Unexpected side products in the conjugation of an amine-derivatized morpholino oligomer with p-isothiocyanate benzyl DTPA and their removal

Energy Technology Data Exchange (ETDEWEB)

Liu Guozheng, E-mail: guozheng.liu@umassmed.ed [Department of Radiology, University of Massachusetts Medical School, Worcester, MA 01655 (United States); Dou Shuping; Liu Yuxia; Liang Minmin; Chen Ling; Cheng Dengfeng [Department of Radiology, University of Massachusetts Medical School, Worcester, MA 01655 (United States); Greiner, Dale [Department of Medicine, University of Massachusetts Medical School, Worcester, MA 01655 (United States); Rusckowski, Mary; Hnatowich, Donald J. [Department of Radiology, University of Massachusetts Medical School, Worcester, MA 01655 (United States)

2011-02-15

In connection with pretargeting, an amine-derivatized morpholino phosphorodiamidate oligomer (NH{sub 2}-cMORF) was conjugated conventionally with p-isothiocyanate benzyl-DTPA (p-SCN-Bn-DTPA). However, after {sup 111}In radiolabeling, unexpected label instability was observed. To understand this instability, the NH{sub 2}-cMORF and, as control, the native cMORF without the amine were conjugated in the conventional manner. Surprisingly, the {sup 111}In labeling of the native cMORF conjugate was equally effective as that of the NH{sub 2}-cMORF conjugate (>95%) despite the absence of the amine group. Furthermore, heating the radiolabeled NH{sub 2}-cMORF and native cMORF conjugates resulted in a 35% loss and a complete loss of the label, respectively. Since the {sup 111}In labeled DTPA is known to be stable, the instability in both cases must be due to some unstable association of DTPA to the cMORF, presumably unstable association to some endogenous sites in cMORF. Based on this assumption, a postconjugation-prepurification heating step was introduced, and labeling efficiency and stability were again investigated. By introducing the heating step, the side products were dissociated, and after purification and labeling, the NH{sub 2}-cMORF conjugate provided a stable label and high labeling efficiency with no need for postlabeling purification. The biodistribution of this radiolabeled conjugate in normal mice showed significantly lower backgrounds compared with the labeled unstable native cMORF conjugate. In conclusion, the conventional conjugation procedure to attach the p-SCN-Bn-DTPA to NH{sub 2}-cMORF resulted in side product(s) that were responsible for the {sup 111}In label instability. Adding a postconjugation-prepurification heating step dissociated the side products, improved the label stability and lowered tissue backgrounds in mice.

Separation of 2-aminobenzoic acid-derivatized glycosaminoglycans and asparagine-linked glycans by capillary electrophoresis.

Science.gov (United States)

Sato, Kae; Sato, Kiichi; Okubo, Akira; Yamazaki, Sunao

2005-01-01

A capillary electrophoresis method was developed for the analysis of oligosaccharides combined with derivatization with 2-aminobenzoic acid. Glycosaminoglycan delta-disaccharides were effectively resolved on a fused-silica capillary tube using 150 mM borate, pH 8.5, as a running electrolyte solution. This analytical method was applied to the identification of glycosaminoglycan in combination with enzymatic digestion. The separation of N-glycans or glucose-oligomers was performed with a phosphate buffer containing polyethylene glycol or borate as an electrolyte solution. This method is expected to be useful in the determination of oligosaccharide structures in a glycoprotein.

Squid pen-inspired chitinous functional materials: Hierarchical chitin fibers by centrifugal jet-spinning and transparent chitin fiber-reinforced composite

Science.gov (United States)

Jeong, Seung-Hwan; Kim, Joong-Kwon; Lim, Young-Woo; Hwang, Hyun-Bin; Kwon, Hee-Young; Bae, Byeong-Soo; Jin, Jungho

2018-01-01

Here, inspired by the fibrous composite structure of a squid pen, we introduce hierarchical chitin fibers (herein, termed "Chiber") and their transparent composites and demonstrate the potential of these chitinous functional materials as a sustainable separation-membrane and reinforcing filler for composites. We employ a centrifugal jet-spinning process to fabricate Chiber with aligned chitin nanofibrillar architectures, for which we discuss the processing-morphology relationship. A nonwoven fiber-mat made of Chiber exhibits excellent adsorbing performance for a toxic ionic dye (Congo Red), and has a low coefficient of thermal expansion comparable to that of glass fibers. Finally, we demonstrate a squid pen-mimetic transparent composite using Chiber and investigate its optical property.

Synthesis and physicochemical characterization of chitin dihexanoate — A new biocompatible chitin derivative — In comparison to chitin dibutyrate

Energy Technology Data Exchange (ETDEWEB)

Skołucka-Szary, Karolina, E-mail: karolina.skolucka@celther.com [Department of Research and Development, Celther Poland Sp. z o.o. ul. Ostrzykowizna 14A, 05-170 Zakroczym (Poland); Ramięga, Aleksandra; Piaskowska, Wanda [Department of Research and Development, Celther Poland Sp. z o.o. ul. Ostrzykowizna 14A, 05-170 Zakroczym (Poland); Janicki, Bartosz [Silesian University of Technology, Faculty of Chemistry, Department of Physical Chemistry and Technology of Polymers, ul. M. Strzody 9, 44-100 Gliwice (Poland); Grala, Magdalena [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz (Poland); Rieske, Piotr [Department of Research and Development, Celther Poland Sp. z o.o. ul. Ostrzykowizna 14A, 05-170 Zakroczym (Poland); Bartczak, Zbigniew [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz (Poland); Piaskowski, Sylwester [Department of Research and Development, Celther Poland Sp. z o.o. ul. Ostrzykowizna 14A, 05-170 Zakroczym (Poland)

2016-03-01

Chitin dihexanoate (DHCH) is the novel biocompatible and technologically friendly highly substituted chitin diester. Here we described optimization of DHCH and chitin dibutyrate (dibutyryl chitin, DBC) synthesis conditions (temperature and reaction time) to obtain desired polymers with high reaction yield, high substitution degree (close to 2) and appropriately high molecular weights. A two-step procedure, employing acidic anhydrides (hexanoic or butyric anhydride) as the acylation agent and methanesulfonic acid both as the catalyst and the reaction medium, was applied. Chemical structures of DBC and DHCH were confirmed by NMR ({sup 1}H and {sup 13}C) and IR investigations. Mechanical properties, thermogravimetric analysis, differential scanning calorimetry and biocompatibility (Neutral red uptake assay, Skin Sensitization and Irritation Tests) were assessed. Both polymers proved highly biocompatible (non-cytotoxic in vitro, non-irritating and non-allergic to skin) and soluble in several organic solvents (dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, acetone, ethanol and others). It is worth emphasizing that DHCH and DBC can be easily processed by solvent casting method and the salt-leaching method, what gives the opportunity to prepare highly porous structures, which can be further successfully applied as the material for wound dressings and scaffolds for tissue engineering. - Highlights: • A new method for chitin dihexanoate (DHCH) synthesis was proposed. • DHCH physicochemical and biological properties were analyzed. • DHCH properties were compared with DBC characteristics. • For synthesis of both, DBC and DHCH methanesulfonic acid was used as the catalyst.

Wastewater treatment with ion-exchange chitin membrane

International Nuclear Information System (INIS)

Paulenova, A.; Fjeld, R. A.; Visacky, V.

2001-01-01

Chitin, poly(N-acetyl-D glucosamine) and chitosan, its deacetylated derivates have recently obtained attention as bio-sorbents, because they shown a great ability to accumulate heavy metals and other pollutants. It was found that recovery of metals is strongly affected by pH. At low acidic pH range 4-5 chitin membrane exhibits better selectivity for lead than for cadmium or zinc. Sorption preference for metals decreases in the order: Pb > Cd > Zn. For uranium, as well for strontium was observed significant increase of recovery at decrease of pH to slightly acidic, close to neutral value. It was shown that chemical behavior of chitin membrane is excellent; ion-exchange nature of chitin was not changed during chitin membrane manufacturing process. Using of chitin membrane instead of chitin flake column brings significant increasing of driving force of the separation process, limited in the case of column experimental design by diffusion coefficient, while in the case of membrane process only by mass transfer coefficient. (authors)

Biodegradation of the chitin-protein complex in crustacean cuticle

Science.gov (United States)

Artur, Stankiewicz B.; Mastalerz, Maria; Hof, C.H.J.; Bierstedt, A.; Flannery, M.B.; Briggs, D.E.G.; Evershed, R.P.

1998-01-01

Arthropod cuticles consist predominantly of chitin cross-linked with proteins. While there is some experimental evidence that this chitin-protein complex may resist decay, the chemical changes that occur during degradation have not been investigated in detail. The stomatopod crustacean Neogonodactylus oerstedii was decayed in the laboratory under anoxic conditions. A combination of pyrolysis-gas chromatography/mass spectrometry and FTIR revealed extensive chemical changes after just 2 weeks that resulted in a cuticle composition dominated by chitin. Quantitative analysis of amino acids (by HPLC) and chitin showed that the major loss of proteins and chitin occurred between weeks 1 and 2. After 8 weeks tyrosine, tryptophan and valine are the most prominent amino acid moieties, showing their resistance to degradation. The presence of cyclic ketones in the pyrolysates indicates that mucopolysaccharides or other bound non-chitinous carbohydrates are also resistant to decay. There is no evidence of structural degradation of chitin prior to 8 weeks when FTIR revealed a reduction in chitin-specific bands. The chemical changes are paralleled by structural changes in the cuticle, which becomes an increasingly open structure consisting of loose chitinous fibres. The rapid rate of decay in the experiments suggests that where chitin and protein are preserved in fossil cuticles degradation must have been inhibited.Arthropod cuticles consist predominantly of chitin cross-linked with proteins. While there is some experimental evidence that this chitin-protein complex may resist decay, the chemical changes that occur during degradation have not been investigated in detail. The stomatopod crustacean Neogonodactylus oerstedii was decayed in the laboratory under anoxic conditions. A combination of pyrolysis-gas chromatography/mass spectrometry and FTIR revealed extensive chemical changes after just 2 weeks that resulted in a cuticle composition dominated by chitin. Quantitative

First report on chitinous holdfast in sponges (Porifera).

Science.gov (United States)

Ehrlich, Hermann; Kaluzhnaya, Oksana V; Tsurkan, Mikhail V; Ereskovsky, Alexander; Tabachnick, Konstantin R; Ilan, Micha; Stelling, Allison; Galli, Roberta; Petrova, Olga V; Nekipelov, Serguei V; Sivkov, Victor N; Vyalikh, Denis; Born, René; Behm, Thomas; Ehrlich, Andre; Chernogor, Lubov I; Belikov, Sergei; Janussen, Dorte; Bazhenov, Vasilii V; Wörheide, Gert

2013-07-07

A holdfast is a root- or basal plate-like structure of principal importance that anchors aquatic sessile organisms, including sponges, to hard substrates. There is to date little information about the nature and origin of sponges' holdfasts in both marine and freshwater environments. This work, to our knowledge, demonstrates for the first time that chitin is an important structural component within holdfasts of the endemic freshwater demosponge Lubomirskia baicalensis. Using a variety of techniques (near-edge X-ray absorption fine structure, Raman, electrospray ionization mas spectrometry, Morgan-Elson assay and Calcofluor White staining), we show that chitin from the sponge holdfast is much closer to α-chitin than to β-chitin. Most of the three-dimensional fibrous skeleton of this sponge consists of spicule-containing proteinaceous spongin. Intriguingly, the chitinous holdfast is not spongin-based, and is ontogenetically the oldest part of the sponge body. Sequencing revealed the presence of four previously undescribed genes encoding chitin synthases in the L. baicalensis sponge. This discovery of chitin within freshwater sponge holdfasts highlights the novel and specific functions of this biopolymer within these ancient sessile invertebrates.

Capillary electrophoresis fingerprinting, quantification and mass-identification of various 9-aminopyrene-1,4,6-trisulfonate-derivatized oligomers derived from plant polysaccharides

NARCIS (Netherlands)

Kabel, M.A.; Heijnis, W.H.; Bakx, E.J.; Kuijpers, I.J.; Voragen, A.G.J.; Schols, H.A.

2006-01-01

Various plant polysaccharide derived mono- and oligosaccharides were derivatized with the fluorescent 9-aminopyrene-1,4,6-trisulfonate (APTS) and subjected to capillary electrophoresis (CE) in combination with laser induced fluorescence (LIF) detection. CE-LIF was suitable for mol-based

Yeast cell wall chitin reduces wine haze formation.

Science.gov (United States)

Ndlovu, Thulile; Divol, Benoit; Bauer, Florian F

2018-04-27

Protein haze formation in bottled wines is a significant concern for the global wine industry and wine clarification before bottling is therefore a common but expensive practice. Previous studies have shown that wine yeast strains can reduce haze formation through the secretion of certain mannoproteins, but it has been suggested that other yeast-dependent haze protective mechanisms exist. On the other hand, addition of chitin has been shown to reduce haze formation, likely because grape chitinases have been shown to be the major contributors to haze. In this study, Chardonnay grape must fermented by various yeast strains resulted in wines with different protein haze levels indicating differences in haze protective capacities of the strains. The cell wall chitin levels of these strains were determined, and a strong correlation between cell wall chitin levels and haze protection capability was observed. To further evaluate the mechanism of haze protection, Escherichia coli -produced GFP-tagged grape chitinase was shown to bind efficiently to yeast cell walls in a cell wall chitin concentration-dependent manner, while commercial chitinase was removed from synthetic wine in quantities also correlated with the cell wall chitin levels of the strains. Our findings suggest a new mechanism of reducing wine haze, and propose a strategy for optimizing wine yeast strains to improve wine clarification. Importance In this study, we establish a new mechanism by which wine yeast strains can impact on the protein haze formation of wines, and demonstrate that yeast cell wall chitin binds grape chitinase in a chitin-concentration dependent manner. We also show that yeast can remove this haze-forming protein from wine. Chitin has in the past been shown to efficiently reduce wine haze formation when added to the wine in high concentration as a clarifying agent. Our data suggest that the selection of yeast strains with high levels of cell wall chitin can reduce protein haze. We also

PIPERIDINE OLIGOMERS AND COMBINATORIAL LIBRARIES THEREOF

DEFF Research Database (Denmark)

1999-01-01

The present invention relates to piperidine oligomers, methods for the preparation of piperidine oligomers and compound libraries thereof, and the use of piperidine oligomers as drug substances. The present invention also relates to the use of combinatorial libraries of piperidine oligomers...... in libraries (arrays) of compounds especially suitable for screening purposes....

Dopamine-Mediated Sclerotization of Regenerated Chitin in Ionic Liquid.

Science.gov (United States)

Oh, Dongyeop X; Shin, Sara; Lim, Chanoong; Hwang, Dong Soo

2013-09-06

Chitin is a promising structural material for biomedical applications, due to its many advantageous properties and abundance in nature. However, its usage and development in the biomedical field have been stagnant, because of chitin's poor mechanical properties in wet conditions and the difficulties in transforming it into an applicable form. To overcome these challenges, we created a novel biomimetic chitin composite. This regenerated chitin, prepared with ionic liquid, showed improved mechanical properties in wet conditions by mimicking insect cuticle and squid beak sclerotization, i.e. , catechol-meditated cross-linking. By ionic liquid-based heat treatment, dopamine oxidation produced melanin-like compounds and dopamine-meditated cross-links without any solvent evaporation and oxidant utilization. The dopamine-meditated sclerotization increased the ultimate tensile strength (UTS) of the regenerated chitin by 2.52-fold, measured after six weeks of phosphate-buffered saline (PBS) submersion. In addition, the linear swelling ratio (LSR) of the chitin film was reduced by about 22%. This strategy raises a possibility of using regenerated chitin as an artificial hard tissue in wet conditions.

A Venom Gland Extracellular Chitin-Binding-Like Protein from Pupal Endoparasitoid Wasps, Pteromalus Puparum, Selectively Binds Chitin

Directory of Open Access Journals (Sweden)

Yu Zhu

2015-11-01

Full Text Available Chitin-binding proteins (CBPs are present in many species and they act in a variety of biological processes. We analyzed a Pteromalus puparum venom apparatus proteome and transcriptome and identified a partial gene encoding a possible CBP. Here, we report cloning a full-length cDNA of a sequence encoding a chitin-binding-like protein (PpCBP from P. puparum, a pupal endoparasitoid of Pieris rapae. The cDNA encoded a 96-amino-acid protein, including a secretory signal peptide and a chitin-binding peritrophin-A domain. Phylogenetic analysis of chitin binding domains (CBDs of cuticle proteins and peritrophic matrix proteins in selected insects revealed that the CBD of PpCBP clustered with the CBD of Nasonia vitripennis. The PpCBP is specifically expressed in the venom apparatus of P. puparum, mostly in the venom gland. PpCBP expression was highest at day one after adult eclosion and much lower for the following five days. We produced a recombinant PpCBP and binding assays showed the recombinant protein selectively binds chitin but not cellulose in vitro. We infer that PpCBP serves a structural role in the venom reservoir, or may be injected into the host to help wound healing of the host exoskeleton.

PROPERTIES OF CHITIN REINFORCES COMPOSITES: A REVIEW

African Journals Online (AJOL)

user

mechanical and thermal properties of chitin reinforced composites. ..... with crabyon fiber and normal viscose filaments. Also. Zhang et al.,[65] successfully blended chitin/cellulose using two different coagulating systems (immersed in 5.

Biopolymer chitin: extraction and characterization; Biopolimero quitina: extracao e caracterizacao

Energy Technology Data Exchange (ETDEWEB)

NONE

2011-07-01

The biopolymers are materials made from renewable sources such as soybean, corn, cane sugar, cellulose and chitin. Chitin is the most abundant biopolymer found in nature, after cellulose. The chemical structure of chitin is distinguished by the hydroxyl group, of structure from cellulose, located at position C-2, which in the chitin is replaced by acetamine group. The objective of this study was to develop the chitin from exoskeletons of Litopenaeus vannamei shrimp, which are discarded as waste, causing pollutions, environmental problems and thus obtain better utilization of these raw materials. It also, show the extraction process and deacetylation of chitosan. The extraction of chitin followed steps of demineralization, desproteinization and deodorization. Chitin and chitosan were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and the thermals properties were analyzed by thermogravimetry (TG/DTG). (author)

Extraction and Characterization of Chitin from the Beetle Holotrichia parallela Motschulsky

Directory of Open Access Journals (Sweden)

Feng Zhu

2012-04-01

Full Text Available Insect chitin was isolated from adult Holotrichia parallela by treatment with 1 M HCl and 1 M NaOH, following by 1% potassium permanganate solution for decolorization. The yield of chitin from this species is 15%. This insect chitin was compared with the commercial a-chitin from shrimp, by infrared spectroscopy, X-ray diffraction, scanning electron microscopy, and elemental analysis. Both chitins exhibited similar chemical structures and physicochemical properties. Adult H. parallela is thus a promising alternative source of chitin.

Extraction and characterization of chitin and chitosan from Nigerian ...

African Journals Online (AJOL)

Chitin was synthesized from Nigerian brown shrimps by a chemical process involving demineralization and deproteinisation. Deacetylation of the chitin was conducted to obtain Chitosan. The chitin and chitosan were characterized using FTIR, XRD and SEM. Proximate and elemental analysis were also conducted.

Preparation of Chitin-PLA laminated composite for implantable application

Directory of Open Access Journals (Sweden)

Romana Nasrin

2017-12-01

Full Text Available The present study explores the possibilities of using locally available inexpensive waste prawn shell derived chitin reinforced and bioabsorbable polylactic acid (PLA laminated composites to develop new materials with excellent mechanical and thermal properties for implantable application such as in bone or dental implant. Chitin at different concentration (1–20% of PLA reinforced PLA films (CTP were fabricated by solvent casting process and laminated chitin-PLA composites (LCTP were prepared by laminating PLA film (obtained by hot press method with CTP also by hot press method at 160 °C. The effect of variation of chitin concentration on the resulting laminated composite's behavior was investigated. The detailed physico-mechanical, surface morphology and thermal were assessed with different characterization technique such as FT-IR, XRD, SEM and TGA. The FTIR spectra showed the characteristic peaks for chitin and PLA in the composites. SEM images showed an excellent dispersion of chitin in the films and composites. Thermogravimetric analysis (TGA showed that the complete degradation of chitin, PLA film, 5% chitin reinforced PLA film (CTP2 and LCTP are 98%, 95%, 87% and 98% respectively at temperature of 500 °C. The tensile strength of the LCTP was found 25.09 MPa which is significantly higher than pure PLA film (18.55 MPa and CTP2 film (8.83 MPa. After lamination of pure PLA and CTP2 film, the composite (LCTP yielded 0.265–1.061% water absorption from 30 min to 24 h immerse in water that is much lower than PLA and CTP. The increased mechanical properties of the laminated films with the increase of chitin content indicated good dispersion of chitin into PLA and strong interfacial actions between the polymer and chitin. The improvement of mechanical properties and the results of antimicrobial and cytotoxicity of the composites also evaluated and revealed the composite would be a suitable candidate for implant application in biomedical

Preparation of Chitin-PLA laminated composite for implantable application.

Science.gov (United States)

Nasrin, Romana; Biswas, Shanta; Rashid, Taslim Ur; Afrin, Sanjida; Jahan, Rumana Akhter; Haque, Papia; Rahman, Mohammed Mizanur

2017-12-01

The present study explores the possibilities of using locally available inexpensive waste prawn shell derived chitin reinforced and bioabsorbable polylactic acid (PLA) laminated composites to develop new materials with excellent mechanical and thermal properties for implantable application such as in bone or dental implant. Chitin at different concentration (1-20% of PLA) reinforced PLA films (CTP) were fabricated by solvent casting process and laminated chitin-PLA composites (LCTP) were prepared by laminating PLA film (obtained by hot press method) with CTP also by hot press method at 160 °C. The effect of variation of chitin concentration on the resulting laminated composite's behavior was investigated. The detailed physico-mechanical, surface morphology and thermal were assessed with different characterization technique such as FT-IR, XRD, SEM and TGA. The FTIR spectra showed the characteristic peaks for chitin and PLA in the composites. SEM images showed an excellent dispersion of chitin in the films and composites. Thermogravimetric analysis (TGA) showed that the complete degradation of chitin, PLA film, 5% chitin reinforced PLA film (CTP2) and LCTP are 98%, 95%, 87% and 98% respectively at temperature of 500 °C. The tensile strength of the LCTP was found 25.09 MPa which is significantly higher than pure PLA film (18.55 MPa) and CTP2 film (8.83 MPa). After lamination of pure PLA and CTP2 film, the composite (LCTP) yielded 0.265-1.061% water absorption from 30 min to 24 h immerse in water that is much lower than PLA and CTP. The increased mechanical properties of the laminated films with the increase of chitin content indicated good dispersion of chitin into PLA and strong interfacial actions between the polymer and chitin. The improvement of mechanical properties and the results of antimicrobial and cytotoxicity of the composites also evaluated and revealed the composite would be a suitable candidate for implant application in biomedical sector.

Chitin utilization by the insect-transmitted bacterium Xylella fastidiosa.

Science.gov (United States)

Killiny, Nabil; Prado, Simone S; Almeida, Rodrigo P P

2010-09-01

Xylella fastidiosa is an insect-borne bacterium that colonizes xylem vessels of a large number of host plants, including several crops of economic importance. Chitin is a polysaccharide present in the cuticle of leafhopper vectors of X. fastidiosa and may serve as a carbon source for this bacterium. Biological assays showed that X. fastidiosa reached larger populations in the presence of chitin. Additionally, chitin induced phenotypic changes in this bacterium, notably increasing adhesiveness. Quantitative PCR assays indicated transcriptional changes in the presence of chitin, and an enzymatic assay demonstrated chitinolytic activity by X. fastidiosa. An ortholog of the chitinase A gene (chiA) was identified in the X. fastidiosa genome. The in silico analysis revealed that the open reading frame of chiA encodes a protein of 351 amino acids with an estimated molecular mass of 40 kDa. chiA is in a locus that consists of genes implicated in polysaccharide degradation. Moreover, this locus was also found in the genomes of closely related bacteria in the genus Xanthomonas, which are plant but not insect associated. X. fastidiosa degraded chitin when grown on a solid chitin-yeast extract-agar medium and grew in liquid medium with chitin as the sole carbon source; ChiA was also determined to be secreted. The gene encoding ChiA was cloned into Escherichia coli, and endochitinase activity was detected in the transformant, showing that the gene is functional and involved in chitin degradation. The results suggest that X. fastidiosa may use its vectors' foregut surface as a carbon source. In addition, chitin may trigger X. fastidiosa's gene regulation and biofilm formation within vectors. Further work is necessary to characterize the role of chitin and its utilization in X. fastidiosa.

Preparation and characterization of α-chitin from cicada sloughs

International Nuclear Information System (INIS)

Sajomsang, Warayuth; Gonil, Pattarapond

2010-01-01

In this study, a new source of insect chitin was proposed. Insect chitin was extracted from cicada sloughs by 1 M HCl and 1 M NaOH treatment for demineralization and deproteinization, respectively. The brown color of this chitin from cicada sloughs was removed using 6% sodium hypochlorite as an oxidizing agent. It was found that the insect chitin extracted from the cicada sloughs has a higher percent recovery than the chitin from rice-field crab shells. The chemical structure and physicochemical properties of α-chitin from cicada sloughs were characterized using elemental analysis (EA), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), proton nuclear magnetic resonance spectroscopy ( 1 H NMR), solid-state 13 C cross-polarization magic-angle-spinning nuclear magnetic resonance (CP/MAS) NMR spectroscopy, X-ray diffractometry (XRD), and thermogravimetry (TG). The degree of acetylation (DA) was determined by EA, 1 H NMR, and 13 C CP/MAS NMR techniques. The DA values of chitin from cicada sloughs were in the range of 97% to 102% depending on each technique. Furthermore, it was found that the DA increased with an increasing thermal property and crystallinity.

A Venom Gland Extracellular Chitin-Binding-Like Protein from Pupal Endoparasitoid Wasps, Pteromalus Puparum, Selectively Binds Chitin

Science.gov (United States)

Chitin-binding proteins (CBPs) existed in various species and involved in different biology processes. In the present study, we cloned a full length cDNA of chitin-binding protein-like (PpCBP-like) from Pteromalus puparum, a pupal endoparasitoid of Pieris rapae. PpCBP-like encoded a 96 putative amin...

Applications of Chitin and Its Derivatives in Biological Medicine

Directory of Open Access Journals (Sweden)

Moon-Moo Kim

2010-12-01

Full Text Available Chitin and its derivatives—as a potential resource as well as multiple functional substrates—have generated attractive interest in various fields such as biomedical, pharmaceutical, food and environmental industries, since the first isolation of chitin in 1811. Moreover, chitosan and its chitooligosaccharides (COS are degraded products of chitin through enzymatic and acidic hydrolysis processes; and COS, in particular, is well suited for potential biological application, due to the biocompatibility and nontoxic nature of chitosan. In this review, we investigate the current bioactivities of chitin derivatives, which are all correlated with their biomedical properties. Several new and cutting edge insights here may provide a molecular basis for the mechanism of chitin, and hence may aid its use for medical and pharmaceutical applications.

Preparation of Chitin, Study of Physicochemical Properties and Biopesticide Activities

Directory of Open Access Journals (Sweden)

Yuli Rohyami

2013-08-01

Full Text Available Chitin was preparated from shrimp shells by chemically method. Preparation was carried out by deproteination shrimp shells powder < 150 mesh with 1 - 2 M NaOH, demineralization followed by reaction with 1.0 M HCl and depigmentation with (1 : 2 : 4, v/v of chloroform : methanol : water. Physicochemical properties of chitin was determined from characterization of infrared spectra, ash value, loss on drying and total of nitrogen. Biopesticide activities of chitin was done to pest Bemisia tabaci at guava leaves with various concentration from 0.5 to 2.0 % chitin on 3 % v/v acetic acid. This study indicated that concentration of NaOH on deproteination process effected to its physicochemicals properties. Effectivity of 2 M NaOH on deproteination reaction was higher than 1 M NaOH . The degree of chitin deacetylation from 2 M NaOH was 13.61% and had lower molar ratio of total nitrogen. The degree of deacetylation of chitin from 1 M NaOH had lower and had higher molar ratio of total nitrogen. Physicochemicals properties of chitin quite an impact on its ability to reduce pest Bemisia tabaci. Biopesticide activity assay showed that treatment for 2 days on average mortality rate of 13.83%. Deacetylation of chitin which has a higher degree have a greaterability biopesticide with a mortality rate of up to 38.24%. This study the effect of deproteination process to biopesticide activities of chitin.Key Words : chitin, degree of deacetilation, molar ratio, biopesticide, Bemisia tabaci

Dopamine-Mediated Sclerotization of Regenerated Chitin in Ionic Liquid

Directory of Open Access Journals (Sweden)

Dongyeop X. Oh

2013-09-01

Full Text Available Chitin is a promising structural material for biomedical applications, due to its many advantageous properties and abundance in nature. However, its usage and development in the biomedical field have been stagnant, because of chitin’s poor mechanical properties in wet conditions and the difficulties in transforming it into an applicable form. To overcome these challenges, we created a novel biomimetic chitin composite. This regenerated chitin, prepared with ionic liquid, showed improved mechanical properties in wet conditions by mimicking insect cuticle and squid beak sclerotization, i.e., catechol-meditated cross-linking. By ionic liquid-based heat treatment, dopamine oxidation produced melanin-like compounds and dopamine-meditated cross-links without any solvent evaporation and oxidant utilization. The dopamine-meditated sclerotization increased the ultimate tensile strength (UTS of the regenerated chitin by 2.52-fold, measured after six weeks of phosphate-buffered saline (PBS submersion. In addition, the linear swelling ratio (LSR of the chitin film was reduced by about 22%. This strategy raises a possibility of using regenerated chitin as an artificial hard tissue in wet conditions.

Ultrasound stimulated release of gallic acid from chitin hydrogel matrix

Energy Technology Data Exchange (ETDEWEB)

Jiang, Huixin; Kobayashi, Takaomi, E-mail: takaomi@nagaokaut.ac.jp

2017-06-01

Ultrasound (US) stimulated drug release was examined in this study using a chitin hydrogel matrix loaded with gallic acid (GA), a drug used for wound healing and anticancer. Using phase inversion, GA-chitin hydrogels were prepared from chitin-dimethylacetamide (DMAc)/lithium chloride (LiCl) solution in the presence of GA, with 24 h exposure of the solution to water vapor. The GA release from the GA-chitin hydrogel was examined under different US powers of 0–30 W at 43 kHz. The effects of GA loading amounts in the hydrogels (0.54, 0.43, and 0.25 mg/cm{sup 3}) and chitin concentrations (0.1, 0.5, and 1 wt%) on the release behaviors were recorded under 43 kHz US exposure at 30 W. Results show that US accelerated the release efficiencies for all samples. Furthermore, the release efficiency increased concomitantly with increasing US power, GA loading amount, and decrease of the chitin concentration. The highest release rate of 0.74 μg/mL·min was obtained from 0.54 mg/cm{sup 3} of GA-loaded hydrogel fabricated from a 0.1 wt% chitin mixture solution under 43 kHz US exposure at 30 W: nine times higher than that of the sample without US exposure. The hydrogel viscoelasticity demonstrated that the US irradiation rigidified the material. FT-IR showed that US can break the hydrogen bonds in the GA-chitin hydrogels. - Highlights: • Ultrasound (US) stimulated Gallic acid (GA) release from chitin hydrogel was studied. • The release efficiency of GA from chitin hydrogel increased nine times when irradiated by 43 kHz US compared with the sample without US. • Generalized 2D correlation and deconvolution study of FT-IR showed that US could promote the GA release by breaking hydrogen bonds.

Ultrasound stimulated release of gallic acid from chitin hydrogel matrix

International Nuclear Information System (INIS)

Jiang, Huixin; Kobayashi, Takaomi

2017-01-01

Ultrasound (US) stimulated drug release was examined in this study using a chitin hydrogel matrix loaded with gallic acid (GA), a drug used for wound healing and anticancer. Using phase inversion, GA-chitin hydrogels were prepared from chitin-dimethylacetamide (DMAc)/lithium chloride (LiCl) solution in the presence of GA, with 24 h exposure of the solution to water vapor. The GA release from the GA-chitin hydrogel was examined under different US powers of 0–30 W at 43 kHz. The effects of GA loading amounts in the hydrogels (0.54, 0.43, and 0.25 mg/cm 3 ) and chitin concentrations (0.1, 0.5, and 1 wt%) on the release behaviors were recorded under 43 kHz US exposure at 30 W. Results show that US accelerated the release efficiencies for all samples. Furthermore, the release efficiency increased concomitantly with increasing US power, GA loading amount, and decrease of the chitin concentration. The highest release rate of 0.74 μg/mL·min was obtained from 0.54 mg/cm 3 of GA-loaded hydrogel fabricated from a 0.1 wt% chitin mixture solution under 43 kHz US exposure at 30 W: nine times higher than that of the sample without US exposure. The hydrogel viscoelasticity demonstrated that the US irradiation rigidified the material. FT-IR showed that US can break the hydrogen bonds in the GA-chitin hydrogels. - Highlights: • Ultrasound (US) stimulated Gallic acid (GA) release from chitin hydrogel was studied. • The release efficiency of GA from chitin hydrogel increased nine times when irradiated by 43 kHz US compared with the sample without US. • Generalized 2D correlation and deconvolution study of FT-IR showed that US could promote the GA release by breaking hydrogen bonds.

Obtention and characterization of chitin and chitosan from M. rosenbergii

International Nuclear Information System (INIS)

Battisti, Marcos V.; Campana Filho, Sergio P.

2001-01-01

Chitin was extracted from previously ground shells of Macrobrachium rosenbergii by applying acid and alkaline treatments, aiming at its demineralization and deprotenization, respectively. Its characteristics and properties were compared with those exhibited by commercial samples of chitin. Commercial chitosan and samples produced by the deacetylation of chitin obtained from M. rosenbergii shells were also compared. Average degrees of acetylation and intrinsic viscosities of the chitosan were determined by 1 H NMR spectroscopy and by capillary viscosimetry, respectively. The results show that the chitin extracted from Macrobrachium rosenbergii has a lower content of inorganic materials as compared to commercial samples but the chitosan obtained from the former chitin sample is very similar to commercial chitosan. (author)

Polycaprolactone-Chitin Nanofibrous Mats as Potential Scaffolds for Tissue Engineering

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Min Sup Kim

2012-01-01

Full Text Available We describe here the preparation of poly(caprolactone (PCL-chitin nanofibrous mats by electrospinning from a blended solution of PCL and chitin dissolved in a cosolvent, 1,1,1,3,3,3-hexafluoro-2-propanol and trifluoroacetic acid. Scanning electron microscopy showed that the neutralized PCL-chitin nanofibrous mats were morphologically stable, with a mean diameter of 340.5±2.6 nm, compared with a diameter of 524.2±12.1 nm for PCL mats. The nanofibrous mats showed decreased water contact angles as the proportion of chitin increased. However, the tensile properties of nanofibrous mats containing 30~50% (wt/wt chitin were enhanced compared with PCL-only mats. In vitro studies showed that the viability of human dermal fibroblasts (HDFs for up to 7 days in culture was higher on composite (OD value: 1.42±0.09 than on PCL-only (0.51±0.14 nanofibrous mats, with viability correlated with chitin concentration. Together, our results suggest that PCL-chitin nanofibrous mats can be used as an implantable substrate to modulate HDF viability in tissue engineering.

Chitins and Chitosans as Immunoadjuvants and Non-Allergenic Drug Carriers

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Riccardo A. A. Muzzarelli

2010-02-01

Full Text Available Due to the fact that some individuals are allergic to crustaceans, the presumed relationship between allergy and the presence of chitin in crustaceans has been investigated. In vivo, chitin is part of complex structures with other organic and inorganic compounds: in arthropods chitin is covalently linked to proteins and tanned by quinones, in fungi it is covalently linked to glucans, while in bacteria chitin is diversely combined according to Gram(+/- classification. On the other hand, isolated, purified chitin is a plain polysaccharide that, at the nano level, presents itself as a highly associated structure, recently refined in terms of regularity, nature of bonds, crystallinity degree and unusual colloidal behavior. Chitins and modified chitins exert a number of beneficial actions, i.e., (i they stimulate macrophages by interacting with receptors on the macrophage surface that mediate the internalization of chitin particles to be degraded by lysozyme and N-acetyl-β-glucosaminidase (such as Nod-like, Toll-like, lectin, Dectin-1, leukotriene 134 and mannose receptors; (ii the macrophages produce cytokines and other compounds that confer non-specific host resistance against bacterial and viral infections, and anti-tumor activity; (iii chitin is a strong Th1 adjuvant that up-regulates Th1 immunity induced by heat-killed Mycobacterium bovis, while down- regulating Th2 immunity induced by mycobacterial protein; (iv direct intranasal application of chitin microparticles into the lung was also able to significantly down-regulate allergic response to Dermatophagoids pteronyssinus and Aspergillus fumigatus in a murine model of allergy; (v chitin microparticles had a beneficial effect in preventing and treating histopathologic changes in the airways of asthmatic mice; (vi authors support the fact that chitin depresses the development of adaptive type 2 allergic responses. Since the expression of chitinases, chitrotriosidase and chitinase-like proteins

Chitins and chitosans as immunoadjuvants and non-allergenic drug carriers.

Science.gov (United States)

Muzzarelli, Riccardo A A

2010-02-21

Due to the fact that some individuals are allergic to crustaceans, the presumed relationship between allergy and the presence of chitin in crustaceans has been investigated. In vivo, chitin is part of complex structures with other organic and inorganic compounds: in arthropods chitin is covalently linked to proteins and tanned by quinones, in fungi it is covalently linked to glucans, while in bacteria chitin is diversely combined according to Gram(+/-) classification. On the other hand, isolated, purified chitin is a plain polysaccharide that, at the nano level, presents itself as a highly associated structure, recently refined in terms of regularity, nature of bonds, crystallinity degree and unusual colloidal behavior. Chitins and modified chitins exert a number of beneficial actions, i.e., (i) they stimulate macrophages by interacting with receptors on the macrophage surface that mediate the internalization of chitin particles to be degraded by lysozyme and N-acetyl-beta-glucosaminidase (such as Nod-like, Toll-like, lectin, Dectin-1, leukotriene 134 and mannose receptors); (ii) the macrophages produce cytokines and other compounds that confer non-specific host resistance against bacterial and viral infections, and anti-tumor activity; (iii) chitin is a strong Th1 adjuvant that up-regulates Th1 immunity induced by heat-killed Mycobacterium bovis, while down- regulating Th2 immunity induced by mycobacterial protein; (iv) direct intranasal application of chitin microparticles into the lung was also able to significantly down-regulate allergic response to Dermatophagoids pteronyssinus and Aspergillus fumigatus in a murine model of allergy; (v) chitin microparticles had a beneficial effect in preventing and treating histopathologic changes in the airways of asthmatic mice; (vi) authors support the fact that chitin depresses the development of adaptive type 2 allergic responses. Since the expression of chitinases, chitrotriosidase and chitinase-like proteins is greatly

Modification of chitin as substrates for chitinase

African Journals Online (AJOL)

sunny t

2015-05-06

May 6, 2015 ... Enzymes are able to bind to their substrates specifically at the active site. The proximity and ... the presence of chitin as a carbon source (Chernin et al.,. 1998). ... Possible rearrangement of chitin structure ... and form larger granules. .... Medium for Enumeration of Actinomycetes in Water and Soil. Appl.

Elevated Chitin Content Reduces the Susceptibility of Candida Species to Caspofungin

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Walker, Louise A.; Gow, Neil A. R.

2013-01-01

The echinocandin antifungal drugs inhibit synthesis of the major fungal cell wall polysaccharide β(1,3)-glucan. Echinocandins have good efficacy against Candida albicans but reduced activity against other Candida species, in particular Candida parapsilosis and Candida guilliermondii. Treatment of Candida albicans with a sub-MIC level of caspofungin has been reported to cause a compensatory increase in chitin content and to select for sporadic echinocandin-resistant FKS1 point mutants that also have elevated cell wall chitin. Here we show that elevated chitin in response to caspofungin is a common response in various Candida species. Activation of chitin synthesis was observed in isolates of C. albicans, Candida tropicalis, C. parapsilosis, and C. guilliermondii and in some isolates of Candida krusei in response to caspofungin treatment. However, Candida glabrata isolates demonstrated no exposure-induced change in chitin content. Furthermore, isolates of C. albicans, C. krusei, C. parapsilosis, and C. guilliermondii which were stimulated to have higher chitin levels via activation of the calcineurin and protein kinase C (PKC) signaling pathways had reduced susceptibility to caspofungin. Isolates containing point mutations in the FKS1 gene generally had higher chitin levels and did not demonstrate a further compensatory increase in chitin content in response to caspofungin treatment. These results highlight the potential of increased chitin synthesis as a potential mechanism of tolerance to caspofungin for the major pathogenic Candida species. PMID:23089748

Dopamine-Mediated Sclerotization of Regenerated Chitin in Ionic Liquid

OpenAIRE

Oh, Dongyeop X.; Shin, Sara; Lim, Chanoong; Hwang, Dong Soo

2013-01-01

Chitin is a promising structural material for biomedical applications, due to its many advantageous properties and abundance in nature. However, its usage and development in the biomedical field have been stagnant, because of chitin’s poor mechanical properties in wet conditions and the difficulties in transforming it into an applicable form. To overcome these challenges, we created a novel biomimetic chitin composite. This regenerated chitin, prepared with ionic liquid, showed improved mecha...

Chitin Scaffolds in Tissue Engineering

Science.gov (United States)

Jayakumar, Rangasamy; Chennazhi, Krishna Prasad; Srinivasan, Sowmya; Nair, Shantikumar V.; Furuike, Tetsuya; Tamura, Hiroshi

2011-01-01

Tissue engineering/regeneration is based on the hypothesis that healthy stem/progenitor cells either recruited or delivered to an injured site, can eventually regenerate lost or damaged tissue. Most of the researchers working in tissue engineering and regenerative technology attempt to create tissue replacements by culturing cells onto synthetic porous three-dimensional polymeric scaffolds, which is currently regarded as an ideal approach to enhance functional tissue regeneration by creating and maintaining channels that facilitate progenitor cell migration, proliferation and differentiation. The requirements that must be satisfied by such scaffolds include providing a space with the proper size, shape and porosity for tissue development and permitting cells from the surrounding tissue to migrate into the matrix. Recently, chitin scaffolds have been widely used in tissue engineering due to their non-toxic, biodegradable and biocompatible nature. The advantage of chitin as a tissue engineering biomaterial lies in that it can be easily processed into gel and scaffold forms for a variety of biomedical applications. Moreover, chitin has been shown to enhance some biological activities such as immunological, antibacterial, drug delivery and have been shown to promote better healing at a faster rate and exhibit greater compatibility with humans. This review provides an overview of the current status of tissue engineering/regenerative medicine research using chitin scaffolds for bone, cartilage and wound healing applications. We also outline the key challenges in this field and the most likely directions for future development and we hope that this review will be helpful to the researchers working in the field of tissue engineering and regenerative medicine. PMID:21673928

Extraction and characterization of chitin and chitosan from ...

African Journals Online (AJOL)

Chitin has been extracted from two Tunisian crustacean species. The obtained chitin was transformed into the more useful soluble chitosan. These products were characterized by their biological activity as antimicrobial and antifungal properties. The tested bacterial strains were Escherichia coli American Type Cell Culture ...

Benzoylurea Chitin Synthesis Inhibitors.

Science.gov (United States)

Sun, Ranfeng; Liu, Chunjuan; Zhang, Hao; Wang, Qingmin

2015-08-12

Benzoylurea chitin synthesis inhibitors are widely used in integrated pest management (IPM) and insecticide resistance management (IRM) programs due to their low toxicity to mammals and predatory insects. In the past decades, a large number of benzoylurea derivatives have been synthesized, and 15 benzoylurea chitin synthesis inhibitors have been commercialized. This review focuses on the history of commercial benzolyphenylureas (BPUs), synthetic methods, structure-activity relationships (SAR), action mechanism research, environmental behaviors, and ecotoxicology. Furthermore, their disadvantages of high risk to aquatic invertebrates and crustaceans are pointed out. Finally, we propose that the para-substituents at anilide of benzoylphenylureas should be the functional groups, and bipartite model BPU analogues are discussed in an attempt to provide new insight for future development of BPUs.

Protective Effect of Chitin Urocanate Nanofibers against Ultraviolet Radiation

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Ikuko Ito

2015-12-01

Full Text Available Urocanic acid is a major ultraviolet (UV-absorbing chromophore. Chitins are highly crystalline structures that are found predominantly in crustacean shells. Alpha-chitin consists of microfibers that contain nanofibrils embedded in a protein matrix. Acid hydrolysis is a common method used to prepare chitin nanofibrils (NFs. We typically obtain NFs by hydrolyzing chitin with acetic acid. However, in the present study, we used urocanic acid to prepare urocanic acid chitin NFs (UNFs and examined its protective effect against UVB radiation. Hos: HR-1 mice coated with UNFs were UVB irradiated (302 nm, 150 mJ/cm2, and these mice showed markedly lower UVB radiation-induced cutaneous erythema than the control. Additionally, sunburn cells were rarely detected in the epidermis of UNFs-coated mice after UVB irradiation. Although the difference was not as significant as UNFs, the number of sunburn cells in mice treated with acetic acid chitin nanofibrils (ANFs tended to be lower than in control mice. These results demonstrate that ANFs have a protective effect against UVB and suggest that the anti-inflammatory and antioxidant effects of NFs influence the protective effect of ANFs against UVB radiation. The combination of NFs with other substances that possess UV-protective effects, such as urocanic acid, may provide an enhanced protective effect against UVB radiation.

Isolation and characterization of chitin and chitosan from marine origin.

Science.gov (United States)

Nwe, Nitar; Furuike, Tetsuya; Tamura, Hiroshi

2014-01-01

Nowadays, chitin and chitosan are produced from the shells of crabs and shrimps, and bone plate of squid in laboratory to industrial scale. Production of chitosan involved deproteinization, demineralization, and deacetylation. The characteristics of chitin and chitosan mainly depend on production processes and conditions. The characteristics of these biopolymers such as appearance of polymer, turbidity of polymer solution, degree of deacetylation, and molecular weight are of major importance on applications of these polymers. This chapter addresses the production processes and conditions to produce chitin, chitosan, and chito-oligosaccharide and methods for characterization of chitin, chitosan, and chito-oligosaccharide. © 2014 Elsevier Inc. All rights reserved.

Fabrication of α-chitin whisker-reinforced poly(vinyl alcohol) nanocomposite nanofibres by electrospinning

International Nuclear Information System (INIS)

Junkasem, Jirawut; Rujiravanit, Ratana; Supaphol, Pitt

2006-01-01

The present contribution reports, for the first time, the successful fabrication of α-chitin whisker-reinforced poly(vinyl alcohol) (PVA) nanocomposite nanofibres by electrospinning. The α-chitin whiskers were prepared from α-chitin flakes from shrimp shells by acid hydrolysis. The as-prepared chitin whiskers exhibited lengths in the range 231-969 nm and widths in the range 12-65 nm, with the average length and width being about 549 and 31 nm, respectively. Successful incorporation of the chitin whiskers within the as-spun PVA/chitin whisker nanocomposite nanofibres was verified by infrared spectroscopic and thermogravimetric methods. The incorporation of chitin whiskers within the as-spun nanocomposite fibre mats increased the Young's modulus by about 4-8 times over that of the neat as-spun PVA fibre mat

Chitin based polyurethanes using hydroxyl terminated polybutadiene, part III: surface characteristics.

Science.gov (United States)

Zia, Khalid Mahmood; Zuber, Mohammad; Saif, Muhammad Jawwad; Jawaid, Mohammad; Mahmood, Kashif; Shahid, Muhammad; Anjum, Muhammad Naveed; Ahmad, Mirza Nadeem

2013-11-01

Hydroxy terminated polybutadiene (HTPB)-chitin based polyurethanes (PUs) with controlled hydrophobicity were synthesized using HTPB and toluene diisocyanate (TDI). The prepolymer was extended with different mass ratios of chitin and 1,4-butane diol (BDO). The effect of chitin contents in chain extender (CE) proportions on surface properties was studied and investigated. Incorporation of chitin contents into the final PU showed decrease in contact angle value of water drop, water absorption (%) and swelling behavior. The antibacterial activity of the prepared samples was affected by varying the chitin contents in the chemical composition of the final PU. The results demonstrated that the use of prepared material can be suggested as non-absorbable suture. Copyright © 2013 Elsevier B.V. All rights reserved.

SEM characterization of anatomical variation in chitin organization in insect and arthropod cuticles.

Science.gov (United States)

Chandran, Rakkiyappan; Williams, Lee; Hung, Albert; Nowlin, Kyle; LaJeunesse, Dennis

2016-03-01

The cuticles of insects and arthropods have some of the most diverse material properties observed in nature, so much so that it is difficult to imagine that all cutciles are primarily composed of the same two materials: a fibrous chitin network and a matrix composed of cuticle proteins. Various factors contribute to the mechanical and optical properties of an insect or arthropod cuticle including the thickness and composition. In this paper, we also identified another factor that may contribute to the optical, surface, and mechanical properties of a cuticle, i.e. the organization of chitin nanofibers and chitin fiber bundles. Self-assembled chitin nanofibers serve as the foundation for all higher order chitin structures in the cuticles of insects and other arthropods via interactions with structural cuticle proteins. Using a technique that enables the characterization of chitin organization in the cuticle of intact insects and arthropod exoskeletons, we demonstrate a structure/function correlation of chitin organization with larger scale anatomical structures. The chitin scaffolds in cuticles display an extraordinarily diverse set of morphologies that may reflect specific mechanical or physical properties. After removal of the proteinaceous and mineral matrix of a cuticle, we observe using SEM diverse nanoscale and micro scale organization of in-situ chitin in the wing, head, eye, leg, and dorsal and ventral thoracic regions of the periodical cicada Magicicada septendecim and in other insects and arthropods. The organization of chitin also appears to have a significant role in the organization of nanoscale surface structures. While microscale bristles and hairs have long been known to be chitin based materials formed as cellular extensions, we have found a nanostructured layer of chitin in the cuticle of the wing of the dog day annual cicada Tibicen tibicens, which may be the scaffold for the nanocone arrays found on the wing. We also use this process to examine

Characteristics of tau oligomers

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Yan eRen

2013-07-01

Full Text Available In Alzheimer disease (AD and other tauopathies, microtubule-associated protein tau becomes hyperphosphorylated, undergoes conformational changes, aggregates, eventually becoming neurofibrillary tangles (NFTs. As accumulating evidence suggests that NFTs themselves may not be toxic, attention is now turning toward the role of intermediate tau oligomers in AD pathophysiology. Sarkosyl extraction is a standard protocol for investigating insoluble tau aggregates in brains. There is a growing consensus that sarkosyl-insoluble tau correlates with the pathological features of tauopathy. While sarkosyl-insoluble tau from tauopathy brains has been well characterized as a pool of filamentous tau, other dimers, multimers, and granules of tau are much less well understood. There are protocols for identifying these tau oligomers. In this mini review, we discuss the characteristics of tau oligomers isolated via different methods and materials.

Comparison of Extraction Methods of Chitin from Ganoderma lucidum Mushroom Obtained in Submerged Culture

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Sandra Patricia Ospina Álvarez

2014-01-01

Full Text Available The chitin was isolated from the Ganoderma lucidum submerged cultures mycelium as potential source of chitin under biotechnological processes. The extraction of chitin was carried out through 5 different assays which involved mainly three phases: pulverization of the mushroom, deproteinization of the mycelia with NaOH solution, and a process of decolorization with potassium permanganate and oxalic acid. The chitin contents extracted from 9-day mycelia were 413, 339, 87, 78, and 144 mg/g−1 (milligrams of chitin/grams of dry biomass for A1, A2, A3, A4, and A5, respectively. Obtained chitin was characterized by X-Ray Diffraction (XRD, by Fourier transform infrared spectroscopy (FTIR, and by thermal analysis (TGA. The results showed that Ganoderma lucidum chitin has similar characteristic of chitin from different fonts. The advantage of the biotechnological processes and the fact that Ganoderma lucidum fungus may be used as a potential raw material for chitin production were demonstrated.

Comparison of Extraction Methods of Chitin from Ganoderma lucidum Mushroom Obtained in Submerged Culture

Science.gov (United States)

Ospina Álvarez, Sandra Patricia; Ramírez Cadavid, David Alexander; Ossa Orozco, Claudia Patricia; Zapata Ocampo, Paola; Atehortúa, Lucía

2014-01-01

The chitin was isolated from the Ganoderma lucidum submerged cultures mycelium as potential source of chitin under biotechnological processes. The extraction of chitin was carried out through 5 different assays which involved mainly three phases: pulverization of the mushroom, deproteinization of the mycelia with NaOH solution, and a process of decolorization with potassium permanganate and oxalic acid. The chitin contents extracted from 9-day mycelia were 413, 339, 87, 78, and 144 mg/g−1 (milligrams of chitin/grams of dry biomass) for A1, A2, A3, A4, and A5, respectively. Obtained chitin was characterized by X-Ray Diffraction (XRD), by Fourier transform infrared spectroscopy (FTIR), and by thermal analysis (TGA). The results showed that Ganoderma lucidum chitin has similar characteristic of chitin from different fonts. The advantage of the biotechnological processes and the fact that Ganoderma lucidum fungus may be used as a potential raw material for chitin production were demonstrated. PMID:24551839

Chitin Adsorbents for Toxic Metals: A Review

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Ioannis Anastopoulos

2017-01-01

Full Text Available Wastewater treatment is still a critical issue all over the world. Among examined methods for the decontamination of wastewaters, adsorption is a promising, cheap, environmentally friendly and efficient procedure. There are various types of adsorbents that have been used to remove different pollutants such as agricultural waste, compost, nanomaterials, algae, etc., Chitin (poly-β-(1,4-N-acetyl-d-glucosamine is the second most abundant natural biopolymer and it has attracted scientific attention as an inexpensive adsorbent for toxic metals. This review article provides information about the use of chitin as an adsorbent. A list of chitin adsorbents with maximum adsorption capacity and the best isotherm and kinetic fitting models are provided. Moreover, thermodynamic studies, regeneration studies, the mechanism of adsorption and the experimental conditions are also discussed in depth.

Determination of chitin in Claviceps

Energy Technology Data Exchange (ETDEWEB)

Schmauder, H P; Groeger, D [Akademie der Wissenschaften der DDR, Halle/Saale. Inst. fuer Biochemie der Pflanzen

1978-01-01

Preparations rich in chitin obtained from the cell walls of ergot fungi were studied by X-ray diffraction and IR-techniques. During the course of fermentation, the yield of chitin was determined using a modified procedure according to Ride and Drysdale (1972). A saprophytic ergotoxine-producing Claviceps purpurea strain (Pepty 695) was found to contain 7-9 ..mu..g glucosamine/mg dry weight of the mycelium in contrast to 3-5 ..mu..g glucosamine/mg dry weight of a non-alkaloid producing C. purpurea strain (PUR 212). There was no remarkable fluctuation of the glucosamine content in strain Pepty 695 during the course of fermentation.

Characterization of FIBCD1 as an acetyl group-binding receptor that binds chitin

DEFF Research Database (Denmark)

Schlosser, Anders; Thomsen, Theresa; Moeller, Jesper B

2009-01-01

Chitin is a highly acetylated compound and the second most abundant biopolymer in the world next to cellulose. Vertebrates are exposed to chitin both through food ingestion and when infected with parasites, and fungi and chitin modulate the immune response in different directions. We have...... fragments. FIBCD1 may play an important role in controlling the exposure of intestine to chitin and chitin fragments, which is of great relevance for the immune defense against parasites and fungi and for immune response modulation....

Chitin enhances biocontrol of Rhodotorula mucilaginosa to postharvest decay of peaches.

Science.gov (United States)

Zhang, Hongyin; Yang, Qiya; Ge, Lingling; Zhang, Guochao; Zhang, Xiaoli; Zhang, Xiaoyun

2016-07-01

Biological control using microbial antagonists is a promising alternative approach to synthetic fungicides. However, effective biological control requires enhancing the consistency and efficacy of the antagonists used to control postharvest diseases. This study investigated the effect of chitin on the biocontrol efficacy of Rhodotorula mucilaginosa against blue mold and Rhizopus decay of peaches and on the protein expression profiles of R. mucilaginosa. The antagonistic activity of R. mucilaginosa harvested from the nutrient yeast dextrose broth (NYDB) with 0.5% chitin added was significantly improved compared with culture in NYDB without chitin. The R. mucilaginosa population cultured in chitin-supplement NYDB and nutrient yeast chitin borth (NYCB) harvested from peach wounds was more than that of R. mucilaginosa cultured in NYDB without chitin throughout the storage period except at 1 d. The protein expression profiles findings revealed that there were several differentially expressed proteins of R. mucilaginosa in the 0.5% chitin-supplemented NYDB and NYCB compared with that of R. mucilaginosa in NYDB. Most of these were cellular proteomes relating to the primary metabolic reactions such as glycoside hydrolases, phosphoribosyl pyrophosphate, and NADH dehydrogenases. Some proteins were also related to signal transmission and stress response. Copyright © 2016 Elsevier B.V. All rights reserved.

A comparative study of sorption of chromium (III) onto chitin and chitosan

Science.gov (United States)

Singh, Pooja; Nagendran, R.

2016-06-01

Heavy metals have always been the most hazardous components in the wastewater of industries like electroplating, automobiles, mining facilities and fertilizer manufacturers. Treatment of heavy metal laden wastewater requires expensive operational and maintenance systems. Food processing industries create a huge amount of shell waste which is sold to poultry farms in powdered form but the quantity thus used is still not comparable to the left over waste. The shell contains chitin which acts as an adsorbent for the heavy metals and can be used to treat heavy metal wastewater. The paper presents a study on the use of chitin and its processed product, chitosan, to remove chromium. Shake flask experiment was conducted to compare the adsorptive capacity of chitin and chitosan for chromium removal from simulated solution and isotherm studies were carried out. The studies showed that the chitosan was a better adsorbent than chitin. Both chitin and chitosan gave best adsorption results at pH 3. Chitin exhibited maximum chromium removal of 49.98 % in 20 min, whereas chitosan showed 50 % removal efficiency at a contact time of 20 min showing higher adsorptive capacity for chromium than chitin. The Langmiur and Freundlich isotherm studies showed very good adsorption capacity and monolayer interaction according to the regression coefficient 0.973 for chitosan and 0.915 for chitin. The regression coefficient for Freundlich isotherm was 0.894 and 0.831 for chitosan and chitin, respectively.

Chitin and chitosan as functional biopolymers for industrial applications

NARCIS (Netherlands)

kardas, I.; Struzczyk, M.H.; Kucharska, M.; Broek, van den L.A.M.; Dam, van J.E.G.

2012-01-01

Chitin research and development seems to be under intensive progress during the last years. Attractive properties of chitin and its derivative—chitosan, for example, biological behavior, and development of their applications caused increased interest of scientists and companies. More and more

Electron beam curing of acrylic oligomers

International Nuclear Information System (INIS)

Seto, J.; Arakawa, S.; Ishimoto, C.; Miyashita, M.; Nagai, T.; Noguchi, T.; Shibata, A.

1984-01-01

The electron-beam curing process of acrylic oligomers, with and without γ-Fe 2 O 3 pigment filler and blended linear polymer, was investigated in terms of molecular structure and reaction mechanism. The polymerized fraction of trimethylolpropane-triacrylate (TMPTA) oligomers increases with increasing total dose, and is independent of the dose rate. Since the reaction rate is linearly dependent on the dose rate, the reaction mechanism involves monomolecular termination. The reaction rate does not depend on the number of functional groups of the oligomer at low doses, but above 0.3 Mrad the rate is slower for oligomers of higher functionality. A gel is formed more readily upon curing of a polyfunctional than a monofunctional oligomer, especially at high conversion to polymer; the resulting loss of flexibility of the polymer chains slows the reaction. Decrease of the molecular weight per functional group results in lower conversion; this is also due to the loss of chain flexibility, which is indicated as well by a higher glass-transition temperature. Modification of the acrylate oligomers with urethane results in more effective cross-linking reactions because of the more rigid molecular chains. Addition of γ-Fe 2 O 3 pigment reduces the reaction rate very little, but has the effect of providing added structural integrity, as indicated by the decrease of solvent-extractable material and the improvement of anti-abrasion properties. However, the flexibility of the coating and its adhesion to a PET base film are diminished. To increase the flexibility, linear polyvinylchloride and/or polyurethane were added to the acrylic oligomers. Final conversion to polymer was nearly 100 percent, and a higher elastic modulus and better antiabrasion properties were realized

Salmonella biofilm formation on Aspergillus niger involves cellulose--chitin interactions.

Directory of Open Access Journals (Sweden)

Maria T Brandl

Full Text Available Salmonella cycles between host and nonhost environments, where it can become an active member of complex microbial communities. The role of fungi in the environmental adaptation of enteric pathogens remains relatively unexplored. We have discovered that S. enterica Typhimurium rapidly attaches to and forms biofilms on the hyphae of the common fungus, Aspergillus niger. Several Salmonella enterica serovars displayed a similar interaction, whereas other bacterial species were unable to bind to the fungus. Bacterial attachment to chitin, a major constituent of fungal cell walls, mirrored this specificity. Pre-incubation of S. Typhimurium with N-acetylglucosamine, the monomeric component of chitin, reduced binding to chitin beads by as much as 727-fold and inhibited attachment to A. niger hyphae considerably. A cellulose-deficient mutant of S. Typhimurium failed to attach to chitin beads and to the fungus. Complementation of this mutant with the cellulose operon restored binding to chitin beads to 79% of that of the parental strain and allowed for attachment and biofilm formation on A. niger, indicating that cellulose is involved in bacterial attachment to the fungus via the chitin component of its cell wall. In contrast to cellulose, S. Typhimurium curli fimbriae were not required for attachment and biofilm development on the hyphae but were critical for its stability. Our results suggest that cellulose-chitin interactions are required for the production of mixed Salmonella-A. niger biofilms, and support the hypothesis that encounters with chitinaceous alternate hosts may contribute to the ecological success of human pathogens.

Effect of gamma radiation on chitin-nanosilver membranes

International Nuclear Information System (INIS)

Singh, Rita; Singh, Durgeshwer

2014-01-01

Antimicrobial wound dressings are indispensable for the effective healing of skin wounds such as burns and ulcers. Various synthetic and natural polymers with good biocompatibility have been used to develop wound dressings. Chitin possesses excellent properties that are advantageous for wound dressing namely biocompatibility, biodegradability and haemostatic activity. Chitin-nanosilver membranes were developed for use as an antimicrobial dressing for wound care. For clinical applications, the wound dressing should be assuredly free of microbial contamination. Gamma irradiation has well appreciated technological advantages and is the most suitable method for the sterilization of biomedical materials. The present study was carried out to evaluate the effect of gamma radiation on the chemical and functional characteristics of the chitin-nanosilver membranes

Structure and Properties of Chitin Whisker Reinforced Papers for Food Packaging Application

Directory of Open Access Journals (Sweden)

Zhihan Li

2015-04-01

Full Text Available In recent years, concerns about environmental waste caused by petroleum-derived chemicals as well as the consumer's demand for high quality food products, have prompted people to pay more attention to developing biodegradable food packaging materials using natural resources such as cellulose fibers and chitin derivatives. In this study, chitin whiskers have been successfully generated by hydrolyzing the α-chitin sample. Then the synthesized nano-sized chitin whiskers were used at ratios from 0.1% to 2% (wt% for improving strength properties of paper sheets by the dip-coating method. Transmission electron microscopy (TEM and field emission scanning electron microscopy (FE-SEM were used to investigate the morphology of chitin whiskers and cellulose fiber compounds. The results showed that coating with chitin whiskers brought about an increase in tear strength, burst strength, and wet and dry tensile strength, with a decrease in Zeta-potential value.

Customizing Properties of β-Chitin in Squid Pen (Gladius by Chemical Treatments

Directory of Open Access Journals (Sweden)

Alessandro Ianiro

2014-12-01

Full Text Available The squid pen (gladius from the Loligo vulgaris was used for preparation of β-chitin materials characterized by different chemical, micro- and nano-structural properties that preserved, almost completely the macrostructural and the mechanical ones. The β-chitin materials obtained by alkaline treatment showed porosity, wettability and swelling that are a function of the duration of the treatment. Microscopic, spectroscopic and synchrotron X-ray diffraction techniques showed that the chemical environment of the N-acetyl groups of the β-chitin chains changes after the thermal alkaline treatment. As a consequence, the crystalline packing of the β-chitin is modified, due to the intercalation of water molecules between β-chitin sheets. Potential applications of these β-chitin materials range from the nanotechnology to the regenerative medicine. The use of gladii, which are waste products of the fishing industry, has also important environmental implications.

Thermal decomposition of natural polysaccharides: Chitin and chitosan

Directory of Open Access Journals (Sweden)

Kuchina Yu.A.

2015-03-01

Full Text Available The results of the thermal analysis of shrimp’s chitin and chitosan have been presented (samples of polysaccharide differed by the deacetylation degree have been studied. The thermal analysis has been carried out by differential thermogravimetry and differential scanning calorimetry. Activation energy of process of chitin and chitosan thermal destruction has been calculated

Chitin and Chitosan as Direct Compression Excipients in Pharmaceutical Applications

Science.gov (United States)

Badwan, Adnan A.; Rashid, Iyad; Al Omari, Mahmoud M.H.; Darras, Fouad H.

2015-01-01

Despite the numerous uses of chitin and chitosan as new functional materials of high potential in various fields, they are still behind several directly compressible excipients already dominating pharmaceutical applications. There are, however, new attempts to exploit chitin and chitosan in co-processing techniques that provide a product with potential to act as a direct compression (DC) excipient. This review outlines the compression properties of chitin and chitosan in the context of DC pharmaceutical applications. PMID:25810109

Chitin and Chitosan as Direct Compression Excipients in Pharmaceutical Applications

Directory of Open Access Journals (Sweden)

Adnan A. Badwan

2015-03-01

Full Text Available Despite the numerous uses of chitin and chitosan as new functional materials of high potential in various fields, they are still behind several directly compressible excipients already dominating pharmaceutical applications. There are, however, new attempts to exploit chitin and chitosan in co-processing techniques that provide a product with potential to act as a direct compression (DC excipient. This review outlines the compression properties of chitin and chitosan in the context of DC pharmaceutical applications.

Physicochemical and antifungal properties of bio-nanocomposite film based on gelatin-chitin nanoparticles.

Science.gov (United States)

Sahraee, Samar; Milani, Jafar M; Ghanbarzadeh, Babak; Hamishehkar, Hamed

2017-04-01

The gelatin-based nanocomposite films containing chitin nanoparticles (N-chitin) with concentrations of 0, 3, 5 and 10% were prepared and their physical, thermal and anti-microbial properties were investigated. Scanning electron microscopy (SEM) micrographs showed that N-chitin size distribution was around 60-70nm which dispersed appropriately at low concentration in gelatin matrix. The results showed that incorporation of N-chitin significantly influenced apparent color and transparency of the gelatin films. The reduced water vapor permeability (WVP) and solubility and higher surface hydrophobicity of the nanocomposite films were obtained by enhancing N-chitin concentration in film formulation. The use of N-chitin up to 5% concentration in the gelatin based nanocomposite film led to improved mechanical properties. Also, the results of differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) confirmed improved stability of nanocomposite films against melting and degradation at high temperatures in comparison to neat gelatin film. The well compatibility of chitin nanoparticles with gelatin polymer was concluded from Fourier transform infrared (FTIR) spectra and X-ray diffraction (XRD) plots. Finally, the gelatin based nanocomposite films had anti-fungal properties against Aspergillus niger in the contact surface zone. Increasing the concentration of N-chitin up to 5% enlarged inhibition zone diameter, but the nanocomposite film containing 10% N-chitin showed smaller inhibition zone. Copyright © 2016 Elsevier B.V. All rights reserved.

Response of the chitinolytic microbial community to chitin amendments of dune soils

NARCIS (Netherlands)

De Boer, W.; Gerards, S.; Klein Gunnewiek, P.J.A.; Modderman, R.

1999-01-01

The dynamics of culturable chitin-degrading microorganisms were studied during a 16-week incubation of chitin-amended coastal dune soils that differed in acidity. Soil samples were incubated at normal (5% Why) and high (15% w/w) moisture levels. More than half of the added chitin was decomposed

Chitin stimulates production of the antibiotic andrimid in a Vibrio corallilyticus strain

DEFF Research Database (Denmark)

Wietz, Matthias; Månsson, Maria; Gram, Lone

2011-01-01

per cell was twofold higher. In cultures with Artemia as live chitin model system, S2052 reached up to 108 cells ml-1, produced andrimid and showed attachment to the exoskeleton and chitinous exuviae. The metabolic focus on andrimid production with chitin indicates that the antibiotic could serve...

Synthesis and characterization of thermally stable oligomer-metal ...

African Journals Online (AJOL)

The thermal stabilities of the oligomer-metal complexes were compared by thermogravimetric (TG) and differential thermal (DTA) analyses. According to TG, oligomer-metal complexes were stable against to temperature and thermooxidative decomposition. The weight losses of oligomer-metal complexes were found to be 5 ...

STRUCTURAL FEATURES OF PLANT CHITINASES AND CHITIN-BINDING PROTEINS

NARCIS (Netherlands)

BEINTEMA, JJ

1994-01-01

Structural features of plant chitinases and chitin-binding proteins are discussed. Many of these proteins consist of multiple domains,of which the chitin-binding hevein domain is a predominant one. X-ray and NMR structures of representatives of the major classes of these proteins are available now,

Improved derivatization protocol for simultaneous determination of ...

African Journals Online (AJOL)

The derivatization reaction was completed in 30 min at 50°C using hexane as solvent. ... higher temperatures and shorter derivatization time, or lower temperatures ... The following were added into a pyrex test tube: 80 µℓ of organic mixture ...

Fibril specific, conformation dependent antibodies recognize a generic epitope common to amyloid fibrils and fibrillar oligomers that is absent in prefibrillar oligomers

Directory of Open Access Journals (Sweden)

Rasool Suhail

2007-09-01

Full Text Available Abstract Background Amyloid-related degenerative diseases are associated with the accumulation of misfolded proteins as amyloid fibrils in tissue. In Alzheimer disease (AD, amyloid accumulates in several distinct types of insoluble plaque deposits, intracellular Aβ and as soluble oligomers and the relationships between these deposits and their pathological significance remains unclear. Conformation dependent antibodies have been reported that specifically recognize distinct assembly states of amyloids, including prefibrillar oligomers and fibrils. Results We immunized rabbits with a morphologically homogeneous population of Aβ42 fibrils. The resulting immune serum (OC specifically recognizes fibrils, but not random coil monomer or prefibrillar oligomers, indicating fibrils display a distinct conformation dependent epitope that is absent in prefibrillar oligomers. The fibril epitope is also displayed by fibrils of other types of amyloids, indicating that the epitope is a generic feature of the polypeptide backbone. The fibril specific antibody also recognizes 100,000 × G soluble fibrillar oligomers ranging in size from dimer to greater than 250 kDa on western blots. The fibrillar oligomers recognized by OC are immunologically distinct from prefibrillar oligomers recognized by A11, even though their sizes overlap broadly, indicating that size is not a reliable indicator of oligomer conformation. The immune response to prefibrillar oligomers and fibrils is not sequence specific and antisera of the same specificity are produced in response to immunization with islet amyloid polypeptide prefibrillar oligomer mimics and fibrils. The fibril specific antibodies stain all types of amyloid deposits in human AD brain. Diffuse amyloid deposits stain intensely with anti-fibril antibody although they are thioflavin S negative, suggesting that they are indeed fibrillar in conformation. OC also stains islet amyloid deposits in transgenic mouse models of type

Simultaneous extraction of chitin and astaxanthin from waste of ...

African Journals Online (AJOL)

This work investigates simple methods for simultaneous extraction of astaxanthin and chitin from industrial waste of the South African West Coast rock lobster Jasus lalandii. Removal of proteins from waste is the critical step to yield intact chitin and astaxanthin. Because common chemical methods destroy astaxanthin and ...

Facile nanofibrillation of chitin derivatives by gas bubbling and ultrasonic treatments in water.

Science.gov (United States)

Tanaka, Kohei; Yamamoto, Kazuya; Kadokawa, Jun-ichi

2014-10-29

In this paper, we report that nanofiber network structures were constructed from chitin derivatives by gas bubbling and ultrasonic treatments in water. When chitin was first subjected to N2 gas bubbling with ultrasonication in water, the SEM images of the product showed nanofiber network morphology. However, nanofiber network was not re-constructed by the same N2 gas bubbling and ultrasonic treatments after agglomeration. We then have paid attention to an amidine group to provide the agglomeration-nanofibrillation behavior of chitin derivatives. An amidinated chitin was synthesized by the reaction of the amino groups in a partially deacetylated chitin with N,N-dimethylacetamide dimethyl acetal, which was subjected to CO2 gas bubbling and ultrasonic treatments in water to convert into an amidinium chitin by protonation. The SEM images of the product clearly showed nanofiber network morphology. We further examined re-nanofibrillation of the agglomerated material, which was obtained by mixing the nanofibrillated amidinium chitin with water, followed by drying under reduced pressure. Consequently, the material was re-nanofibrillated by N2 gas bubbling with ultrasonication in water owing to electrostatic repulsion between the amidinium groups. Furthermore, deprotonation of the amidinium chitin and re-protonation of the resulting amidinated chitin were conducted by alkaline treatment and CO2 gas bubbling-ultrasonic treatments, respectively. The material showed the agglomeration-nanofibrillation behavior during the processes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Pyrolysis of chitin biomass

DEFF Research Database (Denmark)

Qiao, Yan; Chen, Shuai; Liu, Ying

2015-01-01

The thermal degradation of chitin biomass with various molecular structures was investigated by thermogravimetric analysis (TG), and the gaseous products were analyzed by connected mass spectroscopy (MS). The chemical structure and morphology of char residues collected at 750°C using the model...

Surface modification of chitin and chitosan with poly(3-hexylthiophene) via oxidative polymerization

Science.gov (United States)

Hai, Thien An Phung; Sugimoto, Ryuichi

2018-03-01

In the present work, the modification of biomaterials such as chitin and chitosan were successfully prepared by directly grafting poly(3-hexylthiophene) (P3HT) to their surfaces using simple oxidative polymerization with FeCl3. The thermal stability and crystallinity of grafted chitin and chitosan changed upon grafting with P3HT. The build-up of π-π* structure from the P3HT on the surface of chitin and chitosan resulted in the appearance of UV-vis absorption and fluorescence emission peaks in the range from 500 to 600 nm. Introducing P3HT to the surface of chitin and chitosan improved significantly the electrical property of chitin and chitosan with the increase in conductivity from 10-9 to 10-7 S/cm. Furthermore, the usual behavior of hydrophilic surface of chitin and chitosan that turned to hydrophobic with water contact angle of 97.7° and 107.0°, respectively in the presence of P3HT. The mechanism for graft reaction of P3HT to chitin and chitosan was also proposed and discussed.

Surface modification of chitin using ultrasound-assisted and supercritical CO{sub 2} technologies for cobalt adsorption

Energy Technology Data Exchange (ETDEWEB)

Dotto, Guilherme L., E-mail: guilherme_dotto@yahoo.com.br; Cunha, Jeanine M., E-mail: jeaninecunha@gmail.com; Calgaro, Camila O., E-mail: camila.itepjr@gmail.com; Tanabe, Eduardo H., E-mail: edutanabe@yahoo.com.br; Bertuol, Daniel A., E-mail: dbertuol@gmail.com

2015-09-15

Highlights: • Chitin was modified by ultrasound-assisted (UA) and supercritical (SCO{sub 2}) technologies. • Chitin, UA-chitin and SCO{sub 2}-chitin were used as adsorbents for Co(II). • UA and SCO{sub 2} treatments provided increase of 20 and 3 times in chitin surface area. • The Co(II) adsorption capacity increased until 67.8%, using UA-chitin. - Abstract: Ultrasound-assisted (UA) and supercritical CO{sub 2} technologies (SCO{sub 2}) were used to modify the chitin surface and, improve its adsorption characteristics regarding to cobalt. Chitin, before and after the treatments, was characterized by N{sub 2} adsorption isotherms (BET), infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and scanning electron microscopy (SEM). Unmodified and surface modified chitins were used as adsorbents to remove cobalt from aqueous solutions. The adsorption study was performed by equilibrium isotherms and kinetic curves. The chitin particle characteristics, such as, surface area, pore volume and porosity were improved by the UA and SCO{sub 2} treatments. The crystallinity index decreased after the UA and SCO{sub 2} treatments, and also, intense surface modifications were observed. Langmuir and Freundlich models were adequate to represent the adsorption equilibrium. The maximum adsorption capacities were 50.03, 83.94 and 63.08 mg g{sup −1} for unmodified chitin, UA surface modified chitin and SCO{sub 2} surface modified chitin. The adsorption kinetic curves were well represented by the pseudo-second order model. UA and SCO{sub 2} technologies are alternatives to modify the chitin surface and improve its adsorption characteristics.

Interaction of chitin/chitosan with salivary and other epithelial cells-An overview.

Science.gov (United States)

Patil, Sharvari Vijaykumar; Nanduri, Lalitha S Y

2017-11-01

Chitin and its deacetylated form, chitosan, have been widely used for tissue engineering of both epithelial and mesenchymal tissues. Epithelial cells characterised by their sheet-like tight cellular arrangement and polarised nature, constitute a major component in various organs and play a variety of roles including protection, secretion and maintenance of tissue homeostasis. Regeneration of damaged epithelial tissues has been studied using biomaterials such as chitin, chitosan, hyaluronan, gelatin and alginate. Chitin and chitosan are known to promote proliferation of various embryonic and adult epithelial cells. However it is not clearly understood how this activity is achieved or what are the mechanisms involved in the chitin/chitosan driven proliferation of epithelial cells. Mechanistic understanding of influence of chitin/chitosan on epithelial cells will guide us to develop more targeted regenerative scaffold/hydrogel systems. Therefore, current review attempts to elicit a mechanistic insight into how chitin and chitosan interact with salivary, mammary, skin, nasal, lung, intestinal and bladder epithelial cells. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of Coprocessed Chitin-Calcium Carbonate as Multifunctional Tablet Excipient for Direct Compression.

Science.gov (United States)

Chaheen, Mohammad; Sanchez-Ballester, Noelia M; Bataille, Bernard; Yassine, Ahmad; Belamie, Emmanuel; Sharkawi, Tahmer

2018-04-24

Owing to the increasing interest in multifunctional excipients for tableting, coprocessing of individual excipients is regularly used to produce excipients of improved multifunctionality superior to individual excipients or their physical mix. The use of chitin as an excipient in tablet formulation is limited because of certain drawbacks such as poor flowability and low true density. The objective of this work is to improve these properties through coprocessing of chitin with calcium carbonate (CaCO 3 ) by precipitating CaCO 3 on chitin particles using different methods. In addition, optimization of the coprocessed chitin was carried out to improve the excipient's properties. Physicochemical (CaCO 3 content, true density, X-ray diffraction, infrared spectroscopy, and scanning electron microscopy) and functional testing (swelling force, flowability, tensile strength, deformation mechanism, and disintegration time) were used to characterize the coprocessed product. Results showed that the calcite CaCO 3 polymorph is precipitated on the chitin surface and that it interacts with chitin at carbonyl- and amide-group level. In addition, the coprocessed excipient has an improved true density and powder flowability, with CaCO 3 forming single layer on the chitin particles surface. Tableting studies showed that the coprocessed powder exhibited an intermediate deformation behavior between CaCO 3 (most brittle) and chitin (most plastic). Tablets showed acceptable tensile strength and rapid disintegration (2-4 s). These results show the potential use of coprocessed chitin-CaCO 3 as a multifunctional excipient for fast disintegration of tablets produced by direct compression. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Determination of chitin content in fungal cell wall: an alternative flow cytometric method.

Science.gov (United States)

Costa-de-Oliveira, Sofia; Silva, Ana P; Miranda, Isabel M; Salvador, Alexandre; Azevedo, Maria M; Munro, Carol A; Rodrigues, Acácio G; Pina-Vaz, Cidália

2013-03-01

The conventional methods used to evaluate chitin content in fungi, such as biochemical assessment of glucosamine release after acid hydrolysis or epifluorescence microscopy, are low throughput, laborious, time-consuming, and cannot evaluate a large number of cells. We developed a flow cytometric assay, efficient, and fast, based on Calcofluor White staining to measure chitin content in yeast cells. A staining index was defined, its value was directly related to chitin amount and taking into consideration the different levels of autofluorecence. Twenty-two Candida spp. and four Cryptococcus neoformans clinical isolates with distinct susceptibility profiles to caspofungin were evaluated. Candida albicans clinical isolate SC5314, and isogenic strains with deletions in chitin synthase 3 (chs3Δ/chs3Δ) and genes encoding predicted GlycosylPhosphatidylInositol (GPI)-anchored proteins (pga31Δ/Δ and pga62Δ/Δ), were used as controls. As expected, the wild-type strain displayed a significant higher chitin content (P relationship between chitin content and antifungal drug susceptibility phenotype was found, an association was established between the paradoxical growth effect in the presence of high caspofungin concentrations and the chitin content. This novel flow cytometry protocol revealed to be a simple and reliable assay to estimate cell wall chitin content of fungi. Copyright © 2013 International Society for Advancement of Cytometry.

Tandem MS Analysis of Selenamide-Derivatized Peptide Ions

Science.gov (United States)

Zhang, Yun; Zhang, Hao; Cui, Weidong; Chen, Hao

2011-09-01

Our previous study showed that selenamide reagents such as ebselen and N-(phenylseleno)phthalimide (NPSP) can be used for selective and rapid derivatization of protein/peptide thiols in high conversion yield. This paper reports the systematic investigation of MS/MS dissociation behaviors of selenamide-derivatized peptide ions upon collision induced dissociation (CID) and electron transfer dissociation (ETD). In the positive ion mode, derivatized peptide ions exhibit tag-dependent CID dissociation pathways. For instance, ebselen-derivatized peptide ions preferentially undergo Se-S bond cleavage upon CID to produce a characteristic fragment ion, the protonated ebselen ( m/z 276), which allows selective identification of thiol peptides from protein digest as well as selective detection of thiol proteins from protein mixture using precursor ion scan (PIS). In contrast, NPSP-derivatized peptide ions retain their phenylselenenyl tags during CID, which is useful in sequencing peptides and locating cysteine residues. In the negative ion CID mode, both types of tags are preferentially lost via the Se-S cleavage, analogous to the S-S bond cleavage during CID of disulfide-containing peptide anions. In consideration of the convenience in preparing selenamide-derivatized peptides and the similarity of Se-S of the tag to the S-S bond, we also examined ETD of the derivatized peptide ions to probe the mechanism for electron-based ion dissociation. Interestingly, facile cleavage of Se-S bond occurs to the peptide ions carrying either protons or alkali metal ions, while backbone cleavage to form c/z ions is severely inhibited. These results are in agreement with the Utah-Washington mechanism proposed for depicting electron-based ion dissociation processes.

Solid state characterization of α-chitin from Vanessa cardui Linnaeus wings

International Nuclear Information System (INIS)

Schiffman, Jessica D.; Schauer, Caroline L.

2009-01-01

Material properties of the painted lady butterfly, Vanessa cardui Linnaeus were investigated using typical material science techniques. The examined butterflies were raised and hatched from the larvae stage and their chemical and crystalline structure evaluated and compared to that of crab shell (α-chitin) and squid pens from Notodarus sloanii and Loligo pealei (β-chitin). Fourier transmission infrared spectroscopy (FTIR) and X-ray diffraction (XRD) revealed that the painted lady butterflies are composed of α-chitin. Additionally, macro- and microstructure characterization of the chitins was conducted utilizing digital photography and field emission scanning electron microscopy (FESEM). This work demonstrates that common characterization techniques combined with simple sample preparation of biological materials can yield successful material characterization, which could aide the fabrication of biomimetic materials.

Solid state characterization of {alpha}-chitin from Vanessa cardui Linnaeus wings

Energy Technology Data Exchange (ETDEWEB)

Schiffman, Jessica D. [Department of Materials Science and Engineering, Drexel University, Philadelphia, PA (United States); Schauer, Caroline L., E-mail: cschauer@coe.drexel.edu [Department of Materials Science and Engineering, Drexel University, Philadelphia, PA (United States)

2009-05-05

Material properties of the painted lady butterfly, Vanessa cardui Linnaeus were investigated using typical material science techniques. The examined butterflies were raised and hatched from the larvae stage and their chemical and crystalline structure evaluated and compared to that of crab shell ({alpha}-chitin) and squid pens from Notodarus sloanii and Loligo pealei ({beta}-chitin). Fourier transmission infrared spectroscopy (FTIR) and X-ray diffraction (XRD) revealed that the painted lady butterflies are composed of {alpha}-chitin. Additionally, macro- and microstructure characterization of the chitins was conducted utilizing digital photography and field emission scanning electron microscopy (FESEM). This work demonstrates that common characterization techniques combined with simple sample preparation of biological materials can yield successful material characterization, which could aide the fabrication of biomimetic materials.

Graft polymerization of acrylic acid onto chitin nanofiber to improve dispersibility in basic water.

Science.gov (United States)

Ifuku, Shinsuke; Iwasaki, Masayoshi; Morimoto, Minoru; Saimoto, Hiroyuki

2012-09-01

Graft copolymerization of acrylic acid (AA) on chitin nanofibers was carried out with potassium persulfate as a free radical initiator in an aqueous medium. The molar ratio of grafted AA increased with the AA concentration. The grafted chitin nanofibers were characterized by FT-IR, FE-SEM, UV-vis, XRD, and TGA. After polymerization, the characteristic morphology of chitin nanofibers was maintained. Chitin nanofibers grafted with AA were efficiently dissociated and dispersed homogeneously in basic water because of the electrostatic repulsion effect between nanofibers. AA was grafted on the surface and amorphous part of chitin nanofibers, and the original crystalline structure of α-chitin was maintained. At 330 °C, the weight residue of the graft copolymer increased with the grafted AA content. Copyright © 2012 Elsevier Ltd. All rights reserved.

Immobilisation of ligands by radio-derivatized polymers

International Nuclear Information System (INIS)

Varga, J.M.; Fritsch, P.

1995-01-01

The invention relates to radio-derivatized polymers and a method of producing them by contacting non-polymerizable conjugands with radiolysable polymers in the presence of irradiation. The resulting radio-derivatized polymers can be further linked with ligand of organic or inorganic nature to immobilize such ligands. 2 figs., 5 tabs

Characterization of a Chitin-Binding Protein from Bacillus thuringiensis HD-1.

Directory of Open Access Journals (Sweden)

Naresh Arora

Full Text Available Strains of Bacillus thuringiensis produce insecticidal proteins. These strains have been isolated from diverse ecological niches, such as soil, phylloplane, insect cadavers and grain dust. To effectively propagate, these strains produce a range of molecules that facilitate its multiplication in a competing environment. In this report, we have examined synthesis of a chitin-binding protein and evaluated its effect on fungi encountered in environment and its interaction with insecticidal proteins synthesized by B. thuringiensis. The gene encoding chitin-binding protein has been cloned and expressed. The purified protein has been demonstrated to interact with Cry insecticidal protein, Cry1Ac by Circular Dichrosim spectroscopy (CD and in vitro pull down assays. The chitin-binding protein potentiates insecticidal activity of bacillar insecticidal protein, Cry1Ac. Further, chitin-binding protein was fungistatic against several soil fungi. The chitin binding protein is expressed in spore mother cell and deposited along with insecticidal protein, Cry1Ac. It interacts with Cry1Ac to potentiate its insecticidal activity and facilitate propagation of Bacillus strain in environment by inhibiting growth of certain fungi.

Nanosphere Lithography of Chitin and Chitosan with Colloidal and Self-Masking Patterning

Directory of Open Access Journals (Sweden)

Rakkiyappan Chandran

2018-02-01

Full Text Available Complex surface topographies control, define, and determine the properties of insect cuticles. In some cases, these nanostructured materials are a direct extension of chitin-based cuticles. The cellular mechanisms that generate these elaborate chitin-based structures are unknown, and involve complicated cellular and biochemical “bottom-up” processes. We demonstrated that a synthetic “top-down” fabrication technique—nanosphere lithography—generates surfaces of chitin or chitosan that mimic the arrangement of nanostructures found on the surface of certain insect wings and eyes. Chitin and chitosan are flexible and biocompatible abundant natural polymers, and are a sustainable resource. The fabrication of nanostructured chitin and chitosan materials enables the development of new biopolymer materials. Finally, we demonstrated that another property of chitin and chitosan—the ability to self-assemble nanosilver particles—enables a novel and powerful new tool for the nanosphere lithographic method: the ability to generate a self-masking thin film. The scalability of the nanosphere lithographic technique is a major limitation; however, the silver nanoparticle self-masking enables a one-step thin-film cast or masking process, which can be used to generate nanostructured surfaces over a wide range of surfaces and areas.

Preparation of Size-Controlled Silver Nanoparticles and Chitin-Based Composites and Their Antimicrobial Activities

Directory of Open Access Journals (Sweden)

Vinh Quang Nguyen

2013-01-01

Full Text Available A simple method for the preparation of size-controlled spherical silver nanoparticles (Ag NPs was reported for their generation by autoclaving a mixture of silver-containing glass powder and glucose. The particle size is regulated by the glucose concentration, with concentrations of 0.25, 1.0, and 4.0 wt% glucose providing small (3.48±1.83 nm in diameter, medium (6.53±1.78 nm, and large (12.9±2.5 nm particles, respectively. In this study, Ag NP/chitin composites were synthesized by mixing each of these three Ag NP suspensions with a <5% deacetylated (DAc chitin powder (pH 7.0 at room temperature. The Ag NPs were homogenously dispersed and stably adsorbed onto the chitin. The Ag NP/chitin composites were obtained as yellow or brown powders. Approximately 5, 15, and 20 μg of the small, medium, and large Ag NPs, respectively, were estimated to maximally adsorb onto 1 mg of chitin. The bactericidal and antifungal activities of the Ag NP/chitin composites increased as the amount of Ag NPs in the chitin increased. Furthermore, smaller Ag NPs (per weight in the chitin composites provided higher bactericidal and anti-fungal activities.

Biophysical characterization data on Aβ soluble oligomers produced through a method enabling prolonged oligomer stability and biological buffer conditions

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Amanda C. Crisostomo

2015-09-01

Aβ1-40 soluble oligomers are produced that are suitable for biophysical studies requiring sufficient transient stability to exist in their “native” conformation in biological phosphate-saline buffers for extended periods of time. The production involves an initial preparation of highly monomeric Aβ in a phosphate saline buffer that transitions to fibrils and oligomers through time incubation alone, without added detergents or non-aqueous chemicals. This criteria ensures that the only difference between initial monomeric Aβ reactant and subsequent Aβ oligomer products is their degree of peptide assembly. A number of chemical and biophysical methods were used to characterize the monomeric reactants and soluble oligomer and amyloid fibril products, including chemical cross-linking, Western blots, fraction solubility, thioflvain T binding, size exclusion chromatography, transmission electron micrscopy, circular dichroism spectroscopy, and fluorescence resonance energy transfer.

Preparation of Stable Amyloid-β Oligomers Without Perturbative Methods.

Science.gov (United States)

Kotler, Samuel A; Ramamoorthy, Ayyalusamy

2018-01-01

Soluble amyloid-β (Aβ) oligomers have become a focal point in the study of Alzheimer's disease due to their ability to elicit cytotoxicity. A number of recent studies have concentrated on the structural characterization of soluble Aβ oligomers to gain insight into their mechanism of toxicity. Consequently, providing reproducible protocols for the preparation of such oligomers is of utmost importance. The method presented in this chapter details a protocol for preparing an Aβ oligomer, with a primarily disordered secondary structure, without the need for chemical modification or amino acid substitution. Due to the stability of these disordered Aβ oligomers and the reproducibility with which they form, they are amenable for biophysical and high-resolution structural characterization.

Structural and functional properties of prefibrillar α-synuclein oligomers.

Science.gov (United States)

Pieri, Laura; Madiona, Karine; Melki, Ronald

2016-04-14

The deposition of fibrillar alpha-synuclein (α-syn) within inclusions (Lewy bodies and Lewy neurites) in neurons and glial cells is a hallmark of synucleinopathies. α-syn populates a variety of assemblies ranging from prefibrillar oligomeric species to fibrils whose specific contribution to neurodegeneration is still unclear. Here, we compare the specific structural and biological properties of distinct soluble prefibrillar α-syn oligomers formed either spontaneously or in the presence of dopamine and glutaraldehyde. We show that both on-fibrillar assembly pathway and distinct dopamine-mediated and glutaraldehyde-cross-linked α-syn oligomers are only slightly effective in perturbing cell membrane integrity and inducing cytotoxicity, while mature fibrils exhibit the highest toxicity. In contrast to low-molecular weight and unstable oligomers, large stable α-syn oligomers seed the aggregation of soluble α-syn within reporter cells although to a lesser extent than mature α-syn fibrils. These oligomers appear elongated in shape. Our findings suggest that α-syn oligomers represent a continuum of species ranging from unstable low molecular weight particles to mature fibrils via stable elongated oligomers composed of more than 15 α-syn monomers that possess seeding capacity.

Boron-rich oligomers for BNCT

International Nuclear Information System (INIS)

Gula, M.; Perleberg, O.; Gabel, D.

2000-01-01

The synthesis of two BSH derivatives is described, which can be used for oligomerization in DNA-synthesizers. Synthesis pathways lead to final products in five and six steps, respectively. Because of chirality interesting results were expected. NMR-measurements confirm this expectation. Possible oligomers with high concentrations of boron can be attached to biomolecules. These oligomers can be explored with several imaging methods (EELS, PEM) to determine the lower detection limit of boron with these methods. (author)

The demosponge Pseudoceratina purpurea as a new source of fibrous chitin.

Science.gov (United States)

Żółtowska-Aksamitowska, Sonia; Tsurkan, Mikhail V; Lim, Swee-Cheng; Meissner, Heike; Tabachnick, Konstantin; Shaala, Lamiaa A; Youssef, Diaa T A; Ivanenko, Viatcheslav N; Petrenko, Iaroslav; Wysokowski, Marcin; Bechmann, Nicole; Joseph, Yvonne; Jesionowski, Teofil; Ehrlich, Hermann

2018-06-01

Among marine demosponges (Porifera: Demospongiae), only representatives of the order Verongiida have been recognized to synthetize both biologically active substances as well as scaffolds-like fibrous skeletons made of structural aminopolysaccharide chitin. The unique 3D architecture of such scaffolds open perspectives for their applications in waste treatment, biomimetics and tissue engineering. Here, we focus special attention to the demosponge Pseudoceratina purpurea collected in the coastal waters of Singapore. For the first time the detailed description of the isolation of chitin from the skeleton of this sponge and its identification using diverse bioanalytical tools were carried out. Calcofluor white staining, FTIR analysis, electrospray ionization mass spectrometry (ESI-MS), SEM, and fluorescence microscopy as well as a chitinase digestion assay were applied in order to confirm with strong evidence the finding of alpha-chitin in the skeleton of P. purpurea. We suggest that the discovery of chitin within representatives of Pseudoceratinidae family is a perspective step in evaluation of these verongiid sponges as novel renewable sources for both chitin and biologically active metabolites, which are of prospective use for marine oriented biomedicine and pharmacology, respectively. Copyright © 2018 Elsevier B.V. All rights reserved.

Characterization and role of a metalloprotease induced by chitin in Serratia sp. KCK.

Science.gov (United States)

Kim, Hyun-Soo; Golyshin, Peter N; Timmis, Kenneth N

2007-11-01

A metalloprotease induced by chitin in a new chitinolytic bacterium Serratia sp. Strain KCK was purified and characterized. Compared with other Serratia enzymes, it exhibited a rather broad pH activity range (pH 5.0-8.0), and thermostability. The cognate ORF, mpr, was cloned and expressed. Its deduced amino acid sequence showed high similarity to those of bacterial zinc-binding metalloproteases and a well-conserved serralysin family motif. Pretreatment of chitin with the Mpr protein promoted chitin degradation by chitinase A, which suggests that Mpr participates in, and facilitates, chitin degradation by this microorganism.

Desarrollo y validación de un nuevo método para estimar la deshomogenización de quitina en supositorios Development and validation of a new method for chitin dehomogenization estimation in suppositories

Directory of Open Access Journals (Sweden)

Oscar García Pulpeiro

2005-12-01

Full Text Available Se trató por primera vez el desarrollo de un método alternativo sencillo para determinar la deshomogenización de quitina en supositorios rectales. El método propuesto se basa en la determinación de la deshomogenización a partir de la relación de la densidad de quitina presente en la punta y en la base del supositorio. Para el cálculo de la densidad por desplazamiento se tuvo en cuenta el factor de desalojo, así como varios cálculos matemáticos. El método se validó para control de calidad, resultó satisfactorio y se aplicó a 11 formulaciones diferentes. Se comprobó que el aumento del tamaño de partícula y de la dosis de quitina en el supositorio favorece la sedimentación hacia la punta del supositorio. En el intervalo analizado los valores de deshomogenización se consideran mínimos, por lo que no se afectó la calidad tecnológica de las formulaciones estudiadas.For the first time, the development of a simple alternative method to determine chitin dehomogenization in rectal suppositories was addressed in this paper. The suggested method is based on determination of dehomogenization from the ratio of chitin density of the tip and of the base of suppository. For estimation of the sliding density, the clearing factor as well as various mathematical calculations were taken into consideration. The method was validated for quality control, it was satisfactory and applied in 11 formulations. It was proved that the increase in chitin particle size and dose in suppository favors sedimentation to the tip of suppository. In the analyzed interval, the dehomogenization values were considered minimal, so the technological quality of the studied formulations was not affected.

Fabrication of free-standing replicas of fragile, laminar, chitinous biotemplates

Energy Technology Data Exchange (ETDEWEB)

Lakhtakia, Akhlesh; Motyka, Michael A [Materials Research Institute and Department of Engineering Science and Mechanics, Pennsylvania State University, University Park, PA 16802 (United States); MartIn-Palma, Raul J; Pantano, Carlo G [Materials Research Institute and Department of Materials Science and Engineering, Pennsylvania State University, University Park, PA 16802 (United States)], E-mail: akhlesh@psu.edu

2009-09-01

The conformal-evaporated-film-by-rotation technique, followed by the dissolution of chitin in an aqueous solution of orthophosphoric acid, can be used to fabricate free-standing replicas of fragile, laminar, chitinous biotemplates. This novel approach was demonstrated using butterfly wings as biotemplates and GeSeSb chalcogenide glass for replicas. (communication)

Fabrication of free-standing replicas of fragile, laminar, chitinous biotemplates

International Nuclear Information System (INIS)

Lakhtakia, Akhlesh; Motyka, Michael A; MartIn-Palma, Raul J; Pantano, Carlo G

2009-01-01

The conformal-evaporated-film-by-rotation technique, followed by the dissolution of chitin in an aqueous solution of orthophosphoric acid, can be used to fabricate free-standing replicas of fragile, laminar, chitinous biotemplates. This novel approach was demonstrated using butterfly wings as biotemplates and GeSeSb chalcogenide glass for replicas. (communication)

The functions Of LysM Proteins And Chitin Tetra-Saccarides Signaling Pathway in Zebrafish Embryos

DEFF Research Database (Denmark)

Laroche, Fabrice Jean Francois

Chitin is an ancient organic bio-polymer, found in abundance on land and at sea. However, knowledge on chitin functions in animals is lacking. In his research project, Fabrice Laroche studied responses to chitin in zebrafish embryos, and he described chitin signalling pathways. Proteins related...... to chitin responses are increasingly being associated with human diseases. Recently, several lysin motif (LysM)-containing proteins were highlighted for their molecular affinity to chitin-like compounds. Addressing these matters, Fabrice Laroche identified zebrafish and human lysin motif-encoding genes...... and studied their roles – at the cellular level and during zebrafish development. To improve the experimental methods, he developed nanotechnological strategies to genetically modify human embryonic kidney cells and zebrafish. The PhD degree was completed at the Department of Molecular Biology and Genetics...

Electrografting of conductive oligomers and polymers using diazonium electroreduction

International Nuclear Information System (INIS)

Lacroix, Jean Christophe; Trippe-Allard, Gaelle; Ghilane, Jalal; Martin, Pascal

2014-01-01

This paper describes the attachment of conjugated oligomers onto electrode surface through the reduction of diazonium compounds. In this connection some properties of conjugated oligomers and of layers grafted through diazonium electroreduction will first be briefly presented. The electrochemical behavior of conjugated oligomers grafted on a surface using diazonium electroreduction will then be discussed. (paper)

Electrografting of conductive oligomers and polymers using diazonium electroreduction

Science.gov (United States)

Lacroix, Jean Christophe; Trippe-Allard, Gaelle; Ghilane, Jalal; Martin, Pascal

2014-03-01

This paper describes the attachment of conjugated oligomers onto electrode surface through the reduction of diazonium compounds. In this connection some properties of conjugated oligomers and of layers grafted through diazonium electroreduction will first be briefly presented. The electrochemical behavior of conjugated oligomers grafted on a surface using diazonium electroreduction will then be discussed.

Fabrication of magnetic and fluorescent chitin and dibutyrylchitin sub-micron particles by oil-in-water emulsification.

Science.gov (United States)

Blanco-Fernandez, Barbara; Chakravarty, Shatadru; Nkansah, Michael K; Shapiro, Erik M

2016-11-01

Chitin is a carbohydrate polymer with unique pharmacological and immunological properties, however, because of its unwieldy chemistry, the synthesis of discreet sized sub-micron particles has not been well reported. This work describes a facile and flexible method to fabricate biocompatible chitin and dibutyrylchitin sub-micron particles. This technique is based on an oil-in-water emulsification/evaporation method and involves the hydrophobization of chitin by the addition of labile butyryl groups onto chitin, disrupting intermolecular hydrogen bonds and enabling solubility in the organic solvent used as the oil phase during fabrication. The subsequent removal of butyryl groups post-fabrication through alkaline saponification regenerates native chitin while keeping particles morphology intact. Examples of encapsulation of hydrophobic dyes and nanocrystals are demonstrated, specifically using iron oxide nanocrystals and coumarin 6. The prepared particles had diameters between 300-400nm for dibutyrylchitin and 500-600nm for chitin and were highly cytocompatible. Moreover, they were able to encapsulate high amounts of iron oxide nanocrystals and were able to label mammalian cells. We describe a technique to prepare sub-micron particles of highly acetylated chitin (>90%) and dibutyrylchitin and demonstrate their utility as carriers for imaging. Chitin is a polysaccharide capable of stimulating the immune system, a property that depends on the acetamide groups, but its insolubility limits its use. No method for sub-micron particle preparation with highly acetylated chitins have been published. The only approach for the preparation of sub-micron particles uses low acetylation chitins. Dibutyrylchitin, a soluble chitin derivative, was used to prepare particles by oil in water emulsification. Butyryl groups were then removed, forming chitin particles. These particles could be suitable for encapsulation of hydrophobic payloads for drug delivery and cell imaging, as well as

Squid-derived chitin oligosaccharides are a chemotactic signal during colonization by Vibrio fischeri.

Science.gov (United States)

Mandel, Mark J; Schaefer, Amy L; Brennan, Caitlin A; Heath-Heckman, Elizabeth A C; Deloney-Marino, Cindy R; McFall-Ngai, Margaret J; Ruby, Edward G

2012-07-01

Chitin, a polymer of N-acetylglucosamine (GlcNAc), is noted as the second most abundant biopolymer in nature. Chitin serves many functions for marine bacteria in the family Vibrionaceae ("vibrios"), in some instances providing a physical attachment site, inducing natural genetic competence, and serving as an attractant for chemotaxis. The marine luminous bacterium Vibrio fischeri is the specific symbiont in the light-emitting organ of the Hawaiian bobtail squid, Euprymna scolopes. The bacterium provides the squid with luminescence that the animal uses in an antipredatory defense, while the squid supports the symbiont's nutritional requirements. V. fischeri cells are harvested from seawater during each host generation, and V. fischeri is the only species that can complete this process in nature. Furthermore, chitin is located in squid hemocytes and plays a nutritional role in the symbiosis. We demonstrate here that chitin oligosaccharides produced by the squid host serve as a chemotactic signal for colonizing bacteria. V. fischeri uses the gradient of host chitin to enter the squid light organ duct and colonize the animal. We provide evidence that chitin serves a novel function in an animal-bacterial mutualism, as an animal-produced bacterium-attracting synomone.

Application of Spectroscopic Methods for Structural Analysis of Chitin and Chitosan

Directory of Open Access Journals (Sweden)

Jolanta Kumirska

2010-04-01

Full Text Available Chitin, the second most important natural polymer in the world, and its N-deacetylated derivative chitosan, have been identified as versatile biopolymers for a broad range of applications in medicine, agriculture and the food industry. Two of the main reasons for this are firstly the unique chemical, physicochemical and biological properties of chitin and chitosan, and secondly the unlimited supply of raw materials for their production. These polymers exhibit widely differing physicochemical properties depending on the chitin source and the conditions of chitosan production. The presence of reactive functional groups as well as the polysaccharide nature of these biopolymers enables them to undergo diverse chemical modifications. A complete chemical and physicochemical characterization of chitin, chitosan and their derivatives is not possible without using spectroscopic techniques. This review focuses on the application of spectroscopic methods for the structural analysis of these compounds.

[In Vivo Study of Chitin in Fungal Hyphae Based on Confocal Raman Microscopy].

Science.gov (United States)

Li, Xiao-li; Luo, Liu-bin; Zhou, Bin-xiong; Hu, Xiao-qian; Sun, Chan-jun; He, Yong

2016-01-01

Chitin is an important structural polysaccharide of fungal cell wall. In this paper, aerial hyphae of Colletotrichum camelliae Massee was first studied by confocal Raman microscopy in vivo. Firstly, the optimal experimental parameters of hyphae for collecting the Raman spectra were determined, and the typical Raman spectra of hyphae, chitin standard and background were acquired. By comparing analysis, characteristic peaks of chitin were found in hyphae. Then, a region of interesting on hyphae was selected for Raman scanning. Through principal component analysis, the Raman signal of hyphae and background in the scanning area can be separated clearly. Combined with loading weight plot, two main characteristic peaks of hyphae were obtained, 1 622 cm(-1) was belong to chitin and 1 368 cm(-1) was assigned to pectic polysaccharide. Finally, two and three dimension chemical images of fungal hyphae were realized based on Raman fingerprint spectra of chitin in a nondestructive way.

High similarity in physicochemical properties of chitin and chitosan from nymphs and adults of a grasshopper.

Science.gov (United States)

Erdogan, Sevil; Kaya, Murat

2016-08-01

This is the first study to explain the differences in the physicochemical properties of chitin and chitosan obtained from the nymphs and adults of Dociostaurus maroccanus using the same method. Fourier transform infrared spectroscopy, thermogravimetric analysis and x-ray diffraction analysis results demonstrated that the chitins from both the adults and nymphs were in the α-form. The chitin contents of the adults (14%) and nymphs (12%) were of the same order of magnitude. The crystalline index values of chitins from the adult and nymph grasshoppers were 71% and 74%, respectively. Thermal stabilities of the chitins and chitosans from adult and nymph grasshoppers were close to each other. Both the adult (7.2kDa) and nymph (5.6kDa) chitosans had low molar masses. Environmental scanning electron microscopy revealed that the surface morphologies of both chitins consisted of nanofibers and nanopores together, and they were very similar to each other. Consequently, it was determined that the physicochemical properties of the chitins and chitosans from adults and nymphs of D. maroccanus were not very different, so it can be hypothesized that the development of the chitin structure in the nymph has almost been completed and the nymph chitin has the same characteristics as the adult. Copyright © 2016 Elsevier B.V. All rights reserved.

Analysis of chitin-binding proteins from Manduca sexta provides new insights into evolution of peritrophin A-type chitin-binding domains in insects.

Science.gov (United States)

Tetreau, Guillaume; Dittmer, Neal T; Cao, Xiaolong; Agrawal, Sinu; Chen, Yun-Ru; Muthukrishnan, Subbaratnam; Haobo, Jiang; Blissard, Gary W; Kanost, Michael R; Wang, Ping

2015-07-01

In insects, chitin is a major structural component of the cuticle and the peritrophic membrane (PM). In nature, chitin is always associated with proteins among which chitin-binding proteins (CBPs) are the most important for forming, maintaining and regulating the functions of these extracellular structures. In this study, a genome-wide search for genes encoding proteins with ChtBD2-type (peritrophin A-type) chitin-binding domains (CBDs) was conducted. A total of 53 genes encoding 56 CBPs were identified, including 15 CPAP1s (cuticular proteins analogous to peritrophins with 1 CBD), 11 CPAP3s (CPAPs with 3 CBDs) and 17 PMPs (PM proteins) with a variable number of CBDs, which are structural components of cuticle or of the PM. CBDs were also identified in enzymes of chitin metabolism including 6 chitinases and 7 chitin deacetylases encoded by 6 and 5 genes, respectively. RNA-seq analysis confirmed that PMP and CPAP genes have differential spatial expression patterns. The expression of PMP genes is midgut-specific, while CPAP genes are widely expressed in different cuticle forming tissues. Phylogenetic analysis of CBDs of proteins in insects belonging to different orders revealed that CPAP1s from different species constitute a separate family with 16 different groups, including 6 new groups identified in this study. The CPAP3s are clustered into a separate family of 7 groups present in all insect orders. Altogether, they reveal that duplication events of CBDs in CPAP1s and CPAP3s occurred prior to the evolutionary radiation of insect species. In contrast to the CPAPs, all CBDs from individual PMPs are generally clustered and distinct from other PMPs in the same species in phylogenetic analyses, indicating that the duplication of CBDs in each of these PMPs occurred after divergence of insect species. Phylogenetic analysis of these three CBP families showed that the CBDs in CPAP1s form a clearly separate family, while those found in PMPs and CPAP3s were clustered

Effect of Acetyl Group on Mechanical Properties of Chitin/Chitosan Nanocrystal: A Molecular Dynamics Study

Directory of Open Access Journals (Sweden)

Junhe Cui

2016-01-01

Full Text Available Chitin fiber is the load-bearing component in natural chitin-based materials. In these materials, chitin is always partially deacetylated to different levels, leading to diverse material properties. In order to understand how the acetyl group enhances the fracture resistance capability of chitin fiber, we constructed atomistic models of chitin with varied acetylation degree and analyzed the hydrogen bonding pattern, fracture, and stress-strain behavior of these models. We notice that the acetyl group can contribute to the formation of hydrogen bonds that can stabilize the crystalline structure. In addition, it is found that the specimen with a higher acetylation degree presents a greater resistance against fracture. This study describes the role of the functional group, acetyl groups, in crystalline chitin. Such information could provide preliminary understanding of nanomaterials when similar functional groups are encountered.

Tau Oligomers as Pathogenic Seeds: Preparation and Propagation In Vitro and In Vivo.

Science.gov (United States)

Gerson, Julia E; Sengupta, Urmi; Kayed, Rakez

2017-01-01

Tau oligomers have been shown to be the main toxic tau species in a number of neurodegenerative disorders. In order to study tau oligomers both in vitro and in vivo, we have established methods for the reliable preparation, isolation, and detection of tau oligomers. Methods for the seeding of tau oligomers, isolation of tau oligomers from tissue, and detection of tau oligomers using tau oligomer-specific antibodies by biochemical and immunohistochemical methods are detailed below.

Experimental evaluation of new chitin-chitosan graft for duraplasty.

Science.gov (United States)

Pogorielov, M; Kravtsova, A; Reilly, G C; Deineka, V; Tetteh, G; Kalinkevich, O; Pogorielova, O; Moskalenko, R; Tkach, G

2017-02-01

Natural materials such as collagen and alginate have promising applications as dural graft substitutes. These materials are able to restore the dural defect and create optimal conditions for the development of connective tissue at the site of injury. A promising material for biomedical applications is chitosan-a linear polysaccharide obtained by the deacetylation of chitin. It has been found to be nontoxic, biodegradable, biofunctional and biocompatible in addition to having antimicrobial characteristics. In this study we designed new chitin-chitosan substitutes for dura mater closure and evaluated their effectiveness and safety. Chitosan films were produced from 3 % of chitosan (molar mass-200, 500 or 700 kDa, deacetylation rate 80-90%) with addition of 20% of chitin. Antimicrobial effictively and cell viability were analysed for the different molar masses of chitosan. The film containing chitosan of molar mass 200 kDa, had the best antimicrobial and biological activity and was successfully used for experimental duraplasty in an in vivo model. In conclusion the chitin-chitosan membrane designed here met the requirements for a dura matter graft exhibiting the ability to support cell growth, inhibit microbial growth and biodegradade at an appropriate rate. Therefore this is a promising material for clinical duroplasty.

Three-dimensional chitin rings from body segments of a pet diplopod species: Characterization and protein interaction studies

Energy Technology Data Exchange (ETDEWEB)

Kaya, Murat, E-mail: muratkaya3806@yahoo.com [Department of Biotechnology and Molecular Biology, Faculty of Science and Letters, Aksaray University, 68100 Aksaray (Turkey); Mulerčikas, Povilas [Department of Biology and Plant Protection, Lithuanian University of Agriculture, LT-53361 (Lithuania); Sargin, Idris [Department of Chemistry, Faculty of Science, Selcuk University, 42075 Konya (Turkey); Kazlauskaitė, Sonata [Department of Biology and Plant Protection, Lithuanian University of Agriculture, LT-53361 (Lithuania); Baublys, Vykintas [Department of Biology, Vytautas Magnus University, LT-44404 Kaunas (Lithuania); Akyuz, Bahar; Bulut, Esra [Department of Biotechnology and Molecular Biology, Faculty of Science and Letters, Aksaray University, 68100 Aksaray (Turkey); Tubelytė, Vaida [Department of Biology, Vytautas Magnus University, LT-44404 Kaunas (Lithuania)

2016-11-01

Physicochemical characterization of new chitin isolates can provide valuable insights into designing of biomimetic materials. Chitin isolates with a definite three-dimensional (3D) structure can exhibit characteristics that distinguish them from other chitin specimens that are in form of powder or flakes without a definite and uniform shape. Herein, 3D chitin rings were produced from body segments of a diplopod (Archispirostreptus gigas) inhabiting tropical regions. This organism is cultured easily and can reach 38 cm in length, which makes it a suitable source for isolation of chitin. The chitin rings were characterized via TGA, FT-IR, SEM and XRD analyses. Enzymatic digestion test with chitinase demonstrated that chitin isolates had high purity (digestion rate: 97.4%). The source organism had high chitin content; 21.02 ± 2.23% on dry weight. Interactions of the chitin rings with bovine serum albumin (BSA) protein were studied under different conditions (pH: 4.0–8.0, chitin amount: 6–14 mg, contact time: 30–360 min, protein concentration: 0.2–1 mg/mL). The highest BSA adsorption was observed at pH 5.0 at 20 °C. The adsorption equilibrium data exhibited a better fit to Langmuir adsorption and the pseudo-first order kinetic models. The findings presented here can be useful for further studies aiming to develop biocompatible and nontoxic biomaterials. - Highlights: • Three-dimensional ring shaped chitin was produced from a pet diplopod species. • Archispirostreptus gigas has high chitin content; 21.02 ± 2.23% on dry weight. • Chitinase enzyme showed activity on the chitin rings with digestion rate of 97.4%. • The highest bovine serum albumin (BSA) adsorption was observed at pH 5.0 at 20 °C.

Electron beam curing polyurethane acrylate oligomer in air

International Nuclear Information System (INIS)

Zhu, Zhenkang; Chen, Xing; Zhou, Jichun; Ma, Zue-Teh

1988-01-01

It has been found according to our synthesis that a novel kind of polyurethane acrylate oligomer can be cured by electron beam in the presence of oxygen, even at normal atomospheric levels, without any additives. Irradiation of the oligomer with substantially complete cure to a solid non-tacky state is quite remarkable. It has the same gel content (90 %) in air as in nitrogen at dose of 33 kGy. Double bond conversion of the oligomer is about 50 % by I.R. (author)

Chitin Extraction from Crustacean Shells Using Biological Methods – A Review

Directory of Open Access Journals (Sweden)

Wassila Arbia

2013-01-01

Full Text Available After cellulose, chitin is the most widespread biopolymer in nature. Chitin and its derivatives have great economic value because of their biological activities and their industrial and biomedical applications. It can be extracted from three sources, namely crustaceans, insects and microorganisms. However, the main commercial sources of chitin are shells of crustaceans such as shrimps, crabs, lobsters and krill that are supplied in large quantities by the shellfish processing industries. Extraction of chitin involves two steps, demineralisation and deproteinisation, which can be conducted by two methods, chemical or biological. The chemical method requires the use of acids and bases, while the biological method involves microorganisms. Although lactic acid bacteria are mainly applied, other microbial species including proteolytic bacteria have also been successfully implemented, as well as mixed cultures involving lactic acid-producing bacteria and proteolytic microorganisms. The produced lactic acid allows shell demineralisation, since lactic acid reacts with calcium carbonate, the main mineral component, to form calcium lactate.

Chitin Lengthens Power Production in a Sedimentary Microbial Fuel Cell

Science.gov (United States)

2014-01-01

organic carbon sediments demonstrate that chitin enhances and lengthens power production. Keywords—chitin; MFC; microbiology ; iron-reducing bacteria...levels of organic content available as a food source for bacteria in the sediment. Dependent upon applications, there are scenarios where a SMFC...as ethanol, molasses, or vegetable oils. In the case of underwater marine sediment, options for carbon amendment are limited to solid carbon

Early Lotus japonicus root transcriptomic responses to symbiotic and pathogenic fungal exudates

Directory of Open Access Journals (Sweden)

Marco eGiovannetti

2015-06-01

Full Text Available The objective of this study is to evaluate Lotus japonicus transcriptomic responses to arbuscular mycorrhizal (AM germinated spore exudates (GSE, responsible for activating nuclear Ca2+ spiking in plant root epidermis. A microarray experiment was performed comparing gene expression in Lotus rootlets treated with GSE or water after 24 h and 48 h. The transcriptional pattern of selected genes that resulted to be regulated in the array was further evaluated upon different treatments and timings. In particular, Lotus rootlets were treated with: GSE from the pathogenic fungus Colletotrichum trifolii; short chitin oligomers (acknowledged AM fungal signals and long chitin oligomers (as activators of pathogenic responses. This experimental set up has revealed that AM GSE generates a strong transcriptomic response in Lotus roots with an extensive defense-related response after 24 hours and a subsequent downregulation after 48 hours. A similar subset of defense-related genes resulted to be upregulated also upon treatment with C. trifolii GSE, although with an opposite trend. Surprisingly, long chitin oligomers activated both defense-like and symbiosis-related genes. Among the genes regulated in the microarray, promoter-GUS assay showed that LjMATE1 activates in epidermal cells and root hairs.

The use of flow cytometry to monitor chitin synthesis in regenerating protoplasts of Candida albicans.

Science.gov (United States)

Hector, R F; Braun, P C; Hart, J T; Kamarck, M E

1990-01-01

Flow cytometry was used to monitor chitin synthesis in regenerating protoplasts of the yeast Candida albicans. Comparisons of cells stained with Calcofluor White, a fluorochrome with known affinity for chitin, and cells incubated in the presence of N-[3H]-acetylglucosamine, the precursor substrate for chitin, showed a linear relationship between fluorescence and incorporation of label over time. Changes in both the fluorescence and light scatter of regenerating protoplasts treated with inhibitors of fungal chitin synthase were also quantitated by flow cytometry.

Opsigtsvækkende nyt om derivater fra USA

DEFF Research Database (Denmark)

Thinggaard, Frank

1997-01-01

Der er opsigsvækkende nyt fra USA om den regnskabsmæssige behandling af derivater som terminskontrakter, futures, optioner, swaps m.v. Glem alt om historiske anskaffelsespriser. For derivater er der kun ét mål, som kan bruges: markedsværdier (fair-values). Glem alt om snakken om 'off-balance-sheet...

Surface morphology of chitin highly related with the isolated body part of butterfly (Argynnis pandora).

Science.gov (United States)

Kaya, Murat; Bitim, Betül; Mujtaba, Muhammad; Koyuncu, Turgay

2015-11-01

This study was conducted to understand the differences in the physicochemical properties of chitin samples isolated from the wings and the other body parts except the wings (OBP) of a butterfly species (Argynnis pandora). The same isolation method was used for obtaining chitin specimens from both types of body parts. The chitin content of the wings (22%) was recorded as being much higher than the OBP (8%). The extracted chitin samples were characterized via FT-IR, TGA, XRD, SEM, and elemental analysis techniques. Results of these characterizations revealed that the chitins from both structures (wings and OBP) were very similar, except for their surface morphologies. SEM results demonstrated one type of surface morphology for the wings and four different surface morphologies for the OBP. Therefore, it can be hypothesized that the surface morphology of the chitin is highly related with the body part. Copyright © 2015 Elsevier B.V. All rights reserved.

Construction of chitin/PVA composite hydrogels with jellyfish gel-like structure and their biocompatibility.

Science.gov (United States)

He, Meng; Wang, Zhenggang; Cao, Yan; Zhao, Yanteng; Duan, Bo; Chen, Yun; Xu, Min; Zhang, Lina

2014-09-08

High strength chitin/poly(vinyl alcohol) (PVA) composite hydrogels (RCP) were constructed by adding PVA into chitin dissolved in a NaOH/urea aqueous solution, and then by cross-linking with epichlorohydrin (ECH) and freezing-thawing process. The RCP hydrogels were characterized by field emission scanning electron microscopy, FTIR, differential scanning calorimetry, solid-state (13)C NMR, wide-angle X-ray diffraction, and compressive test. The results revealed that the repeated freezing/thawing cycles induced the bicrosslinked networks consisted of chitin and PVA crystals in the composite gels. Interestingly, a jellyfish gel-like structure occurred in the RCP75 gel with 25 wt % PVA content in which the amorphous and crystalline PVA were immobilized tightly in the chitin matrix through hydrogen bonding interaction. The freezing/thawing cycles played an important role in the formation of the layered porous PVA networks and the tight combining of PVA with the pore wall of chitin. The mechanical properties of RCP75 were much higher than the other RCP gels, and the compressive strength was 20× higher than that of pure chitin gels, as a result of broadly dispersing stress caused by the orderly multilayered networks. Furthermore, the cell culture tests indicated that the chitin/PVA composite hydrogels exhibited excellent biocompatibility and safety, showing potential applications in the field of tissue engineering.

Pigments and oligomers for inks - moving towards the best combination

International Nuclear Information System (INIS)

Hutchinson, I.; Smith, S.; Grierson, W.; Devine, E.

1999-01-01

The formulation of UV curable printing inks depends on several complex factors. If the individual components of the ink are not complementary, then performance problems can arise. One critical combination is that between the pigment and the oligomer. In a new approach to improve understanding of pigment/oligomer interactions, the resources of a pigment manufacturer and an oligomer manufacturer have been combined to investigate the problem. Initial screening of process yellow pigments and several oligomer types highlighted performance variations which were then examined in more detail

Identification and first insights into the structure and biosynthesis of chitin from the freshwater sponge Spongilla lacustris.

Science.gov (United States)

Ehrlich, Hermann; Kaluzhnaya, Oksana V; Brunner, Eike; Tsurkan, Mikhail V; Ereskovsky, Alexander; Ilan, Micha; Tabachnick, Konstantin R; Bazhenov, Vasilii V; Paasch, Silvia; Kammer, Martin; Born, René; Stelling, Allison; Galli, Roberta; Belikov, Sergei; Petrova, Olga V; Sivkov, Victor V; Vyalikh, Denis; Hunoldt, Sebastian; Wörheide, Gert

2013-09-01

This work demonstrates that chitin is an important structural component within the skeletal fibers of the freshwater sponge Spongilla lacustris. Using a variety of analytical techniques ((13)C solid state NMR, FT-IR, Raman, NEXAFS, ESI-MS, Morgan-Elson assay and Calcofluor White Staining); we show that this sponge chitin is much closer to α-chitin, known to be present in other animals, than to β-chitin. Genetic analysis confirmed the presence of chitin synthases, which are described for the first time in a sponge. The presence of chitin in both marine (demosponges and hexactinellids) and freshwater sponges indicates that this important structural biopolymer was already present in their common ancestor. Copyright © 2013 Elsevier Inc. All rights reserved.

Evaluación analítica de óvulos de quitina Analytical evaluation of chitin pessaries

Directory of Open Access Journals (Sweden)

Yania Suárez Pérez

2008-12-01

Full Text Available Los óvulos de quitina constituyen nuevos productos en fase de investigación. Para la evaluación analítica de estos, se desarrolló un método gravimétrico directo para supositorios vaginales de diferente dosificación. La técnica se basa en la separación de la quitina de los demás componentes de la formulación según sus diferencias de solubilidad, con el empleo de la filtración al vacío. El método se validó para control de calidad, y se obtuvieron resultados satisfactorios en los parámetros evaluados: linealidad, precisión, exactitud y selectividad.Chitin pessaries are new products under research. For their analytical evaluation, a direct gravimetric method for vaginal suppositories of various dosing was designed. This technique was based on separation of chitin from the rest of the formulation components according to their solubility characteristics, by using vacuum filtering. The method was validated for quality control and the results were satisfactory in terms of the evaluated parameters such as linearity, precision, accuracy and selectivity.

Bacterial communities in chitin-amended soil as revealed by 16S rRNA gene based pyrosequencing

NARCIS (Netherlands)

Cretoiu, Mariana Silvia; Kielak, Anna Maria; Schluter, Andreas; van Elsas, Jan Dirk

Chitin and its derivatives are natural biopolymers that are often used as compounds for the control of soilborne plant pathogens. In spite of recent advances in agricultural practices involving chitin amendments, the microbial communities in chitin-amended soils remain poorly known. The objectives

Bacterial chitinolytic communities respond to chitin and pH alteration in soil

NARCIS (Netherlands)

Kielak-Butterbach, A.M.; Cretoiu, M.S.; Semenov, A.V.; Sørensen, S.J.; van Elsas, J.D.

Chitin amendment is a promising soil management strategy that may enhance the suppressiveness of soil toward plant pathogens. However, we understand very little of the effects of added chitin, including the putative successions that take place in the degradative process. We performed an experiment

Derivatization, characterization, and tribological behavior of an amine-terminated polymer surface

International Nuclear Information System (INIS)

Ren, S.L.; Yang, S.R.; Zhao, Y.P.

2004-01-01

The derivatization, characterization, and micro-tribological behavior of an amine-terminated polymer surface were investigated. Thus, the heptafluorobutyric anhydride (HFBA) derivatized film was characterized by means of contact-angle measurement and X-ray photoelectron spectroscopy (XPS). It was found that the HFBA-derivatized film was generated on the PEI surface in the presence of a chemical amide bond. The tribological properties were characterized as well. The polymer PEI film had relative high adhesion, friction, and poor anti-wear ability, while the HFBA-derivatized polymer film possessed a very low adhesive force of only about 5.5 nN (a pyramidal Si 3 N 4 tip with radius of curvature about 50 nm was used to measure the adhesion), which was more than an order of magnitude lower than that of the silicon substrate surface. Besides, the HFBA-derivatized film registered good friction-reducing ability and thermal stability. Thus, a good alternative method was presented to improve the tribological properties of polymer film by chemisorbing molecules with low surface energy. This makes it feasible for the derivatized polymer film to find promising application in resolving the tribological problems of micro-electromechanical systems (MEMS)

Binding Sites for Amyloid-β Oligomers and Synaptic Toxicity

Science.gov (United States)

Smith, Levi M.; Strittmatter, Stephen M.

2017-01-01

In Alzheimer’s disease (AD), insoluble and fibrillary amyloid-β (Aβ) peptide accumulates in plaques. However, soluble Aβ oligomers are most potent in creating synaptic dysfunction and loss. Therefore, receptors for Aβ oligomers are hypothesized to be the first step in a neuronal cascade leading to dementia. A number of cell-surface proteins have been described as Aβ binding proteins, and one or more are likely to mediate Aβ oligomer toxicity in AD. Cellular prion protein (PrPC) is a high-affinity Aβ oligomer binding site, and a range of data delineates a signaling pathway leading from Aβ complexation with PrPC to neuronal impairment. Further study of Aβ binding proteins will define the molecular basis of this crucial step in AD pathogenesis. PMID:27940601

Bacterial communities in chitin-amended soil as revealed by 16S rRNA gene based pyrosequencing

NARCIS (Netherlands)

Cretoiu, M.S.; Kielak, A.M.; Schluter, A.; van Elsas, J.D.

2014-01-01

Chitin and its derivatives are natural biopolymers that are often used as compounds for the control of soil-borne plant pathogens. In spite of recent advances in agricultural practices involving chitin amendments, the microbial communities in chitin-amended soils remain poorly known. The objectives

Properties of polymethyl methacrylate-based nanocomposites: Reinforced with ultra-long chitin nanofiber extracted from crab shells

International Nuclear Information System (INIS)

Chen, Chuchu; Li, Dagang; Hu, Qinqin; Wang, Ru

2014-01-01

Highlights: • Using waste crab shells to develop high-performance composites by simple method. • Combining the anatomic analysis of crab shell with the design of composite. • Introducing a 4-step all-mechanical treatment to prepare ultra-long chitin fiber. • Incorporation of chitin nanofiber improves properties of PMMA/Chitin composite. - Abstract: Ultra-long chitin nanofibers were incorporated into polymethyl methacrylate (PMMA) resin to prepared PMMA/Chitin nanocomposites with improved properties. Transmission electron microscopy (TEM) images showed that through the introduced 4-step all-mechanical treatment, the average aspect ratio of the obtained chitin fiber was up to 1000 with the length at dozens of micron range. Due to the laminated structure formed by “layer-by-layer” effect, tensile strength and Young’s modulus of the prepared composite were significantly enhanced after the filling of chitin nanofibers, as compared with neat PMMA. Light transmittance test indicated that increasing the fiber content causes little light scattering because the nano-scalar network which is smaller enough than the visible wavelength could well preserve the original transparency of PMMA. Furthermore, chitin nanofiber film with extremely low thermal expansion improved the thermal stability of PMMA in a great degree. This could lead to various commercial applications including flexible electronic printing, organic thin-film photovoltaic devices, and is a significantly environmental move towards the sustainable utilization of marine-river crab shell wastes

Chitin in the Silk Gland Ducts of the Spider Nephila edulis and the Silkworm Bombyx mori

Science.gov (United States)

Davies, Gwilym J. G.; Knight, David P.; Vollrath, Fritz

2013-01-01

Here we report the detection and localisation of chitin in the cuticle of the spinning ducts of both the spider Nephila edulis and the silkworm Bombyx mori. Our observations demonstrate that the duct walls of both animals contain chitin notwithstanding totally independent evolutionary pathways of the systems. We conclude that chitin may well be an essential component for the construction of spinning ducts; we further conclude that in both species chitin may indicate the evolutionary origin of the spinning ducts. PMID:24015298

Chitin-induced T6SS in Vibrio cholerae is dependent on ChiS activation.

Science.gov (United States)

Chourashi, Rhishita; Das, Suman; Dhar, Debarpan; Okamoto, Keinosuke; Mukhopadhyay, Asish K; Chatterjee, Nabendu Sekhar

2018-05-01

Vibrio cholerae regularly colonizes the chitinous exoskeleton of crustacean shells in the aquatic region. The type 6 secretion system (T6SS) in V. cholerae is an interbacterial killing device. This system is thought to provide a competitive advantage to V. cholerae in a polymicrobial community of the aquatic region under nutrient-poor conditions. V. cholerae chitin sensing is known to be initiated by the activation of a two-component sensor histidine kinase ChiS in the presence of GlcNAc2 (N,N'-diacetylchitobiose) residues generated by the action of chitinases on chitin. It is known that T6SS in V. cholerae is generally induced by chitin. However, the effect of ChiS activation on T6SS is unknown. Here, we found that ChiS inactivation resulted in impaired bacterial killing and reduced expression of T6SS genes. Active ChiS positively affected T6SS-mediated natural transformation in V. cholerae. ChiS depletion or inactivation also resulted in reduced colonization on insoluble chitin surfaces. Therefore, we have shown that V. cholerae colonization on chitinous surfaces activates ChiS, which promotes T6SS-dependent bacterial killing and horizontal gene transfer. We also highlight the importance of chitinases in T6SS upregulation.

Preparation of {sup 111}In-DTPA morpholino oligomer for low abdominal accumulation

Energy Technology Data Exchange (ETDEWEB)

Liu Guozheng, E-mail: guozheng.liu@umassmed.ed [Department of Radiology, University of Massachusetts Medical School, Worcester, MA 01655-0243 (United States); Dou Shuping; Rusckowski, Mary [Department of Radiology, University of Massachusetts Medical School, Worcester, MA 01655-0243 (United States); Greiner, Dale [Department of Medicine, University of Massachusetts Medical School, Worcester, MA 01655-0243 (United States); Hnatowich, Donald [Department of Radiology, University of Massachusetts Medical School, Worcester, MA 01655-0243 (United States)

2010-09-15

An ability to quantitate the beta cell mass by noninvasive nuclear imaging will be very useful in the prevention, diagnosis, and treatment of diabetes. However, to be successful, radioactivity from the pancreas must not be obscured by the background radioactivity in the abdomen. Pretargeting offers the promise of achieving high target organ to normal tissue ratios. In preparation for pancreas imaging studies by pretargeting using morpholino oligomers (MORF/cMORF), it was necessary to develop a simple and efficient method to radiolabel the cMORF effector. Because we have shown that labeling the cMORF with {sup 111}In via DTPA reduces excretion into the intestines compared to labeling with {sup 99m}Tc via MAG{sub 3}, the conjugation of DTPA to cMORF was investigated for {sup 111}In labeling. The amine-derivatized cMORF was conjugated with DTPA using 1-ethyl-3(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC) as an alternative to the conventional cyclic anhydride. The conjugation efficiency (represented by the number of DTPA groups attached per cMORF) was investigated by changing the EDC, DTPA, and cMORF molar ratios. Different open columns were considered for the purification of DTPA-cMORF. Before conjugation, each cMORF molecule was confirmed to have an amine by trinitrobenzene sulfonic acid (TNBS) assay using the {omega}-amino butyric acid as positive standard and the non-amine derivatized cMORF as negative standard. The average number of DTPA groups per cMORF was 0.15-0.20 following the conjugation over a cMORF/DTPA molar ratio of 0.5-5 and over a cMORF/EDC molar ratio of 20-60. The conjugation efficiency was lower than expected probably due to steric hindrance. A 1x50 cm P-4 column using ammonium acetate as eluting buffer provided an adequate separation of DTPA-cMORF from free DTPA. The {sup 111}In labeling efficiency by transchelation from acetate exceeded 95%, thus avoiding the need for postlabeling purification. Despite the lower than expected conjugation

Extreme biomimetic approach for synthesis of nanocrystalline chitin-(Ti,Zr)O2 multiphase composites

International Nuclear Information System (INIS)

Wysokowski, Marcin; Motylenko, Mykhaylo; Rafaja, David; Koltsov, Iwona; Stöcker, Hartmut; Szalaty, Tadeusz J.; Bazhenov, Vasilii V.; Stelling, Allison L.; Beyer, Jan; Heitmann, Johannes; Jesionowski, Teofil; Petovic, Slavica; Đurović, Mirko; Ehrlich, Hermann

2017-01-01

This work presents an extreme biomimetics route for the modification of the surface of fibre-based scaffolds of poriferan origin by the creation of novel nanostructured multiphase biocomposites. The exceptional thermal stability of the nanostructured sponge chitin allowed for the formation of a novel nanocrystalline chitin-(Ti,Zr)O 2 composite with a well-defined nanoscale structure under hydrothermal conditions (160 °C). Using a combination of experimental techniques, including X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, EDX mapping and near-edge electron loss spectroscopy (ELNES) in TEM and thermogravimetry/differential scanning calorimetry coupled with mass spectrometry; we showed that this bioorganic scaffold facilitates selective crystallization of TiO 2 , predominantly in form of anatase, over the monoclinic zirconium dioxide (baddeleyite). The control of the crystal morphology through the chitin templates is also demonstrated. Obtained samples were characterized in terms of their photoluminescent properties and photocatalytic performance. These data confirm the high potential of the extreme biomimetics approach for developing a new generation of multiphase biopolymer-based nanostructured materials. - Highlights: • Extreme biomimetically prepared chitin-(Ti,Zr)O 2 and (Ti,Zr)O 2 composites. • Chitin-(Ti,Zr)O 2 composite contains anatase as the most inorganic component. • The mean crystallite size is (31.7 ± 0.3) nm for chitin-(Ti,Zr)O 2 composite. • The mean crystallite size is (2.4 ± 0.5) nm for (Ti,Zr)O 2 composite. • (Ti,Zr)O 2 composite is 2 times more effective photocatalyst than chitin-(Ti,Zr)O 2 .

α-Synuclein oligomers induced by docosahexaenoic acid affect membrane integrity.

Directory of Open Access Journals (Sweden)

Chiara Fecchio

Full Text Available A key feature of Parkinson disease is the aggregation of α-synuclein and its intracellular deposition in fibrillar form. Increasing evidence suggests that the pathogenicity of α-synuclein is correlated with the activity of oligomers formed in the early stages of its aggregation process. Oligomers toxicity seems to be associated with both their ability to bind and affect the integrity of lipid membranes. Previously, we demonstrated that α-synuclein forms oligomeric species in the presence of docosahexaenoic acid and that these species are toxic to cells. Here we studied how interaction of these oligomers with membranes results in cell toxicity, using cellular membrane-mimetic and cell model systems. We found that α-synuclein oligomers are able to interact with large and small unilamellar negatively charged vesicles acquiring an increased amount of α-helical structure, which induces small molecules release. We explored the possibility that oligomers effects on membranes could be due to pore formation, to a detergent-like effect or to fibril growth on the membrane. Our biophysical and cellular findings are consistent with a model where α-synuclein oligomers are embedded into the lipid bilayer causing transient alteration of membrane permeability.

Amyloid-β oligomer detection by ELISA in cerebrospinal fluid and brain tissue.

Science.gov (United States)

Bruggink, Kim A; Jongbloed, Wesley; Biemans, Elisanne A L M; Veerhuis, Rob; Claassen, Jurgen A H R; Kuiperij, H Bea; Verbeek, Marcel M

2013-02-15

Amyloid-β (Aβ) deposits are important pathological hallmarks of Alzheimer's disease (AD). Aβ aggregates into fibrils; however, the intermediate oligomers are believed to be the most neurotoxic species and, therefore, are of great interest as potential biomarkers. Here, we have developed an enzyme-linked immunosorbent assay (ELISA) specific for Aβ oligomers by using the same capture and (labeled) detection antibody. The ELISA predominantly recognizes relatively small oligomers (10-25 kDa) and not monomers. In brain tissue of APP/PS1 transgenic mice, we found that Aβ oligomer levels increase with age. However, for measurements in human samples, pretreatment to remove human anti-mouse antibodies (HAMAs) was required. In HAMA-depleted human hippocampal extracts, the Aβ oligomer concentration was significantly increased in AD compared with nondemented controls. Aβ oligomer levels could also be quantified in pretreated cerebrospinal fluid (CSF) samples; however, no difference was detected between AD and control groups. Our data suggest that levels of small oligomers might not be suitable as biomarkers for AD. In addition, we demonstrate the importance of avoiding HAMA interference in assays to quantify Aβ oligomers in human body fluids. Copyright © 2012 Elsevier Inc. All rights reserved.

Derivatization reagents in liquid chromatography/electrospray ionization tandem mass spectrometry.

Science.gov (United States)

Santa, Tomofumi

2011-01-01

Liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is one of the most prominent analytical techniques owing to its inherent selectivity and sensitivity. In LC/ESI-MS/MS, chemical derivatization is often used to enhance the detection sensitivity. Derivatization improves the chromatographic separation, and enhances the mass spectrometric ionization efficiency and MS/MS detectability. In this review, an overview of the derivatization reagents which have been applied to LC/ESI-MS/MS is presented, focusing on the applications to low molecular weight compounds. 2010 John Wiley & Sons, Ltd.

The Plasmodiophora brassicae genome reveals insights in its life cycle and ancestry of chitin synthases.

Science.gov (United States)

Schwelm, Arne; Fogelqvist, Johan; Knaust, Andrea; Jülke, Sabine; Lilja, Tua; Bonilla-Rosso, German; Karlsson, Magnus; Shevchenko, Andrej; Dhandapani, Vignesh; Choi, Su Ryun; Kim, Hong Gi; Park, Ju Young; Lim, Yong Pyo; Ludwig-Müller, Jutta; Dixelius, Christina

2015-06-18

Plasmodiophora brassicae causes clubroot, a major disease of Brassica oil and vegetable crops worldwide. P. brassicae is a Plasmodiophorid, obligate biotrophic protist in the eukaryotic kingdom of Rhizaria. Here we present the 25.5 Mb genome draft of P. brassicae, developmental stage-specific transcriptomes and a transcriptome of Spongospora subterranea, the Plasmodiophorid causing powdery scab on potato. Like other biotrophic pathogens both Plasmodiophorids are reduced in metabolic pathways. Phytohormones contribute to the gall phenotypes of infected roots. We report a protein (PbGH3) that can modify auxin and jasmonic acid. Plasmodiophorids contain chitin in cell walls of the resilient resting spores. If recognized, chitin can trigger defense responses in plants. Interestingly, chitin-related enzymes of Plasmodiophorids built specific families and the carbohydrate/chitin binding (CBM18) domain is enriched in the Plasmodiophorid secretome. Plasmodiophorids chitin synthases belong to two families, which were present before the split of the eukaryotic Stramenopiles/Alveolates/Rhizaria/Plantae and Metazoa/Fungi/Amoebozoa megagroups, suggesting chitin synthesis to be an ancient feature of eukaryotes. This exemplifies the importance of genomic data from unexplored eukaryotic groups, such as the Plasmodiophorids, to decipher evolutionary relationships and gene diversification of early eukaryotes.

Preparation of metal adsorbents from chitin/chitosan by radiation technology

International Nuclear Information System (INIS)

Nguyen Van Suc; Nguyen Quoc Hien; Ngo Quang Huy; Thai My Phe; Dao Van Hoang; Nguyen Van Hung

2004-01-01

The methods of preparation of metal adsorbents basing on chitin/chitosan were developed. That include the adsorbent from chitin grafted with acrylic acid by different irradiation doses; the clinging chitosan gel beads; the coagulable solution and the chitosan composite filter. The process of metal adsorption for each adsorbent was studied as adsorption kinetic, isothermal adsorption. The results have been applied for removal of some elements as Hg, Pb, Cd, U, Cu, ect. in the wastewater. (NHA)

Diseño y validación de un nuevo método para estimar reductores hidrosolubles asociados con la quitina Design and validation of a new method for estimation of water-soluble reducers associated with chitin

Directory of Open Access Journals (Sweden)

Yania Suárez Pérez

2005-12-01

Full Text Available Se desarrolló por primera vez un método espectrofotométrico para estimar reductores hidrosolubles asociados con la quitina materia prima. Para el ajuste del método se utilizó glucosamina como sustancia de referencia. Las determinaciones se realizaron a 330 nm que fue la longitud de onda de máxima absorción. Se seleccionó como tiempo óptimo de calentamiento 5 min y se verificó la selectividad de la respuesta analítica. Se demostró el cumplimiento de la ley de Lambert-Beer en el intervalo de 100-300 mg/mL. Se obtuvo un extracto acuoso a partir de quitina materia prima procesado para eliminar posibles interferencias, el cual se empleó como control en la validación del método. El método fue lineal, exacto y preciso en el intervalo estudiado. El límite de detección fue de 25,21 mg/mL y el de cuantificación de 65,45 mg/mL.For the first time, a spectrophotometric method to estimate water-soluble reducers associated with raw material chitin was developed. For the purpose of adjusting the method, glucosamine as a reference substance was used. The estimations were made at 330 nm that was the wavelength of maximum absorption. The selected optimal heating time was 5 min; the selectivity of analytical response was checked. The Lambert-Beer law was demonstrated in the 100-300 mg/mL interval. An aqueous extract from raw material chitin was obtained and then processed to eliminate possible interference and be used as a control for the method validation. The method was linear, exact and accurate in the studied interval. The detection limit was 25,21 mg/mL and the quantification limit was 65,45 mg/mL.

Metabolic engineering of the morphology of Aspergillus oryzae by altering chitin synthesis

DEFF Research Database (Denmark)

Muller, C.; Mcintyre, Mhairi; Hansen, Kim

2002-01-01

Morphology and alpha-amylase production during submerged cultivation were examined in a wild-type strain (A1560) and in strains of Aspergillus oryzae in which chitin synthase B (chsB) and chitin synthesis myosin A (csmA) have been disrupted (ChsB/G and CM101). In a flowthrough cell, the growth...

Process for derivatizing carbon nanotubes with diazonium species

Science.gov (United States)

Tour, James M. (Inventor); Bahr, Jeffrey L. (Inventor); Yang, Jiping (Inventor)

2007-01-01

The invention incorporates new processes for the chemical modification of carbon nanotubes. Such processes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications and sensor devices. The methods of derivatization include electrochemical induced reactions thermally induced reactions (via in-situ generation of diazonium compounds or pre-formed diazonium compounds), and photochemically induced reactions. The derivatization causes significant changes in the spectroscopic properties of the nanotubes. The estimated degree of functionality is ca. 1 out of every 20 to 30 carbons in a nanotube bearing a functionality moiety. Such electrochemical reduction processes can be adapted to apply site-selective chemical functionalization of nanotubes. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes ##STR00001##.

Evaluation of Chitin as Natural Coagulant in Water Treatment

Directory of Open Access Journals (Sweden)

V. Saritha

2012-04-01

Full Text Available The use of synthetic coagulants is not regarded as suitable due to health and economic considerations. The present study was aimed to investigate the effects of alum as coagulant in conjunction with chitin as coagulant aid on the removal of turbidity, hardness and Escherichia coli from water. A conventional jar test apparatus was employed for the tests. The experiment was conducted at three different pH conditions of 6, 7 and 8. The dosages chosen were 0.5, 1, 1.5 and 2mg/l. The results showed that turbidity decrease provided also a primary Escherichia coli reduction. Hardness removal efficiency was observed to be 93% at pH 7 with 1mg/l concentration by alum whereas chitin was stable at all the pH ranges showing highest removal at 1 and 1.5mg/l with pH 7. At low concentration chitin showed marginally better performance on hardness. In conclusion, using natural coagulants results in considerable savings in chemicals and sludge handling cost may be achieved.

First Report on Chitin in a Non-Verongiid Marine Demosponge: The Mycale euplectellioides Case.

Science.gov (United States)

Żółtowska-Aksamitowska, Sonia; Shaala, Lamiaa A; Youssef, Diaa T A; Elhady, Sameh S; Tsurkan, Mikhail V; Petrenko, Iaroslav; Wysokowski, Marcin; Tabachnick, Konstantin; Meissner, Heike; Ivanenko, Viatcheslav N; Bechmann, Nicole; Joseph, Yvonne; Jesionowski, Teofil; Ehrlich, Hermann

2018-02-20

Sponges (Porifera) are recognized as aquatic multicellular organisms which developed an effective biochemical pathway over millions of years of evolution to produce both biologically active secondary metabolites and biopolymer-based skeletal structures. Among marine demosponges, only representatives of the Verongiida order are known to synthetize biologically active substances as well as skeletons made of structural polysaccharide chitin. The unique three-dimensional (3D) architecture of such chitinous skeletons opens the widow for their recent applications as adsorbents, as well as scaffolds for tissue engineering and biomimetics. This study has the ambitious goal of monitoring other orders beyond Verongiida demosponges and finding alternative sources of naturally prestructured chitinous scaffolds; especially in those demosponge species which can be cultivated at large scales using marine farming conditions. Special attention has been paid to the demosponge Mycale euplectellioides (Heteroscleromorpha: Poecilosclerida: Mycalidae) collected in the Red Sea. For the first time, we present here a detailed study of the isolation of chitin from the skeleton of this sponge, as well as its identification using diverse bioanalytical tools. Calcofluor white staining, Fourier-transform Infrared Spcetcroscopy (FTIR), electrospray ionization mass spectrometry (ESI-MS), scanning electron microscopy (SEM), and fluorescence microscopy, as well as a chitinase digestion assay were applied in order to confirm with strong evidence the finding of a-chitin in the skeleton of M. euplectellioides . We suggest that the discovery of chitin within representatives of the Mycale genus is a promising step in their evaluation of these globally distributed sponges as new renewable sources for both biologically active metabolites and chitin, which are of prospective use for pharmacology and biomaterials oriented biomedicine, respectively.

First Report on Chitin in a Non-Verongiid Marine Demosponge: The Mycale euplectellioides Case

Directory of Open Access Journals (Sweden)

Sonia Żółtowska-Aksamitowska

2018-02-01

Full Text Available Sponges (Porifera are recognized as aquatic multicellular organisms which developed an effective biochemical pathway over millions of years of evolution to produce both biologically active secondary metabolites and biopolymer-based skeletal structures. Among marine demosponges, only representatives of the Verongiida order are known to synthetize biologically active substances as well as skeletons made of structural polysaccharide chitin. The unique three-dimensional (3D architecture of such chitinous skeletons opens the widow for their recent applications as adsorbents, as well as scaffolds for tissue engineering and biomimetics. This study has the ambitious goal of monitoring other orders beyond Verongiida demosponges and finding alternative sources of naturally prestructured chitinous scaffolds; especially in those demosponge species which can be cultivated at large scales using marine farming conditions. Special attention has been paid to the demosponge Mycale euplectellioides (Heteroscleromorpha: Poecilosclerida: Mycalidae collected in the Red Sea. For the first time, we present here a detailed study of the isolation of chitin from the skeleton of this sponge, as well as its identification using diverse bioanalytical tools. Calcofluor white staining, Fourier-transform Infrared Spcetcroscopy (FTIR, electrospray ionization mass spectrometry (ESI-MS, scanning electron microscopy (SEM, and fluorescence microscopy, as well as a chitinase digestion assay were applied in order to confirm with strong evidence the finding of a-chitin in the skeleton of M. euplectellioides. We suggest that the discovery of chitin within representatives of the Mycale genus is a promising step in their evaluation of these globally distributed sponges as new renewable sources for both biologically active metabolites and chitin, which are of prospective use for pharmacology and biomaterials oriented biomedicine, respectively.

Thin-film Nanofibrous Composite Membranes Containing Cellulose or Chitin Barrier Layers Fabricated by Ionic Liquids

Energy Technology Data Exchange (ETDEWEB)

H Ma; B Hsiao; B Chu

2011-12-31

The barrier layer of high-flux ultrafiltration (UF) thin-film nanofibrous composite (TFNC) membranes for purification of wastewater (e.g., bilge water) have been prepared by using cellulose, chitin, and a cellulose-chitin blend, regenerated from an ionic liquid. The structures and properties of regenerated cellulose, chitin, and a cellulose-chitin blend were analyzed with thermogravimetric analysis (TGA) and wide-angle X-ray diffraction (WAXD). The surface morphology, pore size and pore size distribution of TFNC membranes were determined by SEM images and molecular weight cut-off (MWCO) methods. An oil/water emulsion, a model of bilge water, was used as the feed solution, and the permeation flux and rejection ratio of the membranes were investigated. TFNC membranes based on the cellulose-chitin blend exhibited 10 times higher permeation flux when compared with a commercial UF membrane (PAN10, Sepro) with a similar rejection ratio after filtration over a time period of up to 100 h, implying the practical feasibility of such membranes for UF applications.

Application of chitin and zeolite adsorbents for treatment of low level radioactive liquid wastes

International Nuclear Information System (INIS)

Moattar, F.; Hayeripour, S.

2004-01-01

Two types of shrimp chitin derivatives and two types of Iranian natural zeolite derivates were studied for adsorption and treatment of low-level radioactive liquid waste. Chitin with lowers than 10% and chitosan with higher than 90% deacetylation factor were selected as neutral organic adsorbents. Natural clinoptilolite of Firuzkooh area and Na from derivates of it were selected as natural inorganic adsorbents. The static and dynamic ion exchange experimental results show that the ad adsorption efficiency depend on particle size, Ph, adsorbent type, deacetylation factor ( in chitin adsorbents) and cation type. The best Cs adsorption occurred in Na from clinoptilolite. Nevertheless chitin derivatives, particularly chitosan, are more efficient than zeolite adsorbents for removing of radionuclides such as 137 Cs, 54 Mn, 90 Sr and 60 Co. Adsorption performance was discussed and compared with each other

Bacterial chitinolytic communities respond to chitin and pH alteration in soil

DEFF Research Database (Denmark)

Kielak, Anna; Cretoiu, Mariana; Semenov, Alexander

2013-01-01

by the addition of chitin at different prevailing soil pH values. Interestingly, a major role of Gram-negative bacteria versus a minor one of Actinobacteria in the immediate response to the added chitin (based on 16S rRNA gene abundance and chiA gene types) was indicated. The results of this study enhance our...

Biosorption of gold from computer microprocessor leachate solutions using chitin.

Science.gov (United States)

Côrtes, Letícia N; Tanabe, Eduardo H; Bertuol, Daniel A; Dotto, Guilherme L

2015-11-01

The biosorption of gold from discarded computer microprocessor (DCM) leachate solutions was studied using chitin as a biosorbent. The DCM components were leached with thiourea solutions, and two procedures were tested for recovery of gold from the leachates: (1) biosorption and (2) precipitation followed by biosorption. For each procedure, the biosorption was evaluated considering kinetic, equilibrium, and thermodynamic aspects. The general order model was able to represent the kinetic behavior, and the equilibrium was well represented by the BET model. The maximum biosorption capacities were around 35 mg g(-1) for both procedures. The biosorption of gold on chitin was a spontaneous, favorable, and exothermic process. It was found that precipitation followed by biosorption resulted in the best gold recovery, because other species were removed from the leachate solution in the precipitation step. This method enabled about 80% of the gold to be recovered, using 20 g L(-1) of chitin at 298 K for 4 h. Copyright © 2015 Elsevier Ltd. All rights reserved.

Chitin Synthases with a Myosin Motor-Like Domain Control the Resistance of Aspergillus fumigatus to Echinocandins

Science.gov (United States)

Jiménez-Ortigosa, Cristina; Aimanianda, Vishukumar; Muszkieta, Laetitia; Mouyna, Isabelle; Alsteens, David; Pire, Stéphane; Beau, Remi; Krappmann, Sven; Beauvais, Anne; Dufrêne, Yves F.

2012-01-01

Aspergillus fumigatus has two chitin synthases (CSMA and CSMB) with a myosin motor-like domain (MMD) arranged in a head-to-head configuration. To understand the function of these chitin synthases, single and double csm mutant strains were constructed and analyzed. Although there was a slight reduction in mycelial growth of the mutants, the total chitin synthase activity and the cell wall chitin content were similar in the mycelium of all of the mutants and the parental strain. In the conidia, chitin content in the ΔcsmA strain cell wall was less than half the amount found in the parental strain. In contrast, the ΔcsmB mutant strain and, unexpectedly, the ΔcsmA/ΔcsmB mutant strain did not show any modification of chitin content in their conidial cell walls. In contrast to the hydrophobic conidia of the parental strain, conidia of all of the csm mutants were hydrophilic due to the presence of an amorphous material covering the hydrophobic surface-rodlet layer. The deletion of CSM genes also resulted in an increased susceptibility of resting and germinating conidia to echinocandins. These results show that the deletion of the CSMA and CSMB genes induced a significant disorganization of the cell wall structure, even though they contribute only weakly to the overall cell wall chitin synthesis. PMID:22964252

Star-shaped tetrathiafulvalene oligomers towards the construction of conducting supramolecular assembly.

Science.gov (United States)

Iyoda, Masahiko; Hasegawa, Masashi

2015-01-01

The construction of redox-active supramolecular assemblies based on star-shaped and radially expanded tetrathiafulvalene (TTF) oligomers with divergent and extended conjugation is summarized. Star-shaped TTF oligomers easily self-aggregate with a nanophase separation to produce supramolecular structures, and their TTF units stack face-to-face to form columnar structures using the fastener effect. Based on redox-active self-organizing supramolecular structures, conducting nanoobjects are constructed by doping of TTF oligomers with oxidants after the formation of such nanostructures. Although radical cations derived from TTF oligomers strongly interact in solution to produce a mixed-valence dimer and π-dimer, it seems to be difficult to produce nanoobjects of radical cations different from those of neutral TTF oligomers. In some cases, however, radical cations form nanostructured fibers and rods by controlling the supramolecular assembly, oxidation states, and counter anions employed.

Altering the expression of two chitin synthase genes differentially affects the growth and morphology of Aspergillus oryzae

DEFF Research Database (Denmark)

Müller, Christian; Hjort, C.M.; Hansen, K.

2002-01-01

In Aspergillus oryzae, one full-length chitin synthase (chsB) and fragments of two other chitin synthases (csmA and chsC) were identified. The deduced amino acid sequence of chsB was similar (87% identity) to chsB from Aspergillus nidulans, which encodes a class III chitin synthase. The sequence...

Oligomers and Polymers Based on Pentacene Building Blocks

Science.gov (United States)

Lehnherr, Dan; Tykwinski, Rik R.

2010-01-01

Functionalized pentacene derivatives continue to provide unique materials for organic semiconductor applications. Although oligomers and polymers based on pentacene building blocks remain quite rare, recent synthetic achievements have provided a number of examples with varied structural motifs. This review highlights recent work in this area and, when possible, contrasts the properties of defined-length pentacene oligomers to those of mono- and polymeric systems.

Automated precolumn derivatization procedures in HPLC for biomedical and clinical applications

NARCIS (Netherlands)

Wolf, Johannes Hendrik

1992-01-01

This thesis describes three automated precolumn derivatization procedures for the analysis of carboxylic group-containing compounds. After derivatization with a suitable label, the derivatives are separated on reversed-phashed HPLC and detected by fluorescence. ... Zie: Summary

The hard parts (trophi) of the rotifer mastax do contain chitin: evidence from studies on Brachionus plicatilis.

Science.gov (United States)

Klusemann, J; Kleinow, W; Peters, W

1990-01-01

The jaws (trophi) of the rotifer Brachionus plicatilis are soluble in strong acids but are resistant to long treatments by strong alkali. They show the same buoyant density as chitin and also as the chitin-containing layers of rotifer egg-shells. The presence of chitin in these structures was confirmed using the following techniques: chitosan-tests, thin-layer chromatography of trophi-hydrolysates which revealed glucosamine, by dissolving trophi with chitinase and electron microscopic WGA/gold-labelling. The content of chitin in the trophi was estimated by two different methods to be approx. 64% (50-75%).

Radiation curable oligomers

International Nuclear Information System (INIS)

Huemmer, T.F.; Edison, B.A.

1977-01-01

A process is described for the high energy radiation curing of oligomers for use as coatings. The method is particularly applicable to the reaction products of certain low molecular weight epoxy compounds and certain low molecular weight mono-hydroxy vinyl compounds having at least one vinylic unsaturation. The curable mixture is applied as a thin film and cured very quickly

Electrorheology of aniline oligomers

Czech Academy of Sciences Publication Activity Database

Mrlík, M.; Sedlačík, M.; Pavlínek, V.; Bober, Patrycja; Trchová, Miroslava; Stejskal, Jaroslav; Sáha, P.

2013-01-01

Roč. 291, č. 9 (2013), s. 2079-2086 ISSN 0303-402X R&D Projects: GA ČR GA202/09/1626 Institutional support: RVO:61389013 Keywords : anilin e oligomers * polyaniline * electrorheology Subject RIV: JI - Composite Materials Impact factor: 2.410, year: 2013

Production of High Viscosity Chitosan from Biologically Purified Chitin Isolated by Microbial Fermentation and Deproteinization

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Ekkalak Ploydee

2014-01-01

Full Text Available The objective of this study was to produce high viscosity chitosan from shrimp chitin prepared by using a two-step biological treatment process: decalcification and deproteinization. Glucose was fermented with Lactobacillus pentosus L7 to lactic acid. At a pH of 3.9±0.1, the calcium carbonate of the shells was solubilized in 48 hours. The amounts of residual calcium in the form of ash (1.4±0.5% and crude protein (23.2±2.5% were further eliminated by the activity of proteolytic Bacillus thuringiensis SA. After decalcification and deproteinization of the shrimp shells, residual calcium and crude protein of shrimp chitin flakes were 1.7±0.4% and 3.8±1.3%, respectively. Chitin was deacetylated with 50% NaOH at 121°C for 5 hours. After deacetylation, the chitosan had residual calcium, crude protein content, and degree of acetylation of 1.6±0.6%, 0.4±0.3%, and 83.2±1.5%, respectively. The viscosity of chitosan prepared from chitin extracted by this two-step biological process was 1,007±14.7 mPa·s, whereas chitosan prepared from chemically processed chitin had a viscosity of 323±15.6   mPa·s, indicating that biologically purified chitin gave chitosan with a high quality.

Oligomers and Polymers Based on Pentacene Building Blocks

Directory of Open Access Journals (Sweden)

Dan Lehnherr

2010-04-01

Full Text Available Functionalized pentacene derivatives continue to provide unique materials for organic semiconductor applications. Although oligomers and polymers based on pentacene building blocks remain quite rare, recent synthetic achievements have provided a number of examples with varied structural motifs. This review highlights recent work in this area and, when possible, contrasts the properties of defined-length pentacene oligomers to those of mono- and polymeric systems.

Extreme biomimetic approach for synthesis of nanocrystalline chitin-(Ti,Zr)O{sub 2} multiphase composites

Energy Technology Data Exchange (ETDEWEB)

Wysokowski, Marcin, E-mail: Marcin.Wysokowski@put.poznan.pl [Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Berdychowo 4, 60965, Poznan (Poland); Motylenko, Mykhaylo; Rafaja, David [TU Bergakademie Freiberg, Institute of Materials Science, Gustav-Zeuner-Str. 5, 09596, Freiberg (Germany); Koltsov, Iwona [Laboratory of Nanostructures, Institute of High Pressure Physics of The Polish Academy of Sciences, Sokołowska 29/37, 01-142, Warsaw (Poland); Stöcker, Hartmut [TU Bergakademie Freiberg, Institute of Experimental Physics, Leipziger str. 23, 09596, Freiberg (Germany); Szalaty, Tadeusz J. [Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Berdychowo 4, 60965, Poznan (Poland); Bazhenov, Vasilii V., E-mail: vasily.bazhenov@gmail.com [TU Bergakademie Freiberg, Institute of Experimental Physics, Leipziger str. 23, 09596, Freiberg (Germany); Stelling, Allison L. [Duke University, Department of Biochemistry, Durham, NC, 27708 (United States); Beyer, Jan; Heitmann, Johannes [TU Bergakademie Freiberg, Institute of Applied Physics, Leipziger str. 23, 09596, Freiberg (Germany); Jesionowski, Teofil [Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemical Technology and Engineering, Berdychowo 4, 60965, Poznan (Poland); Petovic, Slavica; Đurović, Mirko [Institute of Marine Biology, Dobrota, 85330, Kotor (Montenegro); Ehrlich, Hermann [TU Bergakademie Freiberg, Institute of Experimental Physics, Leipziger str. 23, 09596, Freiberg (Germany)

2017-02-15

This work presents an extreme biomimetics route for the modification of the surface of fibre-based scaffolds of poriferan origin by the creation of novel nanostructured multiphase biocomposites. The exceptional thermal stability of the nanostructured sponge chitin allowed for the formation of a novel nanocrystalline chitin-(Ti,Zr)O{sub 2} composite with a well-defined nanoscale structure under hydrothermal conditions (160 °C). Using a combination of experimental techniques, including X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, EDX mapping and near-edge electron loss spectroscopy (ELNES) in TEM and thermogravimetry/differential scanning calorimetry coupled with mass spectrometry; we showed that this bioorganic scaffold facilitates selective crystallization of TiO{sub 2}, predominantly in form of anatase, over the monoclinic zirconium dioxide (baddeleyite). The control of the crystal morphology through the chitin templates is also demonstrated. Obtained samples were characterized in terms of their photoluminescent properties and photocatalytic performance. These data confirm the high potential of the extreme biomimetics approach for developing a new generation of multiphase biopolymer-based nanostructured materials. - Highlights: • Extreme biomimetically prepared chitin-(Ti,Zr)O{sub 2} and (Ti,Zr)O{sub 2} composites. • Chitin-(Ti,Zr)O{sub 2} composite contains anatase as the most inorganic component. • The mean crystallite size is (31.7 ± 0.3) nm for chitin-(Ti,Zr)O{sub 2} composite. • The mean crystallite size is (2.4 ± 0.5) nm for (Ti,Zr)O{sub 2} composite. • (Ti,Zr)O{sub 2} composite is 2 times more effective photocatalyst than chitin-(Ti,Zr)O{sub 2}.

Amyloid oligomers and protofibrils, but not filaments, self-replicate from native lysozyme.

Science.gov (United States)

Mulaj, Mentor; Foley, Joseph; Muschol, Martin

2014-06-25

Self-assembly of amyloid fibrils is the molecular mechanism best known for its connection with debilitating human disorders such as Alzheimer's disease but is also associated with various functional cellular responses. There is increasing evidence that amyloid formation proceeds along two distinct assembly pathways involving either globular oligomers and protofibrils or rigid monomeric filaments. Oligomers, in particular, have been implicated as the dominant molecular species responsible for pathogenesis. Yet the molecular mechanisms regulating their self-assembly have remained elusive. Here we show that oligomers/protofibrils and monomeric filaments, formed along distinct assembly pathways, display critical differences in their ability to template amyloid growth at physiological vs denaturing temperatures. At physiological temperatures, amyloid filaments remained stable but could not seed growth of native monomers. In contrast, oligomers and protofibrils not only remained intact but were capable of self-replication using native monomers as the substrate. Kinetic data further suggested that this prion-like growth mode of oligomers/protofibrils involved two distinct activities operating orthogonal from each other: autocatalytic self-replication of oligomers from native monomers and nucleated polymerization of oligomers into protofibrils. The environmental changes to stability and templating competence of these different amyloid species in different environments are likely to be important for understanding the molecular mechanisms underlying both pathogenic and functional amyloid self-assembly.

Characterization of chitin extracted from fish scales of marine fish species purchased from local markets in North Sulawesi, Indonesia

Science.gov (United States)

Rumengan, I. F. M.; Suptijah, P.; Wullur, S.; Talumepa, A.

2017-10-01

Chitin is a biodegradable biopolymer with a variety of commercial applications, including in the food food-supplement industries as a marine-derived nutraceutical. The purpose of this study was to characterize the molecular structure of chitin extracted from fish scales of important marine fish purchased from local markets in North Sulawesi. Chitin compound material was obtained from a specific fish scale, and then sequentially carrying out a boiling treatment to separate it from a complex with collagen. From the scales of two fish species, parrotfish (Chlorurus sordidus) and red snapper (Lutjanus argentimaculatus), the rendemen of chitin obtained were 45 % and 33%, respectively. Structural characteristics of the chitin were discussed by FTIR (Fourier Transform Infrared) analysis data. FTIR analysis was done using infrared spectroscopy, which is the resulting spectrum represents the molecular absorption and transmission, creating a molecular fingerprint of the sample. The molecular structure of chitin, C18H26N2O10, where the hydroxyl group on the second carbon replaced by acetyl amide, was shown by the infrared spectra. In the infrared spectra, chitin from parrot fish scales indicated the amide band at 1627.13 cm-1, and chitin from red snapper fish scales the amide band at 1648.09 cm-1 which are a typical one for marine chitin. The hydroxyl and amino bands at the ranged spectra up to 3500 cm-1. The yields of chitin isolated from fish scale were relatively huge. Some treatments are necessary to confirm the molecular conformation and deacetylation behavior. All products from the extraction of fish scales could be more accessible for structural modifications to develop biocompatible materials for pharmaceutical purposes.

Effects of lattice fluctuations on electronic transmission in metal/conjugated-oligomer/metal structures

International Nuclear Information System (INIS)

Yu, Z.G.; Smith, D.L.; Saxena, A.; Bishop, A.R.

1997-01-01

The electronic transmission across metal/conjugated-oligomer/metal structures in the presence of lattice fluctuations is studied for short oligomer chains. The lattice fluctuations are approximated by static white noise disorder. Resonant transmission occurs when the energy of an incoming electron coincides with a discrete electronic level of the oligomer. The corresponding transmission peak diminishes in intensity with increasing disorder strength. Because of disorder there is an enhancement of the electronic transmission for energies that lie within the electronic gap of the oligomer. If fluctuations are sufficiently strong, a transmission peak within the gap is found at the midgap energy E=0 for degenerate conjugated oligomers (e.g., trans-polyacetylene) and E≠0 for AB-type degenerate oligomers. These results can be interpreted in terms of soliton-antisoliton states created by lattice fluctuations. copyright 1997 The American Physical Society

In vitro degradation of porous nano-hydroxyapatite/collagen/PLLA scaffold reinforced by chitin fibres

International Nuclear Information System (INIS)

Li Xiaoming; Feng Qingling; Cui Fuzhai

2006-01-01

In this paper, a novel porous scaffold for bone tissue engineering was prepared with nano-hydroxyapatite/collagen/Poly-L-lactic acid (PLLA) composite reinforced by chitin fibres. To enhance the strength of the scaffold further, PLLA was linked with chitin fibres by Dicyclohexylcarbodimide (DCC). The structures of the reinforced scaffold with and without linking were characterized by Scanning Electron Microscopy (SEM). The chemical characteristics of the chitin fibres with and without linking were evaluated by Fourier-transformed infrared (FTIR) spectroscopy. The mechanical performance during degradation in vitro was investigated. The results indicated that the nano-hydroxyapatite/collagen/PLLA composite reinforced by chitin fibres with linking kept better mechanical properties than that of the composite without linking. These results denoted that the stronger interfacial bonding strength of the scaffold with linking could decrease the degradation rate in vitro. The reinforced composite with the link-treatment can be severed as a scaffold for bone tissue engineering

Study of Zn, Cd, and Pb Adsorption Using Chitin Extracted from Lobsters from Oman Sea

Directory of Open Access Journals (Sweden)

Alireza Sardashti

2015-10-01

Full Text Available Lobster shells from Konarak Port were collected in October 2002, purified, and dried for the purposes of the present study. Chitin was extracted from the shellsusing the common chemical processes of demineralization, proteinzation, and decolonization, beforepurificationwith 1% CH3COOH and 1% NaCl to obatin an extract containing 12% (w/w chitin. Chitin composition was determined using FT-IR, X-Ray powder diffraction, BET, and C.H.N.S analysis. The FT-IR spectrum of the extracted chitin was corresponded well to the Merck standard one, indicating that it is a linear polymer of N-acetyl-D- glucosamine on which metal ions can be adsorbed. Kinetic study of chitin’s reaction with Zn+2 at pH=6.75 and an ionic strength of 0.02 M indicated that adsorption equilibrium was reached within six hours of mixing. Adsorption Langmuir isotherms for a solution of Zn+2, Cd+2, and Pb+2 ions at an initial concentration of 2×10‒3 M were determined for an ionic strenght of 0.02 M, different pH levels, and at ambient temparature using the discontinued in-pot method. The maximum amounts of metal ions adsorbed on chitin at pH= 6.75 were measured to be 0.119 mol/kg for Cd+2, 0.714 mol/kg for Zn+2, and 1.630 mol/Kg for Pb+2. The overdyeing graphs, Cs= f (pH, show that the adsorption capacity of chitin is influenced by such factors as pH, reaction time, metal ion concantration, and adsorbent particle size. Thus, chitin as a non-toxic natural polymer may be highly recommended for water detoxification from heavy metal ions.

Deletion of a Chitin Synthase Gene in a Citric Acid Producing Strain of Aspergillus niger

Energy Technology Data Exchange (ETDEWEB)

Rinker, Torri E.; Baker, Scott E.

2007-01-29

Citric acid production by the filamentous fungus Aspergillus niger is carried out in a process that causes the organism to drastically alter its morphology. This altered morphology includes hyphal swelling and highly limited polar growth resulting in clumps of swollen cells that eventually aggregate into pellets of approximately 100 microns in diameter. In this pelleted form, A. niger has increased citric acid production as compared to growth in filamentous form. Chitin is a crucial component of the cell wall of filamentous fungi. Alterations in the deposition or production of chitin may have profound effects on the morphology of the organism. In order to study the role of chitin synthesis in pellet formation we have deleted a chitin synthase gene (csmA) in Aspergillus niger strain ATCC 11414 using a PCR based deletion construct. This class of chitin synthases is only found in filamentous fungi and is not present in yeasts. The csmA genes contain a myosin motor domain at the N-terminus and a chitin synthesis domain at the C-terminus. They are believed to contribute to the specialized polar growth observed in filamentous fungi that is lacking in yeasts. The csmA deletion strain (csmAΔ) was subjected to minimal media with and without osmotic stabilizers as well as tested in citric acid production media. Without osmotic stabilizers, the mutant germlings were abnormally swollen, primarily in the subapical regions, and contained large vacuoles. However, this swelling is ultimately not inhibitory to growth as the germlings are able to recover and undergo polar growth. Colony formation was largely unaffected in the absence of osmotic stabilizers. In citric acid production media csmAΔ was observed to have a 2.5 fold increase in citric acid production. The controlled expression of this class of chitin synthases may be useful for improving production of organic acids in filamentous fungi.

Chitin's Functionality as a Novel Disintegrant: Benchmarking Against Commonly Used Disintegrants in Different Physicochemical Environments.

Science.gov (United States)

Chaheen, Mohammad; Soulairol, Ian; Bataille, Bernard; Yassine, Ahmad; Belamie, Emmanuel; Sharkawi, Tahmer

2017-07-01

Disintegrants are used as excipients to ensure rapid disintegration of pharmaceutical tablets and further ensure proper dissolution of the active pharmaceutical ingredient. This study investigates disintegration mechanisms of chitin and common disintegrants. Swelling assessment (swelling force and swelling ratio) in different media, and compaction behavior (pure or mixed with other excipients) tabletability, deformation (Heckel modeling), and compact disintegration times were investigated on the tested disintegrants (alginic acid calcium salt, crospovidone, sodium starch glycolate, croscarmellose sodium, and chitin). Results show that the physicochemical properties of the disintegration medium such as pH and ionic strength, as well as other formulation ingredients, affect the disintegrant functionalities. Heckel analysis using the mean yield pressure "Py" shows that alginic acid calcium salt is the most brittle among the studied disintegrants, while crospovidone has the most plastic deformation mechanism, followed by chitin. Chitin showed good tabletability and disintegration properties that were not influenced by the physicochemical formulation environment. Chitin is largely available and easily modifiable and thus a promising material that could be used as a multifunctional excipient in tablet formulation. Copyright © 2017 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Chitin and Chitosan Preparation from Marine Sources. Structure, Properties and Applications

Science.gov (United States)

Younes, Islem; Rinaudo, Marguerite

2015-01-01

This review describes the most common methods for recovery of chitin from marine organisms. In depth, both enzymatic and chemical treatments for the step of deproteinization are compared, as well as different conditions for demineralization. The conditions of chitosan preparation are also discussed, since they significantly impact the synthesis of chitosan with varying degree of acetylation (DA) and molecular weight (MW). In addition, the main characterization techniques applied for chitin and chitosan are recalled, pointing out the role of their solubility in relation with the chemical structure (mainly the acetyl group distribution along the backbone). Biological activities are also presented, such as: antibacterial, antifungal, antitumor and antioxidant. Interestingly, the relationship between chemical structure and biological activity is demonstrated for chitosan molecules with different DA and MW and homogeneous distribution of acetyl groups for the first time. In the end, several selected pharmaceutical and biomedical applications are presented, in which chitin and chitosan are recognized as new biomaterials taking advantage of their biocompatibility and biodegradability. PMID:25738328

Treatment of chitin-producing wastewater by micro-electrolysis-contact oxidization.

Science.gov (United States)

Yang, Yue-ping; Xu, Xin-hua; Chen, Hai-feng

2004-04-01

The technique of micro-electrolysis-contact oxidization was exploited to treat chitin-producing wastewater. Results showed that Fe-C micro-electrolysis can remove about 30% COD(cr), raise pH from 0.7 to 5.5. The COD(cr) removal efficiency by biochemical process can be more than 80%. During a half year's operation, the whole system worked very stably and had good results, as proved by the fact that every quality indicator of effluent met the expected discharge standards; which means that chitin wastewater can be treated by the technique of micro-electrolysis, contact oxidization.

Current Status and New Perspectives on Chitin and Chitosan as Functional Biopolymers.

Science.gov (United States)

Philibert, Tuyishime; Lee, Byong H; Fabien, Nsanzabera

2017-04-01

The natural biopolymer chitin and its deacetylated product chitosan are found abundantly in nature as structural building blocks and are used in all sectors of human activities like materials science, nutrition, health care, and energy. Far from being fully recognized, these polymers are able to open opportunities for completely novel applications due to their exceptional properties which an economic value is intrinsically entrapped. On a commercial scale, chitosan is mainly obtained from crustacean shells rather than from the fungal and insect sources. Significant efforts have been devoted to commercialize chitosan extracted from fungal and insect sources to completely replace crustacean-derived chitosan. However, the traditional chitin extraction processes are laden with many disadvantages. The present review discusses the potential bioextraction of chitosan from fungal, insect, and crustacean as well as its superior physico-chemical properties. The different aspects of fungal, insects, and crustacean chitosan extraction methods and various parameters having an effect on the yield of chitin and chitosan are discussed in detail. In addition, this review also deals with essential attributes of chitosan for high value-added applications in different fields and highlighted new perspectives on the production of chitin and deacetylated chitosan from different sources with the concomitant reduction of the environmental impact.

Tau oligomers impair memory and induce synaptic and mitochondrial dysfunction in wild-type mice

Directory of Open Access Journals (Sweden)

Jackson George R

2011-06-01

Full Text Available Abstract Background The correlation between neurofibrillary tangles of tau and disease progression in the brains of Alzheimer's disease (AD patients remains an area of contention. Innovative data are emerging from biochemical, cell-based and transgenic mouse studies that suggest that tau oligomers, a pre-filament form of tau, may be the most toxic and pathologically significant tau aggregate. Results Here we report that oligomers of recombinant full-length human tau protein are neurotoxic in vivo after subcortical stereotaxic injection into mice. Tau oligomers impaired memory consolidation, whereas tau fibrils and monomers did not. Additionally, tau oligomers induced synaptic dysfunction by reducing the levels of synaptic vesicle-associated proteins synaptophysin and septin-11. Tau oligomers produced mitochondrial dysfunction by decreasing the levels of NADH-ubiquinone oxidoreductase (electron transport chain complex I, and activated caspase-9, which is related to the apoptotic mitochondrial pathway. Conclusions This study identifies tau oligomers as an acutely toxic tau species in vivo, and suggests that tau oligomers induce neurodegeneration by affecting mitochondrial and synaptic function, both of which are early hallmarks in AD and other tauopathies. These results open new avenues for neuroprotective intervention strategies of tauopathies by targeting tau oligomers.

Antioxidant Activity of Hispidin Oligomers from Medicinal Fungi: A DFT Study

Directory of Open Access Journals (Sweden)

El Hassane Anouar

2014-03-01

Full Text Available Hispidin oligomers are styrylpyrone pigments isolated from the medicinal fungi Inonotus xeranticus and Phellinus linteus. They exhibit diverse biological activities and strong free radical scavenging activity. To rationalize the antioxidant activity of a series of four hispidin oligomers and determine the favored mechanism involved in free radical scavenging, DFT calculations were carried out at the B3P86/6-31+G (d, p level of theory in gas and solvent. The results showed that bond dissociation enthalpies of OH groups of hispidin oligomers (ArOH and spin density delocalization of related radicals (ArO• are the appropriate parameters to clarify the differences between the observed antioxidant activities for the four oligomers. The effect of the number of hydroxyl groups and presence of a catechol moiety conjugated to a double bond on the antioxidant activity were determined. Thermodynamic and kinetic studies showed that the PC-ET mechanism is the main mechanism involved in free radical scavenging. The spin density distribution over phenoxyl radicals allows a better understanding of the hispidin oligomers formation.

Application of Chitin/Chitosan and Their Derivatives in the Papermaking Industry

Directory of Open Access Journals (Sweden)

Zhaoping Song

2018-04-01

Full Text Available Chitin/chitosan and their derivatives have become of great interest as functional materials in many fields within the papermaking industry. They have been employed in papermaking wet-end, paper surface coating, papermaking wastewater treatment, and other sections of the papermaking industry due to their structure and chemical properties. The purpose of this paper is to briefly discuss the application of chitin/chitosan and their derivatives in the papermaking industry. The development of their application in the papermaking area will be reviewed and summarized.

Ferro-based derivatizing agents for LC/MS an LC/EC/MS

NARCIS (Netherlands)

Seiwert, Bettina

2007-01-01

Within this thesis, the development and application of ferrocene-based derivatizing agents for LC/MS and LC/EC/MS is presented. The advantages of derivatization by ferrocenes are the similtaneous introduction of a mass tag and an electroactive group, which make them ideally suited for LC/MS and

A new polyethyleneglycol-derivatized hemoglobin derivative with decreased oxygen affinity and limited toxicity.

Science.gov (United States)

Zolog, Oana; Mot, Augustin; Deac, Florina; Roman, Alina; Fischer-Fodor, Eva; Silaghi-Dumitrescu, Radu

2011-01-01

A new protocol is described for derivatization of hemoglobin with polyethyleneglycol (PEG) via reaction of the unmodified native hemoglobin with an activated amine-reacting polyethylene glycol derivative which, unlike protocols previously described, leads to formation of a peptide bond between hemoglobin and PEG. Dioxygen binding and peroxide reactivities of the derivatized hemoglobin are examined, and found to be within reasonable limits, with the particular observation that, unlike with a few other derivatization protocols, the dioxygen affinity is slightly lower than that of native Hb. In cell culture tests (human umbilical vein epithelial cells, HUVEC), the derivatization protocol induces no toxic effect. These results show promise towards applicability for production of hemoglobin-based blood substitutes.

Adsorption studies of iron(III) on chitin

Indian Academy of Sciences (India)

Unknown

of particle size and dosage of the adsorbant, contact time, initial concentration of the adsorbate and tem- perature were experimentally ... Adsorption; chitin; variable parameters; fraction of adsorption; temperature effect. 1. Introduction. Iron is one of the ... about the presence of iron in drinking water is its ob- jectionable taste.

Papain incorporated chitin dressings for wound debridement sterilized by gamma radiation

Science.gov (United States)

Singh, Durgeshwer; Singh, Rita

2012-11-01

Wound debridement is essential for the removal of necrotic or nonviable tissue from the wound surface to create an environment conducive to healing. Nonsurgical enzymatic debridement is an attractive method due to its effectiveness and ease of use. Papain is a proteolytic enzyme derived from the fruit of Carica papaya and is capable of breaking down a variety of necrotic tissue substrates. The present study was focused on the use of gamma radiation for sterilization of papain dressing with wound debriding activity. Membranes with papain were prepared using 0.5% chitin in lithium chloride/dimethylacetamide solvent and sterilized by gamma radiation. Fluid absorption capacity of chitin-papain membranes without glycerol was 14.30±6.57% in 6 h. Incorporation of glycerol resulted in significant (p<0.001) increase in the absorption capacity. Moisture vapour transmission rate of the membranes was 4285.77±455.61 g/m2/24 h at 24 h. Gamma irradiation at 25 kGy was found suitable for sterilization of the dressings. Infrared (IR) spectral scanning has shown that papain was stable on gamma irradiation at 25-35 kGy. The irradiated chitin-papain membranes were impermeable to different bacterial strains and also exhibited strong bactericidal action against both Gram-positive and Gram-negative bacteria. The fluid handling characteristics and the antimicrobial properties of chitin-papain membranes sterilized by gamma radiation were found suitable for use as wound dressing with debriding activity.

Isolation of proteolytic bacteria from mealworm (Tenebrio molitor) exoskeletons to produce chitinous material.

Science.gov (United States)

da Silva, Fernanda Kerche Paes; Brück, Dieter W; Brück, Wolfram M

2017-09-15

The use of insects as a source of protein is becoming an important factor for feeding an increasing population. After protein extraction for food use, the insect exoskeleton may offer the possibility for the production of added value products. Here, the aim was to isolate bacteria from the surface of farmed mealworms (Tenebrio molitor Linnaeus, 1758) for the production of chitinous material from insect exoskeletons using microbial fermentation. Isolates were screened for proteases and acid production that may aid deproteination and demineralisation of insects through fermentation to produce chitin. Selected isolates were used single-step (isolated bacteria only) or two-step fermentations with Lactobacillus plantarum (DSM 20174). Two-step fermentations with isolates from mealworm exoskeletons resulted in a demineralisation of 97.9 and 98.5% from deproteinated mealworm fractions. Attenuated total reflectance-Fourier- transform infrared spectroscopy analysis showed that crude chitin was produced. However, further optimisation is needed before the process can be upscaled. This is, to our knowledge, the first report using microbial fermentation for the extraction of chitin from insects. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

A Review of the Applications of Chitin and Its Derivatives in Agriculture to Modify Plant-Microbial Interactions and Improve Crop Yields

Directory of Open Access Journals (Sweden)

Russell G. Sharp

2013-11-01

Full Text Available In recent decades, a greater knowledge of chitin chemistry, and the increased availability of chitin-containing waste materials from the seafood industry, have led to the testing and development of chitin-containing products for a wide variety of applications in the agriculture industry. A number of modes of action have been proposed for how chitin and its derivatives can improve crop yield. In addition to direct effects on plant nutrition and plant growth stimulation, chitin-derived products have also been shown to be toxic to plant pests and pathogens, induce plant defenses and stimulate the growth and activity of beneficial microbes. A repeating theme of the published studies is that chitin-based treatments augment and amplify the action of beneficial chitinolytic microbes. This article reviews the evidence for claims that chitin-based products can improve crop yields and the current understanding of the modes of action with a focus on plant-microbe interactions.

Photo-electron spectroscopy study of energy levels in conjugated oligomers

NARCIS (Netherlands)

Veenstra, SC; Heeres, A; Stalmach, U; Wildeman, J; Hadziioannou, G; Sawatzky, GA; Jonkman, HT; Moss, SC

2002-01-01

We report on the valence orbital structure of poly(para-phenylenevinylene) (PPV)-like oligomers. We studied these molecules as isolated oligomers in the gas phase, as well as in thin films deposited on metal substrates. We use a simple model based on a previously reported Hamiltonian that accurately

Aspergillus Cell Wall Chitin Induces Anti- and Proinflammatory Cytokines in Human PBMCs via the Fc-γ Receptor/Syk/PI3K Pathway

Science.gov (United States)

Becker, K. L.; Aimanianda, V.; Wang, X.; Gresnigt, M. S.; Ammerdorffer, A.; Jacobs, C. W.; Gazendam, R. P.; Joosten, L. A. B.; Netea, M. G.

2016-01-01

ABSTRACT Chitin is an important cell wall component of Aspergillus fumigatus conidia, of which hundreds are inhaled on a daily basis. Previous studies have shown that chitin has both anti- and proinflammatory properties; however the exact mechanisms determining the inflammatory signature of chitin are poorly understood, especially in human immune cells. Human peripheral blood mononuclear cells were isolated from healthy volunteers and stimulated with chitin from Aspergillus fumigatus. Transcription and production of the proinflammatory cytokine interleukin-1β (IL-1β) and the anti-inflammatory cytokine IL-1 receptor antagonist (IL-1Ra) were measured from the cell culture supernatant by quantitative PCR (qPCR) or enzyme-linked immunosorbent assay (ELISA), respectively. Chitin induced an anti-inflammatory signature characterized by the production of IL-1Ra in the presence of human serum, which was abrogated in immunoglobulin-depleted serum. Fc-γ-receptor-dependent recognition and phagocytosis of IgG-opsonized chitin was identified as a novel IL-1Ra-inducing mechanism by chitin. IL-1Ra production induced by chitin was dependent on Syk kinase and phosphatidylinositol 3-kinase (PI3K) activation. In contrast, costimulation of chitin with the pattern recognition receptor (PRR) ligands lipopolysaccharide, Pam3Cys, or muramyl dipeptide, but not β-glucan, had synergistic effects on the induction of proinflammatory cytokines by human peripheral blood mononuclear cells (PBMCs). In conclusion, chitin can have both pro- and anti-inflammatory properties, depending on the presence of pathogen-associated molecular patterns and immunoglobulins, thus explaining the various inflammatory signatures reported for chitin. PMID:27247234

Analysis of expression and chitin-binding activity of the wing disc cuticle protein BmWCP4 in the silkworm, Bombyx mori.

Science.gov (United States)

Deng, Hui-Min; Li, Yong; Zhang, Jia-Ling; Liu, Lin; Feng, Qi-Li

2016-12-01

The insect exoskeleton is mainly composed of chitin filaments linked by cuticle proteins. When insects molt, the cuticle of the exoskeleton is renewed by degrading the old chitin and cuticle proteins and synthesizing new ones. In this study, chitin-binding activity of the wing disc cuticle protein BmWCP4 in Bombyx mori was studied. Sequence analysis showed that the protein had a conservative hydrophilic "R&R" chitin-binding domain (CBD). Western blotting showed that BmWCP4 was predominately expressed in the wing disc-containing epidermis during the late wandering and early pupal stages. The immunohistochemistry result showed that the BmWCP4 was mainly present in the wing disc tissues containing wing bud and trachea blast during day 2 of wandering stage. Recombinant full-length BmWCP4 protein, "R&R" CBD peptide (CBD), non-CBD peptide (BmWCP4-CBD - ), four single site-directed mutated peptides (M 1 , M 2 , M 3 and M 4 ) and four-sites-mutated peptide (M F ) were generated and purified, respectively, for in vitro chitin-binding assay. The results indicated that both the full-length protein and the "R&R" CBD peptide could bind with chitin, whereas the BmWCP4-CBD - could not bind with chitin. The single residue mutants M 1 , M 2 , M 3 and M 4 reduced but did not completely abolish the chitin-binding activity, while four-sites-mutated protein M F completely lost the chitin-binding activity. These data indicate that BmWCP4 protein plays a critical role by binding to the chitin filaments in the wing during larva-to-pupa transformation. The conserved aromatic amino acids are critical in the interaction between chitin and the cuticle protein. © 2015 Institute of Zoology, Chinese Academy of Sciences.

Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

Science.gov (United States)

Chuang, Chun-Hua (Inventor)

2012-01-01

.[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280.degree. C. When the imide oligomer melt is cured at about 371.degree. C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above 310.degree. C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280.degree. C. (450-535.degree. F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343.degree. C. (550-650.degree. F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260.degree. C.-280.degree. C..Iaddend.

COMPARISON OF CHITIN STRUCTURES DERIVED FROM THREE COMMON WASP SPECIES (Vespa crabro LINNAEUS, 1758, Vespa orientalis LINNAEUS, 1771 and Vespula germanica (FABRICIUS, 1793)).

Science.gov (United States)

Kaya, Murat; Bağrıaçık, Nil; Seyyar, Osman; Baran, Talat

2015-08-01

There has been no study on the chitin structure of wasp species. Here, we selected the three most common wasp species belonging to the family Vespidae for chitin extraction and characterization. Chitin was isolated from each wasp species and characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffractometry (XRD), elemental analysis (EA), and scanning electron microscopy (SEM). The chitin contents of Vespa crabro, Vespa orientalis, and Vespula germanica were 8.3, 6.4, and 11.9%, respectively. The crystalline index (CrI) values for the chitin extracted from each species were 69.88, 53.92, and 50%, respectively. The most important finding of the study is that although the same method was used to extract chitin from each of the three wasp species, the degree of acetylation was different: for V. crabro and V. orientalis it was 96.85 and 99.82% (the chitin was extremely pure), respectively, whereas that for V. germanica the chitin was 79.83%. © 2015 Wiley Periodicals, Inc.

Phase distribution of products of radiation and post-radiation distillation of biopolymers: Cellulose, lignin and chitin

International Nuclear Information System (INIS)

Ponomarev, A.V.; Kholodkova, E.M.; Metreveli, A.K.; Metreveli, P.K.; Erasov, V.S.; Bludenko, A.V.; Chulkov, V.N.

2011-01-01

Influence of both the absorbed dose and the dose rate of 8 MeV electron-beam radiation on destruction of microcrystalline cellulose, pine lignin and krill chitin was investigated. Two conversion modes were compared: (1) post-radiation distillation PRD and (2) electron-beam distillation EBD. Cellulose, chitin and lignin demonstrate different responses to irradiation and distillation in PRD and EBD modes. Treatment in EBD mode transforms biopolymers to organic liquid more productively than conventional dry distillation and treatment in PRD mode. Both radiation heating and an irradiation without heating intensify chitin and cellulose decomposition and distillation. At the same time lignin decaying rather efficiently in EBD mode appears to be insensitive to a preliminary irradiation in PRD mode up to a dose of 2.4 MGy. - Highlights: → Direct conversion of cellulose, chitin and lignin to organic liquid is intensified by electron-beam irradiation. → Alternative approach to bio-oil production. → Both electron-beam distillation mode and post-radiation distillation mode are effective for cellulose and chitin conversion. → Electron-beam distillation mode is preferable for lignin conversion. → Preliminary deep dehydration of biopolymers is realizable at low dose rates.

Computer simulations and theoretical aspects of the depletion interaction in protein-oligomer mixtures.

Science.gov (United States)

Boncina, M; Rescic, J; Kalyuzhnyi, Yu V; Vlachy, V

2007-07-21

The depletion interaction between proteins caused by addition of either uncharged or partially charged oligomers was studied using the canonical Monte Carlo simulation technique and the integral equation theory. A protein molecule was modeled in two different ways: either as (i) a hard sphere of diameter 30.0 A with net charge 0, or +5, or (ii) as a hard sphere with discrete charges (depending on the pH of solution) of diameter 45.4 A. The oligomers were pictured as tangentially jointed, uncharged, or partially charged, hard spheres. The ions of a simple electrolyte present in solution were represented by charged hard spheres distributed in the dielectric continuum. In this study we were particularly interested in changes of the protein-protein pair-distribution function, caused by addition of the oligomer component. In agreement with previous studies we found that addition of a nonadsorbing oligomer reduces the phase stability of solution, which is reflected in the shape of the protein-protein pair-distribution function. The value of this function in protein-protein contact increases with increasing oligomer concentration, and is larger for charged oligomers. The range of the depletion interaction and its strength also depend on the length (number of monomer units) of the oligomer chain. The integral equation theory, based on the Wertheim Ornstein-Zernike approach applied in this study, was found to be in fair agreement with Monte Carlo results only for very short oligomers. The computer simulations for a model mimicking the lysozyme molecule (ii) are in qualitative agreement with small-angle neutron experiments for lysozyme-dextran mixtures.

Self-propagative replication of Aβ oligomers suggests potential transmissibility in Alzheimer disease.

Directory of Open Access Journals (Sweden)

Amit Kumar

Full Text Available The aggregation of amyloid-β (Aβ peptide and its deposition in parts of the brain form the central processes in the etiology of Alzheimer disease (AD. The low-molecular weight oligomers of Aβ aggregates (2 to 30 mers are known to be the primary neurotoxic agents whose mechanisms of cellular toxicity and synaptic dysfunction have received substantial attention in the recent years. However, how these toxic agents proliferate and induce widespread amyloid deposition throughout the brain, and what mechanism is involved in the amplification and propagation of toxic oligomer species, are far from clear. Emerging evidence based on transgenic mice models indicates a transmissible nature of Aβ aggregates and implicates a prion-like mechanism of oligomer propagation, which manifests as the dissemination and proliferation of Aβ toxicity. Despite accumulating evidence in support of a transmissible nature of Aβ aggregates, a clear, molecular-level understanding of this intriguing mechanism is lacking. Recently, we reported the characterization of unique replicating oligomers of Aβ42 (12-24 mers in vitro called Large Fatty Acid-derived Oligomers (LFAOs (Kumar et al., 2012, J. Biol. Chem. In the current report, we establish that LFAOs possess physiological activity by activating NF-κB in human neuroblastoma cells, and determine the experimental parameters that control the efficiency of LFAO replication by self-propagation. These findings constitute the first detailed report on monomer - oligomer lateral propagation reactions that may constitute potential mechanism governing transmissibility among Aβ oligomers. These data support the previous reports on transmissible mechanisms observed in transgenic animal models.

Comparison of derivatization/ionization techniques for liquid chromatography tandem mass spectrometry analysis of oxylipins.

Science.gov (United States)

Meckelmann, Sven W; Hellhake, Stefan; Steuck, Maryvonne; Krohn, Michael; Schebb, Nils Helge

2017-05-01

The performance of two derivatization and ionization techniques for the quantitative reversed phase liquid chromatography (LC)- mass spectrometry (MS) analysis of hydroxy fatty acids (OH-PUFA) in plasma was evaluated: One used AMPP (N-(4-aminomethylphenyl)pyridinium chloride) leading to a positive charged amid-derivate which can be detected by electrospray ionization (ESI)-MS. Second yielded penta fluorobenzyl bromide (PFB) ester derivates allowing detection in electron capture atmospheric pressure chemical ionization (ecAPCI)-MS. The sensitivity of detection of a comprehensive set of hydroxy fatty acids of n6- and n3- poly unsaturated fatty acids was investigated. On the SCIEX3200 MS the applied PFB derivatization led to poor limits of detection (LOD) of 10-100nM (0.1-1pmol/0.03-0.3ng on column). By contrast, AMPP derivatization led to a similar sensitivity compared to the standard ESI(-) of non derivatized analytes (LOD about 1nM (10fmol/3pg on column)). For several analytes, including 9-HETE, 11-HETE and 17-HDHA the AMPP derivatization improved sensitivity enabling their detection in human plasma. However, precision was reduced by AMPP derivatization and variation in IS recovery indicated a strong matrix influence on the MS-signal. In sum, with the instrumentation used, neither of these derivatization methods improves in our hands the LC-MS based quantification of oxylipins. Copyright © 2017 Elsevier Inc. All rights reserved.

The big six, regnskabsbrugerne og FASBs nye regler om derivater

DEFF Research Database (Denmark)

Thinggaard, Frank

1997-01-01

Artiklen har flere formål. Dels at præsentere FASBs første forslag til den regnskabsmæssige behandling af samtlige derivater. Dels at analysere og sammenligne de enkelte big six revisions-firmaers holdning til forslagets vigtigste emner samt at sammenligne dette med kommentarerne fra en repræsent......Artiklen har flere formål. Dels at præsentere FASBs første forslag til den regnskabsmæssige behandling af samtlige derivater. Dels at analysere og sammenligne de enkelte big six revisions-firmaers holdning til forslagets vigtigste emner samt at sammenligne dette med kommentarerne fra en...... repræsentant for brugerne. Artiklen viser, at revisionsfirmaerne generelt er meget enige i deres bedømmelse af reglerne. De fleste er ikke modstandere af at værdiansætte derivater til fair value. Kritikken går på behandlingen af gevinsterne og tabene, hvor de er bange for den volatilitet, der kan komme i...... virksomhedernes resultater. Især for gevinster og tab på derivater, der sikrer fremtidige cash-flows. Artiklen forklarer nærmere, hvad modstanden består i, hvilket giver en dybere forståelse for, hvordan reglerne virker. Artiklen viser, at brugerne ikke er nær så kritiske som the big six....

Removal of hazardous dye Ponceau-S by using Chitin:

African Journals Online (AJOL)

Sr030111Bin Comp

Key words: Chitin, Ponceau-S, organic bioadsorbent, colored organic, industrial effluents. ..... of cationic azo dye by TiO2/bentonite nanocomposite, J. Photochem. ... effluents to freshwater and estuarine algae, crustaceans and fishes. Environ.

Growth on Chitin Impacts the Transcriptome and Metabolite Profiles of Antibiotic-Producing Vibrio coralliilyticus S2052 and Photobacterium galatheae S2753

DEFF Research Database (Denmark)

Giubergia, Sonia; Phippen, Christopher; Nielsen, Kristian Fog

2017-01-01

Members of the Vibrionaceae family are often associated with chitin-containing organisms, and they are thought to play a major role in chitin degradation. The purpose of the present study was to determine how chitin affects the transcriptome and metabolome of two bioactive Vibrionaceae strains...... potentially involved in host colonization and/or infection. The expression of genes involved in secondary metabolism was also significantly affected by growth on chitin, in one case being 34-fold upregulated. This was reflected in the metabolome, where the antibiotics andrimid and holomycin were produced...... and that their secondary metabolites likely play a crucial role during chitin colonization. IMPORTANCE The bacterial family Vibrionaceae (vibrios) is considered a major player in the degradation of chitin, the most abundant polymer in the marine environment; however, the majority of studies on the topic have focused...

In vitro bioconversion of chitin to pyruvate with thermophilic enzymes.

Science.gov (United States)

Honda, Kohsuke; Kimura, Keisuke; Ninh, Pham Huynh; Taniguchi, Hironori; Okano, Kenji; Ohtake, Hisao

2017-09-01

Chitin is the second most abundant organic compound on the planet and thus has been regarded as an alternative resource to petroleum feedstocks. One of the key challenges in the biological conversion of biomass-derived polysaccharides, such as cellulose and chitin, is to close the gap between optimum temperatures for enzymatic saccharification and microbial fermentation and to implement them in a single bioreactor. To address this issue, in the present study, we aimed to perform an in vitro, one-pot bioconversion of chitin to pyruvate, which is a precursor of a wide range of useful metabolites. Twelve thermophilic enzymes, including that for NAD + regeneration, were heterologously produced in Escherichia coli and semi-purified by heat treatment of the crude extract of recombinant cells. When the experimentally decided concentrations of enzymes were incubated with 0.5 mg mL -1 colloidal chitin (equivalent to 2.5 mM N-acetylglucosamine unit) and an adequate set of cofactors at 70°C, 0.62 mM pyruvate was produced in 5 h. Despite the use of a cofactor-balanced pathway, determination of the pool sizes of cofactors showed a rapid decrease in ATP concentration, most probably due to the thermally stable ATP-degrading enzyme(s) derived from the host cell. Integration of an additional enzyme set of thermophilic adenylate kinase and polyphosphate kinase led to the deceleration of ATP degradation, and the final product titer was improved to 2.1 mM. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Expanded metabolite coverage of Saccharomyces cerevisiae extract through improved chloroform/methanol extraction and tert-butyldimethylsilyl derivatization

DEFF Research Database (Denmark)

Khoomrung, Sakda; Martinez Ruiz, José Luis; Tippmann, Stefan

2015-01-01

and non-polar metabolites were derivatized using tert-butyldimethylsilyl (t-BDMS) dissolved in acetonitrile. Using microwave treatment of the samples, the derivatization process could be completed within 2 h (from >20 h of the conventional method), providing fully derivatized metabolites that contain...

Cytotoxicity and mechanical behavior of chitin-bentonite clay based polyurethane bio-nanocomposites.

Science.gov (United States)

Zia, Khalid Mahmood; Zuber, Mohammad; Barikani, Mehdi; Hussain, Rizwan; Jamil, Tahir; Anjum, Sohail

2011-12-01

Chitin based polyurethane bio-nanocomposites (PUBNC) were prepared using chitin, Delite HPS bentonite nanoclay enriched in montmorillonite (MMT), 4,4'-diphenylmethane diisocyanate (MDI) and polycaprolactone polyol CAPA 231 (3000 g/mol(-1)). The prepolymers having different concentration of Delite HPS bentonite nanoclay were extended with 2 moles of chitin. The structures of the resulted polymers were determined by FT-IR technique. The effect of nanoclay contents on mechanical properties and in vitro biocompatibility was investigated. The mechanical properties of the synthesized materials were improved with increase in the Delite HPS bentonite nanoclay contents. Optimum mechanical properties were obtained from the PU bio-nanocomposite samples having 4% Delite HPS bentonite nanoclay. The results revealed that the final PU bio-nanocomposite having 2% Delite HPS bentonite nanoclay contents is ideal contenders for surgical threads with on going investigations into their in vitro biocompatibility, non-toxicity, and mechanical properties. Copyright © 2011 Elsevier B.V. All rights reserved.

Applications of oligomers for nanostructured conducting polymers.

Science.gov (United States)

Wang, Yue; Tran, Henry D; Kaner, Richard B

2011-01-03

This Feature Article provides an overview of the distinctive nanostructures that aniline oligomers form and the applications of these oligomers for shaping the nanoscale morphologies and chirality of conducting polymers. We focus on the synthetic methods for achieving such goals and highlight the underlying mechanisms. The clear advantages of each method and their possible drawbacks are discussed. Assembly and applications of these novel organic (semi)conducting nanomaterials are also outlined. We conclude this article with our perspective on the main challenges, new opportunities, and future directions for this nascent yet vibrant field of research. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the function of chitin synthase extracellular domains in biomineralization.

Science.gov (United States)

Weiss, Ingrid M; Lüke, Florian; Eichner, Norbert; Guth, Christina; Clausen-Schaumann, Hauke

2013-08-01

Molluscs with various shell architectures evolved around 542-525 million years ago, as part of a larger phenomenon related to the diversification of metazoan phyla. Molluscs deposit minerals in a chitin matrix. The mollusc chitin is synthesized by transmembrane enzymes that contain several unique extracellular domains. Here we investigate the assembly mechanism of the chitin synthase Ar-CS1 via its extracellular domain ArCS1_E22. The corresponding transmembrane protein ArCS1_E22TM accumulates in membrane fractions of the expression host Dictyostelium discoideum. Soluble recombinant ArCS1_E22 proteins can be purified as monomers only at basic pH. According to confocal fluorescence microscopy experiments, immunolabeled ArCS1_E22 proteins adsorb preferably to aragonitic nacre platelets at pH 7.75. At pH 8.2 or pH 9.0 the fluorescence signal is less intense, indicating that protein-mineral interaction is reduced with increasing pH. Furthermore, ArCS1_E22 forms regular nanostructures on cationic substrates as revealed by atomic force microscopy (AFM) experiments on modified mica cleavage planes. These experiments suggest that the extracellular domain ArCS1_E22 is involved in regulating the multiple enzyme activities of Ar-CS1 such as chitin synthesis and myosin movements by interaction with mineral surfaces and eventually by protein assembly. The protein complexes could locally probe the status of mineralization according to pH unless ions and pCO2 are balanced with suitable buffer substances. Taking into account that the intact enzyme could act as a force sensor, the results presented here provide further evidence that shell formation is coordinated physiologically with precise adjustment of cellular activities to the structure, topography and stiffness at the mineralizing interface. Copyright © 2013 Elsevier Inc. All rights reserved.

The structure and dynamics of chitin nanofibrils in an aqueous environment revealed by molecular dynamics simulations

Czech Academy of Sciences Publication Activity Database

Střelcová, Z.; Kulhánek, P.; Friák, Martin; Fabritius, H.; Petrov, M.; Neugebauer, J.; Koča, J.

2016-01-01

Roč. 6, č. 36 (2016), s. 30710-30721 ISSN 2046-2069 Institutional support: RVO:68081723 Keywords : FREE-ENERGY CALCULATIONS * PARTICLE MESH EWALD * ALPHA-CHITIN * CRYSTAL-STRUCTURE * INSECT CHITIN * SURFACE-AREA * AB-INITIO Subject RIV: BO - Biophysics Impact factor: 3.108, year: 2016

Donor-acceptor-donor thienyl/bithienyl-benzothiadiazole/quinoxaline model oligomers: experimental and theoretical studies.

Science.gov (United States)

Pina, João; de Melo, J Seixas; Breusov, D; Scherf, Ullrich

2013-09-28

A comprehensive spectral and photophysical investigation of four donor-acceptor-donor (DAD) oligomers consisting of electron-deficient 2,1,3-benzothiadiazole or quinoxaline moieties linked to electron-rich thienyl or bithienyl units has been undertaken. Additionally, a bis(dithienyl) substituted naphthalene was also investigated. The D-A-D nature of these oligomers resulted in the presence of an intramolecular charge transfer (ICT) state, which was further substantiated by solvatochromism studies (analysis with the Lippert-Mataga formalism). Hereby, significant differences have been obtained for the fluorescence quantum yields of the oligomers in the non-polar solvent methylcyclohexane vs. the polar ethanol. The study was further complemented with the determination of the optimized ground-state molecular geometries for the oligomers together with the prediction of the lowest vertical one-electron excitation energy and the relevant molecular orbital contours using DFT calculations. The electronic transitions show a clear HOMO to LUMO charge-transfer character. In contrast to the thiophene oligomers (the oligothiophenes with n = 1-7), where the intersystem crossing (ISC) yield decreases with n, the studied DAD oligomers were found to show an increase in the ISC efficiency with the number of (donor) thienyl units.

Detection of chitinase activity by 2-aminobenzoic acid labeling of chito-oligosaccharides

NARCIS (Netherlands)

Ghauharali-van der Vlugt, Karen; Bussink, Anton P.; Groener, Johanna E. M.; Boot, Rolf G.; Aerts, Johannes M. F. G.

2009-01-01

Chitinases are hydrolases capable of hydrolyzing the abundant natural polysaccharide chitin. Next to artificial fluorescent substrates, more physiological chito-oligomers are commonly used in chitinase assays. Analysis of chito-oligosaccharides products is generally accomplished by UV detection.

Laser-Induced Population Inversion in Rhodamine 6G for Lysozyme Oligomer Detection.

Science.gov (United States)

Hanczyc, Piotr; Sznitko, Lech

2017-06-06

Fluorescence spectroscopy is a common method for detecting amyloid fibrils in which organic fluorophores are used as markers that exhibit an increase in quantum yield upon binding. However, most of the dyes exhibit enhanced emission only when bound to mature fibrils, and significantly weaker signals are obtained in the presence of amyloid oligomers. In the concept of population inversion, a laser is used as an excitation source to keep the major fraction of molecules in the excited state to create the pathways for the occurrence of stimulated emission. In the case of the proteins, the conformational changes lead to the self-ordering and thus different light scattering conditions that can influence the optical signatures of the generated light. Using this methodology, we show it is possible to optically detect amyloid oligomers using commonly available staining dyes in which population inversion can be induced. The results indicate that rhodamine 6G molecules are complexed with oligomers, and using a laser-assisted methodology, weakly emissive states can be detected. Significant spectral red-shifting of rhodamine 6G dispersed with amyloid oligomers and a notable difference determined by comparison of spectra of the fibrils suggest the existence of specific dye aggregates around the oligomer binding sites. This approach can provide new insights into intermediate oligomer states that are believed to be responsible for toxic seeding in neurodegeneration diseases.

Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

Science.gov (United States)

Chuang, CHun-Hua (Inventor)

2006-01-01

This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

Derivatization reactions in the gas—liquid chromatographic analysis of drugs in biological fluids

NARCIS (Netherlands)

Hulshoff, A.; Lingeman, H.

1984-01-01

Alkylation, acylation, silylation and other derivatization reactions applied to the gas chromatographic analysis of drugs in biological matrices are reviewed. Reaction conditions are discussed in relation to reaction mechanisms. Detector-oriented labelling of drugs, and derivatization with chiral

Aniline oligomers versus polyaniline

Czech Academy of Sciences Publication Activity Database

Stejskal, Jaroslav; Trchová, Miroslava

2012-01-01

Roč. 61, č. 2 (2012), s. 240-251 ISSN 0959-8103 R&D Projects: GA AV ČR IAA400500905; GA AV ČR IAA100500902; GA ČR GA203/08/0686; GA ČR GA202/09/1626 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyaniline * anilin e oligomers * anilin e Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.125, year: 2012

Charge Separation and Recombination in Small Band Gap Oligomer-Fullerene Triads

NARCIS (Netherlands)

Karsten, Bram P.; Bouwer, Ricardo K. M.; Hummelen, Jan C.; Williams, Rene M.; Janssen, Rene A. J.

2010-01-01

Synthesis and photophysics of a series of thiophene-thienopyrazine small band gap oligomers end-capped at both ends with C(60) are presented In these triads a photoinduced electron transfer reaction occurs between the oligomer as a donor and the fullerene as an acceptor Femtosecond photoinduced

Micro-CT imaging of denatured chitin by silver to explore honey bee and insect pathologies.

Directory of Open Access Journals (Sweden)

Peter R Butzloff

Full Text Available BACKGROUND: Chitin and cuticle coatings are important to the environmental and immune defense of honey bees and insect pollinators. Pesticides or environmental effects may target the biochemistry of insect chitin and cuticle coating. Denaturing of chitin involves a combination of deacetylation, intercalation, oxidation, Schweiger-peeling, and the formation of amine hydrochloride salt. The term "denatured chitin" calls attention to structural and property changes to the internal membranes and external carapace of organisms so that some properties affecting biological activities are diminished. METHODOLOGY/PRINCIPAL FINDINGS: A case study was performed on honey bees using silver staining and microscopic computer-tomographic x-ray radiography (micro-CT. Silver nitrate formed counter-ion complexes with labile ammonium cations and reacted with amine hydrochloride. Silver was concentrated in the peritrophic membrane, on the abdomen, in the glossa, at intersegmental joints (tarsi, at wing attachments, and in tracheal air sacs. Imaged mono-esters and fatty acids from cuticle coating on external surfaces were apparently reduced by an alcohol pretreatment. CONCLUSIONS/SIGNIFICANCE: The technique provides 3-dimensional and sectional images of individual honey bees consistent with the chemistries of silver reaction and complex formation with denatured chitin. Environmental exposures and influences such as gaseous nitric oxide intercalant, trace oxidants such as ozone gas, oligosachharide salt conversion, exposure to acid rain, and chemical or biochemical denaturing by pesticides may be studied using this technique. Peritrophic membranes, which protect against food abrasion, microorganisms, and permit efficient digestion, were imaged. Apparent surface damage to the corneal lenses of compound eyes by dilute acid exposure consistent with chitin amine hydrochloride formation was imaged. The technique can contribute to existing insect pathology research, and may

Chitin biological absorbable catheters bridging sural nerve grafts transplanted into sciatic nerve defects promote nerve regeneration.

Science.gov (United States)

Wang, Zhi-Yong; Wang, Jian-Wei; Qin, Li-Hua; Zhang, Wei-Guang; Zhang, Pei-Xun; Jiang, Bao-Guo

2018-06-01

To investigate the efficacy of chitin biological absorbable catheters in a rat model of autologous nerve transplantation. A segment of sciatic nerve was removed to produce a sciatic nerve defect, and the sural nerve was cut from the ipsilateral leg and used as a graft to bridge the defect, with or without use of a chitin biological absorbable catheter surrounding the graft. The number and morphology of regenerating myelinated fibers, nerve conduction velocity, nerve function index, triceps surae muscle morphology, and sensory function were evaluated at 9 and 12 months after surgery. All of the above parameters were improved in rats in which the nerve graft was bridged with chitin biological absorbable catheters compared with rats without catheters. The results of this study indicate that use of chitin biological absorbable catheters to surround sural nerve grafts bridging sciatic nerve defects promotes recovery of structural, motor, and sensory function and improves muscle fiber morphology. © 2018 John Wiley & Sons Ltd.

Structural Investigations of on-pathway Oligomers of α-Synuclein

DEFF Research Database (Denmark)

Pedersen, Martin Nors; Horvath, Istvan; Weise, Christoph F.

Academy of Sciences of the United States of America 108(8): 3246-3251. Horvath, I., et al. (2012). "Mechanisms of protein oligomerization: In-hibitor of functional amyloids templates a-synuclein fibrilla-tion." Journal of the American Chemical Society. Spillantini, M. G., et al. (1997). "[alpha...... by decomposition of SAXS data from the evolving fibrillating solution (Giehm et al. 2011). NMR data have furthermore suggested that the C-terminal is exposed on oligomers obtained by incubation with the ligand FN075 (Horvath et al. 2012). In this study we aim at obtaining SAXS data from isolated stabilized...... oligomer (MAX-lab, May 2012); data analysis is in progress. ITC experiments are furthermore planned to more accurately determine the stoichiometry between α-synuclein and FN075. Horvath and co-workers have already shown that the FN075 stabilized oligomer is on pathway. We have shown that the in...

Characterization of methacrylate-based composites containing thio-urethane oligomers.

Science.gov (United States)

Bacchi, Atais; Nelson, Morgan; Pfeifer, Carmem S

2016-02-01

To evaluate the ability of thio-urethane oligomers to improve the properties of restorative composite resins. Oligomers were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 0-20 wt% to BisGMA-TEGDMA (70-30 wt%). Silanated inorganic fillers were added (70 wt%). Materials were photoactivated at 800 mW/cm(2) filtered to 320-500 nm. Near-IR was used to follow degree of methacrylate conversion (DC). Mechanical properties were evaluated in three-point bending with 2 mm × 2 mm × 25 mm bars for flexural strength/modulus and toughness (FS/E, and T) according to ISO 4049, and 2 mm × 5 mm × 25 mm notched specimens for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Results were analyzed with ANOVA/Tukey's test (α=5%). Significant increase in DC was observed in thio-urethane-containing materials especially for the group with 20 wt% of aliphatic version. Materials composed by oligomers also promoted higher FS, E, and KIC in comparison to controls irrespective of thio-urethane type. A significant increase in toughness was detected by ANOVA, but not distinguished in the groups. The PS was significantly reduced by the presence of thio-urethane for almost all groups. The use of thio-urethane oligomer to compose methacrylate-based restorative composite promote increase in DC, FS, E and KIC while significant reduces PS. A simple additive was shown to reduce stress while increasing convrersion and mechanical properties, mainly fracture toughness. This has he potential of increasing the service life of dental composites, without changing current operatory procedures. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Acrylate oligomers in ultraviolet cured PSA's glass transition, molecular weight versus peel strength

International Nuclear Information System (INIS)

Miller, H.C.

1999-01-01

Typically those not skilled in the art relate Glass Transition Temperature to Pressure Sensitive Adhesives. You need a low Tg material to prepare good pressure sensitive adhesives. This report deals with a wide range acrylate terminated oligomers in a standard formulation. Molecular weight, chemical structure variations are examined versus the Glass Transition of the oligomers and final peel strength. Each formulated adhesive will require unique oligomer properties to reach one hundred newtons per 100 millimeters (5.71 pounds per square inch) peel strength. Excellent peel strengths may be obtained with oligomer molecular weight ranging from six thousand to one thousand molecular weight and glass transition temperatures ranging from minus seventy four degrees centigrade up to thirteen degrees centigrade

Isocyanate-functionalized chitin and chitosan as gelling agents of castor oil.

Science.gov (United States)

Gallego, Rocío; Arteaga, Jesús F; Valencia, Concepción; Franco, José M

2013-06-03

The main objective of this work was the incorporation of reactive isocyanate groups into chitin and chitosan in order to effectively use the products as reactive thickening agents in castor oil. The resulting gel-like dispersions could be potentially used as biodegradable lubricating greases. Three different NCO-functionalized polymers were obtained: two of them by promoting the reaction of chitosan with 1,6-hexamethylene diisocyanate (HMDI), and the other by using chitin instead of chitosan. These polymers were characterized through 1H-NMR, FTIR and thermogravimetric analysis (TGA). Thermal and rheological behaviours of the oleogels prepared by dispersing these polymers in castor oil were studied by means of TGA and small-amplitude oscillatory shear (SAOS) measurements. The evolution and values of the linear viscoelasticity functions with frequency for -NCO-functionalized chitosan- and chitin-based oleogels are quite similar to those found for standard lubricating greases. In relation to long-term stability of these oleogels, no phase separation was observed and the values of viscoelastic functions increase significantly during the first seven days of ageing, and then remain almost constant. TGA analysis showed that the degradation temperature of the resulting oleogels is higher than that found for traditional lubricating greases.

Emerging Biomedical Applications of Nano-Chitins and Nano-Chitosans Obtained via Advanced Eco-Friendly Technologies from Marine Resources

Science.gov (United States)

Muzzarelli, Riccardo A. A.; El Mehtedi, Mohamad; Mattioli-Belmonte, Monica

2014-01-01

The present review article is intended to direct attention to the technological advances made in the 2010–2014 quinquennium for the isolation and manufacture of nanofibrillar chitin and chitosan. Otherwise called nanocrystals or whiskers, n-chitin and n-chitosan are obtained either by mechanical chitin disassembly and fibrillation optionally assisted by sonication, or by e-spinning of solutions of polysaccharides often accompanied by poly(ethylene oxide) or poly(caprolactone). The biomedical areas where n-chitin may find applications include hemostasis and wound healing, regeneration of tissues such as joints and bones, cell culture, antimicrobial agents, and dermal protection. The biomedical applications of n-chitosan include epithelial tissue regeneration, bone and dental tissue regeneration, as well as protection against bacteria, fungi and viruses. It has been found that the nano size enhances the performances of chitins and chitosans in all cases considered, with no exceptions. Biotechnological approaches will boost the applications of the said safe, eco-friendly and benign nanomaterials not only in these fields, but also for biosensors and in targeted drug delivery areas. PMID:25415349

Synthesis of soybean oil-based thiol oligomers.

Science.gov (United States)

Wu, Jennifer F; Fernando, Shashi; Weerasinghe, Dimuthu; Chen, Zhigang; Webster, Dean C

2011-08-22

Industrial grade soybean oil (SBO) and thiols were reacted to generate thiol-functionalized oligomers via a thermal, free radical initiated thiol-ene reaction between the SBO double bond moieties and the thiol functional groups. The effect of the reaction conditions, including thiol concentration, catalyst loading level, reaction time, and atmosphere, on the molecular weight and the conversion to the resultant soy-thiols were examined in a combinatorial high-throughput fashion using parallel synthesis, combinatorial FTIR, and rapid gel permeation chromatography (GPC). High thiol functionality and concentration, high thermal free radical catalyst concentration, long reaction time, and the use of a nitrogen reaction atmosphere were found to favor fast consumption of the SBO, and produced high molecular weight products. The thiol conversion during the reaction was inversely affected by a high thiol concentration, but was favored by a long reaction time and an air reaction atmosphere. These experimental observations were explained by the initial low affinity of the SBO and thiol, and the improved affinity between the generated soy-thiol oligomers and unreacted SBO during the reaction. The synthesized soy-thiol oligomers can be used for renewable thiol-ene UV curable materials and high molecular solids and thiourethane thermal cure materials. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Eco-Friendly Extraction of Biopolymer Chitin and Carotenoids from Shrimp Waste

Science.gov (United States)

Prameela, K.; Venkatesh, K.; Divya vani, K.; Sudesh Kumar, E.; Mohan, CH Murali

2017-08-01

Astaxanthin a nutraceutical and chitin a natural biopolymer present in shrimp waste. In current chemical extraction methods HCl and NaOH are used for extraction and these chemicals are introduced into aquatic ecosystems are spoiling aquatic flora and fauna, pollute the environment and destroy astaxanthin. Lactobacillus species were isolated from gut of Solenocera melantho and characterized phenotypically and genotypically. Initial screening experiments have shown to be an effective and identified as Lactobacillus plantaram based on morphological, biochemical characteristics and molecular analysis. Efficiency of fermentation has shown with good yield of astaxanthin and recovery of chitin. Hence this alternative microbial process is having advantage than existing hazardous, non-economical chemical process.

Preparation of chitin–silica composites by in vitro silicification of two-dimensional Ianthella basta demosponge chitinous scaffolds under modified Stöber conditions

Energy Technology Data Exchange (ETDEWEB)

Wysokowski, Marcin [Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, M. Skłodowskiej-Curie 2, PL-60965 Poznan (Poland); Behm, Thomas [Institute of Experimental Physics, TU Bergakademie Freiberg, Liepziger 23, 09599 Freiberg (Germany); Born, René [Institute of Materials Science, Dresden University of Technology, Helmholtzstraße 10, 01069 Dresden (Germany); Bazhenov, Vasilii V. [Institute of Experimental Physics, TU Bergakademie Freiberg, Liepziger 23, 09599 Freiberg (Germany); Meißner, Heike; Richter, Gert [Faculty of Medicine Carl Gustav Carus, Dresden University of Technology, Fetscherstraße 74, 01307 Dresden (Germany); Szwarc-Rzepka, Karolina [Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, M. Skłodowskiej-Curie 2, PL-60965 Poznan (Poland); Makarova, Anna; Vyalikh, Denis [Institute of Solid State Physics, Dresden University of Technology, Helmholtzstraße 10, 01069 Dresden (Germany); Schupp, Peter [Institute for Chemistry and Biology of the Marine Environment, University of Oldenburg, Emsstr. 20, 26382 Wilhelmshaven (Germany); Jesionowski, Teofil, E-mail: teofil.jesionowski@put.poznan.pl [Institute of Chemical Technology and Engineering, Faculty of Chemical Technology, Poznan University of Technology, M. Skłodowskiej-Curie 2, PL-60965 Poznan (Poland); Ehrlich, Hermann, E-mail: hermann.ehrlich@physik.tu-freiberg.de [Institute of Experimental Physics, TU Bergakademie Freiberg, Liepziger 23, 09599 Freiberg (Germany)

2013-10-15

Chitin is a biopolymer found in cell walls of various fungi and skeletal structures of numerous invertebrates. The occurrence of chitin within calcium- and silica-containing biominerals has inspired development of chitin-based hybrids and composites in vitro with specific physico-chemical and material properties. We show here for the first time that the two-dimensional α-chitin scaffolds isolated from the skeletons of marine demosponge Ianthella basta can be effectively silicified by the two-step method with the use of Stöber silica micro- and nanodispersions under Extreme Biomimetic conditions. The chitin–silica composites obtained at 120 °C were characterized by the presence of spherical SiO{sub 2} particles homogeneously distributed over the chitin fibers, which probably follows from the compatibility of Si–OH groups to the hydroxyl groups of chitin. The biocomposites obtained were characterized by various analytical techniques such as energy dispersive spectrometry, scanning electron microscopy, thermogravimetric/differential thermal analyses as well as X-ray photoelectron spectroscopy, Fourier transform infrared and Raman spectroscopy to determine possible interactions between silica and chitin molecule. The results presented proved that the character and course of the in vitro chitin silicification in Stöber dispersions depended considerably on the degree of hydrolysis of the SiO{sub 2} precursor. - Highlights: • 2D α-chitin scaffolds isolated from marine demosponge can be effectively silicified using Stöber silica. • The chitin–silica composites were obtained under Extreme Biomimetic conditions. • Character and course of the in vitro chitin silicification in Stöber dispersions is discussed.

Different functions of the insect soluble and membrane-bound trehalase genes in chitin biosynthesis revealed by RNA interference.

Directory of Open Access Journals (Sweden)

Jie Chen

Full Text Available BACKGROUND: Trehalase, an enzyme that hydrolyzes trehalose to yield two glucose molecules, plays a pivotal role in various physiological processes. In recent years, trehalase proteins have been purified from several insect species and are divided into soluble (Tre-1 and membrane-bound (Tre-2 trehalases. However, no functions of the two trehalases in chitin biosynthesis in insects have yet been reported. PRINCIPAL FINDINGS: The membrane-bound trehalase of Spodoptera exigua (SeTre-2 was characterized in our laboratory previously. In this study, we cloned the soluble trehalase gene (SeTre-1 and investigated the tissue distribution and developmental expression pattern of the two trehalase genes. SeTre-1 was expressed highly in cuticle and Malpighian tubules, while SeTre-2 was expressed in tracheae and fat body. In the midgut, the two trehalase genes were expressed in different locations. Additionally, the expression profiles of both trehalase mRNAs and their enzyme activities suggest that they may play different roles in chitin biosynthesis. The RNA interference (RNAi of either SeTre-1 or SeTre-2 was gene-specific and effective, with efficiency rates up to 83% at 72 h post injection. After RNAi of SeTre-1 and SeTre-2, significant higher mortality rates were observed during the larva-pupa stage and pupa-adult stage, and the lethal phenotypes were classified and analyzed. Additionally, the change trends of concentration of trehalose and glucose appeared reciprocally in RNAi-mutants. Moreover, knockdown of SeTre-1 gene largely inhibited the expression of chitin synthase gene A (CHSA and reduced the chitin content in the cuticle to two-thirds relative to the control insects. The chitin synthase gene B (CHSB expression, however, was inhibited more by the injection of dsRNA for SeTre-2, and the chitin content in the midgut decreased by about 25%. CONCLUSIONS: SeTre-1 plays a major role in CHSA expression and chitin synthesis in the cuticle, and SeTre-2

Chitin synthases from Saprolegnia are involved in tip growth and represent a potential target for anti-oomycete drugs.

Directory of Open Access Journals (Sweden)

Gea Guerriero

Full Text Available Oomycetes represent some of the most devastating plant and animal pathogens. Typical examples are Phytophthora infestans, which causes potato and tomato late blight, and Saprolegnia parasitica, responsible for fish diseases. Despite the economical and environmental importance of oomycete diseases, their control is difficult, particularly in the aquaculture industry. Carbohydrate synthases are vital for hyphal growth and represent interesting targets for tackling the pathogens. The existence of 2 different chitin synthase genes (SmChs1 and SmChs2 in Saprolegnia monoica was demonstrated using bioinformatics and molecular biology approaches. The function of SmCHS2 was unequivocally demonstrated by showing its catalytic activity in vitro after expression in Pichia pastoris. The recombinant SmCHS1 protein did not exhibit any activity in vitro, suggesting that it requires other partners or effectors to be active, or that it is involved in a different process than chitin biosynthesis. Both proteins contained N-terminal Microtubule Interacting and Trafficking domains, which have never been reported in any other known carbohydrate synthases. These domains are involved in protein recycling by endocytosis. Enzyme kinetics revealed that Saprolegnia chitin synthases are competitively inhibited by nikkomycin Z and quantitative PCR showed that their expression is higher in presence of the inhibitor. The use of nikkomycin Z combined with microscopy showed that chitin synthases are active essentially at the hyphal tips, which burst in the presence of the inhibitor, leading to cell death. S. parasitica was more sensitive to nikkomycin Z than S. monoica. In conclusion, chitin synthases with species-specific characteristics are involved in tip growth in Saprolegnia species and chitin is vital for the micro-organisms despite its very low abundance in the cell walls. Chitin is most likely synthesized transiently at the apex of the cells before cellulose, the major

Rheological study of chitosan acetate solutions containing chitin nanofibrils

Czech Academy of Sciences Publication Activity Database

Mikešová, Jana; Hašek, Jindřich; Tishchenko, Galina; Morganti, P.

2014-01-01

Roč. 112, 4 November (2014), s. 753-757 ISSN 0144-8617 EU Projects: European Commission(XE) 315233 - N-CHITOPACK Institutional support: RVO:61389013 Keywords : rheology * chitosan solutions * chitin nanofibrils Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.074, year: 2014

Bioproduction of Chitooligosaccharides: Present and Perspectives

Directory of Open Access Journals (Sweden)

Woo-Jin Jung

2014-10-01

Full Text Available Chitin and chitosan oligosaccharides (COS have been traditionally obtained by chemical digestion with strong acids. In light of the difficulties associated with these traditional production processes, environmentally compatible and reproducible production alternatives are desirable. Unlike chemical digestion, biodegradation of chitin and chitosan by enzymes or microorganisms does not require the use of toxic chemicals or excessive amounts of wastewater. Enzyme preparations with chitinase, chitosanase, and lysozymeare primarily used to hydrolyze chitin and chitosan. Commercial preparations of cellulase, protease, lipase, and pepsin provide another opportunity for oligosaccharide production. In addition to their hydrolytic activities, the transglycosylation activity of chitinolytic enzymes might be exploited for the synthesis of desired chitin oligomers and their derivatives. Chitin deacetylase is also potentially useful for the preparation of oligosaccharides. Recently, direct production of oligosaccharides from chitin and crab shells by a combination of mechanochemical grinding and enzymatic hydrolysis has been reported. Together with these, other emerging technologies such as direct degradation of chitin from crustacean shells and microbial cell walls, enzymatic synthesis of COS from small building blocks, and protein engineering technology for chitin-related enzymes have been discussed as the most significant challenge for industrial application.

Obtention and characterization of chitin and chitosan from M. rosenbergii; Obtencao e caracterizacao de quitina e quitosana a partr de M. rosenbergii

Energy Technology Data Exchange (ETDEWEB)

Battisti, Marcos V.; Campana Filho, Sergio P. [Sao Paulo Univ., Sao Carlos, SP (Brazil). Inst. de Quimica]. E-mail: scampana@iqsc.sc.usp.br

2001-07-01

Chitin was extracted from previously ground shells of Macrobrachium rosenbergii by applying acid and alkaline treatments, aiming at its demineralization and deprotenization, respectively. Its characteristics and properties were compared with those exhibited by commercial samples of chitin. Commercial chitosan and samples produced by the deacetylation of chitin obtained from M. rosenbergii shells were also compared. Average degrees of acetylation and intrinsic viscosities of the chitosan were determined by {sup 1}H NMR spectroscopy and by capillary viscosimetry, respectively. The results show that the chitin extracted from Macrobrachium rosenbergii has a lower content of inorganic materials as compared to commercial samples but the chitosan obtained from the former chitin sample is very similar to commercial chitosan. (author)

Chitin/clay microspheres with hierarchical architecture for highly efficient removal of organic dyes.

Science.gov (United States)

Xu, Rui; Mao, Jie; Peng, Na; Luo, Xiaogang; Chang, Chunyu

2018-05-15

Numerous adsorbents have been reported for efficient removal of dye from water, but the high cost raw materials and complicated fabrication process limit their practical applications. Herein, novel nanocomposite microspheres were fabricated from chitin and clay by a simple thermally induced sol-gel transition. Clay nanosheets were uniformly embedded in a nanofiber weaved chitin microsphere matrix, leading to their hierarchical architecture. Benefiting from this unique structure, microspheres could efficiently remove methylene blue (MB) through a spontaneous physic-sorption process which fit well with pseudo-second-order and Langmuir isotherm models. The maximal values of adsorption capability obtained by calculation and experiment were 152.2 and 156.7 mg g -1 , respectively. Chitin/clay microspheres (CCM2) could remove 99.99% MB from its aqueous solution (10 mg g -1 ) within 20 min. These findings provide insight into a new strategy for fabrication of dye adsorbents with hierarchical structure from low cost raw materials. Copyright © 2018 Elsevier Ltd. All rights reserved.

Curcumin loaded chitin nanogels for skin cancer treatment via the transdermal route.

Science.gov (United States)

Mangalathillam, Sabitha; Rejinold, N Sanoj; Nair, Amrita; Lakshmanan, Vinoth-Kumar; Nair, Shantikumar V; Jayakumar, Rangasamy

2012-01-07

In this study, curcumin loaded chitin nanogels (CCNGs) were developed using biocompatible and biodegradable chitin with an anticancer curcumin drug. Chitin, as well as curcumin, is insoluble in water. However, the developed CCNGs form a very good and stable dispersion in water. The CCNGs were analyzed by DLS, SEM and FTIR and showed spherical particles in a size range of 70-80 nm. The CCNGs showed higher release at acidic pH compared to neutral pH. The cytotoxicity of the nanogels were analyzed on human dermal fibroblast cells (HDF) and A375 (human melanoma) cell lines and the results show that CCNGs have specific toxicity on melanoma in a concentration range of 0.1-1.0 mg mL(-1), but less toxicity towards HDF cells. The confocal analysis confirmed the uptake of CCNGs by A375. The apoptotic effect of CCNGs was analyzed by a flow-cytometric assay and the results indicate that CCNGs at the higher concentration of the cytotoxic range showed comparable apoptosis as the control curcumin, in which there was negligible apoptosis induced by the control chitin nanogels. The CCNGs showed a 4-fold increase in steady state transdermal flux of curcumin as compared to that of control curcumin solution. The histopathology studies of the porcine skin samples treated with the prepared materials showed loosening of the horny layer of the epidermis, facilitating penetration with no observed signs of inflammation. These results suggest that the formulated CCNGs offer specific advantage for the treatment of melanoma, the most common and serious type of skin cancer, by effective transdermal penetration.

Thio-urethane oligomers improve the properties of light-cured resin cements.

Science.gov (United States)

Bacchi, Ataís; Consani, Rafael L; Martim, Gedalias C; Pfeifer, Carmem S

2015-05-01

Thio-urethanes were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 10-30 phr to BisGMA-UDMA-TEGDMA (5:3:2, BUT). 25 wt% silanated inorganic fillers were added. Commercial cement (Relyx Veneer, 3M-ESPE) was also evaluated with 10-20 phr of aromatic oligomer. Near-IR was used to follow methacrylate conversion (DC) and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS, %) was measured with the bonded disk technique. Results were analyzed with ANOVA/Tukey's test (α=5%). In general terms, for BUT cements, conversion and mechanical properties in flexure increased for selected groups with the addition of thio-urethane oligomers. The aromatic versions resulted in greater FS/FM than aliphatic. Fracture toughness increased by two-fold in the experimental groups (from 1.17 ± 0.36 MPam(1/2) to around 3.23 ± 0.22 MPam(1/2)). Rpmax decreased with the addition of thio-urethanes, though the vitrification point was not statistically different from the control. VS and PS decreased with both oligomers. For the commercial cement, 20 phr of oligomer increased DC, vitrification, reduced Rpmax and also significantly increased KIC, and reduced PS and FM. Thio-urethane oligomers were shown to favorably modify conventional dimethacrylate networks. Significant reductions in polymerization stress were achieved at the same time conversion and fracture toughness increased. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Multicolored, Low-Voltage-Driven, Flexible Organic Electrochromic Devices Based on Oligomers.

Science.gov (United States)

Wan, Zhijun; Zeng, Jinming; Li, Hui; Liu, Ping; Deng, Wenji

2018-04-20

In this study, a series of organic conjugated oligomers containing 3,4-ethylenedioxythiophene (EDOT) and aromatic groups are synthesized, which are as follows: 2,5-di(methyl benzoate)-3,4-ethylenedioxy-thiophene (1EDOT-2B-COOCH 3 ), 5,5'-di(methyl benzoate)-2,2'-bi(3,4-ethylenedioxythiophene) (2EDOT-2B-COOCH 3 ), 5,5″-di(methyl benzoate)-2,2':5',2″-ter(3,4-ethylenedioxythiophene) (3EDOT-2B-COOCH 3 ), and 5,5″'-di(methyl benzoate)-2,2':5',2″: 5″,2″'-quater(3,4-ethylenedioxythiophene) (4EDOT-2B-COOCH 3 ). Using these oligomers as active materials, flexible organic electrochromic devices are fabricated. The device structure is indium tin oxide-PET plastic slide (ITO-PET)/active layer/conducting gel/ITO-PET, and the electrochromic properties of oligomers are investigated. These oligomers exhibit reversible color changes upon electrochemical doping and dedoping. The highest optical contrast is exhibited by 4EDOT-2B-COOCH 3 , which is 75.2% at 700 nm. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Peptide oligomers for holographic data storage

DEFF Research Database (Denmark)

Berg, Rolf Henrik; Hvilsted, Søren; Ramanujam, P.S.

1996-01-01

SEVERAL classes of organic materials (such as photoanisotropic liquid-crystalline polymers(1-4) and photorefractive polymers(5-7)) are being investigated for the development of media for optical data storage. Here we describe a new family of organic materials-peptide oligomers containing azobenzene...

Self-assembly of aniline oligomers

Czech Academy of Sciences Publication Activity Database

Zhao, Y.; Tomšík, Elena; Wang, J.; Morávková, Zuzana; Zhigunov, Alexander; Stejskal, Jaroslav; Trchová, Miroslava

2013-01-01

Roč. 8, č. 1 (2013), s. 129-137 ISSN 1861-4728 R&D Projects: GA ČR GA202/09/1626; GA ČR GAP205/12/0911 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : morphology * oligoaniline * oligomers Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.935, year: 2013

Direct Correlation Between Ligand-Induced α-Synuclein Oligomers and Amyloid-like Fibril Growth

DEFF Research Database (Denmark)

Pedersen, Martin Nors; Foderà, Vito; Horvath, Istvan

2015-01-01

link to disease related degenerative activity. Fibrils formed in the presence and absence of FN075 are indistinguishable on microscopic and macroscopic levels. Using small angle X-ray scattering, we reveal that FN075 induced oligomers are similar, but not identical, to oligomers previously observed......Aggregation of proteins into amyloid deposits is the hallmark of several neurodegenerative diseases such as Alzheimer's and Parkinson's disease. The suggestion that intermediate oligomeric species may be cytotoxic has led to intensified investigations of pre-fibrillar oligomers, which...

Immobilisation of ligands by radio-derivatized polymers; Immobilisering av ligander med radioderiverte polymerer

Energy Technology Data Exchange (ETDEWEB)

Varga, J.M.; Fritsch, P.

1995-01-30

The invention relates to radio-derivatized polymers and a method of producing them by contacting non-polymerizable conjugands with radiolysable polymers in the presence of irradiation. The resulting radio-derivatized polymers can be further linked with ligand of organic or inorganic nature to immobilize such ligands. 2 figs., 5 tabs.

Effect of sub- and supercritical water treatments on the physicochemical properties of crab shell chitin and its enzymatic degradation.

Science.gov (United States)

Osada, Mitsumasa; Miura, Chika; Nakagawa, Yuko S; Kaihara, Mikio; Nikaido, Mitsuru; Totani, Kazuhide

2015-12-10

This study examined the effects of sub- and supercritical water pretreatments on the physicochemical properties of crab shell α-chitin and its enzymatic degradation to obtain N,N'-diacetylchitobiose (GlcNAc)2. Following sub- and supercritical water pretreatments, the protein in the crab shell was removed and the residue of crab shell contained α-chitin and CaCO3. Prolonged pretreatment led to α-chitin decomposition. The reaction of pure α-chitin in sub- and supercritical water pretreatments was investigated separately; we observed lower mean molecular weight and weaker hydrogen bonds compared with untreated α-chitin. (GlcNAc)2 yields from enzymatic degradation of subcritical (350 °C, 7 min) and supercritical water (400 °C, 2.5 min) pretreated crab shell were 8% and 6%, compared with 0% without any pretreatment. This study shows that sub- and supercritical water pretreatments of crab shell provide to an alternative method to the use of acid and base for decalcification and deproteinization of crab shell required for (GlcNAc)2 production. Copyright © 2015 Elsevier Ltd. All rights reserved.

Structural analysis of group II chitinase (ChtII) catalysis completes the puzzle of chitin hydrolysis in insects.

Science.gov (United States)

Chen, Wei; Qu, Mingbo; Zhou, Yong; Yang, Qing

2018-02-23

Chitin is a linear homopolymer of N -acetyl-β-d-glucosamines and a major structural component of insect cuticles. Chitin hydrolysis involves glycoside hydrolase family 18 (GH18) chitinases. In insects, chitin hydrolysis is essential for periodic shedding of the old cuticle ecdysis and proceeds via a pathway different from that in the well studied bacterial chitinolytic system. Group II chitinase (ChtII) is a widespread chitinolytic enzyme in insects and contains the greatest number of catalytic domains and chitin-binding domains among chitinases. In Lepidopterans, ChtII and two other chitinases, ChtI and Chi-h, are essential for chitin hydrolysis. Although ChtI and Chi-h have been well studied, the role of ChtII remains elusive. Here, we investigated the structure and enzymology of Of ChtII, a ChtII derived from the insect pest Ostrinia furnacalis We present the crystal structures of two catalytically active domains of Of ChtII, Of ChtII-C1 and Of ChtII-C2, both in unliganded form and complexed with chitooligosaccharide substrates. We found that Of ChtII-C1 and Of ChtII-C2 both possess long, deep substrate-binding clefts with endochitinase activities. Of ChtII exhibited structural characteristics within the substrate-binding cleft similar to those in Of Chi-h and Of ChtI. However, Of ChtII lacked structural elements favoring substrate binding beyond the active sites, including an extra wall structure present in Of Chi-h. Nevertheless, the numerous domains in Of ChtII may compensate for this difference; a truncation containing one catalytic domain and three chitin-binding modules ( Of ChtII-B4C1) displayed activity toward insoluble polymeric substrates that was higher than those of Of Chi-h and Of ChtI. Our observations provide the last piece of the puzzle of chitin hydrolysis in insects. © 2018 by The American Society for Biochemistry and Molecular Biology, Inc.

Determination of oligomers in virgin and recycled polyethylene terephthalate (PET) samples by UPLC-MS-QTOF.

Science.gov (United States)

Ubeda, Sara; Aznar, Margarita; Nerín, Cristina

2018-03-01

An oligomer is a molecule that consists of a few monomer units. It can be formed during polymer manufacturing and also due to polymer degradation processes or even during use conditions. Since oligomers are not included in chemical databases, their identification is a complex process. In this work, the oligomers present in 20 different PET pellet samples have been determined. Two different sample treatment procedures, solvent extraction and total dissolution, were applied in order to select the most efficient one. The analyses were carried out by UPLC-MS-QTOF. The use of high resolution mass spectrometry allowed the structural elucidation of these compounds and their correct identification. The main oligomers identified were cyclic as well as lineal from the first, second, and third series. All of them were composed of terephthalic acid (TPA), diethylene glycol (DEG), and ethylene glycol (EG). Quantitative values were very different in both procedures. In total dissolution of PET samples, the concentration of oligomers was always, at least, 10 times higher than in solvent extraction; some of the compounds were only detected when total dissolution was used. Results showed that the oligomers with the highest concentration values were dimers and trimers, cyclic, as well as lineal, from the first and second series. The oligomer with the maximum concentration value was TPA 2 -EG-DEG that was found in all the samples in a concentration range from 2493 to 19,290 ng/g PET. No differences between virgin and recycled PET were found. Migration experiments were performed in two PET bottles, and results showed the transference of most of these oligomers to a fat food simulant (ethanol 95%). Graphical abstract Graphical abstract of the two procedures developd and optimized for identifying oligomers in PET pellets and in migration form PET bottles.

Chitin degrading potential of three aquatic actinomycetes and its ...

African Journals Online (AJOL)

PRECIOUS

2009-12-01

Dec 1, 2009 ... chitinase production by all tested actinomycetes was at pH 8. S. canus and M. ... Chitin is the most abundant biopolymer next to cellulose. It is the β –1, ... Microorganisms, lower animals, birds, fungi and plants are known to ...

Chitin elicitation of natural product production in marine bacteria

DEFF Research Database (Denmark)

Månsson, Maria; Wietz, Matthias; Larsen, Thomas Ostenfeld

-negative bacteria (mainly Pseudoalteromonas and Vibrio), we found that some strains were capable of producing antibacterial compounds when grown on chitin, an N-acetyl-D-glucosamine polymer found in the exoskeleton of zooplankton.2 A strain of Vibrio coralliilyticus solely produced the antibiotic andrimid,3...

Effects of Chitin and Its Derivative Chitosan on Postharvest Decay of Fruits: A Review

Directory of Open Access Journals (Sweden)

Weimin Liu

2011-01-01

Full Text Available Considerable economic losses to harvested fruits are caused by postharvest fungal decay during transportation and storage, which can be significantly controlled by synthetic fungicides. However, considering public concern over pesticide residues in food and the environment, there is a need for safer alternatives for the control of postharvest decay to substitute synthetic fungicides. As the second most abundant biopolymer renewable source in nature, chitin and its derivative chitosan are widely used in controlling postharvest decay of fruits. This review aims to introduce the effect of chitin and chitosan on postharvest decay in fruits and the possible modes of action involved. We found most of the actions discussed in these researches rest on physiological mechanisms. All of the mechanisms are summarized to lay the groundwork for further studies which should focus on the molecular mechanisms of chitin and chitosan in controlling postharvest decay of fruits.

Process for derivatizing carbon nanotubes with diazonium species and compositions thereof

Science.gov (United States)

Tour, James M. (Inventor); Bahr, Jeffrey L. (Inventor); Yang, Jiping (Inventor)

2011-01-01

Methods for the chemical modification of carbon nanotubes involve the derivatization of multi- and single-wall carbon nanotubes, including small diameter (ca. 0.7 nm) single-wall carbon nanotubes, with diazonium species. The method allows the chemical attachment of a variety of organic compounds to the side and ends of carbon nanotubes. These chemically modified nanotubes have applications in polymer composite materials, molecular electronic applications, and sensor devices. The methods of derivatization include electrochemical induced reactions, thermally induced reactions, and photochemically induced reactions. Moreover, when modified with suitable chemical groups, the derivatized nanotubes are chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as, mechanical strength or electrical conductivity) to the properties of the composite material as a whole. Furthermore, when modified with suitable chemical groups, the groups can be polymerized to form a polymer that includes carbon nanotubes.

Effect of plagiochin E, an antifungal macrocyclic bis(bibenzyl), on cell wall chitin synthesis in Candida albicans

Institute of Scientific and Technical Information of China (English)

Xiu-zhen WU; Ai-xia CHENG; Ling-mei SUN; Hong-xiang LOU

2008-01-01

Aim: To investigate the effect of plagiochin E (PLE), an antifungal macrocyclic bis(bibenzyl) isolated from liverwort Marchantia polymorpha L, on cell wall chitin synthesis in Candida albicans. Methods: The effect of PLE on chitin synthesis in Candida albicans was investigated at the cellular and molecular lev-els. First, the ultrastructural changes were observed under transmission electron microscopy (TEM). Second, the effects of PLE on chitin synthetase (Chs) activi-ties in vitro were assayed using 6-O-dansyl-N-acetylglucosamine as a fluorescent substrate, and its effect on chitin synthesis in situ was assayed by spheroplast regeneration. Finally, real-time RT-PCR was performed to assay its effect on the expression of Chs genes (CHS). Results: Observation under TEM showed that the structure of the cell wall in Candida albicans was seriously damaged, which suggested that the antifungal activity of PLE was associated with its effect on the cell wail. Enzymatic assays and spheroplast regeneration showed that PLE inhibited chitin synthesis in vitro and in situ. The results of the PCR showed that PLE significantly downregulated the expression of CHS1, and upregulated the expression of CHS2 and CHS3. Because different Chs is regulated at different stages of transcription and post-translation, the downregulation of CHS1 would decrease the level of Chs 1 and inhibit its activity, and the inhibitory effects of PLE on Chs2 and Chs3 would be at the post-translational level or by the inhibi-tion on the enzyme-active center. Conclusion: These results indicate that the antifungal activity of PLE would be attributed to its inhibitory effect on cell wall chitin synthesis in Candida albicans.

Extraction and Characterization of Chitin and Chitosan from Blue Crab and Synthesis of Chitosan Cryogel Scaffolds

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Nimet Bölgen

2016-08-01

Full Text Available Polymeric scaffolds produced by cryogelation technique have attracted increasing attention for tissue engineering applications. Cryogelation is a technique which enables to produce interconnected porous matrices from the frozen reaction mixtures of polymers or monomeric precursors. Chitosan is a biocompatible, biodegradable, nontoxic, antibacterial, antioxidant and antifungal natural polymer that is obtained by deacetylation of chitin, which is mostly found in the exoskeleton of many crustacean. In this study, chitin was isolated from the exoskeleton of blue crap (Callinectes sapidus using a chemical method. Callinectes sapidus samples were collected from a market, as a waste material after it has been consumed as food. Demineralization, deproteinization and decolorization steps were applied to the samples to obtain chitin. Chitosan was prepared from isolated chitin by deacetylation at high temperatures. The chemical compositon of crab shell, extracted chitin and chitosan were characterized with FTIR analyses. And also to determine the physicochemical and functional properties of the produced chitosan; solubility, water binding and fat binding analysis were performed. Chitosan cryogel scaffolds were prepared by crosslinking reaction at cryogenic conditions at constant amount of chitosan (1%, w/v with different ratios of glutaraldehyde (1, 3, and 6%, v/v as crosslinker. The chemical structure of the scaffolds were examined by FTIR. Also, the water uptake capacity of scaffolds have been determined. Collectively, the results suggested that the characterized chitosan cryogels can be potential scaffolds to be used in tissue engineering applications.

Biomedical Activity of Chitin/Chitosan Based Materials—Influence of Physicochemical Properties Apart from Molecular Weight and Degree of N-Acetylation

Directory of Open Access Journals (Sweden)

Mirko X. Weinhold

2011-11-01

Full Text Available The physicochemical nature of chitin and chitosan, which influences the biomedical activity of these compounds, is strongly related to the source of chitin and the conditions of the chitin/chitosan production process. Apart from widely described key factors such as weight-averaged molecular weight (MW and degree of N-acetylation (DA, other physicochemical parameters like polydispersity (MW/MN, crystallinity or the pattern of acetylation (PA have to be taken into consideration. From the biological point of view, these parameters affect a very important factor—the solubility of chitin and chitosan in water and organic solvents. The physicochemical properties of chitosan solutions can be controlled by manipulating solution conditions (temperature, pH, ionic strength, concentration, solvent. The degree of substitution of the hydroxyl and the amino groups or the degree of quaternization of the amino groups also influence the mechanical and biological properties of chitosan samples. Finally, a considerable research effort has been directed towards developing safe and efficient chitin/chitosan-based products because many factors, like the size of nanoparticles, can determine the biomedical characteristics of medicinal products. The influence of these factors on the biomedical activity of chitin/chitosan-based products is presented in this report in more detail.

Concurrent protein synthesis is required for in vivo chitin synthesis in postmolt blue crabs

International Nuclear Information System (INIS)

Horst, M.N.

1990-01-01

Chitin synthesis in crustaceans involves the deposition of a protein-polysaccharide complex at the apical surface of epithelial cells which secrete the cuticle or exoskeleton. The present study involves an examination of in vivo incorporation of radiolabeled amino acids and amino sugars into the cuticle of postmolt blue crabs, Callinectes sapidus. Rates of incorporation of both 3H leucine and 3H threonine were linear with respect to time of incubation. Incorporation of 3H threonine into the endocuticle was inhibited greater than 90% in the presence of the protein synthesis inhibitor, puromycin. Linear incorporation of 14C glucosamine into the cuticle was also demonstrated; a significant improvement of radiolabeling was achieved by using 14C-N-acetylglucosamine as the labeled precursor. Incorporation of 3H-N-acetylglucosamine into the cuticle of postmolt blue crabs was inhibited 89% by puromycin, indicating that concurrent protein synthesis is required for the deposition of chitin in the blue crab. Autoradiographic analysis of control vs. puromycin-treated crabs indicates that puromycin totally blocks labeling of the new endocuticle with 3H glucosamine. These results are consistent with the notion that crustacean chitin is synthesized as a protein-polysaccharide complex. Analysis of the postmolt and intermolt blue crab cuticle indicates that the exoskeleton contains about 60% protein and 40% chitin. The predominant amino acids are arginine, glutamic acid, alanine, aspartic acid, and threonine

Separation of xylose oligomers using centrifugal partition chromatography with a butanol-methanol-water system.

Science.gov (United States)

Lau, Ching-Shuan; Clausen, Edgar C; Lay, Jackson O; Gidden, Jennifer; Carrier, Danielle Julie

2013-01-01

Xylose oligomers are the intermediate products of xylan depolymerization into xylose monomers. An understanding of xylan depolymerization kinetics is important to improve the conversion of xylan into monomeric xylose and to minimize the formation of inhibitory products, thereby reducing ethanol production costs. The study of xylan depolymerization requires copious amount of xylose oligomers, which are expensive if acquired commercially. Our approach consisted of producing in-house oligomer material. To this end, birchwood xylan was used as the starting material and hydrolyzed in hot water at 200 °C for 60 min with a 4 % solids loading. The mixture of xylose oligomers was subsequently fractionated by a centrifugal partition chromatography (CPC) with a solvent system of butanol:methanol:water in a 5:1:4 volumetric ratio. Operating in an ascending mode, the butanol-rich upper phase (the mobile phase) eluted xylose oligomers from the water-rich stationary phase at a 4.89 mL/min flow rate for a total fractionation time of 300 min. The elution of xylose oligomers occurred between 110 and 280 min. The yields and purities of xylobiose (DP 2), xylotriose (DP 3), xylotetraose (DP 4), and xylopentaose (DP 5) were 21, 10, 14, and 15 mg/g xylan and 95, 90, 89, and 68 %, respectively. The purities of xylose oligomers from this solvent system were higher than those reported previously using tetrahydrofuran:dimethyl sulfoxide:water in a 6:1:3 volumetric ratio. Moreover, the butanol-based solvent system improved overall procedures by facilitating the evaporation of the solvents from the CPC fractions, rendering the purification process more efficient.

Injectable Shear-Thinning CaSO4/FGF-18-Incorporated Chitin-PLGA Hydrogel Enhances Bone Regeneration in Mice Cranial Bone Defect Model.

Science.gov (United States)

Sivashanmugam, A; Charoenlarp, Pornkawee; Deepthi, S; Rajendran, Arunkumar; Nair, Shantikumar V; Iseki, Sachiko; Jayakumar, R

2017-12-13

For craniofacial bone regeneration, shear-thinning injectable hydrogels are favored over conventional scaffolds because of their improved defect margin adaptability, easier handling, and ability to be injected manually into deeper tissues. The most accepted method, after autografting, is the use of recombinant human bone morphogenetic protein-2 (BMP-2); however, complications such as interindividual variations, edema, and poor cost-efficiency in supraphysiological doses have been reported. The endogenous synthesis of BMP-2 is desirable, and a molecule which induces this is fibroblast growth factor-18 (FGF-18) because it can upregulate the BMP-2 expression  by supressing noggin. We developed a chitin-poly(lactide-co-glycolide) (PLGA) composite hydrogel by regeneration chemistry and then incorporated CaSO 4 and FGF-18 for this purpose. Rheologically, a 7-fold increase in the elastic modulus was observed in the CaSO 4 -incorporated chitin-PLGA hydrogels as compared to the chitin-PLGA hydrogel. Shear-thinning Herschel-Bulkley fluid nature was observed for both hydrogels. Chitin-PLGA/CaSO 4 gel showed sustained release of FGF-18. In vitro osteogenic differentiation showed an enhanced alkaline phosphatase (ALP) expression in the FGF-18-containing chitin-PLGA/CaSO 4 gel when compared to cells alone. Further, it was confirmed by studying the expression of osteogenic genes [RUNX2, ALP, BMP-2, osteocalcin (OCN), and osteopontin (OPN)], immunofluorescence staining of BMP-2, OCN, and OPN, and alizarin red S staining. Incorporation of FGF-18 in the hydrogel increased the endothelial cell migration. Further, the regeneration potential of the prepared hydrogels was tested in vivo, and longitudinal live animal μ-CT was performed. FGF-18-loaded chitin-PLGA/CaSO 4 showed early and almost complete bone healing in comparison with chitin-PLGA/CaSO 4 , chitin-PLGA/FGF-18, chitin-PLGA, and sham control systems, as confirmed by hematoxylin and eosin and osteoid tetrachrome stainings

Reinforcement of thermoplastic chitosan hydrogel using chitin whiskers optimized with response surface methodology.

Science.gov (United States)

Sun, Guohui; Zhang, Xin; Bao, Zixian; Lang, Xuqian; Zhou, Zhongzheng; Li, Yang; Feng, Chao; Chen, Xiguang

2018-06-01

To strengthen the mechanical strength of thermo-sensitive hydroxybutyl chitosan (HBC) hydrogel, chitin whiskers were used as sticker to fabricate reinforced HBC (HBCW) hydrogel by using response surface methodology. Unlike the intrinsic network of HBC hydrogel, HBCW hydrogel showed a laminar shape with firm structure. The preparation condition was optimized by three-factor-three-level Box-Behnken design. The maximum mechanical strength (1011.11 Pa) was achieved at 50 °C, when the concentrations of HBC and chitin whiskers were 5.1 wt% and 2.0 wt%, respectively. The effects of temperature, pH value and NaCl concentration on mechanical strength of HBCW hydrogels were investigated via the oscillatory stress sweeps. The results showed that HBCW hydrogel could reach the maximum stiffness (∼1126 Pa) at 37 °C pH 12.0. Low pH and high salty ions could decrease the stability of hydrogel, while chitin whiskers could increase the stress tolerance and related ruptured strain of HBCW hydrogels. Copyright © 2018. Published by Elsevier Ltd.

Transforming nanostructured chitin from crustacean waste into beneficial health products: a must for our society

Directory of Open Access Journals (Sweden)

Morganti P

2011-12-01

Full Text Available P Morganti1, G Morganti2, A Morganti3,41Department of Dermatology, Second University of Naples, Naples, Italy; 2Centre of Nanoscience, Mavi Sud s.r.l, Aprilia, Italy; 3Max Planck Institute for Intellectual Property and Competition Law, Munich, Germany; 4Lextray, Milan, ItalyAbstract: Chitin, obtained principally from crustacean waste, is a sugar-like polymer that is available at low cost. It has been shown to be bio- and ecocompatible, and has a very low level of toxicity. Recently, it has become possible to industrially produce pure chitin crystals, named "chitin nanofibrils" (CN for their needle-like shape and nanostructured average size (240 × 5 × 7 nm. Due to their specific chemical and physical characteristics, CN may have a range of industrial applications, from its use in biomedical products and biomimetic cosmetics, to biotextiles and health foods. At present, world offshore disposal of this natural waste material is around 250 billion tons per year. It is an underutilized resource and has the potential to supply a wide range of useful products if suitably recycled, thus contributing to sustainable growth and a greener economy.Keywords: chitin nanofibrils, biomimetic cosmetics, biomedical products, food, nanotechnology, waste

Derivatization of Dextran for Multiply Charged Ion Formation and Electrospray Ionization Time-of-Flight Mass Spectrometric Analysis

Science.gov (United States)

Tapia, Jesus B.; Hibbard, Hailey A. J.; Reynolds, Melissa M.

2017-10-01

We present the use of a simple, one-pot derivatization to allow the polysaccharide dextran to carry multiple positive charges, shifting its molecular weight distribution to a lower m/ z range. We performed this derivatization because molecular weight measurements of polysaccharides by mass spectrometry are challenging because of their lack of readily ionizable groups. The absence of ionizable groups limits proton abstraction and suppresses proton adduction during the ionization process, producing mass spectra with predominantly singly charged metal adduct ions, thereby limiting the detection of large polysaccharides. To address this challenge, we derivatized dextran T1 (approximately 1 kDa) by attaching ethylenediamine, giving dextran readily ionizable, terminal amine functional groups. The attached ethylenediamine groups facilitated proton adduction during the ionization process in positive ion mode. Using the low molecular weight dextran T1, we tracked the number of ethylenediamine attachments by measuring the mass shift from underivatized to derivatized dextran T1. Using electrospray ionization time-of-flight mass spectrometry, we observed derivatized dextran chains ranging from two to nine glucose residues with between one and four attachments/charges. Our success in shifting derivatized dextran T1 toward the low m/ z range suggests potential for this derivatization as a viable route for analysis of high molecular weight polysaccharides using electrospray ionization time-of-flight mass spectrometry. [Figure not available: see fulltext.

In vitro evaluation of paclitaxel loaded amorphous chitin nanoparticles for colon cancer drug delivery.

Science.gov (United States)

Smitha, K T; Anitha, A; Furuike, T; Tamura, H; Nair, Shantikumar V; Jayakumar, R

2013-04-01

Chitin and its derivatives have been widely used in drug delivery applications due to its biocompatible, biodegradable and non-toxic nature. In this study, we have developed amorphous chitin nanoparticles (150±50 nm) and evaluated its potential as a drug delivery system. Paclitaxel (PTX), a major chemotherapeutic agent was loaded into amorphous chitin nanoparticles (AC NPs) through ionic cross-linking reaction using TPP. The prepared PTX loaded AC NPs had an average diameter of 200±50 nm. Physico-chemical characterization of the prepared nanoparticles was carried out. These nanoparticles were proven to be hemocompatible and in vitro drug release studies showed a sustained release of PTX. Cellular internalization of the NPs was confirmed by fluorescent microscopy as well as by flow cytometry. Anticancer activity studies proved the toxicity of PTX-AC NPs toward colon cancer cells. These preliminary results indicate the potential of PTX-AC NPs in colon cancer drug delivery. Copyright © 2012 Elsevier B.V. All rights reserved.

A microfluidic device for the automated derivatization of free fatty acids to fatty acid methyl esters.

Science.gov (United States)

Duong, Cindy T; Roper, Michael G

2012-02-21

Free fatty acid (FFA) compositions are examined in feedstock for biodiesel production, as source-specific markers in soil, and because of their role in cellular signaling. However, sample preparation of FFAs for gas chromatography-mass spectrometry (GC-MS) analysis can be time and labor intensive. Therefore, to increase sample preparation throughput, a glass microfluidic device was developed to automate derivatization of FFAs to fatty acid methyl esters (FAMEs). FFAs were delivered to one input of the device and methanolic-HCl was delivered to a second input. FAME products were produced as the reagents traversed a 29 μL reaction channel held at 55 °C. A Design of Experiment protocol was used to determine the combination of derivatization time (T(der)) and ratio of methanolic-HCl:FFA (R(der)) that maximized the derivatization efficiencies of tridecanoic acid and stearic acid to their methyl ester forms. The combination of T(der) = 0.8 min and R(der) = 4.9 that produced optimal derivatization conditions for both FFAs within a 5 min total sample preparation time was determined. This combination of T(der) and R(der) was used to derivatize 12 FFAs with a range of derivatization efficiencies from 18% to 93% with efficiencies of 61% for tridecanoic acid and 84% for stearic acid. As compared to a conventional macroscale derivatization of FFA to FAME, the microfluidic device decreased the volume of methanolic-HCl and FFA by 20- and 1300-fold, respectively. The developed microfluidic device can be used for automated preparation of FAMEs to analyze the FFA compositions of volume-limited samples.

Aβ42 oligomers selectively disrupt neuronal calcium release.

Science.gov (United States)

Lazzari, Cristian; Kipanyula, Maulilio J; Agostini, Mario; Pozzan, Tullio; Fasolato, Cristina

2015-02-01

Accumulation of amyloid-β (Aβ) peptides correlates with aging and progression of Alzheimer's disease (AD). Aβ peptides, which cause early synaptic dysfunctions, spine loss, and memory deficits, also disturb intracellular Ca(2+) homeostasis. By cytosolic and endoplasmic reticulum Ca(2+) measurements, we here define the short-term effects of synthetic Aβ42 on neuronal Ca(2+) dynamics. When applied acutely at submicromolar concentration, as either oligomers or monomers, Aβ42 did not cause Ca(2+) release or Ca(2+) influx. Similarly, 1-hour treatment with Aβ42 modified neither the resting cytosolic Ca(2+) level nor the long-lasting Ca(2+) influx caused by KCl-induced depolarization. In contrast, Aβ42 oligomers, but not monomers, significantly altered Ca(2+) release from stores with opposite effects on inositol 1,4,5-trisphosphate (IP3)- and caffeine-induced Ca(2+) mobilization without alteration of the total store Ca(2+) content. Ca(2+) dysregulation by Aβ42 oligomers involves metabotropic glutamate receptor 5 and requires network activity and the intact exo-endocytotic machinery, being prevented by tetrodotoxin and tetanus toxin. These findings support the idea that Ca(2+) store dysfunction is directly involved in Aβ42 neurotoxicity and represents a potential therapeutic target in AD-like dementia. Copyright © 2015 Elsevier Inc. All rights reserved.

Systematic dynamic viscoelasticity measurements for chitin nanofibers prepared with various concentrations, disintegration times, acidities, and crystalline structures.

Science.gov (United States)

Suenaga, Shin; Osada, Mitsumasa

2018-04-17

Dynamic viscoelasticities were measured for chitin nanofiber (ChNF) dispersions prepared with various concentrations, disintegration times, acidities, and crystalline structures. The 0.05 w/v% dispersions of pH neutral ChNFs continuously exhibited elastic behavior. The 0.05 w/v% dispersions of acidified ChNFs, on the other hand, transitioned from a colloidal dispersion to a critical gel and then exhibited elastic behavior with increasing ChNF concentration. A double-logarithmic chart of the concentration vs. the storage modulus was prepared and indicated the fractal dimension and the nanostructure in the dispersion. The results determined that the neutral α- and β-ChNFs were dispersed but showed some remaining aggregations and that the acidified β-ChNFs were completely individualized. In addition, the α-chitin steadily disintegrated with increasing disintegration time, and the aspect ratio of the β-chitin decreased as a result of the exscessive disintegration. The storage moduli of the ChNFs were greater than those of chitin solutions, nanorods, and nanowhiskers with the same solids concentrations. Copyright © 2018 Elsevier B.V. All rights reserved.

Surface-Initiated Graft Atom Transfer Radical Polymerization of Methyl Methacrylate from Chitin Nanofiber Macroinitiator under Dispersion Conditions

Directory of Open Access Journals (Sweden)

Ryo Endo

2015-08-01

Full Text Available Surface-initiated graft atom transfer radical polymerization (ATRP of methyl methacrylate (MMA from self-assembled chitin nanofibers (CNFs was performed under dispersion conditions. Self-assembled CNFs were initially prepared by regeneration from a chitin ion gel with 1-allyl-3-methylimidazolium bromide using methanol; the product was then converted into the chitin nanofiber macroinitiator by reaction with α-bromoisobutyryl bromide in a dispersion containing N,N-dimethylformamide. Surface-initiated graft ATRP of MMA from the initiating sites on the CNFs was subsequently carried out under dispersion conditions, followed by filtration to obtain the CNF-graft-polyMMA film. Analysis of the product confirmed the occurrence of the graft ATRP on the surface of the CNFs.

Accumulation of oligomer-prone α-synuclein exacerbates synaptic and neuronal degeneration in vivo.

Science.gov (United States)

Rockenstein, Edward; Nuber, Silke; Overk, Cassia R; Ubhi, Kiren; Mante, Michael; Patrick, Christina; Adame, Anthony; Trejo-Morales, Margarita; Gerez, Juan; Picotti, Paola; Jensen, Poul H; Campioni, Silvia; Riek, Roland; Winkler, Jürgen; Gage, Fred H; Winner, Beate; Masliah, Eliezer

2014-05-01

In Parkinson's disease and dementia with Lewy bodies, α-synuclein aggregates to form oligomers and fibrils; however, the precise nature of the toxic α-synuclein species remains unclear. A number of synthetic α-synuclein mutations were recently created (E57K and E35K) that produce species of α-synuclein that preferentially form oligomers and increase α-synuclein-mediated toxicity. We have shown that acute lentiviral expression of α-synuclein E57K leads to the degeneration of dopaminergic neurons; however, the effects of chronic expression of oligomer-prone α-synuclein in synapses throughout the brain have not been investigated. Such a study could provide insight into the possible mechanism(s) through which accumulation of α-synuclein oligomers in the synapse leads to neurodegeneration. For this purpose, we compared the patterns of neurodegeneration and synaptic damage between a newly generated mThy-1 α-synuclein E57K transgenic mouse model that is prone to forming oligomers and the mThy-1 α-synuclein wild-type mouse model (Line 61), which accumulates various forms of α-synuclein. Three lines of α-synuclein E57K (Lines 9, 16 and 54) were generated and compared with the wild-type. The α-synuclein E57K Lines 9 and 16 were higher expressings of α-synuclein, similar to α-synuclein wild-type Line 61, and Line 54 was a low expressing of α-synuclein compared to Line 61. By immunoblot analysis, the higher-expressing α-synuclein E57K transgenic mice showed abundant oligomeric, but not fibrillar, α-synuclein whereas lower-expressing mice accumulated monomeric α-synuclein. Monomers, oligomers, and fibrils were present in α-synuclein wild-type Line 61. Immunohistochemical and ultrastructural analyses demonstrated that α-synuclein accumulated in the synapses but not in the neuronal cells bodies, which was different from the α-synuclein wild-type Line 61, which accumulates α-synuclein in the soma. Compared to non-transgenic and lower-expressing mice, the

Determination of Diacetyl in Beer by a Precolumn Derivatization-HPLC-UV Method Using 4-(2,3-Dimethyl-6-quinoxalinyl)-1,2-benzenediamine as a Derivatizing Reagent.

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Wang, Ji-Yu; Wang, Xin-Jie; Hui, Xian; Hua, Shui-Hong; Li, Heng; Gao, Wen-Yun

2017-03-29

Diacetyl is an important flavoring compound in many foods, especially in beer. In the present study, we developed and validated a new precolumn derivatization HPLC-UV method for the determination of diacetyl using 4-(2,3-dimethyl-6-quinoxalinyl)-1,2-benzenediamine as a novel derivatizing reagent. After derivatization with the reagent at a pH value 4.0 at ambient temperature for 10 min, diacetyl was analyzed on an ODS column and detected at 254 nm. The results show that the correlation coefficient of the method is 0.9991 in the range of 0.10 to 100.0 μM diacetyl, and the limit of detection is 0.02 μM. The method was further evaluated in the analysis of beer samples with the recoveries ranging from 94.4 to 102.6% and RSDs from 1.36 to 3.33%. The concentrations of diacetyl in 8 beer samples were determined in the range of 0.19 to 0.42 μM. The method established in this study may be well suitable for the determination of diacetyl in beer.

Micro-CT Imaging of Denatured Chitin by Silver to Explore Honey Bee and Insect Pathologies

Science.gov (United States)

Butzloff, Peter R.

2011-01-01

Background Chitin and cuticle coatings are important to the environmental and immune defense of honey bees and insect pollinators. Pesticides or environmental effects may target the biochemistry of insect chitin and cuticle coating. Denaturing of chitin involves a combination of deacetylation, intercalation, oxidation, Schweiger-peeling, and the formation of amine hydrochloride salt. The term “denatured chitin” calls attention to structural and property changes to the internal membranes and external carapace of organisms so that some properties affecting biological activities are diminished. Methodology/Principal Findings A case study was performed on honey bees using silver staining and microscopic computer-tomographic x-ray radiography (micro-CT). Silver nitrate formed counter-ion complexes with labile ammonium cations and reacted with amine hydrochloride. Silver was concentrated in the peritrophic membrane, on the abdomen, in the glossa, at intersegmental joints (tarsi), at wing attachments, and in tracheal air sacs. Imaged mono-esters and fatty acids from cuticle coating on external surfaces were apparently reduced by an alcohol pretreatment. Conclusions/Significance The technique provides 3-dimensional and sectional images of individual honey bees consistent with the chemistries of silver reaction and complex formation with denatured chitin. Environmental exposures and influences such as gaseous nitric oxide intercalant, trace oxidants such as ozone gas, oligosachharide salt conversion, exposure to acid rain, and chemical or biochemical denaturing by pesticides may be studied using this technique. Peritrophic membranes, which protect against food abrasion, microorganisms, and permit efficient digestion, were imaged. Apparent surface damage to the corneal lenses of compound eyes by dilute acid exposure consistent with chitin amine hydrochloride formation was imaged. The technique can contribute to existing insect pathology research, and may provide an

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex

KAUST Repository

Aly, Shawkat Mohammede

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Colloidal chitin nanogels: A plethora of applications under one shell.

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Vishnu Priya, M; Sabitha, M; Jayakumar, R

2016-01-20

Chitin nanogels (CNGs) are a relatively new class of natural polymeric nanomaterials which have a large potential in the field of drug delivery and nanotherapeutics. These nanogels being very biocompatible are non-toxic when internalized by cells. In this review various properties, preparation techniques and applications of CNGs have been described. CNGs because of their nano-size possess certain unique properties which enable them to be used in a number of biomedical applications. CNGs are prepared by simple regeneration technique without using any cross-linkers. Various polymers, drugs and fluorescent dyes can be blended or incorporated or labelled with the chitin hydrogel network. Drugs and molecules encapsulated within CNGs can be used for targeted delivery, in vivo monitoring or even for therapeutic purposes. Here various applications of CNGs in the field of drug delivery, imaging, sensing and therapeutics have been discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Towards the Shell Biorefinery: Sustainable Synthesis of the Anticancer Alkaloid Proximicin A from Chitin.

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Sadiq, Alejandro D; Chen, Xi; Yan, Ning; Sperry, Jonathan

2018-02-09

A shell biorefinery would involve fractionation of crustacean shells and incorporation of the components into value-added products, particularly those that contain nitrogen. In a proof-of-concept study that validates this concept, the anticancer alkaloid proximicin A has been synthesized from the chitin-derived platform chemical 3-acetamido-5-acetylfuran (3A5AF). This study accentuates the leading role chitin is likely to play in the sustainable production of nitrogen-containing fine chemicals that are not directly attainable from lignocellulose. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Co-Processed Chitin-Mannitol as a New Excipient for Oro-Dispersible Tablets

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Nidal Daraghmeh

2015-03-01

Full Text Available This study describes the preparation, characterization and performance of a novel excipient for use in oro-dispersible tablets (ODT. The excipient (Cop–CM consists of chitin and mannitol. The excipient with optimal physicochemical properties was obtained at a chitin: mannitol ratio of 2:8 (w/w and produced by roll compaction (RC. Differential scanning calorimetry (DSC, Fourier transform-Infrared (FT-IR, X-ray powder diffraction (XRPD and scanning electron microscope (SEM techniques were used to characterize Cop–CM, in addition to characterization of its powder and ODT dosage form. The effect of particle size distribution of Cop–CM was investigated and found to have no significant influence on the overall tablet physical properties. The compressibility parameter (a for Cop–CM was calculated from a Kawakita plot and found to be higher (0.661 than that of mannitol (0.576 due to the presence of the highly compressible chitin (0.818. Montelukast sodium and domperidone ODTs produced, using Cop–CM, displayed excellent physicochemical properties. The exceptional binding, fast wetting and superdisintegration properties of Cop–CM, in comparison with commercially available co-processed ODT excipients, results in a unique multifunctional base which can successfully be used in the formulation of oro-dispersible and fast immediate release tablets.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

Energy Technology Data Exchange (ETDEWEB)

Thompson, David N.; Apel, William A.; Thompson, Vicki S.; Ward, Thomas E.

2017-08-15

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

Science.gov (United States)

Thompson, David N; Apel, William A; Thompson, Vicki S; Ward, Thomas E

2013-07-23

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.

Methods of combined bioprocessing and related microorganisms, thermophilic and/or acidophilic enzymes, and nucleic acids encoding said enzymes

Energy Technology Data Exchange (ETDEWEB)

Thompson, David N.; Apel, William A.; Thompson, Vicki S.; Ward, Thomas E.

2016-03-22

A genetically modified organism comprising: at least one nucleic acid sequence and/or at least one recombinant nucleic acid isolated from Alicyclobacillus acidocaldarius and encoding a polypeptide involved in at least partially degrading, cleaving, transporting, metabolizing, or removing polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, xylan-, glucan-, galactan-, or mannan-decorating groups; and at least one nucleic acid sequence and/or at least one recombinant nucleic acid encoding a polypeptide involved in fermenting sugar molecules to a product. Additionally, enzymatic and/or proteinaceous extracts may be isolated from one or more genetically modified organisms. The extracts are utilized to convert biomass into a product. Further provided are methods of converting biomass into products comprising: placing the genetically modified organism and/or enzymatic extracts thereof in fluid contact with polysaccharides, cellulose, lignocellulose, hemicellulose, lignin, starch, sugars, sugar oligomers, carbohydrates, complex carbohydrates, chitin, heteroxylans, glycosides, and/or xylan-, glucan-, galactan-, or mannan-decorating groups.

1-(3-aminopropyl)-3-butylimidazolium bromide for carboxyl group derivatization: potential applications in high sensitivity peptide identification by mass spectrometry.

Science.gov (United States)

Qiao, Xiaoqiang; Zhou, Yuan; Hou, Chunyan; Zhang, Xiaodan; Yang, Kaiguang; Zhang, Lihua; Zhang, Yukui

2013-03-01

The cationic reagent 1-(3-aminopropyl)-3-butylimidazolium bromide (BAPI) was exploited for the derivatization of carboxyl groups on peptides. Nearly 100% derivatization efficiency was achieved with the synthetic peptide RVYVHPI (RI-7). Furthermore, the peptide derivative was stable in a 0.1% TFA/water solution or a 0.1% (v/v) TFA/acetonitrile/water solution for at least one week. The effect of BAPI derivatization on the ionization of the peptide RI-7 was further investigated, and the detection sensitivity was improved >42-fold via matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), thus outperforming the commercial piperazine derivatization approach. Moreover, the charge states of the peptide were largely increased via BAPI derivatization by electrospray ionization (ESI) MS. The results indicate the potential merits of BAPI derivatization for high sensitivity peptide analysis by MS.

Experimental study of the microvascular architecture and bone formation when using a carboxymethyl-chitin for bone repair in extracted sockets

International Nuclear Information System (INIS)

Kinoshita, Tamotsu; Toda, Isumi; Ehara, Yuji; Nakanishi, Ko; Suwa, Fumihiko

2011-01-01

Chitin is an absorbable agent used to promote wound healing and hemostasis, and is also used in medical treatment. We investigated the effects of carboxymethyl-chitin (CM-chitin), a water-soluble derivative of chitin, on bone augmentation. Four maxillary incisors were extracted from 5 adult Crab-eating Macaques, then the extraction sockets on the subjects' right sides were immediately filled with CM-chitin (experimental sites), while the left sides were left unfilled (control). One, two, four, eight, and twelve weeks after the procedure, the animals were euthanized and acrylic resin was injected via the common carotid arteries. Bone-microvascular corrosion casts were made and observed using scanning electron microscopy to determine the volume ratio of newly-formed bone in each socket. After 1 week, newly-formed capillary networks were observed in the sockets of the experimental sites. After 2 weeks, the sockets in both the experimental and control sites were filled with newly-formed capillary networks. After 4 weeks, newly-formed bone was observed in the sockets of both sites and the sockets were also filled with newly-formed bone after 8 weeks. After 12 weeks, trabecular bone was thicker and more compressed than after 8 weeks. Image analysis showed that the volume ratio of newly-formed bone was not significantly different between the experimental and control sites. We concluded that CM-chitin does not obstruct bone augmentation in extracted tooth sockets and is useful to promote angiogenesis in the early stages. (author)

Laccase-Catalyzed Synthesis of Low-Molecular-Weight Lignin-Like Oligomers and their Application as UV-Blocking Materials.

Science.gov (United States)

Lim, Jieyan; Sana, Barindra; Krishnan, Ranganathan; Seayad, Jayasree; Ghadessy, Farid J; Jana, Satyasankar; Ramalingam, Balamurugan

2018-02-02

The laccase-catalyzed oxidative polymerization of monomeric and dimeric lignin model compounds was carried out with oxygen as the oxidant in aqueous medium. The oligomers were characterized by using gel permeation chromatography (GPC) and matrix-assisted laser desorption ionization time-of-flight mass spectroscopy (MALDI-TOF MS) analysis. Oxidative polymerization led to the formation of oligomeric species with a number-average molecular weight (M n ) that ranged from 700 to 2300 Da with a low polydispersity index. Spectroscopic analysis provided insight into the possible modes of linkages present in the oligomers, and the oligomerization is likely to proceed through the formation of C-C linkages between phenolic aromatic rings. The oligomers were found to show good UV light absorption characteristics with high molar extinction coefficient (5000-38 000 m -1  cm -1 ) in the UV spectral region. The oligomers were blended independently with polyvinyl chloride (PVC) by using solution blending to evaluate the compatibility and UV protection ability of the oligomers. The UV/Vis transmittance spectra of the oligomer-embedded PVC films indicated that these lignin-like oligomers possessed a notable ability to block UV light. In particular, oligomers obtained from vanillyl alcohol and the dimeric lignin model were found to show good photostability in accelerated UV weathering experiments. The UV-blocking characteristics and photostability were finally compared with the commercial low-molecular-weight UV stabilizer 2,4-dihydroxybenzophenone. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Films of chitin, chitosan and cellulose obtained from aqueous suspension treated by irradiation of high intensity ultrasound

International Nuclear Information System (INIS)

Almeida, Erika V.R.; Mariano, Mario S.; Campana-Filho, Sergio P.

2011-01-01

Films of chitin, chitin/chitosan and chitin/sisal cellulose were obtained by casting their aqueous suspensions previously treated with irradiation of high intensity ultrasound. The films were characterized for surface morphology by scanning electron microscopy and it is possible notice that the films containing chitosan are much more homogeneous. The thermal behavior of the films was evaluated by dynamic mechanical thermal analysis, differential scanning calorimetry, and thermogravimetric analysis and revealing similarity in comparison with the thermal behavior of polysaccharide isolated. The tensile strength was determined and the film containing chitosan showed the best result when compared to other films. The crystallinity index of the films analyzed by X-ray diffraction showed that the films are amorphous material. The analysis by infrared spectroscopy showed that treatment of aqueous suspensions of polysaccharides with irradiation of high intensity ultrasound did not change the chemical structure of polymers. The crystallinity index was determined by X-ray diffraction, revealing that the films are amorphous materials. The results of this study indicate the possibility of processing of chitin, chitosan and cellulose, polysaccharides whose solubilities are limited to a few solvent systems, by treating their aqueous suspensions with high intensity ultrasound. (author)

Optimization of the All-D Peptide D3 for Aβ Oligomer Elimination.

Directory of Open Access Journals (Sweden)

Antonia Nicole Klein

Full Text Available The aggregation of amyloid-β (Aβ is postulated to be the crucial event in Alzheimer's disease (AD. In particular, small neurotoxic Aβ oligomers are considered to be responsible for the development and progression of AD. Therefore, elimination of thesis oligomers represents a potential causal therapy of AD. Starting from the well-characterized d-enantiomeric peptide D3, we identified D3 derivatives that bind monomeric Aβ. The underlying hypothesis is that ligands bind monomeric Aβ and stabilize these species within the various equilibria with Aβ assemblies, leading ultimately to the elimination of Aβ oligomers. One of the hereby identified d-peptides, DB3, and a head-to-tail tandem of DB3, DB3DB3, were studied in detail. Both peptides were found to: (i inhibit the formation of Thioflavin T-positive fibrils; (ii bind to Aβ monomers with micromolar affinities; (iii eliminate Aβ oligomers; (iv reduce Aβ-induced cytotoxicity; and (v disassemble preformed Aβ aggregates. The beneficial effects of DB3 were improved by DB3DB3, which showed highly enhanced efficacy. Our approach yielded Aβ monomer-stabilizing ligands that can be investigated as a suitable therapeutic strategy against AD.

Resistance mutation conserved between insects and mites unravels the benzoylurea insecticide mode of action on chitin biosynthesis.

Science.gov (United States)

Douris, Vassilis; Steinbach, Denise; Panteleri, Rafaela; Livadaras, Ioannis; Pickett, John Anthony; Van Leeuwen, Thomas; Nauen, Ralf; Vontas, John

2016-12-20

Despite the major role of chitin biosynthesis inhibitors such as benzoylureas (BPUs) in the control of pests in agricultural and public health for almost four decades, their molecular mode of action (MoA) has in most cases remained elusive. BPUs interfere with chitin biosynthesis and were thought to interact with sulfonylurea receptors that mediate chitin vesicle transport. Here, we uncover a mutation (I1042M) in the chitin synthase 1 (CHS1) gene of BPU-resistant Plutella xylostella at the same position as the I1017F mutation reported in spider mites that confers etoxazole resistance. Using a genome-editing CRISPR/Cas9 approach coupled with homology-directed repair (HDR) in Drosophila melanogaster, we introduced both substitutions (I1056M/F) in the corresponding fly CHS1 gene (kkv). Homozygous lines bearing either of these mutations were highly resistant to etoxazole and all tested BPUs, as well as buprofezin-an important hemipteran chitin biosynthesis inhibitor. This provides compelling evidence that BPUs, etoxazole, and buprofezin share in fact the same molecular MoA and directly interact with CHS. This finding has immediate effects on resistance management strategies of major agricultural pests but also on mosquito vectors of serious human diseases such as Dengue and Zika, as diflubenzuron, the standard BPU, is one of the few effective larvicides in use. The study elaborates on how genome editing can directly, rapidly, and convincingly elucidate the MoA of bioactive molecules, especially when target sites are complex and hard to reconstitute in vitro.

Effect of some biological factors on the chitin yield of two crustacean species inhabiting the Egyptian waters

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Amira Talaat Abo-Hashesh

2017-11-01

Full Text Available Objective: To investigate the chitin yield of two commercial crustacean species that are exploited in the Suez Canal region, the Red Sea crab Charybdis natator (C. natator and the Mediterranean mantis shrimp Erugosquilla massavensis (E. massavensis, and to assess the effect of some biological factors such as sex, size and maturity stages of females' ovaries on this yield. Methods: A total of 64 specimens of crabs were collected from the Red Sea and 1 377 mantis shrimps were collected from the Mediterranean Sea. Chitin was obtained after the deproteinization, de-mineralization and de-colorization of 5 g oven dried exoskeletons and values were expressed as g/5 g and percentages. Results: Chitin yield was significantly higher in E. massavensis than C. natator (22.1%, 14.22%, respectively. No significant difference in the yield was recorded between males and females of C. natator (12.9%, 14.9%, respectively, while the yield in E. massavensis males was significantly higher than females (25.3%, 21.2%, respectively. Significant variations in the chitin yield were observed between the different sizes of E. massavensis with the maximum being from the individuals falling in the size range 90–130 mm body length. The yield was at its lowest in the immature stage of C. natator females' ovaries (9.29%. However, the values increased and remained constant for the remaining stages (≥ 18%. Conclusions: The study recommends the use of the mantis shrimp for the production of chitin on commercial scale particularly medium sized males.

PrP(Sc-specific antibodies with the ability to immunodetect prion oligomers.

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Mourad Tayebi

Full Text Available The development of antibodies with binding capacity towards soluble oligomeric forms of PrPSc recognised in the aggregation process in early stage of the disease would be of paramount importance in diagnosing prion diseases before extensive neuropathology has ensued. As blood transfusion appears to be efficient in the transmission of the infectious prion agent, there is an urgent need to develop reagents that would specifically recognize oligomeric forms of the abnormally folded prion protein, PrPSc.To that end, we show that anti-PrP monoclonal antibodies (called PRIOC mAbs derived from mice immunised with native PrP-coated microbeads are able to immunodetect oligomers/multimers of PrPSc. Oligomer-specific immunoreactivity displayed by these PRIOC mAbs was demonstrated as large aggregates of immunoreactive deposits in prion-permissive neuroblastoma cell lines but not in equivalent non-infected or prn-p(0/0 cell lines. In contrast, an anti-monomer PrP antibody displayed diffuse immunoreactivity restricted to the cell membrane. Furthermore, our PRIOC mAbs did not display any binding with monomeric recombinant and cellular prion proteins but strongly detected PrPSc oligomers as shown by a newly developed sensitive and specific ELISA. Finally, PrioC antibodies were also able to bind soluble oligomers formed of Aβ and α-synuclein. These findings demonstrate the potential use of anti-prion antibodies that bind PrPSc oligomers, recognised in early stage of the disease, for the diagnosis of prion diseases in blood and other body fluids.

Amyloid β oligomers induce interleukin-1β production in primary microglia in a cathepsin B- and reactive oxygen species-dependent manner

Energy Technology Data Exchange (ETDEWEB)

Taneo, Jun; Adachi, Takumi [Department of Animal Development and Physiology, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto 606-8501 (Japan); Yoshida, Aiko; Takayasu, Kunio [Responses to Environmental Signals and Stresses, Graduate School of Biostudies, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto, Kyoto 606-8501 (Japan); Takahara, Kazuhiko, E-mail: ktakahar@zoo.zool.kyoto-u.ac.jp [Department of Animal Development and Physiology, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto 606-8501 (Japan); Japan Science and Technology Agency, Core Research for Evolutional Science and Technology (CREST), Tokyo 102-0081 (Japan); Inaba, Kayo [Department of Animal Development and Physiology, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto 606-8501 (Japan); Japan Science and Technology Agency, Core Research for Evolutional Science and Technology (CREST), Tokyo 102-0081 (Japan)

2015-03-13

Amyloid β (Aβ) peptide, a causative agent of Alzheimer's disease, forms two types of aggregates: oligomers and fibrils. These aggregates induce inflammatory responses, such as interleukin-1β (IL-1β) production by microglia, which are macrophage-like cells located in the brain. In this study, we examined the effect of the two forms of Aβ aggregates on IL-1β production in mouse primary microglia. We prepared Aβ oligomer and fibril from Aβ (1–42) peptide in vitro. We analyzed the characteristics of these oligomers and fibrils by electrophoresis and atomic force microscopy. Interestingly, Aβ oligomers but not Aβ monomers or fibrils induced robust IL-1β production in the presence of lipopolysaccharide. Moreover, Aβ oligomers induced endo/phagolysosome rupture, which released cathepsin B into the cytoplasm. Aβ oligomer-induced IL-1β production was inhibited not only by the cathepsin B inhibitor CA-074-Me but also by the reactive oxygen species (ROS) inhibitor N-acetylcysteine. Random chemical crosslinking abolished the ability of the oligomers to induce IL-1β. Thus, multimerization and fibrillization causes Aβ oligomers to lose the ability to induce IL-1β. These results indicate that Aβ oligomers, but not fibrils, induce IL-1β production in primary microglia in a cathepsin B- and ROS-dependent manner. - Highlights: • We prepared amyloid β (Aβ) fibrils with minimum contamination of Aβ oligomers. • Primary microglia (MG) produced IL-1β in response to Aβ oligomers, but not fibrils. • Only Aβ oligomers induced leakage of cathepsin B from endo/phagolysosomes. • IL-1β production in response to Aβ oligomers depended on both cathepsin B and ROS. • Crosslinking reduced the ability of the Aβ oligomers to induce IL-1β from MG.

Causative factors for formation of toxic islet amyloid polypeptide oligomer in type 2 diabetes mellitus

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Jeong HR

2015-11-01

Full Text Available Hye Rin Jeong, Seong Soo A AnDepartment of Bionano Technology, Gachon Medical Research Institute, Gachon University, Gyeonggi-do, Republic of KoreaAbstract: Human islet amyloid polypeptide (h-IAPP is a peptide hormone that is synthesized and cosecreted with insulin from insulin-secreting pancreatic β-cells. Recently, h-IAPP was proposed to be the main component responsible for the cytotoxic pancreatic amyloid deposits in patients with type 2 diabetes mellitus (T2DM. Since the causative factors of IAPP (or amylin oligomer aggregation are not fully understood, this review will discuss the various forms of h-IAPP aggregation. Not all forms of IAPP aggregates trigger the destruction of β-cell function and loss of β-cell mass; however, toxic oligomers do trigger these events. Once these toxic oligomers form under abnormal metabolic conditions in T2DM, they can lead to cell disruption by inducing cell membrane destabilization. In this review, the various factors that have been shown to induce toxic IAPP oligomer formation will be presented, as well as the potential mechanism of oligomer and fibril formation from pro-IAPPs. Initially, pro-IAPPs undergo enzymatic reactions to produce the IAPP monomers, which can then develop into oligomers and fibrils. By this mechanism, toxic oligomers could be generated by diverse pathway components. Thus, the interconnections between factors that influence amyloid aggregation (eg, absence of PC2 enzyme, deamidation, reduction of disulfide bonds, environmental factors in the cell, genetic mutations, copper metal ions, and heparin will be presented. Hence, this review will aid in understanding the fundamental causative factors contributing to IAPP oligomer formation and support studies for investigating novel T2DM therapeutic approaches, such as the development of inhibitory agents for preventing oligomerization at the early stages of diabetic pathology.Keywords: amyloid aggregation, causative factor, IAPP, islet

Dynamics in coarse-grained models for oligomer-grafted silica nanoparticles

KAUST Repository

Hong, Bingbing

2012-01-01

Coarse-grained models of poly(ethylene oxide) oligomer-grafted nanoparticles are established by matching their structural distribution functions to atomistic simulation data. Coarse-grained force fields for bulk oligomer chains show excellent transferability with respect to chain lengths and temperature, but structure and dynamics of grafted nanoparticle systems exhibit a strong dependence on the core-core interactions. This leads to poor transferability of the core potential to conditions different from the state point at which the potential was optimized. Remarkably, coarse graining of grafted nanoparticles can either accelerate or slowdown the core motions, depending on the length of the grafted chains. This stands in sharp contrast to linear polymer systems, for which coarse graining always accelerates the dynamics. Diffusivity data suggest that the grafting topology is one cause of slower motions of the cores for short-chain oligomer-grafted nanoparticles; an estimation based on transition-state theory shows the coarse-grained core-core potential also has a slowing-down effect on the nanoparticle organic hybrid materials motions; both effects diminish as grafted chains become longer. © 2012 American Institute of Physics.

Interchain interactions in charged diacetylenic oligomers carrying bulk substituents revisited

International Nuclear Information System (INIS)

Ottonelli, M.; Izzo, G.M.M.; Comoretto, D.; Musso, G.F.; Dellepiane, G.

2006-01-01

We are studying how the electronic properties of an aggregate, built with conjugated oligomers carrying bulk substituents, are affected by intermolecular interactions. In this paper we apply the CEO (Collective Electronic Oscillator) method, on the basis of the semiempirical INDO/S Hamiltonian, to compute the electronic density matrix modifications following the photon absorption in a doubly charged cluster of two units of a fully carbazolyl-substituted oligodiacetylene tetramer, taken as a model system. The picture that had emerged from our previous calculations based on the less sophisticated CIS (Configuration Interaction including Singles) approach is seen to be confirmed. Despite the large separation between the backbones, a through-space charge transfer occurs between the two oligomers due to the fact that the excess charge, contrary to what is generally believed, is not localized on the conjugated backbone, but is spread out over the carbazolyl moieties of the charged molecule. Consideration of this kind of interaction improves the theoretical results obtained for the isolated charged oligomer chain, and aids in better explaining some features of the experimental photoinduced spectra of the corresponding polymer

ATL9, a RING zinc finger protein with E3 ubiquitin ligase activity implicated in chitin- and NADPH oxidase-mediated defense responses.

Directory of Open Access Journals (Sweden)

Marta Berrocal-Lobo

2010-12-01

Full Text Available Pathogen associated molecular patterns (PAMPs are signals detected by plants that activate basal defenses. One of these PAMPs is chitin, a carbohydrate present in the cell walls of fungi and in insect exoskeletons. Previous work has shown that chitin treatment of Arabidopsis thaliana induced defense-related genes in the absence of a pathogen and that the response was independent of the salicylic acid (SA, jasmonic acid (JA and ethylene (ET signaling pathways. One of these genes is ATL9 ( = ATL2G, which encodes a RING zinc-finger like protein. In the current work we demonstrate that ATL9 has E3 ubiquitin ligase activity and is localized to the endoplasmic reticulum. The expression pattern of ATL9 is positively correlated with basal defense responses against Golovinomyces cichoracearum, a biotrophic fungal pathogen. The basal levels of expression and the induction of ATL9 by chitin, in wild type plants, depends on the activity of NADPH oxidases suggesting that chitin-mediated defense response is NADPH oxidase dependent. Although ATL9 expression is not induced by treatment with known defense hormones (SA, JA or ET, full expression in response to chitin is compromised slightly in mutants where ET- or SA-dependent signaling is suppressed. Microarray analysis of the atl9 mutant revealed candidate genes that appear to act downstream of ATL9 in chitin-mediated defenses. These results hint at the complexity of chitin-mediated signaling and the potential interplay between elicitor-mediated signaling, signaling via known defense pathways and the oxidative burst.

Chitin stimulates expression of acidic mammalian chitinase and eotaxin-3 by human sinonasal epithelial cells in vitro.

Science.gov (United States)

Lalaker, Ashley; Nkrumah, Louis; Lee, Won-Kyung; Ramanathan, Murugappan; Lane, Andrew P

2009-01-01

Sinonasal epithelial cells participate in host defense by initiating innate immune mechanisms against potential pathogens. Antimicrobial innate mechanisms have been shown to involve Th1-like inflammatory responses. Although epithelial cells can also be induced by Th2 cytokines to express proeosinophilic mediators, no environmental agents have been identified that promote this effect. Human sinonasal epithelial cells from patients with chronic rhinosinusitis with nasal polyps (CRSwNPs) and controls were harvested and grown in primary culture. Cell cultures were exposed to a range of concentrations of chitin for 24 hours, and mRNA for acidic mammalian chitinase (AMCase), eotaxin-3, and thymic stromal-derived lymphopoietin (TSLP) were assessed. Other cultures were exposed to interleukin 4 (IL- 4) alone and in combination with dust-mite antigen (DMA) for 36 hours. Extracted mRNA and cell culture supernatant were analyzed for expression of AMCase and eotaxin-3. Chitin induced a dose-dependent expression of AMCase and eotaxin-3 mRNA but not TSLP. Patients with recalcitrant CRSwNPs showed lower baseline expression of AMCase when compared with treatment-responsive CRSwNP and less induction of AMCase expression by chitin. DMA did not directly induce expression of AMCase or eotaxin-3. Expression of eotaxin-3 was stimulated by IL-4 and further enhanced with the addition of DMA. Levels of AMCase were not significantly affected by either IL-4 or DMA exposure. In some cases, the combination of IL-4 and DMA was able to induce AMCase expression in cell cultures not producing AMCase at baseline. The abundant biopolymer chitin appears to be recognized by a yet uncharacterized receptor on sinonasal epithelial cells. Chitin stimulates production of AMCase and eotaxin-3, two pro-Th2 effector proteins. This finding suggests the existence of a novel innate immune pathway for local defense against chitin-containing organisms in the sinonasal tract. Dysregulation of this function could

Morphological study of chitin from Xiphopenaeus kroyeri exoskeletons by using atomic force microscopy (AFM) and CPMAS 13 C NMR

International Nuclear Information System (INIS)

Silva, K.M.; Tavares, M.I.; Andrade, C.T.; Simao, R.A.

1999-01-01

A sample of α chitin was isolated from exoskeletons of Xiphopenaeus kroyeri. This sample ws dissolved in phosphoric acid and recovered as a fibrous precipitate. Atomic force microscopy was used in noncontact mode to obtain images of the native chitin sample. Different morphological features were observed, including rigid rod crystals 200-300 nm wide. Solid state 13 C NMR techniques were used to investigate chitin samples, and revealed molecular order in both samples. The differences observed in the proton spin-lattice relaxation times in the rotating frame, T H1 p were attributed to the formation of hydrogen bonds in preferential sites in the samples. (author)

Introduction of 5'-terminal functional groups into synthetic oligonucleotides for selective immobilization

NARCIS (Netherlands)

Bischoff, Rainer; Coull, J.M.; Regnier, F.E.

1987-01-01

Oligodeoxyribonucleotides terminating in a 5'-primary amine group are synthesized using solid-phase supported phosphoramidite chemistry. The 5'-terminal amine group in the deprotected oligomers is further derivatized with either succinic anhydride to give 5'-carboxylic acid or with

Photoreactive polymer brushes for high-density patterned surface derivatization using a Diels-Alder photoclick reaction.

Science.gov (United States)

Arumugam, Selvanathan; Orski, Sara V; Locklin, Jason; Popik, Vladimir V

2012-01-11

Reactive polymer brushes grown on silicon oxide surfaces were derivatized with photoreactive 3-(hydroxymethyl)naphthalene-2-ol (NQMP) moieties. Upon 300 or 350 nm irradiation, NQMP efficiently produces o-naphthoquinone methide (oNQM), which in turn undergoes very rapid Diels-Alder addition to vinyl ether groups attached to a substrate, resulting in the covalent immobilization of the latter. Any unreacted oNQM groups rapidly add water to regenerate NQMP. High-resolution surface patterning is achieved by irradiating NQMP-derivatized surfaces using photolithographic methods. The Diels-Alder photoclick reaction is orthogonal to azide-alkyne click chemistry, enabling sequential photoclick/azide-click derivatizations to generate complex surface functionalities. © 2011 American Chemical Society

Review of in situ derivatization techniques for enhanced bioanalysis using liquid chromatography with mass spectrometry.

Science.gov (United States)

Baghdady, Yehia Z; Schug, Kevin A

2016-01-01

Accurate and specific analysis of target molecules in complex biological matrices remains a significant challenge, especially when ultra-trace detection limits are required. Liquid chromatography with mass spectrometry is often the method of choice for bioanalysis. Conventional sample preparation and clean-up methods prior to the analysis of biological fluids such as liquid-liquid extraction, solid-phase extraction, or protein precipitation are time-consuming, tedious, and can negatively affect target recovery and detection sensitivity. An alternative or complementary strategy is the use of an off-line or on-line in situ derivatization technique. In situ derivatization can be incorporated to directly derivatize target analytes in their native biological matrices, without any prior sample clean-up methods, to substitute or even enhance the extraction and preconcentration efficiency of these traditional sample preparation methods. Designed appropriately, it can reduce the number of sample preparation steps necessary prior to analysis. Moreover, in situ derivatization can be used to enhance the performance of the developed liquid chromatography with mass spectrometry-based bioanalysis methods regarding stability, chromatographic separation, selectivity, and ionization efficiency. This review presents an overview of the commonly used in situ derivatization techniques coupled to liquid chromatography with mass spectrometry-based bioanalysis to guide and to stimulate future research. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extended Ladder-Type Benzo[ k ]tetraphene-Derived Oligomers

Energy Technology Data Exchange (ETDEWEB)

Lee, Jongbok [Department of Chemistry, Texas A& M University, 3255 TAMU College Station TX 77843-3255 USA; Li, Huanbin [MOE Key Laboratory of Macromolecular Synthesis and Functionalization, State Key Laboratory of Silicon Materials, Department of Polymer Science and Engineering, Zhejiang University, 38 Zheda Rd Hangzhou 310027 China; Kalin, Alexander J. [Department of Chemistry, Texas A& M University, 3255 TAMU College Station TX 77843-3255 USA; Yuan, Tianyu [Department of Materials Science and Engineering, Texas A& M University, 3003 TAMU College Station TX 77843-3003 USA; Wang, Chenxu [Department of Materials Science and Engineering, Texas A& M University, 3003 TAMU College Station TX 77843-3003 USA; Olson, Troy [Department of Chemistry, Texas A& M University, 3255 TAMU College Station TX 77843-3255 USA; Li, Hanying [MOE Key Laboratory of Macromolecular Synthesis and Functionalization, State Key Laboratory of Silicon Materials, Department of Polymer Science and Engineering, Zhejiang University, 38 Zheda Rd Hangzhou 310027 China; Fang, Lei [Department of Chemistry, Texas A& M University, 3255 TAMU College Station TX 77843-3255 USA; Department of Materials Science and Engineering, Texas A& M University, 3003 TAMU College Station TX 77843-3003 USA

2017-10-02

Well-defined, fused-ring aromatic oligomers represent promising candidates for the fundamental understanding and application of advanced carbon-rich materials, though bottom-up synthesis and structure–property correlation of these compounds remain challenging. In this work, an efficient synthetic route was employed to construct extended benzo[k]tetraphene-derived oligomers with up to 13 fused rings. The molecular and electronic structures of these compounds were clearly elucidated. Precise correlation of molecular sizes and crystallization dynamics was established, thus demonstrating the pivotal balance between intermolecular interaction and molecular mobility for optimized processing of highly ordered solids of these extended conjugated molecules.

Thermal analysis and structural characterization of chitinous exoskeleton from two marine invertebrates

International Nuclear Information System (INIS)

Juárez-de la Rosa, B.A.; May-Crespo, J.; Quintana-Owen, P.; Gónzalez-Gómez, W.S.; Yañez-Limón, J.M.; Alvarado-Gil, J.J.

2015-01-01

Highlights: • Thermal analysis of exoskeletons: Antipathes caribbeana and Limulus polyphemus. • DMTA revealed Limulus has a stronger structure with a stepper glass transition. • DSC measurements exhibited a much larger water holding capacity in Antipathes. • X-ray diffraction analysis shows a higher crystallinity index in Limulus • FTIR showed α-chitin structures and high temperature C–N groups prevalence. - ABSTRACT: Thermomechanical and structural properties of two marine species exoskeletons, Antipathes caribbeana (black coral) and Limulus polyphemus (xiphosure), were studied using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). DMTA curves indicate the viscoelastic behavior and glass transition around 255 °C, black coral presented a second transition (175 °C) associated to the acetamide group attached to the α-chitin chain. DSC measurements showed a endothermic peak around 100 °C, with enthalpies of 4.02 and 118.04 J/g, indicating strong differences between exoskeletons respect to their water holding capacity and strength water–polymer interaction. A comparative analysis involving DSC and X-ray diffraction showed that lower values ΔH in xiphosure correspond to a material with a higher crystallinity (30), in contrast black coral exhibits higher values ΔH and a lower crystallinity (19). FTIR confirmed α-chitin based structure, at higher temperature diminishes the amide bands and a new one appears, related to C–N groups

Thermal analysis and structural characterization of chitinous exoskeleton from two marine invertebrates

Energy Technology Data Exchange (ETDEWEB)

Juárez-de la Rosa, B.A., E-mail: balej05@yahoo.com.mx [Laboratory of Natural Polymers, CIAD – Coordinación Guaymas, Carretera al Varadero Nacional km. 6.6, Col. Las Playitas, 85480 Guaymas, Sonora (Mexico); Applied Physics Department, CINVESTAV-IPN Unidad Mérida, Carretera antigua a Progreso, km. 6. Apdo, Postal 73, Cordemex, 97310 Mérida, Yucatan (Mexico); May-Crespo, J.; Quintana-Owen, P.; Gónzalez-Gómez, W.S. [Applied Physics Department, CINVESTAV-IPN Unidad Mérida, Carretera antigua a Progreso, km. 6. Apdo, Postal 73, Cordemex, 97310 Mérida, Yucatan (Mexico); Yañez-Limón, J.M. [Materials and Engineering Science, CINVESTAV-IPN, Unidad Querétaro, Libramiento Norponiente No. 2000, Fracc. Real de Juriquilla, 76230 Santiago de Querétaro, Querétaro (Mexico); Alvarado-Gil, J.J., E-mail: jjag@mda.cinvestav.mx [Applied Physics Department, CINVESTAV-IPN Unidad Mérida, Carretera antigua a Progreso, km. 6. Apdo, Postal 73, Cordemex, 97310 Mérida, Yucatan (Mexico)

2015-06-20

Highlights: • Thermal analysis of exoskeletons: Antipathes caribbeana and Limulus polyphemus. • DMTA revealed Limulus has a stronger structure with a stepper glass transition. • DSC measurements exhibited a much larger water holding capacity in Antipathes. • X-ray diffraction analysis shows a higher crystallinity index in Limulus • FTIR showed α-chitin structures and high temperature C–N groups prevalence. - ABSTRACT: Thermomechanical and structural properties of two marine species exoskeletons, Antipathes caribbeana (black coral) and Limulus polyphemus (xiphosure), were studied using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). DMTA curves indicate the viscoelastic behavior and glass transition around 255 °C, black coral presented a second transition (175 °C) associated to the acetamide group attached to the α-chitin chain. DSC measurements showed a endothermic peak around 100 °C, with enthalpies of 4.02 and 118.04 J/g, indicating strong differences between exoskeletons respect to their water holding capacity and strength water–polymer interaction. A comparative analysis involving DSC and X-ray diffraction showed that lower values ΔH in xiphosure correspond to a material with a higher crystallinity (30), in contrast black coral exhibits higher values ΔH and a lower crystallinity (19). FTIR confirmed α-chitin based structure, at higher temperature diminishes the amide bands and a new one appears, related to C–N groups.

Excitations and optical properties of phenylene-based conjugated polymers and oligomers

Science.gov (United States)

Brazovskii, S.; Kirova, N.; Bishop, A. R.; Klimov, V.; McBranch, D.; Barashkov, N. N.; Ferraris, J. P.

1998-01-01

We present a combined experimental and theoretical study of the ground and photoexcited optical properties of a model oligomer of PPV, MEH-DSB. Our theoretical picture is based upon a band description of electronic states of PPV oligomers, while invoking corrections from Coulomb interactions. The necessary discrete energy levels at low and intermediate energies appear naturally, in addition to the lower energy delocalized states. On this basis we identify the most important features in direct optical absorption for both high (4-6 eV) and low (2-4 eV) photon energies as well as in photoinduced absorption (PA) and stimulated photoemissions (SE) in MEH-DSB solutions, which represent the limit of noninteracting oligomers. While in agreement with previous interpretations for three absorption peaks (2.74, 4.46 and 6.2 eV), we give a new assignment for the most disputed 3.62 eV one as well as for the two PA peaks.

Nitrogen-Containing, Light-Absorbing Oligomers Produced in Aerosol Particles Exposed to Methylglyoxal, Photolysis, and Cloud Cycling.

Science.gov (United States)

De Haan, David O; Tapavicza, Enrico; Riva, Matthieu; Cui, Tianqu; Surratt, Jason D; Smith, Adam C; Jordan, Mary-Caitlin; Nilakantan, Shiva; Almodovar, Marisol; Stewart, Tiffany N; de Loera, Alexia; De Haan, Audrey C; Cazaunau, Mathieu; Gratien, Aline; Pangui, Edouard; Doussin, Jean-François

2018-04-03

Aqueous methylglyoxal chemistry has often been implicated as an important source of oligomers in atmospheric aerosol. Here we report on chemical analysis of brown carbon aerosol particles collected from cloud cycling/photolysis chamber experiments, where gaseous methylglyoxal and methylamine interacted with glycine, ammonium, or methylammonium sulfate seed particles. Eighteen N-containing oligomers were identified in the particulate phase by liquid chromatography/diode array detection/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry. Chemical formulas were determined and, for 6 major oligomer products, MS 2 fragmentation spectra were used to propose tentative structures and mechanisms. Electronic absorption spectra were calculated for six tentative product structures by an ab initio second order algebraic-diagrammatic-construction/density functional theory approach. For five structures, matching calculated and measured absorption spectra suggest that they are dominant light-absorbing species at their chromatographic retention times. Detected oligomers incorporated methylglyoxal and amines, as expected, but also pyruvic acid, hydroxyacetone, and significant quantities of acetaldehyde. The finding that ∼80% (by mass) of detected oligomers contained acetaldehyde, a methylglyoxal photolysis product, suggests that daytime methylglyoxal oligomer formation is dominated by radical addition mechanisms involving CH 3 CO*. These mechanisms are evidently responsible for enhanced browning observed during photolytic cloud events.

Structure–property relationships of synthetic organophosphorus flame retardant oligomers by thermal analysis

International Nuclear Information System (INIS)

Bai, Zhiman; Wang, Xin; Tang, Gang; Song, Lei; Hu, Yuan; Yuen, Richard K.K.

2013-01-01

Highlights: • Oligomers with different chemical components in molecular chains were synthesized. • FP-3 containing three IFR components possessed high thermal stability. • FP-3 possessed lowest flammability. • FP-3 exhibited a synergistic interaction between gas and condensed phase. - Abstract: A series of flame retardant oligomers with different chemical components in molecular chains, designated as FP-1, FP-2 and FP-3, respectively, were successfully synthesized using solution polycondensation and well characterized. The thermal properties and flammability of these oligomers were investigated by thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). The results demonstrated that FP-3 had the lowest flammability in terms of the lowest maximum mass loss rate, and FP-1 possessed the highest thermal stability and char yield, due to its higher stable hexatomic ring structure of piperazine compared with the linear alkane chain structure of neopentyl glycol. The gases evolved during decomposition were analyzed using Fourier transform infrared coupled with the thermogravimetric analyzer (TG–IR) technique. The char residues of the flame retardant oligomers were investigated by scanning electron microscopy (SEM) and Raman spectroscopy. The results demonstrated that FP-3 exhibited a synergistic interaction between the gas phase and condensation phase, increasing its flame retardancy

Patterns of proteolytic cleavage and carbodiimide derivatization in sarcoplasmic reticulum adenosinetriphosphatase

International Nuclear Information System (INIS)

de Ancos, J.G.; Inesi, G.

1988-01-01

Two series of experiments were carried out to characterize (a) peptide fragments of sarcoplasmic reticulum (SR) ATPase, based on proteolysis with different enzymes and distribution of known labels, and (b) specific labeling and functional inactivation patterns, following ATPase derivatization with dicyclohexylcarbodiimide (DCCD) under various conditions. Digestion with trypsin or chymotrypsin results in the initial cleavage of the SR ATPase in two fragments of similar size and then into smaller fragments, while subtilisin and thermolysin immediately yield smaller fragments. Peptide fragments were assigned to segments of the protein primary structure and to functionally relevant domains, such as those containing the 32 P at the active site and the fluorescein isothiocyanate at the nucleotide site. ATPase derivatization with [ 14 C]DCCD under mild conditions produced selective inhibition of ATPase hydrolytic catalysis without significant incorporation of the 14 C radioactive label. This effect is attributed to blockage of catalytically active residues by reaction of the initial DCCD adduct with endogenous or exogenous nucleophiles. ATPase derivatization with [ 14 C]DCCD under more drastic conditions produced inhibition of calcium binding, 14 C radioactive labeling of tryptic fragments A 1 and A 2 (but not of B), and extensive cross-linking. The presence of calcium during derivatization prevented functional inactivation, radioactive labeling of fragment A 2 , and internal cross-linking of fragment A 1 . It is proposed that both A 1 and A 2 fragments participate in formation of the calcium binding domain and that the labeled residues of fragment A 2 are directly involved in calcium complexation. A diagram is constructed, representing the relative positions of labels and functional domains within the ATPase protein

Chitinase and chitin synthase 1: counterbalancing activities in cell separation of Saccharomyces cerevisiae.

Science.gov (United States)

Cabib, E; Silverman, S J; Shaw, J A

1992-01-01

Previous results [E. Cabib, A. Sburlati, B. Bowers & S. J. Silverman (1989) Journal of Cell Biology 108, 1665-1672] strongly suggested that the lysis observed in daughter cells of Saccharomyces cerevisiae defective in chitin synthase 1 (Chs1) was caused by a chitinase that partially degrades the chitin septum in the process of cell separation. Consequently, it was proposed that in wild-type cells, Chs1 acts as a repair enzyme by replenishing chitin during cytokinesis. The chitinase requirement for lysis has been confirmed in two different ways: (a) demethylallosamidin, a more powerful chitinase inhibitor than the previously used allosamidin, is also a much better protector against lysis and (b) disruption of the chitinase gene in chs1 cells eliminates lysis. Reintroduction of a normal chitinase gene, by transformation of those cells with a suitable plasmid, restores lysis. The percentage of lysed cells in strains lacking Chs1 was not increased by elevating the chitinase level with high-copy-number plasmids carrying the hydrolase gene. Furthermore, the degree of lysis varied in different chs1 strains; lysis was abolished in chs1 mutants containing the scs1 suppressor. These results indicate that, in addition to chitinase, lysis requires other gene products that may become limiting.

Inhibition of chitin biosynthesis in cultured imaginal discs: Effects of alpha-amanitin, actinomycin-D, cycloheximide, and puromycin.

Science.gov (United States)

Oberlander, Herbert; Ferkovich, Stephen; Leach, Eddie; Van Essen, Frank

1980-02-01

Wing imaginal discs isolated from last instar larvae of the Indian meal moth,Plodia interpunctella, produced chitin when incubated in vitro with ≧2×10 -7 M 20-hydroxyecdysone. Chitin biosynthesis was initiated 8 h after the conclusion of a 24-h treatment with hormone. Simulataneous incubation of wing discs with 20-hydroxyecdysone and either inhibitors of RNA synthesis (alpha-amanitin, actinomycin-D) or inhibitors of protein systhesis (cycloheximide, puromycin) prevented chitin biosynthesis. We conclude from our results that RNA and protein synthesis must continue undiminished during the hormone-contact period, and that synthesis of protein, but not of new RNA is required during the posthormone culture period. Our findings are consistent with the hypothesis that ecdysteroids stimulate insect metamorphosis by promoting the synthesis of new RNA and protein during a hormone-dependent phase followed by hormone-independent protein synthesis.

FIBCD1 Modulation of the Epithelial Immune Response Elicited by Chitin

DEFF Research Database (Denmark)

Hammond, Mark; Schlosser, Anders; Bak-Thomsen, Theresa Helene

2010-01-01

of NF-jB signalling and downstream synthesis of mucosal epithelial-derived cytokines, TSLP and IL-33, which shapes the local accumulation and activation of Th2 responses. Results: Initial experiments have focused on the establishment of stable FIBCD1 overexpression in HEK293, HCT-116 and A549 epithelial......Background: FIBCD1 is a type II transmembrane protein located on the brush border of intestinal epithelial cells. FIBCD1 binds specifically to acetylated compounds such as chitin through the C-terminal fibrinogen-related domain. Chitin is a highly acetylated homopolymeric b-1,4-N...... or the model ligand acetylated BSA, at different time intervals anddoses and using a luciferase reporter system detection of NFjB activation will be performed and cytokine expression will be quantified via qRT-PCR. Perspectives: Improved understanding of epithelialimmune and inflammatory modulation in response...

Comparison of green method for chitin deacetylation

Science.gov (United States)

Anwar, Muslih; Anggraeni, Ayu Septi; Amin, M. Harisuddin Al

2017-03-01

Developing highly environmentally friendly and cost-effective approaches for the chitosan production has paramount important in the future technology. Deacetylation process is one of the most importing steps to classify the quality of chitosan. This research aimed to study the best method for deacetylation of chitin considered by several factors like the concentration of base, temperature, time and reaction method. From the green chemistry point of view, conventional refluxing method relatively wasted energy compared to another method such as maceration, grinding and sonication. The degree of deacetylation (DD) of chitosan was studied by sonication, resulted in slightly increasing of DD from 73.14 to 73.28% during the time from 0.5 h to 1 h. Deacetylation of chitin with various sodium hydroxide concentration 60, 70 and 80% gave 73.14, 76.36 and 77.88% of DD, respectively. Variation of temperature at 40, 60, and 80 °C was slightly affected on increasing DD from 67.53, 72.84 and 73.14%, respectively. The DD of chitosan significantly increased from 60.19, 74.27 and 81.20% respectively correspondent to varying NaOH concentration 60, 70 and 80% using the maceration method. Solid phase grinding method for half hour resulted in 79.49% of DD. The application of ultrasound grinding method not only was enhanced toward the deacetylation but also favoured the depolymerization process. Moreover, maceration for 7 days with 80% NaOH can be as an alternative method.

Selenium Derivatization of Nucleic Acids for Phase and Structure Determination in Nucleic Acid X-ray Crystallography

Directory of Open Access Journals (Sweden)

Zhen Huang

2008-03-01

Full Text Available Selenium derivatization (via selenomethionine of proteins for crystal structure determination via MAD phasing has revolutionized protein X-ray crystallography. It is estimated that over two thirds of all new crystal structures of proteins have been determined via Se-Met derivatization. Similarly, selenium functionalities have also been successfully incorporated into nucleic acids to facilitate their structure studies and it has been proved that this Se-derivatization has advantages over halogen strategy, which was usually used as a traditional method in this field. This review reports the development of site-specific selenium derivatization of nucleic acids for phase determination since the year of 2001 (mainly focus on the 2’-position of the ribose. All the synthesis of 2’-SeMe modified phosphoramidite building blocks (U, C, T, A, G and the according oligonucleotides are included. In addition, several structures of selenium contained nucleic acid are also described in this paper.

Disruption of Bcchs4, Bcchs6 or Bcchs7 chitin synthase genes in Botrytis cinerea and the essential role of class VI chitin synthase (Bcchs6).

Science.gov (United States)

Morcx, Serena; Kunz, Caroline; Choquer, Mathias; Assie, Sébastien; Blondet, Eddy; Simond-Côte, Elisabeth; Gajek, Karina; Chapeland-Leclerc, Florence; Expert, Dominique; Soulie, Marie-Christine

2013-03-01

Chitin synthases play critical roles in hyphal development and fungal pathogenicity. Previous studies on Botrytis cinerea, a model organism for necrotrophic pathogens, have shown that disruption of Bcchs1 and more particularly Bcchs3a genes have a drastic impact on virulence (Soulié et al., 2003, 2006). In this work, we investigate the role of other CHS including BcCHS4, BcCHS6 and BcCHS7 during the life cycle of B. cinerea. Single deletions of corresponding genes were carried out. Phenotypic analysis indicates that: (i) BcCHS4 enzyme is not essential for development and pathogenicity of the fungus; (ii) BcCHS7 is required for pathogenicity in a host dependant manner. For Bcchs6 gene disruption, we obtained only heterokaryotic strains. Indeed, sexual or asexual purification assays were unsuccessful. We concluded that class VI chitin synthase could be essential for B. cinerea and therefore BcCHS6 represents a valuable antifungal target. Copyright © 2012 Elsevier Inc. All rights reserved.

Detection of methamphetamine in the presence of nicotine using in situ chemical derivatization and ion mobility spectrometry.

Science.gov (United States)

Ochoa, Mariela L; Harrington, Peter B

2004-02-15

The detection of methamphetamine in the presence of nicotine has been successfully accomplished using in situ chemical derivatization with propyl chloroformate as the derivatization reagent and ion mobility spectrometry (IMS). The rapid detection of methamphetamine is important for forensic scientists in order to establish a chain of evidence and link criminals to the crime scene. Nicotine is pervasive in clandestine drug laboratories from cigarette smoke residue. It has been demonstrated that nicotine obscures the methamphetamine peaks in ion mobility spectrometers due to their similar charge affinities and ion mobilities, which makes their detection a challenging task. As a consequence, false positive or negative responses may arise. In situ chemical derivatization poses as a sensitive, accurate, and reproducible alternative to remove the nicotine background when detecting nanogram amounts of methamphetamine. The derivatization agent was coated onto the sample disk, and the derivatization product corresponding to propyl methamphetamine carbamate was detected. In the present study, in situ chemical derivatization was demonstrated to be a feasible method to detect methamphetamine hydrochloride as the carbamate derivative, which was baseline-resolved from the nicotine peak. Alternating least squares (ALS) was used to model the datasets. A mixture containing both compounds revealed reduced mobilities of 1.61 cm(2)/V.s and 1.54 cm(2)/V.s for methamphetamine and nicotine, respectively. The reduced mobility of propyl methamphetamine carbamate was found at 1.35 cm(2)/V.s.

Environmental scanning electron microscopy analysis of Proteus mirabilis biofilms grown on chitin and stainless steel.

Science.gov (United States)

Fernández-Delgado, Milagro; Duque, Zoilabet; Rojas, Héctor; Suárez, Paula; Contreras, Monica; García-Amado, María A; Alciaturi, Carlos

Proteus mirabilis is a human pathogen able to form biofilms on the surface of urinary catheters. Little is known about P. mirabilis biofilms on natural or industrial surfaces and the potential consequences for these settings. The main aim of this work was to assess and compare the adhesion and biofilm formation of P. mirabilis strains from different origins on chitin and stainless steel surfaces within 4 to 96 h. Using environmental scanning electron microscopy, the biofilms of a clinical strain grown on chitin at 4 h showed greater adhesion, aggregation, thickness, and extracellular matrix production than those grown on stainless steel, whereas biofilms of an environmental strain had less aggregation on both surfaces. Biofilms of both P. mirabilis strains developed different structures on chitin, such as pillars, mushrooms, channels, and crystalline-like precipitates between 24 and 96 h, in contrast with flat-layer biofilms produced on stainless steel. Significant differences ( p  biofilm formation. This represents the first study of P. mirabilis showing adhesion, biofilm formation, and development of different structures on surfaces found outside the human host.

Location on chitin in the cyst wall of Entamoeba invadens with colloidal gold tracers.

Science.gov (United States)

Arroyo-Begovich, A; Cárabez-Trejo, A

1982-04-01

Chitin was located in the cyst wall of Entamoeba invadens with colloidal gold-linked wheat germ agglutinin. Cysts stained differentially from trophozoites when encysting cultures were treated with the gold tracer; cysts acquired a wine-red coloration while, in general trophozoites remained unstained. Observation of cells with the electron microscope revealed that the tracer particles were bound specifically to the walls of the surface of the cyst when cells were exposed in suspension, and to the cyst wall cross-section, when cells were exposed to the tracer in thin section, indicating that chitin fibers were distributed on the surface as well as throughout the matrix of the cyst wall.

Phosphopeptide derivatization signatures to identify serine and threonine phosphorylated peptides by mass spectrometry.

Science.gov (United States)

Molloy, M P; Andrews, P C

2001-11-15

The development of rapid, global methods for monitoring states of protein phosphorylation would provide greater insight for understanding many fundamental biological processes. Current best practices use mass spectrometry (MS) to profile digests of purified proteins for evidence of phosphorylation. However, this approach is beset by inherent difficulties in both identifying phosphopeptides from within a complex mixture containing many other unmodified peptides and ionizing phosphopeptides in positive-ion MS. We have modified an approach that uses barium hydroxide to rapidly eliminate the phosphoryl group of serine and threonine modified amino acids, creating dehydroamino acids that are susceptible to nucleophilic derivatization. By derivatizing a protein digest with a mixture of two different alkanethiols, phosphopeptide-specific derivatives were readily distinguished by MS due to their characteristic ion-pair signature. The resulting tagged ion pairs accommodate simple and rapid screening for phosphopeptides in a protein digest, obviating the use of isotopically labeled samples for qualitative phosphopeptide detection. MALDI-MS is used in a first pass manner to detect derivatized phosphopeptides, while the remaining sample is available for tandem MS to reveal the site of derivatization and, thus, phosphorylation. We demonstrated the technique by identifying phosphopeptides from beta-casein and ovalbumin. The approach was further used to examine in vitro phosphorylation of recombinant human HSP22 by protein kinase C, revealing phosphorylation of Thr-63.

Mitochondrial Ca2+ overload underlies Abeta oligomers neurotoxicity providing an unexpected mechanism of neuroprotection by NSAIDs.

Directory of Open Access Journals (Sweden)

Sara Sanz-Blasco

Full Text Available Dysregulation of intracellular Ca(2+ homeostasis may underlie amyloid beta peptide (Abeta toxicity in Alzheimer's Disease (AD but the mechanism is unknown. In search for this mechanism we found that Abeta(1-42 oligomers, the assembly state correlating best with cognitive decline in AD, but not Abeta fibrils, induce a massive entry of Ca(2+ in neurons and promote mitochondrial Ca(2+ overload as shown by bioluminescence imaging of targeted aequorin in individual neurons. Abeta oligomers induce also mitochondrial permeability transition, cytochrome c release, apoptosis and cell death. Mitochondrial depolarization prevents mitochondrial Ca(2+ overload, cytochrome c release and cell death. In addition, we found that a series of non-steroidal anti-inflammatory drugs (NSAIDs including salicylate, sulindac sulfide, indomethacin, ibuprofen and R-flurbiprofen depolarize mitochondria and inhibit mitochondrial Ca(2+ overload, cytochrome c release and cell death induced by Abeta oligomers. Our results indicate that i mitochondrial Ca(2+ overload underlies the neurotoxicity induced by Abeta oligomers and ii inhibition of mitochondrial Ca(2+ overload provides a novel mechanism of neuroprotection by NSAIDs against Abeta oligomers and AD.

Mitochondrial Ca2+ overload underlies Abeta oligomers neurotoxicity providing an unexpected mechanism of neuroprotection by NSAIDs.

Science.gov (United States)

Sanz-Blasco, Sara; Valero, Ruth A; Rodríguez-Crespo, Ignacio; Villalobos, Carlos; Núñez, Lucía

2008-07-23

Dysregulation of intracellular Ca(2+) homeostasis may underlie amyloid beta peptide (Abeta) toxicity in Alzheimer's Disease (AD) but the mechanism is unknown. In search for this mechanism we found that Abeta(1-42) oligomers, the assembly state correlating best with cognitive decline in AD, but not Abeta fibrils, induce a massive entry of Ca(2+) in neurons and promote mitochondrial Ca(2+) overload as shown by bioluminescence imaging of targeted aequorin in individual neurons. Abeta oligomers induce also mitochondrial permeability transition, cytochrome c release, apoptosis and cell death. Mitochondrial depolarization prevents mitochondrial Ca(2+) overload, cytochrome c release and cell death. In addition, we found that a series of non-steroidal anti-inflammatory drugs (NSAIDs) including salicylate, sulindac sulfide, indomethacin, ibuprofen and R-flurbiprofen depolarize mitochondria and inhibit mitochondrial Ca(2+) overload, cytochrome c release and cell death induced by Abeta oligomers. Our results indicate that i) mitochondrial Ca(2+) overload underlies the neurotoxicity induced by Abeta oligomers and ii) inhibition of mitochondrial Ca(2+) overload provides a novel mechanism of neuroprotection by NSAIDs against Abeta oligomers and AD.

Enthalpies of solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in different H-bonding solvents: Methanol, chloroform, and water. Group contribution method as applied to the polar oligomers

Energy Technology Data Exchange (ETDEWEB)

Barannikov, Vladimir P., E-mail: vpb@isc-ras.ru [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation); Guseynov, Sabir S.; Vyugin, Anatoliy I. [Institute of Solution Chemistry, Russian Academy of Sciences, Academicheskaya Str. 1, Ivanovo 153045 (Russian Federation)

2011-12-15

Highlights: > Solvation enthalpy is found for ethylene oxide oligomers in chloroform and methanol. > Coefficients of solute-solute interaction are determined for oligomers in methanol. > Enthalpies of hydrogen bonding of oligomers with chloroform and water are estimated. > Additivity scheme is developed for describing enthalpies of solvation of oligomers. - Abstract: The enthalpies of solution and solvation of ethylene oxide oligomers CH{sub 3}O(CH{sub 2}CH{sub 2}O){sub n}CH{sub 3} (n = 1 to 4) in methanol and chloroform have been determined from calorimetric measurements at T = 298.15 K. The enthalpic coefficients of pairwise solute-solute interaction for methanol solutions have been calculated. The enthalpic characteristics of the oligomers in methanol, chloroform, water and tetrachloromethane have been compared. The hydrogen bonding of the oligomers with chloroform and water molecules is exhibited in the values of solvation enthalpy and coefficient of solute-solute interaction. This effect is not observed for methanol solvent. The thermochemical data evidence an existence of multi-centred hydrogen bonds in associates of polyethers with the solvent molecules. Enthalpies of hydrogen bonding of the oligomers with chloroform and water have been estimated. The additivity scheme has been developed to describe the enthalpies of solvation of ethylene oxide oligomers, unbranched monoethers and n-alkanes in chloroform, methanol, water, and tetrachloromethane. The correction parameters for contribution of repeated polar groups and correction term for methoxy-compounds have been introduced. The obtained group contributions permit to describe the enthalpies of solvation of unbranched monoethers and ethylene oxide oligomers in the solvents with standard deviation up to 0.6 kJ . mol{sup -1}. The values of group contributions and corrections are strongly influenced by solvent properties.

Chitin amendment increases soil suppressiveness toward plant pathogens and modulates the actinobacterial and oxalobacteraceal communities in an experimental agricultural field

NARCIS (Netherlands)

Cretoiu, Mariana Silvia; Korthals, Gerard W.; Visser, Johnny H. M.; van Elsas, Jan Dirk

A long-term experiment on the effect of chitin addition to soil on the suppression of soilborne pathogens was set up and monitored for 8 years in an experimental field, Vredepeel, The Netherlands. Chitinous matter obtained from shrimps was added to soil top layers on two different occasions, and the

Bioremediation of crude oil polluted seawater by a hydrocarbon-degrading bacterial strain immobilized on chitin and chitosan flakes

International Nuclear Information System (INIS)

Gentili, A.R.; Cubitto, M.A.; Ferrero, M.; Rodriguez, M.S.

2006-01-01

In this laboratory-scale study, we examined the potential of chitin and chitosan flakes obtained from shrimp wastes as carrier material for a hydrocarbon-degrading bacterial strain. Flakes decontamination, immobilization conditions and the survival of the immobilized bacterial strain under different storage temperatures were evaluated. The potential of immobilized hydrocarbon-degrading bacterial strain for crude oil polluted seawater bioremediation was tested in seawater microcosms. In terms of removal percentage of crude oil after 15 days, the microcosms treated with the immobilized inoculants proved to be the most successful. The inoculants formulated with chitin and chitosan as carrier materials improved the survival and the activity of the immobilized strain. It is important to emphasize that the inoculants formulated with chitin showed the best performance during storage and seawater bioremediation. (author)

Formation of soluble amyloid oligomers and amyloid fibrils by the multifunctional protein vitronectin

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Langen Ralf

2008-10-01

Full Text Available Abstract Background The multifunctional protein vitronectin is present within the deposits associated with Alzheimer disease (AD, age-related macular degeneration (AMD, atherosclerosis, systemic amyloidoses, and glomerulonephritis. The extent to which vitronectin contributes to amyloid formation within these plaques, which contain misfolded, amyloidogenic proteins, and the role of vitronectin in the pathophysiology of the aforementioned diseases is currently unknown. The investigation of vitronectin aggregation is significant since the formation of oligomeric and fibrillar structures are common features of amyloid proteins. Results We observed vitronectin immunoreactivity in senile plaques of AD brain, which exhibited overlap with the amyloid fibril-specific OC antibody, suggesting that vitronectin is deposited at sites of amyloid formation. Of particular interest is the growing body of evidence indicating that soluble nonfibrillar oligomers may be responsible for the development and progression of amyloid diseases. In this study we demonstrate that both plasma-purified and recombinant human vitronectin readily form spherical oligomers and typical amyloid fibrils. Vitronectin oligomers are toxic to cultured neuroblastoma and retinal pigment epithelium (RPE cells, possibly via a membrane-dependent mechanism, as they cause leakage of synthetic vesicles. Oligomer toxicity was attenuated in RPE cells by the anti-oligomer A11 antibody. Vitronectin fibrils contain a C-terminal protease-resistant fragment, which may approximate the core region of residues essential to amyloid formation. Conclusion These data reveal the propensity of vitronectin to behave as an amyloid protein and put forth the possibilities that accumulation of misfolded vitronectin may contribute to aggregate formation seen in age-related amyloid diseases.

Morintides: cargo-free chitin-binding peptides from Moringa oleifera.

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Kini, Shruthi G; Wong, Ka H; Tan, Wei Liang; Xiao, Tianshu; Tam, James P

2017-03-31

Hevein-like peptides are a family of cysteine-rich and chitin-binding peptides consisting of 29-45 amino acids. Their chitin-binding property is essential for plant defense against fungi. Based on the number of cysteine residues in their sequences, they are divided into three sub-families: 6C-, 8C- and 10C-hevein-like peptides. All three subfamilies contain a three-domain precursor comprising a signal peptide, a mature hevein-like peptide and a C-terminal domain comprising a hinge region with protein cargo in 8C- and 10C-hevein-like peptides. Here we report the isolation and characterization of two novel 8C-hevein-like peptides, designated morintides (mO1 and mO2), from the drumstick tree Moringa oleifera, a drought-resistant tree belonging to the Moringaceae family. Proteomic analysis revealed that morintides comprise 44 amino acid residues and are rich in cysteine, glycine and hydrophilic amino acid residues such as asparagine and glutamine. Morintides are resistant to thermal and enzymatic degradation, able to bind to chitin and inhibit the growth of phyto-pathogenic fungi. Transcriptomic analysis showed that they contain a three-domain precursor comprising an endoplasmic reticulum (ER) signal sequence, a mature peptide domain and a C-terminal domain. A striking feature distinguishing morintides from other 8C-hevein-like peptides is a short and protein-cargo-free C-terminal domain. Previously, a similar protein-cargo-free C-terminal domain has been observed only in ginkgotides, the 8C-hevein-like peptides from a gymnosperm Ginkgo biloba. Thus, morintides, with a cargo-free C-terminal domain, are a stand-alone class of 8C-hevein-like peptides from angiosperms. Our results expand the existing library of hevein-like peptides and shed light on molecular diversity within the hevein-like peptide family. Our work also sheds light on the anti-fungal activity and stability of 8C-hevein-like peptides.

Hierarchical Chitin Fibers with Aligned Nanofibrillar Architectures: A Nonwoven-Mat Separator for Lithium Metal Batteries.

Science.gov (United States)

Kim, Joong-Kwon; Kim, Do Hyeong; Joo, Se Hun; Choi, Byeongwook; Cha, Aming; Kim, Kwang Min; Kwon, Tae-Hyuk; Kwak, Sang Kyu; Kang, Seok Ju; Jin, Jungho

2017-06-27

Here, we introduce regenerated fibers of chitin (Chiber), the second most abundant biopolymer after cellulose, and propose its utility as a nonwoven fiber separator for lithium metal batteries (LMBs) that exhibits an excellent electrolyte-uptaking capability and Li-dendrite-mitigating performance. Chiber is produced by a centrifugal jet-spinning technique, which allows a simple and fast production of Chibers consisting of hierarchically aligned self-assembled chitin nanofibers. Following the scrutinization on the Chiber-Li-ion interaction via computational methods, we demonstrate the potential of Chiber as a nonwoven mat-type separator by monitoring it in Li-O 2 and Na-O 2 cells.

Effect of Conjugation Length on Photoinduced Charge-Transfer in π-Conjugated Oligomer-Acceptor Dyads

KAUST Repository

Jiang, Junlin

2017-05-25

A series of -conjugated oligomer-acceptor dyads were synthesized that feature oligo(phenylene ethynylene) (OPE) conjugated backbones end-capped with a naphthalene diimide (NDI) acceptor. The OPE segments vary in length from 4 to 8 phenylene ethynene units (PEn-NDI, where n = 4, 6 and 8). Fluorescence and transient absorption spectroscopy reveals that intramolecular OPE NDI charge transfer dominates the deactivation of excited states of the PEn-NDI oligomers. Both charge separation (CS) and charge recombination (CR) are strongly exothermic (G0CS ~ -1.1 and G0CR ~ -2.0 eV), and the driving forces do not vary much across the series because the oxidation and reduction potentials and singlet energies of the OPEs do not vary much with their length. Bimolecular photoinduced charge transfer between model OPEs that do not contain the NDI acceptors with methyl viologen was studied, and the results reveal that the absorption of the cation radical state (OPE+•) remains approximately constant ( ~ 575 nm) regardless of oligomer length. This finding suggests that the cation radical (polaron) of the OPE is relatively localized, effectively occupying a confined segment of n 4 repeat units in the longer oligomers. Photoinduced intramolecular electron transfer dynamics in the PEn-NDI series was investigated by UV-visible femtosecond transient absorption spectroscopy with visible and mid-infrared probes. Charge separation occurs on the 1 – 10 ps timescale, with the rates decreasing slightly with increased oligomer length (βCS ~ 0.15 Å-1). The rate for charge-recombination decreases in the sequence PE4-NDI > PE6-NDI ~ PE8-NDI. The discontinuous distance dependence in the rate for charge recombination may be related to the spatial localization of the positive polaron state in the longer oligomers.

Effect of Conjugation Length on Photoinduced Charge-Transfer in π-Conjugated Oligomer-Acceptor Dyads

KAUST Repository

Jiang, Junlin; Alsam, Amani Abdu; Wang, Shanshan; Aly, Shawkat Mohammede; Pan, Zhenxing; Mohammed, Omar F.; Schanze, Kirk S.

2017-01-01

A series of -conjugated oligomer-acceptor dyads were synthesized that feature oligo(phenylene ethynylene) (OPE) conjugated backbones end-capped with a naphthalene diimide (NDI) acceptor. The OPE segments vary in length from 4 to 8 phenylene ethynene units (PEn-NDI, where n = 4, 6 and 8). Fluorescence and transient absorption spectroscopy reveals that intramolecular OPE NDI charge transfer dominates the deactivation of excited states of the PEn-NDI oligomers. Both charge separation (CS) and charge recombination (CR) are strongly exothermic (G0CS ~ -1.1 and G0CR ~ -2.0 eV), and the driving forces do not vary much across the series because the oxidation and reduction potentials and singlet energies of the OPEs do not vary much with their length. Bimolecular photoinduced charge transfer between model OPEs that do not contain the NDI acceptors with methyl viologen was studied, and the results reveal that the absorption of the cation radical state (OPE+•) remains approximately constant ( ~ 575 nm) regardless of oligomer length. This finding suggests that the cation radical (polaron) of the OPE is relatively localized, effectively occupying a confined segment of n 4 repeat units in the longer oligomers. Photoinduced intramolecular electron transfer dynamics in the PEn-NDI series was investigated by UV-visible femtosecond transient absorption spectroscopy with visible and mid-infrared probes. Charge separation occurs on the 1 – 10 ps timescale, with the rates decreasing slightly with increased oligomer length (βCS ~ 0.15 Å-1). The rate for charge-recombination decreases in the sequence PE4-NDI > PE6-NDI ~ PE8-NDI. The discontinuous distance dependence in the rate for charge recombination may be related to the spatial localization of the positive polaron state in the longer oligomers.

Extraction and derivatization of chemical weapons convention relevant aminoalcohols on magnetic cation-exchange resins.

Science.gov (United States)

Singh, Varoon; Garg, Prabhat; Chinthakindi, Sridhar; Tak, Vijay; Dubey, Devendra Kumar

2014-02-14

Analysis and identification of nitrogen containing aminoalcohols is an integral part of the verification analysis of chemical weapons convention (CWC). This study was aimed to develop extraction and derivatization of aminoalcohols of CWC relevance by using magnetic dispersive solid-phase extraction (MDSPE) in combination with on-resin derivatization (ORD). For this purpose, sulfonated magnetic cation-exchange resins (SMRs) were prepared using magnetite nanoparticles as core, styrene and divinylbenzene as polymer coat and sulfonic acid as acidic cation exchanger. SMRs were successfully employed as extractant for targeted basic analytes. Adsorbed analytes were derivatized with hexamethyldisilazane (HMDS) on the surface of extractant. Derivatized (silylated) compounds were analyzed by GC-MS in SIM and full scan mode. The linearity of the method ranged from 5 to 200ngmL(-1). The LOD and LOQ ranged from 2 to 6ngmL(-1) and 5 to 19ngmL(-1) respectively. The relative standard deviation for intra-day repeatability and inter-day intermediate precision ranged from 5.1% to 6.6% and 0.2% to 7.6% respectively. Recoveries of analytes from spiked water samples from different sources varied from 28.4% to 89.3%. Copyright © 2014 Elsevier B.V. All rights reserved.

LC-MS n Analysis of Isomeric Chondroitin Sulfate Oligosaccharides Using a Chemical Derivatization Strategy

Science.gov (United States)

Huang, Rongrong; Pomin, Vitor H.; Sharp, Joshua S.

2011-09-01

Improved methods for structural analyses of glycosaminoglycans (GAGs) are required to understand their functional roles in various biological processes. Major challenges in structural characterization of complex GAG oligosaccharides using liquid chromatography-mass spectrometry (LC-MS) include the accurate determination of the patterns of sulfation due to gas-phase losses of the sulfate groups upon collisional activation and inefficient on-line separation of positional sulfation isomers prior to MS/MS analyses. Here, a sequential chemical derivatization procedure including permethylation, desulfation, and acetylation was demonstrated to enable both on-line LC separation of isomeric mixtures of chondroitin sulfate (CS) oligosaccharides and accurate determination of sites of sulfation by MS n . The derivatized oligosaccharides have sulfate groups replaced with acetyl groups, which are sufficiently stable to survive MS n fragmentation and reflect the original sulfation patterns. A standard reversed-phase LC-MS system with a capillary C18 column was used for separation, and MS n experiments using collision-induced dissociation (CID) were performed. Our results indicate that the combination of this derivatization strategy and MS n methodology enables accurate identification of the sulfation isomers of CS hexasaccharides with either saturated or unsaturated nonreducing ends. Moreover, derivatized CS hexasaccharide isomer mixtures become separable by LC-MS method due to different positions of acetyl modifications.

α-Synuclein oligomers and clinical implications for Parkinson disease

Science.gov (United States)

Kalia, Lorraine V.; Kalia, Suneil K.; McLean, Pamela J.; Lozano, Andres M.; Lang, Anthony E.

2012-01-01

Protein aggregation within the central nervous system has been recognized as a defining feature of neurodegenerative diseases since the early 20th century. Since that time, there has been a growing list of neurodegenerative disorders, including Parkinson disease, which are characterized by inclusions of specific pathogenic proteins. This has led to the long-held dogma that these characteristic protein inclusions, which are composed of large insoluble fibrillar protein aggregates and visible by light microscopy, are responsible for cell death in these diseases. However, the correlation between protein inclusion formation and cytotoxicity is inconsistent suggesting another form of the pathogenic proteins may be contributing to neurodegeneration. There is emerging evidence implicating soluble oligomers, smaller protein aggregates not detectable by conventional microscopy, as potential culprits in the pathogenesis of neurodegenerative diseases. The protein α-synuclein is well recognized to contribute to the pathogenesis of Parkinson disease and is the major component of Lewy bodies and Lewy neurites. However, α-synuclein also forms oligomeric species with certain conformations being toxic to cells. The mechanisms by which these α-synuclein oligomers cause cell death are being actively investigated as they may provide new strategies for diagnosis and treatment of Parkinson disease and related disorders. Here we review the possible role of α-synuclein oligomers in cell death in Parkinson disease and discuss the potential clinical implications. PMID:23225525

Bio-responsive chitin-poly(L-lactic acid) composite nanogels for liver cancer.

Science.gov (United States)

Arunraj, T R; Sanoj Rejinold, N; Ashwin Kumar, N; Jayakumar, R

2014-01-01

Hepatic carcinoma (HCC) is one of the most common cancer and its treatment has been considered a therapeutic challenge. Doxorubicin (Dox) is one of the most important chemotherapeutic agents used in the treatment for liver cancer. However, the efficacy of Dox therapy is restricted by the dose-dependent toxic side effects. To overcome the cardiotoxicity of Dox as well as the current problems of conventional modality treatment of HCC, we developed a locally injectable, biodegradable, and pH sensitive composite nanogels for site specific delivery. Both control and Dox loaded composite nanogel systems were analyzed by DLS, SEM, FTIR and TG/DTA. The size ranges of the control composite nanogels and their drug loaded counterparts were found to be 90±20 and 270±20 nm, respectively. The control chitin-PLA CNGs and Dox-chitin-PLA CNGs showed higher swelling and degradation in acidic pH. Drug entrapment efficiency and in vitro drug release studies were carried out and showed a higher drug release at acidic pH compared to neutral pH. Cellular internalization of the nanogel systems was confirmed by fluorescent microscopy. The cytotoxicity of the composite nanogels was analyzed toward HepG2 (human liver cancer) cell lines. Furthermore, the results of in vitro hemolytic assay and coagulation assay substantiate the blood compatibility of the system. Overall Dox-chitin-PLA CNGs system could be a promising anticancer drug delivery system for liver cancer therapy. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrospun chitosan-based nanocomposite mats reinforced with chitin nanocrystals for wound dressing

CSIR Research Space (South Africa)

Naseria, N

2014-08-01

Full Text Available The aim of this study was to develop electrospun chitosan/polyethylene oxide-based randomly oriented fiber mats reinforced with chitin nanocrystals (ChNC) for wound dressing. Microscopy studies showedporous mats of smooth and beadless fibers...

Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline.

Science.gov (United States)

Patel, Yogesh S

2014-01-01

Novel oligomer metal complexes (2a-f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesized compounds 1 and 2a-f were evaluated for their antibacterial and antifungal activity. The results showed significantly higher antibacterial and antifungal activity of oligomer metal complexes compared to the ligand.

Surface Structures Formed by a Copper(II Complex of Alkyl-Derivatized Indigo

Directory of Open Access Journals (Sweden)

Akinori Honda

2016-10-01

Full Text Available Assembled structures of dyes have great influence on their coloring function. For example, metal ions added in the dyeing process are known to prevent fading of color. Thus, we have investigated the influence of an addition of copper(II ion on the surface structure of alkyl-derivatized indigo. Scanning tunneling microscope (STM analysis revealed that the copper(II complexes of indigo formed orderly lamellar structures on a HOPG substrate. These lamellar structures of the complexes are found to be more stable than those of alkyl-derivatized indigos alone. Furthermore, 2D chirality was observed.

The Antifungal Activity of Functionalized Chitin Nanocrystals in Poly (Lactid Acid Films

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Asier M. Salaberria

2017-05-01

Full Text Available As, in the market, poly (lactic acid (PLA is the most used polymer as an alternative to conventional plastics, and as functionalized chitin nanocrystals (CHNC can provide structural and bioactive properties, their combination sounds promising in the preparation of functional nanocomposite films for sustainable packaging. Chitin nanocrystals were successfully modified via acylation using anhydride acetic and dodecanoyl chloride acid to improve their compatibility with the matrix, PLA. The nanocomposite films were prepared by extrusion/compression approach using different concentrations of both sets of functionalized CHNC. This investigation brings forward that both sets of modified CHNC act as functional agents, i.e., they slightly improved the hydrophobic character of the PLA nanocomposite films, and, very importantly, they also enhanced their antifungal activity. Nonetheless, the nanocomposite films prepared with the CHNC modified with dodecanoyl chloride acid presented the best properties.

Single step synthesis of chitin/chitosan-based graphene oxide–ZnO hybrid composites for better electrical conductivity and optical properties

International Nuclear Information System (INIS)

Anandhavelu, S.; Thambidurai, S.

2013-01-01

Highlights: ► UV absorption at 260–360 nm confirmed strong binding of ZnO with chitosan–GO sheets. ► Chitin-based GO–ZnO shows higher electrical conductivity than chitosan-based GO–ZnO. ► Chitin-based GO–ZnO will useful in sensing, catalysis and energy storage applications. -- Abstract: We synthesized two composites/hybrid composites with a graphene oxide (GO)/mixed GO–ZnO filler using either a chitin or a chitosan matrix. Fourier transform infrared spectroscopy analysis confirmed that chitin had been converted to chitosan during matrix fabrication because only chitosan, ZnO and GO were shown to be present in the composites/hybrid composites. Raman spectroscopy indicated the display of D and G bands at 1345 cm −1 and 1584 cm −1 , respectively. UV absorption peaks appeared at 260–360 nm and 201 nm in both hybrid composites, which indicate a strong binding of ZnO within the chitosan–GO sheets. High resolution scanning electron microscopy and atomic force microscopy studies demonstrated that on a molecular scale ZnO was well dispersed in the hybrid composites. Impedance spectroscopy and a four-probe resistivity method were used for room temperature electrical conductivity measurements. The electrical conductivity of the chitin-based GO–ZnO hybrid composites was estimated to be ∼5.94 × 10 6 S/cm and was greater than that of the chitosan-based GO–ZnO hybrid composite (∼4.13 × 10 6 S/cm). The chitin-based GO–ZnO hybrid composite had a higher optical band gap (3.4 eV) than the chitosan-based GO–ZnO hybrid composite (3.0 eV). The current–voltage measurement showed that electrical sheets resistance of the chitosan-based composites decreased with formation of ZnO

Preparation, characterization, drug release and computational modelling studies of antibiotics loaded amorphous chitin nanoparticles.

Science.gov (United States)

Gayathri, N K; Aparna, V; Maya, S; Biswas, Raja; Jayakumar, R; Mohan, C Gopi

2017-12-01

We present a computational investigation of binding affinity of different types of drugs with chitin nanocarriers. Understanding the chitn polymer-drug interaction is important to design and optimize the chitin based drug delivery systems. The binding affinity of three different types of anti-bacterial drugs Ethionamide (ETA) Methacycline (MET) and Rifampicin (RIF) with amorphous chitin nanoparticles (AC-NPs) were studied by integrating computational and experimental techniques. The binding energies (BE) of hydrophobic ETA, hydrophilic MET and hydrophobic RIF were -7.3kcal/mol, -5.1kcal/mol and -8.1kcal/mol respectively, with respect to AC-NPs, using molecular docking studies. This theoretical result was in good correlation with the experimental studies of AC-drug loading and drug entrapment efficiencies of MET (3.5±0.1 and 25± 2%), ETA (5.6±0.02 and 45±4%) and RIF (8.9±0.20 and 53±5%) drugs respectively. Stability studies of the drug encapsulated nanoparticles showed stable values of size, zeta and polydispersity index at 6°C temperature. The correlation between computational BE and experimental drug entrapment efficiencies of RIF, ETA and MET drugs with four AC-NPs strands were 0.999 respectively, while that of the drug loading efficiencies were 0.854 respectively. Further, the molecular docking results predict the atomic level details derived from the electrostatic, hydrogen bonding and hydrophobic interactions of the drug and nanoparticle for its encapsulation and loading in the chitin-based host-guest nanosystems. The present results thus revealed the drug loading and drug delivery insights and has the potential of reducing the time and cost of processing new antibiotic drug delivery nanosystem optimization, development and discovery. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic heterostructures based on arylenevinylene oligomers deposited by MAPLE

Czech Academy of Sciences Publication Activity Database

Socol, M.; Preda, N.; Vacareanu, L.; Grigoras, M.; Socol, G.; Mihailescu, I. N.; Stanculescu, F.; Jelínek, Miroslav; Stanculescu, A.; Stoicanescu, M.

2014-01-01

Roč. 302, May (2014), s. 216-222 ISSN 0169-4332 Institutional support: RVO:68378271 Keywords : organic heterostructures * MAPLE * oligomer * optoelectronica Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.711, year: 2014

Modified Method for Detection of Benzoylecgonine in Human Urine by GC-MS: Derivatization Using Pentafluoropropanol/Acetic Anhydride.

Science.gov (United States)

Serafin, Michelle C; Paulemon, Kasandra M; Fuller, Zachary J; Bronner, William E

2017-05-01

An existing GC-MS method for detecting benzoylecgonine (BZE) in urine was modified by changing derivatizing reagents. This method modification presents a cost-effective alternative derivatization procedure for the detection of BZE in urine by GC-MS. The combination of pentafluoropropanol and acetic anhydride was found to produce the same reaction product for BZE as pentafluoropropanol with pentafluoropropionic anhydride, while reducing reagent cost. With no anhydride present, derivatization of BZE by pentafluoropropanol did not occur. Published by Oxford University Press 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Microbial Degradation of Lobster Shells to Extract Chitin Derivatives for Plant Disease Management

Directory of Open Access Journals (Sweden)

Gayathri Ilangumaran

2017-05-01

Full Text Available Biodegradation of lobster shells by chitinolytic microorganisms are an environment safe approach to utilize lobster processing wastes for chitin derivation. In this study, we report degradation activities of two microbes, “S223” and “S224” isolated from soil samples that had the highest rate of deproteinization, demineralization and chitinolysis among ten microorganisms screened. Isolates S223 and S224 had 27.3 and 103.8 protease units mg-1 protein and 12.3 and 11.2 μg ml-1 of calcium in their samples, respectively, after 1 week of incubation with raw lobster shells. Further, S223 contained 23.8 μg ml-1 of N-Acetylglucosamine on day 3, while S224 had 27.3 μg ml-1 on day 7 of incubation with chitin. Morphological observations and 16S rDNA sequencing suggested both the isolates were Streptomyces. The culture conditions were optimized for efficient degradation of lobster shells and chitinase (∼30 kDa was purified from crude extract by affinity chromatography. The digested lobster shell extracts induced disease resistance in Arabidopsis by induction of defense related genes (PR1 > 500-fold, PDF1.2 > 40-fold upon Pseudomonas syringae and Botrytis cinerea infection. The study suggests that soil microbes aid in sustainable bioconversion of lobster shells and extraction of chitin derivatives that could be applied in plant protection.

Combined HILIC-ELSD/ESI-MS(n) enables the separation, identification and quantification of sugar beet pectin derived oligomers.

Science.gov (United States)

Remoroza, C; Cord-Landwehr, S; Leijdekkers, A G M; Moerschbacher, B M; Schols, H A; Gruppen, H

2012-09-01

The combined action of endo-polygalacturonase (endo-PGII), pectin lyase (PL), pectin methyl esterase (fungal PME) and RG-I degrading enzymes enabled the extended degradation of methylesterified and acetylated sugar beet pectins (SBPs). The released oligomers were separated, identified and quantified using hydrophilic interaction liquid chromatography (HILIC) with online electrospray ionization ion trap mass spectrometry (ESI-IT-MS(n)) and evaporative light scattering detection (ELSD). By MS(n), the structures of galacturonic acid (GalA) oligomers having an acetyl group in the O-2 and/or O-3 positions eluting from the HILIC column were elucidated. The presence of methylesterified and/or acetylated galacturonic acid units within an oligomer reduced the interaction with the HILIC column significantly compared to the unsubstituted GalA oligomers. The HILIC column enables a good separation of most oligomers present in the digest. The use of ELSD to quantify oligogalacturonides was validated using pure GalA standards and the signal was found to be independent of the chemical structure of the oligomer being detected. The combination of chromatographic and enzymatic strategies enables to distinguish SBPs having different methylesters and acetyl group distribution. Copyright © 2012 Elsevier Ltd. All rights reserved.

Slow Off-rates and Strong Product Binding Are Required for Processivity and Efficient Degradation of Recalcitrant Chitin by Family 18 Chitinases.

Science.gov (United States)

Kurašin, Mihhail; Kuusk, Silja; Kuusk, Piret; Sørlie, Morten; Väljamäe, Priit

2015-11-27

Processive glycoside hydrolases are the key components of enzymatic machineries that decompose recalcitrant polysaccharides, such as chitin and cellulose. The intrinsic processivity (P(Intr)) of cellulases has been shown to be governed by the rate constant of dissociation from polymer chain (koff). However, the reported koff values of cellulases are strongly dependent on the method used for their measurement. Here, we developed a new method for determining koff, based on measuring the exchange rate of the enzyme between a non-labeled and a (14)C-labeled polymeric substrate. The method was applied to the study of the processive chitinase ChiA from Serratia marcescens. In parallel, ChiA variants with weaker binding of the N-acetylglucosamine unit either in substrate-binding site -3 (ChiA-W167A) or the product-binding site +1 (ChiA-W275A) were studied. Both ChiA variants showed increased off-rates and lower apparent processivity on α-chitin. The rate of the production of insoluble reducing groups on the reduced α-chitin was an order of magnitude higher than koff, suggesting that the enzyme can initiate several processive runs without leaving the substrate. On crystalline chitin, the general activity of the wild type enzyme was higher, and the difference was magnifying with hydrolysis time. On amorphous chitin, the variants clearly outperformed the wild type. A model is proposed whereby strong interactions with polymer in the substrate-binding sites (low off-rates) and strong binding of the product in the product-binding sites (high pushing potential) are required for the removal of obstacles, like disintegration of chitin microfibrils. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

New strategy for stable-isotope-aided, multidimensional NMR spectroscopy of DNA oligomers

Energy Technology Data Exchange (ETDEWEB)

Ono, Okira; Tate, Shin-Ichi; Kainosho, Masatsune [Tokyo Metropolitan Univ., Tokyo (Japan)

1994-12-01

Nuclear Magnetic Resonance (NMR) is the most efficient method for determining the solution structures of biomolecules. By applying multidimensional heteronuclear NMR techniques to {sup 13}C/{sup 15}N-labeled proteins, we can determine the solution structures of proteins with molecular mass of 20 to 30kDa at an accuracy similar to that of x-ray crystallography. Improvements in NMR instrumentation and techniques as well as the development of protein engineering methods for labeling proteins have rapidly advanced multidimensional heteronuclear NMR of proteins. In contrast, multidimensional heteronuclear NMR studies of nucleic acids is less advanced because there were no efficient methods for preparing large amounts of labeled DNA/RNA oligomers. In this report, we focused on the chemical synthesis of DNA oligomers labeled at specific residue(s). RNA oligomers with specific labels, which are difficult to synthesize by the enzyme method, can be synthesized by the chemical method. The specific labels are useful for conformational analysis of larger molecules such as protein-nucleic acid complexes.

Ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma

Energy Technology Data Exchange (ETDEWEB)

Xu Xu; Su Rui; Zhao Xin; Liu Zhuang; Zhang Yupu; Li Dan; Li Xueyuan; Zhang Hanqi [College of Chemistry, Jilin University, Changchun 130012 (China); Wang Ziming, E-mail: analchem@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130012 (China)

2011-11-30

Graphical abstract: The extraction and derivatization efficiency of SAs is dependent on type and volume of extraction solvent, type and volume of disperser, microwave power and irradiation time, volume of derivatization reagent, pH of sample solution as well as ionic strength. Highlights: Black-Right-Pointing-Pointer A new, rapid and sensitive method for determining sulfonamides (SAs) was proposed. Black-Right-Pointing-Pointer Derivatization, extraction and preconcentration of SAs were performed in one step. Black-Right-Pointing-Pointer IL-based MADLLME and derivatization were first applied for the determination of SAs. Black-Right-Pointing-Pointer Trace SAs in river water, honey, milk, and pig plasma were determined. - Abstract: The ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0-110.8, 95.4-106.3, 95.0-108.3, and 95.7-107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n = 5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination

Ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma

International Nuclear Information System (INIS)

Xu Xu; Su Rui; Zhao Xin; Liu Zhuang; Zhang Yupu; Li Dan; Li Xueyuan; Zhang Hanqi; Wang Ziming

2011-01-01

Graphical abstract: The extraction and derivatization efficiency of SAs is dependent on type and volume of extraction solvent, type and volume of disperser, microwave power and irradiation time, volume of derivatization reagent, pH of sample solution as well as ionic strength. Highlights: ► A new, rapid and sensitive method for determining sulfonamides (SAs) was proposed. ► Derivatization, extraction and preconcentration of SAs were performed in one step. ► IL-based MADLLME and derivatization were first applied for the determination of SAs. ► Trace SAs in river water, honey, milk, and pig plasma were determined. - Abstract: The ionic liquid-based microwave-assisted dispersive liquid–liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0–110.8, 95.4–106.3, 95.0–108.3, and 95.7–107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n = 5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination of SAs in liquid samples.

Extração, estruturas e propriedades de alfa- e beta-quitina Extraction, structures and properties of alpha- AND beta-chitin

Directory of Open Access Journals (Sweden)

Sergio P. Campana-Filho

2007-06-01

Full Text Available The fact that alpha- and beta-chitin adopt different arrays in the solid state is explored to emphasize their different properties and distinct spectral characteristics and X ray diffraction patterns. The methods for their extraction from the biomass in view of the preservation of their native structures and aiming to fulfill the claims of purity and uniformity for potential applications are discussed. The different arrays adopted by alpha- and beta-chitin also result in distinct reactivities toward the deacetylation reaction. Thus, the deacetylation of beta-chitin is more efficient owing to the better accessibility to amide groups due to the lower crystallinity of this polymorph.

Cigarette Smoke-Exposed Candida albicans Increased Chitin Production and Modulated Human Fibroblast Cell Responses

Directory of Open Access Journals (Sweden)

Humidah Alanazi

2014-01-01

Full Text Available The predisposition of cigarette smokers for development of respiratory and oral bacterial infections is well documented. Cigarette smoke can also contribute to yeast infection. The aim of this study was to investigate the effect of cigarette smoke condensate (CSC on C. albicans transition, chitin content, and response to environmental stress and to examine the interaction between CSC-pretreated C. albicans and normal human gingival fibroblasts. Following exposure to CSC, C. albicans transition from blastospore to hyphal form increased. CSC-pretreated yeast cells became significantly (P<0.01 sensitive to oxidation but significantly (P<0.01 resistant to both osmotic and heat stress. CSC-pretreated C. albicans expressed high levels of chitin, with 2- to 8-fold recorded under hyphal conditions. CSC-pretreated C. albicans adhered better to the gingival fibroblasts, proliferated almost three times more and adapted into hyphae, while the gingival fibroblasts recorded a significantly (P<0.01 slow growth rate but a significantly higher level of IL-1β when in contact with CSC-pretreated C. albicans. CSC was thus able to modulate both C. albicans transition through the cell wall chitin content and the interaction between C. albicans and normal human gingival fibroblasts. These findings may be relevant to fungal infections in the oral cavity in smokers.

Toxic prefibrillar α-synuclein amyloid oligomers adopt a distinctive antiparallel β-sheet structure.

Science.gov (United States)

Celej, María Soledad; Sarroukh, Rabia; Goormaghtigh, Erik; Fidelio, Gerardo D; Ruysschaert, Jean-Marie; Raussens, Vincent

2012-05-01

Parkinson's disease is an age-related movement disorder characterized by the presence in the mid-brain of amyloid deposits of the 140-amino-acid protein AS (α-synuclein). AS fibrillation follows a nucleation polymerization pathway involving diverse transient prefibrillar species varying in size and morphology. Similar to other neurodegenerative diseases, cytotoxicity is currently attributed to these prefibrillar species rather than to the insoluble aggregates. Nevertheless, the underlying molecular mechanisms responsible for cytotoxicity remain elusive and structural studies may contribute to the understanding of both the amyloid aggregation mechanism and oligomer-induced toxicity. It is already recognized that soluble oligomeric AS species adopt β-sheet structures that differ from those characterizing the fibrillar structure. In the present study we used ATR (attenuated total reflection)-FTIR (Fourier-transform infrared) spectroscopy, a technique especially sensitive to β-sheet structure, to get a deeper insight into the β-sheet organization within oligomers and fibrils. Careful spectral analysis revealed that AS oligomers adopt an antiparallel β-sheet structure, whereas fibrils adopt a parallel arrangement. The results are discussed in terms of regions of the protein involved in the early β-sheet interactions and the implications of such conformational arrangement for the pathogenicity associated with AS oligomers.

Interface Bond Improvement of Sisal Fibre Reinforced Polylactide Composites with Added Epoxy Oligomer.

Science.gov (United States)

Hao, Mingyang; Wu, Hongwu; Qiu, Feng; Wang, Xiwen

2018-03-07

To improve the interfacial bonding of sisal fiber-reinforced polylactide biocomposites, polylactide (PLA) and sisal fibers (SF) were melt-blended to fabricate bio-based composites via in situ reactive interfacial compatibilization with addition of a commercial grade epoxy-functionalized oligomer Joncryl ADR @ -4368 (ADR). The FTIR (Fourier Transform infrared spectroscopy) analysis and SEM (scanning electron microscope) characterization demonstrated that the PLA molecular chain was bonded to the fiber surface and the epoxy-functionalized oligomer played a hinge-like role between the sisal fibers and the PLA matrix, which resulted in improved interfacial adhesion between the fibers and the PLA matrix. The interfacial reaction and microstructures of composites were further investigated by thermal and rheological analyses, which indicated that the mobility of the PLA molecular chain in composites was restricted because of the introduction of the ADR oligomer, which in turn reflected the improved interfacial interaction between SF and the PLA matrix. These results were further justified with the calculation of activation energies of glass transition relaxation (∆ E a ) by dynamic mechanical analysis. The mechanical properties of PLA/SF composites were simultaneously reinforced and toughened with the addition of ADR oligomer. The interfacial interaction and structure-properties relationship of the composites are the key points of this study.

The effect of rumen ciliates on chitinolytic activity, chitin content and the number of fungal zoospores in the rumen fluid of sheep.

Science.gov (United States)

Miltko, Renata; Bełżecki, Grzegorz; Herman, Andrzej; Kowalik, Barbara; Skomiał, Jacek

2016-12-01

The objective of this study was to investigate the effect of selected protozoa on the degradation and concentration of chitin and the numbers of fungal zoospores in the rumen fluid of sheep. Three adult ewes were fed a hay-concentrate diet, defaunated, then monofaunated with Entodinium caudatum or Diploplastron affine alone and refaunated with natural rumen fauna. The average density of the protozoa population varied from 6.1 · 10(4) (D. affine) to 42.2 · 10(4) cells/ml rumen fluid (natural rumen fauna). The inoculation of protozoa in the rumen of defaunated sheep increased the total activity of chitinolytic enzymes from 2.9 to 3.6 μmol N-acetylglucosamine/g dry matter (DM) of rumen fluid per min, the chitin concentration from 6.3 to 7.2 mg/g DM of rumen fluid and the number of fungal zoospores from 8.1 to 10.9 · 10(5) cells/ml rumen fluid. All examined indices showed diurnal variations. Ciliate population density was highest immediately prior to feeding and lowest at 4 h thereafter. The opposite effects were observed for the numbers of fungal zoospores, the chitin concentration and chitinolytic activity. Furthermore, it was found that chitin from zoospores may account for up to 95% of total microbial chitin in the rumen fluid of sheep. In summary, the examined ciliate species showed the ability of chitin degradation as well as a positive influence on the development of the ruminal fungal population.

Separation-oriented derivatization of native fluorescent compounds through fluorous labeling followed by liquid chromatography with fluorous-phase.

Science.gov (United States)

Sakaguchi, Yohei; Yoshida, Hideyuki; Todoroki, Kenichiro; Nohta, Hitoshi; Yamaguchi, Masatoshi

2009-06-15

We have developed a new and simple method based on "fluorous derivatization" for LC of native fluorescent compounds. This method involves the use of a column with a fluorous stationary phase. Native fluorescent analytes with target functional groups are precolumn derivatized with a nonfluorescent fluorous tag, and the fluorous-labeled analytes are retained in the column, whereas underivatized substances are not. Only the retained fluorescent analytes are detected fluorometrically at appropriate retention times, and retained substrates without fluorophores are not detected. In this study, biologically important carboxylic acids (homovanillic acid, vanillylmandelic acid, and 5-hydroxyindoleacetic acid) and drugs (naproxen, felbinac, flurbiprofen, and etodolac) were used as model native fluorescent compounds. Experimental results indicate that the fluorous-phase column can selectively retain fluorous compounds including fluorous-labeled analytes on the basis of fluorous separation. We believe that separation-oriented derivatization presented here is the first step toward the introduction of fluorous derivatization in quantitative LC analysis.

Diffusivities and Viscosities of Poly(ethylene oxide) Oligomers †

KAUST Repository

Hong, Bingbing; Escobedo, Fernando; Panagiotopoulos, Athanassios Z.

2010-01-01

Diffusivities and viscosities of poly(ethylene oxide) (PEO) oligomer melts with 1 to 12 repeat units have been obtained from equilibrium molecular dynamics simulations using the TraPPE-UA force field. The simulations generated diffusion coefficients

Synthesis and Electronic Properties of Length-Defined 9,10-Anthrylene-Butadiynylene Oligomers.

Science.gov (United States)

Nagaoka, Maiko; Tsurumaki, Eiji; Nishiuchi, Mai; Iwanaga, Tetsuo; Toyota, Shinji

2018-05-18

Linear π-conjugated oligomers consisting of anthracene and diacetylene units were readily synthesized by a one-pot process that involved desilylation and oxidative coupling from appropriate building units. We were able to isolate length-defined oligomers ranging from 2-mer to 6-mer as stable and soluble solids. The bathochromic shifts in the UV-vis spectra suggested that the π-conjugation was extended with elongation of the linear chain. Cyclic voltammetric measurements showed characteristic reversible oxidation waves that were dependent on the number of anthracene units.

Fluorescence microscopical studies on chitin distribution in the cell wall of giant cells of Saccharomyces uvarum, grown following X-radiaiton treatment

International Nuclear Information System (INIS)

Hoschka, L.

1982-01-01

Teast cells are synchronized and modiated with X-rays (1.0 kGy) in the Cr, phase. Their growth behaviour is observed in suspension cultures and the formation of giant cells noted. The chitin structures are selectively stained with the fluorescent dye Calcofluor white. In the unradiated cells the chitin is deposited at the bud constriction site in the form of rings in the mother cell wall, whereas for irradiated cells only one chitin ring of normal appearance is formed between the mother cell and first bud equivalent. Between further bud equivalents an intensification of fluorescence is occasionally noted, however the organisation of the chitin into a regular ring arrangement is disturbed. In giant cells the facility for primary and secondary septa formation is missing and these are essential for successful cell division. By further experiments it was possible to identify the cause of disturbance in the cell cycle of irradiated cells. Giant cells only form one chitin ring because its DNA is replicated one time only. The major cause triggering the actual formation of giant cells must be considered the missing distribution of the once-rephicated DNA. All processes in the cell cycle dependent on this step are therefore stopped and only bud formation which occurs independently continues along its rhytmical path. (orig./MG) [de

WAFs lead molting retardation of naupliar stages with down-regulated expression profiles of chitin metabolic pathway and related genes in the copepod Tigriopus japonicus.

Science.gov (United States)

Hwang, Dae-Sik; Lee, Min-Chul; Kyung, Do-Hyun; Kim, Hui-Su; Han, Jeonghoon; Kim, Il-Chan; Puthumana, Jayesh; Lee, Jae-Seong

2017-03-01

Oil pollution is considered being disastrous to marine organisms and ecosystems. As molting is critical in the developmental process of arthropods in general and copepods, in particular, the impact will be adverse if the target of spilled oil is on molting. Thus, we investigated the harmful effects of water accommodated fractions (WAFs) of crude oil with an emphasis on inhibition of chitin metabolic pathways related genes and developmental retardation in the copepod Tigriopus japonicus. Also, we analysed the ontology and domain of chitin metabolic pathway genes and mRNA expression patterns of developmental stage-specific genes. Further, the developmental retardation followed by transcriptional modulations in nuclear receptor genes (NR) and chitin metabolic pathway-related genes were observed in the WAFs-exposed T. japonicus. As a result, the developmental time was found significantly (P<0.05) delayed in response to 40% WAFs in comparison with that of control. Moreover, the NR gene, HR3 and chitinases (CHT9 and CHT10) were up-regulated in N4-5 stages, while chitin synthase genes (CHS-1, CHS-2-1, and CHS-2-2) down-regulated in response to WAFs. In brief, a high concentration of WAFs repressed nuclear receptor genes but elicited activation of some of the transcription factors at low concentration of WAFs, resulting in suppression of chitin synthesis. Thus, we suggest that WAF can lead molting retardation of naupliar stages in T. japonicus through down-regulations of chitin metabolism. These findings will provide a better understanding of the mode of action of chitin biosynthesis associated with molting mechanism in WAF-exposed T. japonicus. Copyright © 2016 Elsevier Inc. All rights reserved.

Size-Dependent Affinity of Glycine and Its Short Oligomers to Pyrite Surface: A Model for Prebiotic Accumulation of Amino Acid Oligomers on a Mineral Surface

Science.gov (United States)

Afrin, Rehana; Ganbaatar, Narangerel; Aono, Masashi; Cleaves, H. James; Yano, Taka-aki; Hara, Masahiko

2018-01-01

The interaction strength of progressively longer oligomers of glycine, (Gly), di-Gly, tri-Gly, and penta-Gly, with a natural pyrite surface was directly measured using the force mode of an atomic force microscope (AFM). In recent years, selective activation of abiotically formed amino acids on mineral surfaces, especially that of pyrite, has been proposed as an important step in many origins of life scenarios. To investigate such notions, we used AFM-based force measurements to probe possible non-covalent interactions between pyrite and amino acids, starting from the simplest amino acid, Gly. Although Gly itself interacted with the pyrite surface only weakly, progressively larger unbinding forces and binding frequencies were obtained using oligomers from di-Gly to penta-Gly. In addition to an expected increase of the configurational entropy and size-dependent van der Waals force, the increasing number of polar peptide bonds, among others, may be responsible for this observation. The effect of chain length was also investigated by performing similar experiments using l-lysine vs. poly-l-lysine (PLL), and l-glutamic acid vs. poly-l-glutamic acid. The results suggest that longer oligomers/polymers of amino acids can be preferentially adsorbed on pyrite surfaces. PMID:29370126

Protein misfolding cyclic amplification induces the conversion of recombinant prion protein to PrP oligomers causing neuronal apoptosis.

Science.gov (United States)

Yuan, Zhen; Yang, Lifeng; Chen, Baian; Zhu, Ting; Hassan, Mohammad Farooque; Yin, Xiaomin; Zhou, Xiangmei; Zhao, Deming

2015-06-01

The formation of neurotoxic prion protein (PrP) oligomers is thought to be a key step in the development of prion diseases. Recently, it was determined that the sonication and shaking of recombinant PrP can convert PrP monomers into β-state oligomers. Herein, we demonstrate that β-state oligomeric PrP can be generated through protein misfolding cyclic amplification from recombinant full-length hamster, human, rabbit, and mutated rabbit PrP, and that these oligomers can be used for subsequent research into the mechanisms of PrP-induced neurotoxicity. We have characterized protein misfolding cyclic amplification-induced monomer-to-oligomer conversion of PrP from three species using western blotting, circular dichroism, size-exclusion chromatography, and resistance to proteinase K (PK) digestion. We have further shown that all of the resulting β-oligomers are toxic to primary mouse cortical neurons independent of the presence of PrP(C) in the neurons, whereas the corresponding monomeric PrP were not toxic. In addition, we found that this toxicity is the result of oligomer-induced apoptosis via regulation of Bcl-2, Bax, and caspase-3 in both wild-type and PrP(-/-) cortical neurons. It is our hope that these results may contribute to our understanding of prion transformation within the brain. We found that β-state oligomeric PrPs can be generated through protein misfolding cyclic amplification (PMCA) from recombinant full-length hamster, human, rabbit, and mutated rabbit PrP. β-oligomers are toxic to primary mouse cortical neurons independent of the presence of PrP(C) in the neurons, while the corresponding monomeric PrPs were not toxic. This toxicity is the result of oligomers-induced apoptosis via regulation of Bcl-2, Bax, and caspase-3. These results may contribute to our understanding of prion transformation within the brain. © 2015 International Society for Neurochemistry.

Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Almadori, Y.; Alvarez, L.; Michel, T.; Le Parc, R.; Bantignies, J.L.; Hermet, P.; Sauvajol, J.L. [Laboratoire Charles Coulomb UMR 5521, Universite Montpellier 2, 34095 Montpellier (France); Laboratoire Charles Coulomb UMR 5521, CNRS, 34095 Montpellier (France); Arenal, R. [Laboratoire d' Etude des Microstructures, CNRS-ONERA, 92322 Chatillon (France); Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, U. Zaragoza, 50018 Zaragoza (Spain); Babaa, R. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France); Chemical Engineering Department, University of Technology PETRONAS, UTP, Ipoh-Perak (Malaysia); Jouselme, B.; Palacin, S. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France)

2011-11-15

This study deals with a hybrid system consisting in quaterthiophene derivative encapsulated inside single-walled and multi-walled carbon nanotubes. Investigations of the encapsulation step are performed by transmission electron microscopy. Raman spectroscopy data point out different behaviors depending on the laser excitation energy with respect to the optical absorption of quaterthiophene. At low excitation energy (far from the oligomer resonance window) there is no significant modification of the Raman spectra before and after encapsulation. By contrast, at high excitation energy (close to the oligomer resonance window), Raman spectra exhibit a G-band shift together with an important RBM intensity loss, suggesting a significant charge transfer between the inserted molecule and the host nanotubes. Those results suggest a photo induced process leading to a significant charge transfer. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Chitosan/chitin nanowhiskers composites: effect of plasticisers on the mechanical behaviour

Czech Academy of Sciences Publication Activity Database

Kelnar, Ivan; Kovářová, Jana; Tishchenko, Galina; Kaprálková, Ludmila; Pavlova, Ewa; Carezzi, F.; Morganti, P.

2015-01-01

Roč. 22, č. 2 (2015), 5_1-5_6 ISSN 1022-9760 R&D Projects: GA ČR(CZ) GA13-15255S EU Projects: European Commission(XE) 315233 - N-CHITOPACK Institutional support: RVO:61389013 Keywords : chitosan * chitin nanowhiskers * composite Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.969, year: 2015

Structure and properties of binary mixtures polystyrene-epoxyacrylic oligomers irradiated by electrons

International Nuclear Information System (INIS)

Lomonosova, N.V.

1995-01-01

Using the methods of birefringence, isometrical heating, IR-dichroism and thermal optical analysis change in structure of oriented polymer-oligomer systems on the base of PS (M>10 6 ) and epoxyacrylic (EA) oligomers of aliphatic and aromatic structure is studied during the process of irradiation by fast electrons. Their mechanical properties are studied and it is established that introduction of aliphatic epoxyacrylate to PS and subsequent irradiation allow to obtain composite materials with higher values of strength, modulus of elasticity and softening temperature in isotropic and oriented states. 6 refs., 2 figs., 3 tabs

Analysis of Organic Molecules Extracted from Mars Analogues and Influence of Their Mineralogy Using N-Methyl-N-(tert-butyldimethylsilyl)Trifluoroacetamide Derivatization Coupled with Gas Chromatography Mass Spectrometry in Preparation for the Sample Analysis at Mars Derivatization Experiment on the Mars Science Laboratory Mission

Science.gov (United States)

Stalport, F.; Glavin, D. P.; Eigenbrode, J. L.; Bish, D.; Blake, D.; Coll, P.; Szopa, C.; Buch, A.; McAdam, A.; Dworkin, J. P.;

High-performance liquid chromatographic determination of selenium in coal after derivatization to 2,1,3-benzoselenadiazoles

Energy Technology Data Exchange (ETDEWEB)

Khuhawar, M.Y.; Bozdar, R.B.; Babar, M.A. (Sindh University, Jamshoro (Pakistan). Inst. of Chemistry)

1992-11-01

High-performance liquid chromatography was examined for the determination of selenium after derivatization to 2,1,3-benzoselenadiazoles using 1,2-diaminobenzene, 1,2-diamino-4-nitrobenzene (NDAB), 2,3-diaminonaphthalene and 3,3-diaminobenzidine as derivatizing agents. Elution was carried out using a mixture of chloroform and hexane, with ultraviolet spectrophotometric detection. The 2,1,3-benzoselenadiazoles were extracted into toluene. Linear calibrations were obtained for 0-4[mu]g of selenium in 10 cm[sup 3] of solution and the detection limits were 20-50 ng of selenium in 10 cm[sup 3] of solution. The method was applied to the determination of selenium in coal samples and a shampoo using NDAB as the derivatizing reagent in acidic solution.

Selective amyloid β oligomer assay based on abasic site-containing molecular beacon and enzyme-free amplification.

Science.gov (United States)

Zhu, Linling; Zhang, Junying; Wang, Fengyang; Wang, Ya; Lu, Linlin; Feng, Chongchong; Xu, Zhiai; Zhang, Wen

2016-04-15

Amyloid-beta (Aβ) oligomers are highly toxic species in the process of Aβ aggregation and are regarded as potent therapeutic targets and diagnostic markers for Alzheimer's disease (AD). Herein, a label-free molecular beacon (MB) system integrated with enzyme-free amplification strategy was developed for simple and highly selective assay of Aβ oligomers. The MB system was constructed with abasic site (AP site)-containing stem-loop DNA and a fluorescent ligand 2-amino-5,6,7-trimethyl-1,8-naphyridine (ATMND), of which the fluorescence was quenched upon binding to the AP site in DNA stem. Enzyme-free amplification was realized by target-triggered continuous opening of two delicately designed MBs (MB1 and MB2). Target DNA hybridization with MB1 and then MB2 resulted in the release of two ATMND molecules in one binding event. Subsequent target recycling could greatly amplify the detection sensitivity due to the greatly enhanced turn-on emission of ATMND fluorescence. Combining with Aβ oligomers aptamers, the strategy was applied to analyze Aβ oligomers and the results showed that it could quantify Aβ oligomers with high selectivity and monitor the Aβ aggregation process. This novel method may be conducive to improve the diagnosis and pathogenic study of Alzheimer's disease. Copyright © 2015 Elsevier B.V. All rights reserved.

Flame retardant cotton fabrics by electron beam-induced polymerization of vinyl phosphonate oligomer

International Nuclear Information System (INIS)

Sawai, Takeshi; Ametani, Kazuo; Enomoto, Ichiro

1988-01-01

Vinyl phosphonate oligomer is presently used commercially as a cellulosic flame retardant in conjugation with N-methylol acrylamide, using a persulfate catalyst and a thermal cure. This combination can also be cured at room temperature with electron beams, as can the vinyl phosphonate alone. For the textile application, fixation of flame retardants by electron beams with low energy is one of the most promising applications. For the purpose of preparing flame resistant cotton fabrics such as bed sheets and pajamas, flame retardant curing of vinyl phosphonate oligomer on cotton fabrics was examined using electron beams from a self-sealed electron beam processor and gamma rays from a 60 Co source. A joint investigation was undertaken by the Tokyo Metropolitan Textile Research Institute and Tokyo Metropolitan Isotope Research Center to determine the feasibility of curing vinyl phosphonate oligomer on the cotton fabrics for textile finishing. (author)

Conjugated Polymers and Oligomers: Structural and Soft Matter Aspects

DEFF Research Database (Denmark)

This book identifies modern topics and current trends of structural and soft matter aspects of conjugated polymers and oligomers. Each chapter recognizes an active research line where structural perspective dominates research and therefore the book covers fundamental aspects of persistent...

Effect of phenolic oligomer on adhesion of poly (ethylene terephthalate) film laminated steel sheets by Electron Beam Curing method

International Nuclear Information System (INIS)

Masuhara, Kenichi; Mori, Koji; Koshiishi, Kenji; Sasaki, Takashi.

1995-01-01

Adhesion of poly (ethylene terephthalate) film by Electron Beam Curing (EBC) method which can be thought as an energy-saving process was studied for the purpose of bestowing economically design and distinctness of image on thermosetting high molecular weight polyester precoated steel sheets. Adhesion of EB curable resins onto metal is generally poor. In this report, addition of EB curable phenolic resole oligomer with bifunctional acrylates to the top coat used for precoated steel was studied in order to increase the adhesion of an EB curable adhesive, and it was found that the phenolic oligomer is tremendously effective for the improvement of adhesion. The reasons why the phenolic oligomer provides excellent adhesion were 1) elongation at break of the top coat to which the phenolic oligomer is added is little decreased by EB irradiation, and the formability does not reduce. 2) As the phenolic oligomer is unevenly distributed to the surface layer of the top coat, it is suggested that the contact frequency of the phenolic oligomer to the EB curable adhesive is so high that graft polymerization between them is liable to occur. (author)

Unraveling the Role of Π - Conjugation in Thiophene Oligomers for Optoelectronic Properties by DFT/TDDFT Approach

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Gajalakshmi

Full Text Available ABSTRACT Thiophene oligomer has been investigated using DFT/TDDFT calculations with an aim to check its suitability for opto electronic applications and also to analyse the influence of π-bridge. Our results revealed that thiophene oligomers have excellent π-conjugation throughout. FMO analysis give an estimate of band gap of thiophene oligomer and further revealed HOMO are localized on π - bridge, donor group and LUMO are localized on π - bridge and acceptor group. A TDDFT calculation has been performed to understand the absorption properties of them in gas phase and solvent phase. PCM calculations convey that absorption maxima show positive solvatochromism. Among the designed candidates, the one with more π - bridge show higher wavelength of absorption maxima and would be a choice for better optoelectronic materials. NBO analysis provides support for complete delocalization in these systems. It is interesting to note that oligomer with more π-bridge display an enhanced optoelectronic properties than with less π - bridge.

High-resolution NMR characterization of low abundance oligomers of amyloid-β without purification.

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Kotler, Samuel A; Brender, Jeffrey R; Vivekanandan, Subramanian; Suzuki, Yuta; Yamamoto, Kazutoshi; Monette, Martine; Krishnamoorthy, Janarthanan; Walsh, Patrick; Cauble, Meagan; Holl, Mark M Banaszak; Marsh, E Neil G; Ramamoorthy, Ayyalusamy

2015-07-03

Alzheimer's disease is characterized by the misfolding and self-assembly of the amyloidogenic protein amyloid-β (Aβ). The aggregation of Aβ leads to diverse oligomeric states, each of which may be potential targets for intervention. Obtaining insight into Aβ oligomers at the atomic level has been a major challenge to most techniques. Here, we use magic angle spinning recoupling (1)H-(1)H NMR experiments to overcome many of these limitations. Using (1)H-(1)H dipolar couplings as a NMR spectral filter to remove both high and low molecular weight species, we provide atomic-level characterization of a non-fibrillar aggregation product of the Aβ1-40 peptide using non-frozen samples without isotopic labeling. Importantly, this spectral filter allows the detection of the specific oligomer signal without a separate purification procedure. In comparison to other solid-state NMR techniques, the experiment is extraordinarily selective and sensitive. A resolved 2D spectra could be acquired of a small population of oligomers (6 micrograms, 7% of the total) amongst a much larger population of monomers and fibers (93% of the total). By coupling real-time (1)H-(1)H NMR experiments with other biophysical measurements, we show that a stable, primarily disordered Aβ1-40 oligomer 5-15 nm in diameter can form and coexist in parallel with the well-known cross-β-sheet fibrils.

High-capacity conductive nanocellulose paper sheets for electrochemically controlled extraction of DNA oligomers.

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Aamir Razaq

Full Text Available Highly porous polypyrrole (PPy-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg(-1, were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30-50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m(2 g(-1 of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT(6, (dT(20, and (dT(40 DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules.

Computational Design of High-χ Block Oligomers for Accessing 1 nm Domains.

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Chen, Qile P; Barreda, Leonel; Oquendo, Luis E; Hillmyer, Marc A; Lodge, Timothy P; Siepmann, J Ilja

2018-05-22

Molecular dynamics simulations are used to design a series of high-χ block oligomers (HCBOs) that can self-assemble into a variety of mesophases with domain sizes as small as 1 nm. The exploration of these oligomers with various chain lengths, volume fractions, and chain architectures at multiple temperatures reveals the presence of ordered lamellae, perforated lamellae, and hexagonally packed cylinders. The achieved periods are as small as 3.0 and 2.1 nm for lamellae and cylinders, respectively, which correspond to polar domains of approximately 1 nm. Interestingly, the detailed phase behavior of these oligomers is distinct from that of either solvent-free surfactants or block polymers. The simulations reveal that the behavior of these HCBOs is a product of an interplay between both "surfactant factors" (headgroup interactions, chain flexibility, and interfacial curvature) and "block polymer factors" (χ, chain length N, and volume fraction f). This insight promotes the understanding of molecular features pivotal for mesophase formation at the sub-5 nm length scale, which facilitates the design of HCBOs tailored toward particular desired morphologies.

Backbone conformation affects duplex initiation and duplex propagation in hybridisation of synthetic H-bonding oligomers.

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Iadevaia, Giulia; Núñez-Villanueva, Diego; Stross, Alexander E; Hunter, Christopher A

2018-06-06

Synthetic oligomers equipped with complementary H-bond donor and acceptor side chains form multiply H-bonded duplexes in organic solvents. Comparison of the duplex forming properties of four families of oligomers with different backbones shows that formation of an extended duplex with three or four inter-strand H-bonds is more challenging than formation of complexes that make only two H-bonds. The stabilities of 1 : 1 complexes formed between length complementary homo-oligomers equipped with either phosphine oxide or phenol recognition modules were measured in toluene. When the backbone is very flexible (pentane-1,5-diyl thioether), the stability increases uniformly by an order of magnitude for each additional base-pair added to the duplex: the effective molarities for formation of the first intramolecular H-bond (duplex initiation) and subsequent intramolecular H-bonds (duplex propagation) are similar. This flexible system is compared with three more rigid backbones that are isomeric combinations of an aromatic ring and methylene groups. One of the rigid systems behaves in exactly the same way as the flexible backbone, but the other two do not. For these systems, the effective molarity for formation of the first intramolecular H-bond is the same as that found for the other two backbones, but additional H-bonds are not formed between the longer oligomers. The effective molarities are too low for duplex propagation in these systems, because the oligomer backbones cannot adopt conformations compatible with formation of an extended duplex.

Alzheimer's-associated Aβ oligomers show altered structure, immunoreactivity and synaptotoxicity with low doses of oleocanthal

International Nuclear Information System (INIS)

Pitt, Jason; Roth, William; Lacor, Pascale; Smith, Amos B.; Blankenship, Matthew; Velasco, Pauline; De Felice, Fernanda; Breslin, Paul; Klein, William L.

2009-01-01

It now appears likely that soluble oligomers of amyloid-β 1-42 peptide, rather than insoluble fibrils, act as the primary neurotoxin in Alzheimer's disease (AD). Consequently, compounds capable of altering the assembly state of these oligomers (referred to as ADDLs) may have potential for AD therapeutics. Phenolic compounds are of particular interest for their ability to disrupt Aβ oligomerization and reduce pathogenicity. This study has focused on oleocanthal (OC), a naturally-occurring phenolic compound found in extra-virgin olive oil. OC increased the immunoreactivity of soluble Aβ species, when assayed with both sequence- and conformation-specific Aβ antibodies, indicating changes in oligomer structure. Analysis of oligomers in the presence of OC showed an upward shift in MW and a ladder-like distribution of SDS-stable ADDL subspecies. In comparison with control ADDLs, oligomers formed in the presence of OC (Aβ-OC) showed equivalent colocalization at synapses but exhibited greater immunofluorescence as a result of increased antibody recognition. The enhanced signal at synapses was not due to increased synaptic binding, as direct detection of fluorescently-labeled ADDLs showed an overall reduction in ADDL signal in the presence of OC. Decreased binding to synapses was accompanied by significantly less synaptic deterioration assayed by drebrin loss. Additionally, treatment with OC improved antibody clearance of ADDLs. These results indicate oleocanthal is capable of altering the oligomerization state of ADDLs while protecting neurons from the synaptopathological effects of ADDLs and suggest OC as a lead compound for development in AD therapeutics.

Synergistic influence of phosphorylation and metal ions on tau oligomer formation and coaggregation with α-synuclein at the single molecule level

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Nübling Georg

2012-07-01

Full Text Available Abstract Background Fibrillar amyloid-like deposits and co-deposits of tau and α-synuclein are found in several common neurodegenerative diseases. Recent evidence indicates that small oligomers are the most relevant toxic aggregate species. While tau fibril formation is well-characterized, factors influencing tau oligomerization and molecular interactions of tau and α-synuclein are not well understood. Results We used a novel approach applying confocal single-particle fluorescence to investigate the influence of tau phosphorylation and metal ions on tau oligomer formation and its coaggregation with α-synuclein at the level of individual oligomers. We show that Al3+ at physiologically relevant concentrations and tau phosphorylation by GSK-3β exert synergistic effects on the formation of a distinct SDS-resistant tau oligomer species even at nanomolar protein concentration. Moreover, tau phosphorylation and Al3+ as well as Fe3+ enhanced both formation of mixed oligomers and recruitment of α-synuclein in pre-formed tau oligomers. Conclusions Our findings provide a new perspective on interactions of tau phosphorylation, metal ions, and the formation of potentially toxic oligomer species, and elucidate molecular crosstalks between different aggregation pathways involved in neurodegeneration.

Albizia lebbeck Seed Coat Proteins Bind to Chitin and Act as a Defense against Cowpea Weevil Callosobruchus maculatus.

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Silva, Nadia C M; De Sá, Leonardo F R; Oliveira, Eduardo A G; Costa, Monique N; Ferreira, Andre T S; Perales, Jonas; Fernandes, Kátia V S; Xavier-Filho, Jose; Oliveira, Antonia E A

2016-05-11

The seed coat is an external tissue that participates in defense against insects. In some nonhost seeds, including Albizia lebbeck, the insect Callosobruchus maculatus dies during seed coat penetration. We investigated the toxicity of A. lebbeck seed coat proteins to C. maculatus. A chitin-binding protein fraction was isolated from seed coat, and mass spectrometry showed similarity to a C1 cysteine protease. By ELM program an N-glycosylation interaction motif was identified in this protein, and by molecular docking the potential to interact with N-acetylglucosamine (NAG) was shown. The chitin-binding protein fraction was toxic to C. maculatus and was present in larval midgut and feces but not able to hydrolyze larval gut proteins. It did not interfere, though, with the intestinal cell permeability. These results indicate that the toxicity mechanism of this seed coat fraction may be related to its binding to chitin, present in the larvae gut, disturbing nutrient absorption.

Natural waste materials containing chitin as adsorbents for textile dyestuffs: batch and continuous studies.

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Figueiredo, S A; Loureiro, J M; Boaventura, R A

2005-10-01

In this work three natural waste materials containing chitin were used as adsorbents for textile dyestuffs, namely the Anodonta (Anodonta cygnea) shell, the Sepia (Sepia officinalis) and the Squid (Loligo vulgaris) pens. The selected dyestuffs were the Cibacron green T3G-E (CI reactive green 12), and the Solophenyl green BLE 155% (CI direct green 26), both from CIBA, commonly used in cellulosic fibres dyeing, the most used fibres in the textile industry. Batch equilibrium studies showed that the materials' adsorption capacities increase after a simple and inexpensive chemical treatment, which increases their porosity and chitin relative content. Kinetic studies suggested the existence of a high internal resistance in both systems. Fixed bed column experiments performed showed an improvement in adsorbents' behaviour after chemical treatment. However, in the column experiments, the biodegradation was the main mechanism of dyestuff removal, allowing the materials' bioregeneration. The adsorption was strongly reduced by the pore clogging effect of the biomass. The deproteinised Squid pen (grain size 0.500-1.41 mm) is the adsorbent with highest adsorption capacity (0.27 and 0.037 g/g, respectively, for the reactive and direct dyestuffs, at 20 degrees C), followed by the demineralised Sepia pen and Anodonta shell, behaving like pure chitin in all experiments, but showing inferior performances than the granular activated carbon tested in the column experiments.

Indirubin Derivative 7-Bromoindirubin-3-Oxime (7Bio Attenuates Aβ Oligomer-Induced Cognitive Impairments in Mice

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Liping Chen

2017-11-01

Full Text Available Indirubins are natural occurring alkaloids extracted from indigo dye-containing plants. Indirubins could inhibit various kinases, and might be used to treat chronic myelocytic leukemia, cancer and neurodegenerative disorders. 7-bromoindirubin-3-oxime (7Bio, an indirubin derivative derived from indirubin-3-oxime, possesses inhibitory effects against cyclin-dependent kinase-5 (CDK5 and glycogen synthase kinase-3β (GSK3β, two pharmacological targets of Alzheimer's disease (AD. In this study, we have discovered that 2.3–23.3 μg/kg 7Bio effectively prevented β-amyloid (Aβ oligomer-induced impairments of spatial cognition and recognition without affecting bodyweight and motor functions in mice. Moreover, 7Bio potently inhibited Aβ oligomer-induced expression of interleukin-6 (IL-6 and tumor necrosis factor-α (TNF-α. Furthermore, 7Bio significantly prevented the decreased expression of synapsin-1 and PSD-95, biomarkers of pre-synaptic and post-synaptic proteins in Aβ oligomer-treated mice. The mean optical density (OD with hyper-phosphorylated tau (pTau, glial fibrillary acidic protein (GFAP and CD45 positive staining in the hippocampus of 7Bio-treated mice were significantly decreased compared to those of Aβ oligomer-treated mice. In addition, Western blotting analysis showed that 7Bio attenuated Aβ oligomer-decreased expression of pSer9-GSK3β. Those results suggested that 7Bio could potently inhibit Aβ oligomer-induced neuroinflammation, synaptic impairments, tau hyper-phosphorylation, and activation of astrocytes and microglia, which may contribute to the neuroprotective effects of 7Bio. Based on these findings, we expected that 7Bio might be developed as a novel anti-AD lead compound.

Charge transport and dielectric relaxation processes in anilin-based oligomers

Czech Academy of Sciences Publication Activity Database

Mrlík, M.; Moučka, R.; Ilčíková, M.; Bober, Patrycja; Kazantseva, N.; Špitálský, Z.; Trchová, Miroslava; Stejskal, Jaroslav

2014-01-01

Roč. 192, June (2014), s. 37-42 ISSN 0379-6779 Institutional support: RVO:61389013 Keywords : aniline-based oligomers * conductivity * dielectric properties Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.252, year: 2014

Photopolymerizable silicone monomers, oligomers, and resins

International Nuclear Information System (INIS)

Jacobine, A.F.; Nakos, S.T.

1992-01-01

The purpose of this chapter is to acquaint the general photopolymer researcher with the historical development of the chemistry and technology of photopolymerizable silicone monomers, fluids, and resins. The current status of research in these areas is assessed. The focus of this chapter is not only on the polymer chemistry and application of this technology, but also on important aspects of the synthetic chemistry involved in the preparation of UV-curable silicone monomers, oligomers, and resins. 236 refs., 6 tabs

Theory of microphase separation in homopolymer-oligomer mixtures

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Olemskoi, Alexander [Department of Physical Electronics, Sumy State University, Rimskii-Korsakov St. 2, 40007 Sumy (Ukraine)]. E-mail: alex@ufn.ru; Savelyev, Alexey [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC 27599-3290 (United States)]. E-mail: alexsav@unc.edu

2005-11-01

This work starts with the review of theoretical methods proposed, during past decades, for description of phase behavior in different polymer systems, involving variety of linear polymers (regular and polydisperse block (co)polymers, random polymers) and the polymer systems with non-covalent bonds of different strength. Microphase separation (MS) into different ordered mesophases is known to be the principal property of such systems. It is shown that most of the theoretical approaches proposed for description of the MS are based on the simple random phase approximation (RPA). It turns out, however, that mean field RPA method applied to description of the systems with non-covalent bonds does not provide the whole picture of MS. We show that the problem here arises when one treats both Flory-Huggins non-associated interactions and non-covalent bonds (hydrogen, ionic) within the unified RPA scheme, which is obviously rough for description of the latter type of interactions. Such a theory was developed in a few recent papers for the systems involving weak hydrogen bonds between homopolymer chains and the low molecular weight oligomers (surfactants). However, it leaves some experimental data unaccounted. The purpose of this review is to consider more detailed theory which is able to explain not only all the experimental data for the above systems but also to take into account the strength variation of non-bonding interactions. In particular, we consider the strong ionic interactions, weak hydrogen bonding, and the interactions of intermediate strength between polymer chain and short oligomers within our unifying theory. To develop such a description in a self-consistent way we propose to use a general field theory of stochastic systems. The mesoscopic (lamellar) structure of the periodically alternating layers of stretched homopolymer chains surrounded by perpendicularly oriented oligomeric tails is studied for the systems with both strong (ionic) and weak (hydrogen

Theory of microphase separation in homopolymer-oligomer mixtures

International Nuclear Information System (INIS)

Olemskoi, Alexander; Savelyev, Alexey

2005-01-01

This work starts with the review of theoretical methods proposed, during past decades, for description of phase behavior in different polymer systems, involving variety of linear polymers (regular and polydisperse block (co)polymers, random polymers) and the polymer systems with non-covalent bonds of different strength. Microphase separation (MS) into different ordered mesophases is known to be the principal property of such systems. It is shown that most of the theoretical approaches proposed for description of the MS are based on the simple random phase approximation (RPA). It turns out, however, that mean field RPA method applied to description of the systems with non-covalent bonds does not provide the whole picture of MS. We show that the problem here arises when one treats both Flory-Huggins non-associated interactions and non-covalent bonds (hydrogen, ionic) within the unified RPA scheme, which is obviously rough for description of the latter type of interactions. Such a theory was developed in a few recent papers for the systems involving weak hydrogen bonds between homopolymer chains and the low molecular weight oligomers (surfactants). However, it leaves some experimental data unaccounted. The purpose of this review is to consider more detailed theory which is able to explain not only all the experimental data for the above systems but also to take into account the strength variation of non-bonding interactions. In particular, we consider the strong ionic interactions, weak hydrogen bonding, and the interactions of intermediate strength between polymer chain and short oligomers within our unifying theory. To develop such a description in a self-consistent way we propose to use a general field theory of stochastic systems. The mesoscopic (lamellar) structure of the periodically alternating layers of stretched homopolymer chains surrounded by perpendicularly oriented oligomeric tails is studied for the systems with both strong (ionic) and weak (hydrogen

NEXAFS characterization of DNA components and molecular-orientation of surface-bound DNA oligomers

International Nuclear Information System (INIS)

Samuel, Newton T.; Lee, C.-Y.; Gamble, Lara J.; Fischer, Daniel A.; Castner, David G.

2006-01-01

Single stranded DNA oligomers (ssDNA) immobilized onto solid surfaces forms the basis for several biotechnological applications such as DNA microarrays, affinity separations, and biosensors. Surface structure of Surface-bound oligomers is expected to significantly influence their biological activity and interactions with the environment. In this study near-edge X-ray absorption fine structure spectroscopy (NEXAFS) is used to characterize the components of DNA (nucleobases, nucleotides and nucleosides) and the orientation information of surface-bound ssDNA. The K-edges of carbon, nitrogen and oxygen have spectra with features that are characteristic of the different chemical species present in the nucleobases of DNA. The effect of addition of the DNA sugar and phosphate components on the NEXAFS K-edge spectra was also investigated. The polarization-dependent nitrogen K-edge NEXAFS data show significant changes for different orientations of surface bound ssDNA. These results establish NEXAFS as a powerful technique for chemical and structural characterization of surface-bound DNA oligomers

Various methods for determination of the degree of N-acetylation of chitin and chitosan: a review.

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Kasaai, Mohammad R

2009-03-11

Chitin, chitosan, and their derivatives have been identified as versatile biopolymers for a broad range of agriculture and food applications. Up to now, several methods have been developed to determine degree of N-acetylation, DA, for chitin and chitosan. In this article, an effort has been made to review the available literature information on the DA determination. These methods are classified into three categories: (1) spectroscopy (IR, (1)H NMR, (13)C NMR, (15)N NMR, and UV); (2) conventional (various types of titration, conductometry, potentiometry, ninhydrin assay, adsorption of free amino groups of chitosan by pictric acid); (3) destructive (elemental analysis, acid or enzymatic hydrolysis of chitin/chitosan and followed by the DA measurement by colorimetry or high performance liquid chromatography, pyrolysis-gas chromatography, and thermal analysis using differential scanning calorimetry) methods. These methods have been compared for their performances and limitations as well as their advantages and disadvantages. The use of IR and NMR spectroscopy methods provides a number of advantages. They do not need long-term procedures to prepare samples, and they provide information on the chemical structure. (1)H NMR and UV techniques are more sensitive than IR, (13)C NMR, and (15)N NMR spectroscopy. The IR technique is mostly used for a qualitative evaluation and comparison studies. Conventional methods are not applicable for highly acetylated chitin. The results of the latter methods are affected by ionic strength of the solvent, pH, and temperature of solution. In destructive methods, longer times are needed for the measurements compared to spectroscopy and conventional methods, but they are applicable for the entire range of the DA.

Fungal-type carbohydrate binding modules from the coccolithophore Emiliania huxleyi show binding affinity to cellulose and chitin.

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Rooijakkers, Bart J M; Ikonen, Martina S; Linder, Markus B

2018-01-01

Six fungal-type cellulose binding domains were found in the genome of the coccolithophore Emiliania huxleyi and cloned and expressed in Escherichia coli. Sequence comparison indicate high similarity to fungal cellulose binding domains, raising the question of why these domains exist in coccolithophores. The proteins were tested for binding with cellulose and chitin as ligands, which resulted in the identification of two functional carbohydrate binding modules: EHUX2 and EHUX4. Compared to benchmark fungal cellulose binding domain Cel7A-CBM1 from Trichoderma reesei, these proteins showed slightly lower binding to birch and bacterial cellulose, but were more efficient chitin binders. Finally, a set of cellulose binding domains was created based on the shuffling of one well-functioning and one non-functional domain. These were characterized in order to get more information of the binding domain's sequence-function relationship, indicating characteristic differences between the molecular basis of cellulose versus chitin recognition. As previous reports have showed the presence of cellulose in coccoliths and here we find functional cellulose binding modules, a possible connection is discussed.

Fungal-type carbohydrate binding modules from the coccolithophore Emiliania huxleyi show binding affinity to cellulose and chitin.

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Bart J M Rooijakkers

Full Text Available Six fungal-type cellulose binding domains were found in the genome of the coccolithophore Emiliania huxleyi and cloned and expressed in Escherichia coli. Sequence comparison indicate high similarity to fungal cellulose binding domains, raising the question of why these domains exist in coccolithophores. The proteins were tested for binding with cellulose and chitin as ligands, which resulted in the identification of two functional carbohydrate binding modules: EHUX2 and EHUX4. Compared to benchmark fungal cellulose binding domain Cel7A-CBM1 from Trichoderma reesei, these proteins showed slightly lower binding to birch and bacterial cellulose, but were more efficient chitin binders. Finally, a set of cellulose binding domains was created based on the shuffling of one well-functioning and one non-functional domain. These were characterized in order to get more information of the binding domain's sequence-function relationship, indicating characteristic differences between the molecular basis of cellulose versus chitin recognition. As previous reports have showed the presence of cellulose in coccoliths and here we find functional cellulose binding modules, a possible connection is discussed.

Derivatization and diffusive motion of molecular fullerenes: Ab initio and atomistic simulations

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Berdiyorov, G., E-mail: gberdiyorov@qf.org.qa; Tabet, N. [Qatar Environment and Energy Research Institute (QEERI), Hamad Ben Khalifa University (HBKU), Qatar Foundation, P.O. Box 5825, Doha (Qatar); Harrabi, K. [Department of Physics, King Fahd University of Petroleum and Minerals, 31261 Dhahran (Saudi Arabia); Mehmood, U.; Hussein, I. A. [Department of Chemical Engineering, King Fahd University of Petroleum and Minerals, 31261 Dharan (Saudi Arabia); Peeters, F. M. [Departement Fysica, Universiteit Antwerpen, Groenenborgerlaan 171, B-2020 Antwerpen (Belgium); Zhang, J. [Department of Materials and London Centre for Nanotechnology, Imperial College London, SW7 2AZ London (United Kingdom); McLachlan, M. A. [Department of Materials and Centre for Plastic Electronics, Imperial College London, SW7 2AZ London (United Kingdom)

2015-07-14

Using first principles density functional theory in combination with the nonequilibrium Green's function formalism, we study the effect of derivatization on the electronic and transport properties of C{sub 60} fullerene. As a typical example, we consider [6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM), which forms one of the most efficient organic photovoltaic materials in combination with electron donating polymers. Extra peaks are observed in the density of states (DOS) due to the formation of new electronic states localized at/near the attached molecule. Despite such peculiar behavior in the DOS of an isolated molecule, derivatization does not have a pronounced effect on the electronic transport properties of the fullerene molecular junctions. Both C{sub 60} and PCBM show the same response to finite voltage biasing with new features in the transmission spectrum due to voltage induced delocalization of some electronic states. We also study the diffusive motion of molecular fullerenes in ethanol solvent and inside poly(3-hexylthiophene) lamella using reactive molecular dynamics simulations. We found that the mobility of the fullerene reduces considerably due to derivatization; the diffusion coefficient of C{sub 60} is an order of magnitude larger than the one for PCBM.

Genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food

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Makoto Nakai

2014-01-01

Full Text Available Here, we conducted in vitro genotoxicity tests to evaluate the genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food. Styrene oligomers were extracted with acetone and the extract was subjected to the Ames test (OECD test guideline No. 471 and the in vitro chromosomal aberration test (OECD test guideline No. 473 under good laboratory practice conditions. The concentrations of styrene dimers and trimers in the concentrated extract were 540 and 13,431 ppm, respectively. Extraction with acetone provided markedly higher concentrations of styrene oligomers compared with extraction with 50% ethanol aqueous solution, which is the food simulant currently recommended for use in safety assessments of polystyrene by both the United States Food and Drug Administration and the European Food Safety Authority. And these high concentrations of styrene dimers and trimers were utilized for the evaluation of genotoxicity in vitro. Ames tests using five bacterial tester strains were negative both in the presence or absence of metabolic activation. The in vitro chromosomal aberration test using Chinese hamster lung cells (CHL/IU was also negative. Together, these results suggest that the risk of the genotoxicity of styrene oligomers that migrate from polystyrene food packaging into food is very low.

Nano-fibrin stabilized CaSO4 crystals incorporated injectable chitin composite hydrogel for enhanced angiogenesis & osteogenesis.

Science.gov (United States)

Arun Kumar, R; Sivashanmugam, A; Deepthi, S; Bumgardner, Joel D; Nair, Shantikumar V; Jayakumar, R

2016-04-20

Calcium sulfate (CaSO4), an excellent biodegradable bone forming agent that is an ideal choice as additive in gels, however, its disadvantage being poor gel rheology and angiogenesis. Here, we have synthesized chitin-CaSO4-nano-fibrin based injectable gel system which shows improved rheology and angiogenic potential. Rheological studies showed that the composite gel was a shear thinning gel with elastic modulus of 15.4±0.275kPa; a 1.67 fold increase over chitin control. SEM and XRD analyses revealed the effect of nano-fibrin (nFibrin) in transforming CaSO4 crystal shape from needle to hexagonal. It also masked the retarding effect of CaSO4 towards in vitro early cell attachment and angiogenesis using rabbit adipose derived mesenchymal stem cells (rASCs) and HUVECs, respectively. rASCs osteogenesis was confirmed by spectrophotometric endpoint assay, which showed 6-fold early increase in alkaline phosphatase levels and immuno-cytochemistry analysis. These in vitro results highlight the potential of injectable chitin-CaSO4-nFibrin gel for osteo-regeneration via enhanced angiogenesis. Copyright © 2015 Elsevier Ltd. All rights reserved.

Highly sensitive and specific derivatization strategy to profile and quantitate eicosanoids by UPLC-MS/MS

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Hu, Ting; Tie, Cai; Wang, Zhe; Zhang, Jin-Lan, E-mail: zhjl@imm.ac.cn

2017-01-15

Eicosanoids are signaling molecules mainly oxidized from arachidonic acid (ARA) and eicosapentaenoic acid (EPA) or docosahexaenoic acid (DHA). They have attracted increasing attention from the scientists attributing to their essential physiological functions. However, their quantification have long been challenged by the low abundance, high structure similarity, poor stability and limited ionization efficiency. In this paper, an ultra-high performance liquid chromatograph coupled with tandem mass spectrometry (UPLC-MS/MS) strategy was developed for the comprehensive profiling of more than 60 eicosanoids based on an efficient derivatization reagent 2,4-bis(diethylamino)-6-hydrazino-1,3,5-triazine (T3) and general multiple reaction monitoring (MRM) parameters. Carboxylic acid of eicosanoid was converted to amide in 30 min at 4 °C with derivatization yield larger than 99%. Limits of quantitation (LOQs) for derivatized eicosanoids varied from 0.05 to 50 pg depending on their structures. The sensitivities of derivatized eicosanoids were enhanced by 10- to 5000-folds compared to free eicosanoids. Stabilities of T3 modified eicosanoids were also highly improved compared to free eicosanoids. This new method can also be used to quantify eicosanoids in bio-samples using isotopic internal standards with high efficiency and reliability within 19 min. 46 and 50 eicosanoids in rat plasma and heart tissue from control and acute myocardial ischemia (AMI) model rats were respectively profiled and quantitated using this new method. And 24 of 46 and 25 of 50 eicosanoids were found to be significantly changed between control and model groups. The changed eicosanoids related to AMI modeling were further statistically analyzed and interpreted based on eicosanoid metabolism pathway. - Highlights: • Eicosanoids are important signaling molecules. • A highly sensitive and specific derivatization strategy was developed for eicosanoid profiling. • The strategy was employed for

Highly sensitive and specific derivatization strategy to profile and quantitate eicosanoids by UPLC-MS/MS

International Nuclear Information System (INIS)

Hu, Ting; Tie, Cai; Wang, Zhe; Zhang, Jin-Lan

2017-01-01

Eicosanoids are signaling molecules mainly oxidized from arachidonic acid (ARA) and eicosapentaenoic acid (EPA) or docosahexaenoic acid (DHA). They have attracted increasing attention from the scientists attributing to their essential physiological functions. However, their quantification have long been challenged by the low abundance, high structure similarity, poor stability and limited ionization efficiency. In this paper, an ultra-high performance liquid chromatograph coupled with tandem mass spectrometry (UPLC-MS/MS) strategy was developed for the comprehensive profiling of more than 60 eicosanoids based on an efficient derivatization reagent 2,4-bis(diethylamino)-6-hydrazino-1,3,5-triazine (T3) and general multiple reaction monitoring (MRM) parameters. Carboxylic acid of eicosanoid was converted to amide in 30 min at 4 °C with derivatization yield larger than 99%. Limits of quantitation (LOQs) for derivatized eicosanoids varied from 0.05 to 50 pg depending on their structures. The sensitivities of derivatized eicosanoids were enhanced by 10- to 5000-folds compared to free eicosanoids. Stabilities of T3 modified eicosanoids were also highly improved compared to free eicosanoids. This new method can also be used to quantify eicosanoids in bio-samples using isotopic internal standards with high efficiency and reliability within 19 min. 46 and 50 eicosanoids in rat plasma and heart tissue from control and acute myocardial ischemia (AMI) model rats were respectively profiled and quantitated using this new method. And 24 of 46 and 25 of 50 eicosanoids were found to be significantly changed between control and model groups. The changed eicosanoids related to AMI modeling were further statistically analyzed and interpreted based on eicosanoid metabolism pathway. - Highlights: • Eicosanoids are important signaling molecules. • A highly sensitive and specific derivatization strategy was developed for eicosanoid profiling. • The strategy was employed for

Formation of nitrogen-containing oligomers by methylglyoxal and amines in simulated evaporating cloud droplets.

Science.gov (United States)

De Haan, David O; Hawkins, Lelia N; Kononenko, Julia A; Turley, Jacob J; Corrigan, Ashley L; Tolbert, Margaret A; Jimenez, Jose L

2011-02-01

Reactions of methylglyoxal with amino acids, methylamine, and ammonium sulfate can take place in aqueous aerosol and evaporating cloud droplets. These processes are simulated by drying droplets and bulk solutions of these compounds (at low millimolar and 1 M concentrations, respectively) and analyzing the residuals by scanning mobility particle sizing, nuclear magnetic resonance, aerosol mass spectrometry (AMS), and electrospray ionization MS. The results are consistent with imine (but not diimine) formation on a time scale of seconds, followed by the formation of nitrogen-containing oligomers, methylimidazole, and dimethylimidazole products on a time scale of minutes to hours. Measured elemental ratios are consistent with imidazoles and oligomers being major reaction products, while effective aerosol densities suggest extensive reactions take place within minutes. These reactions may be a source of the light-absorbing, nitrogen-containing oligomers observed in urban and biomass-burning aerosol particles.

Synthesis of alginate oligomers by gamma irradiation and to investigate its antioxidant and prebiotic activity

International Nuclear Information System (INIS)

Bhoir, S.A.; Chawla, S.P.

2016-01-01

Alginate oligomers formed by alginate lyase have been reported to possess antioxidant activity as well as prebiotic activity. Hence, utility of gamma radiation to depolymerise alginate in its aqueous solution was investigated and its antioxidant and prebiotic activities were screened. 1% aqueous solution of sodium alginate was subjected to gamma irradiation and it's reducing power and ability to scavenge DPPH". and O_2"."."-, chelate iron and prevent heat induced β-carotene bleaching was determined. Prebiotic activity was determined by using alginate oligomers to promote prebiotic activity of Lactobacillus plantarum against E coli. Gamma radiation induced depolymerisation of alginate resulted in formation of oligomers with antioxidant and prebiotic activity. These polymers are potential candidates for utilization as natural preservatives and functional foods

Characterizing the Dynamics of α-Synuclein Oligomers Using Hydrogen/Deuterium Exchange Monitored by Mass Spectrometry

DEFF Research Database (Denmark)

Mysling, Simon; Betzer, Cristine; Jensen, Poul Henning

2013-01-01

Soluble oligomers formed by α-synuclein (αSN) are suspected to play a central role in neuronal cell death during Parkinson's disease. While studies have probed the surface structure of these oligomers, little is known about the backbone dynamics of αSN when they form soluble oligomers. Using...... analyses performed on αSN fibrils and indicated a possible zipperlike maturation mechanism for αSN aggregates. We find the protected N-terminus (residues 4-17) to be of particular interest, as this region has previously been observed to be highly dynamic for both monomeric and fibrillar αSN. This region...... has mainly been described in relation to membrane binding of αSN, and structuring may be important in relation to disease....

Synthesis of Citric-Acrylate Oligomer and its in-Situ Reaction with Chrome Tanned Collagen (hide powder)

International Nuclear Information System (INIS)

Haroun, A.A.; Masoud, R.A.; Bronco, S.; Ciardelli, F.

2005-01-01

The purpose of this study was to formulate the new combined system of acrylic and citric acids, which has been prepared by free radical polymerization and esterification reaction at the same time to form citric acrylate (CAC) oligomer through ester linkage and low molecular weight (Mw 2241), in compared with polyacrylic acid. The chemical structure and the reaction mechanism of this oligomer were confirmed by different spectroscopic tools (1 H , 13 C-NMR, ATR-IR), gel permeation chromatography and thermogravimetric analysis (TGA/DTA). The problem of the effect of the masking agents in the chrome tanning of the collagen and the pickling of the hide has been approached from the study of the hydrothermal and mechanical properties, using this new eco-friendly oligomer, which was carried out in-situ treated/grafted chrome tanned collagen (hide powder), and pickled hide. The microemulsion grafting copolymerization of (CAC) using 2.2-azo-bis isobutyronitrile (ABIN), via direct coupling reaction, onto the chrome tanned collagen showed that the free amino groups of the collagen were considered to be a potential site for the in-situ reaction with (CAC) oligomer. Also, using of citric-acrylate (CAC) oligomer, during chrome tanning of leather, instead of the traditional strong acids (sulfuric, hydrochloric and formic) resulted in significant improvement in chrome exhaustion and physical properties

Biochemical and morphological responses to abiotc elicitor chitin in suspension-cultured sugarcane cells

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Maria Izabel Gallão

2010-04-01

Full Text Available Cells of Saccharum officinarum submitted to hydrolyzated chitin for 1 to 8h produced phenolic compounds. These alterations were observed through cytochemical methods using Toluidine Blue and Phloroglucinol/HCl. After 4 h, besides cell wall change, there was a change in nuclear pattern of chitin treated cells. There was a 96% increase in nuclear area in 6 h chitin treated material, as observed by Feulgen reaction. The treated cells showed chromatin compacted regions and a degeneration process of nucleoli. In the outer areas of cell wall, there was a polysaccharide desagregation, confirming results obtained for different plants with the use of other elicitors. Peroxidase activity was maximal after 4 h and decreased progressively. PAL activity started to increase at 4 h of incubation. These results showed that chitin hydrolyzate stimulated a defense response in sugarcane cells.Células de Saccharum officinarum quando submetidas a quitina hidrolisada por 1 a 8h produziram material fenólico. Essas alterações foram observadas por meio de métodos citoquímicos como o Azul de Toluidina e Floroglucinol/HCl. Após 4 h, além das mudanças nas paredes celulares houve uma mudança no padrão nuclear das células tratadas com quitina. Por observação da reação de Feulgen, houve um aumento de 96% na área nuclear no material em 6h. Para as células tratadas foram observadas regiões de cromatina compactada e um processo de degeneração do nucléolo. Nas áreas externas da parede celular existia uma desagregação dos polisacarídios confirmando os resultados obtidos para diferentes plantas com o uso de outros elicitores. A atividade da peroxidase foi maxima após 4 h e então decresceu progressivamente. A atividade da PAL aumentou a partir de 4 h de incubação. Estes resultados mostram que o hidrolisado de quitina estimula as respostas de defesa em células de cana.

Structures of Metalloporphyrin-Oligomer Multianions: Cofacial versus Coplanar Motifs as Resolved by Ion Mobility Spectrometry.

Science.gov (United States)

Brendle, Katrina; Schwarz, Ulrike; Jäger, Patrick; Weis, Patrick; Kappes, Manfred

2016-11-03

We have combined ion mobility mass spectrometry with quantum chemical calculations to investigate the gas-phase structures of multiply negatively charged oligomers of meso-tetra(4-sulfonatophenyl)metalloporphyrins comprising the divalent metal centers Zn II , Cu II , and Pd II . Sets of candidate structures were obtained by geometry optimizations based on calculations at both the semiempirical PM7 and density functional theory (DFT) levels. The corresponding theoretical cross sections were calculated with the projection approximation and also with the trajectory method. By comparing these collision cross sections with the respective experimental values we were able to assign oligomer structures up to the tetramer. In most cases the cross sections of the lowest energy isomers predicted by theory were found to agree with the measurements to within the experimental uncertainty (2%). Specifically, we find that for a given oligomer size the structures are independent of the metal center but depend strongly on the charge state. Oligomers in low charge states with a correspondingly larger number of sodium counterions tend to form stacked, cofacial structures reminiscent of H-aggregate motifs observed in solution. By contrast, in higher charge states, the stack opens to form coplanar structures.

High-level expression and characterization of two chitinases, ChiCH and ChiCW, of Bacillus cereus 28-9 in Escherichia coli

International Nuclear Information System (INIS)

Huang, C.-J.; Chen, C.-Y.

2005-01-01

Many chitinase genes have been cloned and sequenced from prokaryotes and eukaryotes but overexpression of chitinases in Escherichia coli cells was less reported. ChiCH and ChiCW of Bacillus cereus 28-9 belong to two distinct groups based on their amino acid sequences of catalytic domains, and in addition, domain structures of two enzymes are different. In this study, we established an ideal method for high-level expression of chitinases in E. coli as glutathione-S-transferase fusion proteins using pGEX-6P-1 vector. Both ChiCH and ChiCW were successfully highly expressed in E. coli cells as soluble GST-chitinase fusion proteins, and recombinant native ChiCH and ChiCW could be purified after cleavage with PreScission protease to remove GST tag. Purified chitinases were used for biochemical characterization of kinetics, hydrolysis products, and binding activities. The results indicate that ChiCW is an endo-chitinase and effectively hydrolyzes chitin and chito-multimers to chito-oligomers and the end product chitobiose, and ChiCH is an exo-chitinase and degrades chito-oligomers to produce chitobiose. Furthermore, due to higher affinity of ChiCW toward colloidal chitin than Avicel, C-terminal domain of ChiCW should be classified as a chitin-binding domain not a cellulose-binding domain although that was revealed as a cellulose-binding domain by conserved domain analysis. Therefore, the method of high-level expression of chitinases is helpful to studies and applications of chitinases

Natural amyloid-β oligomers acutely impair the formation of a contextual fear memory in mice.

Science.gov (United States)

Kittelberger, Kara A; Piazza, Fabrizio; Tesco, Giuseppina; Reijmers, Leon G

2012-01-01

Memory loss is one of the hallmark symptoms of Alzheimer's disease (AD). It has been proposed that soluble amyloid-beta (Abeta) oligomers acutely impair neuronal function and thereby memory. We here report that natural Abeta oligomers acutely impair contextual fear memory in mice. A natural Abeta oligomer solution containing Abeta monomers, dimers, trimers, and tetramers was derived from the conditioned medium of 7PA2 cells, a cell line that expresses human amyloid precursor protein containing the Val717Phe familial AD mutation. As a control we used 7PA2 conditioned medium from which Abeta oligomers were removed through immunodepletion. Separate groups of mice were injected with Abeta and control solutions through a cannula into the lateral brain ventricle, and subjected to fear conditioning using two tone-shock pairings. One day after fear conditioning, mice were tested for contextual fear memory and tone fear memory in separate retrieval trials. Three experiments were performed. For experiment 1, mice were injected three times: 1 hour before and 3 hours after fear conditioning, and 1 hour before context retrieval. For experiments 2 and 3, mice were injected a single time at 1 hour and 2 hours before fear conditioning respectively. In all three experiments there was no effect on tone fear memory. Injection of Abeta 1 hour before fear conditioning, but not 2 hours before fear conditioning, impaired the formation of a contextual fear memory. In future studies, the acute effect of natural Abeta oligomers on contextual fear memory can be used to identify potential mechanisms and treatments of AD associated memory loss.

Natural Amyloid-Beta Oligomers Acutely Impair the Formation of a Contextual Fear Memory in Mice

Science.gov (United States)

Kittelberger, Kara A.; Piazza, Fabrizio; Tesco, Giuseppina; Reijmers, Leon G.

2012-01-01

Memory loss is one of the hallmark symptoms of Alzheimer's disease (AD). It has been proposed that soluble amyloid-beta (Abeta) oligomers acutely impair neuronal function and thereby memory. We here report that natural Abeta oligomers acutely impair contextual fear memory in mice. A natural Abeta oligomer solution containing Abeta monomers, dimers, trimers, and tetramers was derived from the conditioned medium of 7PA2 cells, a cell line that expresses human amyloid precursor protein containing the Val717Phe familial AD mutation. As a control we used 7PA2 conditioned medium from which Abeta oligomers were removed through immunodepletion. Separate groups of mice were injected with Abeta and control solutions through a cannula into the lateral brain ventricle, and subjected to fear conditioning using two tone-shock pairings. One day after fear conditioning, mice were tested for contextual fear memory and tone fear memory in separate retrieval trials. Three experiments were performed. For experiment 1, mice were injected three times: 1 hour before and 3 hours after fear conditioning, and 1 hour before context retrieval. For experiments 2 and 3, mice were injected a single time at 1 hour and 2 hours before fear conditioning respectively. In all three experiments there was no effect on tone fear memory. Injection of Abeta 1 hour before fear conditioning, but not 2 hours before fear conditioning, impaired the formation of a contextual fear memory. In future studies, the acute effect of natural Abeta oligomers on contextual fear memory can be used to identify potential mechanisms and treatments of AD associated memory loss. PMID:22238679

Coronavirus nucleocapsid proteins assemble constitutively in high molecular oligomers

NARCIS (Netherlands)

Cong, Yingying; Kriegenburg, Franziska; de Haan, Cornelis A. M.; Reggiori, Fulvio

2017-01-01

Coronaviruses (CoV) are enveloped viruses and rely on their nucleocapsid N protein to incorporate the positive-stranded genomic RNA into the virions. CoV N proteins form oligomers but the mechanism and relevance underlying their multimerization remain to be fully understood. Using in vitro pull-down

Effect of Corn Steep Liquor (CSL and Cassava Wastewater (CW on Chitin and Chitosan Production by Cunninghamella elegans and Their Physicochemical Characteristics and Cytotoxicity

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Lúcia Raquel Ramos Berger

2014-02-01

Full Text Available Microbiological processes were used for chitin and chitosan production with Cunninghamella elegans UCP/WFCC 0542 grown in different concentrations of two agro-industrial wastes, corn steep liquor (CSL and cassava wastewater (CW established using a 22 full factorial design. The polysaccharides were extracted by alkali-acid treatment and characterized by infrared spectroscopy, viscosity, thermal analysis, elemental analysis, scanning electron microscopy and X-ray diffraction. The cytotoxicity of chitosan was evaluated for signs of vascular change on the chorioallantoic membrane of chicken eggs. The highest biomass (9.93 g/L was obtained in trial 3 (5% CW, 8% CSL, the greatest chitin and chitosan yields were 89.39 mg/g and 57.82 mg/g, respectively, and both were obtained in trial 2 (10% CW, 4% CSL. Chitin and chitosan showed a degree of deacetylation of 40.98% and 88.24%, and a crystalline index of 35.80% and 23.82%, respectively, and chitosan showed low molecular weight (LMW 5.2 × 103 Da. Chitin and chitosan can be considered non-irritating, due to the fact they do not promote vascular change. It was demonstrated that CSL and CW are effective renewable agroindustrial alternative substrates for the production of chitin and chitosan.

The chiral structure of porous chitin within the wing-scales of Callophrys rubi.

Science.gov (United States)

Schröder-Turk, G E; Wickham, S; Averdunk, H; Brink, F; Fitz Gerald, J D; Poladian, L; Large, M C J; Hyde, S T

2011-05-01

The structure of the porous three-dimensional reticulated pattern in the wing scales of the butterfly Callophrys rubi (the Green Hairstreak) is explored in detail, via scanning and transmission electron microscopy. A full 3D tomographic reconstruction of a section of this material reveals that the predominantly chitin material is assembled in the wing scale to form a structure whose geometry bears a remarkable correspondence to the srs net, well-known in solid state chemistry and soft materials science. The porous solid is bounded to an excellent approximation by a parallel surface to the Gyroid, a three-periodic minimal surface with cubic crystallographic symmetry I4₁32, as foreshadowed by Stavenga and Michielson. The scale of the structure is commensurate with the wavelength of visible light, with an edge of the conventional cubic unit cell of the parallel-Gyroid of approximately 310 nm. The genesis of this structure is discussed, and we suggest it affords a remarkable example of templating of a chiral material via soft matter, analogous to the formation of mesoporous silica via surfactant assemblies in solution. In the butterfly, the templating is achieved by the lipid-protein membranes within the smooth endoplasmic reticulum (while it remains in the chrysalis), that likely form cubic membranes, folded according to the form of the Gyroid. The subsequent formation of the chiral hard chitin framework is suggested to be driven by the gradual polymerisation of the chitin precursors, whose inherent chiral assembly in solution (during growth) promotes the formation of a single enantiomer. Copyright © 2011 Elsevier Inc. All rights reserved.

Solid state properties of oligomers containing dithienothiophene or fluorene residues suitable for field effect transistor devices

International Nuclear Information System (INIS)

Porzio, William; Destri, Silvia; Giovanella, Umberto; Pasini, Mariacecilia; Marin, Luminita; Iosip, Mariana Dana; Campione, Marcello

2007-01-01

A series of three thiophene based oligomers has been extensively characterized. The chemical design has been addressed to obtain ionization potential (IP) and electronic affinity (EA) values matching the work function of commonly used electrode materials. Such IP and EA values were tested by cyclovoltammetry. In order to tune electron-donation and drawing strength the sequence of the molecule subunits in the oligomer has been varied. The thermal properties with particular reference to their stability during preparation and operation were checked by using differential scanning calorimetry, polarised light microscopy and thermogravimetric analysis techniques. Prototypes of thin film field effect transistor, based on this series of oligomers have been electrically and structurally characterized. The long axes of the molecules are oriented nearly perpendicular to the gate insulator, in agreement with both highly sensitive X-ray diffraction and atomic force microscopy. From powder diffraction data the structure of oligomer I was solved. A general relation is envisaged between charge mobility and packing closeness in the series. For the most promising molecule a study of mobility/temperature behaviour was performed yielding interesting results

Quantitation of fumonisin B1 and B2 in feed using FMOC pre-column derivatization with HPLC and fluorescence detection.

Science.gov (United States)

Smith, Lori L; Francis, Kyle A; Johnson, Joseph T; Gaskill, Cynthia L

2017-11-01

Pre-column derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was determined to be effective for quantitation of fumonisins B 1 and B 2 in feed. Liquid-solid extraction, clean-up using immunoaffinity solid phase extraction chromatography, and FMOC-derivatization preceded analysis by reverse phase HPLC with fluorescence. Instrument response was unchanged in the presence of matrix, indicating no need to use matrix-matched calibrants. Furthermore, high method recoveries indicated calibrants do not need to undergo clean-up to account for analyte loss. Established method features include linear instrument response from 0.04-2.5µg/mL and stable derivatized calibrants over 7days. Fortified cornmeal method recoveries from 0.1-30.0μg/g were determined for FB 1 (75.1%-109%) and FB 2 (96.0%-115.2%). Inter-assay precision ranged from 1.0%-16.7%. Method accuracy was further confirmed using certified reference material. Inter-laboratory comparison with naturally-contaminated field corn demonstrated equivalent results with conventional derivatization. These results indicate FMOC derivatization is a suitable alternative for fumonisins B 1 and B 2 quantitation in corn-based feeds. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermodynamically stable amyloid-β monomers have much lower membrane affinity than the small oligomers

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Bidyut eSarkar

2013-04-01

Full Text Available Amyloid beta (Aβ is an extracellular 39-43 residue long peptide present in the mammalian cerebrospinal fluid, whose aggregation is associated with Alzheimer’s disease. Small oligomers of Aβ are currently thought to be the key to toxicity. However, it is not clear why the monomers of Aβ are non-toxic, and at what stage of aggregation toxicity emerges. Interactions of Aβ with cell membranes is thought to be the initiator of toxicity, but membrane-binding studies with different preparations of monomers and oligomers have not settled this issue. We have earlier found that thermodynamically stable Aβ monomers emerge spontaneously from oligomeric mixtures upon long term incubation in physiological solutions (Nag et al, JBC, 2011. Here we show that the membrane-affinity of these stable Aβ monomers is much lower than that of a mixture of small oligomers (containing dimers to decamers, providing a clue to the emergence of toxicity. Fluorescently labeled Aβ40 monomers show negligible binding to cell membranes of a neuronal cell line (RN46A at physiological concentrations (250 nM, while oligomers at the same concentrations show strong binding within 30 minutes of incubation. The increased affinity most likely does not require any specific neuronal receptor, since this difference in membrane-affinity was also observed in a somatic cell-line (HEK 293T. Similar results are also obtained for Aβ42 monomers and oligomers. Minimal amount of cell death is observed at these concentrations even after 36 hours of incubation. It is likely that membrane binding precedes subsequent slower toxic events induced by Aβ. Our results a provide an explanation for the non-toxic nature of Aβ monomers, b suggest that Aβ toxicity emerges at the initial oligomeric phase, and c provide a quick assay for monitoring the benign-to-toxic transformation of Aβ.

Distinct Internalization Pathways of Human Amylin Monomers and Its Cytotoxic Oligomers in Pancreatic Cells

Science.gov (United States)

Trikha, Saurabh; Jeremic, Aleksandar M.

2013-01-01

Toxic human amylin oligomers and aggregates are implicated in the pathogenesis of type 2 diabetes mellitus (TTDM). Although recent studies have shown that pancreatic cells can recycle amylin monomers and toxic oligomers, the exact uptake mechanism and trafficking routes of these molecular forms and their significance for amylin toxicity are yet to be determined. Using pancreatic rat insulinoma (RIN-m5F) beta (β)-cells and human islets as model systems we show that monomers and oligomers cross the plasma membrane (PM) through both endocytotic and non-endocytotic (translocation) mechanisms, the predominance of which is dependent on amylin concentrations and incubation times. At low (≤100 nM) concentrations, internalization of amylin monomers in pancreatic cells is completely blocked by the selective amylin-receptor (AM-R) antagonist, AC-187, indicating an AM-R dependent mechanism. In contrast at cytotoxic (µM) concentrations monomers initially (1 hour) enter pancreatic cells by two distinct mechanisms: translocation and macropinocytosis. However, during the late stage (24 hours) monomers internalize by a clathrin-dependent but AM-R and macropinocytotic independent pathway. Like monomers a small fraction of the oligomers initially enter cells by a non-endocytotic mechanism. In contrast a majority of the oligomers at both early (1 hour) and late times (24 hours) traffic with a fluid-phase marker, dextran, to the same endocytotic compartments, the uptake of which is blocked by potent macropinocytotic inhibitors. This led to a significant increase in extra-cellular PM accumulation, in turn potentiating amylin toxicity in pancreatic cells. Our studies suggest that macropinocytosis is a major but not the only clearance mechanism for both amylin’s molecular forms, thereby serving a cyto-protective role in these cells. PMID:24019897

Chitin and Cellulose Processing in Low-Temperature Electron Beam Plasma

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Tatiana Vasilieva

2017-11-01

Full Text Available Polysaccharide processing by means of low-temperature Electron Beam Plasma (EBP is a promising alternative to the time-consuming and environmentally hazardous chemical hydrolysis in oligosaccharide production. The present paper considers mechanisms of the EBP-stimulated destruction of crab shell chitin, cellulose sulfate, and microcrystalline cellulose, as well as characterization of the produced oligosaccharides. The polysaccharide powders were treated in oxygen EBP for 1–20 min at 40 °C in a mixing reactor placed in the zone of the EBP generation. The chemical structure and molecular mass of the oligosaccharides were analyzed by size exclusion and the reversed phase chromatography, FTIR-spectroscopy, XRD-, and NMR-techniques. The EBP action on original polysaccharides reduces their crystallinity index and polymerization degree. Water-soluble products with lower molecular weight chitooligosaccharides (weight-average molecular mass, Mw = 1000–2000 Da and polydispersity index 2.2 and cellulose oligosaccharides with polymerization degrees 3–10 were obtained. The 1H-NMR analysis revealed 25–40% deacetylation of the EBP-treated chitin and FTIR-spectroscopy detected an increase of carbonyl- and carboxyl-groups in the oligosaccharides produced. Possible reactions of β-1,4-glycosidic bonds’ destruction due to active oxygen species and high-energy electrons are given.

Benzothienobenzothiophene-based conjugated oligomers as semiconductors for stable organic thin-film transistors.

Science.gov (United States)

Yu, Han; Li, Weili; Tian, Hongkun; Wang, Haibo; Yan, Donghang; Zhang, Jingping; Geng, Yanhou; Wang, Fosong

2014-04-09

Two benzothienobenzothiophene (BTBT)-based conjugated oligomers, i.e., 2,2'-bi[1]benzothieno[3,2-b][1]benzothiophene (1) and 5,5'-bis([1]benzothieno[3,2-b][1]benzothiophen-2-yl)-2,2'-bithiophene (2), were prepared and characterized. Both oligomers exhibit excellent thermal stability, with 5% weight-loss temperatures (T(L)) above 370 °C; no phase transition was observed before decomposition. The highest occupied molecular orbital (HOMO) levels of 1 and 2 are -5.3 and -4.9 eV, respectively, as measured by ultraviolet photoelectron spectroscopy. Thin-film X-ray diffraction and atomic force microscopy characterizations indicate that both oligomers form highly crystalline films with large domain sizes on octadecyltrimethoxysilane-modified substrates. Organic thin-film transistors with top-contact and bottom-gate geometry based on 1 and 2 exhibited mobilities up to 2.12 cm(2)/V·s for 1 and 1.39 cm(2)/V·s for 2 in an ambient atmosphere. 1-based devices exhibited great air and thermal stabilities, as evidenced by the slight performance degradation after 2 months of storage under ambient conditions and after thermal annealing at temperatures below 250 °C.

Rapamycin-induced oligomer formation system of FRB-FKBP fusion proteins.

Science.gov (United States)

Inobe, Tomonao; Nukina, Nobuyuki

2016-07-01

Most proteins form larger protein complexes and perform multiple functions in the cell. Thus, artificial regulation of protein complex formation controls the cellular functions that involve protein complexes. Although several artificial dimerization systems have already been used for numerous applications in biomedical research, cellular protein complexes form not only simple dimers but also larger oligomers. In this study, we showed that fusion proteins comprising the induced heterodimer formation proteins FRB and FKBP formed various oligomers upon addition of rapamycin. By adjusting the configuration of fusion proteins, we succeeded in generating an inducible tetramer formation system. Proteins of interest also formed tetramers by fusing to the inducible tetramer formation system, which exhibits its utility in a broad range of biological applications. Copyright © 2015 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Studies on Oligomer Metal Complexes Derived from Bisamic Acid of Pyromellitic Dianhydride and 4-Bromoaniline

OpenAIRE

Patel, Yogesh S.

2014-01-01

Novel oligomer metal complexes (2a–f) of the ligand 2,5-bis((4-bromophenyl)carbamoyl) terephthalic acid (1) were prepared using transition metal salts and characterized by various spectroscopic techniques. The geometry of oligomer metal complexes was carried out by electronic spectral analysis and magnetic measurement studies. Polymeric properties have also been carried out. Ligand was synthesized using pyromellitic dianhydride and 4-bromoaniline. It was duly characterized. All novel synthesi...

Synthesis of Cycloveratrylene Macrocycles and Benzyl Oligomers Catalysed by Bentonite under Microwave/Infrared and Solvent-Free Conditions

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Manuel Salmón

2013-10-01

Full Text Available Tonsil Actisil FF, which is a commercial bentonitic clay, promotes the formation of cycloveratrylene macrocycles and benzyl oligomers from the corresponding benzyl alcohols in good yields under microwave heating and infrared irradiation in the absence of solvent in both cases. The catalytic reaction is sensitive to the type of substituent on the aromatic ring. Thus, when benzyl alcohol was substituted with a methylenedioxy, two methoxy or three methoxy groups, a cyclooligomerisation process was induced. Unsubstituted, methyl and methoxy benzyl alcohols yielded linear oligomers. In addition, computational chemistry calculations were performed to establish a validated mechanistic pathway to explain the growth of the obtained linear oligomers.

Structure and properties of binary polystyrene-epoxy acrylate oligomer mixtures irradiated by electron beams

International Nuclear Information System (INIS)

Lomonosova, N.V.

1995-01-01

The change in the structure of oriented polymer-oligomer systems based on polystyrene (PS) with M > 10 6 and epoxy acrylate oligomers (aliphatic and aromatic) under irradiation by accelerated electrons was studied using birefringence, isometric heating, IR dichroism, and thermooptical analysis. Mechanical properties of these systems were investigated. It was found that, by adding aliphatic epoxy acrylate to PS and further irradiating this mixture, one can obtain both isotropic and oriented composites with higher strengths, elasticity moduli, and glass transition temperatures

Structural basis for new pattern of conserved amino acid residues related to chitin-binding in the antifungal peptide from the coconut rhinoceros beetle Oryctes rhinoceros.

Science.gov (United States)

Hemmi, Hikaru; Ishibashi, Jun; Tomie, Tetsuya; Yamakawa, Minoru

2003-06-20

Scarabaecin isolated from hemolymph of the coconut rhinoceros beetle Oryctes rhinoceros is a 36-residue polypeptide that has antifungal activity. The solution structure of scarabaecin has been determined from twodimensional 1H NMR spectroscopic data and hybrid distance geometry-simulated annealing protocol calculation. Based on 492 interproton and 10 hydrogen-bonding distance restraints and 36 dihedral angle restraints, we obtained 20 structures. The average backbone root-mean-square deviation for residues 4-35 is 0.728 +/- 0.217 A from the mean structure. The solution structure consists of a two-stranded antiparallel beta-sheet connected by a type-I beta-turn after a short helical turn. All secondary structures and a conserved disulfide bond are located in the C-terminal half of the peptide, residues 18-36. Overall folding is stabilized by a combination of a disulfide bond, seven hydrogen bonds, and numerous hydrophobic interactions. The structural motif of the C-terminal half shares a significant tertiary structural similarity with chitin-binding domains of plant and invertebrate chitin-binding proteins, even though scarabaecin has no overall sequence similarity to other peptide/polypeptides including chitin-binding proteins. The length of its primary structure, the number of disulfide bonds, and the pattern of conserved functional residues binding to chitin in scarabaecin differ from those of chitin-binding proteins in other invertebrates and plants, suggesting that scarabaecin does not share a common ancestor with them. These results are thought to provide further strong experimental evidence to the hypothesis that chitin-binding proteins of invertebrates and plants are correlated by a convergent evolution process.

KARAKTERISASI KITIN DEASETILASE TERMOSTABIL ISOLAT BAKTERI ASAL PANCURAN TUJUH, BATURADEN, JAWA TENGAH [Characterization of Thermostable Chitin Deacetylase from Bacteria Strain Pancuran Tujuh, Baturaden, Center of Java

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Deuxianto Hendarsyah3

2006-04-01

Full Text Available Chitin deacetylase is the enzymes that has important role in converting chitin to chitosan. In nature, chitin is the second most abundant natural biopolymer after cellulose. Generally, chitin easily obtained from outer shell of crustaceans, arthropods, and also detectable on cell wall of some type of fungal (Zygomycetes. The chitin deacetylase was isolated from Bacillus sp PT2-3. It was found that the highest specific activity was attained at pH 8 60°C. The addition of 5 mM Zn2+ and 5 mM Mn2+ increased the specific activity of the enzyme, 4.39% and 7.8%, respectively, and the increase was only 2.19% when the addition was 2 mM Mn2+. On the contrary the addition of Ca2+, Mg2+ and Fe2+ decrease the specific activity 46.83%, 41.22% and 47.32%, respectively. The enzyme activity was relatively stable at 60°C for 60 minutes, while lengthen the time to 90 minutes, decreased the activity 15.05 %, and the decrease was 26.13% at temperature of 70°C for 180 minutes.

Fabrication of Chitin/Poly(butylene succinate/Chondroitin Sulfate Nanoparticles Ternary Composite Hydrogel Scaffold for Skin Tissue Engineering

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S. Deepthi

2014-12-01

Full Text Available Skin loss is one of the oldest and still not totally resolved problems in the medical field. Since spontaneous healing of the dermal defects would not occur, the regeneration of full thickness of skin requires skin substitutes. Tissue engineering constructs would provide a three dimensional matrix for the reconstruction of skin tissue and the repair of damage. The aim of the present work is to develop a chitin based scaffold, by blending it with poly(butylene succinate (PBS, an aliphatic, biodegradable and biocompatible synthetic polymer with excellent mechanical properties. The presence of chondroitin sulfate nanoparticles (CSnp in the scaffold would favor cell adhesion. A chitin/PBS/CSnp composite hydrogel scaffold was developed and characterized by SEM (Scanning Electron Microscope, FTIR (Fourier Transform Infrared Spectroscopy, and swelling ratio of scaffolds were analyzed. The scaffolds were evaluated for the suitability for skin tissue engineering application by cytotoxicity, cell attachment, and cell proliferation studies using human dermal fibroblasts (HDF. The cytotoxicity and cell proliferation studies using HDF confirm the suitability of the scaffold for skin regeneration. In short, these results show promising applicability of the developed chitin/PBS/CSnps ternary composite hydrogel scaffolds for skin tissue regeneration.

Chitin mixed in potting soil alters lettuce growth, the survival of zoonotic bacteria on the leaves and associated rhizosphere microbiology.

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Jane eDebode

2016-04-01

Full Text Available Chitin is a promising soil amendment for improving soil quality, plant growth and plant resilience. The objectives of this study were twofold. First, to study the effect of chitin mixed in potting soil on lettuce growth and on the survival of two zoonotic bacterial pathogens, Escherichia coli O157:H7 and Salmonella enterica on the lettuce leaves. Second, to assess the related changes in the microbial lettuce rhizosphere, using phospholipid fatty acid (PLFA analysis and amplicon sequencing of a bacterial 16S rRNA gene fragment and the fungal ITS2. As a result of chitin addition, lettuce fresh yield weight was significantly increased. S. enterica survival in the lettuce phyllosphere was significantly reduced. The E. coli O157:H7 survival was also lowered, but not significantly. Moreover, significant changes were observed in the bacterial and fungal community of the lettuce rhizosphere. PLFA analysis showed a significant increase in fungal and bacterial biomass. Amplicon sequencing showed no increase in fungal and bacterial biodiversity, but relative abundances of the bacterial phyla Acidobacteria, Verrucomicrobia, Actinobacteria, Bacteroidetes, and Proteobacteria and the fungal phyla Ascomycota, Basidiomycota, and Zygomycota were significantly changed. More specifically, a more than tenfold increase was observed for operational taxonomic units (OTUs belonging to the bacterial genera Cellvibrio, Pedobacter, Dyadobacter, and Streptomyces and to the fungal genera Lecanicillium and Mortierella. These genera include several species previously reported to be involved in biocontrol, plant growth promotion, the nitrogen cycle and chitin degradation. These results enhance the understanding of the response of the rhizosphere microbiome to chitin amendment. Moreover, this is the first study to investigate the use of soil amendments to control the survival of S. enterica on plant leaves.

Natural amyloid-β oligomers acutely impair the formation of a contextual fear memory in mice.

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Kara A Kittelberger

Full Text Available Memory loss is one of the hallmark symptoms of Alzheimer's disease (AD. It has been proposed that soluble amyloid-beta (Abeta oligomers acutely impair neuronal function and thereby memory. We here report that natural Abeta oligomers acutely impair contextual fear memory in mice. A natural Abeta oligomer solution containing Abeta monomers, dimers, trimers, and tetramers was derived from the conditioned medium of 7PA2 cells, a cell line that expresses human amyloid precursor protein containing the Val717Phe familial AD mutation. As a control we used 7PA2 conditioned medium from which Abeta oligomers were removed through immunodepletion. Separate groups of mice were injected with Abeta and control solutions through a cannula into the lateral brain ventricle, and subjected to fear conditioning using two tone-shock pairings. One day after fear conditioning, mice were tested for contextual fear memory and tone fear memory in separate retrieval trials. Three experiments were performed. For experiment 1, mice were injected three times: 1 hour before and 3 hours after fear conditioning, and 1 hour before context retrieval. For experiments 2 and 3, mice were injected a single time at 1 hour and 2 hours before fear conditioning respectively. In all three experiments there was no effect on tone fear memory. Injection of Abeta 1 hour before fear conditioning, but not 2 hours before fear conditioning, impaired the formation of a contextual fear memory. In future studies, the acute effect of natural Abeta oligomers on contextual fear memory can be used to identify potential mechanisms and treatments of AD associated memory loss.

Profiling and relative quantification of phosphatidylethanolamine based on acetone stable isotope derivatization

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiang [Oil Crops Research Institute of the Chinese Academy of Agricultural Sciences, Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture (China); Hubei Key Laboratory of Lipid Chemistry and Nutrition (China); Wei, Fang, E-mail: willasa@163.com [Oil Crops Research Institute of the Chinese Academy of Agricultural Sciences, Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture (China); Hubei Key Laboratory of Lipid Chemistry and Nutrition (China); Xu, Ji-qu; Lv, Xin; Dong, Xu-yan [Oil Crops Research Institute of the Chinese Academy of Agricultural Sciences, Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture (China); Hubei Key Laboratory of Lipid Chemistry and Nutrition (China); Han, Xianlin [Center for Metabolic Origins of Disease, Sanford Burnham Prebys Medical Discovery Institute, Orlando, FL 32827 (United States); College of Basic Medical Sciences, Zhejiang Chinese Medical University, 548 Bingwen Road, Hangzhou, Zhejiang 310053 (China); Quek, Siew-young [School of Chemical Science, The University of Auckland, Auckland 1142 (New Zealand); Huang, Feng-hong [Oil Crops Research Institute of the Chinese Academy of Agricultural Sciences, Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture (China); Hubei Key Laboratory of Lipid Chemistry and Nutrition (China); Chen, Hong, E-mail: chenhong@oilcrops.cn [Oil Crops Research Institute of the Chinese Academy of Agricultural Sciences, Key Laboratory of Biology and Genetic Improvement of Oil Crops, Ministry of Agriculture (China); Hubei Key Laboratory of Lipid Chemistry and Nutrition (China)

2016-01-01

Phosphatidylethanolamine (PE) is considered to be one of the pivotal lipids for normal cellular function as well as disease initiation and progression. In this study, a simple, efficient, reliable, and inexpensive method for the qualitative analysis and relative quantification of PE, based on acetone stable isotope derivatization combined with double neutral loss scan-shotgun electrospray ionization tandem-quadrupole mass spectrometry analysis (ASID-DNLS-Shotgun ESI-MS/MS), was developed. The ASID method led to alkylation of the primary amino groups of PE with an isopropyl moiety. The use of acetone (d{sub 0}-acetone) and deuterium-labeled acetone (d{sub 6}-acetone) introduced a 6 Da mass shift that was ideally suited for relative quantitative analysis, and enhanced sensitivity for mass analysis. The DNLS model was introduced to simultaneously analyze the differential derivatized PEs by shotgun ESI-MS/MS with high selectivity and accuracy. The reaction specificity, labeling efficiency, and linearity of the ASID method were thoroughly evaluated in this study. Its excellent applicability was validated by qualitative and relative quantitative analysis of PE species presented in liver samples from rats fed different diets. Using the ASID-DNLS-Shotgun ESI-MS/MS method, 45 PE species from rat livers have been identified and quantified in an efficient manner. The level of total PEs tended to decrease in the livers of rats on high fat diets compared with controls. The levels of PE 32:1, 34:3, 34:2, 36:3, 36:2, 42:10, plasmalogen PE 36:1 and lyso PE 22:6 were significantly reduced, while levels of PE 36:1 and lyso PE 16:0 increased. - Highlights: • A novel isotope reagent acetone was explored for the derivatization of PEs. • The labeling reaction was carried out under mild conditions with high specificity. • Enhanced detection sensitivity of PEs was achieved after derivatization. • The ASID-DNLS-Shotgun MS/MS method was used to relative quantification of PEs.

Charge-carrier selective electrodes for organic bulk heterojunction solar cell by contact-printed siloxane oligomers

International Nuclear Information System (INIS)

Hwang, Hyun-Sik; Khang, Dahl-Young

2015-01-01

‘Smart’ (or selective) electrode for charge carriers, both electrons and holes, in organic bulk-heterojunction (BHJ) solar cells using insertion layers made of hydrophobically-recovered and contact-printed siloxane oligomers between electrodes and active material has been demonstrated. The siloxane oligomer insertion layer has been formed at a given interface simply by conformally-contacting a cured slab of polydimethylsiloxane stamp for less than 100 s. All the devices, either siloxane oligomer printed at one interface only or printed at both interfaces, showed efficiency enhancement when compared to non-printed ones. The possible mechanism that is responsible for the observed efficiency enhancement has been discussed based on the point of optimum symmetry and photocurrent analysis. Besides its simplicity and large-area applicability, the demonstrated contact-printing technique does not involve any vacuum or wet processing steps and thus can be very useful for the roll-based, continuous production scheme for organic BHJ solar cells. - Highlights: • Carrier-selective insertion layer in organic bulk heterojunction solar cells • Simple contact-printing of siloxane oligomers improves cell efficiency. • Printed siloxane layer reduces carrier recombination at electrode surfaces. • Siloxane insertion layer works equally well at both electrode surfaces. • Patterned PDMS stamp shortens the printing time within 100 s

NATURAL POLYMERS: CELLULOSE, CHITIN, CHITOSAN, GELATIN, STARCH, CARRAGEENAN, XYLAN AND DEXTRAN

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Fatma Zohra Benabid

2016-12-01

Full Text Available Biopolymers have been investigated for drug fields. They are widely being studied because of their non-toxic and biocompatible in nature. Biopolymers are used in industries as diverse as paper, plastics, food, textiles, pharmaceuticals, and cosmetics.This review covers different natural polymers, recent techniques applied in their processing and characterization. Advanced applications of natural polymers, including chitin, chitosan, alginate, etc., are discussed.

Identification and characterization of chitin deacetylase2 from the American white moth, Hyphantria cunea (Drury).

Science.gov (United States)

Yan, Xiaoping; Zhao, Dan; Zhang, Yakun; Guo, Wei; Wang, Wei; Zhao, Kunli; Gao, Yujie; Wang, Xiaoyun

2018-05-26

Chitin deacetylases (CDAs) are enzymes that catalyze the conversion of chitin into chitosan, thereby influence the mechanical and permeability properties of structures such as the cuticle and peritrophic matrices. The full length cDNAs of chitin deacetylase2 (CDA2) genes from Hyphantria cunea were fully cloned by PCR amplification. Two cDNA sequences of HcCDA2 were searched from transcriptome of H. cunea and named as HcCDA2a and HcCDA2b. The deduced protein sequences showed that HaCDA2a and HaCDA2b are synthesized as preproteins of 524 and 518 amino acid residues with an 18-amino acid signal peptide, respectively. HcCDA2a and HcCDA2b contained a chitin-binding domain (ChBD), a low-density lipoprotein receptor class A domain (LDLa) and a polysaccharide deacetylase-like catalytic domain (CDA). Gene expression analyses results showed that HcCDA2a and HcCDA2b were both expressed at the head, integument, foregut, midgut, hindgut, Malpighian tubules and fat body, as well as the 1st to 5th days of fifth instar larvae. Western blot analyses revealed that HcCDA2 protein was highly abundant in the head and integument, and the developmental expression result in the fifth instars showed that HcCDA2 was highly present at the first two days. Besides, RT-PCR results showed that HcCDA2a and HcCDA2b were both expressed in integument and head, whether in molting stage or feeding stage. No visiable phenotypic changes were observed after injection of dsHcCDA2b, while lethal phenotypes of cuticle shedding failure and high mortality were resulted from injection of dsHcCDA2a. The silence of HcCDA2a leads to the ecdysis failure and death of H. cunea. These results suggest that HcCDA2 plays an important role during insect development, and provide new candidate targets and basis for developing environment-friendly pesticides. Copyright © 2017. Published by Elsevier B.V.

Removal of methyl violet dye by adsorption onto N-benzyltriazole derivatized dextran

DEFF Research Database (Denmark)

Cho, Eunae; Tahir, Muhammad Nazir; Kim, Hwanhee

2015-01-01

In this work, N-benzyltriazole derivatized dextran was evaluated for its potential as a novel carbohydrate-based adsorbent for the removal of methyl violet dye from water. The modified dextran was synthesized by a click reaction of pentynyl dextran and benzyl azide, and the structure...... was characterized by nuclear magnetic resonance spectroscopy, elemental analysis, and scanning electron microscopy. Dextran was substituted with a triazole-linked benzyl group. For decolorization of the dye effluent, adsorption is a very effective treatment; here, the driving force is based on hydrogen bonding, pi...... stacking, and electrostatic interaction between the methyl violet dye and the N-benzyltriazole derivatized dextran. Batch experiments were carried out to investigate the required contact time and the effects of pH, initial dye concentrations, and temperature. The experimental data were analyzed...

Derivatization reaction-based surface-enhanced Raman scattering (SERS) for detection of trace acetone.

Science.gov (United States)

Zheng, Ying; Chen, Zhuo; Zheng, Chengbin; Lee, Yong-Ill; Hou, Xiandeng; Wu, Li; Tian, Yunfei

2016-08-01

A facile method was developed for determination of trace volatile acetone by coupling a derivatization reaction to surface-enhanced Raman scattering (SERS). With iodide modified Ag nanoparticles (Ag IMNPs) as the SERS substrate, acetone without obvious Raman signal could be converted to SERS-sensitive species via a chemical derivatization reaction with 2,4-dinitrophenylhydrazine (2,4-DNPH). In addition, acetone can be effectively separated from liquid phase with a purge-sampling device and then any serious interference from sample matrices can be significantly reduced. The optimal conditions for the derivatization reaction and the SERS analysis were investigated in detail, and the selectivity and reproducibility of this method were also evaluated. Under the optimal conditions, the limit of detection (LOD) for acetone was 5mgL(-1) or 0.09mM (3σ). The relative standard deviation (RSD) for 80mgL(-1) acetone (n=9) was 1.7%. This method was successfully used for the determination of acetone in artificial urine and human urine samples with spiked recoveries ranging from 92% to 110%. The present method is convenient, sensitive, selective, reliable and suitable for analysis of trace acetone, and it could have a promising clinical application in early diabetes diagnosis. Copyright © 2016 Elsevier B.V. All rights reserved.

β-Chitin and chitosan from squid gladius: Biological activities of chitosan and its application as clarifying agent for apple juice.

Science.gov (United States)

Abdelmalek, Baha Eddine; Sila, Assaâd; Haddar, Anissa; Bougatef, Ali; Ayadi, Mohamed Ali

2017-11-01

Chitin is the second most abundant polysaccharide in biomass after cellulose and the term chitosan usually refers to a family of polymers obtained after chitin deacetylation. The aim of this work was the preparation and the characterization of chitin and chitosan from the gladius (pen) of the European squid (Loligo vulgaris). A high level of deproteinization (more than 80%) was recorded using Alcalase ® with an enzyme/protein ratio of 10U/mg. The demineralization of the gladius was completely achieved within 8h at room temperature in HCl. 13 C NMR, FTIR, and XRD diffractograms of prepared chitin and chitosan were taken and then degree of deacetylation of chitosan was calculated using 13 C CP/MAS-NMR Spectroscopic. Further, in vitro antioxidant capacity of chitosan was evaluated on 1,1-diphenyl-2-picrylhydrazyl method (IC 50 =3.2mgmL -1 ) and the β-carotene bleaching assay (IC 50 =3.3mgmL -1 ). Antimicrobial activity was also investigated and assays indicated that prepared chitosan exhibited marked inhibitory activity against all microbial strains tested. Additionally, chitosan was tested such as clarifying agent for apple juice and showed powerful clarification capability, without affecting nutritional value. Furthermore, the results suggested that prepared chitosan could be used as alternative additive in pharmaceutical preparations and food industry. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of Functionalization Degree on the Rheological Properties of Isocyanate-Functionalized Chitin- and Chitosan-Based Chemical Oleogels for Lubricant Applications

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Rocío Gallego

2014-07-01

Full Text Available This work deals with the influence of functionalization degree on the thermogravimetric and rheological behaviour of NCO-functionalized chitosan- and chitin-based oleogels. Chitosan and chitin were functionalized using different proportions of 1,6-hexamethylene diisocyanate (HMDI and subsequently dispersed in castor oil to promote the chemical reaction between the –NCO group of the modified biopolymer and the –OH group located in the ricinoleic fatty acid chain of castor oil, thus resulting in different oleogels with specific thermogravimetric and rheological characteristics. Biopolymers and oleogels were characterized through Fourier transform infrared spectroscopy (FTIR and thermogravimetric analysis (TGA. Small-amplitude oscillatory shear (SAOS measurements were performed on the oleogels. Oleogels presented suitable thermal resistance, despite the fact that the inclusion of HMDI moieties in the polymer structure led to a reduction in the onset temperature of thermal degradation. The insertion of low amounts of HMDI in both chitin and chitosan produces a drastic reduction in the values of oleogel viscoelastic functions but, above a critical threshold, they increase with the functionalization degree so that isocyanate functionalization results in a chemical tool to modulate oleogel rheological response. Several NCO-functionalized chitosan- and chitin-based oleogel formulations present suitable thermal resistance and rheological characteristics to be proposed as bio-based alternatives to traditional lubricating greases.

The Effect of Poly (Glycerol Sebacate) Incorporation within Hybrid Chitin-Lignin Sol-Gel Nanofibrous Scaffolds.

Science.gov (United States)

Abudula, Tuerdimaimaiti; Gzara, Lassaad; Simonetti, Giovanna; Alshahrie, Ahmed; Salah, Numan; Morganti, Pierfrancesco; Chianese, Angelo; Fallahi, Afsoon; Tamayol, Ali; Bencherif, Sidi A; Memic, Adnan

2018-03-19

Chitin and lignin primarily accumulate as bio-waste resulting from byproducts of crustacean crusts and plant biomass. Recently, their use has been proposed for diverse and unique bioengineering applications, amongst others. However, their weak mechanical properties need to be improved in order to facilitate their industrial utilization. In this paper, we fabricated hybrid fibers composed of a chitin-lignin (CL)-based sol-gel mixture and elastomeric poly (glycerol sebacate) (PGS) using a standard electrospinning approach. Obtained results showed that PGS could be coherently blended with the sol-gel mixture to form a nanofibrous scaffold exhibiting remarkable mechanical performance and improved antibacterial and antifungal activity. The developed hybrid fibers showed promising potential in advanced biomedical applications such as wound care products. Ultimately, recycling these sustainable biopolymers and other bio-wastes alike could propel a "greener" economy.

Atomistic simulation of CO 2 solubility in poly(ethylene oxide) oligomers

KAUST Repository

Hong, Bingbing; Panagiotopoulos, Athanassios Z.

2013-01-01

We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide

Development of a novel selective ESI-MS derivatization reagent - ssynthesis and optimization for the analysis of aldehydes in biological mixtures

NARCIS (Netherlands)

Eggink, M.; Wijtmans, M.; de Esch, I.J.P.; Lingeman, H.; Niessen, W.M.A.; Irth, H.

2008-01-01

In LC-MS, derivatization is primarily used to improve ionization characteristics, especially for analytes that are not (efficiently) ionized by ESI or APCI such as aldehydes, sugars, and steroids. Derivatization strategies are then directed at the incorporation of a group with a permanent charge. A

Investigation of the structure of isobutylene oligomers, used in the capacity of stock for succinimide additives, by the method of proton magnetic resonance

Energy Technology Data Exchange (ETDEWEB)

Iarmoliuk, V.M.; Garun, Ia.E.; Ostroverkhov, V.G.; Pustovit, V.E.; Tikhonov, V.P.

1980-01-01

By the method of proton magnetic resonance, investigation was made of the structure of hydrocarbon framework of isobutylene oligomers of the Salavatsk petrochemical plant, produced by the cation polymerization of the isobutane isobutylene fraction at a temperature from -10 to +20/sup 0/ with A1C1/sub 3/ and used in the production of succinide additives. Determination was made of the qualitative and quantitative compositions of the various structures in the oligomers. It is shown, that as a rule, oligobutenes are not pure oligomers of isobutylene, but represent, at least, fragments of four structures, which can be formed on the basis of isobutylene. The content of the given structures does not affect the reaction capacity of the oligomers in respect to the maleic anhydride. It was established, that the low molecular fraction, contained in oligomers up to 5%, are not isobutylene oligomers, but represent a low molecular polymer of butene-2 and its copolymer with isobutylene.

Hydrazinonicotinic acid derivatization for selective ionization and improved glycan structure characterization by MALDI-MS.

Science.gov (United States)

Jiao, Jing; Yang, Lijun; Zhang, Ying; Lu, Haojie

2015-08-21

The analysis of glycan is important for understanding cell biology and disease processes because the glycans play a key role in many important biological behaviors, such as cell division, cellular localization, tumor immunology and inflammation. Nevertheless, it is still hard work to analyze glycans by MALDI-MS, which generally stems from the inherent low abundance and the low ionization efficiency of glycans. Moreover, the difficulty in generating informative fragmentations further hinders glycans structure characterization. In this work, hydrazinonicotinic acid (HYNIC) was used as a novel derivatized reagent for improved and selective detection of glycans. Through tagging the reducing terminus of glycans with the diazanyl group of HYNIC, significant enhancement of the ionization efficiency of glycans was achieved. After derivatization, the signal to noise ratio (S/N) of the maltoheptaose was improved by more than one order of magnitude in positive mode. HYNIC derivatization also allowed the sensitive detection of sialylated glycan in negative mode, with a 15 fold enhancement of S/N. Interestingly, it is noteworthy that the HYNIC reagent not only effectively labeled the reducing end of glycans in the presence of tryptic peptides, but also suppressed the ionization of peptides, enabling the direct detection of glycans from glycoprotein without separation. Therefore, analysis of glycans became easier due to the omission of a pre-separation step. Importantly, by using different acid reagents as the catalyst, derivatized product signals corresponding to [M + Na](+) or [M + H](+) were obtained respectively, which yield complementary fragmentation patterns for the structure elucidation of glycans. Finally, more than 40 N-glycans were successfully detected in 10 μL human serum using this method.

Macrocyclic 2,7-Anthrylene Oligomers.

Science.gov (United States)

Yamamoto, Yuta; Wakamatsu, Kan; Iwanaga, Tetsuo; Sato, Hiroyasu; Toyota, Shinji

2016-05-06

A macrocyclic compound consisting of six 2,7-anthrylene units was successfully synthesized by Ni-mediated coupling of the corresponding dibromo precursor as a novel π-conjugated compound. This compound was sufficiently stable and soluble in organic solvents due to the presence of mesityl groups. X-ray analysis showed that the molecule had a nonplanar and hexagonal wheel-shaped framework of approximately S6 symmetry. The dynamic process between two S6 structures was observed by using the dynamic NMR technique, the barrier being 58 kJ mol(-1) . The spectroscopic properties of the hexamer were compared with those of analogous linear oligomers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Intrahippocampal Administration of Amyloid-β1–42 Oligomers Acutely Impairs Spatial Working Memory, Insulin Signaling, and Hippocampal Metabolism

Science.gov (United States)

Pearson-Leary, Jiah; McNay, Ewan C.

2017-01-01

Increasing evidence suggests that abnormal brain accumulation of amyloid-β1–42 (Aβ1–42) oligomers plays a causal role in Alzheimer’s disease (AD), and in particular may cause the cognitive deficits that are the hallmark of AD. In vitro, Aβ1–42 oligomers impair insulin signaling and suppress neural functioning. We previously showed that endogenous insulin signaling is an obligatory component of normal hippocampal function, and that disrupting this signaling led to a rapid impairment of spatial working memory, while delivery of exogenous insulin to the hippocampus enhanced both memory and metabolism; diet-induced insulin resistance both impaired spatial memory and prevented insulin from increasing metabolism or cognitive function. Hence, we tested the hypothesis that Aβ1–42 oligomers could acutely impair hippocampal metabolic and cognitive processes in vivo in the rat. Our findings support this hypothesis: Aβ1–42 oligomers impaired spontaneous alternation behavior while preventing the task-associated dip in hippocampal ECF glucose observed in control animals. In addition, Aβ1–42 oligomers decreased plasma membrane translocation of the insulin-sensitive glucose transporter 4 (GluT4), and impaired insulin signaling as measured by phosphorylation of Akt. These data show in vivo that Aβ1–42 oligomers can rapidly impair hippocampal cognitive and metabolic processes, and provide support for the hypothesis that elevated Aβ1–42 leads to cognitive impairment via interference with hippocampal insulin signaling. PMID:22430529

Extracellular Tau Oligomers Induce Invasion of Endogenous Tau into the Somatodendritic Compartment and Axonal Transport Dysfunction

Science.gov (United States)

Swanson, Eric; Breckenridge, Leigham; McMahon, Lloyd; Som, Sreemoyee; McConnell, Ian; Bloom, George S.

2017-01-01

Aggregates composed of the microtubule associated protein, tau, are a hallmark of Alzheimer’s disease and non-Alzheimer’s tauopathies. Extracellular tau can induce the accumulation and aggregation of intracellular tau, and tau pathology can be transmitted along neural networks over time. There are six splice variants of central nervous system tau, and various oligomeric and fibrillar forms are associated with neurodegeneration in vivo. The particular extracellular forms of tau capable of transferring tau pathology from neuron to neuron remain ill defined, however, as do the consequences of intracellular tau aggregation on neuronal physiology. The present study was undertaken to compare the effects of extracellular tau monomers, oligomers, and filaments comprising various tau isoforms on the behavior of cultured neurons. We found that 2N4R or 2N3R tau oligomers provoked aggregation of endogenous intracellular tau much more effectively than monomers or fibrils, or of oligomers made from other tau isoforms, and that a mixture of all six isoforms most potently provoked intracellular tau accumulation. These effects were associated with invasion of tau into the somatodendritic compartment. Finally, we observed that 2N4R oligomers perturbed fast axonal transport of membranous organelles along microtubules. Intracellular tau accumulation was often accompanied by increases in the run length, run time and instantaneous velocity of membranous cargo. This work indicates that extracellular tau oligomers can disrupt normal neuronal homeostasis by triggering axonal tau accumulation and loss of the polarized distribution of tau, and by impairing fast axonal transport. PMID:28482642

β-Isocyanoalanine as an IR probe: comparison of vibrational dynamics between isonitrile and nitrile-derivatized IR probes.

Science.gov (United States)

Maj, Michał; Ahn, Changwoo; Kossowska, Dorota; Park, Kwanghee; Kwak, Kyungwon; Han, Hogyu; Cho, Minhaeng

2015-05-07

An infrared (IR) probe based on isonitrile (NC)-derivatized alanine 1 was synthesized and the vibrational properties of its NC stretching mode were investigated using FTIR and femtosecond IR pump-probe spectroscopy. It is found that the NC stretching mode is very sensitive to the hydrogen-bonding ability of solvent molecules. Moreover, its transition dipole strength is larger than that of nitrile (CN) in nitrile-derivatized IR probe 2. The vibrational lifetime of the NC stretching mode is found to be 5.5 ± 0.2 ps in both D2O and DMF solvents, which is several times longer than that of the azido (N3) stretching mode in azido-derivatized IR probe 3. Altogether these properties suggest that the NC group can be a very promising sensing moiety of IR probes for studying the solvation structure and dynamics of biomolecules.

Simultaneous determination of diastereoisomeric and enantiomeric impurities in SSS-octahydroindole-2-carboxylic acid by chiral high-performance liquid chromatography with pre-column derivatization.

Science.gov (United States)

Wang, Jin Zhao; Zeng, Su; Hu, Gong Yun; Wang, Dan Hua

2009-04-10

SSS-Octahydroindole-2-carboxylic acid (SSS-Oic) is a key intermediate used in the synthesis of some angiotensin-converting enzyme (ACE) inhibitors. The separation of diastereoisomers and enantiomers of Oic was performed using a pre-column derivatization chiral HPLC method. Phenyl isothiocyanate (PITC) was used as the derivatization reagent. Three PITC derivatives of Oic stereoisomers were separated on an Ultron ES-OVM chiral column (150 mm x 4.6 mm, 5 microm). Derivatization conditions such as reaction temperature, reaction time and derivatization reagent concentration were investigated. The chromatographic conditions for separation of the three PITC-Oic derivatives were optimized. The method was successfully applied in the diastereoisomeric and enantiomeric purity test of SSS-Oic.

Alpha-synuclein oligomers - neurotoxic molecules in Parkinson’s disease and other Lewy body disorders

Directory of Open Access Journals (Sweden)

Martin Ingelsson

2016-09-01

Full Text Available Adverse intra- and extracellular effects of toxic α-synuclein are believed to be central to the pathogenesis in Parkinson’s disease and other disorders with Lewy body pathology in the nervous system. One of the physiological roles of α-synuclein relates to the regulation of neurotransmitter release at the presynapse, although it is still unclear whether this mechanism depends on the action of monomers or smaller oligomers. As for the pathogenicity, accumulating evidence suggest that prefibrillar species, rather than the deposits per se, are responsible for the toxicity in affected cells. In particular, larger oligomers or protofibrils of α-synuclein have been shown to impair protein degradation as well as the function of several organelles, such as the mitochondria and the endoplasmic reticulum. Accumulating evidence further suggest that oligomers/protofibrils may have a toxic effect on the synapse, which may lead to disrupted electrophysiological properties. In addition, recent data indicate that oligomeric α-synuclein species can spread between cells, either as free-floating proteins or via extracellular vesicles, and thereby act as seeds to propagate disease between interconnected brain regions. Taken together, several lines of evidence suggest that α-synuclein have neurotoxic properties and therefore should be an appropriate molecular target for therapeutic intervention in Parkinson’s disease and other disorders with Lewy pathology. In this context, immunotherapy with monoclonal antibodies against α-synuclein oligomers/protofibrils should be a particularly attractive treatment option.

Targeting α-synuclein oligomers

DEFF Research Database (Denmark)

van Diggelen, Femke

Parkinson’s Disease (PD) is a complex disease, characterised by degeneration of neocortical, limbic and nigrostriatal neurons. It is unknown what initiates neurodegeneration, but soluble oligomers of the protein α-synuclein (αSn) seem to be particularly toxic, compared to insoluble fibrils...... unique characteristics, e.g. they were recognized by different conformational antibodies and DHA–αSOs also formed a second elongated species in addition to the dominant spherical species. Although further functional testing is needed, this suggests that each species has its own distinct toxic mechanism......+/K+ ATPase, V-type ATPase, VDAC, CaMKII and Rab-3A. The identification of these targets is a first step towards unravelling the toxic pathways which are activated upon synaptic binding of extracellularly added αSOs, and hopefully will contribute to the discovery of new disease modifying compounds, which can...

Immobilization of small molecules and proteins by radio-derivatized polystyrene

International Nuclear Information System (INIS)

Varga, J.M.; Fritsch, P.

1990-01-01

When molded polystyrene (PS) products (e.g., microtiter plates) or latex particles are irradiated with high-energy (1-10 Mrads) gamma rays in the presence of nonpolymerizable small molecules such as aromatic amines, some of these molecules incorporate into PS, which leads to the formation of radio-derivatized PS (RDPS). Two classes of RDPS can be identified regarding their ability for immobilization of biologically important molecules: (1) reactive RDPS that are able to form covalent bonds with molecules such as proteins without the help of cross-linkers, and (2) functionalized RDPS that can be used for the immobilization of molecules with activators (e.g., carbodiimides) or cross-linkers. The method can be used for the production of low-noise supports for binding assays. Most of the RDPS can be produced without impairment of the optical quality of PS, making derivatized microtiter plates suitable for colorimetric assays. The principle can be applied for the preparation of affinity sorbents, e.g., for high-performance affinity chromatography and for the immobilization of enzymes using latex PS particles

Molecular size evolution of oligomers in organic aerosols collected in urban atmospheres and generated in a smog chamber.

Science.gov (United States)

Kalberer, Markus; Sax, Mirjam; Samburova, Vera

2006-10-01

Only a minor fraction of the total organic aerosol mass can be resolved on a molecular level. High molecular weight compounds in organic aerosols have recently gained much attention because this class of compound potentially explains a major fraction of the unexplained organic aerosol mass. These compounds have been identified with different mass spectrometric methods, and compounds with molecular masses up to 1000 Da are found in secondary organic aerosols (SOA) generated from aromatic and terpene precursors in smog chamber experiments. Here, we apply matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) to SOA particles from two biogenic precursors, alpha-pinene and isoprene. Similar oligomer patterns are found in these two SOA systems, but also in SOA from trimethylbenzene, an anthropogenic SOA precursor. However, different maxima molecular sizes were measured for these three SOA systems. While oligomers in alpha-pinene and isoprene have sizes mostly below 600-700 Da, they grow up to about 1000 Da in trimethylbenzene-SOA. The final molecular size of the oligomers is reached early during the particle aging process, whereas other particle properties related to aging, such as the overall acid concentration or the oligomer concentration, increase continuously over a much longer time scale. This kinetic behavior of the oligomer molecular size growth can be explained by a chain growth kinetic regime. Similar oligomer mass patterns were measured in aqueous extracts of ambient aerosol samples (measured with the same technique). Distinct differences between summer and winter were observed. In summer a few single mass peaks were measured with much higher intensity than in winter, pointing to a possible difference in the formation processes of these compounds in winter and summer.

Isolation and Quantification of Polyamide Cyclic Oligomers in Kitchen Utensils and Their Migration into Various Food Simulants.

Science.gov (United States)

Abe, Yutaka; Mutsuga, Motoh; Ohno, Hiroyuki; Kawamura, Yoko; Akiyama, Hiroshi

2016-01-01

Small amounts of cyclic monomers and oligomers are present in polyamide (PA)-based kitchen utensils. In this study, we isolated eight PA-based cyclic monomers and oligomers from kitchen utensils made from PA6 (a polymer of ε-caprolactam) and PA66 (a polymer of 1,6-diaminohexane and adipic acid). Their structures were identified using high-resolution mass spectrometry and 1H- and 13C-nuclear magnetic resonance spectroscopy, and their residual levels in PA-based kitchen utensils and degree of migration into food simulants were quantified by high-performance liquid chromatography/mass spectrometry using purchased PA6 monomer and isolated PA66 monomers, and isolated PA6 and PA66 oligomers as calibration standards. Their total residual levels among 23 PA-based kitchen utensils made from PA6, PA66, and copolymers of PA6 and PA66 (PA6/66) ranged from 7.8 to 20 mg/g. Using water, 20% ethanol, and olive oil as food simulants, the total migration levels of the PA monomers and oligomers ranged from 0.66 to 100 μg/cm2 under most examined conditions. However, the total migration levels of the PA66 monomer and oligomers from PA66 and PA6/66 kitchen utensils into 20% ethanol at 95°C were very high (1,700 and 2,200 μg/cm2, respectively) due to swelling by high-temperature ethanol.

Isolation and Quantification of Polyamide Cyclic Oligomers in Kitchen Utensils and Their Migration into Various Food Simulants.

Directory of Open Access Journals (Sweden)

Yutaka Abe

Full Text Available Small amounts of cyclic monomers and oligomers are present in polyamide (PA-based kitchen utensils. In this study, we isolated eight PA-based cyclic monomers and oligomers from kitchen utensils made from PA6 (a polymer of ε-caprolactam and PA66 (a polymer of 1,6-diaminohexane and adipic acid. Their structures were identified using high-resolution mass spectrometry and 1H- and 13C-nuclear magnetic resonance spectroscopy, and their residual levels in PA-based kitchen utensils and degree of migration into food simulants were quantified by high-performance liquid chromatography/mass spectrometry using purchased PA6 monomer and isolated PA66 monomers, and isolated PA6 and PA66 oligomers as calibration standards. Their total residual levels among 23 PA-based kitchen utensils made from PA6, PA66, and copolymers of PA6 and PA66 (PA6/66 ranged from 7.8 to 20 mg/g. Using water, 20% ethanol, and olive oil as food simulants, the total migration levels of the PA monomers and oligomers ranged from 0.66 to 100 μg/cm2 under most examined conditions. However, the total migration levels of the PA66 monomer and oligomers from PA66 and PA6/66 kitchen utensils into 20% ethanol at 95°C were very high (1,700 and 2,200 μg/cm2, respectively due to swelling by high-temperature ethanol.

A combined semiempirical-DFT study of oligomers within the finite-chain approximation, evolution from oligomers to polymers.

Science.gov (United States)

Derosa, Pedro A

2009-06-01

A computationally cheap approach combining time-independent density functional theory (TIDFT) and semiempirical methods with an appropriate extrapolation procedure is proposed to accurately estimate geometrical and electronic properties of conjugated polymers using just a small set of oligomers. The highest occupied molecular orbital-lowest unoccupied molecular orbital gap (HLG) obtained at a TIDFT level (B3PW91) for two polymers, trans-polyacetylene--the simplest conjugated polymer, and a much larger poly(2-methoxy-5-(2,9-ethyl-hexyloxy)-1,4-phenylenevinylene (MEH-PPV) polymer converge to virtually the same asymptotic value than the excitation energy obtained with time-dependent DFT (TDDFT) calculations using the same functional. For TIDFT geometries, the HLG is found to converge to a value within the experimentally accepted range for the band gap of these polymers, when an exponential extrapolation is used; however if semiempirical geometries are used, a linear fit of the HLG versus 1/n is found to produce the best results. Geometrical parameters are observed to reach a saturation value in good agreement with experimental information, within the length of oligomers calculated here and no extrapolation was considered necessary. Finally, the performance of three different semiempirical methods (AM1, PM3, and MNDO) and for the TIDFT calculations, the performance of 7 different full electron basis sets (6-311+G**, 6-31+ +G**, 6-311+ +G**, 6-31+G**, 6-31G**, 6-31+G*, and 6-31G) is compared and it is determined that the choice of semiempirical method or the basis set does not significantly affect the results. 2008 Wiley Periodicals, Inc.

Detection of the electronic structure of iron-(iii)-oxo oligomers forming in aqueous solutions.

Science.gov (United States)

Seidel, Robert; Kraffert, Katrin; Kabelitz, Anke; Pohl, Marvin N; Kraehnert, Ralph; Emmerling, Franziska; Winter, Bernd

2017-12-13

The nature of the small iron-oxo oligomers in iron-(iii) aqueous solutions has a determining effect on the chemical processes that govern the formation of nanoparticles in aqueous phase. Here we report on a liquid-jet photoelectron-spectroscopy experiment for the investigation of the electronic structure of the occurring iron-oxo oligomers in FeCl 3 aqueous solutions. The only iron species in the as-prepared 0.75 M solution are Fe 3+ monomers. Addition of NaOH initiates Fe 3+ hydrolysis which is followed by the formation of iron-oxo oligomers. At small enough NaOH concentrations, corresponding to approximately [OH]/[Fe] = 0.2-0.25 ratio, the iron oligomers can be stabilized for several hours without engaging in further aggregation. Here, we apply a combination of non-resonant as well as iron 2p and oxygen 1s resonant photoelectron spectroscopy from a liquid microjet to detect the electronic structure of the occurring species. Specifically, the oxygen 1s partial electron yield X-ray absorption (PEY-XA) spectra are found to exhibit a peak well below the onset of liquid water and OH - (aq) absorption. The iron 2p absorption gives rise to signal centered between the main absorption bands typical for aqueous Fe 3+ . Absorption bands in both PEY-XA spectra are found to correlate with an enhanced photoelectron peak near 20 eV binding energy, which demonstrates the sensitivity of resonant photoelectron (RPE) spectroscopy to mixing between iron and ligand orbitals. These various signals from the iron-oxo oligomers exhibit maximum intensity at [OH]/[Fe] = 0.25 ratio. For the same ratio, we observe changes in the pH as well as in complementary Raman spectra, which can be assigned to the transition from monomeric to oligomeric species. At approximately [OH]/[Fe] = 0.3 we begin to observe particles larger than 1 nm in radius, detected by small-angle X-ray scattering.

SAXS and stability studies of iron-induced oligomers of bacterial frataxin CyaY.

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Mostafa Fekry

Full Text Available Frataxin is a highly conserved protein found in both prokaryotes and eukaryotes. It is involved in several central functions in cells, which include iron delivery to biochemical processes, such as heme synthesis, assembly of iron-sulfur clusters (ISC, storage of surplus iron in conditions of iron overload, and repair of ISC in aconitase. Frataxin from different organisms has been shown to undergo iron-dependent oligomerization. At least two different classes of oligomers, with different modes of oligomer packing and stabilization, have been identified. Here, we continue our efforts to explore the factors that control the oligomerization of frataxin from different organisms, and focus on E. coli frataxin CyaY. Using small-angle X-ray scattering (SAXS, we show that higher iron-to-protein ratios lead to larger oligomeric species, and that oligomerization proceeds in a linear fashion as a results of iron oxidation. Native mass spectrometry and online size-exclusion chromatography combined with SAXS show that a dimer is the most common form of CyaY in the presence of iron at atmospheric conditions. Modeling of the dimer using the SAXS data confirms the earlier proposed head-to-tail packing arrangement of monomers. This packing mode brings several conserved acidic residues into close proximity to each other, creating an environment for metal ion binding and possibly even mineralization. Together with negative-stain electron microscopy, the experiments also show that trimers, tetramers, pentamers, and presumably higher-order oligomers may exist in solution. Nano-differential scanning fluorimetry shows that the oligomers have limited stability and may easily dissociate at elevated temperatures. The factors affecting the possible oligomerization mode are discussed.

Chitin-hyaluronan nanoparticles: a multifunctional carrier to deliver anti-aging active ingredients through the skin

Czech Academy of Sciences Publication Activity Database

Morganti, P.; Palombo, M.; Tishchenko, Galina; Yudin, V. E.; Guarneri, F.; Cardillo, M.; Del Ciotto, P.; Carezzi, F.; Morganti, G.; Fabrizi, G.

2014-01-01

Roč. 1, č. 3 (2014), s. 140-158 ISSN 2079-9284 EU Projects: European Commission(XE) 315233 - N-CHITOPACK Institutional support: RVO:61389013 Keywords : chitin nanofibrils * skin aging emulsions * innovative beauty masks Subject RIV: CD - Macromolecular Chemistry

MICROBIAL FERMENTATION OF ABUNDANT BIOPOLYMERS: CELLULOSE AND CHITIN

Energy Technology Data Exchange (ETDEWEB)

Leschine, Susan

2009-10-31

Our research has dealt with seven major areas of investigation: i) characterization of cellulolytic members of microbial consortia, with special attention recently given to Clostridium phytofermentans, a bacterium that decomposes cellulose and produces uncommonly large amounts of ethanol, ii) investigations of the chitinase system of Cellulomonas uda; including the purification and characterization of ChiA, the major component of this enzyme system, iii) molecular cloning, sequence and structural analysis of the gene that encodes ChiA in C. uda, iv) biofilm formation by C. uda on nutritive surfaces, v) investigations of the effects of humic substances on cellulose degradation by anaerobic cellulolytic microbes, vi) studies of nitrogen metabolism in cellulolytic anaerobes, and vii) understanding the molecular architecture of the multicomplex cellulase-xylanase system of Clostridium papyrosolvens. Also, progress toward completing the research of more recent projects is briefly summarized. Major accomplishments include: 1. Characterization of Clostridium phytofermentans, a cellulose-fermenting, ethanol-producing bacterium from forest soil. The characterization of a new cellulolytic species isolated from a cellulose-decomposing microbial consortium from forest soil was completed. This bacterium is remarkable for the high concentrations of ethanol produced during cellulose fermentation, typically more than twice the concentration produced by other species of cellulolytic clostridia. 2. Examination of the use of chitin as a source of carbon and nitrogen by cellulolytic microbes. We discovered that many cellulolytic anaerobes and facultative aerobes are able to use chitin as a source of both carbon and nitrogen. This major discovery expands our understanding of the biology of cellulose-fermenting bacteria and may lead to new applications for these microbes. 3. Comparative studies of the cellulase and chitinase systems of Cellulomonas uda. Results of these studies indicate

ADSORPTION TO CHITIN – A VIABLE AND ORGANISM-PROTECTING METHOD FOR BIOMONITORING METALS PRESENT IN DIFFERENT ENVIRONMENTAL COMPARTMENTS GETTING CONTACTED WITH ARTHROPODS

Directory of Open Access Journals (Sweden)

S. Fränzle

2015-04-01

Full Text Available Among the various biopolymers which cover outer interfaces of organisms, chitin is the most abundant: each year several billion metric tons (possibly even much more are produced by arthropods and processed in soil and litter, wet sediment  (especially in moist soils while otherwise chitin samples can persist virtually unchanged for geological periods of time. Moreover, arthropods, among which Coleoptera are represented by some 400,000 species alone, inhabit almost all ecosystems, way beyond the ecological range of, say, mosses. Given that adsorption of metalliferous analytes (ions, volatile compounds, complexes of whatever net charge to chitin obtained from arthropods can be demonstrated (and it partly was already, it is feasible to obtain data on environmental element contents in all water, soil and gas phase (atmosphere by dissolving, analyzing outermost (part of exocuticle chitin layers. Data on relative uptake contributions/environmental burdens of either compartment can be obtained by both interspecies-comparisons and sampling of different parts of some larger arthropod (abdomen-, outer- and inner wing surfaces of sizable beetles. As just a very thin chitin layer (< 2 µm is ablated from the animal´s outer surface by dissolution using little toxic components, sampling will not cause harm to them, enabling a repeated sampling of the same specimen (e.g. for taking t = 0 starting values and b use of rare or/and protected species. Applications are with both biomonitoring and a better understanding of metal ion transport in ecosystems, e.g. concerning interfacial Mn+ binding to dying zooplankton then sinking below the chemokline of euxinic water bodies. An indirect metal levels monitoring of woody plants and underneath soils also appears feasible.

Length dependence of rectification in organic co-oligomer spin rectifiers

International Nuclear Information System (INIS)

Hu Gui-Chao; Zhang Zhao; Li Ying; Ren Jun-Feng; Wang Chuan-Kui

2016-01-01

The rectification ratio of organic magnetic co-oligomer diodes is investigated theoretically by changing the molecular length. The results reveal two distinct length dependences of the rectification ratio: for a short molecular diode, the charge-current rectification changes little with the increase of molecular length, while the spin-current rectification is weakened sharply by the length; for a long molecular diode, both the charge-current and spin-current rectification ratios increase quickly with the length. The two kinds of dependence switch at a specific length accompanied with an inversion of the rectifying direction. The molecular ortibals and spin-resolved transmission analysis indicate that the dominant mechanism of rectification suffers a change at this specific length, that is, from asymmetric shift of molecular eigenlevels to asymmetric spatial localization of wave functions upon the reversal of bias. This work demonstrates a feasible way to control the rectification in organic co-oligomer spin diodes by adjusting the molecular length. (paper)

The fungicidal properties of the carbon materials obtained from chitin and chitosan promoted by copper salts

Energy Technology Data Exchange (ETDEWEB)

Ilnicka, Anna, E-mail: annakucinska@o2.pl; Walczyk, Mariusz; Lukaszewicz, Jerzy P.

2015-07-01

Renewable raw materials chitin and chitosan (N-deacetylated derivative of chitin) were subjected to action of different copper modifiers that were carbonized in the atmosphere of the N{sub 2} inert gas. As a result of the novel manufacturing procedure, a series of carbon materials was obtained with developed surface area and containing copper derivatives of differentiated form, size, and dispersion. The copper modifier and manufacturing procedure (concentration, carbonization temperature) influence the physical–chemical and fungicide properties of the carbons. The received carbons were chemically characterized using several methods like low-temperature adsorption of nitrogen, X-ray diffraction analysis, scanning electron microscopy, cyclic voltammetry, elemental analysis, and bioassay. Besides chemical testing, some biological tests were performed and let to select carbons with the highest fungicidal activity. Such carbons were characteristic of the specific form of copper derivatives occurring in them, i.e., nanocrystallites of Cu{sup 0} and/or Cu{sub 2}O of high dispersion on the surface of carbon. The carbons may find an application as effective contact fungistatic agents in cosmetology, medicine, food industry, etc. - Highlights: • The novel manufacturing procedure yields new functional carbon materials. • Two biopolymers chitin and chitosan can undergo copper(II) ion modification. • The Cu-modified carbon materials exhibit high fungicidal activity. • The fungicidal activity results from the presence of Cu{sup 0} and Cu{sub 2}O nano-crystallites.

Tumor delivery of antisense oligomer using trastuzumab within a streptavidin nanoparticle

Energy Technology Data Exchange (ETDEWEB)

Wang, Yi [University of Massachusetts Medical School, Division of Nuclear Medicine, Department of Radiology, Worcester, MA (United States); Yale University, Yale PET Center, Department of Diagnostic Radiology, New Haven, CT (United States); Liu, Xinrong; Chen, Ling; Cheng, Dengfeng; Rusckowski, Mary [University of Massachusetts Medical School, Division of Nuclear Medicine, Department of Radiology, Worcester, MA (United States); Hnatowich, Donald J. [University of Massachusetts Medical School, Division of Nuclear Medicine, Department of Radiology, Worcester, MA (United States); Umass Medical School, Department of Radiology, Worcester, MA (United States)

2009-12-15

Trastuzumab (Herceptin trademark) is often internalized following binding to Her2+ tumor cells. The objective of this study was to investigate whether trastuzumab can be used as a specific carrier to deliver antisense oligomers into Her2+ tumor cells both in vitro and in vivo. A biotinylated MORF oligomer antisense to RhoC mRNA and its biotinylated sense control were labeled with either lissamine for fluorescence detection or {sup 99m}Tc for radioactivity detection and were linked to biotinylated trastuzumab via streptavidin. The nanoparticles were studied in SUM190 (RhoC+, Her2+) study and SUM149 (RhoC+, Her2-) control cells in culture and as xenografts in mice. As evidence of unimpaired Her2+ binding of trastuzumab within the nanoparticle, accumulations were clearly higher in SUM190 compared to SUM149 cells and, by whole-body imaging, targeting of SUM190 tumor was similar to that expected for a radiolabeled trastuzumab. As evidence of internalization, fluorescence microscopy images of cells grown in culture and obtained from xenografts showed uniform cytoplasm distribution of the lissamine-MORF. An invasion assay showed decreased RhoC expression in SUM190 cells when incubated with the antisense MORF nanoparticles at only 100 nM. Both in cell culture and in animals, the nanoparticle with trastuzumab as specific carrier greatly improved tumor delivery of the antisense oligomer against RhoC mRNA into tumor cells overexpressing Her2 and may be of general utility. (orig.)

Chemical and Biological Significance of Oenothein B and Related Ellagitannin Oligomers with Macrocyclic Structure

Directory of Open Access Journals (Sweden)

Takashi Yoshida

2018-03-01

Full Text Available In 1990, Okuda et al. reported the first isolation and characterization of oenothein B, a unique ellagitannin dimer with a macrocyclic structure, from the Oenothera erythrosepala leaves. Since then, a variety of macrocyclic analogs, including trimeric–heptameric oligomers have been isolated from various medicinal plants belonging to Onagraceae, Lythraceae, and Myrtaceae. Among notable in vitro and in vivo biological activities reported for oenothein B are antioxidant, anti-inflammatory, enzyme inhibitory, antitumor, antimicrobial, and immunomodulatory activities. Oenothein B and related oligomers, and/or plant extracts containing them have thus attracted increasing interest as promising targets for the development of chemopreventive agents of life-related diseases associated with oxygen stress in human health. In order to better understand the significance of this type of ellagitannin in medicinal plants, this review summarizes (1 the structural characteristics of oenothein B and related dimers; (2 the oxidative metabolites of oenothein B up to heptameric oligomers; (3 the distribution of oenotheins and other macrocyclic analogs in the plant kingdom; and (4 the pharmacological activities hitherto documented for oenothein B, including those recently found by our laboratory.

Ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction and derivatization of sulfonamides in river water, honey, milk, and animal plasma.

Science.gov (United States)

Xu, Xu; Su, Rui; Zhao, Xin; Liu, Zhuang; Zhang, Yupu; Li, Dan; Li, Xueyuan; Zhang, Hanqi; Wang, Ziming

2011-11-30

The ionic liquid-based microwave-assisted dispersive liquid-liquid microextraction (IL-based MADLLME) and derivatization was applied for the pretreatment of six sulfonamides (SAs) prior to the determination by high-performance liquid chromatography (HPLC). By adding methanol (disperser), fluorescamine solution (derivatization reagent) and ionic liquid (extraction solvent) into sample, extraction, derivatization, and preconcentration were continuously performed. Several experimental parameters, such as the type and volume of extraction solvent, the type and volume of disperser, amount of derivatization reagent, microwave power, microwave irradiation time, pH of sample solution, and ionic strength were investigated and optimized. When the microwave power was 240 W, the analytes could be derivatized and extracted simultaneously within 90 s. The proposed method was applied to the analysis of river water, honey, milk, and pig plasma samples, and the recoveries of analytes obtained were in the range of 95.0-110.8, 95.4-106.3, 95.0-108.3, and 95.7-107.7, respectively. The relative standard deviations varied between 1.5% and 7.3% (n=5). The results showed that the proposed method was a rapid, convenient and feasible method for the determination of SAs in liquid samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Co-existence of two different α-synuclein oligomers with different core structures determined by hydrogen/deuterium exchange mass spectrometry

DEFF Research Database (Denmark)

Paslawski, Wojciech; Mysling, Simon; Thomsen, Karen

2014-01-01

Neurodegenerative disorders are characterized by the formation of protein oligomers and amyloid fibrils, which in the case of Parkinson's disease involves the protein α-synuclein (αSN). Cytotoxicity is mainly associated with the oligomeric species, but we still know little about their assembly...... are protected from exchange with D2 O until they dissociate into monomeric αSN by EX1 exchange kinetics. Fewer residues are protected against exchange in oligomer type II, but this type does not revert to αSN monomers. Both oligomers are protected in the core sequence Y39-A89. Based on incubation studies...

Development and evaluation of 5-fluorouracil loaded chitin nanogels for treatment of skin cancer.

Science.gov (United States)

Sabitha, M; Sanoj Rejinold, N; Nair, Amrita; Lakshmanan, Vinoth-Kumar; Nair, Shantikumar V; Jayakumar, R

2013-01-02

This study focuses on development and evaluation of 5-fluorouracil (5-FU) loaded chitin nanogels (FCNGs). It formed good, stable aqueous dispersion with spherical particles in 120-140 nm size range and showed pH responsive swelling and drug release. The FCNGs showed toxicity on melanoma (A375) in a concentration range of 0.4-2.0mg/mL, but less toxicity toward human dermal fibroblast (HDF) cells by MTT assay. Confocal analysis revealed uptake of FCNGs by both cells. From skin permeation experiments, FCNGs showed almost same steady state flux as that of control 5-FU but the retention in the deeper layers of skin was found to be 4-5 times more from FCNGs. Histopathological evaluation revealed loosening of the horny layer of epidermis by interaction of cationically charged chitin, with no observed signs of inflammation and so FCNGs can be a good option for treatment of skin cancers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Regeneration of cello-oligomers via selective depolymerization of cellulose fibers derived from printed paper wastes.

Science.gov (United States)

Voon, Lee Ken; Pang, Suh Cem; Chin, Suk Fun

2016-05-20

Cellulose extracted from printed paper wastes were selectively depolymerized under controlled conditions into cello-oligomers of controllable chain lengths via dissolution in an ionic liquid, 1-allyl-3-methylimidazolium chloride (AMIMCl), and in the presence of an acid catalyst, Amberlyst 15DRY. The depolymerization process was optimized against reaction temperature, concentration of acid catalyst, and reaction time. Despite rapid initial depolymerization process, the rate of cellulose depolymerization slowed down gradually upon prolonged reaction time, with 75.0 wt% yield of regenerated cello-oligomers (mean Viscosimetric Degree of Polymerization value of 81) obtained after 40 min. The depolymerization of cellulose fibers at 80 °C appeared to proceed via a second-order kinetic reaction with respect to the catalyst concentration of 0.23 mmol H3O(+). As such, the cellulose depolymerization process could afford some degree of control on the degree of polymerization or chain lengths of cello-oligomers formed. Copyright © 2016 Elsevier Ltd. All rights reserved.

Organization of the resting TCR in nanoscale oligomers.

Science.gov (United States)

Schamel, Wolfgang W A; Alarcón, Balbino

2013-01-01

Despite the low affinity of the T-cell antigen receptor (TCR) for its peptide/major histocompatibility complex (pMHC) ligand, T cells are very sensitive to their antigens. This paradox can be resolved if we consider that the TCR may be organized into pre-existing oligomers or nanoclusters. Such structures could improve antigen recognition by increasing the functional affinity (avidity) of the TCR-pMHC interaction and by allowing cooperativity between individual TCRs. Up to approximately 20 TCRs become tightly apposed in these nanoclusters, often in a linear manner, and such structures could reflect a relatively generalized phenomenon: the non-random concentration of membrane receptors in specific areas of the plasma membrane known as protein islands. The association of TCRs into nanoclusters can explain the enhanced kinetics of the pMHC-TCR interaction in two dimensional versus three dimensional systems, but also their existence calls for a revision of the TCR triggering models based on pMHC-induced TCR clustering. Interestingly, the B-cell receptor and the FcεRI have also been shown to form nanoclusters, suggesting that the formation of pre-existing receptor oligomers could be widely used in the immune system. © 2012 John Wiley & Sons A/S. Published by Blackwell Publishing Ltd.

Determination of NH_2 concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

International Nuclear Information System (INIS)

Manakhov, Anton; Čechal, Jan; Michlíček, Miroslav; Shtansky, Dmitry V.

2017-01-01

Highlights: • A new method for primary amines derivatization is proposed and validated. • The chemical structure of APTES layer is studied. • The derivatization by 5-iodo 2-furaldehyde allowed to avoid side reactions in contrast to 4-trifluoromethyl benzaldehyde derivatization. - Abstract: The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH_2 groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH_2/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH_2 fraction ∼8.5%. This value is closely matching the NH_2/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH_2/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA derivatization is probably

Single-molecule studies of oligomer extraction and uptake of dyes in poly(dimethylsiloxane) films.

Science.gov (United States)

Lange, Jeffrey J; Collinson, Maryanne M; Culbertson, Christopher T; Higgins, Daniel A

2009-12-15

Single-molecule microscopic methods were used to probe the uptake, mobility, and entrapment of dye molecules in cured poly(dimethylsiloxane) (PDMS) films as a function of oligomer extraction. The results are relevant to the use of PDMS in microfluidic separations, pervaporation, solid-phase microextraction, and nanofiltration. PDMS films were prepared by spin-casting dilute solutions of Sylgard 184 onto glass coverslips, yielding approximately 1.4 microm thick films after curing. Residual oligomers were subsequently extracted from the films by "spin extraction". In this procedure, 200 microL aliquots of isopropyl alcohol were repeatedly dropped onto the film surface and spun off at 2000 rpm. Samples extracted 5, 10, 20, and 40 times were investigated. Dye molecules were loaded into these films by spin-casting nanomolar dye solutions onto the films. Both neutral perylene diimide (N,N'-bis(butoxypropyl)perylene-3,4,9,10-tetracarboxylic diimide) and cationic rhodamine 6G (R6G) dyes were employed. The films were imaged by confocal fluorescence microscopy. The images obtained depict nonzero populations of fixed and mobile molecules in all films. Cross-correlation methods were used to quantitatively determine the population of fixed molecules in a given region, while a Bayesian burst analysis was used to obtain the total population of molecules. The results show that the total amount of dye loaded increases with increased oligomer extraction, while the relative populations of fixed and mobile molecules decrease and increase, respectively. Bulk R6G data also show greater dye loading with increased oligomer extraction.

A Derivatization and Validation Strategy for Determining the Spatial Localization of Endogenous Amine Metabolites in Tissues using MALDI Imaging Mass Spectrometry

Science.gov (United States)

Manier, M. Lisa; Spraggins, Jeffrey M.; Reyzer, Michelle L.; Norris, Jeremy L.; Caprioli, Richard M.

2014-01-01

Imaging mass spectrometry (IMS) studies increasingly focus on endogenous small molecular weight metabolites and consequently bring special analytical challenges. Since analytical tissue blanks do not exist for endogenous metabolites, careful consideration must be given to confirm molecular identity. Here we present approaches for the improvement in detection of endogenous amine metabolites such as amino acids and neurotransmitters in tissues through chemical derivatization and matrix-assisted laser desorption/ionization (MALDI) IMS. Chemical derivatization with 4-hydroxy-3-methoxycinnamaldehyde (CA) was used to improve sensitivity and specificity. CA was applied to the tissue via MALDI sample targets precoated with a mixture of derivatization reagent and ferulic acid (FA) as a MALDI matrix. Spatial distributions of chemically derivatized endogenous metabolites in tissue were determined by high-mass resolution and MSn imaging mass spectrometry. We highlight an analytical strategy for metabolite validation whereby tissue extracts are analyzed by high-performance liquid chromatography (HPLC)-MS/MS to unambiguously identify metabolites and distinguish them from isobaric compounds. PMID:25044893

Liquid chromatography coupled to on-line post column derivatization for the determination of organic compounds: A review on instrumentation and chemistries

International Nuclear Information System (INIS)

Zacharis, Constantinos K.; Tzanavaras, Paraskevas D.

2013-01-01

Graphical abstract: -- Highlights: •Review on liquid chromatography coupled to post-column derivatization. •Overview of instrumentation for post-column derivatization. •Post-column chemistries for analysis of organic compounds. -- Abstract: Analytical derivatization either in pre or post column modes is one of the most widely used sample pretreatment techniques coupled to liquid chromatography. In the present review article we selected to discuss the post column derivatization mode for the analysis of organic compounds. The first part of the review focuses to the instrumentation of post-column setups including not only fundamental components such as pumps and reactors but also less common parts such as static mixers and back-pressure regulators; the second part of the article discusses the most popular “chemistries” that are involved in post column applications, including reagent-less approaches and new sensing platforms such as the popular gold nanoparticles. Some representative recent applications are also presented as tables

Liquid chromatography coupled to on-line post column derivatization for the determination of organic compounds: A review on instrumentation and chemistries

Energy Technology Data Exchange (ETDEWEB)

Zacharis, Constantinos K., E-mail: zacharis@chem.auth.gr [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotelian University of Thessaloniki, GR-54124 Thessaloniki (Greece); Department of Food Technology, School of Food Technology and Nutrition, Alexander Technological Educational Institute (ATEI) of Thessaloniki, 57400 Thessaloniki (Greece); Tzanavaras, Paraskevas D., E-mail: ptzanava@chem.auth.gr [Laboratory of Analytical Chemistry, Department of Chemistry, Aristotelian University of Thessaloniki, GR-54124 Thessaloniki (Greece)

2013-10-10

Graphical abstract: -- Highlights: •Review on liquid chromatography coupled to post-column derivatization. •Overview of instrumentation for post-column derivatization. •Post-column chemistries for analysis of organic compounds. -- Abstract: Analytical derivatization either in pre or post column modes is one of the most widely used sample pretreatment techniques coupled to liquid chromatography. In the present review article we selected to discuss the post column derivatization mode for the analysis of organic compounds. The first part of the review focuses to the instrumentation of post-column setups including not only fundamental components such as pumps and reactors but also less common parts such as static mixers and back-pressure regulators; the second part of the article discusses the most popular “chemistries” that are involved in post column applications, including reagent-less approaches and new sensing platforms such as the popular gold nanoparticles. Some representative recent applications are also presented as tables.

In situ oxidation state profiling of nickel hexacyanoferrate derivatized electrodes using line-imaging Raman spectroscopy and multivariate calibration

International Nuclear Information System (INIS)

Haight, S.M.; Schwartz, D.T.

1999-01-01

Metal hexacyanoferrate compounds show promise as electrochemically switchable ion exchange materials for use in the cleanup of radioactive wastes such as those found in storage basins and underground tanks at the Department of Energy's Hanford Nuclear Reservation. Reported is the use of line-imaging Raman spectroscopy for the in situ determination of oxidation state profiles in nickel hexacyanoferrate derivatized electrodes under potential control in an electrochemical cell. Line-imaging Raman spectroscopy is used to collect 256 contiguous Raman spectra every ∼5 microm from thin films (ca. 80 nm) formed by electrochemical derivatization of nickel electrodes. The cyanide stretching region of the Raman spectrum of the film is shown to be sensitive to iron oxidation state and is modeled by both univariate and multivariate correlations. Although both correlations fit the calibration set well, the multivariate (principle component regression or PCR) model's predictions of oxidation state are less sensitive to noise in the spectrum, yielding a much smoother oxidation state profile than the univariate model. Oxidation state profiles with spatial resolution of approximately 5 microm are shown for a nickel hexacyanoferrate derivatized electrode in reduced, intermediate, and oxidized states. In situ oxidation state profiles indicate that the 647.1 nm laser illumination photo-oxidizes the derivatized electrodes. This observation is confirmed using photoelectrochemical methods

Programmable Oligomers Targeting 5′-GGGG-3′ in the Minor Groove of DNA and NF-κB Binding Inhibition

Science.gov (United States)

Chenoweth, David M.; Poposki, Julie A.; Marques, Michael A.; Dervan, Peter B.

2009-01-01

A series of hairpin oligomers containing benzimidazole (Bi) and imidazopyridine (Ip) rings were synthesized and screened to target 5′-WGGGGW-3′, a core sequence in the DNA binding site of NF-κB, a prolific transcription factor important in biology and disease. Five Bi and Ip containing oligomers bound to the 5′-WGGGGW-3′ site with high affinity. One of the oligomers (Im-Im-Im-Im-γ-PyBi-PyBi-β-Dp) was able to inhibit DNA binding by the transcription factor NF-κB. PMID:17095230

Novel chitin/chitosan-glucan wound dressing: Isolation, characterization, antibacterial activity and wound healing properties

Czech Academy of Sciences Publication Activity Database

Abdel-Mohsen, A. M.; Jancar, J.; Massoud, D.; Fohlerová, Z.; Elhadidy, Hassan; Spotz, Z.; Hebeish, A.

2016-01-01

Roč. 510, č. 1 (2016), s. 86-99 ISSN 0378-5173 R&D Projects: GA MŠk(CZ) LQ1601 Institutional support: RVO:68081723 Keywords : Chitin/chitosan-glucan complex * Nonwoven mat * Surgical wound healing Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.649, year: 2016

Structural fingerprints and their evolution during oligomeric vs. oligomer-free amyloid fibril growth.

Science.gov (United States)

Foley, Joseph; Hill, Shannon E; Miti, Tatiana; Mulaj, Mentor; Ciesla, Marissa; Robeel, Rhonda; Persichilli, Christopher; Raynes, Rachel; Westerheide, Sandy; Muschol, Martin

2013-09-28

Deposits of fibrils formed by disease-specific proteins are the molecular hallmark of such diverse human disorders as Alzheimer's disease, type II diabetes, or rheumatoid arthritis. Amyloid fibril formation by structurally and functionally unrelated proteins exhibits many generic characteristics, most prominently the cross β-sheet structure of their mature fibrils. At the same time, amyloid formation tends to proceed along one of two separate assembly pathways yielding either stiff monomeric filaments or globular oligomers and curvilinear protofibrils. Given the focus on oligomers as major toxic species, the very existence of an oligomer-free assembly pathway is significant. Little is known, though, about the structure of the various intermediates emerging along different pathways and whether the pathways converge towards a common or distinct fibril structures. Using infrared spectroscopy we probed the structural evolution of intermediates and late-stage fibrils formed during in vitro lysozyme amyloid assembly along an oligomeric and oligomer-free pathway. Infrared spectroscopy confirmed that both pathways produced amyloid-specific β-sheet peaks, but at pathway-specific wavenumbers. We further found that the amyloid-specific dye thioflavin T responded to all intermediates along either pathway. The relative amplitudes of thioflavin T fluorescence responses displayed pathway-specific differences and could be utilized for monitoring the structural evolution of intermediates. Pathway-specific structural features obtained from infrared spectroscopy and Thioflavin T responses were identical for fibrils grown at highly acidic or at physiological pH values and showed no discernible effects of protein hydrolysis. Our results suggest that late-stage fibrils formed along either pathway are amyloidogenic in nature, but have distinguishable structural fingerprints. These pathway-specific fingerprints emerge during the earliest aggregation events and persist throughout the

Structural fingerprints and their evolution during oligomeric vs. oligomer-free amyloid fibril growth

Science.gov (United States)

Foley, Joseph; Hill, Shannon E.; Miti, Tatiana; Mulaj, Mentor; Ciesla, Marissa; Robeel, Rhonda; Persichilli, Christopher; Raynes, Rachel; Westerheide, Sandy; Muschol, Martin

2013-09-01

Deposits of fibrils formed by disease-specific proteins are the molecular hallmark of such diverse human disorders as Alzheimer's disease, type II diabetes, or rheumatoid arthritis. Amyloid fibril formation by structurally and functionally unrelated proteins exhibits many generic characteristics, most prominently the cross β-sheet structure of their mature fibrils. At the same time, amyloid formation tends to proceed along one of two separate assembly pathways yielding either stiff monomeric filaments or globular oligomers and curvilinear protofibrils. Given the focus on oligomers as major toxic species, the very existence of an oligomer-free assembly pathway is significant. Little is known, though, about the structure of the various intermediates emerging along different pathways and whether the pathways converge towards a common or distinct fibril structures. Using infrared spectroscopy we probed the structural evolution of intermediates and late-stage fibrils formed during in vitro lysozyme amyloid assembly along an oligomeric and oligomer-free pathway. Infrared spectroscopy confirmed that both pathways produced amyloid-specific β-sheet peaks, but at pathway-specific wavenumbers. We further found that the amyloid-specific dye thioflavin T responded to all intermediates along either pathway. The relative amplitudes of thioflavin T fluorescence responses displayed pathway-specific differences and could be utilized for monitoring the structural evolution of intermediates. Pathway-specific structural features obtained from infrared spectroscopy and Thioflavin T responses were identical for fibrils grown at highly acidic or at physiological pH values and showed no discernible effects of protein hydrolysis. Our results suggest that late-stage fibrils formed along either pathway are amyloidogenic in nature, but have distinguishable structural fingerprints. These pathway-specific fingerprints emerge during the earliest aggregation events and persist throughout the

Exposure Assessment of Acetamide in Milk, Beef, and Coffee Using Xanthydrol Derivatization and Gas Chromatography/Mass Spectrometry.

Science.gov (United States)

Vismeh, Ramin; Haddad, Diane; Moore, Janette; Nielson, Chandra; Bals, Bryan; Campbell, Tim; Julian, Allen; Teymouri, Farzaneh; Jones, A Daniel; Bringi, Venkataraman

2018-01-10

Acetamide has been classified as a possible human carcinogen, but uncertainties exist about its levels in foods. This report presents evidence that thermal decomposition of N-acetylated sugars and amino acids in heated gas chromatograph injectors contributes to artifactual acetamide in milk and beef. An alternative gas chromatography/mass spectrometry protocol based on derivatization of acetamide with 9-xanthydrol was optimized and shown to be free of artifactual acetamide formation. The protocol was validated using a surrogate analyte approach based on d 3 -acetamide and applied to analyze 23 pasteurized whole milk, 44 raw sirloin beef, and raw milk samples from 14 different cows, and yielded levels about 10-fold lower than those obtained by direct injection without derivatization. The xanthydrol derivatization procedure detected acetamide in every food sample tested at 390 ± 60 ppb in milk, 400 ± 80 ppb in beef, and 39 000 ± 9000 ppb in roasted coffee beans.

Purification of a novel chitin-binding lectin with antimicrobial and antibiofilm activities from a bangladeshi cultivar of potato (Solanum tuberosum).

Science.gov (United States)

Hasan, Imtiaj; Ozeki, Yasuhiro; Kabir, Syed Rashel

2014-04-01

A new chitin-binding lectin was purified from a Bangladeshi cultivar 'Deshi' of potato (Solanum tuberosum L.) through anion-exchange and affinity chromatographies using a chitin column. Sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) showed the molecular mass of the lectin as 20,000 Daltons. This molecular mass was almost half of the molecular masses of chitin-binding lectins derived from other potatoes. The lectin showed both bactericidal and growth-inhibiting activities against Gram-positive (Listeria monocytogenes) and Gram-negative (Escherichia coli, Salmonella enteritidis and Shigella boydii) pathogenic bacteria. It also showed antifungal activity against Rhizopus spp., Penicillium spp. and Aspergillus niger. Biofilm produced by the bacterium Pseudomonas aeruginosa was dose-dependently reduced by 5-20% in 24 h after administration of the lectin, which was attributed to the glycan-binding property of the lectin having affinity to GlcNAc polymers. It was the first observation that any potato lectin prevented biofilm formation by P. aeruginosa and, therefore, could have possible applications in clinical microbiology and biomedical science.

The bifunctional plant receptor, OsCERK1, regulates both chitin-triggered immunity and arbuscular mycorrhizal symbiosis in rice.

Science.gov (United States)

Miyata, Kana; Kozaki, Toshinori; Kouzai, Yusuke; Ozawa, Kenjirou; Ishii, Kazuo; Asamizu, Erika; Okabe, Yoshihiro; Umehara, Yosuke; Miyamoto, Ayano; Kobae, Yoshihiro; Akiyama, Kohki; Kaku, Hanae; Nishizawa, Yoko; Shibuya, Naoto; Nakagawa, Tomomi

2014-11-01

Plants are constantly exposed to threats from pathogenic microbes and thus developed an innate immune system to protect themselves. On the other hand, many plants also have the ability to establish endosymbiosis with beneficial microbes such as arbuscular mycorrhizal (AM) fungi or rhizobial bacteria, which improves the growth of host plants. How plants evolved these systems managing such opposite plant-microbe interactions is unclear. We show here that knockout (KO) mutants of OsCERK1, a rice receptor kinase essential for chitin signaling, were impaired not only for chitin-triggered defense responses but also for AM symbiosis, indicating the bifunctionality of OsCERK1 in defense and symbiosis. On the other hand, a KO mutant of OsCEBiP, which forms a receptor complex with OsCERK1 and is essential for chitin-triggered immunity, established mycorrhizal symbiosis normally. Therefore, OsCERK1 but not chitin-triggered immunity is required for AM symbiosis. Furthermore, experiments with chimeric receptors showed that the kinase domains of OsCERK1 and homologs from non-leguminous, mycorrhizal plants could trigger nodulation signaling in legume-rhizobium interactions as the kinase domain of Nod factor receptor1 (NFR1), which is essential for triggering the nodulation program in leguminous plants, did. Because leguminous plants are believed to have developed the rhizobial symbiosis on the basis of AM symbiosis, our results suggest that the symbiotic function of ancestral CERK1 in AM symbiosis enabled the molecular evolution to leguminous NFR1 and resulted in the establishment of legume-rhizobia symbiosis. These results also suggest that OsCERK1 and homologs serve as a molecular switch that activates defense or symbiotic responses depending on the infecting microbes. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

"Nail" and "comb" effects of cholesterol modified NIPAm oligomers on cancer targeting liposomes

KAUST Repository

Li, Wengang; Deng, Lin; Moosa, Basem; Wang, Guangchao; Mashat, Afnan; Khashab, Niveen M.

2014-01-01

Thermosensitive liposomes are a promising approach to controlled release and reduced drug cytotoxicity. Low molecular weight N-isopropylacrylamide (NIPAm) oligomers (NOs) with different architectures (main chain NOs (MCNOs) and side chain NOs (SCNOs)) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and radical polymerization and then separately used to prepare thermosensitive liposomes. A more controlled and enhanced release was observed for both NO liposomes compared to pristine ones. Two release mechanisms depending on the oligomer architecture, namely "nail" for MCNOs and "comb" for SCNOs, are proposed. In addition to thermosensitivity, the cancer targeting property of NO liposomes was achieved by further biotinylation of the delivery system. © The Royal Society of Chemistry.

[Analysis of thickening polysaccharides by the improved diethyldithioacetal derivatization method].

Science.gov (United States)

Akiyama, Takumi; Yamazaki, Takeshi; Tanamoto, Kenichi

2011-01-01

The identification test for thickening polysaccharides containing neutral saccharides and uronic acids was investigated by GC analysis of constituent monosaccharides. The reported method, in which monosaccharides were converted to diethyldithioacetal derivatives with ethanethiol followed by trimethylsilylation, was improved in terms of operability and reproducibility of GC/MS analysis. The suitability of the improved diethyldithioacetal derivatization method was determined for seven thickening polysaccharides, i.e., carob bean gum, guar gum, karaya gum, gum arabic, gum ghatti, tragacanth gum and peach gum. The samples were acid-hydrolyzed to form monosaccharides. The hydrolysates were derivatized and analyzed with GC/FID. Each sugar derivative was detected as a single peak and was well separated from others on the chromatograms. The amounts of constituent monosaccharides in thickening polysaccharides were successfully estimated. Seven polysaccharides were distinguished from each other on the basis of constituent monosaccharides. Further examination of the time period of hydrolysis of polysaccharides using peach gum showed that the optimal times were not the same for all monosaccharides. A longer time was needed to hydrolyze glucuronic acid than neutral saccharides. The findings suggest that hydrolysis time may sometimes affect the analytical results on composition of constituent monosaccharides in polysaccharides.

Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers

Science.gov (United States)

Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)

2009-01-01

Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.

Amyloid oligomer structure characterization from simulations: A general method

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Phuong H., E-mail: phuong.nguyen@ibpc.fr [Laboratoire de Biochimie Théorique, UPR 9080, CNRS Université Denis Diderot, Sorbonne Paris Cité IBPC, 13 rue Pierre et Marie Curie, 75005 Paris (France); Li, Mai Suan [Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Derreumaux, Philippe, E-mail: philippe.derreumaux@ibpc.fr [Laboratoire de Biochimie Théorique, UPR 9080, CNRS Université Denis Diderot, Sorbonne Paris Cité IBPC, 13 rue Pierre et Marie Curie, 75005 Paris (France); Institut Universitaire de France, 103 Bvd Saint-Germain, 75005 Paris (France)

2014-03-07

Amyloid oligomers and plaques are composed of multiple chemically identical proteins. Therefore, one of the first fundamental problems in the characterization of structures from simulations is the treatment of the degeneracy, i.e., the permutation of the molecules. Second, the intramolecular and intermolecular degrees of freedom of the various molecules must be taken into account. Currently, the well-known dihedral principal component analysis method only considers the intramolecular degrees of freedom, and other methods employing collective variables can only describe intermolecular degrees of freedom at the global level. With this in mind, we propose a general method that identifies all the structures accurately. The basis idea is that the intramolecular and intermolecular states are described in terms of combinations of single-molecule and double-molecule states, respectively, and the overall structures of oligomers are the product basis of the intramolecular and intermolecular states. This way, the degeneracy is automatically avoided. The method is illustrated on the conformational ensemble of the tetramer of the Alzheimer's peptide Aβ{sub 9−40}, resulting from two atomistic molecular dynamics simulations in explicit solvent, each of 200 ns, starting from two distinct structures.

Theoretical study of stability geometrical and electronic structure of (BeHsub(2))sub(n) oligomers

Energy Technology Data Exchange (ETDEWEB)

Sukhanov, L P; Boldyrev, A I; Charkin, O P [AN SSSR, Moscow. Inst. Novykh Khimicheskikh Problem

1983-01-01

The Hartree-Fock-Ruthane method with the Roos-Siegbahn two-exponent basis is used to calculate stability, geometrical and electronic structures of (BeHsub(2))sub(n) oligomers, where n=1, 2, 3, 4 and 6. It is shown that with the growth of oligomerization degree n stability of linear band structure is increased as compared with other configurations including high-coordination volumetric ones. Tendencies in formation with n growth of geometrical, energetic characteristics, electronic structure of (BeHsub(2))sub(n) oligomers of band type are analysed.

Viscosity of nanoconfined polyamide-6,6 oligomers: atomistic reverse nonequilibrium molecular dynamics simulation.

Science.gov (United States)

Eslami, Hossein; Müller-Plathe, Florian

2010-01-14

Our new simulation scheme in isosurface-isothermal-isobaric ensemble [Eslami, H.; Mozaffari, F.; Moghadasi, J.; Müller-Plathe, F. J. Chem. Phys. 2008, 129, 194702], developed to simulate confined fluids in equilibrium with bulk, is applied to simulate polyamide-6,6 oligomers confined between graphite surfaces. The reverse nonequilibrium molecular dynamics simulation technique is employed to shear the graphite surfaces. In this work, six confined systems, with different surface separations, as well as the bulk fluid are simulated. Our results show a viscosity increase with respect to the bulk fluid, with decreasing distance between surfaces. Also, the calculated viscosities of the confined systems show an oscillatory behavior with maxima corresponding to well-formed layers between the surfaces. We observe a substantial slip at the surfaces, with the slip length depending on the shear rate and on the slit width. The slip length and the slip velocity show oscillatory behavior with out-of-phase oscillations with respect to the solvation force oscillations. Moreover, the temperature difference between coldest and hottest parts of the simulation box depends on the shear rate and on the layering effect (solvation force oscillations). An analysis of oligomer deformation under flow shows preferential alignment of oligomers parallel to the surfaces with increasing shear rate.

NMR studies of DNA oligomers and their interactions with minor groove binding ligands

Energy Technology Data Exchange (ETDEWEB)

Fagan, Patricia A. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

1996-05-01

The cationic peptide ligands distamycin and netropsin bind noncovalently to the minor groove of DNA. The binding site, orientation, stoichiometry, and qualitative affinity of distamycin binding to several short DNA oligomers were investigated by NMR spectroscopy. The oligomers studied contain A,T-rich or I,C-rich binding sites, where I = 2-desaminodeoxyguanosine. I•C base pairs are functional analogs of A•T base pairs in the minor groove. The different behaviors exhibited by distamycin and netropsin binding to various DNA sequences suggested that these ligands are sensitive probes of DNA structure. For sites of five or more base pairs, distamycin can form 1:1 or 2:1 ligand:DNA complexes. Cooperativity in distamycin binding is low in sites such as AAAAA which has narrow minor grooves, and is higher in sites with wider minor grooves such as ATATAT. The distamycin binding and base pair opening lifetimes of I,C-containing DNA oligomers suggest that the I,C minor groove is structurally different from the A,T minor groove. Molecules which direct chemistry to a specific DNA sequence could be used as antiviral compounds, diagnostic probes, or molecular biology tools. The author studied two ligands in which reactive groups were tethered to a distamycin to increase the sequence specificity of the reactive agent.

Ochratoxin A removal from red wine by several oenological fining agents: bentonite, egg albumin, allergen-free adsorbents, chitin and chitosan.

Science.gov (United States)

Quintela, S; Villarán, M C; López De Armentia, I; Elejalde, E

2012-01-01

The ability of several oenological fining agents to remove ochratoxin A (OTA) from red wine was studied. The adsorbents tested were activated sodium bentonite, egg albumin, allergen-free adsorbents (complex PVPP, plant protein and amorphous silica (complex) and high molecular weight gelatine), and the non-toxic biodegradable polymers (chitin and chitosan). Several dosages within the oenological use range were tested and the wine pH, colour parameters and polyphenol concentration impact associated with each fining agent were studied. Generally, OTA removal achieved in all treatments was higher when the adsorbent dosage increased, but the impact on wine quality also was higher. Chitin at 50 g hl(-1) removed 18% the OTA without affecting significantly the wine-quality parameters. At the highest dosage tested the gelatine and complex treatments achieved greater OTA removal (up to 39-40%) compared with bentonite, egg albumin and chitin. Moreover, the gelatine and the complex had a lower impact on colour parameters and polyphenol concentration compared with chitosan, whilst OTA was reduced to around 40%. Chitosan achieved the greatest OTA removal (67%), but it strongly affected the wine-quality parameters. Otherwise, bentonite showed a relative efficiency to remove OTA, but the CI value decreased considerably. The egg albumin treatment only removed OTA up to 16% and moreover affected strongly the CI value and CIELab parameters. The results of this survey showed that the non-toxic chitin adsorbent and the allergen-free adsorbents tested could be considered as alternative fining agents to reduce OTA in red wine.

A novel Arabidopsis CHITIN ELICITOR RECEPTOR KINASE 1 (CERK1) mutant with enhanced pathogen-induced cell death and altered receptor processing.

Science.gov (United States)

Petutschnig, Elena K; Stolze, Marnie; Lipka, Ulrike; Kopischke, Michaela; Horlacher, Juliane; Valerius, Oliver; Rozhon, Wilfried; Gust, Andrea A; Kemmerling, Birgit; Poppenberger, Brigitte; Braus, Gerhard H; Nürnberger, Thorsten; Lipka, Volker

2014-12-01

Plants detect pathogens by sensing microbe-associated molecular patterns (MAMPs) through pattern recognition receptors. Pattern recognition receptor complexes also have roles in cell death control, but the underlying mechanisms are poorly understood. Here, we report isolation of cerk1-4, a novel mutant allele of the Arabidopsis chitin receptor CERK1 with enhanced defense responses. We identified cerk1-4 in a forward genetic screen with barley powdery mildew and consequently characterized it by pathogen assays, mutant crosses and analysis of defense pathways. CERK1 and CERK1-4 proteins were analyzed biochemically. The cerk1-4 mutation causes an amino acid exchange in the CERK1 ectodomain. Mutant plants maintain chitin signaling capacity but exhibit hyper-inducible salicylic acid concentrations and deregulated cell death upon pathogen challenge. In contrast to chitin signaling, the cerk1-4 phenotype does not require kinase activity and is conferred by the N-terminal part of the receptor. CERK1 undergoes ectodomain shedding, a well-known process in animal cell surface proteins. Wild-type plants contain the full-length CERK1 receptor protein as well as a soluble form of the CERK1 ectodomain, whereas cerk1-4 plants lack the N-terminal shedding product. Our work suggests that CERK1 may have a chitin-independent role in cell death control and is the first report of ectodomain shedding in plants. © 2014 The Authors. New Phytologist © 2014 New Phytologist Trust.

Determination of NH{sub 2} concentration on 3-aminopropyl tri-ethoxy silane layers and cyclopropylamine plasma polymers by liquid-phase derivatization with 5-iodo 2-furaldehyde

Energy Technology Data Exchange (ETDEWEB)

Manakhov, Anton, E-mail: ant-manahov@ya.ru [National University of Science and Technology “MISiS”, Leninsky pr. 4, Moscow 119049 (Russian Federation); RG Plasma Technologies, CEITEC—Central European Institute of Technology, Masaryk University, Kotlářská, 2, 61137 Brno (Czech Republic); Čechal, Jan [CEITEC—Central European Institute of Technology, Brno University of Technology, Purkyňova 123, 612 00 Brno (Czech Republic); Institute of Physical Engineering, Brno University of Technology, Technická 2896/2, 616 69 Brno (Czech Republic); Michlíček, Miroslav [RG Plasma Technologies, CEITEC—Central European Institute of Technology, Masaryk University, Kotlářská, 2, 61137 Brno (Czech Republic); Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlářská 2, 61137 Brno (Czech Republic); Shtansky, Dmitry V. [National University of Science and Technology “MISiS”, Leninsky pr. 4, Moscow 119049 (Russian Federation)

2017-08-31

Highlights: • A new method for primary amines derivatization is proposed and validated. • The chemical structure of APTES layer is studied. • The derivatization by 5-iodo 2-furaldehyde allowed to avoid side reactions in contrast to 4-trifluoromethyl benzaldehyde derivatization. - Abstract: The quantification of concentration of primary amines, e.g. in plasma polymerized layers is a very important task for surface analysis. However, the commonly used procedure, such as gas phase derivatization with benzaldehydes, shows several drawbacks, the most important of which are the side reaction effects. In the present study we propose and validate a liquid phase derivatization using 5-iodo 2-furaldehyde (IFA). It was demonstrated that the content of NH{sub 2} groups can be determined from the atomic concentrations measured by X-ray photoelectron spectroscopy (XPS), in particular from the ratio of I 3d and N 1s peak intensities. First, we demonstrate the method on a prototypical system such as 3-aminopropyl tri-ethoxy silane (APTES) layer. Here the XPS analysis carried out after reaction of APTES layer with IFA gives the fraction of primary amines (NH{sub 2}/N) of 38.3 ± 7.9%. Comparing this value with that obtained by N 1s curve fitting of APTES layer giving 40.9 ± 9.5% of amine groups, it can be concluded that all primary amines were derivatized by reaction with IFA. The second system to demonstrate the method comprises cyclopropylamine (CPA) plasma polymers that were free from conjugated imines. In this case the method gives the NH{sub 2} fraction ∼8.5%. This value is closely matching the NH{sub 2}/N ratio estimated by 4-trifluoromethyl benzaldehyde (TFBA) derivatization. The reaction of IFA with CPA plasma polymer exhibiting high density of conjugated imines revealed the NH{sub 2}/N fraction of ∼10.8%. This value was significantly lower compared to 17.3% estimated by TFBA derivatization. As the overestimated density of primary amines measured by TFBA

Formation of a stable oligomer of beta-2 microglobulin requires only transient encounter with Cu(II).

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Calabrese, Matthew F; Miranker, Andrew D

2007-03-16

Beta-2 Microglobulin (beta2m) is a small, globular protein, with high solubility under conditions comparable to human serum. A complication of hemodialysis in renal failure patients is the deposition of unmodified beta2m as amyloid fibers. In vitro, exposure of beta2m to equimolar Cu(2+) under near-physiological conditions can result in self-association leading to amyloid fiber formation. Previously, we have shown that the early steps in this process involve a catalyzed structural rearrangement followed by formation of discrete oligomers. These oligomers, however, have a continued requirement for Cu(2+) while mature fibers are resistant to addition of metal chelate. Here, we report that the transition from Cu(2+) dependent to chelate resistant states occurs in the context of small oligomers, dimeric to hexameric in size. These species require Cu(2+) to form, but once generated, do not need metal cation for stability. Importantly, this transition occurs gradually over several days and the resulting oligomers are isolatable and kinetically stable on timescales exceeding weeks. In addition, formation is enhanced by levels of urea similar to those found in hemodialysis patients. Our results are consistent with our hypothesis that transient encounter of full-length wild-type beta2m with transition metal cation at the dialysis membrane interface is causal to dialysis related amyloidosis.

Analysis of L-serine-O-phosphate in cerebrospinal spinal fluid by derivatization-liquid chromatography/mass spectrometry.

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McNaney, Colleen A; Benitex, Yulia; Luchetti, David; Labasi, Jeffrey M; Olah, Timothy V; Morgan, Daniel G; Drexler, Dieter M

2014-05-01

L-serine-O-phosphate (L-SOP), the precursor of L-serine, is a potent agonist against the group III metabotropic glutamate receptors (mGluRs) and, thus, is of interest as a potential biomarker for monitoring modulation of neurotransmitter release. So far, no reports are available on the analysis of L-SOP in cerebrospinal fluid (CSF). Here a novel method is presented to determine L-SOP levels in CSF employing precolumn derivatization with (5-N-succinimidoxy-5-oxopentyl)triphenylphosphonium bromide (SPTPP) coupled to liquid chromatography/mass spectrometry (derivatization-LC/MS, d-LC/MS). Copyright © 2014 Elsevier Inc. All rights reserved.

Some biological actions of PEG-conjugated RNase A oligomers

Czech Academy of Sciences Publication Activity Database

Poučková, P.; Škvor, J.; Gotte, G.; Vottariello, F.; Slavík, Tomáš; Matoušek, Josef; Laurents, D. V.; Libonati, M.; Souček, J.

2006-01-01

Roč. 53, č. 1 (2006), s. 79-85 ISSN 0028-2685 R&D Projects: GA ČR GA523/04/0755; GA MZd NR8233 Grant - others:Spanish Ministerio de Ciencia y Technologia BQU2003-05227 Institutional research plan: CEZ:AV0Z50450515 Keywords : RNase A oligomers * polyethylene glycol conjugates * anti-tumour activity Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 1.247, year: 2006

In situ derivatization and hollow fiber membrane microextraction for gas chromatographic determination of haloacetic acids in water

Energy Technology Data Exchange (ETDEWEB)

Varanusupakul, Pakorn [Chromatography and Separation Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Patumwan, Bangkok 10330 (Thailand)], E-mail: pakorn.v@chula.ac.th; Vora-adisak, Narongchai; Pulpoka, Bancha [Chromatography and Separation Research Unit, Department of Chemistry, Faculty of Science, Chulalongkorn University, Phayathai Road, Patumwan, Bangkok 10330 (Thailand)

2007-08-15

An alternative method for gas chromatographic determination of haloacetic acids (HAAs) in water using direct derivatization followed by hollow fiber membrane liquid-phase microextraction (HF-LPME) has been developed. The method has improved the sample preparation step according to the conventional US EPA Method 552.2 by combining the derivatization and the extraction into one step prior to determination by gas chromatography electron captured detector (GC-ECD). The HAAs were derivatized with acidic methanol into their methyl esters and simultaneously extracted with supported liquid hollow fiber membrane in headspace mode. The derivatization was attempted directly in water sample without sample evaporation. The HF-LPME was performed using 1-octanol as the extracting solvent at 55 deg. C for 60 min with 20% Na{sub 2}SO{sub 4}. The linear calibration curves were observed for the concentrations ranging from 1 to 300 {mu}g L{sup -1} with the correlation coefficients (R{sup 2}) being greater than 0.99. The method detection limits of most analytes were below 1 {mu}g L{sup -1} except DCAA and MCAA that were 2 and 18 {mu}g L{sup -1}, respectively. The recoveries from spiked concentration ranged from 97 to 109% with %R.S.D. less than 12%. The method was applied for determination of HAAs in drinking water and tap water samples. The method offers an easy one step high sample throughput sample preparation for gas chromatographic determination of haloacetic acids as well as other contaminants in water.

In situ derivatization and hollow fiber membrane microextraction for gas chromatographic determination of haloacetic acids in water

International Nuclear Information System (INIS)

Varanusupakul, Pakorn; Vora-adisak, Narongchai; Pulpoka, Bancha

2007-01-01

An alternative method for gas chromatographic determination of haloacetic acids (HAAs) in water using direct derivatization followed by hollow fiber membrane liquid-phase microextraction (HF-LPME) has been developed. The method has improved the sample preparation step according to the conventional US EPA Method 552.2 by combining the derivatization and the extraction into one step prior to determination by gas chromatography electron captured detector (GC-ECD). The HAAs were derivatized with acidic methanol into their methyl esters and simultaneously extracted with supported liquid hollow fiber membrane in headspace mode. The derivatization was attempted directly in water sample without sample evaporation. The HF-LPME was performed using 1-octanol as the extracting solvent at 55 deg. C for 60 min with 20% Na 2 SO 4 . The linear calibration curves were observed for the concentrations ranging from 1 to 300 μg L -1 with the correlation coefficients (R 2 ) being greater than 0.99. The method detection limits of most analytes were below 1 μg L -1 except DCAA and MCAA that were 2 and 18 μg L -1 , respectively. The recoveries from spiked concentration ranged from 97 to 109% with %R.S.D. less than 12%. The method was applied for determination of HAAs in drinking water and tap water samples. The method offers an easy one step high sample throughput sample preparation for gas chromatographic determination of haloacetic acids as well as other contaminants in water

Mass Spectrometric Characterization of Oligomers in Pseudomonas aeruginosa Azurin Solutions

Czech Academy of Sciences Publication Activity Database

Sokolová, L.; Williamson, H.; Sýkora, Jan; Hof, Martin; Gray, H. B.; Brutschy, B.; Vlček, Antonín

2011-01-01

Roč. 115, č. 16 (2011), s. 4790-4800 ISSN 1520-6106 R&D Projects: GA MŠk(CZ) ME10124; GA MŠk(CZ) LC06063 Institutional research plan: CEZ:AV0Z40400503 Keywords : mass spectrometry * oligomers * pseudomonas aeruginosa azurin solutions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.696, year: 2011

Humans Can Taste Glucose Oligomers Independent of the hT1R2/hT1R3 Sweet Taste Receptor.

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Lapis, Trina J; Penner, Michael H; Lim, Juyun

2016-08-23

It is widely accepted that humans can taste mono- and disaccharides as sweet substances, but they cannot taste longer chain oligo- and polysaccharides. From the evolutionary standpoint, the ability to taste starch or its oligomeric hydrolysis products would be highly adaptive, given their nutritional value. Here, we report that humans can taste glucose oligomer preparations (average degree of polymerization 7 and 14) without any other sensorial cues. The same human subjects could not taste the corresponding glucose polymer preparation (average degree of polymerization 44). When the sweet taste receptor was blocked by lactisole, a known sweet inhibitor, subjects could not detect sweet substances (glucose, maltose, and sucralose), but they could still detect the glucose oligomers. This suggests that glucose oligomer detection is independent of the hT1R2/hT1R3 sweet taste receptor. Human subjects described the taste of glucose oligomers as "starchy," while they describe sugars as "sweet." The dose-response function of glucose oligomer was also found to be indistinguishable from that of glucose on a molar basis. © The Author 2016. Published by Oxford University Press. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

GalaxyHomomer: a web server for protein homo-oligomer structure prediction from a monomer sequence or structure.

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Baek, Minkyung; Park, Taeyong; Heo, Lim; Park, Chiwook; Seok, Chaok

2017-07-03

Homo-oligomerization of proteins is abundant in nature, and is often intimately related with the physiological functions of proteins, such as in metabolism, signal transduction or immunity. Information on the homo-oligomer structure is therefore important to obtain a molecular-level understanding of protein functions and their regulation. Currently available web servers predict protein homo-oligomer structures either by template-based modeling using homo-oligomer templates selected from the protein structure database or by ab initio docking of monomer structures resolved by experiment or predicted by computation. The GalaxyHomomer server, freely accessible at http://galaxy.seoklab.org/homomer, carries out template-based modeling, ab initio docking or both depending on the availability of proper oligomer templates. It also incorporates recently developed model refinement methods that can consistently improve model quality. Moreover, the server provides additional options that can be chosen by the user depending on the availability of information on the monomer structure, oligomeric state and locations of unreliable/flexible loops or termini. The performance of the server was better than or comparable to that of other available methods when tested on benchmark sets and in a recent CASP performed in a blind fashion. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Effector-mediated suppression of chitin-triggered immunity by Magnaporthe oryzae is necessary for rice blast disease

NARCIS (Netherlands)

Mentlak, T.A.; Kombrink, A.; Shinya, T.; Ryder, L.S.; Otomo, I.; Saitoh, H.; Terauchi, R.; Nishizawa, Y.; Shibuya, N.; Thomma, B.P.H.J.; Talbot, N.J.

2012-01-01

Plants use pattern recognition receptors to defend themselves from microbial pathogens. These receptors recognize pathogen-associated molecular patterns (PAMPs) and activate signaling pathways that lead to immunity. In rice (Oryza sativa), the chitin elicitor binding protein (CEBiP) recognizes

On-matrix derivatization extraction of chemical weapons convention relevant alcohols from soil.

Science.gov (United States)

Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Dubey, D K; Pardasani, Deepak

2013-10-11

Present study deals with the on-matrix derivatization-extraction of aminoalcohols and thiodiglycols, which are important precursors and/or degradation products of VX analogues and vesicants class of chemical warfare agents (CWAs). The method involved hexamethyldisilazane (HMDS) mediated in situ silylation of analytes on the soil. Subsequent extraction and gas chromatography-mass spectrometry analysis of derivatized analytes offered better recoveries in comparison to the procedure recommended by the Organization for the Prohibition of Chemical Weapons (OPCW). Various experimental conditions such as extraction solvent, reagent and catalyst amount, reaction time and temperature were optimized. Best recoveries of analytes ranging from 45% to 103% were obtained with DCM solvent containing 5%, v/v HMDS and 0.01%, w/v iodine as catalyst. The limits of detection (LOD) and limit of quantification (LOQ) with selected analytes ranged from 8 to 277 and 21 to 665ngmL(-1), respectively, in selected ion monitoring mode. Copyright © 2013 Elsevier B.V. All rights reserved.

Quantification of Carbonyl Compounds Generated from Ozone-Based Food Colorants Decomposition Using On-Fiber Derivatization-SPME-GC-MS

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Wenda Zhu

2014-12-01

Full Text Available Fruit leathers (FLs production produces some not-to-specification material, which contains valuable ingredients like fruit pulp, sugars and acidulates. Recovery of FL for product recycling requires decolorization. In earlier research, we proved the efficiency of an ozone-based decolorization process; however, it produces carbonyls as major byproducts, which could be of concern. A headspace solid-phase microextraction with on-fiber derivatization followed by gas chromatography-mass spectrometry was developed for 10 carbonyls analysis in ozonated FL solution/suspension. Effects of dopant concentration, derivatization temperature and time were studied. The adapted method was used to analyze ozonated FL solution/suspension samples. Dopant concentration and derivatization temperature were optimized to 17 mg/mL and 60 °C, respectively. Competitive extraction was studied, and 5 s extraction time was used to avoid non-linear derivatization of 2-furfural. The detection limits (LODs for target carbonyls ranged from 0.016 and 0.030 µg/L. A much lower LOD (0.016 ppb for 2-furfural was achieved compared with 6 and 35 ppb in previous studies. Analysis results confirmed the robustness of the adapted method for quantification of carbonyls in recycled process water treated with ozone-based decolorization. Ethanal, hexanal, 2-furfural, and benzaldehyde were identified as byproducts of known toxicity but all found below levels for concern.

Nanoparticle for delivery of antisense γPNA oligomers targeting CCR5.

Science.gov (United States)

Bahal, Raman; McNeer, Nicole Ali; Ly, Danith H; Saltzman, W Mark; Glazer, Peter M

2013-01-01

The development of a new class of peptide nucleic acids (PNAs), i.e., gamma PNAs (γPNAs), creates the need for a general and effective method for its delivery into cells for regulating gene expression in mammalian cells. Here we report the antisense activity of a recently developed hydrophilic and biocompatible diethylene glycol (miniPEG)-based gamma peptide nucleic acid called MPγPNAs via its delivery by poly(lactide-co-glycolide) (PLGA)-based nanoparticle system. We show that MPγPNA oligomers designed to bind to the selective region of chemokine receptor 5 (CC R5) transcript, induce potent and sequence-specific antisense effects as compared with regular PNA oligomers. In addition, PLGA nanoparticle delivery of MPγPNAs is not toxic to the cells. The findings reported in this study provide a combination of γPNA technology and PLGA-based nanoparticle delivery method for regulating gene expression in live cells via the antisense mechanism.

Presence of a large β(1-3)glucan linked to chitin at the Saccharomyces cerevisiae mother-bud neck suggests involvement in localized growth control.

Science.gov (United States)

Cabib, Enrico; Blanco, Noelia; Arroyo, Javier

2012-04-01

Previous results suggested that the chitin ring present at the yeast mother-bud neck, which is linked specifically to the nonreducing ends of β(1-3)glucan, may help to suppress cell wall growth at the neck by competing with β(1-6)glucan and thereby with mannoproteins for their attachment to the same sites. Here we explored whether the linkage of chitin to β(1-3)glucan may also prevent the remodeling of this polysaccharide that would be necessary for cell wall growth. By a novel mild procedure, β(1-3)glucan was isolated from cell walls, solubilized by carboxymethylation, and fractionated by size exclusion chromatography, giving rise to a very high-molecular-weight peak and to highly polydisperse material. The latter material, soluble in alkali, may correspond to glucan being remodeled, whereas the large-size fraction would be the final cross-linked structural product. In fact, the β(1-3)glucan of buds, where growth occurs, is solubilized by alkali. A gas1 mutant with an expected defect in glucan elongation showed a large increase in the polydisperse fraction. By a procedure involving sodium hydroxide treatment, carboxymethylation, fractionation by affinity chromatography on wheat germ agglutinin-agarose, and fractionation by size chromatography on Sephacryl columns, it was shown that the β(1-3)glucan attached to chitin consists mostly of high-molecular-weight material. Therefore, it appears that linkage to chitin results in a polysaccharide that cannot be further remodeled and does not contribute to growth at the neck. In the course of these experiments, the new finding was made that part of the chitin forms a noncovalent complex with β(1-3)glucan.

Chitin nanofibrils for rapid and efficient removal of metal ions from water system.

Science.gov (United States)

Liu, Dagang; Zhu, Yi; Li, Zehui; Tian, Donglin; Chen, Lei; Chen, Peng

2013-10-15

Joint mechanical defibrillation was successfully used to downsize chitin micro-particles (CMP) into nanofibrils without changing its chemical or crystalline structure. The fine chitin nanofibrils (CNF) bearing width of about 50 nm and length of more than 1 μm were then developed as heavy metal ion sorbents. The uptake performance of CNF dependent on pH, ionic concentration, time, and temperature was investigated. Results show that fixation amount of Cd(II), Ni(II), Cu(II), Zn(II), Pb(II), Cr(III) on CNF was up to 2.94, 2.30, 2.22, 2.06, 1.46, and 0.31 mmol/g, respectively, much higher than CMP due to high specific surface area and widely distributed pores of CNF. Adsorption kinetics of CMP and CNF followed pseudo-second-order model and Freundlich isotherm although CNF exhibited higher rate constant and sorption capacity than that of CMP. The defibrillated CNF is renewable, feasible, easily recyclable, and is thought as good candidate for heavy metal ion treatment due to their low sorption energy, rapid and efficient uptake capacity. Copyright © 2013 Elsevier Ltd. All rights reserved.

Organization in sol-gel polymerization of methacrylate co-oligomers containing trimethoxysilylpropyl methacrylate

Czech Academy of Sciences Publication Activity Database

Vraštil, J.; Matějka, Libor; Špaček, V.; Večeřa, M.; Prokůpek, L.

2005-01-01

Roč. 46, č. 25 (2005), s. 11232-11240 ISSN 0032-3861 Institutional research plan: CEZ:AV0Z40500505 Keywords : organic-inorganic hybrid * sol-gel process * oligomers Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.849, year: 2005

Paenibacillus larvae chitin-degrading protein PlCBP49 is a key virulence factor in American Foulbrood of honey bees.

Directory of Open Access Journals (Sweden)

Eva Garcia-Gonzalez

2014-07-01

Full Text Available Paenibacillus larvae, the etiological agent of the globally occurring epizootic American Foulbrood (AFB of honey bees, causes intestinal infections in honey bee larvae which develop into systemic infections inevitably leading to larval death. Massive brood mortality might eventually lead to collapse of the entire colony. Molecular mechanisms of host-microbe interactions in this system and of differences in virulence between P. larvae genotypes are poorly understood. Recently, it was demonstrated that the degradation of the peritrophic matrix lining the midgut epithelium is a key step in pathogenesis of P. larvae infections. Here, we present the isolation and identification of PlCBP49, a modular, chitin-degrading protein of P. larvae and demonstrate that this enzyme is crucial for the degradation of the larval peritrophic matrix during infection. PlCBP49 contains a module belonging to the auxiliary activity 10 (AA10, formerly CBM33 family of lytic polysaccharide monooxygenases (LPMOs which are able to degrade recalcitrant polysaccharides. Using chitin-affinity purified PlCBP49, we provide evidence that PlCBP49 degrades chitin via a metal ion-dependent, oxidative mechanism, as already described for members of the AA10 family. Using P. larvae mutants lacking PlCBP49 expression, we analyzed in vivo biological functions of PlCBP49. In the absence of PlCBP49 expression, peritrophic matrix degradation was markedly reduced and P. larvae virulence was nearly abolished. This indicated that PlCBP49 is a key virulence factor for the species P. larvae. The identification of the functional role of PlCBP49 in AFB pathogenesis broadens our understanding of this important family of chitin-binding and -degrading proteins, especially in those bacteria that can also act as entomopathogens.

Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

Directory of Open Access Journals (Sweden)

Y. Tan

2012-01-01

Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

A Fluorescent Oligothiophene-Bis-Triazine ligand interacts with PrP fibrils and detects SDS-resistant oligomers in human prion diseases.

Science.gov (United States)

Imberdis, Thibaut; Ayrolles-Torro, Adeline; Duarte Rodrigues, Alysson; Torrent, Joan; Alvarez-Martinez, Maria Teresa; Kovacs, Gabor G; Verdier, Jean-Michel; Robitzer, Mike; Perrier, Véronique

2016-01-26

Prion diseases are characterized by the accumulation in the central nervous system of an abnormally folded isoform of the prion protein, named PrP(Sc). Aggregation of PrP(Sc) into oligomers and fibrils is critically involved in the pathogenesis of prion diseases. Oligomers are supposed to be the key neurotoxic agents in prion disease, so modulation of prion aggregation pathways with small molecules can be a valuable strategy for studying prion pathogenicity and for developing new diagnostic and therapeutic approaches. We previously identified thienyl pyrimidine compounds that induce SDS-resistant PrP(Sc) (rSDS-PrP(Sc)) oligomers in prion-infected samples. Due to the low effective doses of the thienyl pyrimidine hits, we synthesized a quaterthiophene-bis-triazine compound, called MR100 to better evaluate their diagnostic and therapeutic potentials. This molecule exhibits a powerful activity inducing rSDS-PrP(Sc) oligomers at nanomolar concentrations in prion-infected cells. Fluorescence interaction studies of MR100 with mouse PrP fibrils showed substantial modification of the spectrum, and the interaction was confirmed in vitro by production of rSDS-oligomer species upon incubation of MR100 with fibrils in SDS-PAGE gel. We further explored whether MR100 compound has a potential to be used in the diagnosis of prion diseases. Our results showed that: (i) MR100 can detect rSDS-oligomers in prion-infected brain homogenates of various species, including human samples from CJD patients; (ii) A protocol, called "Rapid Centrifugation Assay" (RCA), was developed based on MR100 property of inducing rSDS-PrP(Sc) oligomers only in prion-infected samples, and avoiding the protease digestion step. RCA allows the detection of both PK-sensitive and PK-resistant PrP(Sc) species in rodents samples but also from patients with different CJD forms (sporadic and new variant); (iii) A correlation could be established between the amount of rSDS-PrP(Sc) oligomers revealed by MR100 and the

[Determination of bisphenol A from toys and food contact materials by derivatization and gas chromatography-mass spectrometry].

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