versatile pathway to medium- and large-ring heterocycles. Model reactions were further realized on macro- and micro-scales. We recently described PDC cyclizations of ω-phthalimidoalkynoates to produce macrocyclic alkynes with ring-sizes up to 17. In recent study, we expanded the portfolio of this reaction and investigated the photochemistry of related aryl-linked phthalimides in Scheme 1. Based on these approaches, we demonstrated that ω-phthalimido-ortho/meta-phenoxy carboxylates undergo efficient PDC cyclizations. While the yields of ω-phthalimido-ortho-phenoxy carboxylates steadily decreased with increasing chain-length and the maximum yield of the 6-membered product was obtained in 75%, the yields of meta-phenoxy carboxylates steadily increased with increasing chain-length and the extended 16-membered product was subsequently obtained in 48% yield.

Decellularized Bovine Articular Cartilage Matrix Reinforced by Carboxylated-SWCNT for Tissue Engineering Application

Directory of Open Access Journals (Sweden)

Zari Majidi Mohammadie

2018-01-01

Full Text Available ABSTRACT Nanotubes with their unique properties have diversified mechanical and biological applications. Due to similarity of dimensions with extracellular matrix (ECM elements, these materials are used in designing scaffolds. In this research, Carboxylated Single-Wall Carbon Nanotubes in optimization of decellularized scaffold of bovine articular cartilage was used. At first, the articular cartilage was decellularized. Then the scaffolds were analyzed in: (i decellularized scaffolds, and (ii scaffolds plunged into homogenous suspension of nanotubes in distilled water, were smeared with Carboxylated-SWCNT. The tissue rings derived from the rabbit's ear were assembled with reinforced scaffolds and they were placed in a culture media for 15 days. The scaffolds in two groups and the assembled scaffolds underwent histologic and electron microscopy. Scanning electron microscopy showed that the structure of ECM of articular cartilage has been maintained well after decellularization. Fourier transform infrared analysis showed that the contents of ECM have not been changed under treatment process. Atomic force microscopy analysis showed the difference in surface topography and roughness of group (ii scaffolds in comparison with group (i. Transmission electron microscopy studies showed the Carboxylated-SWCNT bond with the surface of decellularized scaffold and no penetration of these compounds into the scaffold. The porosity percentage with median rate of 91.04 in group (i scaffolds did not have significant difference with group (ii scaffolds. The electron microscopy observations confirmed migration and penetration of the blastema cells into the group (ii assembled scaffolds. This research presents a technique for provision of nanocomposite scaffolds for cartilage engineering applications.

Synthesis and characterization of silver nanoparticles from (bis)alkylamine silver carboxylate precursors

Energy Technology Data Exchange (ETDEWEB)

Uznanski, Pawel, E-mail: puznansk@cbmm.lodz.pl; Zakrzewska, Joanna [Centre of Molecular and Macromolecular Studies, PAS (Poland); Favier, Frederic, E-mail: fredf@univ-montp2.fr [Université Montpellier II, ICGM - UMR5253- Equipe AIME (France); Kazmierski, Slawomir; Bryszewska, Ewa [Centre of Molecular and Macromolecular Studies, PAS (Poland)

2017-03-15

A comparative study of amine and silver carboxylate adducts [R{sub 1}COOAg-2(R{sub 2}NH{sub 2})] (R{sub 1} = 1, 7, 11; R{sub 2} = 8, 12) as a key intermediate in NPs synthesis is carried out via differential scanning calorimetry, solid-state FT-infrared spectroscopy, {sup 13}C CP MAS NMR, powder X-ray diffraction and X-ray photoelectron spectroscopy, and various solution NMR spectroscopies ({sup 1}H and {sup 13}C NMR, pulsed field gradient spin-echo NMR, and ROESY). It is proposed that carboxyl moieties in the presence of amine ligands are bound to silver ions via chelating bidentate type of coordination as opposed to bridging bidentate coordination of pure silver carboxylates resulting from the formation of dimeric units. All complexes are packed as lamellar bilayer structures. Silver carboxylate/amine complexes show one first-order melting transition. The evidence presented in this study shows that phase behavior of monovalent metal carboxylates are controlled, mainly, by head group bonding. In solution, insoluble silver salt is stabilized by amine molecules which exist in dynamic equilibrium. Using (bis)amine-silver carboxylate complex as precursor, silver nanoparticles were fabricated. During high-temperature thermolysis, the (bis)amine-carboxylate adduct decomposes to produce silver nanoparticles of small size. NPs are stabilized by strongly interacting carboxylate and trace amounts of amine derived from the silver precursor interacting with carboxylic acid. A corresponding aliphatic amide obtained from silver precursor at high-temperature reaction conditions is not taking part in the stabilization. Combining NMR techniques with FTIR, it was possible to follow an original stabilization mechanism.

High-level production of C-11-carboxyl-labeled amino acids

International Nuclear Information System (INIS)

Washburn, L.C.; Sun, T.T.; Byrd, B.L.; Hayes, R.L.; Butler, T.A.; Callahan, A.P.

1979-01-01

Carbon-11-labeled amino acids have significant potential as agents for positron tomographic functional imaging. We have developed a rapid, high-temperature, high-pressure modification of the Buecherer--Strecker amino acid synthesis and found it to be quite general for the production of C-11-carboxyl-labeled neutral amino acids. Production of C-11-carboxyl-labeled DL-tryptophan requires certain modifications in the procedure. Twelve different amino acids have been produced to date by this technique. Synthesis and chromatographic purification require approximately 40 min, and C-11-carboxyl-labeled amino acids have been produced in yields of up to 425 mCi. Two C-11-carboxyl-labeled amino acids are being investigated clinically for tumor scanning and two others for pancreatic imaging. Over 120 batches of the various agents have been produced for clinical use over a three-year period

Actinides: why are they important biologically

International Nuclear Information System (INIS)

Durbin, P.W.

1978-01-01

The following topics are discussed: actinide elements in energy systems; biological hazards of the actinides; radiation protection standards; and purposes of actinide biological research with regard to toxicity, metabolism, and therapeutic regimens

The relative importance of physical and biological energy in landscape evolution

Science.gov (United States)

Turowski, J. M.; Schwanghart, W.

2017-12-01

Landscapes are formed by the interplay of uplift and geomorphic processes, including interacting and competing physical and biological processes. For example, roots re-inforce soil and thereby stabilize hillslopes and the canopy cover of the forest may mediate the impact of precipitation. Furthermore, plants and animals act as geomorphic agents, directly altering landscape response and dynamics by their actions: tree roots may crack rocks, thus changing subsurface water flows and exposing fresh material for denudation; fungi excrete acids that accelerate rates of chemical weathering, and burrowing animals displace soil and rocks while digging holes for shelter or in search of food. Energetically, landscapes can be viewed as open systems in which topography stores potential energy above a base level. Tectonic processes add energy to the system by uplift and mechanically altering rock properties. Especially in unvegetated regions, erosion and transport by wind can be an important geomorphic process. Advection of atmospheric moisture in high altitudes provides potential energy that is converted by water fluxes through catchments. At the same time, the conversion of solar energy through atmospheric and biological processes drives primary production of living organisms. If we accept that biota influence geomorphic processes, then what is their energetic contribution to landscape evolution relative to physical processes? Using two case studies, we demonstrate that all components of energy input are negligible apart from biological production, quantified by net primary productivity (NPP) and potential energy conversion by water that is placed high up in the landscape as rainfall and leaves it as runoff. Assuming that the former is representative for biological energy and the latter for physical energy, we propose that the ratio of these two values can be used as a proxy for the relative importance of biological and physical processes in landscape evolution. All necessary

The Importance of Biological Databases in Biological Discovery.

Science.gov (United States)

Baxevanis, Andreas D; Bateman, Alex

2015-06-19

Biological databases play a central role in bioinformatics. They offer scientists the opportunity to access a wide variety of biologically relevant data, including the genomic sequences of an increasingly broad range of organisms. This unit provides a brief overview of major sequence databases and portals, such as GenBank, the UCSC Genome Browser, and Ensembl. Model organism databases, including WormBase, The Arabidopsis Information Resource (TAIR), and those made available through the Mouse Genome Informatics (MGI) resource, are also covered. Non-sequence-centric databases, such as Online Mendelian Inheritance in Man (OMIM), the Protein Data Bank (PDB), MetaCyc, and the Kyoto Encyclopedia of Genes and Genomes (KEGG), are also discussed. Copyright © 2015 John Wiley & Sons, Inc.

Effect of alkali metal ions on the pyrrole and pyridine π-electron systems in pyrrole-2-carboxylate and pyridine-2-carboxylate molecules: FT-IR, FT-Raman, NMR and theoretical studies

Science.gov (United States)

Świderski, G.; Wojtulewski, S.; Kalinowska, M.; Świsłocka, R.; Lewandowski, W.

2011-05-01

The FT-IR, FT-Raman and 1H and 13C NMR spectra of pyrrole-2-carboxylic acid (PCA) and lithium, sodium, potassium, rubidium and caesium pyrrole-2-carboxylates were recorded, assigned and compared in the Li → Na → K → Rb → Cs salt series. The effect of alkali metal ions on the electronic system of ligands was discussed. The obtained results were compared with previously reported ones for pyridine-2-carboxylic acid and alkali metal pyridine-2-carboxylates. Calculations for pyrrole-2-carboxylic acid and Li, Na, K pyrrole-2-carboxylates in B3LYP/6-311++G ** level and Møller-Plesset method in MP2/6-311++G ** level were made. Bond lengths, angles and dipole moments as well as aromaticity indices (HOMA, EN, GEO, I 6) for the optimized structures of pyrrole-2-carboxylic acid (PCA) and lithium, sodium, potassium pyrrole-2-carboxylates were also calculated. The degree of perturbation of the aromatic system of ligand under the influence of metals in the Li → Cs series was investigated with the use of statistical methods (linear correlation), calculated aromaticity indices and Mulliken, NBO and ChelpG population analysis method. Additionally, the Bader theory (AIM) was applied to setting the characteristic of the bond critical points what confirmed the influence of alkali metals on the pyrrole ring.

Carboxylic acid exchangers in analytical chemistry

International Nuclear Information System (INIS)

Venkateswarlu, Ch.

1976-01-01

The literature on the use of carboxylic acid exchangers in inorganic analytical chemistry is reviewed. It is classified under two heads, based on the ionic form in which the exchanger is employed, viz., the salt form and the acid form. In the salt form, the separations reported in the beginning are mostly carried out in alkaline medium, employing ammonia and its derivatives as complexing agents to hold cations in solution. This was followed by the use of ammonium ion as an eluent from heavy weakly or neutral solutions. There are a few separations reported making use of EDTA as eluent. It appears that separation of some anions from cations can be achieved with greater ease with these exchangers than with sulphonic acid type. Contary to the general belief, carboxylic acid exchangers are used in H + form to achieve some analytical separations of cations of interest. These exchangers exhibit better sorption of some cations in presence of complexing agents containing basic nitrogen as a donor. In fact, a careful study of these exchangers with different matrices might yield really selective exchangers, than the chelating ones known commercially. From the separation cited, carboxylic acid exchangers appear to have greater potentialities in their applications, than what is normally expected. (author)

Properties of the Carboxylate ion exchange resins

International Nuclear Information System (INIS)

Allard, Bert; Dario, Maarten; Boren, Hans; Torstenfelt, Boerje; Puigdomenech, Ignasi; Johansson, Claes

2002-09-01

Weakly acidic, carboxylic resin has been selected, together with strong base anion resins, for water purification at the Forsmark 1 and 2 reactors. For the strong (but not the weak) ion exchange resin the Nuclear Power Inspectorate has given permission to dispose the spent resins in the SFR 1 (the Final Repository for Radioactive Operational Waste). This report gives a review of the carboxylic resins and comes to the conclusion that the resins are very stable and that there should not exist any risks for increased leaching of radionuclides from SFR 1 if these resins are disposed (compared to the strong resins)

Atom-scale depth localization of biologically important chemical elements in molecular layers.

Science.gov (United States)

Schneck, Emanuel; Scoppola, Ernesto; Drnec, Jakub; Mocuta, Cristian; Felici, Roberto; Novikov, Dmitri; Fragneto, Giovanna; Daillant, Jean

2016-08-23

In nature, biomolecules are often organized as functional thin layers in interfacial architectures, the most prominent examples being biological membranes. Biomolecular layers play also important roles in context with biotechnological surfaces, for instance, when they are the result of adsorption processes. For the understanding of many biological or biotechnologically relevant phenomena, detailed structural insight into the involved biomolecular layers is required. Here, we use standing-wave X-ray fluorescence (SWXF) to localize chemical elements in solid-supported lipid and protein layers with near-Ångstrom precision. The technique complements traditional specular reflectometry experiments that merely yield the layers' global density profiles. While earlier work mostly focused on relatively heavy elements, typically metal ions, we show that it is also possible to determine the position of the comparatively light elements S and P, which are found in the most abundant classes of biomolecules and are therefore particularly important. With that, we overcome the need of artificial heavy atom labels, the main obstacle to a broader application of high-resolution SWXF in the fields of biology and soft matter. This work may thus constitute the basis for the label-free, element-specific structural investigation of complex biomolecular layers and biological surfaces.

Kinetics study of thermal decomposition of calcium carboxylate salts

International Nuclear Information System (INIS)

Landoll, Michael P.; Holtzapple, Mark T.

2013-01-01

The MixAlco™ process ferments lignocellulosic biomass to carboxylate salts that are thermally decomposed into ketones, which are then chemically converted to a wide variety of chemicals and fuels. To perform these decompositions, suitable reaction models are necessary to properly design, scale, and optimize commercial reactors. For three salt types (calcium acetate, and two types of mixed calcium carboxylate salts), activation energy was determined using three isoconversional methods that employed TGA curves at different heating rates. For all three salt types, activation energy varied significantly with conversion. The average activation energy for calcium acetate was 556.75 kJ mol −1 , and the activation energies for the two mixed calcium carboxylate salts were 232.87, and 176.55 kJ mol −1 . In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak–Berggren model provides the best universal fit for all three salt types. -- Highlights: •Calcium carboxylate salts from fermentation broth thermally decompose to ketones. •Activation energy varies with conversion for all three salt types. •Sestak–Berggren model provides best fit overall for all three salt types

Kinetics study of thermal decomposition of sodium carboxylate salts

International Nuclear Information System (INIS)

Landoll, Michael P.; Holtzapple, Mark T.

2012-01-01

The MixAlco™ process ferments lignocellulosic biomass to carboxylate salts that are thermally decomposed into ketones, which are then chemically converted to a wide variety of chemicals and fuels. To perform these decompositions, suitable reaction models are necessary to properly design, scale, and optimize commercial reactors. For three salt types (sodium acetate, and two types of mixed sodium carboxylate salts), activation energy was determined using three isoconversional methods that employed TGA curves at different heating rates. For all three salt types, activation energy varied significantly with conversion. The average activation energy for sodium acetate was 226.65 kJ/mol, and the activation energies for the two mixed sodium carboxylate salts were 195.61, and 218.18 kJ/mol. In addition, three functions of conversion were employed to see which one best modeled the experimental data. The Sestak-Berggren model fits all three salt types best. -- Highlights: ► Sodium carboxylate salts from fermentation broth thermally decompose to ketones. ► Activation energy varies with conversion for all three salt types. ► Sestak-Berggren model provides best fit for all three salt types.

Phosphazene-promoted metal-free ring-opening polymerization of ethylene oxide initiated by carboxylic acid

KAUST Repository

Zhao, Junpeng

2014-03-11

The effectiveness of carboxylic acid as initiator for the anionic ring-opening polymerization of ethylene oxide was investigated with a strong phosphazene base (t-BuP4) used as promoter. Kinetic study showed an induction period, i.e., transformation of carboxylic acid to hydroxyl ester, followed by slow chain growth together with simultaneous and fast end-group transesterification, which led to poly(ethylene oxide) (PEO) consisting of monoester (monohydroxyl), diester, and dihydroxyl species. An appropriate t-BuP4/acid ratio was proven to be essential to achieve better control over the polymerization and low dispersity of PEO. This work provides important information and enriches the toolbox for macromolecular and biomolecular engineering with protic initiating sites. © 2014 American Chemical Society.

Transition metal-catalyzed carboxylation reactions with carbon dioxide.

Science.gov (United States)

Martin, Ruben; Tortajada, Andreu; Juliá-Hernández, Francisco; Borjesson, Marino; Moragas, Toni

2018-05-03

Driven by the inherent synthetic potential of CO2 as an abundant, inexpensive and renewable C1 chemical feedstock, the recent years have witnessed renewed interest in devising catalytic CO2 fixations into organic matter. Although the formation of C-C bonds via catalytic CO2 fixation remained rather limited for a long period of time, a close look into the recent literature data indicates that catalytic carboxylation reactions have entered a new era of exponential growth, evolving into a mature discipline that allows for streamlining the synthesis of carboxylic acids, building blocks of utmost relevance in industrial endeavours. These strategies have generally proven broadly applicability and convenient to perform. However, substantial challenges still need to be addressed reinforcing the need to cover metal-catalyzed carboxylation arena in a conceptual and concise manner, delineating the underlying new principles that are slowly emerging in this vibrant area of expertise. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carboxylated Polyurethanes Containing Hyperbranched Polyester Soft Segments

Directory of Open Access Journals (Sweden)

Žigon, M.

2006-09-01

Full Text Available hyperbranched polyester soft segments (HB PU with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylolpropionic acid of the fourth pseudo-generation (Boltorn H40 and hexamethylene (HDI or isophorone diisocyanate (IPDI. The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios rNCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young's modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures.

Corrosion and Heat Transfer Characteristics of Water Dispersed with Carboxylate Additives and Multi Walled Carbon Nano Tubes

Science.gov (United States)

Moorthy, Chellapilla V. K. N. S. N.; Srinivas, Vadapalli

2016-10-01

This paper summarizes a recent work on anti-corrosive properties and enhanced heat transfer properties of carboxylated water based nanofluids. Water mixed with sebacic acid as carboxylate additive found to be resistant to corrosion and suitable for automotive environment. The carboxylated water is dispersed with very low mass concentration of carbon nano tubes at 0.025, 0.05 and 0.1 %. The stability of nanofluids in terms of zeta potential is found to be good with carboxylated water compared to normal water. The heat transfer performance of nanofluids is carried out on an air cooled heat exchanger similar to an automotive radiator with incoming air velocities across radiator at 5, 10 and 15 m/s. The flow Reynolds number of water is in the range of 2500-6000 indicating developing flow regime. The corrosion resistance of nanofluids is found to be good indicating its suitability to automotive environment. There is a slight increase in viscosity and marginal decrease in the specific heat of nanofluids with addition of carboxylate as well as CNTs. Significant improvement is observed in the thermal conductivity of nanofluids dispersed with CNTs. During heat transfer experimentation, the inside heat transfer coefficient and overall heat transfer coefficient has also improved markedly. It is also found that the velocity of air and flow rate of coolant plays an important role in enhancement of the heat transfer coefficient and overall heat transfer coefficient.

Adsorption Equilibrium Equation of Carboxylic Acids on Anion-Exchange Resins in Water.

Science.gov (United States)

Kanazawa, Nobuhiro; Urano, Kohei; Kokado, Naohiro; Urushigawa, Yoshikuni

2001-06-01

The adsorption of propionic acid and benzoic acid on anion-exchange resins was analyzed, and an adsorption equilibrium equation of carboxylic acids was proposed. The adsorption of carboxylic acids on the anion-exchange resins was considered to be the sum of the physical adsorption of the molecule and the ion-exchange adsorption of the ion, which were independent of each other. For the physical adsorption of carboxylic acids, it was conformed to the Freundlich equation. For the ion-exchange adsorption of carboxylate ions, the equilibrium equation corresponded well with the experimental results for wide ranges of concentration and pH. The equation contains a selectivity coefficient S(A)(Cl) for the chloride ion versus the carboxylate ion, which was considered essentially a constant. The influent of the bicarbonate ion from carbon dioxide in air could also be expressed by the additional equilibrium equation with the selectivity coefficient S(HCO(3))(Cl) for the chloride ion versus the bicarbonate ion. Consequently, an adsorption equilibrium equation can estimate the equilibrium adsorption amounts. Even the effect of a coexisting bicarbonate ion is inconsequential when the parameters of the Freundlich isotherm equation and the selectivity coefficients of the carboxylate ion and the bicarbonate ion in each resin are determined in advance. Copyright 2001 Academic Press.

Biotin Carboxyl Carrier Protein in Barley Chloroplast Membranes

DEFF Research Database (Denmark)

Kannangara, C. G.; Jense, C J

1975-01-01

Biotin localized in barley chloroplast lamellae is covalently bound to a single protein with an approximate molecular weight of 21000. It contains one mole of biotin per mole of protein and functions as a carboxyl carrier in the acetyl-CoA carboxylase reaction. The protein was obtained by solubil...... by solubilization of the lamellae in phenol/acetic acid/8 M urea. Feeding barley seedlings with [14C]-biotin revealed that the vitamin is not degraded into respiratory substrates by the plant, but is specifically incorporated into biotin carboxyl carrier protein....

Carboxyl-terminal Truncations of ClC-Kb Abolish Channel Activation by Barttin Via Modified Common Gating and Trafficking.

Science.gov (United States)

Stölting, Gabriel; Bungert-Plümke, Stefanie; Franzen, Arne; Fahlke, Christoph

2015-12-18

ClC-K chloride channels are crucial for auditory transduction and urine concentration. Mutations in CLCNKB, the gene encoding the renal chloride channel hClC-Kb, cause Bartter syndrome type III, a human genetic condition characterized by polyuria, hypokalemia, and alkalosis. In recent years, several Bartter syndrome-associated mutations have been described that result in truncations of the intracellular carboxyl terminus of hClC-Kb. We here used a combination of whole-cell patch clamp, confocal imaging, co-immunoprecipitation, and surface biotinylation to study the functional consequences of a frequent CLCNKB mutation that creates a premature stop codon at Trp-610. We found that W610X leaves the association of hClC-Kb and the accessory subunit barttin unaffected, but impairs its regulation by barttin. W610X attenuates hClC-Kb surface membrane insertion. Moreover, W610X results in hClC-Kb channel opening in the absence of barttin and prevents further barttin-mediated activation. To describe how the carboxyl terminus modifies the regulation by barttin we used V166E rClC-K1. V166E rClC-K1 is active without barttin and exhibits prominent, barttin-regulated voltage-dependent gating. Electrophysiological characterization of truncated V166E rClC-K1 demonstrated that the distal carboxyl terminus is necessary for slow cooperative gating. Since barttin modifies this particular gating process, channels lacking the distal carboxyl-terminal domain are no longer regulated by the accessory subunit. Our results demonstrate that the carboxyl terminus of hClC-Kb is not part of the binding site for barttin, but functionally modifies the interplay with barttin. The loss-of-activation of truncated hClC-Kb channels in heterologous expression systems fully explains the reduced basolateral chloride conductance in affected kidneys and the clinical symptoms of Bartter syndrome patients. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Plastic scintillators with high loading of one or more metal carboxylates

Science.gov (United States)

Cherepy, Nerine; Sanner, Robert Dean

2016-01-12

In one embodiment, a material includes at least one metal compound incorporated into a polymeric matrix, where the metal compound includes a metal and one or more carboxylate ligands, where at least one of the one or more carboxylate ligands includes a tertiary butyl group, and where the material is optically transparent. In another embodiment, a method includes: processing pulse traces corresponding to light pulses from a scintillator material; and outputting a result of the processing, where the scintillator material comprises at least one metal compound incorporated into a polymeric matrix, the at least one metal compound including a metal and one or more carboxylate ligands, where at least one of the one or more carboxylate ligands has a tertiary butyl group, and where the scintillator material is optically transparent and has an energy resolution at 662 keV of less than about 20%.

Chiral metal-organic frameworks bearing free carboxylic acids for organocatalyst encapsulation.

Science.gov (United States)

Liu, Yan; Xi, Xiaobing; Ye, Chengcheng; Gong, Tengfei; Yang, Zhiwei; Cui, Yong

2014-12-08

Two chiral carboxylic acid functionalized micro- and mesoporous metal-organic frameworks (MOFs) are constructed by the stepwise assembly of triple-stranded heptametallic helicates with six carboxylic acid groups. The mesoporous MOF with permanent porosity functions as a host for encapsulation of an enantiopure organic amine catalyst by combining carboxylic acids and chiral amines in situ through acid-base interactions. The organocatalyst-loaded framework is shown to be an efficient and recyclable heterogeneous catalyst for the asymmetric direct aldol reactions with significantly enhanced stereoselectivity in relative to the homogeneous organocatalyst. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

4-Hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester derivatives as potent anti-tumor agents.

Science.gov (United States)

Hayakawa, Ichiro; Shioya, Rieko; Agatsuma, Toshinori; Furukawa, Hidehiko; Naruto, Shunji; Sugano, Yuichi

2004-01-19

Based on the structure of 4-hydroxy-3-methyl-6-phenylbenzofuran-2-carboxylic acid ethyl ester (1), which exhibits selective cytotoxicity against a tumorigenic cell line, (2,4-dimethoxyphenyl)-(4-hydroxy-3-methyl-6-phenylbenzofuran-2-yl)-methanone (18m) was designed and synthesized as a biologically stable derivative containing no ester group. Although the potency of 18m was almost the same as our initial hit compound 1, 18m is expected to last longer in the human body as an anticancer agent.

Thermodynamic properties of alkyl 1H-indole carboxylate derivatives: A combined experimental and computational study

International Nuclear Information System (INIS)

Carvalho, Tânia M.T.; Amaral, Luísa M.P.F.; Morais, Victor M.F.; Ribeiro da Silva, Maria D.M.C.

2016-01-01

Highlights: • Combustion of methyl 1H-indole-3-carboxylate and ethyl 1H-indole-2-carboxylate by static bomb calorimetry. • The Knudsen mass-loss effusion technique was used to measure the vapour pressures of compounds at different temperatures. • Enthalpies of sublimation of methyl 1H-indole-3-carboxylate and ethyl 1H-indole-2-carboxylate. • Gas-phase enthalpies of formation of methyl 1H-indole-3-carboxylate and ethyl 1H-indole-2-carboxylate have been derived. • Gas-phase enthalpies of formation estimated from G3(MP2) calculations. - Abstract: The standard (p"o = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, of methyl 1H-indole-3-carboxylate and ethyl 1H-indole-2-carboxylate, at T = 298.15 K, were derived from measurements of the standard massic energies of combustion using a static bomb combustion calorimeter. The Knudsen effusion technique was used to measure the vapour pressures as a function of the temperature, which allowed determining the standard molar enthalpies of sublimation of these compounds. The standard (p"o = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, were calculated by combining, for each compound, the standard molar enthalpy of formation, in the crystalline phase, and the standard molar enthalpy of sublimation, yielding −(207.6 ± 3.6) kJ·mol"−"1 and −(234.4 ± 2.4) kJ·mol"−"1, for methyl 1H-indole-3-carboxylate and ethyl 1H-indole-2-carboxylate, respectively. Quantum chemical studies were also conducted, in order to complement the experimental study. The gas-phase enthalpies of formation were estimated from high level ab initio molecular orbital calculations, at the G3(MP2) level, for the compounds studied experimentally, extending the study to the methyl 1H-indole-2-carboxylate and ethyl 1H-indole-3-carboxylate. The results obtained were compared with the experimental data and were also analysed in terms of structural enthalpic group contributions.

Conjugates of 1'-Aminoferrocene-1-carboxylic Acid and Proline: Synthesis, Conformational Analysis and Biological Evaluation

Directory of Open Access Journals (Sweden)

Monika Kovačević

2014-08-01

Full Text Available Our previous studies showed that alteration of dipeptides Y-Fca-Ala-OMe (III into Y-Ala-Fca-OMe (IV (Y = Ac, Boc; Fca = 1'-aminoferrocene-1-carboxylic acid significantly influenced their conformational space. The novel bioconjugates Y-Fca-Pro-OMe (1, Y = Ac; 2, Y = Boc and Y-Pro-Fca-OMe (3, Y = Boc; 4, Y = Ac have been prepared in order to investigate the influence of proline, a well-known turn-inducer, on the conformational properties of small organometallic peptides with an exchanged constituent amino acid sequences. For this purpose, peptides 1–4 were subjected to detailed spectroscopic analysis (IR, NMR, CD spectroscopy in solution. The conformation of peptide 3 in the solid state was determined. Furthermore, the ability of the prepared conjugates to inhibit the growth of estrogen receptor-responsive MCF-7 mammary carcinoma cells and HeLa cervical carcinoma cells was tested.

Measuring the concentration of carboxylic acid groups in torrefied spruce wood.

Science.gov (United States)

Khazraie Shoulaifar, Tooran; Demartini, Nikolai; Ivaska, Ari; Fardim, Pedro; Hupa, Mikko

2012-11-01

Torrefaction is moderate thermal treatment (∼200-300°C) to improve the energy density, handling and storage properties of biomass fuels. In biomass, carboxylic sites are partially responsible for its hygroscopic. These sites are degraded to varying extents during torrefaction. In this paper, we apply methylene blue sorption and potentiometric titration to measure the concentration of carboxylic acid groups in spruce wood torrefied for 30min at temperatures between 180 and 300°C. The results from both methods were applicable and the values agreed well. A decrease in the equilibrium moisture content at different humidity was also measured for the torrefied wood samples, which is in good agreement with the decrease in carboxylic acid sites. Thus both methods offer a means of directly measuring the decomposition of carboxylic groups in biomass during torrefaction as a valuable parameter in evaluating the extent of torrefaction which provides new information to the chemical changes occurring during torrefaction. Copyright © 2012 Elsevier Ltd. All rights reserved.

Synthesis and biological evaluation of some N-(3-(1H-tetrazol-5-yl) phenyl)acetamide derivatives as novel non-carboxylic PTP1B inhibitors designed through bioisosteric modulation.

Science.gov (United States)

Maheshwari, Neelesh; Karthikeyan, Chandrabose; Bhadada, Shraddha V; Sahi, Chandan; Verma, Amit K; Hari Narayana Moorthy, N S; Trivedi, Piyush

2018-06-08

Described herein is the synthesis and biological evaluation of a series of non-carboxylic inhibitors of Protein Tyrosine Phosphatase 1B designed using bioisosteric replacement strategy. Six N-(3-(1H-tetrazol-5-yl)phenyl)acetamide derivatives designed employing the aforementioned strategy were synthesized and screened for PTP1B inhibitory activity. Among the synthesized compounds, compound NM-03 exhibited the most potent inhibitory activity with IC 50 value of 4.48 µM. Docking studies with NM-03 revealed the key interactions with desired amino acids in the binding site of PTP1B. Furthermore, compound NM-03 also elicited good in vivo activity. Taken together, the results of this study establish N-(3-(1H-tetrazole-5-yl)phenyl)-2-(benzo[d]oxazol-2-ylthio)acetamide (NM-03) as a valuable lead molecule with great potential for PTP1B inhibitor development targeting diabetes. Copyright © 2018 Elsevier Inc. All rights reserved.

Ovalbumin with Glycated Carboxyl Groups Shows Membrane-Damaging Activity

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Ching-Chia Tang

2017-02-01

Full Text Available The aim of the present study was to investigate whether glycated ovalbumin (OVA showed novel activity at the lipid-water interface. Mannosylated OVA (Man-OVA was prepared by modification of the carboxyl groups with p-aminophenyl α-dextro (d-mannopyranoside. An increase in the number of modified carboxyl groups increased the membrane-damaging activity of Man-OVA on cell membrane-mimicking vesicles, whereas OVA did not induce membrane permeability in the tested phospholipid vesicles. The glycation of carboxyl groups caused a notable change in the gross conformation of OVA. Moreover, owing to their spatial positions, the Trp residues in Man-OVA were more exposed, unlike those in OVA. Fluorescence quenching studies suggested that the Trp residues in Man-OVA were located on the interface binds with the lipid vesicles, and their microenvironment was abundant in positively charged residues. Although OVA and Man-OVA showed a similar binding affinity for lipid vesicles, the lipid-interacting feature of Man-OVA was distinct from that of OVA. Chemical modification studies revealed that Lys and Arg residues, but not Trp residues, played a crucial role in the membrane-damaging activity of Man-OVA. Taken together, our data suggest that glycation of carboxyl groups causes changes in the structural properties and membrane-interacting features of OVA, generating OVA with membrane-perturbing activities at the lipid-water interface.

Enhanced detection of amino acids in hydrophilic interaction chromatography electrospray tandem mass spectrometry with carboxylic acids as mobile phase additives.

Science.gov (United States)

Yin, Dengyang; Hu, Xunxiu; Liu, Dantong; Du, Wencheng; Wang, Haibo; Guo, Mengzhe; Tang, Daoquan

2017-06-01

Liquid chromatography coupled with mass spectrometry technique has been widely used in the analysis of biological targets such as amino acids, peptides, and proteins. In this work, eight common single carboxylic acids or diacids, which contain different pKa have been investigated as the additives to the analysis of amino acids. As the results, carboxylic acid additive can improve the signal intensity of acidity amino acids such as Asp and Glu and the chromatographic separation of basic amino acids such as Arg, His, and Lys. In particular, the diacids have better performance than single acids. The proposed mechanism is that the diacid has hydrogen bond interaction with amino acids to reduce their polarity/amphiprotic characteristics. Besides, oxalic acid has been found having better enhancement than phthalic acid by overall consideration. Therefore, we successfully quantified the 15 amino acids in Sepia bulk pharmaceutical chemical by using oxalic acid as the additive.

Synthesis and fluorescence study of phenylcoumarin/cyanophenylbenzocoumarin-3-carboxylates

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Hosanagara N. Harishkumar

2012-01-01

Full Text Available The absorption and fluorescence spectra of phenylcoumarin and cyanophenylbenzocoumarin-3-carboxylates 6a-f and 9a-e have been investigated in chloroform, acetonitrile and ethanol. The substituting groups with varying electron donating ability such as N,N-diethyl amine and morpholine at 7-position, in phenylcoumarin-3-carboxylate 6a-f exhibits fluorescence at a longer wavelength i.e. 420-460 nm in chloroform and 460-504 nm in acetonitrile. However the morpholine derivatives 6f-j did not show fluorescence in chloroform. In another series of cyanophenylbenzocoumarin-3-carboxylates 9a-e, the compound 9c exhibits fluorescence at 546 nm in ethanol and 256 nm in acetonitrile, and lower emission wavelength i.e. 356 nm in chloroform. Further the compounds 6e , 9b, 9d and 9e exhibited high quantum yield in ethanol i.e., Φ F = 0.79, 0.70, 0.80 and 0.74 respectively compare to Rhodamine B ( Φ F = 0.24 in ethanol.

Interaction Between the Biotin Carboxyl Carrier Domain and the Biotin Carboxylase Domain in Pyruvate Carboxylase from Rhizobium etli†

Science.gov (United States)

Lietzan, Adam D.; Menefee, Ann L.; Zeczycki, Tonya N.; Kumar, Sudhanshu; Attwood, Paul V.; Wallace, John C.; Cleland, W. Wallace; Maurice, Martin St.

2011-01-01

Pyruvate carboxylase (PC) catalyzes the ATP-dependent carboxylation of pyruvate to oxaloacetate, an important anaplerotic reaction in mammalian tissues. To effect catalysis, the tethered biotin of PC must gain access to active sites in both the biotin carboxylase domain and the carboxyl transferase domain. Previous studies have demonstrated that a mutation of threonine 882 to alanine in PC from Rhizobium etli renders the carboxyl transferase domain inactive and favors the positioning of biotin in the biotin carboxylase domain. We report the 2.4 Å resolution X-ray crystal structure of the Rhizobium etli PC T882A mutant which reveals the first high-resolution description of the domain interaction between the biotin carboxyl carrier protein domain and the biotin carboxylase domain. The overall quaternary arrangement of Rhizobium etli PC remains highly asymmetrical and is independent of the presence of allosteric activator. While biotin is observed in the biotin carboxylase domain, its access to the active site is precluded by the interaction between Arg353 and Glu248, revealing a mechanism for regulating carboxybiotin access to the BC domain active site. The binding location for the biotin carboxyl carrier protein domain demonstrates that tethered biotin cannot bind in the biotin carboxylase domain active site in the same orientation as free biotin, helping to explain the difference in catalysis observed between tethered biotin and free biotin substrates in biotin carboxylase enzymes. Electron density located in the biotin carboxylase domain active site is assigned to phosphonoacetate, offering a probable location for the putative carboxyphosphate intermediate formed during biotin carboxylation. The insights gained from the T882A Rhizobium etli PC crystal structure provide a new series of catalytic snapshots in PC and offer a revised perspective on catalysis in the biotin-dependent enzyme family. PMID:21958016

Highly visible-light luminescence properties of the carboxyl-functionalized short and ultrashort MWNTs

International Nuclear Information System (INIS)

Luo Yongsong; Xia Xiaohong; Liang Ying; Zhang Yonggang; Ren Qinfeng; Li Jialin; Jia Zhijie; Tang Yiwen

2007-01-01

Luminescence of the short multiwalled carbon nanotubes (MWNTs) conjugated with carboxylic acid groups has been studied. The results show that the carboxyl-functionalized short MWNTs could emit luminescence and the emission peak appears at 500 nm with a corresponding optimal excitation wavelength centering at 310 nm. When the short MWNTs are filtered through 0.15 μm polytetrafluoroethylene (PTFE) membrane, the ultrashort MWNTs are obtained from the filtrate. An interesting feature for the ultrashort MWNTs is that the emission intensity is strengthened and the peak is slightly blue shifted to 460 nm. This result indicates that the luminescence properties of MWNTs are strongly affected by the tube length. After chemical oxidization cutting, defects and carboxylic acid groups at the tube end and/or sidewall can be produced; the more shorten of MWNTs, the better dispersion and carboxylic passivation of the nanotubes, and the more intense luminescence emissions. The broad emissions are logically attributed to the trapping of excitation energy by defect sites in the carboxyl-functionalized nanotube structure. - Graphical abstract: Luminescence of the short and ultrashort multiwalled carbon nanotubes (MWNTs) conjugated with carboxylic acid groups, which is logically attributed to the trapping of excitation energy by defect sites, has been studied

Nitrile rubber and carboxylated nitrile rubber resistance to soybean biodiesel

Directory of Open Access Journals (Sweden)

Felipe Nunes Linhares

2018-03-01

Full Text Available Abstract Biodiesel has been considered a suitable substitute for petroleum diesel, but their chemical composition differs greatly. For this reason, biodiesel interacts differently than petroleum diesel with various materials, including rubbers. Therefore, the resistance of some elastomers should be thoroughly evaluated, specifically those which are commonly used in automotive industry. Nitrile rubber (NBR is widely used to produce vehicular parts that are constantly in contact with fuels. This paper aimed to assess the resistance of carboxylated nitrile rubber (XNBR with 28% of acrylonitrile content to soybean biodiesel in comparison with non-carboxylated nitrile rubber samples, with high and medium acrylonitrile content (33 and 45%. NBR with medium acrylonitrile content showed little resistance to biodiesel. However, carboxylated nitrile rubber even with low acrylonitrile content had similar performance to NBR with high acrylonitrile content.

Biosynthesis of quinoxaline antibiotics: Purification and characterization of the quinoxaline-2-carboxylic acid activating enzyme from Streptomyces triostinicus

International Nuclear Information System (INIS)

Glund, K.; Schlumbohm, W.; Bapat, M.; Keller, U.

1990-01-01

A quinoxaline-2-carboxylic acid activating enzyme was purified to homogeneity from triostin-producing Streptomyces triostinicus. It could also be purified from quinomycin-producing Streptomyces echinatus. Triostins and quinomycins are peptide lactones that contain quinoxaline-2-carboxylic acid as chromophoric moiety. The enzyme catalyzes the ATP-pyrophosphate exchange reaction dependent on quinoxaline-2-carboxylic acid and the formation of the corresponding adenylate. Besides quinoxaline-2-carboxylic acid, the enzyme also catalyzes the formation of adenylates from quinoline-2-carboxylic acid and thieno[3,2-b]pyridine-5-carboxylic acid. No adenylates were seen from quinoline-3-carboxylic acid, quinoline-4-carboxylic acid, pyridine-2-carboxylic acid, and 2-pyrazinecarboxylic acid. Previous work revealed that quinoline-2-carboxylic acid and thieno[3,2-b]pyridine-5-carboxylic acid became efficiently incorporated into the corresponding quinoxaline antibiotic analogues in vivo. Together with the data described here, this suggests that the enzyme is part of the quinoxaline antibiotics synthesizing enzyme system. The enzyme displays a native molecular weight of 42,000, whereas in its denatured form it is a polypeptide of Mr 52,000-53,000. It resembles in its behavior actinomycin synthetase I, the chromophore activating enzyme involved in actinomycin biosynthesis

Sea Cucumber Glycosides: Chemical Structures, Producing Species and Important Biological Properties.

Science.gov (United States)

Mondol, Muhammad Abdul Mojid; Shin, Hee Jae; Rahman, M Aminur; Islam, Mohamad Tofazzal

2017-10-17

Sea cucumbers belonging to echinoderm are traditionally used as tonic food in China and other Asian countries. They produce abundant biologically active triterpene glycosides. More than 300 triterpene glycosides have been isolated and characterized from various species of sea cucumbers, which are classified as holostane and nonholostane depending on the presence or absence of a specific structural unit γ(18,20)-lactone in the aglycone. Triterpene glycosides contain a carbohydrate chain up to six monosaccharide units mainly consisting of d-xylose, 3-O-methy-d-xylose, d-glucose, 3-O-methyl-d-glucose, and d-quinovose. Cytotoxicity is the common biological property of triterpene glycosides isolated from sea cucumbers. Besides cytotoxicity, triterpene glycosides also exhibit antifungal, antiviral and hemolytic activities. This review updates and summarizes our understanding on diverse chemical structures of triterpene glycosides from various species of sea cucumbers and their important biological activities. Mechanisms of action and structural-activity relationships (SARs) of sea cucumber glycosides are also discussed briefly.

Synthesis of new oxovanadium (IV) complexes of potential insulinmimetic activity with coumarin-3-carboxylic acid ligands and substituted derivatives

International Nuclear Information System (INIS)

Salas Fernandez, Paloma; Alvino de la Sota, Nora; Galli Rigo-Righi, Carla

2013-01-01

This work comprises the design and synthesis of four new oxovanadium (IV) complexes, a metal which possesses insulin-mimetic action. Coumarin-3-carboxylic acid and three of its 6 -and 6,8- derivatives were used as ligands. Coumarins are of interest due to their well-known biological properties and pharmacological applications; these include the insulino-sensibilizing effect of certain alcoxy-hydroxy-derivatives which might lead to the eventual existence of a synergetic effect with the active metal center. The synthesis of the vanadyl complexes was preceded by the synthesis of the coumarin-3-carboxylic acid and its 6-bromo- derivative, as well as the syntheses of three derivatives not previously reported: 6-bromo-8-metoxi-, 6-bromo-8-nitro-, and 6-bromo-8-hydroxy-, which were prepared by a Knoevenagel condensation reaction. The complexes, on their part, were prepared by a metathesis reaction between VOSO 4 and the corresponding ligands, on the basis of methods reported for other vanadyl complexes and under strict pH control. The coumarin-3-carboxylic ligands and the derivatives were characterized by 1 H-NMR-, FTIR- and UV-Vis-spectroscopy. In the case of the complexes, their paramagnetic character did not allow for NMR characterization, being thus identified by FT-IR-spectroscopy and by the quantitative determination of their vanadium contents. (author)

Development of technology for fabrication of lithium CPS on basis of CNT-reinforced carboxylic fabric

Energy Technology Data Exchange (ETDEWEB)

Tazhibayeva, Irina, E-mail: tazhibayeva@ntsc.kz [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan); Baklanov, Viktor; Ponkratov, Yuriy [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan); Abdullin, Khabibulla [Institute of Experimental and Theoretical Physics of Kazakh National University, Almaty (Kazakhstan); Kulsartov, Timur; Gordienko, Yuriy; Zaurbekova, Zhanna [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan); Lyublinski, Igor [JSC «Red Star», Moscow (Russian Federation); NRNU «MEPhI», Moscow (Russian Federation); Vertkov, Alexey [JSC «Red Star», Moscow (Russian Federation); Skakov, Mazhyn [Institute of Atomic Energy, National Nuclear Center of RK, Kurchatov (Kazakhstan)

2017-04-15

Highlights: • Preliminary study of carboxylic fabric wettability with liquid lithium is presented. • Preliminary studies of carboxylic fabric wettability with liquid lithium consist in carrying out of experiments at temperatures 673,773 and 873 К in vacuum during long time. • A scheme of experimental device for manufacturing of lithium CPS and matrix filling procedure with liquid lithium are presented. • The concept of lithium limiter with CPS on basis of CNT-reinforced carboxylic fabric is proposed. - Abstract: The paper describes the analysis of liquid lithium interaction with materials based on carbon, the manufacture technology of capillary-porous system (CPS) matrix on basis of CNT-reinforced carboxylic fabric. Preliminary study of carboxylic fabric wettability with liquid lithium is presented. The development of technology includes: microstructural studies of carboxylic fabric before its CNT-reinforcing; validation of CNT-reinforcing technology; mode validation of CVD-method for CNT synthesize; study of synthesized carbon structures. Preliminary studies of carboxylic fabric wettability with liquid lithium consist in carrying out of experiments at temperatures 673, 773 and 873 К in vacuum during long time. The scheme of experimental device for manufacturing of lithium CPS and matrix filling procedure with liquid lithium are presented. The concept of lithium limiter with CPS on basis of CNT-reinforced carboxylic fabric is proposed.

Development of technology for fabrication of lithium CPS on basis of CNT-reinforced carboxylic fabric

International Nuclear Information System (INIS)

Tazhibayeva, Irina; Baklanov, Viktor; Ponkratov, Yuriy; Abdullin, Khabibulla; Kulsartov, Timur; Gordienko, Yuriy; Zaurbekova, Zhanna; Lyublinski, Igor; Vertkov, Alexey; Skakov, Mazhyn

2017-01-01

Highlights: • Preliminary study of carboxylic fabric wettability with liquid lithium is presented. • Preliminary studies of carboxylic fabric wettability with liquid lithium consist in carrying out of experiments at temperatures 673,773 and 873 К in vacuum during long time. • A scheme of experimental device for manufacturing of lithium CPS and matrix filling procedure with liquid lithium are presented. • The concept of lithium limiter with CPS on basis of CNT-reinforced carboxylic fabric is proposed. - Abstract: The paper describes the analysis of liquid lithium interaction with materials based on carbon, the manufacture technology of capillary-porous system (CPS) matrix on basis of CNT-reinforced carboxylic fabric. Preliminary study of carboxylic fabric wettability with liquid lithium is presented. The development of technology includes: microstructural studies of carboxylic fabric before its CNT-reinforcing; validation of CNT-reinforcing technology; mode validation of CVD-method for CNT synthesize; study of synthesized carbon structures. Preliminary studies of carboxylic fabric wettability with liquid lithium consist in carrying out of experiments at temperatures 673, 773 and 873 К in vacuum during long time. The scheme of experimental device for manufacturing of lithium CPS and matrix filling procedure with liquid lithium are presented. The concept of lithium limiter with CPS on basis of CNT-reinforced carboxylic fabric is proposed.

Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

Energy Technology Data Exchange (ETDEWEB)

Poole, Loree Joanne [Univ. of California, Berkeley, CA (United States); King, C. Judson [Univ. of California, Berkeley, CA (United States)

1990-03-01

Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO₂ and H₂S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The

ISCB Ebola Award for Important Future Research on the Computational Biology of Ebola Virus.

Directory of Open Access Journals (Sweden)

Peter D. Karp

2015-01-01

Full Text Available Speed is of the essence in combating Ebola; thus, computational approaches should form a significant component of Ebola research. As for the development of any modern drug, computational biology is uniquely positioned to contribute through comparative analysis of the genome sequences of Ebola strains as well as 3-D protein modeling. Other computational approaches to Ebola may include large-scale docking studies of Ebola proteins with human proteins and with small-molecule libraries, computational modeling of the spread of the virus, computational mining of the Ebola literature, and creation of a curated Ebola database. Taken together, such computational efforts could significantly accelerate traditional scientific approaches. In recognition of the need for important and immediate solutions from the field of computational biology against Ebola, the International Society for Computational Biology (ISCB announces a prize for an important computational advance in fighting the Ebola virus. ISCB will confer the ISCB Fight against Ebola Award, along with a prize of US$2,000, at its July 2016 annual meeting (ISCB Intelligent Systems for Molecular Biology [ISMB] 2016, Orlando, Florida.

Enhancement of carboxylic acid degradation with sulfate radical generated by persulfate activation.

Science.gov (United States)

Criquet, J; Nebout, P; Karpel Vel Leitner, N

2010-01-01

The aim of this work was to investigate the generation of sulfate radical for the removal of two carboxylic acids in aqueous solution: acetic and citric acids. From photochemical and radiolytic processes, kinetics of the degradation of these two carboxylic acids was studied as a function of the pH of the solution. It was shown that the maximum of acetic acid degradation occurred at pH 5. Above this pH, competitive reactions with the carbon mineralized inhibit the reaction of with the solute. In the case of citric acid, pH has only a little effect on the kinetic of citric acid degradation. The determination of mineralization yields shows several differences depending on carboxylic acids and pH. The degradation of both carboxylic acids was also studied in the radiolysis process whether with or without persulfate addition. A comparison of the processes of sulfate radical production is presented.

Enrichment of Nanodiamond Surfaces with Carboxyl Groups for Doxorubicin Loading and Release

Science.gov (United States)

Astuti, Y.; Saputra, F. D.; Wuning, S.; Arnelli; Bhaduri, G.

2017-02-01

In their pristine state, nanodiamond crystals produced via detonation techniques containing several functional groups present on the surface including amine, amide, alcohol, carbonyl, and carboxyl. These functional groups facilitate nanodiamond to interact drugs so as to nanodiamond is potential for medical application such as drug delivery. Even though research on t he use of nanodiamond for this application has been conducted widely, research on the effect of enrichment of nanodiamond surface with carboxyl functional groups for drug loading and release has not been explored extensively. Therefore, in this paper, the effect of carboxyl-terminated nanodiamond (ND-COOH) on drug loading and release will be presented. The enrichment of nanodiamond with carboxyl groups was undertaken by treating nanodiamond with sulphuric acid and nitric acid. The results show that the doxorubicin (DOX) loading and release efficiencies of ND pristine are higher than that of ND-COOH.

50 CFR 216.191 - Designation of Offshore Biologically Important Marine Mammal Areas.

Science.gov (United States)

2010-10-01

...) Detailed information on the biology of marine mammals within the area, including estimated population size... Important Marine Mammal Areas. 216.191 Section 216.191 Wildlife and Fisheries NATIONAL MARINE FISHERIES SERVICE, NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION, DEPARTMENT OF COMMERCE MARINE MAMMALS...

In situ Recovery of Bio-Based Carboxylic Acids

Energy Technology Data Exchange (ETDEWEB)

Karp, Eric M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Saboe, Patrick [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Manker, Lorenz [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Michener, William E [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Peterson, Darren J [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Brandner, David [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Deutch, Stephen P [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Cywar, Robin [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Beckham, Gregg T [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Kumar, Manish [Pennsylvania State University

2018-03-16

The economics of chemical and biological processes is often dominated by the expense of downstream product separations from dilute product streams. Continuous separation techniques, such as in situ product recovery (ISPR), are attractive in that they can concentrate products from a reactor and minimize solvent loss, thereby increasing purity and sustainability of the process. In bioprocesses, ISPR can have an additional advantage of increasing productivity by alleviating product inhibition on the microorganism. In this work, we developed a liquid-liquid extraction (LLE)-based ISPR system integrated with downstream distillation to selectively purify free carboxylic acids, which were selected as exemplary bioproducts due to their ability to be produced at industrially relevant titers and productivities. Equilibrium constants for the extraction of carboxylic acids into a phosphine-oxide based organic phase were experimentally determined. Complete recovery of acids from the extractant and recyclability of the organic phase were demonstrated through multiple extraction-distillation cycles. Using these data, an equilibrium model was developed to predict the acid loading in the organic phase as a function of the extraction equilibrium constant, initial aqueous acid concentration, pH, organic to aqueous volume ratio, and temperature. A distillation process model was then used to predict the energy input required to distill neat acid from an organic phase as a function of the acid loading in the organic phase feed. The heat integrated distillation train can achieve neat recovery of acetic acid with an energy input of 2.6 MJ kg-1 of acetic acid. This LLE-based ISPR system integrated with downstream distillation has an estimated carbon footprint of less than 0.36 kg CO2 per kg of acetic acid, and provides a green approach to enable both new industrial bioprocesses, and process intensification of existing industrial operations by (1) increasing the productivity and titer of

Synthesis and study of dioxouranium (6) carboxylate complexes with ammonia

International Nuclear Information System (INIS)

Spitsyn, V.I.; Mazo, G.N.; Dunaev, K.M.; Santalova, N.A.

1980-01-01

Heterophase synthesis of a series of ammonia complexes of dioxouranium (6) carboxylates namely, UO 2 (HCOO) 2 x2NH 3 , UO 2 (CH 3 COO) 2 x2NH 3 , UO 2 (CH 3 CH 2 OO) 2 x2NH 3 is presented and their properties and structure are studied. Comparison of infrared spectra of dioxouranium (6) carboxylates and their ammonia complexes has shown that NH 3 molecule introduction changes in principle the coordination of azidoligand turning out bridge carboxylate groups into island ones and weakening their bonds with central cations. In spectra of all diammiacates the shift of bands of deformational and valent oscillations of N-H bond in comparison with spectrum of pure ammonia tells about NH 3 coordination with metal. Complexes thermolysis has been studied under iso- and polythermal conditions. General diagram of thermal decay is presented [ru

Analytical study of zirconium and hafnium α-hydroxy carboxylates

International Nuclear Information System (INIS)

Terra, V.R.

1991-01-01

The analytical study of zirconium and hafnium α-hydroxy carboxylates was described. For this purpose dl-mandelic, dl-p-bromo mandelic, dl-2-naphthyl glycolic, and benzilic acids were prepared. These were used in conjunction with glycolic, dl-lactic, dl-2-hydroxy isovaleric, dl-2-hydroxy hexanoic, and dl-2-hydroxy dodecanoic acids in order to synthesize the zirconium(IV) and hafnium(IV) tetrakis(α-hydroxy carboxylates). The compounds were characterized by melting point determination, infrared spectroscopy, thermogravimetric analysis, calcination to oxides and X-ray diffractometry by the powder method. (C.G.C)

Effect of Producing Different Phenazines on Bacterial Fitness and Biological Control in Pseudomonas chlororaphis 30-84

Directory of Open Access Journals (Sweden)

Jun Myoung Yu

2018-02-01

Full Text Available Pseudomonas chlororaphis 30-84 is a biological control agent selected for its ability to suppress diseases caused by fungal pathogens. P. chlororaphis 30-84 produces three phenazines: phenazine-1-carboxylic acid (PCA, 2-hydroxy-phenazine-1-carboxylic acid (2OHPCA and a small amount of 2-hydroxy-phenazine (2OHPHZ, and these are required for fungal pathogen inhibition and wheat rhizosphere competence. The two, 2-hydroxy derivatives are produced from PCA via the activity of a phenazine-modifying enzyme encoded by phzO. In addition to the seven biosynthetic genes responsible for the production of PCA, many other Pseudomonas strains possess one or more modifying genes, which encode enzymes that act independently or together to convert PCA into other phenazine derivatives. In order to understand the fitness effects of producing different phenazines, we constructed isogenic derivatives of P. chlororaphis 30-84 that differed only in the type of phenazines produced. Altering the type of phenazines produced by P. chlororaphis 30-84 enhanced the spectrum of fungal pathogens inhibited and altered the degree of take-all disease suppression. These strains also differed in their ability to promote extracellular DNA release, which may contribute to the observed differences in the amount of biofilm produced. All derivatives were equally important for survival over repeated plant/harvest cycles, indicating that the type of phenazines produced is less important for persistence in the wheat rhizosphere than whether or not cells produce phenazines. These findings provide a better understanding of the effects of different phenazines on functions important for biological control activity with implications for applications that rely on introduced or native phenazine producing populations.

Thermal stability of carboxylic acid functionality in coal; Sekitanchu ni sonzaisuru karubokishiruki no netsubunkai kyodo

Energy Technology Data Exchange (ETDEWEB)

Tsutsumi, Y.; Aida, T. [Kinki University, Osaka (Japan). Faculty of Engineering

1996-10-28

Carboxyl in coal was focused in discussing its pyrolytic behavior while tracking change of its absolute amount relative to the heating temperatures. A total of four kinds of coals, consisting of two kinds brown coals, sub-bituminous coal and bituminous coal were used. Change in the absolute amount of carboxyl due to heating varies with coalification degree. Decomposition starts in the bituminous coal from around 300{degree}C, and is rapidly accelerated when 400{degree}C is exceeded. Carboxyls in brown coals exist two to three times as much as those in bituminous and sub-bituminous coals, of which 40% is decomposed at a temperature as low as about 300{degree}C. Their pyrolytic behavior at temperatures higher than 400{degree}C resembles that of the bituminous coal. Carboxyls consist of those easy to decompose and difficult to decompose. Aromatic and aliphatic carboxylic acids with simple structure are stable at temperatures lower than 300{degree}C, and decompose abruptly from about 400{degree}C, hence their behavior resembles that of carboxyls in bituminous and sub-bituminous coals. Structure of low-temperature decomposing carboxyls in brown coals is not known, but it is assumed that humic acid originated from natural materials remains in the structure. 4 refs., 3 figs., 1 tab.

Don’t bust the biological soil crust: Preserving and restoring an important desert resource

Science.gov (United States)

Sue Miller; Steve Warren; Larry St. Clair

2017-01-01

Biological soil crusts are a complex of microscopic organisms growing on the soil surface in many arid and semi-arid ecosystems. These crusts perform the important role of stabilizing soil and reducing or eliminating water and wind erosion. One of the largest threats to biological soil crusts in the arid and semi-arid areas of the western United States is mechanical...

First principles study of edge carboxylated graphene quantum dots

Science.gov (United States)

Abdelsalam, Hazem; Elhaes, Hanan; Ibrahim, Medhat A.

2018-05-01

The structure stability and electronic properties of edge carboxylated hexagonal and triangular graphene quantum dots are investigated using density functional theory. The calculated binding energies show that the hexagonal clusters with armchair edges have the highest stability among all the quantum dots. The binding energy of carboxylated graphene quantum dots increases by increasing the number of carboxyl groups. Our study shows that the total dipole moment significantly increases by adding COOH with the highest value observed in triangular clusters. The edge states in triangular graphene quantum dots with zigzag edges produce completely different energy spectrum from other dots: (a) the energy gap in triangular zigzag is very small as compared to other clusters and (b) the highest occupied molecular orbital is localized at the edges which is in contrast to other clusters where it is distributed over the cluster surface. The enhanced reactivity and the controllable energy gap by shape and edge termination make graphene quantum dots ideal for various nanodevice applications such as sensors. The infrared spectra are presented to confirm the stability of the quantum dots.

In situ SERS and X-ray photoelectron spectroscopy studies on the pH-dependant adsorption of anthraquinone-2-carboxylic acid on silver electrode

Energy Technology Data Exchange (ETDEWEB)

Li, Dan, E-mail: dany@sit.edu.cn [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China); Jia, Shaojie [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China); Fodjo, Essy Kouadio [Laboratory of Physical Chemistry, University Felix Houphouet Boigny, 22 BP 582, Abidjan 22, Cote d’Ivoire (Cote d' Ivoire); Xu, Hu [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China); Wang, Yuhong, E-mail: yuhong_wang502@sit.edu.cn [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China); Deng, Wei [School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418 (China)

2016-03-30

Graphical abstract: The orientation of anthraquinone-2-carboxylic acid (AQ-2-COOH) has been investigated by in situ surface-enhanced Raman scattering (in situ SERS) spectroelectrochemistry and angle-resolved X-ray photoelectron spectroscopy (AR-XPS) on silver surface. - Highlights: • The adsorption behavior of anthraquinone-2-carboxylic acid (AQ-2-COOH) on Ag electrode is influenced by the pH. • The pH-dependant adsorption of AQ-2-COOH has been confirmed by in situ surface-enhanced Raman scattering (in situ SERS) spectroelectrochemistry and angle-resolved X-ray photoelectron spectroscopy (AR-XPS). • The results can provide insights into electron transfer reactions of AQ-2-COOH in biological systems. - Abstract: In this study, in situ surface-enhanced Raman scattering (SERS) spectroelectrochemistry and angle-resolved X-ray photoelectron spectroscopy (AR-XPS) are used to investigate the redox reaction and adsorption behavior of anthraquinone-2-carboxylic acid (AQ-2-COOH) on an Ag electrode at different pH values. The obtained results indicate that AQ-2-COOH is adsorbed tilted on the Ag electrode through O-atom of ring carbonyl in a potential range from −0.3 to −0.5 V vs. SCE, but the orientation turns to more tilted orientation with both O-atom of the ring carbonyl and carboxylate group in positive potential region for pH 6.0 and 7.4. However, at pH 10.0, the orientation adopts tilted conformation constantly on the Ag electrode with both O-atom of the anthraquinone ring and carboxylate group in the potential range from −0.3 to −0.5 V vs. SCE or at positive potentials. Moreover, the adsorption behavior of AQ-2-COOH has been further confirmed by AR-XPS on the Ag surface. Proposed reasons for the observed changes in orientation are presented.

Atom-Economical Dimerization Strategy by the Rhodium-Catalyzed Addition of Carboxylic Acids to Allenes: Protecting-Group-Free Synthesis of Clavosolide A and Late-Stage Modification.

Science.gov (United States)

Haydl, Alexander M; Breit, Bernhard

2015-12-14

Natural products of polyketide origin with a high level of symmetry, in particular C2 -symmetric diolides as a special macrolactone-based product class, often possess a broad spectrum of biological activity. An efficient route to this important structural motif was developed as part of a concise and highly convergent synthesis of clavosolide A. This strategy features an atom-economic "head-to-tail" dimerization by the stereoselective rhodium-catalyzed addition of carboxylic acids to terminal allenes with the simultaneous construction of two new stereocenters. The excellent efficiency and selectivity with which the C2 -symmetric core structures were obtained are remarkable considering the outcome under classical dimerization conditions. Furthermore, this approach facilitates late-stage modification and provides ready access to potential new lead structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aspartate and glutamate mimetic structures in biologically active compounds.

Science.gov (United States)

Stefanic, Peter; Dolenc, Marija Sollner

2004-04-01

Glutamate and aspartate are frequently recognized as key structural elements for the biological activity of natural peptides and synthetic compounds. The acidic side-chain functionality of both the amino acids provides the basis for the ionic interaction and subsequent molecular recognition by specific receptor sites that results in the regulation of physiological or pathophysiological processes in the organism. In the development of new biologically active compounds that possess the ability to modulate these processes, compounds offering the same type of interactions are being designed. Thus, using a peptidomimetic design approach, glutamate and aspartate mimetics are incorporated into the structure of final biologically active compounds. This review covers different bioisosteric replacements of carboxylic acid alone, as well as mimetics of the whole amino acid structure. Amino acid analogs presented include those with different distances between anionic moieties, and analogs with additional functional groups that result in conformational restriction or alternative interaction sites. The article also provides an overview of different cyclic structures, including various cycloalkane, bicyclic and heterocyclic analogs, that lead to conformational restriction. Higher di- and tripeptide mimetics in which carboxylic acid functionality is incorporated into larger molecules are also reviewed. In addition to the mimetic structures presented, emphasis in this article is placed on their steric and electronic properties. These mimetics constitute a useful pool of fragments in the design of new biologically active compounds, particularly in the field of RGD mimetics and excitatory amino acid agonists and antagonists.

Properties of the Carboxylate ion exchange resins; Karboxylatjonbytarmassans egenskaper

Energy Technology Data Exchange (ETDEWEB)

Allard, Bert; Dario, Maarten [Oerebro Univ. (Sweden); Boren, Hans [Linkoepings Univ. (Sweden); Torstenfelt, Boerje [Swedpower, Stockholm (Sweden); Puigdomenech, Ignasi; Johansson, Claes [Swedish Nuclear Fuel and Waste Management Co., Stockholm (Sweden)

2002-09-01

Weakly acidic, carboxylic resin has been selected, together with strong base anion resins, for water purification at the Forsmark 1 and 2 reactors. For the strong (but not the weak) ion exchange resin the Nuclear Power Inspectorate has given permission to dispose the spent resins in the SFR 1 (the Final Repository for Radioactive Operational Waste). This report gives a review of the carboxylic resins and comes to the conclusion that the resins are very stable and that there should not exist any risks for increased leaching of radionuclides from SFR 1 if these resins are disposed (compared to the strong resins)

How important is biological ice nucleation in clouds on a global scale?

International Nuclear Information System (INIS)

Hoose, C; Kristjansson, J E; Burrows, S M

2010-01-01

The high ice nucleating ability of some biological particles has led to speculations about living and dead organisms being involved in cloud ice and precipitation formation, exerting a possibly significant influence on weather and climate. In the present study, the role of primary biological aerosol particles (PBAPs) as heterogeneous ice nuclei is investigated with a global model. Emission parametrizations for bacteria, fungal spores and pollen based on recent literature are introduced, as well as an immersion freezing parametrization based on classical nucleation theory and laboratory measurements. The simulated contribution of PBAPs to the global average ice nucleation rate is only 10 -5 %, with an uppermost estimate of 0.6%. At the same time, observed PBAP concentrations in air and biological ice nucleus concentrations in snow are reasonably well captured by the model. This implies that 'bioprecipitation' processes (snow and rain initiated by PBAPs) are of minor importance on the global scale.

Preparations and applications in UV curing coatings of epoxy acrylates containing carboxyl

International Nuclear Information System (INIS)

Wu Yu Min

1999-01-01

This paper introduces preparations of epoxy acrylates containing carboxyl through the reactions of epoxy acrylates with butanedioic anhydride, pentanedioic anhydride, cis-butenedioic anhydride, phthalic anhydride, tetrabromophthalic anhydride and -tetrahydrophthalic anhydride. These epoxy acrylates containing carboxyl have been applied to UV-curing coatings and their effects on properties of UV-curing coatings have been studied

Biology: An Important Agricultural Engineering Mechanism

Science.gov (United States)

Henderson, S. M.

1974-01-01

Describes the field of bioengineering with particular emphasis on agricultural engineering, and presents the results of a survey of schools that combine biology and engineering in their curricula. (JR)

Vitamin K-dependent carboxylation of pulmonary surfactant-associated proteins

International Nuclear Information System (INIS)

Rannels, S.R.; Gallaher, K.J.; Wallin, R.; Rannels, D.E.

1987-01-01

Rat type II pneumocytes expressed vitamin K-dependent carboxylase activity that incorporated 14 CO 2 into microsomal protein precursors of molecular weights similar to those of surfactant-associated proteins (SAP). Compared to carboxylated precursor proteins present in the liver, these molecules appeared to be unique to the lung. Antibodies raised against purified rat surfactant reacted with SAP resolved by NaDodSO 4 /PAGE and with surfactant-containing lamellar bodies in type II pneumocyte cytoplasm. NaDodSO 4 /PAGE of microsomal proteins, after carboxylase-catalyzed incorporation of 14 CO 2 , demonstrated radiolabeled, immunoreactive products identical to SAP. The presence of γ-carboxyglutamic acid in these proteins was confirmed by HPLC analysis of SAP hydrolysates. Furthermore, lung carboxylase activity and SAP matured over similar time courses during fetal lung development. These results show that SAP are carboxylated by type II cells via a vitamin K-dependent pathway analogous to that for hepatic carboxylation of clotting factors. Further analogy to the clotting system suggest that γ-carboxyglutamic acid residues in SAP polypeptides play a role in Ca 2+ binding and thus in the known requirements for both cation and SAP in the physiological function of pulmonary surfactant

Carboxylic acid-functionalized SBA-15 nanorods for gemcitabine delivery

International Nuclear Information System (INIS)

Bahrami, Zohreh; Badiei, Alireza; Ziarani, Ghodsi Mohammadi

2015-01-01

The present study deals with the functionalization of mesoporous silica nanoparticles as drug delivery systems. Mono, di, and tri amino-functionalized SBA-15 nanorods were synthesized by post-grafting method using (3-aminopropyl) triethoxysilane, N-(2-aminoethyl-)3- aminopropyltrimethoxysilane, and 3-[2-(2-aminoethylamino) ethylamino] propyl trimethoxysilane, respectively. The carboxylic acid derivatives of the amino-functionalized samples were obtained using succinic anhydride. Tminopropyltrimethoxysilanehe obtained modified materials were investigated as matrixes for the anticancer drug (gemcitabine) delivery. The prepared samples were characterized by SAXS, N 2 adsorption/desorption, SEM, transmission electron microscopy, thermogravimetric analysis, and FTIR and UV spectroscopies. The adsorption and release properties of all samples were studied. It was revealed that the adsorption capacity and release behavior of gemcitabine were highly dependent on the type of the introduced functional groups. The carboxylic acid-modified samples have higher loading content, due to the strong interaction with gemcitabine. The maximum content of deposited drug in the modified SBA-15 nanorods is close to 40 wt%. It was found that the surface functionalization leads toward significant decrease of the drug release rate. The carboxylic acid-functionalized samples have slower release rate in contrast with the amino-functionalized samples

Single amino acid substitution in important hemoglobinopathies does not disturb molecular function and biological process

Directory of Open Access Journals (Sweden)

Viroj Wiwanitkit

2008-06-01

Full Text Available Viroj WiwanitkitDepartment of Laboratory Medicine, Faculty of Medicine, Chulalongkorn University, Bangkok, ThailandAbstract: Hemoglobin is an important protein found in the red cells of many animals. In humans, the hemoglobin is mainly distributed in the red blood cell. Single amino acid substitution is the main pathogenesis of most hemoglobin disorders. Here, the author used a new gene ontology technology to predict the molecular function and biological process of four important hemoglobin disorders with single substitution. The four studied important abnormal hemoglobins (Hb with single substitution included Hb S, Hb E, Hb C, and Hb J-Baltimore. Using the GoFigure server, the molecular function and biological process in normal and abnormal hemoglobins was predicted. Compared with normal hemoglobin, all studied abnormal hemoglobins had the same function and biological process. This indicated that the overall function of oxygen transportation is not disturbed in the studied hemoglobin disorders. Clinical findings of oxygen depletion in abnormal hemoglobin should therefore be due to the other processes rather than genomics, proteomics, and expression levels.Keywords: hemoglobin, amino acid, substitution, function

Cofactor balance by nicotinamide nucleotide transhydrogenase (NNT) coordinates reductive carboxylation and glucose catabolism in the tricarboxylic acid (TCA) cycle.

Science.gov (United States)

Gameiro, Paulo A; Laviolette, Laura A; Kelleher, Joanne K; Iliopoulos, Othon; Stephanopoulos, Gregory

2013-05-03

Cancer and proliferating cells exhibit an increased demand for glutamine-derived carbons to support anabolic processes. In addition, reductive carboxylation of α-ketoglutarate by isocitrate dehydrogenase 1 (IDH1) and 2 (IDH2) was recently shown to be a major source of citrate synthesis from glutamine. The role of NAD(P)H/NAD(P)(+) cofactors in coordinating glucose and glutamine utilization in the tricarboxylic acid (TCA) cycle is not well understood, with the source(s) of NADPH for the reductive carboxylation reaction remaining unexplored. Nicotinamide nucleotide transhydrogenase (NNT) is a mitochondrial enzyme that transfers reducing equivalents from NADH to NADPH. Here, we show that knockdown of NNT inhibits the contribution of glutamine to the TCA cycle and activates glucose catabolism in SkMel5 melanoma cells. The increase in glucose oxidation partially occurred through pyruvate carboxylase and rendered NNT knockdown cells more sensitive to glucose deprivation. Importantly, knocking down NNT inhibits reductive carboxylation in SkMel5 and 786-O renal carcinoma cells. Overexpression of NNT is sufficient to stimulate glutamine oxidation and reductive carboxylation, whereas it inhibits glucose catabolism in the TCA cycle. These observations are supported by an impairment of the NAD(P)H/NAD(P)(+) ratios. Our findings underscore the role of NNT in regulating central carbon metabolism via redox balance, calling for other mechanisms that coordinate substrate preference to maintain a functional TCA cycle.

Carboxylic acid effects on the size and catalytic activity of magnetite nanoparticles.

Science.gov (United States)

Hosseini-Monfared, Hassan; Parchegani, Fatemeh; Alavi, Sohaila

2015-01-01

Magnetite nanoparticles (Fe3O4-NPs) were successfully synthesized in diethylene glycol in the presence of carboxylic acids. They were characterized using XRD, SEM and FTIR. Carboxylic acid plays a critical role in determining the morphology, particle size and size distribution of the resulting particles. The results show that as-prepared magnetite nanoparticles are monodisperse and highly crystalline. The nanoparticles can be easily dispersed in aqueous media and other polar solvents due to coated by a layer of hydrophilic polyol and carboxylic acid ligands in situ. Easily prepared Fe3O4-NPs have been shown to be an active, recyclable, and highly selective catalyst for the epoxidation of cyclic olefins with aqueous 30% H2O2. Copyright © 2014 Elsevier Inc. All rights reserved.

Facile synthesis of α-hydroxy carboxylic acids from the corresponding α-amino acids

DEFF Research Database (Denmark)

Stuhr-Hansen, Nicolai; Padrah, Shahrokh; Strømgaard, Kristian

2014-01-01

An effective and improved procedure is developed for the synthesis of α-hydroxy carboxylic acids by treatment of the corresponding protonated α-amino acid with tert-butyl nitrite in 1,4-dioxane-water. The amino moiety must be protonated and located α to a carboxylic acid function in order...

High performance flexible pH sensor based on carboxyl-functionalized and DEP aligned SWNTs

International Nuclear Information System (INIS)

Liu, Lu; Shao, Jinyou; Li, Xiangming; Zhao, Qiang; Nie, Bangbang; Xu, Chuan; Ding, Haitao

2016-01-01

Highlights: • The flexible chemiresistive pH sensor based on two-terminal microsensors eliminating the need for a reference electrode, is simple in structure and can be fabricated on a variety of substrates such as PET, PI and PVC. • SWNTs as an ideal one dimensional material are carboxyl-functionalized to make the pH sensor show high sensitivity and outstanding flexibility for practical applications. • DEP technique is used to manipulate and position SWNTs into appropriate locations and desired formations to improve the metal-nanotube interface and highly rapid detection of pH value, resulting in better overall device performance. • Mechanical bendability of the pH sensor, which arises from the combination of flexible PET substrates and SWNTs, offer a significant improvement for applications that are difficult or impossible to achieve with traditional sensors on rigid substrates. - Abstract: The detection and control of the pH is very important in many biomedical and chemical reaction processes. A miniaturized flexible pH sensor that is light weight, robust, and conformable is very important in many applications, such as multifunctional lab-on-a-chip systems or wearable biomedical devices. In this work, we demonstrate a flexible chemiresistive pH sensor based on dielectrophoresis (DEP) aligned carboxyl-functionalized single-walled carbon nanotubes (SWNTs). Decorated carboxyl groups can react with hydrogen (H"+) and hydroxide (OH"−) ions, enabling the sensor to be capable of sensing the pH. DEP is used to deposit well-organized and highly aligned SWNTs in desired locations, which improves the metal-nanotube interface and highly rapid detection of the pH, resulting in better overall device performance. When pH buffer solutions are dropped onto such SWNTs, the H"+ and OH"− ions caninteract with the carboxyl groups and affect the generation of holes and electrons in the SWNTs, leading to resistance variations in the SWNTs. The results shows that the

High performance flexible pH sensor based on carboxyl-functionalized and DEP aligned SWNTs

Energy Technology Data Exchange (ETDEWEB)

Liu, Lu; Shao, Jinyou, E-mail: jyshao@mail.xjtu.edu.cn; Li, Xiangming; Zhao, Qiang; Nie, Bangbang; Xu, Chuan; Ding, Haitao

2016-11-15

Highlights: • The flexible chemiresistive pH sensor based on two-terminal microsensors eliminating the need for a reference electrode, is simple in structure and can be fabricated on a variety of substrates such as PET, PI and PVC. • SWNTs as an ideal one dimensional material are carboxyl-functionalized to make the pH sensor show high sensitivity and outstanding flexibility for practical applications. • DEP technique is used to manipulate and position SWNTs into appropriate locations and desired formations to improve the metal-nanotube interface and highly rapid detection of pH value, resulting in better overall device performance. • Mechanical bendability of the pH sensor, which arises from the combination of flexible PET substrates and SWNTs, offer a significant improvement for applications that are difficult or impossible to achieve with traditional sensors on rigid substrates. - Abstract: The detection and control of the pH is very important in many biomedical and chemical reaction processes. A miniaturized flexible pH sensor that is light weight, robust, and conformable is very important in many applications, such as multifunctional lab-on-a-chip systems or wearable biomedical devices. In this work, we demonstrate a flexible chemiresistive pH sensor based on dielectrophoresis (DEP) aligned carboxyl-functionalized single-walled carbon nanotubes (SWNTs). Decorated carboxyl groups can react with hydrogen (H{sup +}) and hydroxide (OH{sup −}) ions, enabling the sensor to be capable of sensing the pH. DEP is used to deposit well-organized and highly aligned SWNTs in desired locations, which improves the metal-nanotube interface and highly rapid detection of the pH, resulting in better overall device performance. When pH buffer solutions are dropped onto such SWNTs, the H{sup +} and OH{sup −} ions caninteract with the carboxyl groups and affect the generation of holes and electrons in the SWNTs, leading to resistance variations in the SWNTs. The results

Modification of polysulfone with pendant carboxylic acid functionality ...

Indian Academy of Sciences (India)

polysulfone (PSF) by in situ generated chloromethyl radical in presence of stannic chloride in tetrachloroethane and .... vert the nitrile group to carboxylic acid was reported (Reddy ..... PEG molecular weight vs rejection at 35 psi pressure.

Phosphorescent emissions of phosphine copper(I) complexes bearing 8-hydroxyquinoline carboxylic acid analogue ligands

Energy Technology Data Exchange (ETDEWEB)

Małecki, Jan G., E-mail: gmalecki@us.edu.pl [Department of Crystallography, Institute of Chemistry, University of Silesia, Szkolna 9 street, 40-006 Katowice (Poland); Łakomska, Iwona, E-mail: iwolak@chem.umk.pl [Department of Chemistry, Nicolaus Copernicus University, Toruń (Poland); Maroń, Anna [Department of Crystallography, Institute of Chemistry, University of Silesia, Szkolna 9 street, 40-006 Katowice (Poland); Szala, Marcin [Institute of Chemistry, University of Silesia, ul. Szkolna 9, 40-006 Katowice (Poland); Fandzloch, Marzena [Department of Chemistry, Nicolaus Copernicus University, Toruń (Poland); Nycz, Jacek E., E-mail: jacek.nycz@us.edu.pl [Institute of Chemistry, University of Silesia, ul. Szkolna 9, 40-006 Katowice (Poland)

2015-05-15

The pseudotetrahedral complexes of [Cu(PPh{sub 3}){sub 2}(L)], where L=8-hydroxy-2-methylquinoline-7-carboxylic acid (1), 8-hydroxy-2,5-dimethylquinoline-7-carboxylic acid (2) or 5-chloro-8-hydroxy-2-methylquinoline-7-carboxylic acid (3) have been synthesized and structurally characterized by X-ray crystallography. Their properties have been examined through combinations of IR, NMR, electronic absorption spectroscopy and cyclic voltammetry. The complexes exhibit extraordinary photophysical properties. Complex (1) in solid state exhibits an emission quantum yield of 4.67% and an excited life time of 1.88 ms (frozen DCM solution up to 6.7 ms). When dissolved in a coordinating solvent (acetonitrile) the charge transfer emission was quenched on a microsecond scale. - Highlights: • Synthesis of copper(I) complexes with 8-hydroxyquinoline carboxylic acid ligands. • Very long lived phosphorescent copper(I) complexes. • [Cu(PPh{sub 3}){sub 2}(L)] where L=8-hydroxy-2-methylquinoline-7-carboxylic acid luminesce in the solid state exhibits extremely long lifetime on millisecond scale (1.9 ms). • In frozen MeOH:EtOH solution lifetime increases to 7 ms. • Quantum efficiency equal to 4.7%.

The Importance of Spatiotemporal Information in Biological Motion Perception: White Noise Presented with a Step-like Motion Activates the Biological Motion Area.

Science.gov (United States)

Callan, Akiko; Callan, Daniel; Ando, Hiroshi

2017-02-01

Humans can easily recognize the motion of living creatures using only a handful of point-lights that describe the motion of the main joints (biological motion perception). This special ability to perceive the motion of animate objects signifies the importance of the spatiotemporal information in perceiving biological motion. The posterior STS (pSTS) and posterior middle temporal gyrus (pMTG) region have been established by many functional neuroimaging studies as a locus for biological motion perception. Because listening to a walking human also activates the pSTS/pMTG region, the region has been proposed to be supramodal in nature. In this study, we investigated whether the spatiotemporal information from simple auditory stimuli is sufficient to activate this biological motion area. We compared spatially moving white noise, having a running-like tempo that was consistent with biological motion, with stationary white noise. The moving-minus-stationary contrast showed significant differences in activation of the pSTS/pMTG region. Our results suggest that the spatiotemporal information of the auditory stimuli is sufficient to activate the biological motion area.

40 CFR 721.2088 - Carboxylic acids, (C6-C9) branched and linear.

Science.gov (United States)

2010-07-01

... linear. 721.2088 Section 721.2088 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.2088 Carboxylic acids, (C6-C9) branched and linear. (a) Chemical... as carboxylic acids, (C6-C9) branched and linear (PMNs P-93-313, 314, 315, and 316) are subject to...

Complexation of carboxylate on smectite surfaces.

Science.gov (United States)

Liu, Xiandong; Lu, Xiancai; Zhang, Yingchun; Zhang, Chi; Wang, Rucheng

2017-07-19

We report a first principles molecular dynamics (FPMD) study of carboxylate complexation on clay surfaces. By taking acetate as a model carboxylate, we investigate its inner-sphere complexes adsorbed on clay edges (including (010) and (110) surfaces) and in interlayer space. Simulations show that acetate forms stable monodentate complexes on edge surfaces and a bidentate complex with Ca 2+ in the interlayer region. The free energy calculations indicate that the complexation on edge surfaces is slightly more stable than in interlayer space. By integrating pK a s and desorption free energies of Al coordinated water calculated previously (X. Liu, X. Lu, E. J. Meijer, R. Wang and H. Zhou, Geochim. Cosmochim. Acta, 2012, 81, 56-68; X. Liu, J. Cheng, M. Sprik, X. Lu and R. Wang, Geochim. Cosmochim. Acta, 2014, 140, 410-417), the pH dependence of acetate complexation has been revealed. It shows that acetate forms inner-sphere complexes on (110) in a very limited mildly acidic pH range while it can complex on (010) in the whole common pH range. The results presented in this study form a physical basis for understanding the geochemical processes involving clay-organics interactions.

The Conversion of Carboxylic Acids to Ketones: A Repeated Discovery

Science.gov (United States)

Nicholson, John W.; Wilson, Alan

2004-09-01

This article describes the history of the reaction converting carboxylic acids to ketones. The reaction has been rediscovered several times, yet has actually been known for centuries. The best known version of the process is the Dakin West reaction (1928), which applies to α-amino acids and also involves the simultaneous conversion of the amine group to amido functionality. Unlike other examples, this particular reaction has attracted a reasonable amount of attention and it appears to be better known than the conversion of simple carboxylic acids to ketones. However, this reaction was described as long ago as 1612, when Beguin published an account of it in his book, Tyrocinium Chymicum . Since then, many chemists have rediscovered the reaction, apparently independently. One of the earliest modern accounts was by W. H. Perkin, Sr., in 1886, who made various simple ketones by refluxing the appropriate carboxylic acids with base. However, this work has been largely ignored, including by his son, W. H. Perkin, Jr., who used a more complicated base-catalyzed ketonization to prepare small ring compounds in the early years of the 20th century. Other articles detailing the application of ketonization to organic acids are discussed, including our own work, which employed the process to crosslink carboxylated polymers for possible technical application in coatings. Despite its relative obscurity, the reaction was used by Woodward et al. in the total synthesis of strychnine, reported in 1963, and this is discussed in detail at the end of the article. See Featured Molecules .

Destination of organic pollutants during electrochemical oxidation of biologically-pretreated dye wastewater using boron-doped diamond anode

Energy Technology Data Exchange (ETDEWEB)

Zhu, Xiuping [Department of Environmental Engineering, Peking University, the Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing100871 (China); Ni, Jinren, E-mail: nijinren@iee.pku.edu.cn [Department of Environmental Engineering, Peking University, the Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing100871 (China); Wei, Junjun; Xing, Xuan; Li, Hongna [Department of Environmental Engineering, Peking University, the Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing100871 (China)

2011-05-15

Electrochemical oxidation of biologically-pretreated dye wastewater was performed in a boron-doped diamond (BDD) anode system. After electrolysis of 12 h, the COD was decreased from 532 to 99 mg L{sup -1} (<100 mg L{sup -1}, the National Discharge Standard of China). More importantly, the destination of organic pollutants during electrochemical oxidation process was carefully investigated by molecular weight distribution measurement, resin fractionation, ultraviolet-visible spectroscopy, HPLC and GC-MS analysis, and toxicity test. As results, most organic pollutants were completely removed by electrochemical oxidation and the rest was primarily degraded to simpler compounds (e.g., carboxylic acids and short-chain alkanes) with less toxicity, which demonstrated that electrochemical oxidation of biologically-pretreated dye wastewater with BDD anode was very effective and safe. Especially, the performance of BDD anode system in degradation of large molecular organics such as humic substances makes it very promising in practical applications as an advanced treatment of biologically-pretreated wastewaters.

Destination of organic pollutants during electrochemical oxidation of biologically-pretreated dye wastewater using boron-doped diamond anode

International Nuclear Information System (INIS)

Zhu, Xiuping; Ni, Jinren; Wei, Junjun; Xing, Xuan; Li, Hongna

2011-01-01

Electrochemical oxidation of biologically-pretreated dye wastewater was performed in a boron-doped diamond (BDD) anode system. After electrolysis of 12 h, the COD was decreased from 532 to 99 mg L -1 ( -1 , the National Discharge Standard of China). More importantly, the destination of organic pollutants during electrochemical oxidation process was carefully investigated by molecular weight distribution measurement, resin fractionation, ultraviolet-visible spectroscopy, HPLC and GC-MS analysis, and toxicity test. As results, most organic pollutants were completely removed by electrochemical oxidation and the rest was primarily degraded to simpler compounds (e.g., carboxylic acids and short-chain alkanes) with less toxicity, which demonstrated that electrochemical oxidation of biologically-pretreated dye wastewater with BDD anode was very effective and safe. Especially, the performance of BDD anode system in degradation of large molecular organics such as humic substances makes it very promising in practical applications as an advanced treatment of biologically-pretreated wastewaters.

ATR-FTIR Spectroscopic Evidence for Biomolecular Phosphorus and Carboxyl Groups Facilitating Bacterial Adhesion to Iron Oxides

Science.gov (United States)

Parikh, Sanjai J.; Mukome, Fungai N.D.; Zhang, Xiaoming

2014-01-01

Attenuated total reflectance (ATR) Fourier transform infrared (FTIR) spectroscopy has been used to probe the binding of bacteria to hematite (α-Fe2O3) and goethite (α-FeOOH). In situ ATR-FTIR experiments with bacteria (Pseudomonas putida, P. aeruginosa, Escherichia coli), mixed amino acids, polypeptide extracts, deoxyribonucleic acid (DNA), and a suite of model compounds were conducted. These compounds represent carboxyl, catecholate, amide, and phosphate groups present in siderophores, amino acids, polysaccharides, phospholipids, and DNA. Due in part to the ubiquitous presence of carboxyl groups in biomolecules, numerous IR peaks corresponding to outer-sphere or unbound (1400 cm−1) and inner-sphere (1310-1320 cm−1) coordinated carboxyl groups are noted following reaction of bacteria and biomolecules with α-Fe2O3 and α-FeOOH. However, the data also reveal that the presence of low-level amounts (i.e., 0.45-0.79%) of biomolecular phosphorous groups result in strong IR bands at ~1043 cm−1, corresponding to inner-sphere Fe-O-P bonds, underscoring the importance of bacteria associated P-containing groups in biomolecule and cell adhesion. Spectral comparisons also reveal slightly greater P-O-Fe contributions for bacteria (Pseudomonad, E. coli) deposited on α-FeOOH, as compared to α-Fe2O3. This data demonstrates that slight differences in bacterial adhesion to Fe oxides can be attributed to bacterial species and Fe-oxide minerals. However, more importantly, the strong binding affinity of phosphate in all bacteria samples to both Fe-oxides results in the formation of inner-sphere Fe-O-P bonds, signifying the critical role of biomolecular P in the initiation of bacterial adhesion. PMID:24859052

Precipitation stripping of neodymium from carboxylate extractant with aqueous oxalic acid solutions

International Nuclear Information System (INIS)

Konishi, Yasuhiro; Asai, Satoru; Murai, Tetuya

1993-01-01

This paper describes a precipitation stripping method in which neodymium ions are stripped from carboxylate extractant in organic solvent and simultaneously precipitated with aqueous oxalic acid solution. For the single-stage process, a quantitative criterion for precipitating oxalate powders was derived theoretically, and stripping experiments were done under the precipitation conditions. The resultant precipitates were neodymium oxalate, which is completely free from contamination by the carboxylate extractant and the organic solvent. The overall rate of stripping was controlled by the transfer of neodymium carboxylate in the organic solution, indicating that the presence of oxalic acid in the aqueous phase has no effect on the stripping rate. These findings demonstrate the feasibility of combining the conventional stripping and precipitation stages in a solvent extraction process for separation and purification of rare earths

Alpha-bungarotoxin binding to target cell in a developing visual system by carboxylated nanodiamond

International Nuclear Information System (INIS)

Liu, K-K; Chen, P-Y; Lee, Tony J F; Chao, J-I; Chen, M-F; Cheng, C-L; Chang, C-C; Ho, Y-P

2008-01-01

Biological molecules conjugating with nanoparticles are valuable for applications including bio-imaging, bio-detection, and bio-sensing. Nanometer-sized diamond particles have excellent electronic and chemical properties for bio-conjugation. In this study, we manipulated the carboxyl group produced on the surface of nanodiamond (carboxylated nanodiamond, cND) for conjugating with alpha-bungarotoxin (α-BTX), a neurotoxin derived from Bungarus multicinctus with specific blockade of alpha7-nicotinic acetylcholine receptor (α7-nAChR). The electrostatic binding of cND-α-BTX was mediated by the negative charge of the cND and the positive charge of the α-BTX in physiological pH conditions. Sodium dodecyl sulfate-polyacrylamide gel analysis and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI/TOF-MS) spectra displayed that α-BTX proteins were conjugated with cND particles via non-covalent bindings. The green fluorescence of the cND particles combining with the red fluorescence of tetramethylrhodamine-labeled α-BTX presented a yellow color at the same location, which indicated that α-BTX proteins were conjugated with cND particles. Xenopus laevis's oocytes expressed the human α7-nAChR proteins by microinjection with α7-nAChR mRNA. The cND-α-BTX complexes were bound to α7-nAChR locating on the cell membrane of oocytes and human lung A549 cancer cells analyzed by laser scanning confocal microscopy. The choline-evoked α7-nAChR-mediated inward currents of the oocytes were blocked by cND-α-BTX complexes in a concentration-dependent manner using two-electrode voltage-clamp recording. Furthermore, the fluorescence intensity of cND-α-BTX binding on A549 cells could be quantified by flow cytometry. These results indicate that cND-conjugated α-BTX still preserves its biological activity in blocking the function of α7-nAChR, and provide a visual system showing the binding of α-BTX to α7-nAChR

Alpha-bungarotoxin binding to target cell in a developing visual system by carboxylated nanodiamond

Energy Technology Data Exchange (ETDEWEB)

Liu, K-K; Chen, P-Y; Lee, Tony J F; Chao, J-I [Institute of Pharmacology and Toxicology, Tzu Chi University, Hualien 970, Taiwan (China); Chen, M-F [Neuro-Medical Scientific Center, Tzu Chi General Hospital, Hualien 970, Taiwan (China); Cheng, C-L [Department of Physics, National Dong Hwa University, Hualien 974, Taiwan (China); Chang, C-C [Department of Biological Science and Technology, National Chiao Tung University, Hsin-Chu 300, Taiwan (China); Ho, Y-P [Department of Chemistry, National Dong Hwa University, Hualien 974, Taiwan (China)], E-mail: chaoji@mail.tcu.edu.tw

2008-05-21

Biological molecules conjugating with nanoparticles are valuable for applications including bio-imaging, bio-detection, and bio-sensing. Nanometer-sized diamond particles have excellent electronic and chemical properties for bio-conjugation. In this study, we manipulated the carboxyl group produced on the surface of nanodiamond (carboxylated nanodiamond, cND) for conjugating with alpha-bungarotoxin ({alpha}-BTX), a neurotoxin derived from Bungarus multicinctus with specific blockade of alpha7-nicotinic acetylcholine receptor ({alpha}7-nAChR). The electrostatic binding of cND-{alpha}-BTX was mediated by the negative charge of the cND and the positive charge of the {alpha}-BTX in physiological pH conditions. Sodium dodecyl sulfate-polyacrylamide gel analysis and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI/TOF-MS) spectra displayed that {alpha}-BTX proteins were conjugated with cND particles via non-covalent bindings. The green fluorescence of the cND particles combining with the red fluorescence of tetramethylrhodamine-labeled {alpha}-BTX presented a yellow color at the same location, which indicated that {alpha}-BTX proteins were conjugated with cND particles. Xenopus laevis's oocytes expressed the human {alpha}7-nAChR proteins by microinjection with {alpha}7-nAChR mRNA. The cND-{alpha}-BTX complexes were bound to {alpha}7-nAChR locating on the cell membrane of oocytes and human lung A549 cancer cells analyzed by laser scanning confocal microscopy. The choline-evoked {alpha}7-nAChR-mediated inward currents of the oocytes were blocked by cND-{alpha}-BTX complexes in a concentration-dependent manner using two-electrode voltage-clamp recording. Furthermore, the fluorescence intensity of cND-{alpha}-BTX binding on A549 cells could be quantified by flow cytometry. These results indicate that cND-conjugated {alpha}-BTX still preserves its biological activity in blocking the function of {alpha}7-nAChR, and provide a visual

Silver-Catalyzed Dehydrogenative Synthesis of Carboxylic Acids from Primary Alcohols

DEFF Research Database (Denmark)

Ghalehshahi, Hajar Golshadi; Madsen, Robert

2017-01-01

A simple silver-catalyzed protocol has been developed for the acceptorless dehydrogenation of primary alcohols into carboxylic acids and hydrogen gas. The procedure uses 2.5 % Ag2 CO3 and 2.5-3 equiv of KOH in refluxing mesitylene to afford the potassium carboxylate which is then converted...... into the acid with HCl. The reaction can be applied to a variety of benzylic and aliphatic primary alcohols with alkyl and ether substituents, and in some cases halide, olefin, and ester functionalities are also compatible with the reaction conditions. The dehydrogenation is believed to be catalyzed by silver...

Cyclodextrin derivatives with cyanohydrin and carboxylate groups as artificial glycosidases

DEFF Research Database (Denmark)

Bols, Mikael; Ortega-Caballero, Fernando

2006-01-01

Two cyclodextrin derivatives (1 and 2) were prepared in an attempt to create glycosidase mimics with a general acid catalyst and a nucleophilic carboxylate group. The catalysts 1 and 2 were found to catalyse the hydrolysis of 4-nitrophenyl beta-D-glucopyranoside at pH 8.0, but rapidly underwent...... decomposition with loss of hydrogen cyanide to convert the cyanohydrin to the corresponding aldehyde. The initial rate of the catalysis shows that the cyanohydrin group in these molecules functions as a good catalyst, but that the carboxylate has no positive effect. The decomposition product aldehydes display...

Extraction characteristics of trivalent lanthanides and actinides in mixtures of dinonylnaphthalenesulfonic acid and carboxylic acids

International Nuclear Information System (INIS)

West, M.H.

1983-03-01

Dinonylnaphthalenesulfonic acid (HDNNS) has been shown to be an effective liquid cation exchanger for the extraction of metal ions. This extractant has proven to be successful in the extraction of trivalent lanthanides and actinides in the pH range of 2.0 to 3.0, although it shows little selectivity for individual ions because of its strong acid character. In an effort to improve the selectivity of HDNNS between trivalent lanthanides and actinides, carboxylic acids were added to the organic phase and the effects on the extraction characteristics of HDNNS were investigated. Three carboxylic acids - nonanoic, cyclohexanecarboxylic, and cyclohexanebutyric - were studied with the following metals: Am(III), Cm(III), Ce(III), Eu(III), and Tm(III). The distributions of the metal ions were studied holding the HDNNS concentration constant while varying the carboxylic acid concentrations over a range of 1.0 x 10 -5 M to 1.0 M. Results indicated that the greatest enhancement of the extraction occurred at a carboxylic acid concentration of 1.0 x 10 -2 M with negative effects occurring at 0.5 M and 1.0 M. The effects on the extraction of the trivalent lanthanides and actinides were interpreted in terms of the structural differences of the carboxylic acids, the effect of the carboxylic acids on the HDNNS extraction mechanism, and the ionic properties of the metals studied

One-step hydrothermal synthesis of carboxyl-functionalized upconversion phosphors for bioapplications.

Science.gov (United States)

Yang, Jianping; Shen, Dengke; Li, Xiaomin; Li, Wei; Fang, Yin; Wei, Yong; Yao, Chi; Tu, Bo; Zhang, Fan; Zhao, Dongyuan

2012-10-22

In this paper, we report a facile one-step hydrothermal method to synthesize phase-, size-, and shape-controlled carboxyl-functionalized rare-earth fluorescence upconversion phosphors by using a small-molecule binary acid, such as malonic acid, oxalic acid, succinic acid, or tartaric acid as capping agent. The crystals, from nano- to microstructures with diverse shapes that include nanospheres, microrods, hexagonal prisms, microtubes, microdisks, polygonal columns, and hexagonal tablets, can be obtained with different reaction times, reaction temperatures, molar ratios of capping agent to sodium hydroxide, and by varying the binary acids. Fourier transform infrared, thermogravimetric analysis, and upconversion luminescence spectra measurements indicate that the synthesized NaYF(4):Yb/Er products with hydrophilic carboxyl-functionalized surface offer efficient upconversion luminescent performance. Furthermore, the antibody/secondary antibody conjugation can be realized by the carboxyl-functionalized surfaces of the upconversion phosphors, thus indicating the potential bioapplications of these kinds of materials. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cofactor Balance by Nicotinamide Nucleotide Transhydrogenase (NNT) Coordinates Reductive Carboxylation and Glucose Catabolism in the Tricarboxylic Acid (TCA) Cycle*♦

Science.gov (United States)

Gameiro, Paulo A.; Laviolette, Laura A.; Kelleher, Joanne K.; Iliopoulos, Othon; Stephanopoulos, Gregory

2013-01-01

Cancer and proliferating cells exhibit an increased demand for glutamine-derived carbons to support anabolic processes. In addition, reductive carboxylation of α-ketoglutarate by isocitrate dehydrogenase 1 (IDH1) and 2 (IDH2) was recently shown to be a major source of citrate synthesis from glutamine. The role of NAD(P)H/NAD(P)+ cofactors in coordinating glucose and glutamine utilization in the tricarboxylic acid (TCA) cycle is not well understood, with the source(s) of NADPH for the reductive carboxylation reaction remaining unexplored. Nicotinamide nucleotide transhydrogenase (NNT) is a mitochondrial enzyme that transfers reducing equivalents from NADH to NADPH. Here, we show that knockdown of NNT inhibits the contribution of glutamine to the TCA cycle and activates glucose catabolism in SkMel5 melanoma cells. The increase in glucose oxidation partially occurred through pyruvate carboxylase and rendered NNT knockdown cells more sensitive to glucose deprivation. Importantly, knocking down NNT inhibits reductive carboxylation in SkMel5 and 786-O renal carcinoma cells. Overexpression of NNT is sufficient to stimulate glutamine oxidation and reductive carboxylation, whereas it inhibits glucose catabolism in the TCA cycle. These observations are supported by an impairment of the NAD(P)H/NAD(P)+ ratios. Our findings underscore the role of NNT in regulating central carbon metabolism via redox balance, calling for other mechanisms that coordinate substrate preference to maintain a functional TCA cycle. PMID:23504317

Catalytic transformation of functionalized carboxylic acids using multifunctional rhenium complexes.

Science.gov (United States)

Naruto, Masayuki; Agrawal, Santosh; Toda, Katsuaki; Saito, Susumu

2017-06-13

Carboxylic acids (CAs) are one of the most ubiquitous and important chemical feedstocks available from biorenewable resources, CO 2 , and the petrochemical industry. Unfortunately, chemoselective catalytic transformations of CH n CO 2 H (n = 1-3) groups into other functionalities remain a significant challenge. Herein, we report rhenium V complexes as extremely effective precatalysts for this purpose. Compared to previously reported heterogeneous and homogeneous catalysts derived from high- or low-valent metals, the present method involves a α-C-H bond functionalization, a hydrogenation, and a hydrogenolysis, which affords functionalized alcohols with a wide substrate scope and high chemoselectivity under relatively mild reaction conditions. The results represent an important step toward a paradigm shift from 'low-valent' to 'high-valent' metal complexes by exploring a new portfolio of selective functional group transformations of highly oxygenated organic substrates, as well as toward the exploitation of CAs as a valuable biorenewable feedstock.

catalysed ortho-carboxylation of acetanilide with CO

Indian Academy of Sciences (India)

Abstract. The mechanism of palladium(II)-catalysed carboxylation of acetanilide with CO has been investi- gated using density functional theory calculation done at the B3LYP/6-31G(d, p)(SDD for Pd) level of theory. Solvent effects on these reactions have been explored by calculation that included a polarizable continuum.

Vitamin K-Dependent Carboxylation of Matrix Gla Protein Influences the Risk of Calciphylaxis.

Science.gov (United States)

Nigwekar, Sagar U; Bloch, Donald B; Nazarian, Rosalynn M; Vermeer, Cees; Booth, Sarah L; Xu, Dihua; Thadhani, Ravi I; Malhotra, Rajeev

2017-06-01

Matrix Gla protein (MGP) is a potent inhibitor of vascular calcification. The ability of MGP to inhibit calcification requires the activity of a vitamin K-dependent enzyme, which mediates MGP carboxylation. We investigated how MGP carboxylation influences the risk of calciphylaxis in adult patients receiving dialysis and examined the effects of vitamin K deficiency on MGP carboxylation. Our study included 20 patients receiving hemodialysis with calciphylaxis (cases) and 20 patients receiving hemodialysis without calciphylaxis (controls) matched for age, sex, race, and warfarin use. Cases had higher plasma levels of uncarboxylated MGP (ucMGP) and carboxylated MGP (cMGP) than controls. However, the fraction of total MGP that was carboxylated (relative cMGP concentration = cMGP/[cMGP + uncarboxylated MGP]) was lower in cases than in controls (0.58±0.02 versus 0.69±0.03, respectively; P =0.003). In patients not taking warfarin, cases had a similarly lower relative cMGP concentration. Each 0.1 unit reduction in relative cMGP concentration associated with a more than two-fold increase in calciphylaxis risk. Vitamin K deficiency associated with lower relative cMGP concentration in multivariable adjusted analyses ( β =-8.99; P =0.04). In conclusion, vitamin K deficiency-mediated reduction in relative cMGP concentration may have a role in the pathogenesis of calciphylaxis. Whether vitamin K supplementation can prevent and/or treat calciphylaxis requires further study. Copyright © 2017 by the American Society of Nephrology.

Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Dron, Julien [Laboratoire de Chimie et Environnement, Marseille Universites (case 29), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France)], E-mail: julien.dron@up.univ-mrs.fr; Eyglunent, Gregory; Temime-Roussel, Brice; Marchand, Nicolas; Wortham, Henri [Laboratoire de Chimie et Environnement, Marseille Universites (case 29), 3 place Victor Hugo, 13331 Marseille Cedex 3 (France)

2007-12-12

The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF{sub 3}/methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L{sup -1}. Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices.

Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry

International Nuclear Information System (INIS)

Dron, Julien; Eyglunent, Gregory; Temime-Roussel, Brice; Marchand, Nicolas; Wortham, Henri

2007-01-01

The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF 3 /methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L -1 . Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices

Thiosemicarbazones: preparation methods, synthetic applications and biological importance; Tiossemicarbazonas: metodos de obtencao, aplicacoes sinteticas e importancia biologica

Energy Technology Data Exchange (ETDEWEB)

Tenorio, Romulo P.; Goes, Alexandre J.S. [Universidade Federal de Pernambuco, Recife, PE (Brazil). Dept. de Antibioticos]. E-mail: ajsg@ufpe.br; Lima, Jose G. de; Faria, Antonio R. de; Alves, Antonio J.; Aquino, Thiago M. de [Universidade Federal de Pernambuco, Recife, PE (Brazil). Dept. de Ciencias Farmaceuticas

2005-11-15

Thiosemicarbazones are a class of compounds known by their chemical and biological properties, such as antitumor, antibacterial, antiviral and antiprotozoal activity. Their ability to form chelates with metals has great importance in their biological activities. Their synthesis is very simple, versatile and clean, usually giving high yields. They are largely employed as intermediates, in the synthesis of others compounds. This article is a survey of some of these characteristics showing their great importance to organic and medicinal chemistry. (author)

2-Isopropyl-5-methylcyclohexyl quinoline-2-carboxylate

Directory of Open Access Journals (Sweden)

E. Fazal

2014-01-01

Full Text Available In the title compound, C20H25NO2, the cyclohexyl ring adopts a slightly disordered chair conformation. The dihedral angle between the mean planes of the quinoline ring and the carboxylate group is 22.2 (6°. In the crystal, weak C—H...N interactions make chains along [010].

Methyl 3-(Quinolin-2-ylindolizine-1-carboxylate

Directory of Open Access Journals (Sweden)

Roumaissa Belguedj

2015-12-01

Full Text Available A novel compound, methyl 3-(quinolin-2-ylindolizine-1-carboxylate (2 has been synthesized by cycloaddition reaction of 1-(quinolin-2-ylmethylpyridinium ylide (1 with methyl propiolate in presence of sodium hydride in THF. The structure of this compound was established by IR, 1H-NMR, 13C-NMR and MS data

Quantification of the xylem-to-phloem transfer of amino acids by use of inulin (14C)carboxylic acid as xylem transfer marker

International Nuclear Information System (INIS)

Van Bel, A.J.

1984-01-01

Inulin ( 14 C)carboxylic acid and 14 C-labelled amino acid (α-aminoisobutyric acid (aib) and valine) solutions were introduced into the transpiration stream through the cut stem bases of young (4-12 leaves) tomato plants. Inulin carboxylic acid (inu) was translocated exclusively by the xylem, whereas the amino acid distribution resulted from both xylem and phloem import. Comparison of the distribution of inu and aib permitted a quantitative assessment of the xylem-to-phloem transfer in the stem. Of aib, 20.6% traversed from xylem to phloem in a plant with 12 leaves. The phloem import was not evenly distributed over the leaves and varied from 0% (first five leaves) to 95% (top leaf) of the aib import per leaf. Doubling the flow rates in the xylem reduced the aib supply to 25% in the top leaf and 55% in the next leaf, which reflects a reduced xylem-to-phloem transfer. (author)

Cyclohex-1-ene carboxylic acids: synthesis and biological evaluation of novel inhibitors of human 5 alpha reductase.

Science.gov (United States)

Baston, Eckhard; Salem, Ola I A; Hartmann, Rolf W

2003-03-01

In search of novel nonsteroidal mimics of steroidal inhibitors of 5 alpha reductase, 4-(2-phenylethyl)cyclohex-1-ene carboxylic acids 1-5 were synthesized with different substituents in para position of the phenyl ring (1: N, N-diisopropylcarbamoyl, 2: phenyl, 3: phenoxy, 4: benzoyl, and 5: benzyl). The principal synthetic approach for the desired compounds consisted of a Wittig olefination between 1, 4-dioxaspiro [4.5]-decane-8-carbaldehyde (4g and the appropriate phosphonium salts. The compounds were tested for inhibition of human 5 alpha reductase isozymes 1 and 2 using DU 145 cells and preparations from prostatic tissue, respectively. They turned out to be good inhibitors of the prostatic isozyme 2 with compound 1 being the most potent one (IC(50) = 760 nM). Isozyme 1 was only slightly inhibited. It is concluded that the novel structures are appropriate for being further optimized, aiming at the development of a novel drug for the treatment of benign prostatic hyperplasia.

Carboxylated dithiafulvenes and tetrathiafulvalene vinylogues: synthesis, electronic properties, and complexation with zinc ions

Directory of Open Access Journals (Sweden)

Yunfei Wang

2015-06-01

Full Text Available A class of carboxyl and carboxylate ester-substituted dithiafulvene (DTF derivatives and tetrathiafulvalene vinylogues (TTFVs has been synthesized and their electronic and electrochemical redox properties were characterized by UV–vis spectroscopic and cyclic voltammetric analyses. The carboxyl-TTFV was applied as a redox-active ligand to complex with Zn(II ions, forming a stable Zn-TTFV coordination polymer. The structural, electrochemical, and thermal properties of the coordination polymer were investigated by infrared spectroscopy, cyclic voltammetry, powder X-ray diffraction, and differential scanning calorimetric analyses. Furthermore, the microscopic porosity and surface area of the Zn-TTFV coordination polymer were measured by nitrogen gas adsorption analysis, showing a BET surface of 148.2 m2 g−1 and an average pore diameter of 10.2 nm.

Chemical rescue of the post-translationally carboxylated lysine mutant of allantoinase and dihydroorotase by metal ions and short-chain carboxylic acids.

Science.gov (United States)

Ho, Ya-Yeh; Huang, Yen-Hua; Huang, Cheng-Yang

2013-04-01

Bacterial allantoinase (ALLase) and dihydroorotase (DHOase) are members of the cyclic amidohydrolase family. ALLase and DHOase possess similar binuclear metal centers in the active site in which two metals are bridged by a post-translationally carboxylated lysine. In this study, we determined the effects of carboxylated lysine and metal binding on the activities of ALLase and DHOase. Although DHOase is a metalloenzyme, purified DHOase showed high activity without additional metal supplementation in a reaction mixture or bacterial culture. However, unlike DHOase, ALLase had no activity unless some specific metal ions were added to the reaction mixture or culture. Substituting the metal binding sites H59, H61, K146, H186, H242, or D315 with alanine completely abolished the activity of ALLase. However, the K146C, K146D and K146E mutants of ALLase were still active with about 1-6% activity of the wild-type enzyme. These ALLase K146 mutants were found to have 1.4-1.7 mol metal per mole enzyme subunit, which may indicate that they still contained the binuclear metal center in the active site. The activity of the K146A mutant of the ALLase and the K103A mutant of DHOase can be chemically rescued by short-chain carboxylic acids, such as acetic, propionic, and butyric acids, but not by ethanol, propan-1-ol, and imidazole, in the presence of Co2+ or Mn2+ ions. However, the activity was still ~10-fold less than that of wild-type ALLase. Overall, these results indicated that the 20 natural basic amino acid residues were not sufficiently able to play the role of lysine. Accordingly, we proposed that during evolution, the post-translational modification of carboxylated lysine in the cyclic amidohydrolase family was selected for promoting binuclear metal center self-assembly and increasing the nucleophilicity of the hydroxide at the active site for enzyme catalysis. This kind of chemical rescue combined with site-directed mutagenesis may also be used to identify a binuclear metal

Determination of Carboxylic Acids and Water-soluble Inorganic Ions ...

African Journals Online (AJOL)

NICO

radiation balance.4,5 Major water-soluble inorganic ions are associated with atmospheric ... molecular weight carboxylic acids in aerosol samples collected from a rural ... include biomass burning, agriculture, livestock and soil dust. Tropical ...

SYNTHESIS OF FLAVANONE-6-CARBOXYLIC ACID DERIVATIVES FROM SALICYLIC ACID DERIVATIVE

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Muhammad Idham Darussalam Mardjan

2012-02-01

Full Text Available Synthesis of flavanone-6-carboxylic acid derivatives had been conducted via the route of chalcone. The synthesis was carried out from salicylic acid derivative, i.e. 4-hydroxybenzoic acid, via esterification, Fries rearrangement, Claisen-Schmidt condensation and 1,4-nucleophilic addition reactions. Structure elucidation of products was performed using FT-IR, 1H-NMR, GC-MS and UV-Vis spectrometers. Reaction of 4-hydroxybenzoic acid with methanol catalyzed with sulfuric acid produced methyl 4-hydroxybenzoate in 87% yield. The acid-catalyzed-acetylation of the product using acetic anhydride gave methyl 4-acetoxybenzoate in 75% yield. Furthermore, solvent-free Fries rearrangement of methyl 4-acetoxybenzoate in the presence of AlCl3 produced 3-acetyl-4-hydroxybenzoic acid as the acetophenone derivatives in 67% yield. Then, Claisen-Schmidt condensation of the acetophenone and benzaldehyde derivatives of p-anisaldehyde and veratraldehyde in basic condition gave 2'-hydroxychalcone-5'-carboxylic acid derivatives  in 81 and 71 % yield, respectively. Finally, the ring closure reaction of the chalcone yielded the corresponding flavanone-6-carboxylic acids in 67 and 59% yield, respectively.

Highly Carboxylated Cellulose Nanofibers via Succinic Anhydride Esterification of Wheat Fibers and Facile Mechanical Disintegration.

Science.gov (United States)

Sehaqui, H; Kulasinski, K; Pfenninger, N; Zimmermann, T; Tingaut, P

2017-01-09

We report herein the preparation of 4-6 nm wide carboxyl-functionalized cellulose nanofibers (CNF) via the esterification of wheat fibers with cyclic anhydrides (maleic, phtalic, and succinic) followed by an energy-efficient mechanical disintegration process. Remarkable results were achieved via succinic anhydride esterification that enabled CNF isolation by a single pass through the microfluidizer yielding a transparent and thick gel. These CNF carry the highest content of carboxyl groups ever reported for native cellulose nanofibers (3.8 mmol g -1 ). Compared to conventional carboxylated cellulose nanofibers prepared via Tempo-mediated oxidation of wheat fibers, the present esterified CNF display a higher molar-mass and a better thermal stability. Moreover, highly carboxylated CNF from succinic anhydride esterification were effectively integrated into paper filters for the removal of lead from aqueous solution and are potentially of interest as carrier of active molecules or as transparent films for packaging, biomedical or electronic applications.

Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

International Nuclear Information System (INIS)

Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying; Kim, Nayoung; Wang, Jing

2015-01-01

Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH 3 CO 2 NH 4 ) and sodium acetate (CH 3 CO 2 Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example

Carboxylic acid functionalization of halloysite nanotubes for sustained release of diphenhydramine hydrochloride

Energy Technology Data Exchange (ETDEWEB)

Zargarian, S. Sh.; Haddadi-Asl, V., E-mail: haddadi@aut.ac.ir; Hematpour, H. [Amirkabir University of Technology, Department of Polymer Engineering and Color Technology (Iran, Islamic Republic of)

2015-05-15

Halloysite nanotubes (HNT) (cylindrical shape with external diameter and length in the range of 30–80 nm and 0.2–1 µm, respectively) were functionalized with 3-aminopropyltriethoxysilane (APTES) from hydroxyl groups by a coupling reaction. Subsequently, maleic anhydride was attached to the APTES moieties to yield carboxylic acid-functionalized HNT. Loading and subsequent release of a model drug molecule diphenhydramine hydrochloride (DPH) on modified and unmodified nanotubes were investigated. Morphology of HNT was studied by electron microscopy. Successful attachment of APTES and carboxylic acid groups to halloysite and drug loading were evaluated by Fourier transform infrared spectroscopy. The amount of surface modification and drug adsorption capacity were calculated via thermogravimetric analysis. The ordered crystal structure of loaded drug was evaluated by X-ray diffraction. UV–Visible spectrophotometer was used to study drug release from modified and unmodified samples. Carboxylated halloysite exhibits higher loading capacity and prolonged release of DPH as compared to that of the natural halloysite.

Carboxylic acid functionalization of halloysite nanotubes for sustained release of diphenhydramine hydrochloride

International Nuclear Information System (INIS)

Zargarian, S. Sh.; Haddadi-Asl, V.; Hematpour, H.

2015-01-01

Halloysite nanotubes (HNT) (cylindrical shape with external diameter and length in the range of 30–80 nm and 0.2–1 µm, respectively) were functionalized with 3-aminopropyltriethoxysilane (APTES) from hydroxyl groups by a coupling reaction. Subsequently, maleic anhydride was attached to the APTES moieties to yield carboxylic acid-functionalized HNT. Loading and subsequent release of a model drug molecule diphenhydramine hydrochloride (DPH) on modified and unmodified nanotubes were investigated. Morphology of HNT was studied by electron microscopy. Successful attachment of APTES and carboxylic acid groups to halloysite and drug loading were evaluated by Fourier transform infrared spectroscopy. The amount of surface modification and drug adsorption capacity were calculated via thermogravimetric analysis. The ordered crystal structure of loaded drug was evaluated by X-ray diffraction. UV–Visible spectrophotometer was used to study drug release from modified and unmodified samples. Carboxylated halloysite exhibits higher loading capacity and prolonged release of DPH as compared to that of the natural halloysite

Organotin(IV) Carboxylates as Promising Potential Drug Candidates in the Field of Cancer Chemotherapy.

Science.gov (United States)

Sirajuddin, Muhammad; Ali, Saqib

2016-01-01

Medicinal inorganic chemistry plays an important role in exploring the properties of metal ions for the designing of new drugs. The field has been stimulated by the success of cis-platin, the world best selling anticancer drug and platinum complexes with reduced toxicity, oral activity and activity against resistant tumors are currently on clinical trial. The use of cis-platin is, however, severely limited by its toxic side-effects. This has stimulated chemists to employ different strategies in the development of new metal-based anticancer agents with different mechanisms of action. The discovery of new non-covalent interactions with the classical target, DNA, was the first developing step in the treatment of cancer. The use of organometallic compounds as a medicine is very common now a days because it offers potential advantages over the more common organic-based drugs. In this article we have highlighted the anticancer activity of the organotin(IV) carboxylates published in the last few years (from 2008 to 2016). In most cases they present lower IC50 values than those of cisplatin, which indicates their high activity against the cancer cell lines. The summarized data reveal that every year new organotin(IV) carboxylate complexes are synthesized with the aim of new anticancer agent with much better results than the than the corresponding activity of cis-platin or other clinically approved drugs. In addition to the advantages of high activity, compared to the platinum compound, tin complexes are much cheaper. Thus by using organotin carboxylate for clinical medicine, cost reduction, dosage reduction and effect enhancement will be reached. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Experimental and theoretical elucidation of structural and antioxidant properties of vanillylmandelic acid and its carboxylate anion

Science.gov (United States)

Dimić, Dušan; Milenković, Dejan; Ilić, Jelica; Šmit, Biljana; Amić, Ana; Marković, Zoran; Dimitrić Marković, Jasmina

2018-06-01

Vanillylmandelic acid (VMA), an important metabolite of catecholamines that is routinely screened as tumor marker, was investigated by the various spectroscopic techniques (IR, Raman, UV-Vis, antioxidant decolorization assay and NMR). Structures optimized by the employment of five common functionals (M05-2X, M06-2X, B3LYP, CAM-B3LYP, B3LYP-D3) were compared with the crystallographic data. The M05-2X functional reproduced the most reliable experimental bond lengths and angles (correlation coefficient >0.999). The importance of intramolecular hydrogen bonds for structural stability was discussed and quantified by the NBO analysis. The most prominent bands in vibrational spectrum were analyzed and compared to the experimental data. The positions of the carbon and hydrogen atoms in NMR spectra were well reproduced. The differences in UV-Vis spectrum were investigated by adding the explicit solvent and by performing NBO and QTAIM analyses. The discrepancy in the two spectra of about 50 nm could be explained by the solvent effect on carboxyl group. The most probable antioxidant activity mechanism was discussed for VMA and its carboxylate anion. The Molecular Docking study with the C - reactive protein additionally proved that variety of functional groups present in VMA and its anion allowed strong hydrogen and hydrophobic interactions.

Biocompatible and detectable carboxylated nanodiamond on human cell

Energy Technology Data Exchange (ETDEWEB)

Liu, K-K [Institute of Pharmacology and Toxicology, Tzu Chi University, Hualien 970, Taiwan (China); Cheng, C-L [Department of Physics, National Dong Hwa University, Hualien 974, Taiwan (China); Chang, C-C [Department of Biological Science and Technology, National Chiao Tung University, Hsin-Chu 300, Taiwan (China); Chao, J-I [Institute of Pharmacology and Toxicology, Tzu Chi University, Hualien 970, Taiwan (China)

2007-08-15

Surface-modified carboxylated nanometre-sized diamond (cND) has been applied for the conjugation of biological molecules such as DNA and protein. In this study, we evaluated the biocompatibility and detection of cNDs and carbon nanotubes on human lung A549 epithelial cells and HFL-1 normal fibroblasts. Treatment with 5 or 100 nm cND particles, 0.1-100 {mu}g ml{sup -1}, did not reduce the cell viability and alter the protein expression profile in lung cells; however, carbon nanotubes induced cytotoxicity in these cells. The cNDs particles were accumulated in A549 cells, which were observed by atomic force microscopy and laser scanning confocal microscopy. Both 5 and 100 nm cNDs particles exhibited the green fluorescence and were ingested into cells. Moreover, the fluorescence intensities were increased in cells via a concentration-dependent manner after treatment with 5 and 100 nm cNDs, which can be detected by flow cytometer analysis. The fluorescence intensities of 5 nm cNDs were relative higher than 100 nm cNDs in cells at equal concentration treatment. The observation demonstrated that cND-interacting with cell is detectable by a confocal microscope, flow cytometer and atomic force microscope. These nanoparticles may be useful for further biomedical applications based on the properties of uptake ability, detectability and little cytotoxicity in human cells.

Biocompatible and detectable carboxylated nanodiamond on human cell

International Nuclear Information System (INIS)

Liu, K-K; Cheng, C-L; Chang, C-C; Chao, J-I

2007-01-01

Surface-modified carboxylated nanometre-sized diamond (cND) has been applied for the conjugation of biological molecules such as DNA and protein. In this study, we evaluated the biocompatibility and detection of cNDs and carbon nanotubes on human lung A549 epithelial cells and HFL-1 normal fibroblasts. Treatment with 5 or 100 nm cND particles, 0.1-100 μg ml -1 , did not reduce the cell viability and alter the protein expression profile in lung cells; however, carbon nanotubes induced cytotoxicity in these cells. The cNDs particles were accumulated in A549 cells, which were observed by atomic force microscopy and laser scanning confocal microscopy. Both 5 and 100 nm cNDs particles exhibited the green fluorescence and were ingested into cells. Moreover, the fluorescence intensities were increased in cells via a concentration-dependent manner after treatment with 5 and 100 nm cNDs, which can be detected by flow cytometer analysis. The fluorescence intensities of 5 nm cNDs were relative higher than 100 nm cNDs in cells at equal concentration treatment. The observation demonstrated that cND-interacting with cell is detectable by a confocal microscope, flow cytometer and atomic force microscope. These nanoparticles may be useful for further biomedical applications based on the properties of uptake ability, detectability and little cytotoxicity in human cells

Anaerobic Fermentation for Production of Carboxylic Acids as Bulk Chemicals from Renewable Biomass.

Science.gov (United States)

Wang, Jufang; Lin, Meng; Xu, Mengmeng; Yang, Shang-Tian

Biomass represents an abundant carbon-neutral renewable resource which can be converted to bulk chemicals to replace petrochemicals. Carboxylic acids have wide applications in the chemical, food, and pharmaceutical industries. This chapter provides an overview of recent advances and challenges in the industrial production of various types of carboxylic acids, including short-chain fatty acids (acetic, propionic, butyric), hydroxy acids (lactic, 3-hydroxypropionic), dicarboxylic acids (succinic, malic, fumaric, itaconic, adipic, muconic, glucaric), and others (acrylic, citric, gluconic, pyruvic) by anaerobic fermentation. For economic production of these carboxylic acids as bulk chemicals, the fermentation process must have a sufficiently high product titer, productivity and yield, and low impurity acid byproducts to compete with their petrochemical counterparts. System metabolic engineering offers the tools needed to develop novel strains that can meet these process requirements for converting biomass feedstock to the desirable product.

Spectroscopic Observation of Water-Mediated Deformation of the CARBOXYLATE-M2+ (M= Mg, Ca) Contact Ion Pair

Science.gov (United States)

Kelleher, Patrick J.; DePalma, Joseph W.; Johnson, Mark

2016-06-01

The binding of alkaline earth dications to the biologically relevant carboxylate ligand has previously been studied using vibrational sum frequency generation (VSFG) spectroscopy of the air-water interface, infrared multiple photon dissociation (IRMPD) spectroscopy of clusters, and DFT methods. These results suggest the presence of both monodentate and bidentate binding motifs of the M2+ ions to the cayboxyl head groups depending on the extent of solvation. We revisit these systems using vibrational predissociation spectroscopy to measure the gas-phase vibrational spectra of the D2-tagged microhydrated [MgOAc(H2O)n=1-5]+ and [CaOAc(H2O)n=1-6]+ clusters. The spectra show that [MgOAc(H2O)n]+ switches from bidentate to monodentate binding promptly at n = 5, while [CaOAc(H2O)n]+ retains its bidentate attachment such that the sixth water molecule initiates the second solvation shell. The difference in binding behavior between these two divalent metal ions is analyzed in the context of the local acidity of the solvent water molecules and the strength of the metal-carboxylate and metal-water interactions. This cluster study provides insight into the chemical physics underlying the unique and surprising impacts of Mg2+ and Ca2+ on the chemistry mediated by sea spray aerosols. Funding for this work was provided by the NSF's Center for Aerosol Impacts on Climate and the Environment.

Aldehydes, ketones, and carboxylic acids formed radiolytically in aqueous solutions of cyanides and simple nitriles

International Nuclear Information System (INIS)

Negron-Mendoza, A.; Draganic, Z.D.; Navarro-Gonzalez, R.; Graganic, I.G.

1983-01-01

A systematic search for aldehydes, ketones, and carboxylic acids was carried out in aqueous solutions of HCN, NH 4 CN, CH 3 CN, and C 2 H 4 CN, that had received multikilogray doses of 60 Co γ radiation. About 30 radiolytic products were identified, among them a large variety of dicarboxylic and tricarboxylic acids. Some of them might be of significant interest in molecular evolution studies of prebiotic processes. They originate in the free-radical-initiated chemical reactions where the additional oligomerization processes are particularly important. Most of the radiolytic products appear in both cyanides and nitriles and point to the importance of reactions involving the carbon-nitrogen triple bond

Supramolecular Coordination Assemblies Constructed From Multifunctional Azole-Containing Carboxylic Acids

Directory of Open Access Journals (Sweden)

Yuheng Deng

2010-05-01

Full Text Available This paper provides a brief review of recent progress in the field of metal coordination polymers assembled from azole-containing carboxylic acids and gives a diagrammatic summary of the diversity of topological structures in the resulting infinite metal-organic coordination networks (MOCNs. Azole-containing carboxylic acids are a favorable kind of multifunctional ligand to construct various metal complexes with isolated complexes and one, two and three dimensional structures, whose isolated complexes are not the focus of this review. An insight into the topology patterns of the infinite coordination polymers is provided. Analyzed topologies are compared with documented topologies and catalogued by the nature of nodes and connectivity pattern. New topologies which are not available from current topology databases are described and demonstrated graphically.

New Synthesis, Structure and Analgesic Properties of Methyl 1-R-4-Methyl-2,2-Dioxo-1H-2λ6,1-Benzothiazine-3-Carboxylates

Directory of Open Access Journals (Sweden)

Liliana Azotla-Cruz

2017-01-01

Full Text Available According to the principles of the methodology of bioisosteric replacements a series of methyl 1-R-4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylates has been obtained as potential analgesics. In addition, a fundamentally new strategy for the synthesis of compounds of this chemical class involving the introduction of N-alkyl substituent at the final stage in 2,1-benzothiazine nucleus already formed has been proposed. Using nuclear magnetic resonance (NMR spectroscopy, mass spectrometry and X-ray diffraction analysis it has been proven that in the DMSO/K2CO3 system the reaction of methyl 4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylate and alkyl halides leads to formation of N-substituted derivatives with good yields regardless of the structure of the alkylating agent. The peculiarities of NMR (1Н and 13С spectra of the compounds synthesized, their mass spectrometric behavior and the spatial structure are discussed. In N-benzyl derivative the ability to form a monosolvate with methanol has been found. According to the results of the pharmacological testing conducted on the model of the thermal tail-flick it has been determined that replacement of 4-ОН-group in methyl 1-R-4-hydroxy-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylates for the methyl group is actually bioisosteric since all methyl 1-R-4-methyl-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylates synthesized demonstrated a statistically significant analgesic effect. The majority of the substances can inhibit the thermal pain response much more effective than piroxicam in the same dose. Under the same conditions as an analgesic the N-methyl-substituted analog exceeds not only piroxicam, but more active meloxicam as well. Therefore, it deserves in-depth biological studies on other experimental models.

Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

Energy Technology Data Exchange (ETDEWEB)

Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying [ETH Zurich, Institute of Environmental Engineering (Switzerland); Kim, Nayoung [EMPA, Building Energy Materials and Components (Switzerland); Wang, Jing, E-mail: jing.wang@ifu.baug.ethz.ch [ETH Zurich, Institute of Environmental Engineering (Switzerland)

2015-10-15

Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH{sub 3}CO{sub 2}NH{sub 4}) and sodium acetate (CH{sub 3}CO{sub 2}Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example.

Approaching an experimental electron density model of the biologically active trans -epoxysuccinyl amide group-Substituent effects vs. crystal packing

Energy Technology Data Exchange (ETDEWEB)

Shi, Ming W.; Stewart, Scott G.; Sobolev, Alexandre N.; Dittrich, Birger; Schirmeister, Tanja; Luger, Peter; Hesse, Malte; Chen, Yu-Sheng; Spackman, Peter R.; Spackman, Mark A.; Grabowsky, Simon (Heinrich-Heine); (Freie); (UC); (Bremen); (JG-UM); (UWA)

2017-01-24

The trans-epoxysuccinyl amide group as a biologically active moiety in cysteine protease inhibitors such as loxistatin acid E64c has been used as a benchmark system for theoretical studies of environmental effects on the electron density of small active ingredients in relation to their biological activity. Here, the synthesis and the electronic properties of the smallest possible active site model compound are reported to close the gap between the unknown experimental electron density of trans-epoxysuccinyl amides and the well-known function of related drugs. Intramolecular substituent effects are separated from intermolecular crystal packing effects on the electron density, which allows us to predict the conditions under which an experimental electron density investigation on trans-epoxysuccinyl amides will be possible. In this context, the special importance of the carboxylic acid function in the model compound for both crystal packing and biological activity is revealed through the novel tool of model energy analysis.

Preparation and reactivity of carboxylic acid-terminated boron-doped diamond electrodes

International Nuclear Information System (INIS)

Niedziolka-Joensson, Joanna; Boland, Susan; Leech, Donal; Boukherroub, Rabah; Szunerits, Sabine

2010-01-01

The paper reports on the formation of carboxy-terminated boron-doped diamond (BDD) electrodes. The carboxylic acid termination was prepared in a controlled way by reacting photochemically oxidized BDD with succinic anhydride. The resulting interface was readily employed for the linking of an amine-terminated ligand such as an osmium complex bearing an amine terminal group. The interfaces were characterized using X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Contact angle measurements were used to follow the changes in surface wetting properties due to surface functionalization. The chemical reactivity of the carboxyl-terminated BDD was investigated by covalent coupling of the acid groups to an amine-terminated osmium complex.

VIRAL TESTING USING BIOLOGICAL AND SEROLOGICAL ASSAY FOR MOST IMPORTANT VIRUSES TO PLUM

Directory of Open Access Journals (Sweden)

Catita Plopa

2014-12-01

Full Text Available Establishing an accurate diagnosis in terms of viral for propagation of fruit tree is very important, it represents the most effective method of protection against viruses. Based on these considerations the primary objective of this study is to detect viruses with the highest incidence in plum by biological and ELISA serological methods, to a number of 85 samples taken from 17 varieties. Serologic testing on DAS-ELISA diagnosed 3 positive samples to Plum pox virus (PPV, 2 positives sample to Prunus necrotic ring spot virus (PNRSV and one positive sample to Prune dwarf virus (PDV. There were not positive samples to Apple chlorotic leaf spot virus (ACLSV. The tests conducted on woody indicator plants by grafting on protect conditions and after 3-24 months assured of diagnosis for PPV, PDV, PNRSV and ACLSV viruses. The biological indicators: ‘GF 305’, ‘Tuleu dulce’ and ‘Vânăt de Italia’, have shown symptoms for PNRSV for two samples.On biological indicator ‘Vânăt de Italia’ and ‘Tuleu dulce’ not appeared symptoms for ‘Centenar’variety tested for PPV, although the symptoms were obvious on ‘GF 305’ indicator, but viral infection was confirmed by ELISA test. Symptoms that indicate the presence of PDV occurred by ‘Vânăt de Italia’ biological indicator.

Nano-graphene oxide carboxylation for efficient bioconjugation applications: a quantitative optimization approach

Energy Technology Data Exchange (ETDEWEB)

Imani, Rana; Emami, Shahriar Hojjati, E-mail: semami@aut.ac.ir [Amirkabir University of Technology, Department of Biomedical Engineering (Iran, Islamic Republic of); Faghihi, Shahab, E-mail: shahabeddin.faghihi@mail.mcgill.ca, E-mail: sfaghihi@nigeb.ac.ir [National Institute of Genetic Engineering and Biotechnology, Tissue Engineering and Biomaterials Division (Iran, Islamic Republic of)

2015-02-15

A method for carboxylation of graphene oxide (GO) with chloroacetic acid that precisely optimizes and controls the efficacy of the process for bioconjugation applications is proposed. Quantification of COOH groups on nano-graphene oxide sheets (NGOS) is performed by novel colorimetric methylene blue (MB) assay. The GO is synthesized and carboxylated by chloroacetic acid treatment under strong basic condition. The size and morphology of the as-prepared NGOS are characterized by scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effect of acid to base molar ratio on the physical, chemical, and morphological properties of NGOS is analyzed by Fourier-transformed infrared spectrometry (FTIR), UV–Vis spectroscopy, X-ray diffraction (XRD), AFM, and zeta potential. For evaluation of bioconjugation efficacy, the synthesized nano-carriers with different carboxylation ratios are functionalized by octaarginine peptide sequence (R8) as a biomolecule model containing amine groups. The quantification of attached R8 peptides to graphene nano-sheets’ surface is performed with a colorimetric-based assay which includes the application of 2,4,6-Trinitrobenzene sulfonic acid (TNBS). The results show that the thickness and lateral size of nano-sheets are dramatically decreased to 0.8 nm and 50–100 nm after carboxylation process, respectively. X-ray analysis shows the nano-sheets interlaying space is affected by the alteration of chloroacetic acid to base ratio. The MB assay reveals that the COOH groups on the surface of NGOS are maximized at the acid to base ratio of 2 which is confirmed by FTIR, XRD, and zeta potential. The TNBS assay also shows that bioconjugation of the optimized carboxylated NGOS sample with octaarginine peptide is 2.5 times more efficient compared to bare NGOS. The present work provides evidence that treatment of GO by chloroacetic acid under an optimized condition would create a functionalized high

Nano-graphene oxide carboxylation for efficient bioconjugation applications: a quantitative optimization approach

Science.gov (United States)

Imani, Rana; Emami, Shahriar Hojjati; Faghihi, Shahab

2015-02-01

A method for carboxylation of graphene oxide (GO) with chloroacetic acid that precisely optimizes and controls the efficacy of the process for bioconjugation applications is proposed. Quantification of COOH groups on nano-graphene oxide sheets (NGOS) is performed by novel colorimetric methylene blue (MB) assay. The GO is synthesized and carboxylated by chloroacetic acid treatment under strong basic condition. The size and morphology of the as-prepared NGOS are characterized by scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effect of acid to base molar ratio on the physical, chemical, and morphological properties of NGOS is analyzed by Fourier-transformed infrared spectrometry (FTIR), UV-Vis spectroscopy, X-ray diffraction (XRD), AFM, and zeta potential. For evaluation of bioconjugation efficacy, the synthesized nano-carriers with different carboxylation ratios are functionalized by octaarginine peptide sequence (R8) as a biomolecule model containing amine groups. The quantification of attached R8 peptides to graphene nano-sheets' surface is performed with a colorimetric-based assay which includes the application of 2,4,6-Trinitrobenzene sulfonic acid (TNBS). The results show that the thickness and lateral size of nano-sheets are dramatically decreased to 0.8 nm and 50-100 nm after carboxylation process, respectively. X-ray analysis shows the nano-sheets interlaying space is affected by the alteration of chloroacetic acid to base ratio. The MB assay reveals that the COOH groups on the surface of NGOS are maximized at the acid to base ratio of 2 which is confirmed by FTIR, XRD, and zeta potential. The TNBS assay also shows that bioconjugation of the optimized carboxylated NGOS sample with octaarginine peptide is 2.5 times more efficient compared to bare NGOS. The present work provides evidence that treatment of GO by chloroacetic acid under an optimized condition would create a functionalized high surface

Nano-graphene oxide carboxylation for efficient bioconjugation applications: a quantitative optimization approach

International Nuclear Information System (INIS)

Imani, Rana; Emami, Shahriar Hojjati; Faghihi, Shahab

2015-01-01

A method for carboxylation of graphene oxide (GO) with chloroacetic acid that precisely optimizes and controls the efficacy of the process for bioconjugation applications is proposed. Quantification of COOH groups on nano-graphene oxide sheets (NGOS) is performed by novel colorimetric methylene blue (MB) assay. The GO is synthesized and carboxylated by chloroacetic acid treatment under strong basic condition. The size and morphology of the as-prepared NGOS are characterized by scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effect of acid to base molar ratio on the physical, chemical, and morphological properties of NGOS is analyzed by Fourier-transformed infrared spectrometry (FTIR), UV–Vis spectroscopy, X-ray diffraction (XRD), AFM, and zeta potential. For evaluation of bioconjugation efficacy, the synthesized nano-carriers with different carboxylation ratios are functionalized by octaarginine peptide sequence (R8) as a biomolecule model containing amine groups. The quantification of attached R8 peptides to graphene nano-sheets’ surface is performed with a colorimetric-based assay which includes the application of 2,4,6-Trinitrobenzene sulfonic acid (TNBS). The results show that the thickness and lateral size of nano-sheets are dramatically decreased to 0.8 nm and 50–100 nm after carboxylation process, respectively. X-ray analysis shows the nano-sheets interlaying space is affected by the alteration of chloroacetic acid to base ratio. The MB assay reveals that the COOH groups on the surface of NGOS are maximized at the acid to base ratio of 2 which is confirmed by FTIR, XRD, and zeta potential. The TNBS assay also shows that bioconjugation of the optimized carboxylated NGOS sample with octaarginine peptide is 2.5 times more efficient compared to bare NGOS. The present work provides evidence that treatment of GO by chloroacetic acid under an optimized condition would create a functionalized high

Solid state structure of thorium(IV) complexes with common aminopoly-carboxylate ligands

International Nuclear Information System (INIS)

Thuery, Pierre

2011-01-01

The crystal structures of the complexes formed by reaction of thorium(IV) nitrate with iminodiacetic acid (H 2 IDA), nitrilotriacetic acid (H 3 NTA), and ethylenediaminetetraacetic acid (H 4 EDTA) under hydrothermal conditions are reported. In [Th(HIDA) 2 (C 2 O 4 )].H 2 O (1), the metal atom is chelated by two carboxylate groups from two HIDA - anions and by two oxalate ligands formed in situ; two additional oxygen atoms from two more HIDA - anions complete the ten-coordinate environment of bi-capped square anti-prismatic geometry. The uncoordinated nitrogen atom is protonated and involved in hydrogen bonding. Two different ligands are present in [Th(NTA)(H 2 NTA)(H 2 O)].H 2 O (2), one of them being a O 3 ,N-chelating tri-anion which acts also as a bridge toward two neighboring metal ions, and the other being a bis-monodentate bridging species with an uncoordinated carboxylic arm and a central ammonium group. An aqua ligand completes the nine-coordinated, capped square anti-prismatic metal environment. The EDTA 4- anion in [Th(EDTA)(H 2 O)].2H 2 O (3) is chelating through one oxygen atom from each carboxylate group and the two nitrogen atoms, as in a previously reported molecular complex. Two carboxylate groups are bridging, which, with the addition of an aqua ligand, gives a capped square anti-prismatic coordination polyhedron. Aminopoly-carboxylate ligands have been much investigated in relation with actinide decorporation and nuclear wastes management studies, and the present results add to the structural information available on their complexes with thorium(IV), which has mainly been obtained up to now by extended X-ray absorption fine structure (EXAFS) spectroscopy. In particular, the bridging (non-chelating) coordination mode of H 2 NTA - is a novel feature in this context. All three complexes crystallize as two-dimensional assemblies and are thus novel examples of thorium-organic coordination polymers. (author)

Silver(I) and copper(II)-imidazolium carboxylates: Efficient catalysts ...

Indian Academy of Sciences (India)

GANESAN PRABUSANKAR

the reaction between corresponding carboxylic acid ligands and metal salts. These new metal .... g), DMF (2 mL) and water (1 mL) was added; then, the sus- pension was ..... ence of five mol% potassium hydroxide as base in 1 and. Scheme 3.

X-ray absorption spectroscopy in biological systems. Opportunities and limitations

Energy Technology Data Exchange (ETDEWEB)

Bovenkamp, Gudrun Lisa

2013-05-15

X-ray absorption spectroscopy has become more important for applications in the material sciences, geology, environmental science and biology, specifically in the field of molecular biology. The scope of this thesis is to add more experimental evidence in order to show how applicable X-ray absorption near edge structure (XANES) is to biology. Two biological systems were investigated, at the molecular level, lead uptake in plants and the effect of silver on bacteria. This investigation also included an analysis of the sensitivity of Pb L{sub 3}- and Ag L{sub 3}-XANES spectra with regard to their chemical environment. It was shown that Pb L{sub 3}- and Ag L{sub 3}-XANES spectra are sensitive to an environment with at least differences in the second coordination shell. The non-destructive and element specific properties of XANES are the key advantages that were very important for this investigation. However, in both projects the adequate selection of reference compounds, which required in some cases a chemical synthesis, was the critical factor to determine the chemical speciation and, finally, possible uptake and storage mechanisms for plants and antibacterial mechanisms of silver. The chemical environment of Pb in roots and leaves of plants from four different plant families and a lichen from a former lead mining site in the Eifel mountains in Germany was determined using both solid compounds and aqueous solutions of different ionic strength, which simulate the plant environment. The results can be interpreted in such a way that lead is sorbed on the surface of cell walls. Silver bonding as reaction with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli bacteria was determined using inorganic silver compounds and synthesized silver amino acids. Silver binds to sulfur, amine and carboxyl groups in amino acids.

X-ray absorption spectroscopy in biological systems. Opportunities and limitations

International Nuclear Information System (INIS)

Bovenkamp, Gudrun Lisa

2013-05-01

X-ray absorption spectroscopy has become more important for applications in the material sciences, geology, environmental science and biology, specifically in the field of molecular biology. The scope of this thesis is to add more experimental evidence in order to show how applicable X-ray absorption near edge structure (XANES) is to biology. Two biological systems were investigated, at the molecular level, lead uptake in plants and the effect of silver on bacteria. This investigation also included an analysis of the sensitivity of Pb L 3 - and Ag L 3 -XANES spectra with regard to their chemical environment. It was shown that Pb L 3 - and Ag L 3 -XANES spectra are sensitive to an environment with at least differences in the second coordination shell. The non-destructive and element specific properties of XANES are the key advantages that were very important for this investigation. However, in both projects the adequate selection of reference compounds, which required in some cases a chemical synthesis, was the critical factor to determine the chemical speciation and, finally, possible uptake and storage mechanisms for plants and antibacterial mechanisms of silver. The chemical environment of Pb in roots and leaves of plants from four different plant families and a lichen from a former lead mining site in the Eifel mountains in Germany was determined using both solid compounds and aqueous solutions of different ionic strength, which simulate the plant environment. The results can be interpreted in such a way that lead is sorbed on the surface of cell walls. Silver bonding as reaction with Staphylococcus aureus, Listeria monocytogenes, and Escherichia coli bacteria was determined using inorganic silver compounds and synthesized silver amino acids. Silver binds to sulfur, amine and carboxyl groups in amino acids.

Methyl (Sp-2-(diphenylphosphinoferrocene-1-carboxylate

Directory of Open Access Journals (Sweden)

Petr Štěpnička

2009-10-01

Full Text Available The title compound, [Fe(C5H5(C19H16O2P], obtained serendipitously during recrystallization of 1-hydroxybenzotriazolyl (Sp-2-(diphenylphosphinoferrocene-1-carboxylate from methanol, crystallizes in the chiral space group P212121. Its crystal structure not only confirms the anticipated absolute configuration but also establishes a rather regular geometry for the ferrocene unit, devoid of any significant deformation due to the attached substituents. In the crystal, symmetry-related molecules are linked via weak C—H...O interactions.

Carbon dioxide utilization via carbonate-promoted C-H carboxylation.

Science.gov (United States)

Banerjee, Aanindeeta; Dick, Graham R; Yoshino, Tatsuhiko; Kanan, Matthew W

2016-03-10

Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.

Biotransformation of fluorophenyl pyridine carboxylic acids by the model fungus Cunninghamella elegans.

Science.gov (United States)

Palmer-Brown, William; Dunne, Brian; Ortin, Yannick; Fox, Mark A; Sandford, Graham; Murphy, Cormac D

2017-09-01

1. Fluorine plays a key role in the design of new drugs and recent FDA approvals included two fluorinated drugs, tedizolid phosphate and vorapaxar, both of which contain the fluorophenyl pyridyl moiety. 2. To investigate the likely phase-I (oxidative) metabolic fate of this group, various fluorinated phenyl pyridine carboxylic acids were incubated with the fungus Cunninghamella elegans, which is an established model of mammalian drug metabolism. 3.  19 F NMR spectroscopy established the degree of biotransformation, which varied depending on the position of fluorine substitution, and gas chromatography-mass spectrometry (GC-MS) identified alcohols and hydroxylated carboxylic acids as metabolites. The hydroxylated metabolites were further structurally characterised by nuclear magnetic resonance spectroscopy (NMR), which demonstrated that hydroxylation occurred on the 4' position; fluorine in that position blocked the hydroxylation. 4. The fluorophenyl pyridine carboxylic acids were not biotransformed by rat liver microsomes and this was a consequence of inhibitory action, and thus, the fungal model was crucial in obtaining metabolites to establish the mechanism of catabolism.

Synthesis, characterization and metal coordination of a potential β-lactamase inhibitor: 5-Methyl-2-phenoxymethyl-3-H-imidazole-4-carboxylic acid (PIMA

Directory of Open Access Journals (Sweden)

Chiara Romagnoli

2017-12-01

Full Text Available Among relevant metal ions in biological systems, zinc and iron play a key role as active partners of the catalytic machinery. In particular, the inhibition of metal enzymes that are involved in physiological and pathological processes has been deeply investigated for the rational design of selective and efficient drugs based on chelators. Since imidazole histidine residue is one of the most versatile sites in proteins, especially in enzymes acting in the presence of metal ions as cofactors, in this work the synthesis and characterization of a new imidazole derivative, namely 5-methyl-2-phenoxymethyl-3-H-imidazole-4-carboxylic acid (PIMA is reported. PIMA was designed as metallo-β-lactamase inhibitor thanks to its similarity with penicillin V, a β-lactam antibiotic inactivated by metallo-β-lactamase, for which there are no commercially available inhibitors. The evaluation of PIMA coordinating ability toward iron, zinc, and gallium, these latter selected as a non-paramagnetic probe for iron, is performed by theoretical DFT calculations and in solution by experimental techniques, i.e. potentiometry, UV–vis and NMR spectroscopy. PIMA exhibits an efficient metal chelating ability; the prevailing species in physiological condition are ML3 for Fe3+ and Ga3+ and ML2 for Zn2+, in which chelation is due to deprotonated carboxylic oxygen and imidazole nitrogen in the N,O donor set. The demonstrated ability of PIMA to chelate zinc ion, combined with its structure similarity with penicillin V, supports further exploration of this imidazole-4-carboxylate as metallo-β-lactamase inhibitor.

Late-stage diversification of biologically active pyridazinones via a direct C-H functionalization strategy.

Science.gov (United States)

Li, Wei; Fan, Zhoulong; Geng, Kaijun; Xu, Youjun; Zhang, Ao

2015-01-14

Divergent C-H functionalization reactions (arylation, carboxylation, olefination, thiolation, acetoxylation, halogenation, naphthylation) using a pyridazinone moiety as an internal directing group were successfully established. This approach offers a late-stage, ortho-selective diversification of a biologically active pyridazinone scaffold. Seven series of novel pyridazinone analogues were synthesized conveniently as the synthetic precursors of potential sortase A (SrtA) inhibitors.

CARBOXYLIC ACIDS OF HERB OF THYMUS CRETACEUS KLOK. ET SCHOST

Directory of Open Access Journals (Sweden)

V. N. Bubenchikova

2014-01-01

Full Text Available We have studied carboxylic acids of the herb of Thymus cretaceus Klok. et Schost which is widespread on a territory of some regions (Belgorod, Voronezh. The study was carried out using gas-liquid chromatography at Agilent Technologies 6890 chromatographer with massspectrometric detector 5973 N. Acids concentration was calculated by means of inner standard.We have established that carboxylic acids of Thymus cretaceus are represented by 34 compounds. Palmitic (1779.02 mg/kg, behenic (1084.15 mg/kg, levulinic (986.24 mg/kg and linoleic acids (678.82 mg/kg predominate among fatty acids; citric (9835.14 mg/kg, malonic (447.91 mg/kg and oxalic acids (388.32 mg/kg predominate among organic acids; andferulic acid predominate amongphenolcarbonic acids.

A comparison of properties between carboxylated acrylic rubbers prepared by γ-ray irradiation and chemical method

International Nuclear Information System (INIS)

Wang Weiwei; Chang Zhenqi; Wang Mozhen; Zhang Zhicheng; Lv Pin

2006-01-01

Acrylic rubbers (ACM) carboxylated by acrylic acid or itaconic acid were prepared by 60 Co γ-ray or chemical-initiator (K 2 S 2 O 8 ) induced emulsion copolymerization. The polymers were characterized by Fourier transform infrared spectroscopy (FT-IR). Acid value, molecular weight and polydispersity index (PDI) of the polymers were determined by non-aqueous titration method and gel permeation chromatography (GPC), respectively. Vulcanization and mechanical properties of the filled ACM were studied by rheometric measurement, gel fraction analysis, mechanical property tests and dynamic mechanical thermal analysis (DMTA). The results show that the ACMs prepared by γ-ray irradiation have lower acid value, higher molecular weight and narrower PDI than chemically prepared ACMs of the same compositions. The itaconic acid carboxylated ACM has better cure characteristics and mechanical properties than the acrylic acid carboxylated ACM. The itaconic acid carboxylated ACM prepared by γ-ray irradiation has higher gel fraction and better cure characteristics as well as mechanical properties than that prepared by chemical method. (authors)

Carboxylated nanodiamond and re-oxygenation process of gamma irradiated red blood cells

International Nuclear Information System (INIS)

Acosta-Elias, M.; Sarabia-Sainz, A.; Silva-Campa, E.; Angulo-Molina, A.; Soto-Puebla, D.; Barboza-Flores, M.; Melendrez, R.; Alvarez-Garcia, S.; Pedroza-Montero, M.; Pedroso-Santana, S.; Santacruz-Gomez, K.; Castaneda, B.

2015-01-01

Nanodiamonds (NDs) possess exceptional physical, chemical, and biological properties, which make them suitable for potential biomedical applications. They are biocompatible and their usefulness as effective Raman/fluorescence probes for labeling as well as for drug delivery has been demonstrated. Related to their biocompatibility, the interaction between NDs and red blood cells (RBCs) is of great interest. In this work, the influence of carboxylated NDs (cNDs) in the re-oxygenation capability of both γ-irradiated and stored RBCs was studied. The standard 25 Gy γ dose recommended to prevent transfusion associated graft-versus-host disease was used. A 5-day maximum storage time was used to evaluate the ''storage lesion''. The hemoglobin (Hb) oxygenation state was assessed by Raman microspectroscopy and the morphologic changes on cells were tracked by optical imaging. Our results show that irradiated RBCs have a better re-oxygenation capability and morphological recovery when they are in presence of cNDs. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Carboxylated nanodiamond and re-oxygenation process of gamma irradiated red blood cells

Energy Technology Data Exchange (ETDEWEB)

Acosta-Elias, M. [Doctorado en Nanotecnologia, Universidad de Sonora (Mexico); Sarabia-Sainz, A.; Silva-Campa, E.; Angulo-Molina, A.; Soto-Puebla, D.; Barboza-Flores, M.; Melendrez, R.; Alvarez-Garcia, S.; Pedroza-Montero, M. [Departamento de Investigacion en Fisica, Universidad de Sonora, Hermosillo (Mexico); Pedroso-Santana, S. [Doctorado en Ciencias (Fisica), Universidad de Sonora, Hermosillo (Mexico); Santacruz-Gomez, K.; Castaneda, B. [Departamento de Fisica, Universidad de Sonora, Hermosillo (Mexico)

2015-11-15

Nanodiamonds (NDs) possess exceptional physical, chemical, and biological properties, which make them suitable for potential biomedical applications. They are biocompatible and their usefulness as effective Raman/fluorescence probes for labeling as well as for drug delivery has been demonstrated. Related to their biocompatibility, the interaction between NDs and red blood cells (RBCs) is of great interest. In this work, the influence of carboxylated NDs (cNDs) in the re-oxygenation capability of both γ-irradiated and stored RBCs was studied. The standard 25 Gy γ dose recommended to prevent transfusion associated graft-versus-host disease was used. A 5-day maximum storage time was used to evaluate the ''storage lesion''. The hemoglobin (Hb) oxygenation state was assessed by Raman microspectroscopy and the morphologic changes on cells were tracked by optical imaging. Our results show that irradiated RBCs have a better re-oxygenation capability and morphological recovery when they are in presence of cNDs. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

The Halogenated Metabolism of Brown Algae (Phaeophyta, Its Biological Importance and Its Environmental Significance

Directory of Open Access Journals (Sweden)

Stéphane La Barre

2010-03-01

Full Text Available Brown algae represent a major component of littoral and sublittoral zones in temperate and subtropical ecosystems. An essential adaptive feature of this independent eukaryotic lineage is the ability to couple oxidative reactions resulting from exposure to sunlight and air with the halogenations of various substrates, thereby addressing various biotic and abiotic stresses i.e., defense against predators, tissue repair, holdfast adhesion, and protection against reactive species generated by oxidative processes. Whereas marine organisms mainly make use of bromine to increase the biological activity of secondary metabolites, some orders of brown algae such as Laminariales have also developed a striking capability to accumulate and to use iodine in physiological adaptations to stress. We review selected aspects of the halogenated metabolism of macrophytic brown algae in the light of the most recent results, which point toward novel functions for iodide accumulation in kelps and the importance of bromination in cell wall modifications and adhesion properties of brown algal propagules. The importance of halogen speciation processes ranges from microbiology to biogeochemistry, through enzymology, cellular biology and ecotoxicology.

Cholesterol oxidation products and their biological importance

Czech Academy of Sciences Publication Activity Database

Kulig, W.; Cwiklik, Lukasz; Jurkiewicz, P.; Rog, T.; Vattulainen, I.

2016-01-01

Roč. 199, Sep (2016), s. 144-160 ISSN 0009-3084 R&D Projects: GA ČR(CZ) GBP208/12/G016 Institutional support: RVO:61388963 Keywords : cholesterol * oxidation * oxysterols * biological membranes * biophysical properties Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.361, year: 2016

Dimerization of Carboxylic Acids: An Equation of State Approach

DEFF Research Database (Denmark)

Tsivintzelis, Ioannis; Kontogeorgis, Georgios; Panayiotou, Costas

2017-01-01

The association term of the nonrandom hydrogen bonding theory, which is an equation of state model, is extended to describe the dimerization of carboxylic acids in binary mixtures with inert solvents and in systems of two different acids. Subsequently, the model is applied to describe the excess...

Synthesis and Biological Activity of 2,5-Bisubstituted Derivatives of 1,3,4-Thiadiazol-2,5-dithiol

Directory of Open Access Journals (Sweden)

T. S. Zhivotova

2013-01-01

Full Text Available By reaction of 1,3,4-thiadiazol-2,5-dithiol with different organohalogens, chlorides of carboxylic acids, acrylic acid derivatives, alkaloids, and secondary amines, various derivatives of 2,5-bi-substituted 1,3,4-thiadiazole were synthesized, and biological properties of some of them were studied.

Analysis of carboxylate coordination function of the isomeric lanthanide pyridinedicarboxylates by means of vibration spectroscopy

International Nuclear Information System (INIS)

Puntus, L.; Zolin, V.; Kudryashova, V.

2004-01-01

The investigation of IR spectra of salts of six isomers of pyridinedicarboxylic acid (PDA): 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-pyridinedicarboxylic acids, have demonstrated that properties of these salts are dependent on the bonding manner of carboxylate groups and on coordination of heterocyclic nitrogen atom. The most prominent differences in properties and spectra of 2,6- and 3,4-PDA salts are conditioned correspondingly by monodentate and bidentate coordination functions of the carboxylate groups in these compounds. The correlation of the breathing vibration frequency, reflecting the rigidity of the heterocyclic ring, with position of the carboxylate substituents, conditioning intramolecular charge transfer (CT), was postulated and proved by shifts of the breathing vibration frequency dependent on the structure of isomeric ligand

Water-soluble Manganese and Iron Mesotetrakis(carboxyl)porphyrin: DNA Binding, Oxidative Cleavage, and Cytotoxic Activities.

Science.gov (United States)

Shi, Lei; Jiang, Yi-Yu; Jiang, Tao; Yin, Wei; Yang, Jian-Ping; Cao, Man-Li; Fang, Yu-Qi; Liu, Hai-Yang

2017-06-29

Two new water-soluble metal carboxyl porphyrins, manganese (III) meso -tetrakis (carboxyl) porphyrin and iron (III) meso -tetrakis (carboxyl) porphyrin, were synthesized and characterized. Their interactions with ct-DNA were investigated by UV-Vis titration, fluorescence spectra, viscosity measurement and CD spectra. The results showed they can strongly bind to ct-DNA via outside binding mode. Electrophoresis experiments revealed that both complexes can cleave pBR322 DNA efficiently in the presence of hydrogen peroxide, albeit 2-Mn exhibited a little higher efficiency. The inhibitor tests suggest the oxidative DNA cleavage by these two complexes may involve hydroxyl radical active intermediates. Notably, 2-Mn exhibited considerable photocytotoxicity against Hep G2 cell via triggering a significant generation of ROS and causing disruption of MMP after irradiation.

Direct enantioselective conjugate addition of carboxylic acids with chiral lithium amides as traceless auxiliaries.

Science.gov (United States)

Lu, Ping; Jackson, Jeffrey J; Eickhoff, John A; Zakarian, Armen

2015-01-21

Michael addition is a premier synthetic method for carbon-carbon and carbon-heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B.

Carboxylated nanodiamonds inhibit γ-irradiation damage of human red blood cells.

Science.gov (United States)

Santacruz-Gomez, K; Silva-Campa, E; Melendrez-Amavizca, R; Teran Arce, F; Mata-Haro, V; Landon, P B; Zhang, C; Pedroza-Montero, M; Lal, R

2016-04-07

Nanodiamonds when carboxylated (cNDs) act as reducing agents and hence could limit oxidative damage in biological systems. Gamma (γ)-irradiation of whole blood or its components is required in immunocompetent patients to prevent transfusion-associated graft versus host disease (TA-GVHD). However, γ-irradiation of blood also deoxygenates red blood cells (RBCs) and induces oxidative damage, including abnormalities in cellular membranes and hemolysis. Using atomic force microscopy (AFM) and Raman spectroscopy, we examined the effect of cNDs on γ-irradiation mediated deoxygenation and morphological damage of RBCs. γ-Radiation induced several morphological phenotypes, including stomatocytes, codocytes and echinocytes. While stomatocytes and codocytes are reversibly damaged RBCs, echinocytes are irreversibly damaged. AFM images show significantly fewer echinocytes among cND-treated γ-irradiated RBCs. The Raman spectra of γ-irradiated RBCs had more oxygenated hemoglobin patterns when cND-treated, resembling those of normal, non-irradiated RBCs, compared to the non-cND-treated RBCs. cND inhibited hemoglobin deoxygenation and morphological damage, possibly by neutralizing the free radicals generated during γ-irradiation. Thus cNDs have the therapeutic potential to preserve the quality of stored blood following γ-irradiation.

Student perceptions: Importance of and satisfaction with aspects of an online biology course

Science.gov (United States)

Hendry, Sheila R.

Research of student satisfaction with various facets of an online biology course, as well as the perceived importance of these aspects, was conducted during the summer and fall 2004 semesters within a course, History of Biology, at a university in the southeastern United States. This research is based on the theory of transactional distance, which involves dialogue between the teacher and student, the physical environments of both the student and teacher, and the emotional environments of each. Student ratings of importance and satisfaction regarding aspects of convenience, grade earned/knowledge learned, emotional health, communication, and student support were collected toward the end of each semester, via the online course, using the researcher-designed Student Perceptions Survey. Statistics with repeated measures ANOVA, using an alpha of 0.05, determined differences between importance and satisfaction ratings for each of these aspects. Students perceived grade earned/knowledge learned to be the most important aspect of learning online, although it is not an aspect unique to online courses. All of the aspects included in the study were found to be at least somewhat important. Convenience was the aspect with which students were most satisfied, with students at least somewhat satisfied with the other aspects. Although convenience is an inherent strength of the online course format, instructors should be aware of how important it is to design requirements of the online class to help students acquire knowledge while allowing them to do so at their own pace. Well-structured content, prompt feedback, encouragement of quality student-instructor communication, and student support are all parts of a positive online course experience. The Student Perceptions Survey, created specifically for this research, can have substantial value both in the creation of new online courses and in the evaluation of pre-existing courses. It can provide important information that can be

Synthesis and characterization of carboxylic cation exchange bio-resin for heavy metal remediation.

Science.gov (United States)

Kulkarni, Vihangraj V; Golder, Animes Kumar; Ghosh, Pranab Kumar

2018-01-05

A new carboxylic bio-resin was synthesized from raw arecanut husk through mercerization and ethylenediaminetetraacetic dianhydride (EDTAD) carboxylation. The synthesized bio-resin was characterized using thermogravimetric analysis, field emission scanning electron microscopy, proximate & ultimate analyses, mass percent gain/loss, potentiometric titrations, and Fourier transform infrared spectroscopy. Mercerization extracted lignin from the vesicles on the husk and EDTAD was ridged in to, through an acylation reaction in dimethylformamide media. The reaction induced carboxylic groups as high as 0.735mM/g and a cation exchange capacity of 2.01meq/g functionalized mercerized husk (FMH). Potentiometric titration data were fitted to a newly developed single-site proton adsorption model (PAM) that gave pKa of 3.29 and carboxylic groups concentration of 0.741mM/g. FMH showed 99% efficiency in Pb(II) removal from synthetic wastewater (initial concentration 0.157mM), for which the Pb(II) binding constant was 1.73×10 3 L/mol as estimated from modified PAM. The exhaustion capacity was estimated to be 18.7mg/g of FMH. Desorption efficiency of Pb(II) from exhausted FMH was found to be about 97% with 0.1N HCl. The FMH simultaneously removed lead and cadmium below detection limit from a real lead acid battery wastewater along with the removal of Fe, Mg, Ni, and Co. Copyright © 2017 Elsevier B.V. All rights reserved.

Biosynthesis of Bacterial Cellulose/Carboxylic Multi-Walled Carbon Nanotubes for Enzymatic Biofuel Cell Application

Directory of Open Access Journals (Sweden)

Pengfei Lv

2016-03-01

Full Text Available Novel nanocomposites comprised of bacterial cellulose (BC with carboxylic multi-walled carbon nanotubes (c-MWCNTs incorporated into the BC matrix were prepared through a simple method of biosynthesis. The biocathode and bioanode for the enzyme biological fuel cell (EBFC were prepared using BC/c-MWCNTs composite injected by laccase (Lac and glucose oxidase (GOD with the aid of glutaraldehyde (GA crosslinking. Biosynthesis of BC/c-MWCNTs composite was characterized by digital photos, scanning electron microscope (SEM, and Fourier Transform Infrared (FTIR. The experimental results indicated the successful incorporation of c-MWCNTs into the BC. The electrochemical and biofuel performance were evaluated by cyclic voltammetry (CV and linear sweep voltammetry (LSV. The power density and current density of EBFCs were recorded at 32.98 µW/cm3 and 0.29 mA/cm3, respectively. Additionally, the EBFCs also showed acceptable stability. Preliminary tests on double cells indicated that renewable BC have great potential in the application field of EBFCs.

Preparation of conjugated poly(ethyl acetylene carboxylate) as optical limiter of laser radiation

International Nuclear Information System (INIS)

Allaf, A. W.; Al-Zier, A.; Al-Naima, D.

2009-03-01

The optical limiting action of poly (ethylacetylene carboxylate) dissolved in dichloroethane were investigated under irradiation with 8 ns laser pulses at 532 nm. The optical limiting measurements were performed at a series of concentrations. The threshold limiting fluence was observed for high concentrations at 5 J/cm 2 with a transmission of about 20 %. No optical limiting action was observed at very low concentration of the prepared polymer in the dichloroethane solvent. The observed data show that poly (ethylacetylene carboxylate) has the potential for the use as optical limiting material for future applications. (author)

Carboxylic Terminated Thermo-Responsive Copolymer Hydrogel and Improvement in Peptide Release Profile

Directory of Open Access Journals (Sweden)

Zi-Kun Rao

2018-02-01

Full Text Available To improve the release profile of peptide drugs, thermos-responsive triblock copolymer poly (ε-caprolactone-co-p-dioxanone-b-poly (ethylene glycol-b-poly (ε-caprolactone-co-p-dioxanone (PECP was prepared and end capped by succinic anhydride to give its carboxylic terminated derivative. Both PCEP block copolymer and its end group modified derivative showed temperature-dependent reversible sol-gel transition in water. The carboxylic end group could significantly decrease the sol-gel transition temperature by nearly 10 °C and strengthen the gel due to enhanced intermolecular force among triblock copolymer chains. Furthermore, compared with the original PECP triblock copolymer, HOOC–PECP–COOH copolymer displayed a retarded and sustained release profile for leuprorelin acetate over one month while effectively avoiding the initial burst. The controlled release was believed to be related to the formation of conjugated copolymer-peptide pair by ionic interaction and enhanced solubility of drug molecules into the hydrophobic domains of the hydrogel. Therefore, carboxyl terminated HOOC–PECP–COOH hydrogel was a promising and well-exhibited sustained release carrier for peptide drugs with the advantage of being able to develop injectable formulation by simple mixing.

Direct Enantioselective Conjugate Addition of Carboxylic Acids with Chiral Lithium Amides as Traceless Auxiliaries

Science.gov (United States)

2016-01-01

Michael addition is a premier synthetic method for carbon–carbon and carbon–heteroatom bond formation. Using chiral dilithium amides as traceless auxiliaries, we report the direct enantioselective Michael addition of carboxylic acids. A free carboxyl group in the product provides versatility for further functionalization, and the chiral reagent can be readily recovered by extraction with aqueous acid. The method has been applied in the enantioselective total synthesis of the purported structure of pulveraven B. PMID:25562717

Thermodynamics of formation of cadmium dicarboxylate and carboxylate mixed complexes with benzimidazole

Energy Technology Data Exchange (ETDEWEB)

Kharitonov, G V; Bolotov, V M; Kharitonova, R I [Voronezhskij Tekhnologicheskij Inst. (USSR)

1980-01-01

Thermodynamic parameters of the mixed complexing of cadmium propionate, butyrate, valerate, succinate, maleinate and malate with benzimidazole in 20 % aqUeous-ethanol solution of 0.1 M KNO/sub 3/ are studied using polarographic method. It is shown that stability of mixed complexes of cadmium carboxylates with benzimidazole is connected with the process enthalpy and is determined by covalency of the metal-carboxylate bond. Increasing length of hydrocarbon chain of acyl group of monobasic acids hampers amine coordination with central complexing agent (..delta..S<0). The presence of dicarboxylate-ion in the inner coordination sphere decreases the enthalpy and increases the entropy of the process (..delta..S>0).

Low-molecular-weight poly-carboxylate as crystal growth modifier in ...

Indian Academy of Sciences (India)

Biomineralization; growth modifier; amino acid; low-molecular-weight chiral poly- carboxylate; calcium ... They are also used as gravity sensors, for metal storage and .... The pH of the solutions was maintained at ~10⋅0 for different periods of ...

Light dependence of carboxylation capacity for C3 photosynthesis models

Science.gov (United States)

Photosynthesis at high light is often modelled by assuming limitation by the maximum capacity of Rubisco carboxylation at low carbon dioxide concentrations, by electron transport capacity at higher concentrations, and sometimes by triose-phosphate utilization rate at the highest concentrations. Pho...

Metal-Catalyzed Intra- and Intermolecular Addition of Carboxylic Acids to Alkynes in Aqueous Media: A Review

Directory of Open Access Journals (Sweden)

Javier Francos

2017-11-01

Full Text Available The metal-catalyzed addition of carboxylic acids to alkynes is a very effective tool for the synthesis of carboxylate-functionalized olefinic compounds in an atom-economical manner. Thus, a large variety of synthetically useful lactones and enol-esters can be accessed through the intra- or intermolecular versions of this process. In order to reduce the environmental impact of these reactions, considerable efforts have been devoted in recent years to the development of catalytic systems able to operate in aqueous media, which represent a real challenge taking into account the tendency of alkynes to undergo hydration in the presence of transition metals. Despite this, different Pd, Pt, Au, Cu and Ru catalysts capable of promoting the intra- and intermolecular addition of carboxylic acids to alkynes in a selective manner in aqueous environments have appeared in the literature. In this review article, an overview of this chemistry is provided. The synthesis of β-oxo esters by catalytic addition of carboxylic acids to terminal propargylic alcohols in water is also discussed.

Engineering Copper Carboxylate Functionalities on Water Stable Metal–Organic Frameworks for Enhancement of Ammonia Removal Capacities

Energy Technology Data Exchange (ETDEWEB)

Joshi, Jayraj N.; Garcia-Gutierrez, Erika Y.; Moran, Colton M.; Deneff, Jacob I.; Walton, Krista S.

2017-02-02

Functionalization of copper carboxylate groups on a series of UiO-66 metal organic framework (MOF) analogues and their corresponding impact on humid and dry ammonia adsorption behavior were studied. Relative locations of possible carboxylic acid binding sites for copper on the MOF analogues were varied on ligand and missing linker defect sites. Materials after copper incorporation exhibited increased water vapor and ammonia affinity during isothermal adsorption and breakthrough experiments, respectively. The introduction of copper markedly increased ammonia adsorption capacities for all adsorbents possessing carboxyl binding sites. In particular, the new MOF UiO-66-(COOCu)2 displayed the highest ammonia breakthrough capacities of 6.38 and 6.84 mmol g–1 under dry and humid conditions, respectively, while retaining crystallinity and porosity. Relative carboxylic acid site locations were also found to impact sorbent stability, as missing linker defect functionalized materials degraded under humid conditions after copper incorporation. Postsynthetic metal insertion provides a method for adding sites that are analogous to open metal sites while maintaining good structural stability.

Kinetic analysis of the reactivity of aliphatic cyclic alcohols and carboxylic acids in the T-for-H exchange reaction

International Nuclear Information System (INIS)

Tamura, Kiyoshi; Imaizumi, Hiroshi; Kano, Naoki

2007-01-01

In order to quantitatively evaluate the influence of tritium ( 3 He or T) on various functional groups in environment, the hydrogen isotope exchange reaction (T-for-H exchange reaction) between tritium-labeled poly-(vinyl alcohol) and each aliphatic cyclic alcohol (or carboxylic acid) has been dynamically observed in the range of 50 to 90degC. Consequently, the activities of the aliphatic cyclic alcohol and carboxylic acid increased with increasing reaction time. Applying in A''-McKay plot method to the observed data, the rate constants (k) for these materials were obtained. Using the k, the relation between the number of carbon atoms in the ring in each alcohol and the reactivity of the alcohol was quantitatively compared. Then, to clarify the effect of relative atomic charge of O atom (connected with the H atom in the hydroxy (or carboxy) group in the material) on the reactivity of the material, the MOPAC method was used. From both the above-mentioned and the obtained previously, the following nine items were found as to aliphatic cyclic alcohols (and carboxylic acids) in the T-for-H exchange reaction. (1) The reactivity of aliphatic cyclic alcohols (and carboxylic acids) depends on the temperature. (2) The reactivity of the cyclic materials decreases with increasing number of carbon atoms in the ring. (3) The reactivity of the aliphatic cyclic carboxylic acid seems to be smaller than that of aliphatic cyclic alcohol, and be larger than that of aliphatic cyclic amine. (4) For aliphatic cyclic alcohols, correlation exists between k and relative atomic charges of O atom obtained by the MOPAC method, but the tendency for aliphatic cyclic carboxylic acid is not clear. (5) As to having the same number of carbon atoms in each ring, the reactivity of the aliphatic cyclic carboxylic acid including the side chain is smaller than of the aliphatic cyclic carboxylic acid including no side chain. (6) The reactivity of aliphatic cyclic carboxylic acid is larger than that of

Ionizing radiation - one of the most important link of the energetic chain in biological cell

Energy Technology Data Exchange (ETDEWEB)

Goraczko, W. [Technical Univ. Poznan, Radio- and Photochemistry Dept., Poznan (Poland)

1999-09-01

High (large) and low (small) doses of ionizing radiation consistently induce opposite physiologic effects in biological systems. The effects of low doses cannot be inferred by interpolation between the result from groups exposed to high doses and controls irradiated only by Natural Background Radiation. Stimulation ('bio-positive') effects by low-level doses of ionizing radiation are called radiation hormesis. It is still controversial idea, however it was found that some biological objects (yeast, seeds, animals) after gamma irradiation by low-level doses (10-50 times more NBR) can increase their development. The result of present researches demonstrate that the excitation of living system by gamma quanta (high energy) initiates prolonged secondary emission that influences biota and activates many important processes in biological systems. According to the excitation theory of bio-molecules the author suggests that gamma irradiation in low-level doses excites such molecules as DNA and proteins, and this being followed by a long-termed secondary coherent radiation. The spectral analysis of this secondary emission confirmed the contribution of the UV component to the total emission. The data obtaining by using SPC method (single photon counting) make possible a partial understanding of the radiation hormesis phenomenon and suggest closer relationship to UV emission from biological systems during mitotic processes. The experiments with humic acid (high doses) and glycine (low doses) confirm the author hypothesis that gamma-irradiated organic compounds are capable to emit secondary radiation. This secondary radiation probably plays very significant role in the intercellular communication inside the living systems. In conclusion the author proposed de-excitation processes in bio-molecules as a common denominator of UV and ionizing radiation interacting with living cells. Finally he refers to the Cerenkov radiation which is created inside the biological cells

Ionizing radiation - one of the most important link of the energetic chain in biological cell

International Nuclear Information System (INIS)

Goraczko, W.

1999-01-01

High (large) and low (small) doses of ionizing radiation consistently induce opposite physiologic effects in biological systems. The effects of low doses cannot be inferred by interpolation between the result from groups exposed to high doses and controls irradiated only by Natural Background Radiation. Stimulation ('bio-positive') effects by low-level doses of ionizing radiation are called radiation hormesis. It is still controversial idea, however it was found that some biological objects (yeast, seeds, animals) after gamma irradiation by low-level doses (10-50 times more NBR) can increase their development. The result of present researches demonstrate that the excitation of living system by gamma quanta (high energy) initiates prolonged secondary emission that influences biota and activates many important processes in biological systems. According to the excitation theory of bio-molecules the author suggests that gamma irradiation in low-level doses excites such molecules as DNA and proteins, and this being followed by a long-termed secondary coherent radiation. The spectral analysis of this secondary emission confirmed the contribution of the UV component to the total emission. The data obtaining by using SPC method (single photon counting) make possible a partial understanding of the radiation hormesis phenomenon and suggest closer relationship to UV emission from biological systems during mitotic processes. The experiments with humic acid (high doses) and glycine (low doses) confirm the author hypothesis that gamma-irradiated organic compounds are capable to emit secondary radiation. This secondary radiation probably plays very significant role in the intercellular communication inside the living systems. In conclusion the author proposed de-excitation processes in bio-molecules as a common denominator of UV and ionizing radiation interacting with living cells. Finally he refers to the Cerenkov radiation which is created inside the biological cells. Because

Experimental and Theoretical Studies on Corrosion Inhibition of Niobium and Tantalum Surfaces by Carboxylated Graphene Oxide

Directory of Open Access Journals (Sweden)

Valbonë Mehmeti

2018-05-01

Full Text Available The corrosion of two different metals, niobium and tantalum, in aqueous sulfuric acid solution has been studied in the presence and absence of carboxylated graphene oxide. Potentiodynamic measurements indicate that this nanomaterial inhibits corrosion due to its adsorption on the metal surfaces. The adsorbed layer of carboxylated graphene hinders two electrochemical reactions: the oxidation of the metal and the transport of metal ions from the metal to the solution but also hydrogen evolution reaction by acting as a protective barrier. The adsorption behavior at the molecular level of the carboxylated graphene oxide with respect to Nb, NbO, Ta, and TaO (111 surfaces is also investigated using Molecular Dynamic and Monte Carlo calculations.

Effect of carboxyl anchoring groups in asymmetric zinc phthalocyanine with large steric hindrance on the dye-sensitized solar cell performance

Energy Technology Data Exchange (ETDEWEB)

Shi, Wenye; Peng, Bosi; Lin, Li; Li, Renjie; Zhang, Jing, E-mail: jzhang03@whu.edu.cn; Peng, Tianyou, E-mail: typeng@whu.edu.cn

2015-08-01

Asymmetric zinc phthalocyanines containing tribenzonaphtho-condensed porphyrazine with six bulky diphenylphenoxy and one or two carboxyl groups are used as sensitizers for dye-sensitized solar cells (DSSCs). It is found that Zn-tri-PcNc-4 having two carboxyl groups shows a slight redshift in the Q-band absorption but a significantly decreased absorbance as compared with Zn-tri-PcNc-8 having one carboxyl group, and Zn-tri-PcNc-4 can be more stably and perpendicularly grafted onto the TiO{sub 2} surface than Zn-tri-PcNc-8, which further leads to the differences in the interfacial charge transfer dynamics and dye-loaded amount. Zn-tri-PcNc-4 with two carboxyl groups grafted onto the TiO{sub 2} electrode surface of DSSC results in a photovoltaic conversion efficiency of 3.22%, higher than that (3.01%) of the analog with one carboxyl group (Zn-tri-PcNc-8), which exhibits a lower short-circuit current but much higher open-circuit voltage. The additional carboxyl group in Zn-tri-PcNc-4 leads to the enhanced dye-loaded amount and the molecular orbital energy level shift toward positive direction, causing more efficient electron injection and higher short-circuit current than Zn-tri-PcNc-8; while the two carboxyl groups of Zn-tri-PcNc-4 would cause more protonation of TiO{sub 2} surface, which possibly leads to the downward shift of TiO{sub 2} conduction band edge, and then to the decreased open-circuit voltage. The present results demonstrate the molecular engineering aspect of ZnPc dyes in which the fine tuning of the energy levels and molecular structures is crucial for high conversion efficiency of DSSCs. - Highlights: • ZnPcs with six diphenylphenoxy and one/two carboxyl groups are used as dyes for DSSCs. • Effect of carboxyl group number on the ZnPc-sensitized cell property are scrutinized. • Grafting two carboxyl groups on ZnPc leads to the enhanced photocurrent and efficiency. • ZnPc with one COOH has a higher open-circuit voltage than its analog with two

Two types of essential carboxyl groups in Rhodospirillum rubrum proton ATPase

International Nuclear Information System (INIS)

Ceccarelli, E.; Vallejos, R.H.

1983-01-01

Two different types of essential carboxyl groups were detected in the extrinsic component of the proton ATPase of Rhodospirillum rubrum. Chemical modification of R. rubrum chromatophores or its solubilized ATPase by Woodward's reagent K resulted in inactivation of photophosphorylating and ATPase activities. The apparent order of reaction was nearly 1 with respect to reagent concentration and similar K1 were obtained for the soluble and membrane-bound ATPases suggesting that inactivation was associated with modification of one essential carboxyl group located in the soluble component of the proton ATPase. Inactivation was prevented by adenine nucleotides but not by divalent cations. Dicyclohexylcarbodiimide completely inhibited the solubilized ATPase with a K1 of 5.2 mM and a K2 of 0.81 min-1. Mg2+ afforded nearly complete protection with a Kd of 2.8 mM. Two moles of [14C]dicyclohexylcarbodiimide were incorporated per mole of enzyme for complete inactivation but in the presence of 30 mM MgCl2 only one mole was incorporated and there was no inhibition. The labeling was recovered mostly from the beta subunit. The incorporation of the labeled reagent into the ATPase was not prevented by previous modification with Woodward's reagent K. It is concluded that both reagents modified two different essential carboxyl groups in the soluble ATPase from R. rubrum

Chemo-spectroscopic sensor for carboxyl terminus overexpressed in carcinoma cell membrane.

Science.gov (United States)

Stanca, Sarmiza E; Matthäus, Christian; Neugebauer, Ute; Nietzsche, Sandor; Fritzsche, Wolfgang; Dellith, Jan; Heintzmann, Rainer; Weber, Karina; Deckert, Volker; Krafft, Christoph; Popp, Jürgen

2015-10-01

Certain carboxyl groups of the plasma membrane are involved in tumorgenesis processes. A gold core-hydroxyapatite shell (AuHA) nanocomposite is introduced as chemo-spectroscopic sensor to monitor these carboxyl groups of the cell membrane. Hydroxyapatite (HA) plays the role both of a chemical detector and of a biocompatible Raman marker. The principle of detection is based on chemical interaction between the hydroxyl groups of the HA and the carboxyl terminus of the proteins. The AuHA exhibits a surface enhanced Raman scattering (SERS) signal at 954 cm(-1) which can be used for its localization. The bio-sensing capacity of AuHA towards human skin epidermoid carcinoma (A431) and Chinese hamster ovary (CHO) cell lines is investigated using Raman microspectroscopic imaging. The localization of AuHA on cells is correlated with scanning electron microscopy, transmission electron microscopy and structured illumination fluorescence microscopy. This qualitative approach is a step towards a quantitative study of the proteins terminus. This method would enable further studies on the molecular profiling of the plasma membrane, in an attempt to provide accurate cell identification. Using a gold core-hydroxyapatite shell (AuHA) nanocomposite, the authors in this paper showed the feasibility of detecting and differentiating cell surface molecules by surface enhanced Raman scattering. Copyright © 2015 Elsevier Inc. All rights reserved.

Heterocycles [h]-Fused Onto 4-Oxoquinoline-3-Carboxylic Acid, Part VIII [1]. Convenient Synthesis and Antimicrobial Properties of Substituted Hexahydro[1,4]diazepino[2,3-h]quinoline-9-carboxylic acid and Its Tetrahydroquino[7,8-b]benzodiazepine Analog

Directory of Open Access Journals (Sweden)

Yusuf M. Al-Hiari

2008-11-01

Full Text Available [1,4]Diazepino[2,3-h]quinolone carboxylic acid 3 and its benzo-homolog tetrahydroquino[7,8-b]benzodiazepine-3-carboxylic acid 5 were prepared via PPAcatalyzed thermal lactamization of the respective 8-amino-7-substituted-1,4-dihydroquinoline-3-carboxylic acid derivatives 8, 10. The latter compounds were obtained by reduction of their 8-nitro-7-substituted-1,4-dihydroquinoline-3-carboxylic acid precursors 7, 9 which, in turn, were prepared by reaction of 7-chloro-1-cyclopropyl-6-fluoro-8-nitro-1,4-dihydroquinoline-3-carboxylic acid (6 with each of β-alanine and anthranilic acid. All intermediates and target compounds were characterized using elemental analysis, NMR, IR and MS spectral data. The prepared targets and the intermediates have shown interesting antibacterial activity mainly against Gram positive strains. In particular, compound 8 showed good activity against S. aureus (MIC = 0.39 μg/mL and B. subtilis (MIC = 0.78 μg/mL. Compounds 5a and 9 have also displayed good antifungal activity against C. albicans (MIC = 1.56 μg/mL and 0.78 μg/mL, respectively. None of the compounds tested showed any anticancer activity against solid breast cancer cell line MCF-7 cells or a human breast adenocarcinoma cell line.

Synthesis, crystal structures, and luminescent properties of two series' of new lanthanide (III) amino-carboxylate-phosphonates.

Science.gov (United States)

Zhou, Tian-Hua; Yi, Fei-Yan; Li, Pei-Xin; Mao, Jiang-Gao

2010-02-01

Hydrothermal reactions of lanthanide(III) chlorides with 4-HOOC-C(6)H(4)-CH(2)NHCH(2)PO(3)H(2) (H(3)L) at different ligand-to-metal (L/M) ratios afforded nine new lanthanide(III) carboxylate-phosphonates with two types of 3D network structures, namely, LnCl(HL)(H(2)O)(2) (Ln = Sm, 1; Eu, 2; Gd, 3; Tb, 4; Dy, 5; Er, 6) and [Ln(2)(HL)(H(2)L)(L)(H(2)O)(2)].4H(2)O (Ln = Nd, 7; Sm, 8; Eu, 9). Compounds 1-6 are isostructural and feature a 3D network in which the LnO(7)Cl polyhedra are interconnected by bridging CPO(3) tetrahedra into 2D inorganic layers parallel to the bc plane. These layers are further cross-linked by organic groups of the carboxylate-phosphonate ligands via the coordination of the carboxylate groups into a pillared-layered architecture. Compounds 7-9 are also isostructural and feature a 3D open-framework composed of 1D lanthanide(III) phosphonate inorganic slabs which are further bridged by organic groups of the carboxylate-phosphonate liagnds via the coordination of the carboxylate groups, forming large 1D tunnels along the b-axis which are filled by lattice water molecules. Luminescent measurements indicate that compounds 2, 4, and 5 show strong emission bands in red, green, and yellow light region, respectively. Magnetic properties of 2, 3, 5, and 7 have also been studied.

A Concise Synthesis and the Antibacterial Activity of 5,6-Dimethoxynaphthalene-2-carboxylic Acid

OpenAIRE

GÖKSU, Süleyman; UĞUZ, Metin Tansu

2014-01-01

5,6-Dimethoxynaphthalene-2-carboxylic acid was synthesized in 7 steps and with an overall yield of 46%. Bromination of 2-naphthol, and methylation with dimethyl sulfate followed by Friedel-Crafts acylation with AcCl gave 2-acetyl-5-bromo-6-methoxynaphthalene. 2-Acetyl-5-bromo-6-methoxynaphthalene was converted to 5-bromo-6- methoxynaphthalene-2-carboxylic acid by a haloform reaction. The esterification of the acid with methanol, methoxylation with NaOCH3 in the presence of CuI and s...

Carboxylated fullerene at the oil/water interface

OpenAIRE

Li, R; Chai, Y; Jiang, Y; Ashby, PD; Toor, A; Russell, TP

2017-01-01

© 2017 American Chemical Society. The self-assembly of carboxylated fullerene with poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) with different molecular weights, poly-2-vinylpyridine, and amine-terminated polystyrene, at the interface between toluene and water was investigated. For all values of the pH, the functionalized fullerene interacted with the polymers at the water/toluene interface, forming a nanoparticle network, reducing the interfacial tension. At pH values of 4.84 and 7.8, robust,...

Specific determination of clinical and toxicological important substances in biological samples by LC-MS

International Nuclear Information System (INIS)

Mitulovic, G.

2001-02-01

This thesis of this dissertation is the specific determination of clinical and toxicological important substances in biological samples by LC-MS. Nicotine was determined in serum after application of nicotine plaster and nicotine nasal spray with HPLC-ESI-MS. Cotinine was determined direct in urine with HPLC-ESI-MS. Short time anesthetics were determined in blood and cytostatics were determined in liquor with HPLC-ESI-MS. (botek)

Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

Science.gov (United States)

Vaïtilingom, M.; Charbouillot, T.; Deguillaume, L.; Maisonobe, R.; Parazols, M.; Amato, P.; Sancelme, M.; Delort, A.-M.

2011-08-01

The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H2O2) as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10-10-10-11 M s-1). The chemical composition (marine or continental origin) had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5. In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH) radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10-12 M) led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10-14 M), microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach. Combining these two approaches (experimental and theoretical), our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more efficient than its biodegradation; the biodegradation of acetate and succinate seemed to exceed their photodegradation.

The investigation of the reactions of some pyrazole-3-carboxylic acids with various diamines and diols

Directory of Open Access Journals (Sweden)

Rahmi Kasımoğulları

2012-06-01

Full Text Available In this study, some new derivatives were synthesized of 4-benzoyl-1-(3-nitrophenyl-5-phenyl-1H-pyrazole-3-carboxylic acid (1 and 4-(ethoxycarbonyl-1-(3-nitrophenyl-5-phenyl-1H-pyrazole-3-carboxylic acid (2 that they were pyrazole carboxylic acid derivatives. Firstly, 1 and 2 reacted with SOCl2 to transform them into acyl chlorides (3, 4. Then various bis-carboxamide derivatives (5–8 were obtained from the reaction of 3 and 4 with various diamines and also a ;#946;-hydroxy ester (9 derivative was obtained from the reaction of 3 with ethylene glycol. The structures of synthesized compounds were elucidated with using FT-IR, 1H NMR, 13C NMR and elemental analysis methods.

Hydrothermal syntheses, characterizations and crystal structures of a new lead(II) carboxylate-phosphonate with a double layer structure and a new nickel(II) carboxylate-phosphonate containing a hydrogen-bonded 2D layer with intercalation of ethylenediamines

International Nuclear Information System (INIS)

Song, J.-L.; Mao, J.-G.; Sun, Y.-Q.; Zeng, H.-Y.; Kremer, R.K.; Clearfield, Abraham

2004-01-01

Hydrothermal reactions of N,N-bis(phosphonomethyl)aminoacetic acid (HO 2 CCH 2 N(CH 2 PO 3 H 2 ) 2 ) with metal(II) salts afforded two new metal carboxylate-phosphonates, namely, Pb 2 [O 2 CCH 2 N(CH 2 PO 3 )(CH 2 PO 3 H)]·H 2 O (1) and {NH 3 CH 2 CH 2 NH 3 }{Ni[O 2 CCH 2 N(CH 2 PO 3 H) 2 ](H 2 O) 2 } 2 (2). Among two unique lead(II) ions in the asymmetric unit of complex 1, one is five coordinated by five phosphonate oxygen atoms from 5 ligands, whereas the other one is five-coordinated by a tridentate chelating ligand (1 N and 2 phosphonate O atoms) and two phosphonate oxygen atoms from two other ligands. The carboxylate group of the ligand remains non-coordinated. The bridging of above two types of lead(II) ions through phosphonate groups resulted in a double layer with the carboxylate group of the ligand as a pendant group. These double layers are further interlinked via hydrogen bonds between the carboxylate groups into a 3D network. The nickel(II) ion in complex 2 is octahedrally coordinated by a tetradentate chelating ligand (two phosphonate oxygen atoms, one nitrogen and one carboxylate oxygen atoms) and two aqua ligands. These {Ni[O 2 CCH 2 N(CH 2 PO 3 H) 2 ][H 2 O] 2 } - anions are further interlinked via hydrogen bonds between non-coordinated phosphonate oxygen atoms to form a hydrogen bonded 2D layer. The 2H-protonated ethylenediamine cations are intercalated between two layers, forming hydrogen bonds with the non-coordinated carboxylate oxygen atoms. Results of magnetic measurements for complex 2 indicate that there is weak Curie-Weiss behavior with θ=-4.4 K indicating predominant antiferromagnetic interaction between the Ni(II) ions. Indication for magnetic low-dimension magnetism could not be detected

Coupling chemical and biological catalysis: a flexible paradigm for producing biobased chemicals.

Science.gov (United States)

Schwartz, Thomas J; Shanks, Brent H; Dumesic, James A

2016-04-01

Advances in metabolic engineering have allowed for the development of new biological catalysts capable of selectively de-functionalizing biomass to yield platform molecules that can be upgraded to biobased chemicals using high efficiency continuous processing allowed by heterogeneous chemical catalysis. Coupling these disciplines overcomes the difficulties of selectively activating COH bonds by heterogeneous chemical catalysis and producing petroleum analogues by biological catalysis. We show that carboxylic acids, pyrones, and alcohols are highly flexible platforms that can be used to produce biobased chemicals by this approach. More generally, we suggest that molecules with three distinct functionalities may represent a practical upper limit on the extent of functionality present in the platform molecules that serve as the bridge between biological and chemical catalysis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of Carboxylic Acids and Water-soluble Inorganic Ions ...

African Journals Online (AJOL)

Atmospheric aerosol samples of PM2.5 and PM10 were collected in April–May 2011 from a rural site in Tanzania and analyzed for water-soluble inorganic ions and low molecular weight carboxylic acids using ion chromatography. PM2.5 and PM10 low-volume samplers with quartz fibre filters were deployed and aerosol ...

Metal extraction by amides of carboxylic acids

International Nuclear Information System (INIS)

Skorovarov, D.I.; Chumakova, G.M.; Rusin, L.I.; Ul'anov, V.S.; Sviridova, R.A.; Sviridov, A.L.

1988-01-01

Extraction ability of various amides was studied. Data on extraction of rare earths, vanadium, molybdenum, rhenium, uranium, niobium, tantalum by N,N-dibutyl-amides of acetic, nonanic acids and fatly synthetic acids of C 7 -C 9 fractions are presented. Effect of salting-out agents, inorganic acid concentrations on extraction process was studied. Potential ability of using amides of carboxylic acids for extractional concentration of rare earths as well as for recovery and separation of iron, rhenium, vanadium, molybdenum, uranium, niobium, and tantalum was shown

Substrate specificity within a family of outer membrane carboxylate channels.

Directory of Open Access Journals (Sweden)

Elif Eren

2012-01-01

Full Text Available Many Gram-negative bacteria, including human pathogens such as Pseudomonas aeruginosa, do not have large-channel porins. This results in an outer membrane (OM that is highly impermeable to small polar molecules, making the bacteria intrinsically resistant towards many antibiotics. In such microorganisms, the majority of small molecules are taken up by members of the OprD outer membrane protein family. Here we show that OprD channels require a carboxyl group in the substrate for efficient transport, and based on this we have renamed the family Occ, for outer membrane carboxylate channels. We further show that Occ channels can be divided into two subfamilies, based on their very different substrate specificities. Our results rationalize how certain bacteria can efficiently take up a variety of substrates under nutrient-poor conditions without compromising membrane permeability. In addition, they explain how channel inactivation in response to antibiotics can cause resistance but does not lead to decreased fitness.

Versatile Multicomponent Reaction Macrocycle Synthesis Using α-Isocyano-ω-carboxylic Acids

NARCIS (Netherlands)

Liao, George P; Abdelraheem, Eman M M; Neochoritis, Constantinos G; Kurpiewska, Katarzyna; Kalinowska-Tłuścik, Justyna; McGowan, David C; Dömling, Alexander

2015-01-01

The direct macrocycle synthesis of α-isocyano-ω-carboxylic acids via an Ugi multicomponent reaction is introduced. This multicomponent reaction (MCR) protocol differs by being especially short, convergent, and versatile, giving access to 12-22 membered rings.

Carboxylated SiO2-coated α-Fe nanoparticles: towards a versatile platform for biomedical applications.

Science.gov (United States)

Kohara, Kaori; Yamamoto, Shinpei; Seinberg, Liis; Murakami, Tatsuya; Tsujimoto, Masahiko; Ogawa, Tetsuya; Kurata, Hiroki; Kageyama, Hiroshi; Takano, Mikio

2013-03-28

Carboxylated SiO2-coated α-Fe nanoparticles have been successfully prepared via CaH2-mediated reduction of SiO2-coated Fe3O4 nanoparticles followed by surface carboxylation. These α-Fe-based nanoparticles, which are characterized by ease of coating with additional functional groups, a large magnetization of 154 emu per g-Fe, enhanced corrosion resistivity, excellent aqueous dispersibility, and low cytotoxicity, have potential to be a versatile platform in biomedical applications.

Influence of carboxyl group formation on ammonia adsorption of NiO-templated nanoporous carbon surfaces

Energy Technology Data Exchange (ETDEWEB)

Meng, Long-Yue [Department of Chemistry, Inha University, 100 Inharo, Nam-gu, Incheon 402-751 (Korea, Republic of); Park, Soo-Jin, E-mail: sjpark@inha.ac.kr [Department of Chemistry, Inha University, 100 Inharo, Nam-gu, Incheon 402-751 (Korea, Republic of)

2012-11-15

The scope of this work was to control the surface functional groups of nanoporous carbons (NPs) by oxidizing agents (nitric acid and hydrogen peroxide) treatments and to investigate the relation between carboxyl group and ammonia removal efficiency. The NPs were directly prepared from a cation exchange resin by the carbonization of a mixture with Ni acetate at 900 Degree-Sign C. N{sub 2}/-196 Degree-Sign C adsorption, Boehm's titrations, and X-ray photoelectron spectroscopy (XPS) analyzes were employed to confirm the physicochemical properties of NPs. The ammonia removal efficiency was confirmed by temperature programmed desorption (TPD) technique. In the result, the oxygen content of NPs increased after various treatments and the highest content of carboxyl group formation appeared at a 2:3 volume ratio of HNO{sub 3}/H{sub 2}O{sub 2}. It was also found that the oxidation treatment led to an increase in ammonia removal efficiency of NPs, mainly due to an increase of acid oxygen functional groups (such as carboxyl) on NPs surfaces. -- Graphical abstract: The nanoporous carbons were prepared from an exchange resin by the carbonization of a mixture with Ni acetate for ammonia adsorption. Highlights: Black-Right-Pointing-Pointer The carbons were prepared from an exchange resin by the carbonization of a mixture with Ni acetate. Black-Right-Pointing-Pointer The carbon surfaces were modified with HNO{sub 3}/H{sub 2}O{sub 2} solution at different volume radio. Black-Right-Pointing-Pointer The highest content of carboxyl group formation appeared at a 2:3 volume ratio of HNO{sub 3}/H{sub 2}O{sub 2}. Black-Right-Pointing-Pointer The acid oxygen functional groups (such as carboxyl) on carbon surfaces led to an increase in ammonia adsorption.

Synthesis of first row transition metal carboxylate complexes by ring ...

Indian Academy of Sciences (India)

tion of pyromellitic dianhydride with methanol and ring opening of pyromellitic dianhydride takes place. The corresponding carboxylate complex formed dur- ing the process can be crystallised by adding biden- tate nitrogen donor ligands such as 1,10-phenanthroline or 2,2 - bipyridine.20 From the reaction with 1,10-.

Thermodynamic studies of the complexation of plutonium(IV) by linear and macrocyclic poly-amino-carboxylate ligands

International Nuclear Information System (INIS)

Burgat, Romain

2007-01-01

In the framework of a collaboration between the CEA (Commissariat a l Energie Atomique) of Valduc and the ICMUB (Institut de Chimie Moleculaire de l Universite de Bourgogne), a study platform of the structural and physico-chemical properties of the radioelements U, Pu and Am complexes has been implemented. The plutonium(IV) complexation has been studied in a molar nitrate medium. The affinity of three linear poly-amino-carboxylates (EDTA, CDTA and DTPA) towards plutonium(IV) has then been estimated. For the three ligands, the formation constants of the monoleptic complexes Pu(EDTA), Pu(CDTA) and [Pu(DTPA)] - have been determined in a (H,K)NO 3 1 M medium and then extrapolated at a zero ionic force with the specific interactions theory (SIT). For the three complexes, mono-hydroxylated monoleptic species have been observed. With the EDTA and the CDTA, protonated dileptic complexes of a general formula [Pu(L) 2 H h ] (4-h)- have been revealed too. Nevertheless, the steric hindrance around the metallic center is too important to allow to a second molecule of DTPA to coordinate the Pu 4+ cation. The exclusive formation of the species [Pu(DTPA)] - and [Pu(DTPA)(OH)] 2- has been confirmed by capillary electrophoresis (EC-ICP-MS). On account of the preliminary results obtained during the titration of the cyclame tetraacetic product (TETRA) in presence of plutonium(IV), the adding of a competitive ligand such as EDTA has been considered for the study of the complexation of this radioelement by macrocyclic ligands. At last, the affinity of different macrocyclic ligands containing either four amide functions (TETAMMe 2 and TETAMMEt 2 ) or carboxylate groups (TETA, DOTPr and TETPr) towards lanthanides(III) has been estimated too. Although the complexation reaction be fast with the two first ligands, these complexes are less stable than those formed with the carboxylic macrocycles. (O.M.)

Guest-host chemistry with dendrimers—binding of carboxylates in aqueous solution

DEFF Research Database (Denmark)

Ficker, Mario; Petersen, Johannes Fabritius; Hansen, Jon Stefan

2015-01-01

Recognition and binding of anions in water is difficult due to the ability of water molecules to form strong hydrogen bonds and to solvate the anions. The complexation of two different carboxylates with 1-(4-carbomethoxypyrrolidone)-terminated PAMAM dendrimers was studied in aqueous solution using...... the carboxylate-dendrimer interaction selectively. The binding stoichiometry for 3-hydroxy-2-naphthoate was found to be two strongly bound guest molecules per dendrimer and an additional 40 molecules with weak binding affinity. The NOESY NMR showed a clear binding correlation of sodium 3-hydroxy-2-naphthoate...... with the lyophilic dendrimer core, possibly with the two high affinity guest molecules. In comparison, sodium 2-naphthoate showed a weaker binding strength and had a stoichiometry of two guests per dendrimer with no additional weakly bound guests. This stronger dendrimer interaction with sodium 3-hydroxy-2...

Importance of the hexagonal lipid phase in biological membrane organisation

Directory of Open Access Journals (Sweden)

Juliette eJouhet

2013-12-01

Full Text Available Abstract:Domains are present in every natural membrane. They are characterised by a distinctive protein and/or lipid composition. Their size is highly variable from the nano- to the micrometer scale. The domains confer specific properties to the membrane leading to original structure and function. The determinants leading to domain organisation are therefore important but remain obscure. This review presents how the ability of lipids to organize into hexagonal II or lamellar phases can promote particular local structures within membranes. Since biological membranes are composed of a mixture of lipids, each with distinctive biophysical properties, lateral and transversal sorting of lipids can promote creation of domains inside the membrane through local modulation of the lipid phase. Lipid biophysical properties have been characterized for long based on in vitro analyses using non-natural lipid molecules; their re-examinations using natural lipids might open interesting perspectives on membrane architecture occurring in vivo in various cellular and physiological contexts.

Importance of the hexagonal lipid phase in biological membrane organization.

Science.gov (United States)

Jouhet, Juliette

2013-01-01

Domains are present in every natural membrane. They are characterized by a distinctive protein and/or lipid composition. Their size is highly variable from the nano- to the micrometer scale. The domains confer specific properties to the membrane leading to original structure and function. The determinants leading to domain organization are therefore important but remain obscure. This review presents how the ability of lipids to organize into hexagonal II or lamellar phases can promote particular local structures within membranes. Since biological membranes are composed of a mixture of lipids, each with distinctive biophysical properties, lateral and transversal sorting of lipids can promote creation of domains inside the membrane through local modulation of the lipid phase. Lipid biophysical properties have been characterized for long based on in vitro analyses using non-natural lipid molecules; their re-examinations using natural lipids might open interesting perspectives on membrane architecture occurring in vivo in various cellular and physiological contexts.

Synthesis and biological evaluation of (3-arylisoxazol-5-yl methyl 6-fluoro-4-oxo-4H-chromene-2-carboxylates as antioxidant and antimicrobial agents

Directory of Open Access Journals (Sweden)

Battula Kumaraswamy

2017-01-01

Full Text Available A series of novel (3-aryl-1,2-oxazol-5-yl methyl 6-fluoro-4-oxo-4H- -chromene-2-carboxylate derivatives (C1-C12 were synthesized by Cu (I catalyzed reaction of in situ generated nitrile oxides with prop-2-yn-1-yl 6-fluoro-4-oxo-4H-chromene-2-carboxylate in good yields and investigated their antioxidant and antimicrobial activities. Among all the synthesized compounds, C1 (IC50: 16.43 ± 0.57 μM and C12 (IC50:15.98 ± 0.72 μM have registered good antioxidant activity as compared to the standard drug Trolox. Compound-C1, C3, and C6 have registered very good inhibition against all gram-positive and gram-negative bacterial strains with MIC values ranging from 9.375 to 37.5 (μg mL-1. Compound-C7, C8, C9, C10, and C11 have registered good inhibition against B. subtilis and S. aureus with MIC values ranging from 18.75 to 37.5 (μg mL-1. Compound-C10 and C11 against P. aero-ginosa have shown prominent activity than the standard drug Penicillin (MIC: 12.5 μg mL-1 with MIC 9.375 μg mL-1 (~ 1.33 fold potent than Penicillin. Compound-C7, C8, and C9 have registered good to moderate antifungal activity against four tested fungal strains with MIC values ranging from 18.75 and 37.5 μg mL-1

Synthesis and protonation behavior of carboxylate-functionalized poly(propylene imine) dendrimers

NARCIS (Netherlands)

Duijvenbode, van R.C.; Rajanayagam, A.; Koper, G.J.M.; Baars, M.W.P.L.; Waal, de B.F.M.; Meijer, E.W.; Borkovec, M.

2000-01-01

Five generations of carboxylate-functionalized poly(propyleneimine) dendrimers have been synthesized starting from a double Michael addition of amine-functionalized poly(propyleneimine) dendrimers to methyl acrylate followed by basic hydrolysis using LiOH in a water/methanol mixture. The dendritic

(Liquid + liquid) equilibria measurements for ternary systems (sulfolane + a carboxylic acid + n-heptane) at T = 303.15 K and at 0.1 MPa

International Nuclear Information System (INIS)

Cele, N.P.; Bahadur, I.; Redhi, G.G.; Ebenso, E.E.

2016-01-01

Highlights: • The (liquid + liquid) equilibrium for (sulfolane + a carboxylic acid + heptane) was measured. • Selectivity values for solvent separation efficiency were calculated. • Separation of carboxylic acids from heptane is feasible by extraction. • Three parameter equations have been fitted to the binodal curve data. • The NRTL and UNIQUAC models were used to correlate the experimental data. - Abstract: In the present work, new (liquid + liquid) equilibrium (LLE) values are reported for ternary systems {sulfolane(1) + acetic acid, or propanoic acid, or butanoic acid, or 2-methylpropanoic acid, or pentanoic acid, or 3-methylbutanoic acid (2) + n-heptane (3)} at T = 303.15 K and at p = 0.1 MPa. The mutual solubility of carboxylic acid in sulfolane is dependent on the length and structure of the alkyl chain of the carboxylic acid; it progressively increases with an increase in the alkyl chain of the carboxylic acid. The single phase homogenous region increases as the alkyl chain of the carboxylic acid increases. The n-heptane is most soluble in the carboxylic acid mixtures with long alkyl chain, that is, (3-methylbutanoic acid + sulfolane) and (pentanoic acid + sulfolane) systems and least soluble in the carboxylic acid with short alkyl chain (acetic acid + sulfolane) system. Carboxylic acid together with many other oxygenates and hydrocarbons are produced by SASOL Company in South Africa using the Fischer–Tropsch process. The details about this process are given in introduction section. The NRTL and UNIQUAC models were used to correlate the experimental tie-lines and to calculate the phase compositions of the ternary systems. It was found that the NRTL model fits the experimental values significantly better than the UNIQUAC model.

Concomitant carboxylate and oxalate formation from the activation of CO{sub 2} by a thorium(III) complex

Energy Technology Data Exchange (ETDEWEB)

Formanuik, Alasdair; Ortu, Fabrizio; Mills, David P. [School of Chemistry, The University of Manchester (United Kingdom); Inman, Christopher J. [Department of Chemistry and Biochemistry, School of Life Sciences, University of Sussex, Brighton (United Kingdom); Kerridge, Andrew [Department of Chemistry, Lancaster University (United Kingdom); Castro, Ludovic; Maron, Laurent [LPCNO, CNRA et INSA, Universite Paul Sabatier, Toulouse (France)

2016-12-12

Improving our comprehension of diverse CO{sub 2} activation pathways is of vital importance for the widespread future utilization of this abundant greenhouse gas. CO{sub 2} activation by uranium(III) complexes is now relatively well understood, with oxo/carbonate formation predominating as CO{sub 2} is readily reduced to CO, but isolated thorium(III) CO{sub 2} activation is unprecedented. We show that the thorium(III) complex, [Th(Cp''){sub 3}] (1, Cp''={C_5H_3(SiMe_3)_2-1,3}), reacts with CO{sub 2} to give the mixed oxalate-carboxylate thorium(IV) complex [{Th(Cp'')_2[κ"2-O_2C{C_5H_3-3,3'-(SiMe_3)_2}]}{sub 2}(μ-κ{sup 2}:κ{sup 2}-C{sub 2}O{sub 4})] (3). The concomitant formation of oxalate and carboxylate is unique for CO{sub 2} activation, as in previous examples either reduction or insertion is favored to yield a single product. Therefore, thorium(III) CO{sub 2} activation can differ from better understood uranium(III) chemistry. (copyright 2016 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

Density functional theory prediction of pKa for carboxylated single-wall carbon nanotubes and graphene

Science.gov (United States)

Li, Hao; Fu, Aiping; Xue, Xuyan; Guo, Fengna; Huai, Wenbo; Chu, Tianshu; Wang, Zonghua

2017-06-01

Density functional calculations have been performed to investigate the acidities for the carboxylated single-wall carbon nanotubes and graphene. The pKa values for different COOH-functionalized models with varying lengths, diameters and chirality of nanotubes and with different edges of graphene were predicted using the SMD/M05-2X/6-31G* method combined with two universal thermodynamic cycles. The effects of following factors, such as, the functionalized position of carboxyl group, the Stone-Wales and single vacancy defects, on the acidity of the functionalized nanotube and graphene have also been evaluated. The deprotonated species have undergone decarboxylation when the hybridization mode of the carbon atom at the functionalization site changed from sp2 to sp3 both for the tube and graphene. The knowledge of the pKa values of the carboxylated nanotube and graphene could be of great help for the understanding of the nanocarbon materials in many diverse areas, including environmental protection, catalysis, electrochemistry and biochemistry.

Kinetic studies on the carboxylation of 6-amino-penicillanic acid to 8-hydroxy-penillic acid

DEFF Research Database (Denmark)

Henriksen, Claus Maxel; Holm, SS; Schipper, D.

1997-01-01

The carboxylation in aqueous solution of 6-amino-penicillanic acid (6-APA) to 8-hydroxy-penillic acid (8-HPA) was studied at 25 degrees C and pH 6.5. During sparging with either a citrate buffer or a chemically defined cultivation medium containing 6-APA with mixtures of carbon dioxide and air (2.......7-41% (v/v) CO2), the kinetics for conversion of 6-APA was followed by HPLC. In the citrate buffer 6-APA was converted by two competitive reactions each following first order kinetics with respect to the concentration of 6-APA: 1. carboxylation into 8-HPA; and 2. slow conversion into an unknown compound....... Formation of the unknown compound was not observed in the cultivation medium. The carboxylation of 6-APA was also found to be first order with respect to the concentration of dissolved carbon dioxide. The rate constant for formation of 8-HPA did not differ significantly in the cultivation medium compared...

Solvent-Free Esterification of Carboxylic Acids Using Supported Iron Oxide Nanoparticles as an Efficient and Recoverable Catalyst

Directory of Open Access Journals (Sweden)

Fatemeh Rajabi

2016-07-01

Full Text Available Supported iron oxide nanoparticles on mesoporous materials (FeNP@SBA-15 have been successfully utilized in the esterification of a variety carboxylic acids including aromatic, aliphatic, and long-chain carboxylic acids under convenient reaction conditions. The supported catalyst could be easily recovered after reaction completion and reused several times without any loss in activity after up to 10 runs.

Synthesis of aminocarbonyl N-acylhydrazones by a three-component reaction of isocyanides, hydrazonoyl chlorides, and carboxylic acids.

Science.gov (United States)

Giustiniano, Mariateresa; Meneghetti, Fiorella; Mercalli, Valentina; Varese, Monica; Giustiniano, Francesco; Novellino, Ettore; Tron, Gian Cesare

2014-10-17

A novel one-pot multicomponent synthesis of α-aminocarbonyl N-acylhydrazones starting from readily available hydrazonoyl chlorides, isocyanides, and carboxylic acids is reported. The strategy exploits the ability of the carboxylic acid as a third component to suppress all competing reactions between nitrile imines and isocyanides, channeling the course of the reaction toward the formation of this novel class of compounds.

A facile and novel approach towards carboxylic acid functionalization of multiwalled carbon nanotubes and efficient water dispersion

KAUST Repository

Rehman, Ata Ur

2013-10-01

A convenient, cheap and mild covalent functionalization route for multiwalled carbon nanotubes (MWCNTs) have been developed for the first time. The MWCNTs were treated with wet chemical oxidants (NaNO2/HCl, HNO3/H2O2) in order to modify MWCNTs with carboxyl groups. Surface functionality groups and morphology of MWCNTs were analyzed by FTIR, TGA, SEM and TEM. The results consistently confirmed the formation of carboxyl functionalities on MWCNTs, while the structure of MWCNTs has remained relatively intact. Functionalized MWCNTs showed good dispersion in aqueous media than untreated MWCNTs. Results show that NaNO2/HCl treatment is best suited for the chemical functionalization, giving optimum surface carboxyl groups and minimum length shortening of MWCNTs. © 2013 Elsevier B.V.

A facile and novel approach towards carboxylic acid functionalization of multiwalled carbon nanotubes and efficient water dispersion

KAUST Repository

Rehman, Ata Ur; Abbas, Syed Mustansar; Ammad, Hafiz Muhammad; Badshah, Amin; Ali, Zulfiqar; Anjum, Dalaver H.

2013-01-01

A convenient, cheap and mild covalent functionalization route for multiwalled carbon nanotubes (MWCNTs) have been developed for the first time. The MWCNTs were treated with wet chemical oxidants (NaNO2/HCl, HNO3/H2O2) in order to modify MWCNTs with carboxyl groups. Surface functionality groups and morphology of MWCNTs were analyzed by FTIR, TGA, SEM and TEM. The results consistently confirmed the formation of carboxyl functionalities on MWCNTs, while the structure of MWCNTs has remained relatively intact. Functionalized MWCNTs showed good dispersion in aqueous media than untreated MWCNTs. Results show that NaNO2/HCl treatment is best suited for the chemical functionalization, giving optimum surface carboxyl groups and minimum length shortening of MWCNTs. © 2013 Elsevier B.V.

Sodium effect on self-organization of amphiphilic carboxylates: formation of structured micelles and superlattices.

Science.gov (United States)

Rosenlehner, Karin; Schade, Boris; Böttcher, Christoph; Jäger, Christof M; Clark, Timothy; Heinemann, Frank W; Hirsch, Andreas

2010-08-16

Not only the self-aggregation of dendritic polycarboxylates into structurally persistent micelles, but also that of the micelles themselves into superlattices is controlled by alkali-metal counterions and shows a pronounced sodium effect. Our combined experimental and computational work has revealed the formation of superlattices for the first time. The behavior of a variety of amphiphilic carboxylates and the different effects of the alkali cations Li(+), Na(+), and K(+) have been investigated by conductivity measurements, cryogenic transmission electron microscopy (cryo-TEM), and molecular-dynamics (MD) simulations. Together, these show that sodium salts of the amphiphiles give the most stable micelles, followed by lithium and potassium. Our results suggest that ion multiplets in bridging positions, rather than contact ion pairs, are responsible for the enhanced stability and the formation of hexagonally ordered superlattices with sodium counterions. Potassium ions do not form such ion multiplets and cannot therefore induce aggregation of the micelles. This sodium effect has far-reaching consequences for a large number of biological and technical systems and sheds new light on the origin of specific-ion effects.

1-Allyl-3-amino-1H-pyrazole-4-carboxylic acid

Directory of Open Access Journals (Sweden)

Feng-Ling Yang

2008-12-01

Full Text Available The title compound, C7H9N3O2, was prepared by alkaline hydrolysis of ethyl 1-allyl-3-amino-1H-pyrazole-4-carboxylate. The crystal structure is stabilized by three types of intermolecular hydrogen bond (N—H...O, N—H...N and O—H...N.

[14C]-radiolabeling of {[trans-(8β)]-6-methyl-1-(1-methylethyl) ergoline-8-carboxylic acid, 4-methoxycyclohexyl ester (Z)-2-buteneidioate (1:1)}

International Nuclear Information System (INIS)

Marzoni, G.; Wheeler, W.J.; Garbrecht, W.L.

1988-01-01

The 5HT 2 -receptor antagonist, [ 14 C]-labeled brace[trans-(8β)]-6-methyl-1-(1-methylethyl)ergoline-8-carboxylic acid, 4-methoxycyclohexyl ester (Z)-2-butenedioate (1:1)brace (LY281067) was synthesized from unlabeled 6-methyl-1-(1-methylethyl)ergoline-8-carboxylic acid. The [ 14 C] label was introduced into the carboxyl group attached to the 8 position of the ergoline nucleus. This site is stable to metabolism. The synthesis involves removal of an unlabeled carboxyl group and subsequent reinsertion of a [ 14 C]-labeled carboxyl group into the same position. The radiolabel is not introduced until near the end of the synthesis which allows for ease of handling and scale-up of intermediates. (author)

The potential impact of carboxylic-functionalized multi-walled carbon nanotubes on trypsin: A Comprehensive spectroscopic and molecular dynamics simulation study.

Directory of Open Access Journals (Sweden)

Maryam Noordadi

Full Text Available In this study, we report a detailed experimental, binding free energy calculation and molecular dynamics (MD simulation investigation of the interactions of carboxylic-functionalized multi-walled carbon nanotubes (COOH-f-MWCNTs with porcine trypsin (pTry. The enzyme exhibits decreased thermostability at 330K in the presence of COOH-f-MWCNTs. Furthermore, the activity of pTry also decreases in the presence of COOH-f-MWCNTs. The restricted diffusion of the substrate to the active site of the enzyme was observed in the experiment. The MD simulation analysis suggested that this could be because of the blocking of the S1 pocket of pTry, which plays a vital role in the substrate selectivity. The intrinsic fluorescence of pTry is quenched with increase in the COOH-f-MWCNTs concentration. Circular dichroism (CD and UV-visible absorption spectroscopies indicate the ability of COOH-f-MWCNTs to experience conformational change in the native structure of the enzyme. The binding free energy calculations also show that electrostatics, π-cation, and π-π stacking interactions play important roles in the binding of the carboxylated CNTs with pTry. The MD simulation results demonstrated that the carboxylated CNTs adsorb to the enzyme stronger than the CNT without the-COOH groups. Our observations can provide an example of the nanoscale toxicity of COOH-f-MWCNTs for proteins, which is a critical issue for in vivo application of COOH-f-MWCNTs.

How well are you teaching one of the most important biological concepts for humankind? A call to action

Science.gov (United States)

Bonar, Scott A.; Fife, Deanna A.; Bonar, John S.

2016-01-01

We represent several generations of biology educators – with teaching experiences beginning in the 1940s and continuing to the present, from elementary school to graduate-level programs. We find the vast array of subjects that biology teachers can now cover both thrilling and mind-boggling. Depending on the grade level, units exist that focus on neurobiology, forensics, DNA analysis, biotechnology, marine biology, and a host of other topics.Although science teachers cover a potpourri of advanced topics, we must ask ourselves – no matter our biology-teaching responsibilities – how well we are teaching carrying capacity, one of the most fundamental biological concepts for our society, knowledge of which becomes more important every day. As biology teachers, most of you know that carrying capacity is defined as the maximum population an environment can sustain, given the amounts of food, habitat, and other resources available. Every environment – from your goldfish bowl to the local forest to planet Earth – can only sustain a set number (weight) of a particular species, based on available resources and space. Currently, most science classes teach …

Atmospheric chemistry of carboxylic acids: microbial implication versus photochemistry

Directory of Open Access Journals (Sweden)

M. Vaïtilingom

2011-08-01

Full Text Available The objective of this work was to compare experimentally the contribution of photochemistry vs. microbial activity to the degradation of carboxylic acids present in cloud water. For this, we selected 17 strains representative of the microflora existing in real clouds and worked on two distinct artificial cloud media that reproduce marine and continental cloud chemical composition. Photodegradation experiments with hydrogen peroxide (H₂O₂ as a source of hydroxyl radicals were performed under the same microcosm conditions using two irradiation systems. Biodegradation and photodegradation rates of acetate, formate, oxalate and succinate were measured on both media at 5 °C and 17 °C and were shown to be on the same order of magnitude (around 10⁻¹⁰–10⁻¹¹ M s⁻¹. The chemical composition (marine or continental origin had little influence on photodegradation and biodegradation rates while the temperature shift from 17 °C to 5 °C decreased biodegradation rates of a factor 2 to 5.

In order to test other photochemical scenarios, theoretical photodegradation rates were calculated considering hydroxyl (OH radical concentration values in cloud water estimated by cloud chemistry modelling studies and available reaction rate constants of carboxylic compounds with both hydroxyl and nitrate radicals. Considering high OH concentration ([OH] = 1 × 10⁻¹² M led to no significant contribution of microbial activity in the destruction of carboxylic acids. On the contrary, for lower OH concentration (at noon, [OH] = 1 × 10⁻¹⁴ M, microorganisms could efficiently compete with photochemistry and in similar contributions than the ones estimated by our experimental approach.

Combining these two approaches (experimental and theoretical, our results led to the following conclusions: oxalate was only photodegraded; the photodegradation of formate was usually more

Ion exchange properties of carboxylate bagasse

International Nuclear Information System (INIS)

Nada, A.M.A.; Hassan, M.L.

2005-01-01

Bagasse fibers were chemically modified using three different reactions: esterification using monochloro acetic acid, esterification using succinic anhydride, and oxidation using sodium periodate and sodium chlorite to prepare cation exchanger bearing carboxylic groups. Bagasse was crosslinked using epichlorohydrin before chemical modification to avoid loss of its constituents during the chemical modification. The structure of the prepared derivatives was proved using Fourier transform infrared (FTIR) and chemical methods. The ability of the prepared bagasse cation exchangers to adsorb heavy metal ions (Cu +2 , Ni +2 , Cr +3 , Fe +3 ), on a separate basis or in a mixture of them, at different metal ion concentration was tested. Thermal stability of the different bagasse derivative was studied using thermogravimetric analysis (TGA)

Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

Directory of Open Access Journals (Sweden)

Jianbo Tan

2017-12-01

Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

Selectivity in stripping of alkali-metal cations from crown ether carboxylate complexes

International Nuclear Information System (INIS)

Bartsch, R.A.; Walkowiak, W.; Robison, T.W.

1992-01-01

To probe the effect of structural variations within the ionophore upon the efficiency and selectivity of solvent extraction, a variety of crown ether carboxylic acids and phosphonic acid monoesters have been synthesized. In other studies the influence of the organic diluent upon extraction efficiency and selectivity has been probed for such proton-ionizable crown ethers. In the present investigation, attention is focused upon selectivity in the stripping step. Although the efficiency of metal ion stripping is often examined in solvent extraction studies, the selectivity of competitive metal ion release under different conditions is much less frequently considered. In this study, competitive stripping of metal ions from chloroform solutions of five-alkali-metal crown ether carboxylates by varying concentrations of aqueous hydrochloric acid is examined. Alkali metals used were Li, Na, K, Rb, and Cs

Carboxylated, Fe-filled multiwalled carbon nanotubes as versatile catalysts for O2 reduction and H2 evolution reactions at physiological pH.

Science.gov (United States)

Bracamonte, M Victoria; Melchionna, Michele; Stopin, Antoine; Giulani, Angela; Tavagnacco, Claudio; Garcia, Yann; Fornasiero, Paolo; Bonifazi, Davide; Prato, Maurizio

2015-09-01

The development of new electrocatalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) at physiological pH is critical for several fields, including fuel cells and biological applications. Herein, the assembly of an electrode based on carboxyl-functionalised hydrophilic multiwalled carbon nanotubes (MWCNTs) filled with Fe phases and their excellent performance as electrocatalysts for ORR and HER at physiological pH are reported. The encapsulated Fe dramatically enhances the catalytic activity, and the graphitic shells play a double role of efficiently mediating the electron transfer to O2 and H2 O reactants and providing a cocoon that prevents uncontrolled Fe oxidation or leaching. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transport of biologically important nutrients by wind in an eroding cold desert

Science.gov (United States)

Sankey, Joel B.; Germino, Matthew J.; Benner, Shawn G.; Glenn, Nancy F.; Hoover, Amber N.

2012-01-01

Wind erosion following fire is an important landscape process that can result in the redistribution of ecologically important soil resources. In this study we evaluated the potential for a fire patch in a desert shrubland to serve as a source of biologically important nutrients to the adjacent, downwind, unburned ecosystem. We analyzed nutrient concentrations (P, K, Ca, Mg, Cu, Fe, Mn, Al) in wind-transported sediments, and soils from burned and adjacent unburned surfaces, collected during the first to second growing seasons after a wildfire that burned in 2007 in Idaho, USA in sagebrush steppe; a type of cold desert shrubland. We also evaluated the timing of potential wind erosion events and weather conditions that might have contributed to nutrient availability in downwind shrubland. Findings indicated that post-fire wind erosion resulted in an important, but transient, addition of nutrients on the downwind shrubland. Aeolian sediments from the burned area were enriched relative to both the up- and down-wind soil and indicated the potential for a fertilization effect through the deposition of the nutrient-enriched sediment during the first, but not second, summer after wildfire. Weather conditions that could have produced nutrient transport events might have provided increased soil moisture necessary to make nutrients accessible for plants in the desert environment. Wind transport of nutrients following fire is likely important in the sagebrush steppe as it could contribute to pulses of resource availability that might, for example, affect plant species differently depending on their phenology, and nutrient- and water-use requirements.

Basicity of carboxylic acids: resonance in the cation and substituent effects

Czech Academy of Sciences Publication Activity Database

Böhm, S.; Exner, Otto

2005-01-01

Roč. 29, - (2005), s. 336-342 ISSN 1144-0546 R&D Projects: GA MŠk(CZ) LN00A032 Institutional research plan: CEZ:AV0Z4055905 Keywords : basicity * carboxylic acids Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.574, year: 2005

Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

Energy Technology Data Exchange (ETDEWEB)

Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

2008-01-08

We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings.

Characterization of selective binding of alkali cations with carboxylate by x-ray absorption spectroscopy of liquid microjets

International Nuclear Information System (INIS)

Saykally, Richard J; Uejio, Janel S.; Schwartz, Craig P.; Duffin, Andrew M.; Drisdell, Walter S.; Cohen, Ronald C.; Saykally, Richard J.

2008-01-01

We describe an approach for characterizing selective binding between oppositely charged ionic functional groups under biologically relevant conditions. Relative shifts in K-shell x-ray absorption spectra of aqueous cations and carboxylate anions indicate the corresponding binding strengths via perturbations of carbonyl antibonding orbitals. XAS spectra measured for aqueous formate and acetate solutions containing lithium, sodium, and potassium cations reveal monotonically stronger binding of the lighter metals, supporting recent results from simulations and other experiments. The carbon K-edge spectra of the acetate carbonyl feature centered near 290 eV clearly indicate a preferential interaction of sodium versus potassium, which was less apparent with formate. These results are in accord with the Law of Matching Water Affinities, relating relative hydration strengths of ions to their respective tendencies to form contact ion pairs. Density functional theory calculations of K-shell spectra support the experimental findings

Gold nanostar-enhanced surface plasmon resonance biosensor based on carboxyl-functionalized graphene oxide

International Nuclear Information System (INIS)

Wu, Qiong; Sun, Ying; Ma, Pinyi; Zhang, Di; Li, Shuo; Wang, Xinghua; Song, Daqian

2016-01-01

A new high-sensitivity surface plasmon resonance (SPR) biosensor based on biofunctional gold nanostars (AuNSs) and carboxyl-functionalized graphene oxide (cGO) sheets was described. Compared with spherical gold nanoparticles (AuNPs), the anisotropic structure of AuNSs, which concentrates the electric charge density on its sharp tips, could enhance the local electromagnetic field and the electronic coupling effect significantly. cGO was obtained by a diazonium reaction of graphene oxide (GO) with 4-aminobenzoic acid. Compared with GO, cGO could immobilize more antibodies due to the abundant carboxylic groups on its surface. Testing results show that there are fairly large improvements in the analytical performance of the SPR biosensor using cGO/AuNSs-antigen conjugate, and the detection limit of the proposed biosensor is 0.0375 μg mL"−"1, which is 32 times lower than that of graphene oxide-based biosensor. - Highlights: • A sensitive and versatile SPR biosensor was constructed for detection of pig IgG. • Biofunctional gold nanostars were used to amplify the response signals. • The strategy employed carboxyl-functionalized graphene oxide as biosensing substrate. • The detection limit of the proposed biosensor is 32 times lower than that of graphene oxide-based biosensor.

Gold nanostar-enhanced surface plasmon resonance biosensor based on carboxyl-functionalized graphene oxide

Energy Technology Data Exchange (ETDEWEB)

Wu, Qiong; Sun, Ying; Ma, Pinyi; Zhang, Di; Li, Shuo; Wang, Xinghua; Song, Daqian, E-mail: songdq@jlu.edu.cn

2016-03-24

A new high-sensitivity surface plasmon resonance (SPR) biosensor based on biofunctional gold nanostars (AuNSs) and carboxyl-functionalized graphene oxide (cGO) sheets was described. Compared with spherical gold nanoparticles (AuNPs), the anisotropic structure of AuNSs, which concentrates the electric charge density on its sharp tips, could enhance the local electromagnetic field and the electronic coupling effect significantly. cGO was obtained by a diazonium reaction of graphene oxide (GO) with 4-aminobenzoic acid. Compared with GO, cGO could immobilize more antibodies due to the abundant carboxylic groups on its surface. Testing results show that there are fairly large improvements in the analytical performance of the SPR biosensor using cGO/AuNSs-antigen conjugate, and the detection limit of the proposed biosensor is 0.0375 μg mL{sup −1}, which is 32 times lower than that of graphene oxide-based biosensor. - Highlights: • A sensitive and versatile SPR biosensor was constructed for detection of pig IgG. • Biofunctional gold nanostars were used to amplify the response signals. • The strategy employed carboxyl-functionalized graphene oxide as biosensing substrate. • The detection limit of the proposed biosensor is 32 times lower than that of graphene oxide-based biosensor.

Monitoring of airborne biological particles in outdoor atmosphere. Part 1: Importance, variability and ratios.

Science.gov (United States)

Núñez, Andrés; Amo de Paz, Guillermo; Rastrojo, Alberto; García, Ana M; Alcamí, Antonio; Gutiérrez-Bustillo, A Montserrat; Moreno, Diego A

2016-03-01

The first part of this review ("Monitoring of airborne biological particles in outdoor atmosphere. Part 1: Importance, variability and ratios") describes the current knowledge on the major biological particles present in the air regarding their global distribution, concentrations, ratios and influence of meteorological factors in an attempt to provide a framework for monitoring their biodiversity and variability in such a singular environment as the atmosphere. Viruses, bacteria, fungi, pollen and fragments thereof are the most abundant microscopic biological particles in the air outdoors. Some of them can cause allergy and severe diseases in humans, other animals and plants, with the subsequent economic impact. Despite the harsh conditions, they can be found from land and sea surfaces to beyond the troposphere and have been proposed to play a role also in weather conditions and climate change by acting as nucleation particles and inducing water vapour condensation. In regards to their global distribution, marine environments act mostly as a source for bacteria while continents additionally provide fungal and pollen elements. Within terrestrial environments, their abundances and diversity seem to be influenced by the land-use type (rural, urban, coastal) and their particularities. Temporal variability has been observed for all these organisms, mostly triggered by global changes in temperature, relative humidity, et cetera. Local fluctuations in meteorological factors may also result in pronounced changes in the airbiota. Although biological particles can be transported several hundreds of meters from the original source, and even intercontinentally, the time and final distance travelled are strongly influenced by factors such as wind speed and direction. [Int Microbiol 2016; 19(1):1-1 3]. Copyright© by the Spanish Society for Microbiology and Institute for Catalan Studies.

Volatility of atmospherically relevant alkylaminium carboxylate salts.

Science.gov (United States)

Lavi, Avi; Segre, Enrico; Gomez-Hernandez, Mario; Zhang, Renyi; Rudich, Yinon

2015-05-14

Heterogeneous neutralization reactions of ammonia and alkylamines with sulfuric acid play an important role in aerosol formation and particle growth. However, little is known about the physical and chemical properties of alkylaminium salts of organic acids. In this work we studied the thermal stability and volatility of alkylaminium carboxylate salts of short aliphatic alkylamines with monocarboxylic and dicarboxylic acids. The enthalpy of vaporization and saturation vapor pressure at 298 K were derived using the kinetic model of evaporation and the Clausius-Clapeyron relation. The vapor pressure of alkylaminium dicarboxylate salts is ∼10(-6) Pa, and the vaporization enthalpy ranges from 73 to 134 kJ mol(-1). Alkylaminium monocarboxylate salts show high thermal stability, and their thermograms do not follow our evaporation model. Hence, we inferred their vapor pressure from their thermograms as comparable to that of ammonium sulfate (∼10(-9) Pa). Further characterization showed that alkylaminium monocarboxylates are room temperature protic ionic liquids (RTPILs) that are more hygroscopic than ammonium sulfate (AS). We suggest that the irregular thermograms result from an incomplete neutralization reaction leading to a mixture of ionic and nonionic compounds. We conclude that these salts are expected to contribute to new particle formation and particle growth under ambient conditions and can significantly enhance the CCN activity of mixed particles in areas where SO2 emissions are regulated.

Controlled surface functionalization of silica-coated magnetic nanoparticles with terminal amino and carboxyl groups

International Nuclear Information System (INIS)

Kralj, Slavko; Drofenik, Miha; Makovec, Darko

2011-01-01

General and versatile methods for the functionalization of superparamagnetic, silica-coated, maghemite nanoparticles by surface amino and/or carboxyl groups have been established. The nanoparticles were synthesized using co-precipitation from aqueous solutions and coated with a thin layer of silica using the hydrolysis and condensation of tetraethoxysilane (TEOS). For the amino functionalization, 3-(2-aminoethylamino)propylmethyldimethoxysilane (APMS) was grafted onto the nanoparticle surfaces in their aqueous suspensions. The grafting process was followed by measurements of the ζ-potential and a determination of the concentration of the surface amino groups with conductometric titrations. The surface concentration of the amino groups could be varied by increasing the amount of APMS in the grafting process up to approximately 2.3 –NH 2 groups per nm 2 . The carboxyl functionalization was obtained in two ways: (i) by a ring-opening linker elongation reaction of the surface amines at the functionalized nanoparticles with succinic anhydride (SA) in non-aqueous medium, and (ii) by reacting the APMS and SA first, followed by grafting of the carboxyl-terminated reagent onto the nanoparticle surfaces. Using the first method, the SA only reacted with the terminal primary amino groups (–NH 2 ) of the surface-grafted APMS molecules. Infra-red spectroscopy (ATR FTIR) and mass spectrometry (HRMS) showed that the second method enables the bonding of up to two SA molecules per one APMS molecule, since the SA reacted with both the primary (–NH 2 ) and secondary amino (–NH–) groups of the APMS molecule. When using both methods, the ratio between the surface amino and carboxyl groups can be controlled.

Optimization of polycrystalline platinum catalytic activity opposite to carboxylic acids oxidation

International Nuclear Information System (INIS)

Le Naour, C.; Moisy, P.; Blanc, P.; Madic, C.

1994-01-01

In electro nuclear industry, in the aim to reduce the quantity of wastes coming from the spent fuels reprocessing, the use of reagents as some carboxylic acids is considered: after use, these reagents are completely decomposed in gaseous products, which can be filtered and released in environment

Interaction of 1-iodochlordecone, as radioactive tracer, with the carboxylate group on activated carbon

International Nuclear Information System (INIS)

Gamboa-Carballo, Juan José; Melchor-Rodríguez, Kenia; Hernández-Valdés, Daniel; Jáuregui-Haza, Ulises Javier

2016-01-01

Chlordecone is a synthetic organo chlorinated compound that has been used as pesticide. It has been identified and listed as persistent organic pollutant by the Stockholm Convention. The use of activated carbon filters is one of the most widely popular solutions for water decontamination. The chlordecone labeled with radioactive iodine (1-iodochordecone) is a potential radioactive tracer for studying adsorption, environmental availability and bio-distribution of chlordecone. The selection of the best suited activation carbon for this type of contaminants is mainly an empiric process, increasing the costs of research. A simplified activation carbon model, consisting of a seven ring graphene sheet with a functional group (carboxylate) was used to assess the interaction of chlordecone and 1-iodochlordecone with this surface group under neutral pH conditions over the adsorption process. The Multiple Minima Hypersurface methodology with the semiempirical Hamiltonian PM7 was used. The results indicate that for carboxylate, in neutral conditions, significant associations appear which suggest chemisorption in activated carbon. No significant differences were observed for the interactions of chlordecone and 1 iodochlordecone with carboxylate, making 1-iodochlordecone a good candidate as a radioactive tracer in medical research. (author)

n-Octyl gallate as inhibitor of pyruvate carboxylation and lactate gluconeogenesis.

Science.gov (United States)

Eler, Gabrielle Jacklin; Santos, Israel Souza; de Moraes, Amarilis Giaretta; Comar, Jurandir Fernando; Peralta, Rosane Marina; Bracht, Adelar

2015-04-01

The alkyl gallates are found in several natural and industrial products. In the latter products, these compounds are added mainly for preventing oxidation. In the present work, the potencies of methyl gallate, n-propyl gallate, n-pentyl gallate, and n-octyl gallate as inhibitors of pyruvate carboxylation and lactate gluconeogenesis were evaluated. Experiments were done with isolated mitochondria and the isolated perfused rat liver. The potency of the gallic acid esters as inhibitors of pyruvate carboxylation in isolated mitochondria obeyed the following decreasing sequence: n-octyl gallate > n-pentyl gallate > n-propyl gallate > methyl gallate. A similar sequence of decreasing potency for lactate gluconeogenesis inhibition in the perfused liver was found in terms of the portal venous concentration. Both actions correlate with the lipophilicity of the compounds. The effects are harmful at high concentrations. At appropriate concentrations, however, octyl gallate should act therapeutically because its inhibitory action on gluconeogenesis will contribute further to its proposed antihyperglycemic effects. © 2014 Wiley Periodicals, Inc.

Raman spectra of thiolated arsenicals with biological importance.

Science.gov (United States)

Yang, Mingwei; Sun, Yuzhen; Zhang, Xiaobin; McCord, Bruce; McGoron, Anthony J; Mebel, Alexander; Cai, Yong

2018-03-01

Surface enhanced Raman scattering (SERS) has great potential as an alternative tool for arsenic speciation in biological matrices. SERS measurements have advantages over other techniques due to its ability to maintain the integrity of arsenic species and its minimal requirements for sample preparation. Up to now, very few Raman spectra of arsenic compounds have been reported. This is particularly true for thiolated arsenicals, which have recently been found to be widely present in humans. The lack of data for Raman spectra in arsenic speciation hampers the development of new tools using SERS. Herein, we report the results of a study combining the analysis of experimental Raman spectra with that obtained from density functional calculations for some important arsenic metabolites. The results were obtained with a hybrid functional B3LYP approach using different basis sets to calculate Raman spectra of the selected arsenicals. By comparing experimental and calculated spectra of dimethylarsinic acid (DMA V ), the basis set 6-311++G** was found to provide computational efficiency and precision in vibrational frequency prediction. The Raman frequencies for the rest of organoarsenicals were studied using this basis set, including monomethylarsonous acid (MMA III ), dimethylarsinous acid (DMA III ), dimethylmonothioarinic acid (DMMTA V ), dimethyldithioarsinic acid (DMDTA V ), S-(Dimethylarsenic) cysteine (DMA III (Cys)) and dimethylarsinous glutathione (DMA III GS). The results were compared with fingerprint Raman frequencies from As─O, As─C, and As─S obtained under different chemical environments. These fingerprint vibrational frequencies should prove useful in future measurements of different species of arsenic using SERS. Copyright © 2017 Elsevier B.V. All rights reserved.

LIQUID-CHROMATOGRAPHIC ANALYSIS OF CARBOXYLIC-ACIDS USING N-(4-AMINOBUTYL)-N-ETHYLISOLUMINOL AS CHEMILUMINESCENT LABEL - DETERMINATION OF IBUPROFEN IN SALIVA

NARCIS (Netherlands)

STEIJGER, OM; LINGEMAN, H; BRINKMAN, UAT; HOLTHUIS, JJM; SMILDE, AK; DOORNBOS, DA

1993-01-01

N-(4-Aminobutyl)-N-ethylisoluminol was used for labelling of carboxylic acids. The derivatization reaction was carried out with 1-hydroxybenzotriazole as pre-activator of the carboxylic acid function and N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide as the coupling reagent. Optimum conditions for

Liquid chromatographic analysis of carboxylic acids using N-(4-aminobutyl)-N-ethylisoluminol as chemiluminescent label: determination of ibuprofen in saliva

NARCIS (Netherlands)

Steijger, O. M.; Lingeman, H.; Brinkman, U. A.; Holthuis, J. J.; Smilde, A. K.; Doornbos, D. A.

1993-01-01

N-(4-Aminobutyl)-N-ethylisoluminol was used for labelling of carboxylic acids. The derivatization reaction was carried out with 1-hydroxybenzotriazole as pre-activator of the carboxylic acid function and N-ethyl-N'-(3-dimethylaminopropyl)carbodiimide as the coupling reagent. Optimum conditions for

Gelsolin functions as a metastasis suppressor in B16-BL6 mouse melanoma cells and requirement of the carboxyl-terminus for its effect.

Science.gov (United States)

Fujita, H; Okada, F; Hamada , J; Hosokawa, M; Moriuchi, T; Koya, R C; Kuzumaki, N

2001-09-01

Gelsolin, an actin-binding protein, is implicated as a critical regulator in cell motility. In addition, we have reported that cellular levels of gelsolin are decreased in various tumor cells, and overexpression of gelsolin by gene transfer suppresses tumorigenicity. We sought to assess the effects of gelsolin overexpression on metastasis and to determine the importance of a carboxyl-terminus that confers Ca(2+) dependency on gelsolin for effects of its overexpression. Expression vectors with cDNA encoding either full-length wild-type or His321 mutant form, isolated from a flat revertant of Ras-transformed cells and a carboxyl-terminal truncate, C-del of gelsolin, were transfected into a highly metastatic murine melanoma cell line, B16-BL6. Expression of introduced cDNA in transfectants was confirmed using Western blotting, 2-dimensional gel electrophoresis and reverse transcription-polymerase chain reaction (RT-PCR). We characterized phenotypes of transfectants, such as growth rate, colony formation in soft agar, cell motility and metastasis formation in vivo. Transfectants expressing the wild-type, His321 mutant and C-del gelsolin exhibited reduced growth ability in soft agar. Although expression of integrin beta1 or alpha4 on the cell surface of transfectants was not changed, wild-type and His321 mutant gelsolin, except for C-del gelsolin, exhibited retardation of cell spreading, reduced chemotatic migration to fibronectin and suppressed lung colonization in spontaneous metastasis assay. Gelsolin may function as a metastasis suppressor as well as a tumor suppressor gene. The carboxyl-terminus of gelsolin is important for retardation of cell spreading, reduced chemotasis and metastasis suppression. Copyright 2001 Wiley-Liss, Inc.

Multifunctional PEG-carboxylate copolymer coated superparamagnetic iron oxide nanoparticles for biomedical application

Science.gov (United States)

Illés, Erzsébet; Szekeres, Márta; Tóth, Ildikó Y.; Szabó, Ákos; Iván, Béla; Turcu, Rodica; Vékás, Ladislau; Zupkó, István; Jaics, György; Tombácz, Etelka

2018-04-01

Biocompatible magnetite nanoparticles (MNPs) were prepared by post-coating the magnetic nanocores with a synthetic polymer designed specifically to shield the particles from non-specific interaction with cells. Poly(ethylene glycol) methyl ether methacrylate (PEGMA) macromonomers and acrylic acid (AA) small molecular monomers were chemically coupled by quasi-living atom transfer radical polymerization (ATRP) to a comb-like copolymer, P(PEGMA-co-AA) designated here as P(PEGMA-AA). The polymer contains pendant carboxylate moieties near the backbone and PEG side chains. It is able to bind spontaneously to MNPs; stabilize the particles electrostatically via the carboxylate moieties and sterically via the PEG moieties; provide high protein repellency via the structured PEG layer; and anchor bioactive proteins via peptide bond formation with the free carboxylate groups. The presence of the P(PEGMA-AA) coating was verified in XPS experiments. The electrosteric (i.e., combined electrostatic and steric) stabilization is efficient down to pH 4 (at 10 mM ionic strength). Static magnetization and AC susceptibility measurements showed that the P(PEGMA-AA)@MNPs are superparamagnetic with a saturation magnetization value of 55 emu/g and that both single core nanoparticles and multicore structures are present in the samples. The multicore components make our product well suited for magnetic hyperthermia applications (SAR values up to 17.44 W/g). In vitro biocompatibility, cell internalization, and magnetic hyperthermia studies demonstrate the excellent theranostic potential of our product.

Chirality- and sequence-selective successive self-sorting via specific homo- and complementary-duplex formations

Science.gov (United States)

Makiguchi, Wataru; Tanabe, Junki; Yamada, Hidekazu; Iida, Hiroki; Taura, Daisuke; Ousaka, Naoki; Yashima, Eiji

2015-01-01

Self-recognition and self-discrimination within complex mixtures are of fundamental importance in biological systems, which entirely rely on the preprogrammed monomer sequences and homochirality of biological macromolecules. Here we report artificial chirality- and sequence-selective successive self-sorting of chiral dimeric strands bearing carboxylic acid or amidine groups joined by chiral amide linkers with different sequences through homo- and complementary-duplex formations. A mixture of carboxylic acid dimers linked by racemic-1,2-cyclohexane bis-amides with different amide sequences (NHCO or CONH) self-associate to form homoduplexes in a completely sequence-selective way, the structures of which are different from each other depending on the linker amide sequences. The further addition of an enantiopure amide-linked amidine dimer to a mixture of the racemic carboxylic acid dimers resulted in the formation of a single optically pure complementary duplex with a 100% diastereoselectivity and complete sequence specificity stabilized by the amidinium–carboxylate salt bridges, leading to the perfect chirality- and sequence-selective duplex formation. PMID:26051291

Photothermal therapy of Lewis lung carcinoma in mice using gold nanoshells on carboxylated polystyrene spheres

Science.gov (United States)

Liu, Huiyu; Chen, Dong; Tang, Fangqiong; Du, Gangjun; Li, Linlin; Meng, Xianwei; Liang, Wei; Zhang, Yangde; Teng, Xu; Li, Yi

2008-11-01

A new approach towards the design of gold nanoshells on carboxylated polystyrene spheres (GNCPSs) is reported here. Gold nanoshells were self-assembled on the surface of carboxylated polystyrene spheres by a seed growth method. Chitosan (CHI) was used as a functional agent of carboxylated polystyrene spheres for attaching gold seeds. The surface plasmon resonance (SPR) peak of GNCPSs can be tuned, greatly redshifted, over a broad spectral range including the near-infrared (NIR) wavelength region, which provides maximal penetration of light through tissue. Irradiation of GNCPSs at their peak extinction coefficient results in the conversion of light to heat energy that produces a local rise in temperature. Our study revealed that the Lewis lung carcinoma (LLC) in mice treated with GNCPSs exposed to a low dose of NIR light (808 nm, 4 W cm-2) induced irreversible tissue damage. The tumor volumes of the treatment group by GNCPSs were significantly lower than those of control groups, with an average inhibition rate over 55% (P<0.005). This study proves that GNCPSs are promising in plasmonic photothermal tumor therapy.

Photothermal therapy of Lewis lung carcinoma in mice using gold nanoshells on carboxylated polystyrene spheres

International Nuclear Information System (INIS)

Liu Huiyu; Chen Dong; Tang Fangqiong; Li Linlin; Meng Xianwei; Li Yi; Du Gangjun; Liang Wei; Zhang Yangde; Teng Xu

2008-01-01

A new approach towards the design of gold nanoshells on carboxylated polystyrene spheres (GNCPSs) is reported here. Gold nanoshells were self-assembled on the surface of carboxylated polystyrene spheres by a seed growth method. Chitosan (CHI) was used as a functional agent of carboxylated polystyrene spheres for attaching gold seeds. The surface plasmon resonance (SPR) peak of GNCPSs can be tuned, greatly redshifted, over a broad spectral range including the near-infrared (NIR) wavelength region, which provides maximal penetration of light through tissue. Irradiation of GNCPSs at their peak extinction coefficient results in the conversion of light to heat energy that produces a local rise in temperature. Our study revealed that the Lewis lung carcinoma (LLC) in mice treated with GNCPSs exposed to a low dose of NIR light (808 nm, 4 W cm -2 ) induced irreversible tissue damage. The tumor volumes of the treatment group by GNCPSs were significantly lower than those of control groups, with an average inhibition rate over 55% (P<0.005). This study proves that GNCPSs are promising in plasmonic photothermal tumor therapy.

Proton-conducting membranes based on benzimidazole-containing sulfonated poly(ether ether ketone) compared with their carboxyl acid form

Energy Technology Data Exchange (ETDEWEB)

Li, Hongtao; Wu, Jing; Zhao, Chengji; Zhang, Gang; Zhang, Yang; Shao, Ke; Xu, Dan; Lin, Haidan; Han, Miaomiao; Na, Hui [Alan G MacDiarmid Institute, College of Chemistry, Jilin University, Changchun 130012 (China)

2009-10-15

A series of sulfonated poly(ether ether ketone) containing pendant carboxyl (C-SPEEKs) have been synthesized using a nucleophilic polycondesation reaction. A condensation reaction between 1,2-diaminobenzene and carboxyl resulted in a new series of copolymers containing benzimidazole groups (SPEEK-BIms). The expected structures of the sulfonated copolymers are confirmed by {sup 1}H NMR. The dependence of ion exchange capacity, water uptake, proton conductivity and methanol diffusion coefficient of SPEEK-BIm membranes has been studied and compared with their carboxyl acid form. The results suggest that the introduction of benzimidazole groups may be responsible for many excellent properties of the membranes for fuel cell. It is noticeable that the markedly improved oxidative stability is benefit for the application of membrane. (author)

Additional Nucleophile-Free FeCl3-Catalyzed Green Deprotection of 2,4-Dimethoxyphenylmethyl-Protected Alcohols and Carboxylic Acids.

Science.gov (United States)

Sawama, Yoshinari; Masuda, Masahiro; Honda, Akie; Yokoyama, Hiroki; Park, Kwihwan; Yasukawa, Naoki; Monguchi, Yasunari; Sajiki, Hironao

2016-01-01

The deprotection of the methoxyphenylmethyl (MPM) ether and ester derivatives can be generally achieved by the combinatorial use of a catalytic Lewis acid and stoichiometric nucleophile. The deprotections of 2,4-dimethoxyphenylmethyl (DMPM)-protected alcohols and carboxylic acids were found to be effectively catalyzed by iron(III) chloride without any additional nucleophile to form the deprotected mother alcohols and carboxylic acids in excellent yields. Since the present deprotection proceeds via the self-assembling mechanism of the 2,4-DMPM protective group itself to give the hardly-soluble resorcinarene derivative as a precipitate, the rigorous purification process by silica-gel column chromatography was unnecessary and the sufficiently-pure alcohols and carboxylic acids were easily obtained in satisfactory yields after simple filtration.

Modeling Donnan Dialysis Separation for Carboxylic Anion Recovery

DEFF Research Database (Denmark)

Prado Rubio, Oscar Andres; Møllerhøj, Martin; Jørgensen, Sten Bay

2010-01-01

layers and membranes. Donnan equilibrium, flux continuity of the transported ions, the electroneutrality condition and Faraday's law are employed to describe the electrical potential and concentration discontinuities at the interfaces. The Nernst-Planck equation is used to model the ion transport though...... boundary layers and membranes. The model consists of a system of partial differential equations that are solved numerically. The aim of this paper is to corroborate this general model for several monoprotic carboxylic acids reported in the literature. The model reproduces satisfactorily experimental fluxes...

Low-Dose Daily Intake of Vitamin K(2) (Menaquinone-7) Improves Osteocalcin γ-Carboxylation: A Double-Blind, Randomized Controlled Trials.

Science.gov (United States)

Inaba, Naoko; Sato, Toshiro; Yamashita, Takatoshi

2015-01-01

Vitamin K is essential for bone health, but the effects of low-dose vitamin K intake in Japanese subjects remain unclear. We investigated the effective minimum daily menaquinone-7 dose for improving osteocalcin γ-carboxylation. Study 1 was a double-blind, randomized controlled dose-finding trial; 60 postmenopausal women aged 50-69 y were allocated to one of four dosage group and consumed 0, 50, 100, or 200 μg menaquinone-7 daily for 4 wk, respectively, with a controlled diet in accordance with recommended daily intakes for 2010 in Japan. Study 2 was a double-blind, randomized placebo-controlled trial based on the results of Study 1; 120 subjects aged 20-69 y were allocated to the placebo or MK-7 group and consumed 0 or 100 μg menaquinone-7 daily for 12 wk, respectively. In both studies, circulating carboxylated osteocalcin and undercarboxylated osteocalcin were measured. The carboxylated osteocalcin/undercarboxylated osteocalcin ratio decreased significantly from baseline in the 0 μg menaquinone-7 group, in which subjects consumed the recommended daily intake of vitamin K with vitamin K1 and menaquinone-4 (Study 1). Menaquinone-7 increased the carboxylated osteocalcin/undercarboxylated osteocalcin ratio dose dependently, and significant effects were observed in both the 100 and 200 μg groups compared with the 0 μg group. Undercarboxylated osteocalcin concentrations decreased significantly, and the carboxylated osteocalcin/undercarboxylated osteocalcin ratio increased significantly in the 100 μg menaquinone-7 group compared with the placebo group (Study 2). Daily menaquinone-7 intake ≥100 μg was suggested to improve osteocalcin γ-carboxylation.

Formation and High-order Carboxylic Acids (RCOOH) in Interstellar Analogous Ices of Carbon Dioxide (CO2) and Methane(CH4)

Science.gov (United States)

Zhu, Cheng; Turner, Andrew M.; Abplanalp, Matthew J.; Kaiser, Ralf I.

2018-01-01

This laboratory study simulated the abiotic formation of carboxylic acids (RCOOH) in interstellar analogous ices of carbon dioxide (CO2) and methane (CH4) at 10 K upon exposure to energetic electrons. The chemical processing of the ices and the subsequent warm-up phase were monitored online and in situ, exploiting Fourier Transform Infrared Spectrometry and quadrupole mass spectrometry. Characteristic absorptions of functional groups of carboxylic acids (RCOOH) were observed in the infrared spectra of the irradiated ice. Two proposed reaction mechanisms replicated the kinetic profiles of the carboxylic acids along with the decay profile of the precursors during the irradiation via hydrocarbon formation, followed by carboxylation and/or through acetic acid along with mass growth processes of the alkyl chain. Mass spectra recorded during the warm-up phase demonstrated that these acids are distributed from acetic acid (CH3COOH) up to decanoic acid (C9H19COOH). High-dose irradiation studies (91 ± 14 eV) converted low-molecular-weight acids such as acetic acid (CH3COOH) and propionic acid (C2H5COOH) to higher-molecular-weight carboxylic acids, compared to low-dose irradiation studies (18 ± 3 eV). The traces of the {{{H}}}2{{C}}= {{C}}({OH}{)}2+ (m/z = 60) fragment—a link to linear carboxylic acids—implied that higher-order acids (C n H2n+1COOH, n ≥ 5) are likely branched, which correlates with the recent analysis of the structures of the monocarboxylic acids in the Murchison meteorite.

Screening of biologically important Zn2 + by a chemosensor with fluorescent turn on-off mechanism

Science.gov (United States)

Khan, Tanveer A.; Sheoran, Monika; Nikhil Raj M., Venkata; Jain, Surbhi; Gupta, Diksha; Naik, Sunil G.

2018-01-01

Reported herein the synthesis, characterization and biologically important zinc ion binding propensity of a weakly fluorescent chemosensor, 4-methyl-2,6-bis((E)-(2-(4-phenylthiazol-2-yl)hydrazono)methyl)phenol (1). 1H NMR spectroscopic titration experiment reveals the binding knack of 1 to the essential Zn2 +. The photo-physical studies of 1 exhibit an enhancement in the fluorescence by several folds upon binding with the zinc ions attributed to PET-off process, with a binding constant value of 5.22 × 103 M- 1. 1 exhibits an excellent detection range for Zn2 + with lower detection limit value of 2.31 × 10- 8 M. The selectivity of 1 was studied with various mono and divalent metal cations and it was observed that most cations either quenches the fluorescence or remains unchanged except for Cd2 +, which shows a slight enhancement in fluorescence intensity of 1. The ratiometric displacement of Cd2 + ions by Zn2 + ions shows an excellent selectivity towards in-situ detection of Zn2 + ions. Photo-physical studies also support the reversible binding of 1 to Zn2 + ions having on and off mechanism in presence of EDTA. Such recognition of the biologically important zinc ions finds potential application in live cell imaging.

Biocompatibility studies of polyacrylonitrile membranes modified with carboxylated polyetherimide

Energy Technology Data Exchange (ETDEWEB)

Senthilkumar, S.; Rajesh, S.; Jayalakshmi, A.; Mohan, D., E-mail: mohantarun@gmail.com

2013-10-15

Poly (ether-imide) (PEI) was carboxylated and used as the hydrophilic modification agent for the preparation of polyacrylonitrile (PAN) membranes. Membranes were prepared with different blend compositions of PAN and CPEI by diffusion induced precipitation. The modified membranes were characterized by thermo gravimetric analysis (TGA), mechanical analysis, scanning electron microscopy (SEM) and contact angle measurement to understand the influence of CPEI on the properties of the membranes. The biocompatibility studies exhibited reduced plasma protein adsorption, platelet adhesion and thrombus formation on the modified membrane surface. The complete blood count (CBC) results of CPEI incorporated membranes showed stable CBC values and significant decrease in the complement activation were also observed. In addition to good cytocompatibility, monocytes cultured on these modified membranes exhibited improved functional profiles in 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay. Thus it could be concluded that PAN/CPEI membranes with excellent biocompatibility can be useful for hemodialysis. Highlights: • Carboxylated PEI was prepared and utilized as hydrophilic modification agent. • CPEI incorporated into PAN to improved biocompatibility and cyto compatibility • Biocompatibility of membranes was correlated with morphology and hydrophilicity. • Antifouling studies of the PAN/CPEI membranes was studied by BSA as model foulant.

Ultrasonic-assisted preparation of graphene oxide carboxylic acid polyvinyl alcohol polymer film and studies of thermal stability and surface resistivity.

Science.gov (United States)

Li, Yongshen; Li, Jihui; Li, Yuehai; Li, Yali; Song, Yunan; Niu, Shuai; Li, Ning

2018-01-01

In this paper, flake graphite, nitric acid and acetic anhydride are used to prepare graphene oxide carboxylic acid (GO-COOH) via an ultrasonic-assisted method, and GO-COOH and polyvinyl alcohol polymer (PVA) are used to synthesize graphene oxide carboxylic acid polyvinyl alcohol polymer (GO-COOPVA) via the ultrasonic-assisted method, and GO-COOPVA is used to manufacture graphene oxide carboxylic acid polyvinyl alcohol polymer film (GO-COOPVA film) via a solidification method, and the structure and morphology of GO-COOH, GO-COOPVA and GO-COOPVA film are characterized, and the thermal stability and surface resistivity are measured in the case of the different amount of GO-COOH. Based on the characterization and measurement, it has been successively confirmed and attested that carboxyl groups implant on 2D lattice of GO to form GO-COOH, and GO-COOH and PVA have the esterification reaction to produce GO-COOPVA, and GO-COOPVA consists of 2D lattice of GO-COOH and the chain of PVA connected in the form of carboxylic ester, and GO-COOPVA film is composed of GO-COOPVA, and the thermal stability of GO-COOPVA film obviously improves in comparison with PVA film, and the surface resistivity of GO-COOPVA film clearly decreases. Copyright © 2017 Elsevier B.V. All rights reserved.

Fluorescent porous silicon biological probes with high quantum efficiency and stability.

Science.gov (United States)

Tu, Chang-Ching; Chou, Ying-Nien; Hung, Hsiang-Chieh; Wu, Jingda; Jiang, Shaoyi; Lin, Lih Y

2014-12-01

We demonstrate porous silicon biological probes as a stable and non-toxic alternative to organic dyes or cadmium-containing quantum dots for imaging and sensing applications. The fluorescent silicon quantum dots which are embedded on the porous silicon surface are passivated with carboxyl-terminated ligands through stable Si-C covalent bonds. The porous silicon bio-probes have shown photoluminescence quantum yield around 50% under near-UV excitation, with high photochemical and thermal stability. The bio-probes can be efficiently conjugated with antibodies, which is confirmed by a standard enzyme-linked immunosorbent assay (ELISA) method.

Growth kinetics of racemic heptahelicene-2-carboxylic acid nanowires on calcite (104)

Czech Academy of Sciences Publication Activity Database

Einax, M.; Richter, T.; Nimmrich, M.; Rahe, P.; Stará, Irena G.; Starý, Ivo; Kühnle, A.; Maass, P.

2016-01-01

Roč. 145, č. 13 (2016), č. článku 134702. ISSN 0021-9606 Institutional support: RVO:61388963 Keywords : heptahelicene-2-carboxylic acid nanowires * nc-AFM * calcite * growth kinetics Subject RIV: CC - Organic Chemistry Impact factor: 2.965, year: 2016

2-Oxo-1,2-dihydroquinoline-4-carboxylic acid monohydrate

Directory of Open Access Journals (Sweden)

Yassir Filali Baba

2016-06-01

Full Text Available In the title compound, C10H7NO3·H2O, O—H...O hydrogen bonds involving the carboxyl groups, the keto groups and the lattice water molecules form stepped sheets approximately parallel to {010} which are tied together by pairwise N—H...O interactions. The asymmetric unit contains two independent quinolone derivatives and two water molecules, one of which is disordered over two positions, of equal occupancy.

Creating biological nanomaterials using synthetic biology

International Nuclear Information System (INIS)

Rice, MaryJoe K; Ruder, Warren C

2014-01-01

Synthetic biology is a new discipline that combines science and engineering approaches to precisely control biological networks. These signaling networks are especially important in fields such as biomedicine and biochemical engineering. Additionally, biological networks can also be critical to the production of naturally occurring biological nanomaterials, and as a result, synthetic biology holds tremendous potential in creating new materials. This review introduces the field of synthetic biology, discusses how biological systems naturally produce materials, and then presents examples and strategies for incorporating synthetic biology approaches in the development of new materials. In particular, strategies for using synthetic biology to produce both organic and inorganic nanomaterials are discussed. Ultimately, synthetic biology holds the potential to dramatically impact biological materials science with significant potential applications in medical systems. (review)

Creating biological nanomaterials using synthetic biology.

Science.gov (United States)

Rice, MaryJoe K; Ruder, Warren C

2014-02-01

Synthetic biology is a new discipline that combines science and engineering approaches to precisely control biological networks. These signaling networks are especially important in fields such as biomedicine and biochemical engineering. Additionally, biological networks can also be critical to the production of naturally occurring biological nanomaterials, and as a result, synthetic biology holds tremendous potential in creating new materials. This review introduces the field of synthetic biology, discusses how biological systems naturally produce materials, and then presents examples and strategies for incorporating synthetic biology approaches in the development of new materials. In particular, strategies for using synthetic biology to produce both organic and inorganic nanomaterials are discussed. Ultimately, synthetic biology holds the potential to dramatically impact biological materials science with significant potential applications in medical systems.

Organocatalyzed, Visible-Light Photoredox-Mediated, One-Pot Minisci Reaction Using Carboxylic Acids via N-(Acyloxy)phthalimides.

Science.gov (United States)

Sherwood, Trevor C; Li, Ning; Yazdani, Aliza N; Dhar, T G Murali

2018-03-02

An improved, one-pot Minisci reaction has been developed using visible light, an organic photocatalyst, and carboxylic acids as radical precursors via the intermediacy of in situ-generated N-(acyloxy)phthalimides. The conditions employed are mild, demonstrate a high degree of functional group tolerance, and do not require a large excess of the carboxylic acid reactant. As a result, this reaction can be applied to drug-like scaffolds and molecules with sensitive functional groups, enabling late-stage functionalization, which is of high interest to medicinal chemistry.

Facile syntheses of isotope-labeled chiral octahydroindole-2-carboxylic acid and its N-methyl analog

International Nuclear Information System (INIS)

Yinsheng Zhang

2012-01-01

We have synthesized deuterium and carbon-14 labeled enantiomerically pure octahydroindole-2-carboxylic acid (PD0140417), N-methyl octahydroindole-2-carboxylic acid (PD0348183) and their racemic analogs (PD0108405 and PD0338055). [ring-U- 14 C]PD0140417 was prepared from [ring-U- 14 C]benzoic acid in a seven-step synthesis in 6.2% overall radiochemical yield. [ 14 C]PD0348183 was prepared from [ 14 C]BaCO 3 in a five-step synthesis in 16% radiochemical yield. Additionally, [D]PD0108405 and [D]PD0338055 were synthesized by direct platinum-catalyzed hydrogenation with deuterium gas. (author)

[Chloroquine analogues from benzofuro- and benzothieno[3,2-b]-4-pyridone-2-carboxylic acid esters].

Science.gov (United States)

Gölitzer, K; Meyer, H; Jomaa, H; Wiesner, J

2004-08-01

The amides 7 were synthesized from the annulated methyl 4-pyridone-2-carboxylates 4 via the carboxylic acids 5 and their acid chlorides by reacting with the novaldiamine base 6. The alcohol 8b, obtained from DIBAH reduction of the ester 4b, was transformed to the chloromethyl derivative 9 which reacted with 6 and 18-crown-6 leading to the 2-novaldiaminomethyl-4-pyridone 10. Compound 10 was obtained with higher yield from DIBAH reduction of the amide 7b. The substances 7 and 10 were inactive when tested against the chloroquine resistant Plasmodium falciparum strain Dd2.

Carboxylated magnetic nanoparticles as MRI contrast agents: Relaxation measurements at different field strengths

Energy Technology Data Exchange (ETDEWEB)

Jedlovszky-Hajdu, Angela, E-mail: angela.hajdu@net.sote.hu [Laboratory of Nanochemistry, Department of Biophysics and Radiation Biology, Semmelweis University, Nagyvarad Sq 4, H-1089 Budapest (Hungary); Tombacz, Etelka, E-mail: tombacz@chem.u-szeged.hu [Department of Physical Chemistry and Material Science, University of Szeged, Aradi Vt. Sq 1, Szeged 6720 (Hungary); Banyai, Istvan, E-mail: banyai.istvan@science.unideb.hu [Department of Colloid and Environmental Chemistry, University of Debrecen (Hungary); Babos, Magor, E-mail: babosmagor@yahoo.com [Euromedic Diagnostics Szeged Ltd., Semmelweis St 6, Szeged 6720 (Hungary); Palko, Andras, E-mail: palko@radio.szote.u-szeged.hu [Faculty of Medicine, Department of Radiology, University of Szeged (Hungary)

2012-09-15

At the moment the biomedical applications of magnetic fluids are the subject of intensive scientific interest. In the present work, magnetite nanoparticles (MNPs) were synthesized and stabilized in aqueous medium with different carboxylic compounds (citric acid (CA), polyacrylic acid (PAA), and sodium oleate (NaOA)), in order to prepare well stabilized magnetic fluids (MFs). The magnetic nanoparticles can be used in the magnetic resonance imaging (MRI) as contrast agents. Magnetic resonance relaxation measurements of the above MFs were performed at different field strengths (i.e., 0.47, 1.5 and 9.4 T) to reveal the field strength dependence of their magnetic responses, and to compare them with that of ferucarbotran, a well-known superparamagnetic contrast agent. The measurements showed characteristic differences between the tested magnetic fluids stabilized by carboxylic compounds and ferucarbotran. It is worthy of note that our magnetic fluids have the highest r2 relaxivities at the field strength of 1.5 T, where the most of the MRI works in worldwide. - Highlights: Black-Right-Pointing-Pointer Magnetic resonance relaxation measurements were done at different field strengths. Black-Right-Pointing-Pointer Results show characteristic differences between the tested carboxylated MFs. Black-Right-Pointing-Pointer r1 and r2 relaxivities depend on the thickness of the protecting layer. Black-Right-Pointing-Pointer MFs have high r2/r1 ratios at each magnetic field.

Synthesis and crystal structures of 2-methyl-4-aryl-5-oxo-5H-indeno [1,2-b] pyridine carboxylate derivatives

DEFF Research Database (Denmark)

Pandian, Ramesh; Naushad, Edayadulla; Vijayakumar, Vinodhkumar

2014-01-01

pyridine derivatives through oxidation. Consequently, the interest in this aromatization reaction, investigation of a wide range of 1, 4-DHPs continues to attract the attention of researchers. Herein, we report the preparation of pyridine derivatives and the crystal structures determined by X......-ray crystallographic methods.Results: The crystal structures and conformational studies of two organic compounds, namely ethyl 2-methyl-4-phenyl-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate (I) and ethyl 2-methyl-4-(4 chlorophenyl)-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate (II) are reported. The terminal ethyl......) dimer running along 011 direction.Conclusion: The crystal structures ethyl 2-methyl-4-phenyl-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate and ethyl 2-methyl-4-(4 chlorophenyl)-5-oxo-5H-indeno [1,2-b] pyridine-3-carboxylate have been investigated in detail. The terminal ethyl group of compound I...

Difference between Extra- and Intracellular T1 Values of Carboxylic Acids Affects the Quantitative Analysis of Cellular Kinetics by Hyperpolarized NMR

DEFF Research Database (Denmark)

Karlsson, Magnus; Jensen, Pernille Rose; Ardenkjær-Larsen, Jan Henrik

2016-01-01

on the quantification of intracellular metabolicactivity. It is expected that the significantly shorter T1valueof the carboxylic moieties inside cells is a result of macro-molecular crowding. An artificial cytosol has been preparedand applied to predict the T1of other carboxylic acids. Wedemonstrate the value......Incomplete knowledge of the longitudinal relaxationtime constant (T1) leads to incorrect assumptions in quantita-tive kinetic models of cellular systems, studied by hyper-polarized real-time NMR. Using an assay that measures theintracellular signal of small carboxylic acids in living cells...

(2S,4R-4-Fluoropyrrolidinium-2-carboxylate

Directory of Open Access Journals (Sweden)

David B. Hobart Jr

2012-08-01

Full Text Available The crystal structure of the title compound, C5H8FNO2, at 100 K, displays intermolecular N—H...O hydrogen bonding between the ammonium and carboxylate groups as a result of its zwitterionic nature in the solid state. The five-membered ring adopts an envelope conformation with the C atom at the 3-position as the flap. The compound is of interest with respect to the synthesis and structural properties of synthetic collagens. The absolute structure was determined by comparison with the commercially available material.

Role of cysteine residues in the carboxyl-terminus of the follicle-stimulating hormone receptor in intracellular traffic and postendocytic processing

Directory of Open Access Journals (Sweden)

Brenda Melo-Nava

2016-07-01

Full Text Available Posttranslational modifications occurring during the biosynthesis of G protein-coupled receptors include glycosylation and palmitoylation at conserved cysteine residues located in the carboxyl-terminus (Ctail of the receptor. In a number of these receptors, these modifications play an important role in receptor function and particularly, in intracellular trafficking. In the present study, the three cysteine residues present in the carboxyl-terminus of the human FSHR were replaced with glycine by site-directed mutagenesis. Wild-type and mutant (Cys627/629/655Gly FSHRs were then transiently expressed in HEK-293 cells and analyzed for cell-surface plasma membrane expression, agonist-stimulated signaling and internalization, and postendocytic processing in the abscence and presence of lysosome and/or proteasome inhibitors. Compared with the wild-type FSHR, the triple mutant FSHR exhibited ~70% reduction in plasma membrane expression as well as a profound attenuation in agonist-stimulated cAMP production and ERK1/2 phosphorylation. Incubation of HEK-293 cells expressing the wild-type FSHR with 2-bromopalmitate (palmitoylation inhibitor for 6 h, decreased plasma membrane expression of the receptor by ~30%. The internalization kinetics and β-arrestin 1 and 2 recruitment were similar between the wild-type and triple mutant FSHR as disclosed by assays performed in non-equilibrium binding conditions and by confocal microscopy. Cells expressing the mutant FSHR recycled the internalized FSHR back to the plasma membrane less efficiently than those expressing the wild-type FSHR, an effect that was counteracted by proteasome but not by lysosome inhibition. These results indicate that replacement of the cysteine residues present in the carboxyl-terminus of the FSHR, impairs receptor trafficking from the endoplasmic reticulum/Golgi apparatus to the plasma membrane and its recycling from endosomes back to the cell surface following agonist

The importance of handling high-value biologicals: Physico-chemical instability and immunogenicity of monoclonal antibodies.

Science.gov (United States)

Laptoš, Tomislav; Omersel, Jasna

2018-04-01

The present review specifies the various chemical and physical factors that can influence drug stability and immunogenicity, and the treatment outcomes of antibody biologicals. Although monoclonal antibodies (mAbs) are known to be more resistant to environmental changes compared with other proteins, the molecules themselves can be subjected to chemical and physical processes that promote their degradation and transformation into their specific amino-acid moieties. With increasing use of medicinal products that contain mAbs, and their self-administration by the patients, the issue of the correct manipulation of these drugs is of increasing importance. This review summarises the correct handling of mAb biologicals from the point of view of the pharmacist, clinical biochemist and patient, as is supported by relevant cases from the literature and our own data and experience. In particular, if there is a break in the cold chain, both healthcare professionals and patients need to be aware of the potential pharmacokinetics and pharmacodynamics alterations to these biologicals. Furthermore, any alterations in the protein structure can induce harmful immune reactions, including anaphylaxis and cytokine storms, or result in the production of neutralising or blocking Abs. Overall, considering also that treatment costs usually remain high, drug stability can have a tremendous effect on the clinical, humanistic and economic outcomes of such treatments.

N-acylsulfonamides: Synthetic routes and biological potential in medicinal chemistry.

Science.gov (United States)

Ammazzalorso, Alessandra; De Filippis, Barbara; Giampietro, Letizia; Amoroso, Rosa

2017-12-01

Sulfonamide is a common structural motif in naturally occurring and synthetic medicinal compounds. The rising interest in sulfonamides and N-acyl derivatives is attested by the large number of drugs and lead compounds identified in last years, explored in different fields of medicinal chemistry and showing biological activity. Many acylsulfonamide derivatives were designed and synthesized as isosteres of carboxylic acids, being the characteristics of these functional groups very close. Starting from chemical routes to N-acylsulfonamides, this review explores compounds of pharmaceutical interest, developed as enzymatic inhibitors or targeting receptors. © 2017 John Wiley & Sons A/S.

Capillary electrophoresis in the analysis of biologically important thiols

Czech Academy of Sciences Publication Activity Database

Lačná, J.; Kubáň, Petr; Foret, František

2017-01-01

Roč. 38, č. 1 (2017), s. 203-222 ISSN 0173-0835 Institutional support: RVO:68081715 Keywords : biological thiols * capillary electrophoresis * clinical applications Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 2.744, year: 2016

Crystal structure of ethyl 2,4-dichloroquinoline-3-carboxylate

Directory of Open Access Journals (Sweden)

Alberto Cabrera

2015-12-01

Full Text Available In the crystal structure of the title compound, C12H9Cl2NO2, the mean planes through the quinoline and carboxylate groups have r.m.s. deviations of 0.006 and 0.021 Å, respectively, and form a dihedral angle of 87.06 (19°. In the crystal, molecules are linked via very weak C—H...O hydrogen bonds, forming chains, which propagate along the c-axis direction.

Studies on carboxylated graphene oxide incorporated polyetherimide mixed matrix ultrafiltration membranes

Energy Technology Data Exchange (ETDEWEB)

Kaleekkal, Noel Jacob, E-mail: noeljacob89@gmail.com [Membrane Laboratory, Department of Chemical Engineering, ACT, Anna University, Chennai, 600025 (India); Thanigaivelan, A., E-mail: thanichemstar@gmail.com [Membrane Laboratory, Department of Chemical Engineering, ACT, Anna University, Chennai, 600025 (India); Rana, Dipak, E-mail: rana@uottawa.ca [Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur Private, Ottawa, Ontario, K1N 6N5 (Canada); Mohan, D., E-mail: mohantarun@gmail.com [Membrane Laboratory, Department of Chemical Engineering, ACT, Anna University, Chennai, 600025 (India)

2017-01-15

In this work the graphene oxide prepared by the modified Hummers’ method was effectively carboxylated. These carboxylated graphene oxide (c-GO) microsheets was characterized by X-ray diffraction analysis, Raman shift, zeta potential, and their morphology was observed using a high resolution scanning/transmission electron microscopy. Polyetherimide mixed matrix membranes (MMMs) were fabricated by the non-solvent induced phase separation technique with varying concentration of this microsheet. The presence of these microsheets on the membrane surface was confirmed by Fourier transform infrared spectroscopy, Raman spectroscopy and could also be confirmed visually by optical images. The membranes were further characterized; they showed a greater water flux, higher porosity, and sufficient thermal stability. Incorporation of these microsheets improved the hydrophilicity of the membrane confirmed by the lower contact angle values, which in turn explained the lower interfacial free energy, the increase in work of adhesion, the higher solid-vapor free energy and the spreading coefficient. Membranes loaded with 0.3 wt% of c-GO showed a flux recovery of 94% and only a small flux decline even after 180 min of filtration of humic acid (HA) solution. The efficiency of these membranes in removal of HA, toxic metal ions was also investigated. The bacterial anti-adhesion property of c-GO in the membranes was also explored using Escherichia coli, as a model bio-foulant. The charge of the microsheets and their unique architecture imparts higher hydrophilicity and greater fouling resistance along with improved permeation flux when incorporated into the polymer matrix. - Highlights: • Novel membranes by incorporating carboxylated GO into polyetherimide matrix. • Modified membranes exhibited greater porosity, flux and high humic acid rejection. • Nanoplatelets improved the flux recovery ratio to >94%. • Liquid phase polymer based retention utilized for toxic heavy metal

Localized conformational interrogation of antibody and antibody-drug conjugates by site-specific carboxyl group footprinting.

Science.gov (United States)

Pan, Lucy Yan; Salas-Solano, Oscar; Valliere-Douglass, John F

Establishing and maintaining conformational integrity of monoclonal antibodies (mAbs) and antibody-drug conjugates (ADCs) during development and manufacturing is critical for ensuring their clinical efficacy. As presented here, we applied site-specific carboxyl group footprinting (CGF) for localized conformational interrogation of mAbs. The approach relies on covalent labeling that introduces glycine ethyl ester tags onto solvent-accessible side chains of protein carboxylates. Peptide mapping is used to monitor the labeling kinetics of carboxyl residues and the labeling kinetics reflects the conformation or solvent-accessibility of side chains. Our results for two case studies are shown here. The first study was aimed at defining the conformational changes of mAbs induced by deglycosylation. We found that two residues in C H 2 domain (D268 and E297) show significantly enhanced side chain accessibility upon deglycosylation. This site-specific result highlighted the advantage of monitoring the labeling kinetics at the amino acid level as opposed to the peptide level, which would result in averaging out of highly localized conformational differences. The second study was designed to assess conformational effects brought on by conjugation of mAbs with drug-linkers. All 59 monitored carboxyl residues displayed similar solvent-accessibility between the ADC and mAb under native conditions, which suggests the ADC and mAb share similar side chain conformation. The findings are well correlated and complementary with results from other assays. This work illustrated that site-specific CGF is capable of pinpointing local conformational changes in mAbs or ADCs that might arise during development and manufacturing. The methodology can be readily implemented within the industry to provide comprehensive conformational assessment of these molecules.

Phase behavior and micellar properties of carboxylic acid end group modified pluronic surfactants

NARCIS (Netherlands)

Custers, J.P.A.; Broeke, van den L.J.P.; Keurentjes, J.T.F.

2007-01-01

The micellar behavior of three different carboxylic acid end standing (CAE) surfactants has been characterized using conductometry, differential scanning calorimetry, isothermal titration calorimetry, and dynamic light scattering. The CAE surfactants are modified high molecular weight Pluronic

The need for and the importance of biological indicators of radiation effects with special reference to injuries in radiation accidents

International Nuclear Information System (INIS)

Koeteles, G.J.; Bianco, A.

1982-01-01

The need for further research on the existing and new biological indicators of radiation injury has been expressed. The studies on the radiation-induced alterations of membrane structure and function stimulated investigations aiming to develop an indicator based on membrane-phenomena. The co-ordinated research programme on ''Cell Membrane Probes as Biological Indicators of Radiation Injury in Radiation Accidents'' was initiated in mid 1977 and terminated in 1980. Within this programme many basic observations were made in connection with altered features of various animal and human cell membranes. Molecular, biophysical, biochemical and cell biological approaches were performed. The rapid reaction within minutes or hours of membranes against relatively low doses of various types of irradiations were described and the effects proved to be transitory, i.e. membrane regeneration occurred within hours. These dose- and timedependent alterations suggest the possibility of developing a biological indicator which would give signals at the earliest period after radiation injury when no other biological informations are available. The importance of a system of biological indicators is emphasized. (author)

In Vitro Reactivity of Carboxylic Acid-CoA Thioesters with Glutathione

DEFF Research Database (Denmark)

Sidenius, Ulrik; Skonberg, Christian; Olsen, Jørgen

2004-01-01

was to investigate whether a correlation could be found between the structure of acyl-CoA thioesters and their reactivities toward the tripeptide, glutathione (ç- Glu-Cys-Gly).  The  acyl-CoA  thioesters  of  eight  carboxylic  acids  (ibuprofen,  clofibric  acid, indomethacin,  fenbufen,  tolmetin,  salicylic  acid......The chemical reactivity of acyl-CoA thioesters toward nucleophiles has been demonstrated in several recent studies. Thus, intracellularly formed acyl-CoAs of xenobiotic carboxylic acids may react covalently with endogenous proteins and potentially lead to adverse effects. The purpose of this study......,  2-phenoxypropionic  acid,  and  (4-chloro-2-methyl-phenoxy)acetic  acid  (MCPA))  were  synthesized,  and  each  acyl-CoA  (0.5  mM)  was incubated with glutathione (5.0 mM) in 0.1 M potassium phosphate (pH 7.4, 37 °C). All of the acyl-CoAs reacted with glutathione to form the respective acyl...

The importance of living botanical collections for plant biology and the next generation of evo-devo research

Directory of Open Access Journals (Sweden)

Andrew eGroover

2012-06-01

Full Text Available Living botanical collections include germplasm repositories, long-term experimental plantings, and botanical gardens. We present here a series of vignettes to illustrate the central role that living collections have played in plant biology research, including evo-devo research. Looking towards the future, living collections will become increasingly important in support of future evo-devo research. The driving force behind this trend is nucleic acid sequencing technologies, which are rapidly becoming more powerful and cost-effective, and which can be applied to virtually any species. This allows for more extensive sampling, including non-model organisms with unique biological features and plants from diverse phylogenetic positions. Importantly, a major challenge for sequencing-based evo-devo research is to identify, access, and propagate appropriate plant materials. We use a vignette of the ongoing One Thousand Transcriptomes project as an example of the challenges faced by such projects. We conclude by identifying some of the pinch-points likely to be encountered by future evo-devo researchers, and how living collections can help address them.

4D-Qsar Study of Some Pyrazole Pyridine Carboxylic Acid Derivatives by Electron Conformational-Genetic Algorithm Method.

Science.gov (United States)

Tuzun, Burak; Yavuz, Sevtap Caglar; Sabanci, Nazmiye; Saripinar, Emin

2018-05-13

In the present work, pharmacophore identification and biological activity prediction for 86 pyrazole pyridine carboxylic acid derivatives were made using the electron conformational genetic algorithm approach which was introduced as a 4D-QSAR analysis by us in recent years. In the light of the data obtained from quantum chemical calculations at HF/6-311 G** level, the electron conformational matrices of congruity (ECMC) were constructed by EMRE software. Comparing the matrices, electron conformational submatrix of activity (ECSA, Pha) was revealed that are common for these compounds within a minimum tolerance. A parameter pool was generated considering the obtained pharmacophore. To determine the theoretical biological activity of molecules and identify the best subset of variables affecting bioactivities, we used the nonlinear least square regression method and genetic algorithm. The results obtained in this study are in good agreement with the experimental data presented in the literature. The model for training and test sets attained by the optimum 12 parameters gave highly satisfactory results with R2training= 0.889, q2=0.839 and SEtraining=0.066, q2ext1 = 0.770, q2ext2 = 0.750, q2ext3=0.824, ccctr = 0.941, ccctest = 0.869 and cccall = 0.927. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Synthesis, Characterization and catalytic activity of triorganotin(IV) carboxylates for the production of biodiesel from rocket seed oil

International Nuclear Information System (INIS)

Tariq, M.; Ali, S.

2013-01-01

Organotin(IV) carboxylates have a wide range of industrial applications such as antifouling paints, PVC stabilization, ion carries in electrochemical membranes and homogeneous catalysts. The catalytic application of organotin carboxylates are in the field of silicone curing, polyurethane formation and esterification. Only a limited literature is available regarding the use of organotin carboxylates in the transesterification of vegetable oil to produce biodiesel . The present study deals with the synthesis of some new triorganotin(IV) carboxylates for their subsequent use as catalyst for transesterification of rocket seed oil to produce biodiesel. The three new triorganotin(IV) i.e. (Me/sub 3/SnL) (1),(Bu/sub 3/Snl) (2) and (Ph/sub 3/SnL) (3), were synthesized by refluxing sodium salt of ligand (NaL), where L=O/sub 2/C(CH/sub 3/)C=CHC/sub 6/H/sub 4/F with trimethyl, tributyl and triphenyl tin(IV) chlorides, respectively for 10 hrs. The synthesized compounds were characterized by instrumental techniques like FT-IR and NMR (1H, 13C). The catalytic activity of these compounds was assessed for transesterification of triglycerides in rocket seed oil to produce biodiesel. All the tested compounds showed good catalytic activity in the order 1> 2 > 3. (author)

The mechanism of mediated oxidation of carboxylates with ferrocene as redox catalyst in absence of grafting effects. An experimental and theoretical approach

International Nuclear Information System (INIS)

Hernández-Muñoz, Lindsay S.; Galano, Annia; Astudillo-Sánchez, Pablo D.; Abu-Omar, Mahdi M.; González, Felipe J.

2014-01-01

Graphical abstract: - Highlights: • The mechanism of mediated oxidation of carboxylates. • Thermodynamics of the mediated Kolbe and Non-Kolbe mechanisms. • The oxidation of acetate and diphenylacetate ions by using ferrocene as redox catalyst. • Simulation and DFT calculations of the mediated oxidation of carboxylates. • Radical and carbocationic pathways in the carboxylate oxidation in acetonitrile. - Abstract: The oxidation of tetrabutylammonium carboxylates by using ferrocene derivatives as redox mediators has been recently used to perform the covalent grafting of carbon surfaces with organic and organometallic groups. Due to the intervention of this surface process, a partial description of the reaction mechanism has only been stated. Therefore, this article concerns about two features of the oxidation of carboxylates mediated by ferrocene. In the first part, it is discussed that in the oxidation of acetate ions by using ferrocene as redox catalyst, the gap between both oxidation potentials is very high, which means that the homogeneous electron transfer between the acetate ion and the electrochemically generated ferrocenium ion is energetically unfavorable. However, by using density functional theory calculations, it has been shown that the whole set of coupled chemical reactions involved either in a Kolbe or Non-Kolbe pathway drive the overall mechanisms towards a thermodynamically favorable situation. In order to avoid the strong covalent grafting process that occurs during the mediated oxidation of acetate ions, the second part of this work deals with the oxidation of tetrabutylammonium diphenylacetate by using ferrocene as a redox mediator in acetonitrile on glassy carbon electrodes. With this carboxylate, no electrode inhibition process occurs and, therefore cyclic voltammetry simulation was done to propose the electrochemical and chemical steps that are present when a carboxylate oxidation is performed in the presence of ferrocene derivatives

Leaf-specific pathogenesis-related 10 homolog, PgPR-10.3, shows in silico binding affinity with several biologically important molecules

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Jin Haeng Han

2015-10-01

Conclusion: Although ginseng PR-10.3 gene is expressed in all organs of 3-wk-old plantlets, its expression is restricted to leaves in mature 2-yr-old ginseng plants. The putative binding property of PgPR-10.3 with Re is intriguing. Further verification of binding affinity with other biologically important molecules in the large hydrophobic cavity of PgPR-10.3 may provide an insight into the biological features of PR-10 proteins.

Nitrogen Retention in Coastal Marine Sediments—a Field Study of the Relative Importance of Biological and Physical Removal in a Danish Estuary

DEFF Research Database (Denmark)

Laurentius Nielsen, Søren; Risgaard-Petersen, Nils; Banta, Gary

2017-01-01

The aim of this study was to elucidate the relative importance of physical versus biological loss processes for the removal of microphytobenthic (MPB) bound nitrogen in a coastal environment at different times of the year via a dual isotope labeling technique. We used 51Cr, binding to inorganic...... were able to discern the relative importance of physical and biological processes. The isotope marking was supplemented with measurements of sediment chlorophyll biomass and oxygen fluxes, allowing us to evaluate MPB biomass as well as primary production vs. respiration in the sediment. In spring...... was physically dominated due to low MPB biomasses and activity combined with a significant storm event. Our data support the hypothesis that the relative balance between physical and biological processes in determining retention and removal of MPB-bound nitrogen changes seasonally....

Coupling of carboxylic groups onto the surface of polystyrene parts during fused filament fabrication

Science.gov (United States)

Nagel, Jürgen; Zimmermann, Philipp; Schubert, Oliver; Simon, Frank; Schlenstedt, Kornelia

2017-11-01

A method for the fabrication of polystyrene parts, modified with carboxylic groups during Fused Filament Fabrication (FFF), is being introduced. This method is based on the application of a thin layer of a reactive polymer carrying carboxylic groups on a substrate surface. A polystyrene film is printed on top of this layer. During contact between the hot melt and the reactive layer, a Friedel-Crafts type acylation using a green catalyst takes place, which attaches the reactive polymer to the polystyrene surface. The modified surface is homogeneous, hydrophilic and able to bind copper ions. The method could be used to fabricate unique parts of polystyrene with tailored surface functionalisation. It could be applied for laboratory use, e.g. for the manufacture of lab-on-a-chip devices.

DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster

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Corneliu I. Oprea

2013-01-01

Full Text Available We report results of density functional theory (DFT calculations of a metal-free dye, 5-(4-sulfophenylazosalicylic acid disodium salt, known as Mordant Yellow 10 (MY-10, used as sensitizer for TiO2 dye-sensitized solar cells (DSSCs. Given the need to better understand the behavior of the dyes adsorbed on the TiO2 nanoparticle, we studied various single and double deprotonated forms of the dye bound to a TiO2 cluster, taking advantage of the presence of the carboxyl, hydroxyl, and sulfonic groups as possible anchors. We discuss various binding configurations to the TiO2 substrate and the charge transfer from the pigment to the oxide by means of DFT calculations. In agreement with other reports, we find that the carboxyl group tends to bind in bidentate bridging configurations. The salicylate uses both the carboxyl and hydroxyl substituent groups for either a tridentate binding to adjacent Ti(IV ions or a bidentate Ti-O binding together with an O-H-O binding, due to the rotation of the carboxyl group out of the plane of the dye. The sulfonic group prefers a tridentate binding. We analyze the propensity for electron transfer of the various dyes and find that for MY-10, as a function of the anchor group, the DSSC performance decreases in the order hydroxyl + carboxyl > carboxyl > sulfonate.

Calculation of the biological effect of fractionated radiotherapy: the importance of radiation-induced apoptosis

International Nuclear Information System (INIS)

Olsen, D.R.

1995-01-01

The total effect (TE) has been calculated for two different fractionation formalisms: the consecutive and repetitive fractionation mechanism, using a modified linear quadratic (LQ) model which includes the effect of apoptosis. For a given total dose, an increase in TE is seen when increasing the dose per fraction as well as the apoptotic fraction (F a ). Also, the TE increases with increasing α/β ratio (of the modified LQ model). The ratio of TE for tumour tissue and TE for late reacting tissue is calculated assuming the absence of apoptosis in late reacting tissue and a common value of α/β (of the modified LQ model). The biological effect ratio (BR) is higher for a large F a and low doses per fraction, than for large doses per fraction and a small F a . Assuming a consecutive fractionation mechanism, the TE formalism is unable to predict a log cell kill of more than 3 for β values of 0.010-0.028. It is less dependent on dose per fraction and F a than the repetitive fractionation mechanism. The biological effect ratio is only slightly higher than 1, and is less influenced by F a , dose per fraction and α/β ratio. A repetitive fractionation mechanism is also consistent with the preliminary results of published fractionation experiments. The calculations indicate that designing fractionation regimes for optimization of biological effect is a process where the role of apoptotic cell inactivation must be maximized, and where the influence of mitotic cell inactivation may be of less importance. (author)

Developmental biology, the stem cell of biological disciplines.

Science.gov (United States)

Gilbert, Scott F

2017-12-01

Developmental biology (including embryology) is proposed as "the stem cell of biological disciplines." Genetics, cell biology, oncology, immunology, evolutionary mechanisms, neurobiology, and systems biology each has its ancestry in developmental biology. Moreover, developmental biology continues to roll on, budding off more disciplines, while retaining its own identity. While its descendant disciplines differentiate into sciences with a restricted set of paradigms, examples, and techniques, developmental biology remains vigorous, pluripotent, and relatively undifferentiated. In many disciplines, especially in evolutionary biology and oncology, the developmental perspective is being reasserted as an important research program.

Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

KAUST Repository

Li, Yang; Tu, Xingchen; Wang, Minglang; Wang, Hao; Sanvito, Stefano; Hou, Shimin

2014-01-01

© 2014 AIP Publishing LLC. The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

The influence of addition of papain enzyme and Carboxyl Methyl Cellulose on the textural properties of Tofu

Science.gov (United States)

Faridah; Fachraniah; Arifien; Sari, C. M.

2018-03-01

Papain enzyme and carboxyl methyl cellulosa was used in tofu production as coagulant and thickener. Papain enzyme is a protease enzyme that can break proteins. Papain enzymeuseful as coagulant to replace acid and base coagulant. The goal of this study is to observe papain enzyme as coagulant and carboxyl methyl cellulose as thickener to increase characteristic of tofu. Tofu is from soy milk has been pasteurized at 70 °C with the addition of papain enzyme and carboxyl methly cellulose. The concenration of papain enzyme is varied such as 200, 400, 800, and 1000 ppm. After Temperature reachs at 90 °C, carboxyl methyl cellulosa is added in soy milk to produce tofu. This study focuses on introducing papain enzyme as coagulant as well as investigating its potential in improving tofu making process productivity. Further the present work attempts to determine the synergistic effect of combining CMC/enzyme in tofu characteristic. This research was conducted with soy milk pasteurized at 70 °C with increasing papain enzyme. Protein from tofu was determined by using Spectrophotometer UV-VIS Shimadzu UV-1800 type. The highest protein concentration of the papain enzyme was found in 1000 ppm with CMC concentration of 0.6% w/v and based on organoleptic tests that the adding CMC and enzyme papain does not effect the taste, smell, texture and color of tofu. The taste of tofu produced is similar to the taste of tofu in the market.

Microscopic mechanism of electron transfer through the hydrogen bonds between carboxylated alkanethiol molecules connected to gold electrodes

KAUST Repository

Li, Yang

2014-11-07

© 2014 AIP Publishing LLC. The atomic structure and the electron transfer properties of hydrogen bonds formed between two carboxylated alkanethiol molecules connected to gold electrodes are investigated by employing the non-equilibrium Green\\'s function formalism combined with density functional theory. Three types of molecular junctions are constructed, in which one carboxyl alkanethiol molecule contains two methylene, -CH2, groups and the other one is composed of one, two, or three -CH2 groups. Our calculations show that, similarly to the cases of isolated carboxylic acid dimers, in these molecular junctions the two carboxyl, -COOH, groups form two H-bonds resulting in a cyclic structure. When self-interaction corrections are explicitly considered, the calculated transmission coefficients of these three H-bonded molecular junctions at the Fermi level are in good agreement with the experimental values. The analysis of the projected density of states confirms that the covalent Au-S bonds localized at the molecule-electrode interfaces and the electronic coupling between -COOH and S dominate the low-bias junction conductance. Following the increase of the number of the -CH2 groups, the coupling between -COOH and S decreases deeply. As a result, the junction conductance decays rapidly as the length of the H-bonded molecules increases. These findings not only provide an explanation to the observed distance dependence of the electron transfer properties of H-bonds, but also help the design of molecular devices constructed through H-bonds.

Mathematical biology

CERN Document Server

Murray, James D

1993-01-01

The book is a textbook (with many exercises) giving an in-depth account of the practical use of mathematical modelling in the biomedical sciences. The mathematical level required is generally not high and the emphasis is on what is required to solve the real biological problem. The subject matter is drawn, e.g. from population biology, reaction kinetics, biological oscillators and switches, Belousov-Zhabotinskii reaction, reaction-diffusion theory, biological wave phenomena, central pattern generators, neural models, spread of epidemics, mechanochemical theory of biological pattern formation and importance in evolution. Most of the models are based on real biological problems and the predictions and explanations offered as a direct result of mathematical analysis of the models are important aspects of the book. The aim is to provide a thorough training in practical mathematical biology and to show how exciting and novel mathematical challenges arise from a genuine interdisciplinary involvement with the biosci...

Boron-Catalyzed N-Alkylation of Amines using Carboxylic Acids.

Science.gov (United States)

Fu, Ming-Chen; Shang, Rui; Cheng, Wan-Min; Fu, Yao

2015-07-27

A boron-based catalyst was found to catalyze the straightforward alkylation of amines with readily available carboxylic acids in the presence of silane as the reducing agent. Various types of primary and secondary amines can be smoothly alkylated with good selectivity and good functional-group compatibility. This metal-free amine alkylation was successfully applied to the synthesis of three commercial medicinal compounds, Butenafine, Cinacalcet. and Piribedil, in a one-pot manner without using any metal catalysts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A miniaturized electrochemical toxicity biosensor based on graphene oxide quantum dots/carboxylated carbon nanotubes for assessment of priority pollutants

Energy Technology Data Exchange (ETDEWEB)

Zhu, Xiaolin; Wu, Guanlan; Lu, Nan [School of Environment, Northeast Normal University, Changchun 130117 (China); Yuan, Xing, E-mail: yuanx@nenu.edu.cn [School of Environment, Northeast Normal University, Changchun 130117 (China); Li, Baikun, E-mail: baikun@engr.uconn.edu [Department of Civil and Environmental Engineering, University of Connecticut, Storrs, CT 06269 (United States)

2017-02-15

Highlights: • Graphene oxide quantum dots/carboxylated carbon nanotubes hybrid was developed. • The cytotoxicity detection vessel was miniaturized to the 96-well plate. • The electrochemical behavior of HepG2 cell was investigated for the first time. • The mixture signal of adenine and hypoxanthine was separated successfully. • The biosensor was used to assess the toxicity of heavy metals and phenols. - Abstract: The study presented a sensitive and miniaturized cell-based electrochemical biosensor to assess the toxicity of priority pollutants in the aquatic environment. Human hepatoma (HepG2) cells were used as the biological recognition agent to measure the changes of electrochemical signals and reflect the cell viability. The graphene oxide quantum dots/carboxylated carbon nanotubes hybrid was developed in a facile and green way. Based on the hybrid composite modified pencil graphite electrode, the cell culture and detection vessel was miniaturized to a 96-well plate instead of the traditional culture dish. In addition, three sensitive electrochemical signals attributed to guanine/xanthine, adenine, and hypoxanthine were detected simultaneously. The biosensor was used to evaluate the toxicity of six priority pollutants, including Cd, Hg, Pb, 2,4-dinitrophenol, 2,4,6-trichlorophenol, and pentachlorophenol. The 24 h IC{sub 50} values obtained by the electrochemical biosensor were lower than those of conventional MTT assay, suggesting the enhanced sensitivity of the electrochemical assay towards heavy metals and phenols. This platform enables the label-free and sensitive detection of cell physiological status with multi-parameters and constitutes a promising approach for toxicity detection of pollutants. It makes possible for automatical and high-throughput analysis on nucleotide catabolism, which may be critical for life science and toxicology.

Synthesis and antifungal activity of the derivatives of novel pyrazole carboxamide and isoxazolol pyrazole carboxylate.

Science.gov (United States)

Sun, Jialong; Zhou, Yuanming

2015-03-09

A series of pyrazole carboxamide and isoxazolol pyrazole carboxylate derivatives were designed and synthesized in this study. The structures of the compounds were elucidated based on spectral data (infrared, proton nuclear magnetic resonance and mass spectroscopy). Then, all of the compounds were bioassayed in vitro against four types of phytopathogenic fungi (Alternaria porri, Marssonina coronaria, Cercospora petroselini and Rhizoctonia solani) using the mycelium growth inhibition method. The results showed that some of the synthesized pyrazole carboxamides displayed notable antifungal activity. The isoxazole pyrazole carboxylate 7ai exhibited significant antifungal activity against R. solani, with an EC50 value of 0.37 μg/mL. Nonetheless, this value was lower than that of the commercial fungicide, carbendazol.

Use of technical mixtures of carboxylic acids to the extraction of silver

International Nuclear Information System (INIS)

Smulek, W.

1983-01-01

The application of technical mixtures of carboxylic acids, obtained from a Polish oil mill, to the extraction of silver, gold, and europium is described. The distribution ratio is given as a function of HNO 3 and H 2 SO 4 concentrations, extractant and metal concentrations, and nature of diluent. (author)

The important of living botanical collections for plant biology and the “next generation” of evo-devo research

Science.gov (United States)

Michael Dosmann; Andrew Groover

2012-01-01

Living botanical collections include germplasm repositories, long-term experimental plantings, and botanical gardens. We present here a series of vignettes to illustrate the central role that living collections have played in plant biology research, including evo-devo research. Looking towards the future, living collections will become increasingly important in support...

Isoprenoid-derived plant signaling molecules: biosynthesis and biological importance

Czech Academy of Sciences Publication Activity Database

Tarkowská, Danuše; Strnad, Miroslav

2018-01-01

Roč. 247, č. 5 (2018), s. 1051-1066 ISSN 0032-0935 R&D Projects: GA MŠk(CZ) LO1204 Institutional support: RVO:61389030 Keywords : Dimethylallyl diphosphate * Isopentenyl diphosphate * Isoprenoids * Phytoecdysteroids * Plant hormones * Terpenoids Subject RIV: EB - Genetics ; Molecular Biology OBOR OECD: Biochemical research methods Impact factor: 3.361, year: 2016

tert-Butyl 4-carbamoyl-3-methoxyimino-4-methylpiperidine-1-carboxylate

Directory of Open Access Journals (Sweden)

Yucheng Wang

2008-12-01

Full Text Available The title compound, C13H23N3O4, was prepared starting from ethyl N-benzyl-3-oxopiperidine-4-carboxylate through a nine-step reaction, including hydrogenation, Boc (tert-butoxycarbonyl protection, methylation, oximation, hydrolysis, esterification and ammonolysis. In the crystal structure, molecules are linked by intermolecular N—H...O hydrogen bonds to form a porous three-dimensional network with solvent-free hydrophobic channels extending along the c axis.

Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

Science.gov (United States)

Duncan, Kyle D.; Volmer, Dietrich A.; Gill, Chris G.; Krogh, Erik T.

2016-03-01

Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H]-) ions with limited selective fragmentation. However, carboxylates cationized with Ba2+ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba]+ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]+ and [BaOH]+). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling.

Science.gov (United States)

Duncan, Kyle D; Volmer, Dietrich A; Gill, Chris G; Krogh, Erik T

2016-03-01

Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M - H](-)) ions with limited selective fragmentation. However, carboxylates cationized with Ba(2+) have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M - H + Ba](+) precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH](+) and [BaOH](+)). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

Copper coordination polymers constructed from thiazole-5-carboxylic acid: Synthesis, crystal structures, and structural transformation

Energy Technology Data Exchange (ETDEWEB)

Meundaeng, Natthaya; Rujiwatra, Apinpus [Department of Chemistry, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Prior, Timothy J., E-mail: t.prior@hull.ac.uk [Chemistry, University of Hull, Kingston upon Hull HU6 7RX (United Kingdom)

2017-01-15

We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu{sup 2+} coordination polymers with different dimensionality, namely, 1D [Cu{sub 2}(5-tza){sub 2}(1,10-phenanthroline){sub 2}(NO{sub 3}){sub 2}] (1), 2D [Cu(5-tza){sub 2}(MeOH){sub 2}] (2), and 3D [Cu(5-tza){sub 2}]·H{sub 2}O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza){sub 2}]·1.5H{sub 2}O upon heat treatment for 2 h. This 2D network can adsorb water and convert to 3 upon exposure to air. - Highlights: • Rare examples of coordination polymers of thiazole-5-carboxylic acid were prepared. • Non-covalent interactions play a key role on the assembly of the complexes in solid state. • Structural transformation of a 2D framework to a 3D upon removal of methanol is observed.

Substituted Pyrazinecarboxamides: Synthesis and Biological Evaluation

Directory of Open Access Journals (Sweden)

Katarina Kralova

2006-03-01

Full Text Available Condensation of the corresponding chlorides of some substituted pyrazine-2-carboxylic acids (pyrazine-2-carboxylic acid, 6-chloropyrazine-2-carboxylic acid, 5-tert-butylpyrazine-2-carboxylic acid or 5-tert-butyl-6-chloropyrazine-2-carboxylic acid withvarious ring-substituted aminothiazoles or anilines yielded a series of amides. Thesyntheses, analytical and spectroscopic data of thirty newly prepared compounds arepresented. Structure-activity relationships between the chemical structures and the anti-mycobacterial, antifungal and photosynthesis-inhibiting activity of the evaluatedcompounds are discussed. 3,5-Bromo-4-hydroxyphenyl derivatives of substitutedpyrazinecarboxylic acid, 16-18, have shown the highest activity against Mycobacteriumtuberculosis H37Rv (54-72% inhibition. The highest antifungal effect againstTrichophyton mentagrophytes, the most susceptible fungal strain tested, was found for5-tert-butyl-6-chloro-N-(4-methyl-1,3-thiazol-2-ylpyrazine-2-carboxamide (8, MIC =31.25 μmol·mL-1. The most active inhibitors of oxygen evolution rate in spinachMolecules 2006, 11 243 chloroplasts were the compounds 5-tert-butyl-6-chloro-N-(5-bromo-2-hydroxyphenyl- pyrazine-2-carboxamide (27, IC50 = 41.9 μmol·L-1 and 5-tert-butyl-6-chloro-N-(1,3- thiazol-2-yl-pyrazine-2-carboxamide (4, IC50 = 49.5 μmol·L-1.

Photochemistry of Fe(Iii)-Carboxylates in Polysaccharide-Based Materials with Tunable Mechanical Properties

Science.gov (United States)

Giammanco, Giuseppe E.

We present the formulation and study of light-responsive materials based on carboxylate-containing polysaccharides. The functional groups in these natural polymers allow for strong interactions with transition metal ions such as Fe(III). The known photochemistry of hydroxycarboxylic acids in natural waters inspired us in exploring the visible light induced photochemistry of the carboxylates in these polysaccharides when coordinated to Fe(III) ions. Described in this dissertation are the design and characterization of the Fe(III)-polysaccharide materials, specifically the mechanistic aspects of the photochemistry and the effects that these reactions have on the structure of the polymer materials. We present a study of the quantitative photochemistry of different polysaccharide systems, where the presence of uronic acids was important for the photoreaction to take place. Alginate (Alg), pectate (Pec), hyaluronic acid (Hya), xanthan gum (Xan), and a polysaccharide extracted from the Noni fruit (NoniPs), were among the natural uronic acid-containing polysaccharide (UCPS) systems we analyzed. Potato starch, lacking of uronate groups, did not present any photochemistry in the presence of Fe(III); however, we were able to induce a photochemical response in this polysaccharide upon chemical manipulation of its functional groups. Important structure-function relationships were drawn from this study. The uronate moiety present in these polysaccharides is then envisioned as a tool to induce response to light in a variety of materials. Following this approach, we report the formulation of materials for controlled drug release, able to encapsulate and release different drug models only upon illumination with visible light. Furthermore, hybrid hydrogels were prepared from UPCS and non-responsive polymers. Different properties of these materials could be tuned by controlling the irradiation time, intensity and location. These hybrid gels were evaluated as scaffolds for tissue

Simple quantification of surface carboxylic acids on chemically oxidized multi-walled carbon nanotubes

Science.gov (United States)

Gong, Hyejin; Kim, Seong-Taek; Lee, Jong Doo; Yim, Sanggyu

2013-02-01

The surface of multi-walled carbon nanotube (MWCNT) was chemically oxidized using nitric acid and sulfuric-nitric acid mixtures. Thermogravimetric analysis, transmission electron microscopy and infrared spectroscopy revealed that the use of acid mixtures led to higher degree of oxidation. More quantitative identification of surface carboxylic acids was carried out using X-ray photoelectron spectroscopy (XPS) and acid-base titration. However, these techniques are costly and require very long analysis times to promptly respond to the extent of the reaction. We propose a much simpler method using pH measurements and pre-determined pKa value in order to estimate the concentration of carboxylic acids on the oxidized MWCNT surfaces. The results from this technique were consistent with those obtained from XPS and titration, and it is expected that this simple quantification method can provide a cheap and fast way to monitor and control the oxidation reaction of MWCNT.

On the intermediacy of carboxyphosphate in biotin-dependent carboxylations

International Nuclear Information System (INIS)

Ogita, Takeshi; Knowles, J.R.

1988-01-01

In the ATP-dependent carboxylation of biotin that is catalyzed by most biotin-dependent carboxylases, a fundamental mechanistic question is whether the ATP activates bicarbonate (via the formation of carboxyphosphate as an intermediate) or whether the ATP activates biotin (via the formation of O-phosphobiotin). The authors have resorted to three mechanistic tests using the biotin carboxylase subunit of acetyl-CoA carboxylase from Escherichia coli: positional isotope exchange, intermediate trapping, and 18 O tracer experiments on the ATPase activity. First, no catalysis of positional isotope exchange in adenosine 5'-([α,β- 18 O,β,β- 18 O 2 ]triphosphate) was observed when either biotin or bicarbonate was absent, nor was any exchange seen in the presence of both N-1-methylbiotin and bicarbonate. Second, the putative carboxyphosphate intermediate could not be trapped as its trimethyl ester, under conditions of incubation and analysis where the authentic triester was shown to be adequately stable. In the third test, however, they showed that the ATPase activity of biotin carboxylase that is seen in the absence of biotin, an activity that is known to parallel the normal carboxylase reaction when biotin is present, occurs with the transfer of an 18 O label directly from [ 18 O]bicarbonate into the product P i . This result suggests that the bicarbonate-dependent biotin-independent ATPase reaction catalyzed by biotin carboxylase goes via carboxyphosphate and that the carboxylation of biotin itself may proceed analogously

Diaqua­bis­(pyridine-2-carboxyl­ato-κ2 N,O)manganese(II) dimethyl­formamide hemisolvate

Science.gov (United States)

Golenya, Irina A.; Boyko, Alexander N.; Kalibabchuk, Valentina A.; Haukka, Matti; Tomyn, Stefania V.

2011-01-01

There are two crystallographically independent complex mol­ecules with very similar geometries in the unit cell of the title compound, [Mn(C6H4NO2)2(H2O)2]·0.5C3H7NO. The central ion is situated in a distorted octa­hedral environment of two N- and four O-donor atoms from two pyridine-2-carboxyl­ate ligands and two cis-disposed water mol­ecules. The carboxyl­ate ligands are coordinated in a chelate fashion with the formation of two five-membered rings. In the crystal, the complex mol­ecules are connected by O—H⋯O hydrogen bonds between the coordinated water mol­ecules and the uncoordinated carboxyl­ate O atoms, thus forming hydrogen-bonded walls disposed perpendicularly to the bc plane. PMID:22219799

3-Carboxyquinolin-1-ium-2-carboxylate monohydrate

Directory of Open Access Journals (Sweden)

Qing Zhang

2012-03-01

Full Text Available The title compound, C11H7NO4·H2O, contains a 3-carboxyquinolin-1-ium-2-carboxylate (qda zwitterion and one water molecule. In the crystal, pairs of N—H...O hydrogen bonds link the molecules into inversion dimers, and these dimers are further connected by O—H...O hydrogen bonds into a three-dimensional supramolecular architecture. In addition, π–π interactions occur between pyridine and benzene rings from different qda ligands [centroid–centroid distance = 3.749 (1 Å] and the dihedral angles of the –CO2H and –CO2 groups to the quinoline system are 8.47 (3 and 88.16 (6°, respectively.

On the formation of niacin (vitamin B3) and pyridine carboxylic acids in interstellar model ices

Energy Technology Data Exchange (ETDEWEB)

McMurtry, Brandon M.; Turner, Andrew M.; Saito, Sean E.J.; Kaiser, Ralf I. [W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, Hawaii, HI 96822 (United States); Department of Chemistry, University of Hawaii at Manoa, Honolulu, Hawaii, HI 96822 (United States)

2016-06-15

The formation of pyridine carboxylic acids in interstellar ice grains was simulated by electron exposures of binary pyridine (C{sub 5}H{sub 5}N)-carbon dioxide (CO{sub 2}) ice mixtures at 10 K under contamination-free ultrahigh vacuum conditions. Chemical processing of the pristine ice and subsequent warm-up phase was monitored on line and in situ via Fourier transform infrared spectroscopy to probe for the formation of new radiation induced species. In the infrared spectra of the irradiated ice, bands assigned to nicotinic acid (niacin; vitamin B3; m-C{sub 5}H{sub 4}NCOOH) along with 2,3-, 2,5-, 3,4-, and 3,5-pyridine dicarboxylic acid (C{sub 5}H{sub 3}N(COOH){sub 2}) were unambiguously identified along with the hydroxycarbonyl (HOCO) radical. Our study suggests that the reactive pathway responsible for pyridine carboxylic acids formation involves a HOCO intermediate, which forms through the reaction of suprathermal hydrogen ejected from pyridine with carbon dioxide. The newly formed pyridinyl radical may then undergo radical–radical recombination with a hydroxycarbonyl radical to form a pyridine carboxylic acid.

The fate of nanocarriers as nanomedicines in vivo: important considerations and biological barriers to overcome.

Science.gov (United States)

Moros, M; Mitchell, S G; Grazú, V; de la Fuente, J M

2013-01-01

Many pharmaceuticals on the market suffer from two significant limitations to their activity: lack of specificity toward the pathological site and poor aqueous solubility. Both factors therefore require the application of a large total dose of a drug to achieve high local concentration, causing numerous off-target toxic effects. Consequently, the grand aim of targeted drug delivery - the often-referred "magic bullet" - promises to improve drug concentration at the target site and maximize therapeutic response. Nanomaterial drug delivery systems have been explored extensively in the recent years for just this purpose. In the field of medicine, nanocarriers (NCs) have the potential to improve the biodistribution and pharmacokinetic characteristics of drugs, thereby reducing side effects while improving the therapeutic effect of drugs. Many nanomaterials are exquisitely designed and possess potent properties, yet it is extremely important to note that a general understanding of the interaction of nanomaterials with biological systems is essential for any such model properties to be effective in vivo, since the body presents a host of biological 'barriers' that will be encountered drug NCs. This review offers a general overview of the different biological obstacles that a NC must negotiate before it can carry out its desired role as a medicinal agent. From this standpoint we suggest aspects that should be considered for the rational design of novel nanomaterials possessing physicochemical properties that are appropriate for therapeutic or theragnostic applications.

CsF-promoted carboxylation of aryl(hetaryl) terminal alkynes with atmospheric CO_2 at room temperature

International Nuclear Information System (INIS)

Yu, B.; Yang, Z.Z.; Zhao, Y.F.; Zhang, H.Y.; Yang, P.; Gao, X.; Liu, Z.M.

2017-01-01

A CsF-promoted carboxylation of aryl(hetaryl) terminal alkynes with atmospheric CO_2 in the presence of trimethylsilylacetylene was developed to give functionalized propiolic acid products at room temperature. A wide range of propiolic acids bearing functional groups was successfully obtained in good to excellent yields. Mechanistic studies demonstrate that in the carboxylation process the alkynyl-silane intermediate was first in situ generated, which was then trapped by CO_2, giving rise to the corresponding functionalized propiolic acids after acidification. The advantages of this approach include avoiding use of transition-metal catalysts, wide substrate scope together with excellent functional group tolerance, ambient conditions and a facile work-up procedure. (authors)

Pyrazole carboxamides and carboxylic acids as protein kinase inhibitors in aberrant eukaryotic signal transduction

DEFF Research Database (Denmark)

Persson, Tobias; Yde, Christina W.; Rasmussen, Jakob Ewald

2007-01-01

Densely functionalised pyrazole carboxamides and carboxylic acids were synthesised in an expedient manner through saponification and transamidation, respectively, of ester-functionalised pyrazoles. This synthetic protocol allowed for three diversifying steps in which appendages on the pyrazole...

Effect of organic bases on extraction of gadolinium carboxylates

International Nuclear Information System (INIS)

Sukhan, V.V.; Frankovskij, V.A.

1982-01-01

The effect of pyridine, 2-aminopyridine, benzylamine, antipyrine and o-phenanthroline on the extraction of capronates and bromocapronates of gadolinium with chloroform is studied. Out of the studied organic bases benzylamine produces the highest synergetic effect. In the absence of organic bases gadolinium carboxylates, solvated by three molecules of carbonic acids, are extracted into organic phase. A possihility of extractional separation of gadolinium from comparable amounts of iron with the mixture of 1 M solutions of caproic or bromocaproic acids with 1 M benzylamine from 0.1 M solution of tartaric acids is shown [ru

Edge-carboxylated graphene nanoflakes from nitric acid oxidised arc-discharge material

OpenAIRE

NICOLOSI, VALERIA

2010-01-01

PUBLISHED Graphene nanoflakes (GNFs) with average diameters of 30 nm have been prepared by a single-step oxidation procedure using single-wall carbon nanotube arc-discharge material and nitric acid. The GNFs are predominately single sheets containing a small number of internal defects. The edges are decorated with primarily carboxylic acid groups which allow facile chemical functionalisation and cross-linking of the fragments using multivalent cations

Synthesis of N-acylurea derivatives from carboxylic acids and N,N ...

Indian Academy of Sciences (India)

acid 1 (scheme 1) to the basic nitrogen of the carbodi- imide 2, followed by addition of the carboxylate to form the O-acyl isourea 3. It is known10 that in low dielec- tric constant solvents such as CH2Cl2, formation of 3 occurs instantaneously and, in the absence of a nucle- ophile or a base, it can be stable for many hours.

Tuning metal–carboxylate coordination in crystalline metal–organic frameworks through surfactant media

Energy Technology Data Exchange (ETDEWEB)

Gao, Junkuo [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ye, Kaiqi [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012 (China); He, Mi [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore); Xiong, Wei-Wei; Cao, Wenfang; Lee, Zhi Yi [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Wang, Yue [State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun 130012 (China); Wu, Tom [Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore); Huo, Fengwei [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Liu, Xiaogang [Department of Chemistry, National University of Singapore, Singapore 117543 (Singapore); Institute of Materials Research Engineering, Agency for Science, Technology and Research, Singapore 117602 (Singapore); Zhang, Qichun, E-mail: qczhang@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore)

2013-10-15

Although it has been widely demonstrated that surfactants can efficiently control the size, shape and surface properties of micro/nanocrystals of metal–organic frameworks (MOFs) due to the strong interactions between surfactants and crystal facets of MOFs, the use of surfactants as reaction media to grow MOF single crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These factors strongly motivate us to develop a new synthetic strategy: growing crystalline MOFs in surfactants. In this report, eight new two-dimensional (2D) or three-dimensional (3D) MOFs have been successfully synthesized in an industrially-abundant and environmentally-friendly surfactant: polyethylene glycol-200 (PEG-200). Eight different coordination modes of carboxylates, ranging from monodentate η{sup 1} mode to tetra-donor coordination µ{sub 3}-η{sup 1}:η{sup 2}:η{sup 1} mode, have been founded in our research. The magnetic properties of Co-based MOFs were investigated and MOF NTU-Z6b showed a phase transition with a Curie temperature (T{sub c}) at 5 K. Our strategy of growing crystalline MOFs in surfactant could offer exciting opportunities for preparing novel MOFs with diverse structures and interesting properties. - Graphical abstract: Surfactants have been used as reaction media to grow MOF single crystals for the first time. Eight new two-dimensional or three-dimensional MOFs were successfully synthesized in surfactant polyethylene glycol-200 (PEG-200). Coordination modes of carboxylates up to eight were founded. Our strategy of growing crystalline MOFs in surfactant could offer exciting opportunities for preparing novel MOFs with diverse structures and interesting properties. Display Omitted - Highlights: • Surfactant-thermal synthesis of crystalline metal–organic frameworks. • Eight new 2-D or 3-D metal–organic frameworks

Syntheses, structures, photoluminescence and photocatalysis of 2D layered lanthanide-carboxylates with 2, 2′-dithiodibenzoic acid

Energy Technology Data Exchange (ETDEWEB)

Ding, Ling; Zhong, Jie-Cen; Qiu, Xing-Tai; Sun, Yan-Qiong, E-mail: sunyq@fzu.edu.cn; Chen, Yi-Ping

2017-02-15

Two series of lanthanide-carboxylates, [Ln(2,2′-dtba)(2,2′-Hdtba)(EtOH)]{sub n} (I:Ln=Eu(1a), Dy(1b)) and [Ln(2,2′-dtba)(2,2′-Hdtba)(4,4′-bpy){sub 0.5}]{sub n} (II:Ln=Eu(2a), Dy(2b), Tb(2c) 2,2′-H{sub 2}dtba=2,2′-dithiodibenzoic acid, 4,4′-bpy=4,4′-bipyridine) have been synthesized under hydrothermal conditions. Interestingly, the H{sub 2}dtba organic ligand was generated by in situ S–S reaction of 2-mercaptobenzoic acid. Compounds I and II possess different 2D layered structures based on similar 1D [Ln(2,2′-dtba)]{sup +} chains. Photoluminescence studies reveal that compounds I and II exhibit strong lanthanide characteristic emission bands. Remarkably, Compounds 1b and 2a both exhibit good photocatalytic activity for degradation of Rhodamine-B (Rh-B) under the simulated sunlight irradiation. - Graphical abstract: Two series of lanthanide-carboxylates have been in situ synthesized under hydrothermal conditions. The lanthanide-carboxylates exhibit strong lanthanide characteristic emission bands and good photocatalytic activity for degradation of Rhodamine-B. - Highlights: • 2D layered lanthanide-carboxylates with 2,2′-dithiodibenzoic acid. • In situ S–S reaction of 2-mercaptobenzoic acid under hydrothermal condition. • The Emission spectra of I and II exhibit the characteristic transition of lanthanide ions. • Compounds 1b and 2a exhibit good photocatalytic activity for degradation of Rhodamine-B.

Ethylene biosynthesis by 1-aminocyclopropane-1-carboxylic acid oxidase: a DFT study.

Science.gov (United States)

Bassan, Arianna; Borowski, Tomasz; Schofield, Christopher J; Siegbahn, Per E M

2006-11-24

The reaction catalyzed by the plant enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO) was investigated by using hybrid density functional theory. ACCO belongs to the non-heme iron(II) enzyme superfamily and carries out the bicarbonate-dependent two-electron oxidation of its substrate ACC (1-aminocyclopropane-1-carboxylic acid) concomitant with the reduction of dioxygen and oxidation of a reducing agent probably ascorbate. The reaction gives ethylene, CO(2), cyanide and two water molecules. A model including the mononuclear iron complex with ACC in the first coordination sphere was used to study the details of O-O bond cleavage and cyclopropane ring opening. Calculations imply that this unusual and complex reaction is triggered by a hydrogen atom abstraction step generating a radical on the amino nitrogen of ACC. Subsequently, cyclopropane ring opening followed by O-O bond heterolysis leads to a very reactive iron(IV)-oxo intermediate, which decomposes to ethylene and cyanoformate with very low energy barriers. The reaction is assisted by bicarbonate located in the second coordination sphere of the metal.

Synthesis and Antifungal Activity of the Derivatives of Novel Pyrazole Carboxamide and Isoxazolol Pyrazole Carboxylate

Directory of Open Access Journals (Sweden)

Jialong Sun

2015-03-01

Full Text Available A series of pyrazole carboxamide and isoxazolol pyrazole carboxylate derivatives were designed and synthesized in this study. The structures of the compounds were elucidated based on spectral data (infrared, proton nuclear magnetic resonance and mass spectroscopy. Then, all of the compounds were bioassayed in vitro against four types of phytopathogenic fungi (Alternaria porri, Marssonina coronaria, Cercospora petroselini and Rhizoctonia solani using the mycelium growth inhibition method. The results showed that some of the synthesized pyrazole carboxamides displayed notable antifungal activity. The isoxazole pyrazole carboxylate 7ai exhibited significant antifungal activity against R. solani, with an EC50 value of 0.37 μg/mL. Nonetheless, this value was lower than that of the commercial fungicide, carbendazol.

Synthesis of a novel poly-thiolated magnetic nano-platform for heavy metal adsorption. Role of thiol and carboxyl functions

International Nuclear Information System (INIS)

Odio, Oscar F.; Lartundo-Rojas, Luis; Palacios, Elia Guadalupe; Martínez, Ricardo; Reguera, Edilso

2016-01-01

Graphical abstract: Poly-thiols capping of magnetite nanoparticles for Pb(2+) and Cd(2+) adsorption. Display Omitted - Highlights: • A novel magnetic nano-platform containing free thiol and carboxyl groups is reported. • Thiols are protected by disulfide bridges during magnetite functionalization. • Adsorption of Pb"2"+ and Cd"2"+ onto the nano-platform was studied by XPS measurements. • Metal-sulfur interactions dominate if free thiol groups are present. • Metal-carboxyl interactions dominate if thiol groups are depleted by oxidation. - Abstract: We report a novel strategy for the synthesis of magnetic nano-platforms containing free thiol groups. It first involves the synthesis of a poly(acrylic acid) copolymer containing disulfide bridges between the linear chains through di-ester linkages, followed by the anchoring of this new ligand to magnetite nanoparticles using a ligand exchange reaction. Finally, free −SH groups are obtained by treating the resulting disulfide-functionalized magnetic nano-system with tributyl phosphine as reducing agent. The characterization of the resulting 17 nm nanoparticles (Fe_3O_4@PAA-HEDred) by FTIR and TGA confirms the attachment of the copolymer through iron carboxylates. XRD, TEM and magnetic measurements indicate an increase in the inorganic core diameter and the occurrence of strong magnetic inter-particle interactions during the exchange reaction, although coercitivity and remanence drop to near zero at room temperature. Afterwards, Fe_3O_4@PAA-HEDred nanoparticles were tested as sorbent for Pb"2"+ and Cd"2"+ cations in aqueous media. XPS measurements were performed in order to unravel the role of both carboxyl and thiol functions in the adsorption process. For the sake of comparison, the same study was performed using bare Fe_3O_4 nanoparticles and a nanosystem with disulfide groups (Fe_3O_4@DMSA). The joint analysis of the Pb 4f, Cd 3d, Fe 2p and S 2p high resolution spectra for the nanostructured materials

Synthesis of a novel poly-thiolated magnetic nano-platform for heavy metal adsorption. Role of thiol and carboxyl functions

Energy Technology Data Exchange (ETDEWEB)

Odio, Oscar F. [Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, La Habana 10400 (Cuba); Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada-Unidad Legaria, IPN, 11500 México City (Mexico); Lartundo-Rojas, Luis [Centro de Nanociencias y Micro-Nanotecnologías, IPN, 07738 México City (Mexico); Palacios, Elia Guadalupe [Instituto Politécnico Nacional, ESIQIE, UPALM Zacatenco, 07738 México City (Mexico); Martínez, Ricardo [Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, La Habana 10400 (Cuba); Reguera, Edilso, E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada-Unidad Legaria, IPN, 11500 México City (Mexico)

2016-11-15

Graphical abstract: Poly-thiols capping of magnetite nanoparticles for Pb(2+) and Cd(2+) adsorption. Display Omitted - Highlights: • A novel magnetic nano-platform containing free thiol and carboxyl groups is reported. • Thiols are protected by disulfide bridges during magnetite functionalization. • Adsorption of Pb{sup 2+} and Cd{sup 2+} onto the nano-platform was studied by XPS measurements. • Metal-sulfur interactions dominate if free thiol groups are present. • Metal-carboxyl interactions dominate if thiol groups are depleted by oxidation. - Abstract: We report a novel strategy for the synthesis of magnetic nano-platforms containing free thiol groups. It first involves the synthesis of a poly(acrylic acid) copolymer containing disulfide bridges between the linear chains through di-ester linkages, followed by the anchoring of this new ligand to magnetite nanoparticles using a ligand exchange reaction. Finally, free −SH groups are obtained by treating the resulting disulfide-functionalized magnetic nano-system with tributyl phosphine as reducing agent. The characterization of the resulting 17 nm nanoparticles (Fe{sub 3}O{sub 4}@PAA-HEDred) by FTIR and TGA confirms the attachment of the copolymer through iron carboxylates. XRD, TEM and magnetic measurements indicate an increase in the inorganic core diameter and the occurrence of strong magnetic inter-particle interactions during the exchange reaction, although coercitivity and remanence drop to near zero at room temperature. Afterwards, Fe{sub 3}O{sub 4}@PAA-HEDred nanoparticles were tested as sorbent for Pb{sup 2+} and Cd{sup 2+} cations in aqueous media. XPS measurements were performed in order to unravel the role of both carboxyl and thiol functions in the adsorption process. For the sake of comparison, the same study was performed using bare Fe{sub 3}O{sub 4} nanoparticles and a nanosystem with disulfide groups (Fe{sub 3}O{sub 4}@DMSA). The joint analysis of the Pb 4f, Cd 3d, Fe 2p and S 2p high

Antioxidant activity of hydrated carboxylated nanodiamonds and its influence on water γ-radiolysis

Science.gov (United States)

Santacruz-Gomez, Karla; Sarabia-Sainz, A.; Acosta-Elias, M.; Sarabia-Sainz, M.; Janetanakit, Woraphong; Khosla, Nathan; Melendrez, R.; Pedroza Montero, Martin; Lal, Ratnesh

2018-03-01

Water radiolysis involves chemical decomposition of the water molecule into free radicals after exposure to ionizing radiation. These free radicals have deleterious effects on normal cell physiology. Carboxylated nanodiamonds (cNDs) appear to modulate the deleterious effects of γ-irradiation on the pathophysiology of red blood cells (RBCs). In the present work, the antioxidant activity of hydrated cNDs (h-cNDs) on limiting oxidative damage (the water radiolysis effect) by γ-irradiation was confirmed. Our results show that h-cNDs have remarkable free radical scavenging ability and preserve the enzymatic activity of catalase after γ-irradiation. The underlying mechanism through which nanodiamonds exhibit antioxidant activity appears to depend on their colloidal stability. This property of detonation synthesized nanodiamonds is improved after carboxylation, which in turn influences changes in the hydrogen bond strength in water. The observed stability of h-cNDs in water and their antioxidant activity correlates with their protective effect on RBCs against γ-irradiation.

Matrix-Assisted Laser Desorption Ionization Mass Spectrometry of Compounds Containing Carboxyl Groups Using CdTe and CuO Nanoparticles

OpenAIRE

Megumi Sakurai; Taro Sato; Jiawei Xu; Soichi Sato; Tatsuya Fujino

2018-01-01

Matrix-assisted laser desorption ionization mass spectrometry of compounds containing carboxyl groups was carried out by using semiconductor nanoparticles (CdTe and CuO) as the matrix. Salicylic acid (Sal), glucuronic acid (Glu), ibuprofen (Ibu), and tyrosine (Tyr) were ionized as deprotonated species (carboxylate anions) by using electrons ejected from CdTe after the photoexcitation. When CuO was used as the matrix, the peak intensity of Tyr became high compared with that obtained with CdTe....

Sensitive method for dosing carboxylic functions of carbons and its application to the study of thermally processed carbon blacks

International Nuclear Information System (INIS)

Bernardin, Jacques

1968-01-01

This research thesis reports the development of a sensitive method for the dosing of carboxylic functions present at the surface of carbon blacks, and the use of this method to study the evolution of a carbon black during heat treatments. After a brief description of modes of fabrication of carbon blacks and of their structure, the author proposes an overview of knowledge on their oxidation and functional analysis. After having outlined that existing methods do not allow the measurement of function quantities less than ten micro-equivalent per gram of carbon, the author reports the development of a method which allows such measurements. By using this method, the author shows that carboxylic groups of a carbon black, oxidized by air or not, decompose during degassing by forming carbon dioxide, and that, reciprocally, the released carbon dioxide is exclusively produced by the decomposition of carboxylic groups [fr

Synthesis of omega-hydroxy carboxylic acids and alpha,omega-dimethyl ketones using alpha,omega-diols as alkylating agents.

Science.gov (United States)

Iuchi, Yosuke; Hyotanishi, Megumi; Miller, Brittany E; Maeda, Kensaku; Obora, Yasushi; Ishii, Yasutaka

2010-03-05

Synthesis of omega-hydroxy carboxylic acids and alpha,omega-dimethyl diketones was successfully achieved by using alpha,omega-diols as alkylating agents under the influence of an iridium catalyst. For example, the alkylation of butyl cyanoacetate with 1,13-tridecanediol in the presence of [IrCl(cod)](2) or [IrCl(coe)(2)](2) gave rise to butyl 2-cyano-15-hydroxypentadecanoate in good yield which is easily converted to cyclopentadecanolide (CPDL). In addition, the alkylation of acetone with 1,10-decanediol in the presence of [IrCl(cod)](2) and KOH resulted in an important muscone precursor, 2,15-hexadecanedione (HDDO), in good yield.

Proof of concept of a "greener" protein purification/enrichment method based on carboxylate-terminated carbosilane dendrimer-protein interactions.

Science.gov (United States)

González-García, Estefanía; Maly, Marek; de la Mata, Francisco Javier; Gómez, Rafael; Marina, María Luisa; García, María Concepción

2016-11-01

Protein sample preparation is a critical and an unsustainable step since it involves the use of tedious methods that usually require high amount of solvents. The development of new materials offers additional opportunities in protein sample preparation. This work explores, for the first time, the potential application of carboxylate-terminated carbosilane dendrimers to the purification/enrichment of proteins. Studies on dendrimer binding to proteins, based on protein fluorescence intensity and emission wavelengths measurements, demonstrated the interaction between carboxylate-terminated carbosilane dendrimers and proteins at all tested pH levels. Interactions were greatly affected by the protein itself, pH, and dendrimer concentration and generation. Especially interesting was the interaction at acidic pH since it resulted in a significant protein precipitation. Dendrimer-protein interactions were modeled observing stable complexes for all proteins. Carboxylate-terminated carbosilane dendrimers at acidic pH were successfully used in the purification/enrichment of proteins extracted from a complex sample. Graphical Abstract Images showing the growing turbidity of solutions containing a mixture of proteins (lysozyme, myoglobin, and BSA) at different protein:dendrimer ratios (1:0, 1:1, 1:8, and 1:20) at acidic pH and SDS-PAGE profiles of the corresponsing supernatants. Comparison of SDS-PAGE profiles for the pellets obtained during the purification of proteins present in a complex sample using a conventional "no-clean" method based on acetone precipitation and the proposed "greener" method using carboxylate-terminated carbosilane dendrimer at a 1:20 protein:dendrimer ratio.

Changes of sour taste and the composition of carboxylic acids induced in brewed coffee by γ-irradiation on green beans and storage of roast beans

International Nuclear Information System (INIS)

Tomoda, Goro; Matsuyama, Jun; Nagano, Akiko; Namatame, Mitsuko; Morita, Yoshiaki.

1980-01-01

Brazil santos green coffee beans were irradiated with 60 Co-γ rays at doses of 0, 0.05, 0.5 and 1.5 Mrad respectively and changes of the composition of carboxylic acids in roast beans were analyzed by means of GLC together with those of the organoleptic properties of roast beans during storage by use of the cup testing. The total acid content immediately after roasting was about 6,000 mg/100 g (roast beans) and the composition of carboxylic acids was as follows. Chlorogenic acid: hydroxy-carboxylic acids: mono-carboxylic acid: others = 73 : 18 : 7 : 2. Fresh coffee flavour was influenced markedly especially in acid taste by both irradiation of γ-rays on green beans and storage of roast beans, because of the change of above acids composition. On γ-ray irradiation, the change of the acid composition were more clear than that of stored roast beans. Therefore, the quality of γ-irradiated coffee beans seems to be closely associated with the ratio of hydroxy-carboxylic acids mg/ monocarboxylic acids mg, but little with total acid content. (author)

Phosphazene-promoted metal-free ring-opening polymerization of ethylene oxide initiated by carboxylic acid

KAUST Repository

Zhao, Junpeng; Pahovnik, David; Gnanou, Yves; Hadjichristidis, Nikolaos

2014-01-01

The effectiveness of carboxylic acid as initiator for the anionic ring-opening polymerization of ethylene oxide was investigated with a strong phosphazene base (t-BuP4) used as promoter. Kinetic study showed an induction period, i.e., transformation

The protonation state of small carboxylic acids at the water surface from photoelectron spectroscopy

Czech Academy of Sciences Publication Activity Database

Ottosson, N.; Wernersson, Erik; Söderström, J.; Pokapanich, W.; Kaufmann, S.; Svensson, S.; Persson, I.; Öhrwall, G.; Björneholm, O.

2011-01-01

Roč. 13, č. 26 (2011), s. 12261-12267 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506 Keywords : water surface * carboxylic acids * photoelectron spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

Mono-carboxylate conversion coatings for AZ31 Mg alloy protection

Energy Technology Data Exchange (ETDEWEB)

Frignani, A.; Grassi, V.; Zucchi, F.; Zanotto, F. [Corrosion Study Centre A. Dacco, University of Ferrara (Italy)

2011-11-15

Conversion coatings on a magnesium alloy were obtained by dipping AZ31 specimens in aqueous solutions of sodium salts of mono-carboxylic acids (stearic, palmitic, myristic, lauric, mono-carboxylate ion concentration from 1 to 5 mM, depending on the salt solubility) for 24 and 72 h at room temperature, or 24 h at 50 C. The influence exerted by the treatment time, bath temperature and alkyl chain length on the efficiency of these coatings was studied. The performances of the coatings were evaluated by potentiodynamic polarization curve recording after 1 h immersion in 0.05 M Na{sub 2}SO{sub 4} solution, while their temporal evolution was monitored by electrochemical impedance spectroscopy (EIS) spectra during 24 h. Further and long lasting tests were carried out also in 0.1 M NaCl solution. The efficiency of the coatings depended on the aliphatic chain length, and increased as the treatment time and the bath temperature were increased. The coating of lower homologue only hindered the cathodic process, while those of the higher homologues markedly inhibited the anodic process too. The best performances were displayed by 24 h-50 C stearic conversion coating, which maintained a very high efficiency for over 800 h immersion in 0.05 M sulphate solution. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Characterization of Lactobacillus salivarius alanine racemase: short-chain carboxylate-activation and the role of A131.

Science.gov (United States)

Kobayashi, Jyumpei; Yukimoto, Jotaro; Shimizu, Yasuhiro; Ohmori, Taketo; Suzuki, Hirokazu; Doi, Katsumi; Ohshima, Toshihisa

2015-01-01

Many strains of lactic acid bacteria produce high concentrations of d-amino acids. Among them, Lactobacillus salivarius UCC 118 produces d-alanine at a relative concentration much greater than 50 % of the total d, l-alanine (100d/d, l-alanine). We characterized the L. salivarius alanine racemase (ALR) likely responsible for this d-alanine production and found that the enzyme was activated by carboxylates, which is an unique characteristic among ALRs. In addition, alignment of the amino acid sequences of several ALRs revealed that A131 of L. salivarius ALR is likely involved in the activation. To confirm that finding, an L. salivarius ALR variant with an A131K (ALR(A131K)) substitution was prepared, and its properties were compared with those of ALR. The activity of ALR(A131K) was about three times greater than that of ALR. In addition, whereas L. salivarius ALR was strongly activated by low concentrations (e.g., 1 mM) of short chain carboxylates, and was inhibited at higher concentrations (e.g., 10 mM), ALR(A131K) was clearly inhibited at all carboxylate concentrations tested (1-40 mM). Acetate also increased the stability of ALR such that maximum activity was observed at 35 °C and pH 8.0 without acetate, but at 50 °C in the presence of 1 mM acetate. On the other hand, maximum ALR(A131K) activity was observed at 45 °C and around pH 9.0 with or without acetate. It thus appears that A131 mediates the activation and stabilization of L. salivarius ALR by short chain carboxylates.

Zonula occludens toxin structure-function analysis. Identification of the fragment biologically active on tight junctions and of the zonulin receptor binding domain.

Science.gov (United States)

Di Pierro, M; Lu, R; Uzzau, S; Wang, W; Margaretten, K; Pazzani, C; Maimone, F; Fasano, A

2001-06-01

Zonula occludens toxin (Zot) is an enterotoxin elaborated by Vibrio cholerae that increases intestinal permeability by interacting with a mammalian cell receptor with subsequent activation of intracellular signaling leading to the disassembly of the intercellular tight junctions. Zot localizes in the bacterial outer membrane of V. cholerae with subsequent cleavage and secretion of a carboxyl-terminal fragment in the host intestinal milieu. To identify the Zot domain(s) directly involved in the protein permeating effect, several zot gene deletion mutants were constructed and tested for their biological activity in the Ussing chamber assay and their ability to bind to the target receptor on intestinal epithelial cell cultures. The Zot biologically active domain was localized toward the carboxyl terminus of the protein and coincided with the predicted cleavage product generated by V. cholerae. This domain shared a putative receptor-binding motif with zonulin, the Zot mammalian analogue involved in tight junction modulation. Amino acid comparison between the Zot active fragment and zonulin, combined with site-directed mutagenesis experiments, confirmed the presence of an octapeptide receptor-binding domain toward the amino terminus of the processed Zot.

Synthesis and Transformations of di-endo-3-Aminobicyclo-[2.2.2]oct-5-ene-2-carboxylic Acid Derivatives

Directory of Open Access Journals (Sweden)

Márta Palkó

2011-09-01

Full Text Available all-endo-3-amino-5-hydroxybicyclo[2.2.2]octane-2-carboxylic acid (13 and all-endo-5-amino-6-(hydroxymethylbicyclo[2.2.2]octan-2-ol (10 were prepared via dihydro-1,3-oxazine or g-lactone intermediates by the stereoselective functionalization of an N-protected derivative of endo-3-aminobicyclo[2.2.2]oct-5-ene-2-carboxylic acid (2. Ring closure of b-amino ester 4 resulted in tricyclic pyrimidinones 15 and 16. The structures, stereochemistry and relative configurations of the synthesized compounds were determined by IR and NMR.

Preparation methods, reactivity and biological importance of 4-thiazolidinones; Metodos de obtencao, reatividade e importancia biologica de 4-tiazolidinonas

Energy Technology Data Exchange (ETDEWEB)

Liesen, Andre P.; Aquino, Thiago M. de; Goes, Alexandre J.S. [Universidade Federal de Pernambuco (UFPE)e, PE (Brazil). Dept. de Antibioticos]. E-mail: ajsg@ufpe.br; Lima, Jose G. de; Faria, Antonio R. de; Alves, Antonio J. [Universidade Federal de Pernambuco (UFPE)e, PE (Brazil). Dept. de Ciencias Farmaceuticas

2008-07-01

Molecules containing the 4-thiazolidinone ring are known to possess a wide range of biological properties including antimicrobial and antiinflammatory activities among others. These compounds can be synthesized by cyclization reactions involving alpha-haloacetic acid or alpha-mercaptoacetic acid and employed in several chemoselective reactions. Comprehensive reviews have been written on 4-thiazolidinones in 1961 by Brown and in 1980 by Singh et al. In the recent literature, some new synthesis methods for 4-thiazolidinone derivatives and several reactions have been reported. These advances warrant to review the chemical and biological properties of compounds with this important heterocycle employed in synthetic organic chemistry and medicinal chemistry (author)

Important biological activities induced by Thalassophryne maculosa fish venom.

Science.gov (United States)

Sosa-Rosales, Josefina Ines; Piran-Soares, Ana Amélia; Farsky, Sandra H P; Takehara, Harumi Ando; Lima, Carla; Lopes-Ferreira, Mônica

2005-02-01

The accidents caused by Thalassophryne maculosa fish venoms are frequent and represent a public health problem in some regions of Venezuela. Most accidents occur in the fishing communities and tourists. The clinical picture is characterized by severe pain, dizziness, fever, edema, and necrosis. Due to the lack of efficient therapy it may take weeks, or even months for complete recovery of the victims. The investigations presented here were undertaken to assess the eletrophoretical profile and principal biological properties of the T. maculosa venom. Venom obtained from fresh captured specimens of this fish was tested in vitro or in animal models for a better characterization of its toxic activities. In contrast to other fish venoms, T. maculosa venom showed relative low LD50. The injection of venom in the footpad of mice reproduced a local inflammatory lesion similar to that described in humans. Significant increase of the nociceptive and edematogenic responses was observed followed within 48 h by necrosis. Pronounced alterations on microvascular hemodynamics were visualized after venom application. These alterations were represented by fibrin depots and thrombus formation followed by complete venular stasis and transient arteriolar contraction. T. maculosa venom is devoid of phospholipase A2 activity, but the venom showed proteolytic and myotoxic activities. SDS-Page analysis of the crude venom showed important bands: one band located above 97 M(w), one band between 68 and 97 M(w), one major band between 29 and 43 M(w) and the last one located below 18.4 M(w) Then, the results presented here support that T. maculosa venom present a mixture of bioactive toxins involved in a local inflammatory lesion.

Polyoxyethylene alkyl ether carboxylic acids: An overview of a neglected class of surfactants with multiresponsive properties.

Science.gov (United States)

Chiappisi, Leonardo

2017-12-01

In this work, an overview on aqueous solutions of polyoxyethylene alkyl ether carboxylic acids is given. Unique properties arise from the combination of the nonionic, temperature-responsive polyoxyethylene block with the weakly ionic, pH-responsive carboxylic acid termination in a single surfactant headgroup. Accordingly, this class of surfactant finds broad application across very different sectors. Despite their large use on an industrial and a technical scale, the literature lacks a systematic and detailed characterization of their physico-chemical properties which is provided herein. In addition, a comprehensive overview is given of their self-assembly and interfacial behavior, of their use as colloidal building blocks and for large-scale applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and complexation properties towards uranyl cation of carboxylic acid derivatives of p-tert-butyl-calix[6]arene

International Nuclear Information System (INIS)

Souane, R.

2005-03-01

In the fuel reprocessing plants radioactive metals, and more particularly, uranium in UO 2 2+ form in the various installations, have many varied physico-chemical forms and there is a risk of exposure and internal contamination in the nuclear industry. It is necessary to exert a medical control to ensure the protection of the health of the workers. This medical control is done by dosing uranyl cation in the urine of the exposed people. This work forms part of this context. Indeed, we prepared a ligand able to complex the ion uranyl and which is also to be grafted on a solid support. In the family of calixarenes, the calix[6]arenes functionalized by three or four carboxylic functions were selected like chelating molecules of the ion uranyl. The properties of complexation of these calixarenes were studied by potentiometry in methanol, under these conditions balances of protonation and complexation were determined and the constant partners were obtained using the Hyperquad program. We synthesized tri-carboxylic calix[6]arenes comprising of the groupings nitro (NO 2 ) in para position of phenol in order to see the influence of a substitution in para position on the complexation. We also synthesized calix[6]arenes tetra-carboxylic in order to show the role of an additional carboxylic acid grouping. The potentiometric study determined thermodynamic parameters of protonation and complexation of carboxylic calix[6]arenes. The results of the complexation highlighted which complex UO 2 L corresponding to the ligand para-tert-butyl-calix[6]arene tetra-acid is more stable than that corresponding to the ligand mono-nitro calix[6]arene tri-acid (ΔlogΒ110 = 4.3), and than the effect of the groupings nitro in para position has low influence on the complexation of UO 2 2+ . This makes it possible to consider as possible the grafting of the calix[6]arenes which one knows the behaviour of trapping. To this end we synthesized the ligand 23. (author)

Carboxyl-terminal Truncations of ClC-Kb Abolish Channel Activation by Barttin Via Modified Common Gating and Trafficking*

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Stölting, Gabriel; Bungert-Plümke, Stefanie; Franzen, Arne; Fahlke, Christoph

2015-01-01

ClC-K chloride channels are crucial for auditory transduction and urine concentration. Mutations in CLCNKB, the gene encoding the renal chloride channel hClC-Kb, cause Bartter syndrome type III, a human genetic condition characterized by polyuria, hypokalemia, and alkalosis. In recent years, several Bartter syndrome-associated mutations have been described that result in truncations of the intracellular carboxyl terminus of hClC-Kb. We here used a combination of whole-cell patch clamp, confocal imaging, co-immunoprecipitation, and surface biotinylation to study the functional consequences of a frequent CLCNKB mutation that creates a premature stop codon at Trp-610. We found that W610X leaves the association of hClC-Kb and the accessory subunit barttin unaffected, but impairs its regulation by barttin. W610X attenuates hClC-Kb surface membrane insertion. Moreover, W610X results in hClC-Kb channel opening in the absence of barttin and prevents further barttin-mediated activation. To describe how the carboxyl terminus modifies the regulation by barttin we used V166E rClC-K1. V166E rClC-K1 is active without barttin and exhibits prominent, barttin-regulated voltage-dependent gating. Electrophysiological characterization of truncated V166E rClC-K1 demonstrated that the distal carboxyl terminus is necessary for slow cooperative gating. Since barttin modifies this particular gating process, channels lacking the distal carboxyl-terminal domain are no longer regulated by the accessory subunit. Our results demonstrate that the carboxyl terminus of hClC-Kb is not part of the binding site for barttin, but functionally modifies the interplay with barttin. The loss-of-activation of truncated hClC-Kb channels in heterologous expression systems fully explains the reduced basolateral chloride conductance in affected kidneys and the clinical symptoms of Bartter syndrome patients. PMID:26453302

Simultaneous determination of dopamine, uric acid and nitrite using carboxylated graphene oxide/lanthanum modified electrode

International Nuclear Information System (INIS)

Ye, Fengying; Feng, Chenqi; Jiang, Jibo; Han, Sheng

2015-01-01

Highlights: • The carboxylated graphene oxide/lanthanum-modified glassy carbon electrode (GO-COOLa/GCE) was successfully utilized for the simultaneous detection and quantification of DA, UA and NO 2 − . • Combining the benefits of carboxylated graphene oxide and lanthanum, the modified sensor displayed large peak separations, long linear ranges and low detection limits for simultaneously detecting DA, UA and NO 2 − . • The GO-COOLa/GCE electrode showed well stability, good repeatability, rapid response, and high catalytic performance toward the oxidations of DA, UA and NO 2 − . - Abstract: A bare glassy carbon electrode (GCE) was reformed by carboxylated graphene oxide/lanthanum, and the modified electrode, called GO-COOLa/GCE, was fabricated for simultaneously detecting dopamine (DA), uric acid (UA) and nitrite (NO 2 − ) by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and amperometry. Several factors which affected the electrocatalytic activity of the GO-COOLa/GCE electrode, such as the effect of pH, scan rate and concentration were studied. Due to the combination of carboxylated graphene oxide and lanthanum ions, the GO-COOLa/GCE sensor showed rapid response, excellent selectivity and high catalytic performance toward the electrooxidation of DA, UA and NO 2 − . In optimized conditions, two linear response ranges for determining DA were obtained over ranges of 0.01-1.96×10 2 μM and 1.96×10 2 -1.23×10 3 μM with detection limit of 0.018 μM (S/N = 3). And the responses of the GO-COOLa/GCE electrode for UA and NO 2 − were linear in the region of 1-1.53×10 3 μM and 1-2.75×10 3 μM with detection limits of 0.058 μM and 0.070 μM, respectively. Furthermore, this reformed electrode was successfully used to the detection of DA, UA and NO 2 − in real urine and serum samples, showing its promising application in the electroanalysis of real samples.

Importancia de la biología molecular para la Fisioterapia moderna Importance of molecular biology for the modern Physical Therapy

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Carolina Ramírez Ramírez

2011-12-01

body, for that reason, molecular biology offers professionals a better understanding of the effect of these types of interventions implemented in different tissues. Thus, the Physical therapists should be aware about the importance of this basic science and its clinical use in everyday problem solving that generate a new evidence-based practice to contribute to professional development. Salud UIS 2011; 43 (3: 317-320

Recurrent De Novo Mutations Affecting Residue Arg1 38 of Pyrroline-5-Carboxylate Synthase Cause a Progeroid Form of Autosomal-Dominant Cutis Laxa

NARCIS (Netherlands)

Fischer-Zirnsak, Björn; Escande-Beillard, Nathalie; Ganesh, Jaya; Tan, Yu Xuan; Al Bughaili, Mohammed; Lin, Angela E.; Sahai, Inderneel; Bahena, Paulina; Reichert, Sara L.; Loh, Abigail; Wright, Graham D.; Liu, Jaron; Rahikkala, Elisa; Pivnick, Eniko K.; Choudhri, Asim F.; Krüger, Ulrike; Zemojtel, Tomasz; van Ravenswaaij-Arts, Conny; Mostafavi, Roya; Stolte-Dijkstra, Irene; Symoens, Sofie; Pajunen, Leila; Al-Gazali, Lihadh; Meierhofer, David; Robinson, Peter N.; Mundlos, Stefan; Villarroel, Camilo E.; Byers, Peter; Masri, Amira; Robertson, Stephen P.; Schwarze, Ulrike; Callewaert, Bert; Reversade, Bruno; Kornak, Uwe

2015-01-01

Progeroid disorders overlapping with De Barsy syndrome (DBS) are collectively denoted as autosomal-recessive cutis laxa type 3 (ARCL3). They are caused by biallelic mutations in PYCR1 or ALDH18A1, encoding pyrroline-5-carboxylate reductase 1 and pyrroline-5-carboxylate synthase (P5CS), respectively,

6-Substituted 3,4-dihydro-naphthalene-2-carboxylic acids: synthesis and structure-activity studies in a novel class of human 5alpha reductase inhibitors.

Science.gov (United States)

Baston, Eckhard; Salem, Ola I A; Hartmann, Rolf W

2002-10-01

Novel 3,4-dihydro-naphthalene-2-carboxylic acids were synthesized and evaluated for 5alpha reductase inhibitory activity. This enzyme exists in two isoforms and is a pharmacological target for the treatment of benign prostatic hyperplasia, male pattern baldness and acne. In the present study non-steroidal compounds capable of mimicking the transition state of the steroidal substrates were prepared. The synthetic strategy for the preparation of compounds 1-6 consisted of triflation followed by subsequent Heck-type carboxylation or methoxy carbonylation for 6-phenyl-3,4-dihydronaphthalen-2(1H)-one 1c. A Negishi-type coupling reaction between 6-(trifluoro-methanesulfonyloxy)-3,4-dihydro-naphthalene-2-carboxylic acid methyl ester 7b and various aryl bromides led, after further transformations, to 6-substituted 3,4-dihydro-naphthalene-2-carboxylic acids 7-15. In a similar way the corresponding naphthalene-2-carboxylic acids 16 and 17 were obtained. The DU 145 cell line and prostate homogenates served as enzyme sources for the human type 1 and type 2 isozymes, whereas ventral prostate was employed to evaluate rat isozyme inhibitory potency. The most active inhibitors identified in this study were 6-[4-(N,N-dicyclohexylaminocarbonyl)phenyl]-3,4-dihydro-naphthalene-2-carboxylic acid (3) (IC50 = 0.09 microM, rat type 1), 6-[3-(N,N-dicyclohexylaminocarbonyl)phenyl]-3,4-dihydro-naphthalene-2-carboxylic acid (13) (IC50 = 0.75 microM, human type 2; IC50 = 0.81 microM, human type 1) and 6-[4-(N,N-diisopropylamino-carbonyl)phenyl]naphthalene-2-carboxylic acid (16) (IC50 = 0.2 microM, human type 2). The latter compound was shown to deactivate the enzyme in an uncompetitive manner (Ki = 90 nM; Km, Testosterone = 0.8-1.0 microM) similar to the steroidal inhibitor Epristeride. Select inhibitors (13 and 16) were tested in vivo using testosterone propionate-treated, juvenile, orchiectomized SD-rats. None of the compounds was active at a dose of 25 mg/kg. This result might in part be

Design of co-crystals/salts of some Nitrogenous bases and some derivatives of thiophene carboxylic acids through a combination of hydrogen and halogen bonds.

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Jennifer, Samson Jegan; Muthiah, Packianathan Thomas

2014-01-01

The utility of N-heterocyclic bases to obtain molecular complexes with carboxylic acids is well studied. Depending on the solid state interaction between the N-heterocyclic base and a carboxylic acid a variety of neutral or ionic synthons are observed. Meanwhile, pyridines and pyrimidines have been frequently chosen in the area of crystal engineering for their multipurpose functionality. HT (hetero trimers) and LHT (linear heterotetramers) are the well known synthons that are formed in the presence of pyrimidines and carboxylic acids. Fourteen crystals involving various substituted thiophene carboxylic acid derivatives and nitrogenous bases were prepared and characterized by using single crystal X-ray diffraction. The 14 crystals can further be divided into two groups [1a-7a], [8b-14b] based on the nature of the nitrogenous base. Carboxylic acid to pyridine proton transfer has occurred in 3 compounds of each group. In addition to the commonly occurring hydrogen bond based pyridine/carboxylic acid and pyrimidine/carboxylic acid synthons which is the reason for assembly of primary motifs, various other interactions like Cl…Cl, Cl…O, C-H…Cl, C-H…S add additional support in organizing these supermolecules into extended architectures. It is also interesting to note that in all the compounds π-π stacking occurs between the pyrimidine-pyrimidine or pyridine-pyridine or acid-acid moieties rather than acid-pyrimidine/pyridine. In all the compounds (1a-14b) either neutral O-H…Npyridyl/pyrimidine or charge-assisted Npyridinium-H…Ocarboxylate hydrogen bonds are present. The HT (hetero trimers) and LHT (linear heterotetramers) are dominant in the crystal structures of the adducts containing N-heterocyclic bases with two proton acceptors (1a-7a). Similar type supramolecular ladders are observed in 5TPC44BIPY (8b), TPC44BIPY (9b), TPC44TMBP (11b). Among the seven compounds [8b-14b] the extended ligands are linear in all except for the TMBP (10b, 11b, 12b). The

Photoinduced catalytic synthesis of biologically important metabolites from formaldehyde and ammonia under plausible "prebiotic" conditions

Science.gov (United States)

Delidovich, I. V.; Taran, O. P.; Simonov, A. N.; Matvienko, L. G.; Parmon, V. N.

2011-08-01

The article analyzes new and previously reported data on several catalytic and photochemical processes yielding biologically important molecules. UV-irradiation of formaldehyde aqueous solution yields acetaldehyde, glyoxal, glycolaldehyde and glyceraldehyde, which can serve as precursors of more complex biochemically relevant compounds. Photolysis of aqueous solution of acetaldehyde and ammonium nitrate results in formation of alanine and pyruvic acid. Dehydration of glyceraldehyde catalyzed by zeolite HZSM-5-17 yields pyruvaldehyde. Monosaccharides are formed in the course of the phosphate-catalyzed aldol condensation reactions of glycolaldehyde, glyceraldehyde and formaldehyde. The possibility of the direct synthesis of tetroses, keto- and aldo-pentoses from pure formaldehyde due to the combination of the photochemical production of glycolahyde and phosphate-catalyzed carbohydrate chain growth is demonstrated. Erythrulose and 3-pentulose are the main products of such combined synthesis with selectivity up to 10%. Biologically relevant aldotetroses, aldo- and ketopentoses are more resistant to the photochemical destruction owing to the stabilization in hemiacetal cyclic forms. They are formed as products of isomerization of erythrulose and 3-pentulose. The conjugation of the concerned reactions results in a plausible route to the formation of sugars, amino and organic acids from formaldehyde and ammonia under presumed 'prebiotic' conditions.

Synthesis of carboxyl superparamagnetic ultrasmall iron oxide (USPIO) nanoparticles by a novel flocculation-redispersion process

International Nuclear Information System (INIS)

Cheng Changming; Kou Geng; Wang Xiaoliang; Wang Shuhui; Gu Hongchen; Guo Yajun

2009-01-01

We report a novel flocculation-redispersion method to synthesize and purify the biocompatible superparamagnetic ultrasmall iron oxide (USPIO) nanoparticles coated with carboxyl dextran derivative. First, USPIO nanoparticles were synthesized and flocculated to form the large clusters through bridging effect of polyvinyl alcohol (PVA) during coprecipitation process. Then the flocculated USPIO was separated and purified from the solution conveniently through magnetic sedimentation. Finally, USPIO in the clusters were released again and well dispersed through electrostatic repelling effect of citric acid with the aid of ultrasonic. The dispersed carboxyl-functionalized USPIO was conjugated with the monoclonal antibodies. And it has been proved that the antibodies anchored on USPIO still retained their bioactivity after the conjugation. These results implied that the USPIO synthesized have good potential as active targeting molecular probe in biomedical application.

Performances of carbon-based screen-printed electrodes modified by diazonium salts with various carboxylic functions for trace metal sensors

International Nuclear Information System (INIS)

Bouden, Sarra; Bellakhal, Nizar; Chausse, Annie; Vautrin-Ul, Christine

2014-01-01

The electrochemically induced functionalization of carbon-based screen-printed-electrodes (SPEs) by phenyl groups, having one or two carboxylic functions, was achieved by reduction of in situ generated diazonium salts in aqueous media. The corresponding diazonium cations of 4-aminobenzoic acid, 4-aminophthalic acid, 3-(4-aminophenyl) propionic acid, 3-(4-aminophenyl)-2-propenoic acid and 5-aminoisophthalic acid were generated in situ with sodium nitrite in aqueous H_2SO_4. The electrochemical detection of Pb(II) with the grafted SPEs was investigated using Pb(II) 5 * 10"-"8 M solutions. The performances of the grafted SPEs were found to be dependent on the number of carboxylic groups, on their position on the phenyl ring, on the olefinic or the aliphatic character of the chain bearing the carboxylic group. The performances of mono-4-carboxyphenyl and 3,5-dicarboxyphenyl grafted SPEs for Cd(II) and Cu(II) trace detection were tested and compared. (authors)

Thermodynamic studies on corrosion inhibition of aqueous solutions of amino/carboxylic acids toward copper by EMF measurement

International Nuclear Information System (INIS)

Spah, Manjula; Spah, Dal Chand; Deshwal, Balraj; Lee, Seungmoon; Chae, Yoon-Keun; Park, Jin Won

2009-01-01

Electromotive force (E) measurements were made on an electrochemical cell [Cu x Hg|CuCl 2 (m) in a solvent S|AgCl-Ag] (where S is a dilute aqueous solution (0.01 m) of amino acid (glycine, alanine, methionine and glutamic acid) or aliphatic carboxylic acid (formic acid, acetic acid, n-butyric acid and glutaric acid)) at 30 deg. C. These measured E values were used to compute the dissociation constants (K 1 and K 2 ) and the degree of dissociation (α 1 and α 2 ) by iterative procedures. The standard cell potential (E o ) and the mean activity coefficient (γ ± ) of CuCl 2 were also determined. The E o data were next used to evaluate the Gibbs energy of transfer (ΔG tr 0 ) of CuCl 2 from water to dilute aqueous solutions of the amino/carboxylic acids. The negative ΔG tr 0 values suggested that these acids act as potential corrosion inhibitors. The magnitudes of ΔG tr 0 values show that the amino acids act as better corrosion inhibitors towards copper than the aliphatic carboxylic acids.

CARBOXYLATION OF SILVER NANOPARTICLES FOR THE IMMOBILIZATION OF β-GALACTOSIDASE AND ITS EFFICACY IN GALACTO-OLIGOSACCHARIDES PRODUCTION

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Shakeel Ahmed Ansari

2015-03-01

Full Text Available The present study investigated the carboxylation of silver nanoparticles (AgNPs by 1:3 nitric acid-sulfuric acid mixtures for immobilizing Aspergillus oryzae β-galactosidase. Carboxylated AgNPs retained 93% enzyme upon immobilization and the enzyme did not leach out appreciably from the modified nanosupport in the presence of 100 mmol L-1 NaCl. Atomic force micrograph revealed the binding of β-galactosidase on the modified AgNPs. The optimal pH for soluble and carboxylated AgNPs adsorbed β-galactosidase (IβG was observed at pH 4.5 while the optimal operating temperature was broadened from 50 ºC to 60 ºC for IβG. Michaelis constant, Km was increased two and a half fold for IβG while Vmax decreases slightly as compared to soluble enzyme. β-galactosidase immobilized on surface functionalized AgNPs retained 70% biocatalytic activity even at 4% galactose concentration as compared to enzyme in solution. Our study showed that IβG produces greater amount of galacto-oligosaccharides at higher temperatures (50 ºC and 60 ºC from 0.1 mol L-1 lactose solution at pH 4.5 as compared to previous reports.

Organic carboxylate anions effect on the structures of a series of Mn(II) complexes based on 2-phenylimidazo[4,5-f]1,10-phenanthroline ligand

International Nuclear Information System (INIS)

Wang Xiuli; Chen Yongqiang; Liu Guocheng; Lin Hongyan; Zhang Jinxia

2009-01-01

In our efforts to tune the structures of Mn(II) complexes by selection of organic carboxylic acid ligands, six new complexes [Mn(PIP) 2 Cl 2 ] (1), [Mn(PIP) 2 (4,4'-bpdc)(H 2 O)].2H 2 O (2), [Mn(PIP) 2 (1,4-bdc)] (3), [Mn(PIP)(1,3-bdc)] (4), [Mn(PIP) 2 (2,6-napdc)].H 2 O (5), and [Mn(PIP)(1,4-napdc)].H 2 O (6) were obtained, where PIP=2-phenylimidazo[4,5-f]1,10-phenanthroline, 4,4'-H 2 bpdc=biphenyl-4,4'-dicarboxylic acid, 1,4-H 2 bdc=benzene-1,4-dicarboxylic acid, 1,3-H 2 bdc=benzene-1,3-dicarboxylic acid, 2,6-H 2 napdc=2,6-naphthalenedicarboxylic acid, 1,4-H 2 napdc=1,4-naphthalenedicarboxylic acid. All complexes have been structurally characterized by IR, elemental analyses, and single crystal X-ray diffraction. Structural analyses show that complexes 1 and 2 possess mononuclear structures, complexes 3, 4, and 5 feature chain structures, and complex 6 exhibits a 2D (4,4) network. The structural difference of 1-6 indicates that organic carboxylate anions play important roles in the formation of such coordination architectures. Furthermore, the thermal properties of complexes 1-6 and the magnetic property of 4 have been investigated. - Graphical Abstract: Through selecting organic carboxylate anions, six Mn(II) complexes have been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction.

Effect of the cement type on compatibility with carboxylate super plasticisers

International Nuclear Information System (INIS)

Bundyra-Oracz, G.; Kurdowski, W.

2011-01-01

An empirical study was conducted to gain a fuller understanding of the interactions taking place in cement superplasticiser systems. To this end, two clinkers of clinkers of known chemical and phase composition were prepared in this study to gain insight into such interactions. One contained no tricalcium aluminate (C1), while the other had a 9% C 3 A content (C2). These clinkers were ground to approximately 340 m 2 /kg and blended with gypsum only or gypsum and Klein compound (3CaOx3Al 2 O 3 xCaSO 4 ) (1, 2). Sufficient compound was added to C1 to ensure the formation of about the same amount of ettringite after 0.5 and 1 h of hydration as found in cement C2 + gypsum. The admixture used was a carboxylate superplasticiser. Rheology measurements showed that while paste yield stress was correlated to ettringite formation, no such simple relationship was observed for plastic viscosity. Plastic viscosity depended on the total hydrates formed, i.e., not only as ettringite but also as C-S-H gel. The findings revealed that in clinkers with very low sulfate and potassium contents, the rheology of carboxylate-containing cement paste is primarily controlled by ettringite formation. (Author) 15 refs.

Self-Standing Nanocellulose Janus-Type Films with Aldehyde and Carboxyl Functionalities.

Science.gov (United States)

Nypelö, Tiina; Amer, Hassan; Konnerth, Johannes; Potthast, Antje; Rosenau, Thomas

2018-03-12

Nanocellulose-based self-standing films are becoming a substrate for flexible electronics, diagnostics, and sensors. Strength and surface chemistry are vital variables for these film-based endeavors, the former is one of the assets of nanocellulose. To contribute to the latter, nanocellulose films are tuned with a side-specific functionalization, having an aldehyde and a carboxyl side. The functionalities were obtained combining premodification of the film components by periodate oxidation with ozone post-treatment. Periodate oxidation of cellulose nanocrystals results in film components that interact through intra- and intermolecular hemiacetals and lead to films with an elastic modulus of 11 GPa. The ozone treatment of one film side induces conversion of the aldehyde into carboxyl functionalities. The ozone treatment on individual crystals was largely destructive. Remarkably, such degradation is not observed for the self-standing film, and the film strength at break is preserved. Preserving a physically intact film despite ozone treatment is a credit to using the dry film structure held together by interparticle covalent linkages. Additionally, gas-phase post-treatment avoids disintegration that could result from immersion into solvents. The crystalline cellulose "Janus" film is suggested as an interfacial component in biomaterial engineering, separation technology, or in layered composite materials for tunable affinity between the layers.

Surface Patterning of Benzene Carboxylic Acids on Graphite: Influence of structure, solvent, and concentration on molecular self-assembly

Science.gov (United States)

Florio, Gina; Stiso, Kimberly; Campanelli, Joseph; Dessources, Kimberly; Folkes, Trudi

2012-02-01

Scanning tunneling microscopy (STM) was used to investigate the molecular self-assembly of four different benzene carboxylic acid derivatives at the liquid/graphite interface: pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), trimellitic acid (1,2,4-benzenetricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid), and 1,3,5-benzenetriacetic acid. A range of two dimensional networks are observed that depend sensitively on the number of carboxylic acids present, the nature of the solvent, and the solution concentration. We will describe our recent efforts to determine (a) the preferential two-dimensional structure(s) for each benzene carboxylic acid at the liquid/graphite interface, (b) the thermodynamic and kinetic factors influencing self-assembly (or lack thereof), (c) the role solvent plays in the assembly, (e) the effect of in situ versus ex situ dilution on surface packing density, and (f) the temporal evolution of the self-assembled monolayer. Results of computational analysis of analog molecules and model monolayer films will also be presented to aid assignment of network structures and to provide a qualitative picture of surface adsorption and network formation.

Determining aromatic and aliphatic carboxylic acids in biomass-derived oil samples using 2,4-dinitrophenylhydrazine and liquid chromatography-electrospray injection-mass spectrometry/mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Lewis, Samuel A.; Connatser, Raynella M.; Olarte, Mariefel V.; Keiser, James R.

2018-01-01

Converting biomass to a useful fuel commonly incorporates the pyrolysis of the biomass feed stock. The base liquid fraction usually contains high concentrations of ketones, aldehydes and carboxylic acids, of which each can cause detrimental issues related to the storage and upgrading process. Knowing the carbonyl species and the concentration of each will provide value information to the pyrolysis researchers, specifically as that community branches into more targeted end-products such as jet fuel or biogenic-derived oxygenate-containing fuel products. The analysis of aldehydes, ketones and small alkyl carboxylic acids using 2,4-dinitrophenylhydrazine (DNPH) derivation method has been well documented and the method is commonly used the analytical community. By using liquid chromatograph coupled to tandem mass spectrometry, biomass sample analysis can be complete with identification of most carbonyl species. The issue of identifying isobaric ketone and aldehyde compounds can be resolved by utilizing differences in retention time or characteristic fragment ions of ketones and aldehydes. One issue which could not resolved using published methods was identifying aromatic or large non-aromatic carboxylic acids from their corresponding hydroxyl aldehyde or ketone analogs. By modifying the current method for determining carbonyls in biomass samples, carboxylic and hydroxyl-carbonyl can be determined. A careful adjustment of the pH during the extraction procedure and extended heating time of the DNPH solution allowed for the successful derivation of aromatic carboxylic acids. Like other dinitrophenylhydrazones, carboxylic acid derivatives also produce a unique secondary ion pattern, which was useful to distinguish these species from the non-acid analogs.

Thermophysical properties of carboxylic and amino acid buffers at subzero temperatures: relevance to frozen state stabilization.

Science.gov (United States)

Sundaramurthi, Prakash; Suryanarayanan, Raj

2011-06-02

Macromolecules and other thermolabile biologicals are often buffered and stored in frozen or dried (freeze-dried) state. Crystallization of buffer components in frozen aqueous solutions and the consequent pH shifts were studied in carboxylic (succinic, malic, citric, tartaric acid) and amino acid (glycine, histidine) buffers. Aqueous buffer solutions were cooled from room temperature (RT) to -25 °C and the pH of the solution was measured as a function of temperature. The thermal behavior of frozen solutions was investigated by differential scanning calorimetry (DSC), and the crystallized phases were identified by X-ray diffractometry (XRD). Based on the solubility of the neutral species of each buffer system over a range of temperatures, it was possible to estimate its degree of supersaturation at the subambient temperature of interest. This enabled us to predict its crystallization propensity in frozen systems. The experimental and the predicted rank orderings were in excellent agreement. The malate buffer system was robust with no evidence of buffer component crystallization and hence negligible pH shift. In the citrate and tartrate systems, at initial pH pI. In the histidine buffer system, depending on the initial pH, either histidine or histidine HCl crystallized.

Real-time monitoring of calcium carbonate and cationic peptide deposition on carboxylate-SAM using a microfluidic SAW biosensor

Directory of Open Access Journals (Sweden)

Anna Pohl

2014-10-01

Full Text Available A microfluidic biosensor with surface acoustic wave technology was used in this study to monitor the interaction of calcium carbonate with standard carboxylate self-assembled monolayer sensor chips. Different fluids, with and without biomolecular components, were investigated. The pH-dependent surface interactions of two bio-inspired cationic peptides, AS8 and ES9, which are similar to an extracellular domain of the chitin synthase involved in mollusc shell formation, were also investigated in a biological buffer system. A range of experimental conditions are described that are suitable to study non-covalent molecular interactions in the presence of ionic substances, such as, mineral precursors below the solubility equilibrium. The peptide ES9, equal to the mollusc chitin synthase epitope, is less sensitive to changes in pH than its counterpart AS8 with a penta-lysine core, which lacks the flanking acidic residues. This study demonstrates the extraordinary potential of microfluidic surface acoustic wave biosensors to significantly expand our experimental capabilities for studying the principles underlying biomineralization in vitro.

Real-time monitoring of calcium carbonate and cationic peptide deposition on carboxylate-SAM using a microfluidic SAW biosensor.

Science.gov (United States)

Pohl, Anna; Weiss, Ingrid M

2014-01-01

A microfluidic biosensor with surface acoustic wave technology was used in this study to monitor the interaction of calcium carbonate with standard carboxylate self-assembled monolayer sensor chips. Different fluids, with and without biomolecular components, were investigated. The pH-dependent surface interactions of two bio-inspired cationic peptides, AS8 and ES9, which are similar to an extracellular domain of the chitin synthase involved in mollusc shell formation, were also investigated in a biological buffer system. A range of experimental conditions are described that are suitable to study non-covalent molecular interactions in the presence of ionic substances, such as, mineral precursors below the solubility equilibrium. The peptide ES9, equal to the mollusc chitin synthase epitope, is less sensitive to changes in pH than its counterpart AS8 with a penta-lysine core, which lacks the flanking acidic residues. This study demonstrates the extraordinary potential of microfluidic surface acoustic wave biosensors to significantly expand our experimental capabilities for studying the principles underlying biomineralization in vitro.

Phytochemical and biological assessment of medicinally important plant ochradenus arabicus

International Nuclear Information System (INIS)

Hussain, J.

2014-01-01

Jabal Al-Akhdar (Oman) is one of diverse floral region of Arabian Peninsula. Ochradenus arabicus, is an important medicinal plant to local people of the area. However, little is known about its potential role in biological activities against various emerging ailments. The collected plant samples were extracted with methanol and fractionated into n-hexane (JOAH), ethyl acetate (JOAE), chloroform (JOAC), n-butanol (JOAB) and water (JOAAQ). Various concentrations of these fractions were tested for their antimicrobial, anticancer, antioxidant, antidiabetic, phenolics, flavonoids, allopathic and nutrition quality properties. The results showed that fruits and leaves of O. arabicus have higher levels of carbohydrate, crude fats, fibres, proteins, moisture, ash and energy values. In phytotoxic activities, JOAAQ inhibited the lettuce seed germination and growth. The anticancer activities of fractions showed that JOAE, JOAB and JOAAQ are potent to reduce the cancer cell viability of HT29, HCT116, HepG2 and MCF-7 lines with a concentration of 1000 micro g/ml. JOAB showed a meagre activity of 12% in Glucosidase inhibition assay. The total phenolic and flavonoid contents were significantly higher in JOAE, which also resulted in higher DPPH radical scavenging activity as compared to other fractions and control. JOAE also exhibited higher antibacterial and antifungal activities. The results of current findings suggest that O. arabicus is a potential medicinal plants, which could be subjected to advance column chromatography for lead compounds using a bioassay guided approach. (author)

Degradation of chitosan hydrogel dispersed in dilute carboxylic acids by solution plasma and evaluation of anticancer activity of degraded products

Science.gov (United States)

Chokradjaroen, Chayanaphat; Rujiravanit, Ratana; Theeramunkong, Sewan; Saito, Nagahiro

2018-01-01

Chitosan is a polysaccharide that has been extensively studied in the field of biomedicine, especially its water-soluble degraded products called chitooligosaccharides (COS). In this study, COS were produced by the degradation of chitosan hydrogel dispersed in a dilute solution (i.e., 1.55 mM) of various kinds of carboxylic acids using a non-thermal plasma technology called solution plasma (SP). The degradation rates of chitosan were influenced by the type of carboxylic acids, depending on the interaction between chitosan and each carboxylic acid. After SP treatment, the water-soluble degraded products containing COS could be easily separated from the water-insoluble residue of chitosan hydrogel by centrifugation. The production yields of the COS were mostly higher than 55%. Furthermore, the obtained COS products were evaluated for their inhibitory effect as well as their selectivity against human lung cancer cells (H460) and human lung normal cells (MRC-5).

Chemo-enzymatic epoxidation of olefins by carboxylic acid esters and hydrogen peroxide

Energy Technology Data Exchange (ETDEWEB)

Ruesch gen. Klaas, M.; Warwel, S. [Inst. for Biochemistry and Technology of Lipids, H.P. Kaufmanm-Inst., Federal Centre for Cereal, Potato and Lipid Research, Muenster (Germany)

1998-12-31

Ethylen and, recently, butadiene can be epoxidized directly with oxygen and for the epoxidation of propylene, the use of heterogeneous transition metals and organic peroxides (Halcon-Process) is the major player. But, beside from those notable exceptions, all other epoxidations, including large ones like the epoxidation of plant oils as PVC-stabilizers (about 200.000 t/year), are carried out with peroxy acids. Because mcpba is far to expensive for most applications, short chain peracids like peracetic acid are used. Being much less stable than mcpba and thus risky handled in large amounts and high concentrations, these peroxy acids were preferably prepared in-situ. However, conventional in-situ formation of peracids has the serious drawback, that a strong acid is necessary to catalyze peroxy acid formation from the carboxylic acid and hydrogen peroxide. The presence of a strong acid in the reaction mixture often results in decreased selectivity because of the formation of undesired by-products by opening of the oxirane ring. Therefore, we propose a new method for epoxidation based on the in-situ preparation of percarboxylic acids from carboxylic acid esters and hydrogen peroxide catalyzed by a commercial, immobilized lipase. (orig.)

Gas chromatographic-mass spectrometric investigation of n-alkanes and carboxylic acids in bottom sediments of the northern Caspian Sea

Science.gov (United States)

Kenzhegaliev, Akimgali; Zhumagaliev, Sagat; Kenzhegalieva, Dina; Orazbayev, Batyr

2018-03-01

Prior to the start of experimental oil production in the Kashagan field (northern part of the Caspian Sea), n-alkanes and carboxylic acids contained in samples obtained from bottom sediments in the area of artificial island "D" were investigated by gas chromatography-mass spectrometry. Concentrations of 10 n-alkanes (composed of C10-C13, C15-C20) and 11 carboxylic acids (composed of C6-C12, C14-C16) were identified and measured. Concentrations of individual alkanes and carboxylic acids in bottom sediments of the various samples varied between 0.001 ÷ 0.88 μg/g and 0.001 ÷ 1.94 μg/g, respectively. Mass spectra, in particular the M+ molecular ion peak and the most intense peaks of fragment ions, are given. The present study illustrates the stability of molecular ions to electronic ionisation and the main fragment ions to the total ion current and shows that the initial fragmentation of alkanes implies radical cleavage of C2H5 rather than CH3. All aliphatic monocarboxylic acids studied were characterised by McLafferty rearrangement leading to the formation of F4 cation-radical with m/z 60 and F3 cation-radical with m/z 88 in the case of ethylhexanoic acid. The formation of oxonium ions presents another important aspect of acid fragmentation. Using mass numbers of oxonium ions and rearrangement ions allows determination of the substitution character in α- and β- C atoms. The essence of our approach is to estimate the infiltration of hydrocarbon fluids from the enclosing formation into sea water, comprising an analysis of derivatives of organic compounds in bottom sediments. Thus, concentrations of derived organic molecules can serve as a basis for estimates of the depth at which hydrocarbon fluids leak, i.e., to serve as an auxiliary technique in the search for hydrocarbon deposits and to repair well leaks.

Redshift or adduct stabilization -- a computational study of hydrogen bonding in adducts of protonated carboxylic acids

DEFF Research Database (Denmark)

Olesen, Solveig Gaarn; Hammerum, Steen

2009-01-01

It is generally expected that the hydrogen bond strength in a D-H-A adduct is predicted by the difference between the proton affinities of D and A, measured by the adduct stabilization, and demonstrated by the IR redshift of the D-H bond stretching vibrational frequency. These criteria do...... not always yield consistent predictions, as illustrated by the hydrogen bonds formed by the E and Z OH groups of protonated carboxylic acids. The delta-PA and the stabilization of a series of hydrogen bonded adducts indicate that the E OH group forms the stronger hydrogen bonds, whereas the bond length...... carboxylic acids are different. The OH bond length and IR redshift afford the better measure of hydrogen bond strength....

The importance of biological factors affecting trace metal concentration as revealed from accumulation patterns in co-occurring terrestrial invertebrates

Energy Technology Data Exchange (ETDEWEB)

Hendrickx, Frederik; Maelfait, Jean-Pierre; Bogaert, Nicolas; Tojal, Catarina; Du Laing, Gijs; Tack, Filip M.G.; Verloo, Marc G

2004-02-01

As physicochemical properties of the soil highly influence the bioavailable fraction of a particular trace metal, measured metal body burdens in a particular species are often assumed to be more reliable estimators of the contamination of the biota. To test this we compared the Cd, Cu and Zn content of three spiders (generalist predators) and two amphipods (detritivores), co-occurring in seven tidal marshes along the river Schelde, between each other and with the total metal concentrations and the concentrations of four sequential extractions of the soils. Correlations were significant in only one case and significant sitexspecies interactions for all metals demonstrate that factors affecting metal concentration were species and site specific and not solely determined by site specific characteristics. These results emphasize that site and species specific biological factors might be of the utmost importance in determining the contamination of the biota, at least for higher trophic levels. A hypothetical example clarifies these findings. - Site and species specific biological factors are important in determining contamination of biota.

RNAi-mediated silencing of enolase confirms its biological importance in Clonorchis sinensis.

Science.gov (United States)

Wang, Xiaoyun; Chen, Wenjun; Tian, Yanli; Huang, Yan; Li, Xuerong; Yu, Xinbing

2014-04-01

Clonorchis sinensis (C. sinensis) infection is still a common public health problem in freshwater fish consumption areas in Asian countries. More molecular evidence are required to speed up the prevention strategies to control this kind of infectious disease. In the present study, to confirm the biological importance of Csenolase followed by our previous observations of the key metabolic enzyme, we explored the RNA silence effect of the Csenolase-derived RNA interference (RNAi) in C. sinensis. The extramembranous region aa105-226 was selected as the target sequence of RNA silence. Csenolase-derived double strand RNA (dsRNA-Csenolase, 366 bp) was synthetized and delivered into C. sinensis by soaking approach. The penetration of dsRNA into adult worms and metacercariae was tracked using fluorescently labeled RNA. Western blotting and qRT-PCR experiments were performed to determine dsRNA-Csenolase-silencing effect. Our results showed that, after incubating for 120 h, dsRNA-Csenolase could effectively target and downregulate the expression of Csenolase in both adult worms (P sinensis adult worms (P sinensis, allowing further applications in identifying functional genes in C. sinensis.

FACE Analysis as a Fast and Reliable Methodology to Monitor the Sulfation and Total Amount of Chondroitin Sulfate in Biological Samples of Clinical Importance

Directory of Open Access Journals (Sweden)

Evgenia Karousou

2014-06-01

Full Text Available Glycosaminoglycans (GAGs due to their hydrophilic character and high anionic charge densities play important roles in various (pathophysiological processes. The identification and quantification of GAGs in biological samples and tissues could be useful prognostic and diagnostic tools in pathological conditions. Despite the noteworthy progress in the development of sensitive and accurate methodologies for the determination of GAGs, there is a significant lack in methodologies regarding sample preparation and reliable fast analysis methods enabling the simultaneous analysis of several biological samples. In this report, developed protocols for the isolation of GAGs in biological samples were applied to analyze various sulfated chondroitin sulfate- and hyaluronan-derived disaccharides using fluorophore-assisted carbohydrate electrophoresis (FACE. Applications to biologic samples of clinical importance include blood serum, lens capsule tissue and urine. The sample preparation protocol followed by FACE analysis allows quantification with an optimal linearity over the concentration range 1.0–220.0 µg/mL, affording a limit of quantitation of 50 ng of disaccharides. Validation of FACE results was performed by capillary electrophoresis and high performance liquid chromatography techniques.

Carboxylate-intercalated layered double hydroxides aged under microwave-hydrothermal treatment

International Nuclear Information System (INIS)

Benito, P.; Labajos, F.M.; Mafra, L.; Rocha, J.; Rives, V.

2009-01-01

Carboxylate-intercalated (terephthalate, TA and oxalate, ox) layered double hydroxides (LDHs) are aged under a microwave-hydrothermal treatment. The influence of the nature of the interlayer anion during the ageing process is studied. Characterization results show that the microwave-hydrothermal method can be extended to synthesize LDHs with anions different than carbonate, like TA. LDH-TA compounds are stable under microwave irradiation for increasing periods of time and the solids show an improved order both in the layers and in the interlayer region as evidenced by powder X-ray diffraction (PXRD), 27 Al MAS NMR and FT-IR spectroscopy. Furthermore, cleaning of the surface through removal of some organic species adsorbed on the surface of the particles also occurs during the microwave-hydrothermal treatment. Conversely, although the expected increase in crystallinity is observed in LDH-ox samples, the side-reaction between Al 3+ and ox is also enhanced under microwave irradiation, and a partial destruction of the structure takes place with an increase in the M 2+ /M 3+ ratio and consequent modification of the cell parameters. - Graphical Abstract: The influence of the nature of the interlayer anion during the ageing process of carboxylate-intercalated (TA and ox) hydrotalcite-like compounds (HTlcs) is studied. Well crystallized for TA-containing compounds were obtained. However, the non-desired side-reaction of ox with the aluminum of the layers is enhanced by the microwaves and a partial destruction of the structure takes place

A structural and functional model for the 1-aminocyclopropane-1-carboxylic acid oxidase.

Science.gov (United States)

Sallmann, Madleen; Oldenburg, Fabio; Braun, Beatrice; Réglier, Marius; Simaan, A Jalila; Limberg, Christian

2015-10-12

The hitherto most realistic low-molecular-weight analogue for the 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO) is reported. The ACCOs 2-His-1-carboxylate iron(II) active site was mimicked by a TpFe moiety, to which the natural substrate ACC could be bound. The resulting complex [Tp(Me,Ph) FeACC] (1), according to X-ray diffraction analysis performed for the nickel analogue, represents an excellent structural model, featuring ACC coordinated in a bidentate fashion-as proposed for the enzymatic substrate complex-as well as a vacant coordination site that forms the basis for the first successful replication also of the ACCO function: 1 is the first known ACC complex that reacts with O2 to produce ethylene. As a FeOOH species had been suggested as intermediate in the catalytic cycle, H2 O2 was tested as the oxidant, too, and indeed evolution of ethylene proceeded even more rapidly to give 65 % yield. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrophobic, ductile, and transparent nanocellulose films with quaternary alkylammonium carboxylates on nanofibril surfaces.

Science.gov (United States)

Shimizu, Michiko; Saito, Tsuguyuki; Fukuzumi, Hayaka; Isogai, Akira

2014-11-10

Hydrophobic, ductile, and transparent nanocellulose films were prepared by casting and drying aqueous dispersions of 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose nanofibrils (TOCNs) with quaternary alkylammoniums (QAs) as counterions for the surface carboxylate groups. TOCN films with tetramethylammonium and tetraethylammonium carboxylates showed high optical transparencies, strain-to-failure values (14-22%), and work-of-fracture values (20-27 MJ m(-3)). The ductility of these films was likely caused by the alkyl chains of the QA groups densely covering the TOCN surfaces and being present at the interfaces between the TOCN elements in the films. The water contact angle of the TOCN-QA films increased to ∼100° by introducing tetra(n-butyl)ammonium groups as counterions. Thus, TOCN film properties can be controlled by changing the chemical structure of the counterions from Na to QAs. The hydrophilic TOCN surfaces can be changed to hydrophobic simply and efficiently by the conversion from TOCN-Na to TOCN-QA, when TOCNs are used as nanofillers in hydrophobic polymer matrices.

Role of Carboxylate ligands in the Synthesis of AuNPs: Size Control, Molecular Interaction and Catalytic Activity

KAUST Repository

Aljohani, Hind Abdullah

2016-05-22

Nanoparticles (NPs) are the basis of nanotechnology and finding numerous applications in various fields such as health, electronics, environment, personal care products, transportation, and catalysis. To fulfill these functions, the nanoparticles must be synthesized, passivated to control their chemical reactivity, stabilized against aggregation and functionalized to achieve specific performances. The chemistry of metal nanoparticles especially that of noble metals (Gold, Platinum…) is a growing field. The nanoparticles have indeed different properties from those of the corresponding bulk material. These properties are largely influenced by several parameters; the most important are the size, shape, and the local environment of the nanoparticles. One of the most common synthetic methods for the preparation of gold nanoparticles (AuNPs) is based on stabilization by citrate. Since it was reported first by Turkevich et al. in 1951, this synthetic scheme has been widely used, studied and a substantial amount of important information regarding this system has been reported in the literature. The most popular method developed by Frens for controlling the size of the noble gold nanoparticles based on citrate was achieved by varying the concentration of sodium citrate. Despite a large number of investigations focused on utilizing Cit-AuNPs, the structural details of citrate anions adsorbed on the AuNP surface are still unknown. It is known only that citrate anions “coordinate” to the metal surface by inner sphere complexation of the carboxylate groups and there are trace amounts of AuCl4−, Cl−, and OH− on the metal surface. Moreover, it is generally accepted that the ligand shell morphology of Au nanoparticles can be partly responsible for important properties such as oxidation of carbon monoxide. The use of Au-NPs in heterogeneous catalysis started mostly with Haruta who discovered the effect of particle size on the activity for carbon monoxide oxidation at

Marine molecular biology: An emerging field of biological sciences

Digital Repository Service at National Institute of Oceanography (India)

Thakur, N.L.; Jain, R.; Natalio, F.; Hamer, B.; Thakur, A.N.; Muller, W.E.G.

An appreciation of the potential applications of molecular biology is of growing importance in many areas of life sciences, including marine biology. During the past two decades, the development of sophisticated molecular technologies...

Catalytic conversion of carboxylic acids in bio-oil for liquid hydrocarbons production

International Nuclear Information System (INIS)

Wang, Shurong; Guo, Zuogang; Cai, Qinjie; Guo, Long

2012-01-01

Bio-oil must be upgraded to be suitable for use as a high-grade transport fuel. Crude bio-oil has a high content of carboxylic acids which can cause corrosion, and the high oxygen content of these acids also reduces the oil’s heating value. In this paper, acetic acid and propanoic acid were chosen as the model carboxylic acids in bio-oil. Their behavior in the production of liquid hydrocarbons during a catalytic conversion process was investigated in a micro-fixed bed reactor. The liquid organic phase from this catalytic conversion process mainly consisted of liquid hydrocarbons and phenol derivatives. Under the condition of low Liquid Hourly Space Velocity (LHSV), the liquid organic phase from acetic acid cracking had a selectivity of 22% for liquid hydrocarbons and a selectivity of 65% for phenol derivatives. The composition of the organic products changed considerably with the LHSV increasing to 3 h −1 . The selectivity for liquid hydrocarbons increased up to 52% while that for phenol derivatives decreased to 32%. Propanoic acid performed much better in producing liquid hydrocarbons than acetic acid. Its selectivity for liquid hydrocarbons was as high as 80% at LHSV = 3 h −1 . A mechanism for this catalytic conversion process was proposed according to the analysis of the components in the liquid organic phases. The pathways of the main compounds formation in the liquid organic phases were proposed, and the reason why liquid hydrocarbons were more effectively produced when using propanoic acid rather than acetic acid was also successfully explained. In addition, BET and SEM characterization were used to analyze the catalyst coke deposition. -- Graphical abstract: Display Omitted Highlights: ► High content of carboxylic acids in bio-oil causes its corrosiveness. ► Acetic acid and propanoic acid are two dominant acids in bio-oil. ► Liquid hydrocarbons were produced by cracking of these two dominant acids. ► A mechanism model was proposed to explain

Controlled Electrochemical Carboxylation of Graphene To Create a Versatile Chemical Platform for Further Functionalization

DEFF Research Database (Denmark)

Bjerglund Pedersen, Emil; Kongsfelt, Mikkel; Shimizu, Kyoko

2014-01-01

An electrochemical approach is introduced for the versatile carboxylation of multi-layered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate (i.e., graphene chemically vapor-deposited on Ni) is negatively charged at -1.9 V versus Ag/AgI in a degassed solution to allow for intercalation...... of Bu4N+ and, thereby, separation of the individual graphene sheets. In the next step, the strongly activated and nucleophilic graphene is allowed to react with added carbon dioxide in an addition reaction, introducing carboxylate groups stabilized by Bu4N+ already present. This procedure may be carried...... solution at the graphene electrode for a given time. The same functionalization degree is obtained for all multi-layered regions, independent of the number of graphene sheets, which is due to the fact that the entire graphene structure is opened in response to the intercalation of Bu4N+. Hence...

Intramolecular electron transfer through a bridging carboxylate group coordinated to two cobalt(III)-ions

International Nuclear Information System (INIS)

Wieghardt, K.

1978-01-01

Reduction of the binuclear μ-p-nitrobenzoato -di-μ-hydroxo -bis[triammine cobalt(III)] cation with (CH 3 ) 2 COH radicals yields a radical cation with the p-nitrobenzoato radical being coordinated to two cobalt(III) ions at the carboxylic group. The unprotonated form of this species undergoes intramolecular electron transfer producing Co(II) (k = (3.3 +- 0.3). x 10 3 s -1 ). The role of the carboxylate group in the intramolecular electron transfer process is tentatively assessed in terms of an intramolecular outer-sphere reaction because of lack of overlap of the donor orbitals (π) and the acceptor orbital (sigma). The protonated form of the radical cation (pKsub(a) = 2.5) disproportionates via a bimolecular process without production of Co(II). The effect of two coordinated Co(III) ions as compared to only one on the properties of the nitrobenzoate radical anion are discussed. (orig.) 891 HK 892 GM [de

Transition Metal Catalyzed Synthesis of Carboxylic Acids, Imines, and Biaryls

DEFF Research Database (Denmark)

Santilli, Carola; Madsen, Robert

the carboxylate.  Manganese catalyzed radical Kumada-type reaction between aryl halidesand aryl Grignard reagents. The reaction between aryl halides and aryl Grignard reagents catalyzed by MnCl2 has been extended to several methyl-substituted aryl iodide reagents byperforming the reaction at 120 ˚C in a microwave...... oven (Scheme ii). A limitation of the heterocoupling process is the concomitant dehalogenation of the aryl halide and homocoupling of the Grignard reagent leading low to moderate yields of the desired heterocoupling product. The mechanism of the cross-coupling process was investigated by performing two...

Consolidated bioprocessing of microalgal biomass to carboxylates by a mixed culture of cow rumen bacteria using anaerobic sequencing batch reactor (ASBR).

Science.gov (United States)

Zhao, Baisuo; Liu, Jie; Frear, Craig; Holtzapple, Mark; Chen, Shulin

2016-12-01

This study employed mixed-culture consolidated bioprocessing (CBP) to digest microalgal biomass in an anaerobic sequencing batch reactor (ASBR). The primary objectives are to evaluate the impact of hydraulic residence time (HRT) on the productivity of carboxylic acids and to characterize the bacterial community. HRT affects the production rate and patterns of carboxylic acids. For the 5-L laboratory-scale fermentation, a 12-day HRT was selected because it offered the highest productivity of carboxylic acids and it synthesized longer chains. The variability of the bacterial community increased with longer HRT (R 2 =0.85). In the 5-L laboratory-scale fermentor, the most common phyla were Firmicutes (58.3%), Bacteroidetes (27.4%), and Proteobacteria (11.9%). The dominant bacterial classes were Clostridia (29.8%), Bacteroidia (27.4%), Tissierella (26.2%), and Betaproteobacteria (8.9%). Copyright © 2016 Elsevier Ltd. All rights reserved.

ON THE FORMATION OF BENZOIC ACID AND HIGHER-ORDER BENZENE CARBOXYLIC ACIDS IN INTERSTELLAR MODEL ICE GRAINS

Energy Technology Data Exchange (ETDEWEB)

McMurtry, Brandon M.; Saito, Sean E. J.; Turner, Andrew M.; Chakravarty, Harish K.; Kaiser, Ralf I. [W. M. Keck Research Laboratory in Astrochemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States)

2016-11-10

With a binary ice mixture of benzene (C{sub 6}H{sub 6}) and carbon dioxide (CO{sub 2}) at 10 K under contamination-free ultrahigh vacuum conditions, the formation of benzene carboxylic acids in interstellar ice grains was studied. Fourier transform infrared spectroscopy was used to probe for the formation of new species during the chemical processing of the ice mixture and during the following temperature-programmed desorption. Newly formed benzene carboxylic acid species, i.e., benzoic acid, as well as meta - and para -benzene dicarboxylic acid, were assigned using newly emerging bands in the infrared spectrum; a reaction mechanism, along with rate constants, was proposed utilizing the kinetic fitting of the coupled differential equations.

l-2-Nitrimino-1,3-diazepane-4-carboxylic acid

Directory of Open Access Journals (Sweden)

Harutyun A. Karapetyan

2008-05-01

Full Text Available The cyclic form of l-nitroarginine, C6H10N4O4, crystallizes with two independent molecules in the asymmetric unit. According to the geometrical parameters, similar in both molecules, the structure corresponds to that of l-2-nitrimino-1,3-diazepane-4-carboxylic acid; there are, however, conformational differences between the independent molecules, one of them being close to a twisted chair while the other might be described as a rather flattened boat. All six active H atoms in the two molecules are involved in hydrogen bonds, two of which are intramolecular and four intermolecular, forming an infinite chain of molecules along the b axis.

Synthesis of carboxyl-capped and bright YVO4:Eu,Bi nanoparticles and their applications in immunochromatographic test strip assay

International Nuclear Information System (INIS)

Luo, Min; Sun, Tian-Ying; Wang, Jia-Hong; Yang, Peng; Gan, Liang; Liang, Li-Lei; Yu, Xue-Feng; Gong, Xing-Hou

2013-01-01

Graphical abstract: - Highlights: • The morphology and properties of YVO 4 :Eu,Bi nanoparticles were investigated. • YVO 4 :Eu,Bi were coupled with IgG for bioprobes due to their good properties. • YVO 4 :Eu,Bi were applied to immunochromatographic test strip assay. - Abstract: Carboxyl-capped YVO 4 :Eu,Bi nanoparticles with average diameter of ∼10 nm were synthesized via a copolymer of phosphono and carboxylic acid mediated hydrothermal method. Under a 350 nm ultraviolet light excitation, the YVO 4 :Eu,Bi NPs exhibit sharp and bright red emission peaked at 615 nm and with highest quantum yield of ∼43%. Furthermore, the nanoparticles show good water/buffer stability and feasible bioconjugation benefiting from the carboxylic groups on their surface. Based on these kind optical and surface properties of the YVO 4 :Eu,Bi nanoparticles, an immunochromatographic test strip assay for quantitative determination of human IgG was achieved. This protocol can be extended to other rare-earth nanoparticles with the purpose of developing bioprobes for desired applications

High-resolution satellite imagery is an important yet underutilized resource in conservation biology.

Science.gov (United States)

Boyle, Sarah A; Kennedy, Christina M; Torres, Julio; Colman, Karen; Pérez-Estigarribia, Pastor E; de la Sancha, Noé U

2014-01-01

Technological advances and increasing availability of high-resolution satellite imagery offer the potential for more accurate land cover classifications and pattern analyses, which could greatly improve the detection and quantification of land cover change for conservation. Such remotely-sensed products, however, are often expensive and difficult to acquire, which prohibits or reduces their use. We tested whether imagery of high spatial resolution (≤5 m) differs from lower-resolution imagery (≥30 m) in performance and extent of use for conservation applications. To assess performance, we classified land cover in a heterogeneous region of Interior Atlantic Forest in Paraguay, which has undergone recent and dramatic human-induced habitat loss and fragmentation. We used 4 m multispectral IKONOS and 30 m multispectral Landsat imagery and determined the extent to which resolution influenced the delineation of land cover classes and patch-level metrics. Higher-resolution imagery more accurately delineated cover classes, identified smaller patches, retained patch shape, and detected narrower, linear patches. To assess extent of use, we surveyed three conservation journals (Biological Conservation, Biotropica, Conservation Biology) and found limited application of high-resolution imagery in research, with only 26.8% of land cover studies analyzing satellite imagery, and of these studies only 10.4% used imagery ≤5 m resolution. Our results suggest that high-resolution imagery is warranted yet under-utilized in conservation research, but is needed to adequately monitor and evaluate forest loss and conversion, and to delineate potentially important stepping-stone fragments that may serve as corridors in a human-modified landscape. Greater access to low-cost, multiband, high-resolution satellite imagery would therefore greatly facilitate conservation management and decision-making.

Carboxylate derivatives of tributyltin (IV) complexes as anticancer and antileishmanial agents.

Science.gov (United States)

Waseem, Durdana; Butt, Arshad Farooq; Haq, Ihsan-Ul; Bhatti, Moazzam Hussain; Khan, Gul Majid

2017-04-04

Tributyltin (IV) compounds are promising candidates for drug development. In the current study, we evaluated in-vitro and in-silico profile of carboxylate derivatives of tributyltin (IV) complexes. ADMET and drug-likeliness properties were predicted using MetaPrint2D React, preADMET, SwissADME and Molsoft tools. SwissTargetPrediction predicted molecular targets for compounds. In-vitro bioactivity was evaluated by quantifying cytotoxicity against HepG2, THP-1 cell lines, isolated lymphocytes and leishmania promastigotes as well as measuring protein kinase (PK) inhibition activity. Results indicate partial compliance of compounds with drug-likeliness rules. Ch-409 complies with WDI and Lipinski rules. ADMET profile prediction shows strong plasma protein binding except for Ch-409, low to high GI absorption and BBB penetration (C brain /C blood  = 0.942-11; caco-2 cells permeability 20.13-26.75 nm/sec), potential efflux by P-glycoprotein, metabolism by CYP3A4, medium inhibition of hERG, mutagenicity and capacity to be detoxified by glutathionation and glucuronidation. Molecular targets include proteases, enzymes, membrane receptors, transporters and ion channels where Ch-409 targets membrane receptors only. Compounds are significantly (p tributyltin (IV) complexes possess significant antileishmanial and cytotoxic potential. These are promising compounds for the development of antileishmanial and anticancer drugs. Graphical Abstract Carboxylate derivatives of tributyltin (IV) complexes as anticancer and antileishmanial agents.

Synthesis, radiosynthesis, in vitro and preliminary in vivo evaluation of biphenyl carboxylic and hydroxamic matrix metalloproteinase (MMP) inhibitors as potential tumor imaging agents

International Nuclear Information System (INIS)

Oltenfreiter, Ruth; Staelens, Ludovicus; Hillaert, Ulrik; Heremans, An; Noel, Agnes; Frankenne, Francis; Slegers, Guido

2005-01-01

Excess matrix degradation is one of the hallmarks of cancer and is an important factor in the process of tumor progression. It is implicated in invasion, metastasis, growth, angiogenesis and migration. Many characteristics of matrix metalloproteinases (MMPs) make them attractive therapeutic and diagnostic targets. MMP expression is upregulated at the tumor site, with localization of activity in the tumor or the surrounding stroma, providing a target for medical imaging techniques. Radioiodinated carboxylic and hydroxamic MMP inhibitors 2-(4'-[ 123 I] iodo-biphenyl-4-sulfonylamino)-3-methyl-butyric acid (9) and 2-(4'-[ 123 I] iodo-biphenyl-4-sulfonylamino)-3-methyl-butyramide (11), their unlabelled standards and precursors were synthesized. Radioiodination was conducted by electrophilic aromatic substitution of the tributylstannyl precursors and resulted in radiochemical yields of 70+/-5% (n=6) and 60+/-5% (n=4), respectively. In vitro zymography and enzyme assays showed for both hydroxamic acid and carboxylic acid compounds a good inhibition activity and a high selectivity for MMP-2. In vivo biodistribution in NMRI mice showed no long-term accumulation in organs and the possibility to accumulate in the tumor in a later phase of this study

Synthesis, radiosynthesis, in vitro and preliminary in vivo evaluation of biphenyl carboxylic and hydroxamic matrix metalloproteinase (MMP) inhibitors as potential tumor imaging agents

Energy Technology Data Exchange (ETDEWEB)

Oltenfreiter, Ruth [Laboratory of Radiopharmacy, Ghent University, Harelbekestraat 72, 9000 Ghent (Belgium)]. E-mail: ruth.oltenfreiter@ugent.be; Staelens, Ludovicus [Laboratory of Radiopharmacy, Ghent University, Harelbekestraat 72, 9000 Ghent (Belgium); Hillaert, Ulrik [Laboratory for Medicinal Chemistry, Ghent University, Harelbekestraat 72, 9000 Ghent (Belgium); Heremans, An; Noel, Agnes [Laboratory of Tumor and Developmental Biology, University of Liege, Sart-Tilman, Liege (Belgium); Frankenne, Francis [Laboratory of Tumor and Developmental Biology, University of Liege, Sart-Tilman, Liege (Belgium); Slegers, Guido [Laboratory of Radiopharmacy, Ghent University, Harelbekestraat 72, 9000 Ghent (Belgium)

2005-06-01

Excess matrix degradation is one of the hallmarks of cancer and is an important factor in the process of tumor progression. It is implicated in invasion, metastasis, growth, angiogenesis and migration. Many characteristics of matrix metalloproteinases (MMPs) make them attractive therapeutic and diagnostic targets. MMP expression is upregulated at the tumor site, with localization of activity in the tumor or the surrounding stroma, providing a target for medical imaging techniques. Radioiodinated carboxylic and hydroxamic MMP inhibitors 2-(4'-[{sup 123}I] iodo-biphenyl-4-sulfonylamino)-3-methyl-butyric acid (9) and 2-(4'-[{sup 123}I] iodo-biphenyl-4-sulfonylamino)-3-methyl-butyramide (11), their unlabelled standards and precursors were synthesized. Radioiodination was conducted by electrophilic aromatic substitution of the tributylstannyl precursors and resulted in radiochemical yields of 70+/-5% (n=6) and 60+/-5% (n=4), respectively. In vitro zymography and enzyme assays showed for both hydroxamic acid and carboxylic acid compounds a good inhibition activity and a high selectivity for MMP-2. In vivo biodistribution in NMRI mice showed no long-term accumulation in organs and the possibility to accumulate in the tumor in a later phase of this study.

Carboxylated nitrile butadiene rubber/hybrid filler composites

Directory of Open Access Journals (Sweden)

Ahmad Mousa

2012-08-01

Full Text Available The surface properties of the OSW and NLS are measured with the dynamic contact-angle technique. The x-ray photoelectron spectroscopy (XPS of the OSW reveals that the OSW possesses various reactive functional groups namely hydroxyl groups (OH. Hybrid filler from NLS and OSW were incorporated into carboxylated nitrile rubber (XNBR to produce XNBR hybrid composites. The reaction of OH groups from the OSW with COOH of the XNBR is checked by attenuated total reflectance spectra (ATR-IR of the composites. The degree of curing ΔM (maximum torque-minimum torque as a function of hybrid filler as derived from moving die rheometer (MDR is reported. The stress-strain behavior of the hybrid composites as well as the dynamic mechanical thermal analysis (DMTA is studied. Bonding quality and dispersion of the hybrid filler with and in XNBR are examined using scanning-transmission electron microscopy (STEM in SEM.

Using carboxylated nanocrystalline cellulose as an additive in cellulosic paper and poly (vinyl alcohol) fiber paper.

Science.gov (United States)

Cha, Ruitao; Wang, Chengyu; Cheng, Shaoling; He, Zhibin; Jiang, Xingyu

2014-09-22

Specialty paper (e.g. cigarette paper and battery diaphragm paper) requires extremely high strength properties. The addition of strength agents plays an important role in increasing strength properties of paper. Nanocrystalline cellulose (NCC), or cellulose whiskers, has the potential to enhance the strength properties of paper via improving inter-fibers bonding. This paper was to determine the potential of using carboxylated nanocrystalline cellulose (CNCC) to improve the strength properties of paper made of cellulosic fiber or poly (vinyl alcohol) (PVA) fiber. The results indicated that the addition of CNCC can effectively improve the strength properties. At a CNCC dosage of 0.7%, the tear index and tensile index of the cellulosic paper reached the maximum of 12.8 mN m2/g and 100.7 Nm/g, respectively. More importantly, when increasing the CNCC dosage from 0.1 to 1.0%, the tear index and tensile index of PVA fiber paper were increased by 67.29%, 22.55%, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Construction and expression of eukaryotic expression vectors of full-length, amino-terminus and carboxyl-terminus Raf gene

Directory of Open Access Journals (Sweden)

Zhuomin WANG

2008-06-01

Full Text Available Background and objective Raf is a key molecule in the Ras-Raf-MEK-ERK signal transduction pathway and is highly activated in different human carcinomas. However, its biological functions and regulation mechanisms are still unclear. The aims of this study were to construct eukaryotic expression vectors with Raf full encoding region, truncated amino-terminus and carboxyl-terminus, respectively. Methods Eukaryotic expression vectors of pCMV-Tag2b-Raf-1, pCMV-Tag2b-N-Raf and pCMV-Tag2b-C-Raf were constructed by gene recombination technique and confirmed by restriction enzyme analysis and DNA sequencing. Furthermore, the expression of these fusion proteins was detected by western blot in transient transfected 293T cells. Results The sequences and open reading frames of these three vectors were completely consistent with experimental design. All target proteins can be detected in 293T cells. Conclusion Eukaryotic expression vectors of pCMV-Tag2b-Raf-1, pCMV-Tag2b-N-Raf and pCMV-Tag2b-C-Raf were successfully constructed and can be expressed in 293T cells.

Exploring the reductive capacity of Pyrococcus furiosus : the reduction of carboxylic acids and pyridine nucleotides

NARCIS (Netherlands)

Ban, van den E.C.D.

2001-01-01

This Ph.D. project started in 1997 and its main goal was to obtain insight in the reductive capacity of the hyperthermophilic archaeon Pyrococcus furiosus . The research was focused on the biocatalytic reduction of carboxylic