Diamond surface functionalization with biomimicry – Amine surface tether and thiol moiety for electrochemical sensors

International Nuclear Information System (INIS)

Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

2014-01-01

Highlights: • Diamond surfaces were functionalized with organic molecules using a novel approach. • Used biomimicry to select a molecule to bind NO, similar to the human body. • Molecular orbital theory predicted the molecule-analyte oxidation behavior. • A thiol moiety was attached to an amine surface tether on the diamond surface. • XPS analysis verified each surface functionalization step. - Abstract: The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen–oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis

Diamond surface functionalization with biomimicry - Amine surface tether and thiol moiety for electrochemical sensors

Science.gov (United States)

Sund, James B.; Causey, Corey P.; Wolter, Scott D.; Parker, Charles B.; Stoner, Brian R.; Toone, Eric J.; Glass, Jeffrey T.

2014-05-01

The surface of conducting diamond was functionalized with a terminal thiol group that is capable of binding and detecting nitrogen-oxygen species. The functionalization process employed multiple steps starting with doped diamond films grown by plasma enhanced chemical vapor deposition followed by hydrogen termination and photochemical attachment of a chemically protected amine alkene. The surface tether was deprotected to reveal the amine functionality, which enabled the tether to be extended with surface chemistry to add a terminal thiol moiety for electrochemical sensing applications. Each step of the process was validated using X-ray photoelectron spectroscopy analysis.

Differential Labeling of Free and Disulfide-Bound Thiol Functions in Proteins

NARCIS (Netherlands)

Seiwert, B.; Hayen, H.; Karst, U.

2008-01-01

A method for the simultaneous determination of the number of free cysteine groups and disulfide-bound cysteine groups in proteins has been developed based on the sequential labeling of free and bound thiol functionalities with two ferrocene-based maleimide reagents. Liquid

Hypochlorite-induced oxidation of thiols

DEFF Research Database (Denmark)

Davies, Michael Jonathan; Hawkins, C L

2000-01-01

-molecular-weight thiols such as reduced glutathione (GSH), and sulfur-containing amino acids in proteins, are major targets for HOCl. Radicals have not generally been implicated as intermediates in thiol oxidation by HOCl, though there is considerable literature evidence for the involvement of radicals in the metal ion......-, thermal- or UV light-catalysed decomposition of sulfenyl or sulfonyl chlorides which are postulated intermediates in thiol oxidation. In this study we show that thiyl radicals are generated on reaction of a number of low-molecular-weight thiols with HOCl. With sub-stoichiometric amounts of HOCl, relative...... to the thiol, thiyl radicals are the major species detected by EPR spin trapping. When the HOCl is present in excess over the thiol, additional radicals are detected with compounds which contain amine functions; these additional radicals are assigned to nitrogen-centered species. Evidence is presented...

Phosphoryl functionalized mesoporous silica for uranium adsorption

International Nuclear Information System (INIS)

Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun; Hongyu, Gong; Yujun, Zhang

2017-01-01

Highlights: • Phosphoryl functionalized mesoporous silica (TBP-SBA-15) is synthesized. • The amino and phosphoryl groups are successfully grafted on SBA-15. • TBP-SBA-15 has high and rapid uranium adsorption capacity in broad pH range. • The U(VI) adsorption of TBP-SBA-15 is spontaneous and belongs to chemical adsorption. - Abstract: Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N_2 adsorption–desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG"0, ΔH"0 and ΔS"0) confirmed that the adsorption process was endothermic and spontaneous.

Phosphoryl functionalized mesoporous silica for uranium adsorption

Energy Technology Data Exchange (ETDEWEB)

Xue, Guo; Yurun, Feng; Li, Ma; Dezhi, Gao; Jie, Jing; Jincheng, Yu; Haibin, Sun [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Hongyu, Gong, E-mail: gong_hongyu@163.com [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China); Yujun, Zhang, E-mail: yujunzhangcn@163.com [Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials of Ministry of Education, Shandong University, Jinan 250061 (China); Key Laboratory of Special Functional Aggregated Materials, Ministry of Education, Shandong University, Jinan 250061 (China)

2017-04-30

Highlights: • Phosphoryl functionalized mesoporous silica (TBP-SBA-15) is synthesized. • The amino and phosphoryl groups are successfully grafted on SBA-15. • TBP-SBA-15 has high and rapid uranium adsorption capacity in broad pH range. • The U(VI) adsorption of TBP-SBA-15 is spontaneous and belongs to chemical adsorption. - Abstract: Phosphoryl functionalized mesoporous silica (TBP-SBA-15) was synthesized by modified mesoporous silica with γ-amino propyl triethoxy silane and tributyl phosphate. The obtained samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), small angle X-ray diffraction (SAXRD), thermo-gravimetric/differential thermalanalyzer (TG/DTA), N{sub 2} adsorption–desorption (BET) and Fourier transform infrared spectroscopy (FT-IR) techniques. Results showed that TBP-SBA-15 had large surface areas with ordered channel structure. Moreover, the effects of adsorption time, sorbent dose, solution pH, initial uranium concentration and temperature on the uranium adsorption behaviors were investigated. TBP-SBA-15 showed a high uranium adsorption capacity in a broad range of pH values. The U(VI) adsorption rate of TBP-SBA-15 was fast and nearly achieved completion in 10 min with the sorbent dose of 1 g/L. The U(VI) adsorption of TBP-SBA-15 followed the pseudo-second-order kinetic model and Freundlich isotherm model, indicating that the process was belonged to chemical adsorption. Furthermore, the thermodynamic parameters (ΔG{sup 0}, ΔH{sup 0} and ΔS{sup 0}) confirmed that the adsorption process was endothermic and spontaneous.

Organosulfonic acid-functionalized mesoporous composites based on natural rubber and hexagonal mesoporous silica

Energy Technology Data Exchange (ETDEWEB)

Nuntang, Sakdinun; Poompradub, Sirilux [Fuels Research Center, Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Patumwan, Bangkok 10330 (Thailand); Butnark, Suchada [PTT Research and Technology Institute, PTT Public Company Limited, Wangnoi, Ayutthaya 13170 (Thailand); Yokoi, Toshiyuki; Tatsumi, Takashi [Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503 (Japan); Ngamcharussrivichai, Chawalit, E-mail: Chawalit.Ng@Chula.ac.th [Fuels Research Center, Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Patumwan, Bangkok 10330 (Thailand); Center of Excellence on Petrochemical and Materials Technology (PETROMAT), Chulalongkorn University, Patumwan, Bangkok 10330 (Thailand)

2014-10-15

This study is the first report on synthesis, characterization and catalytic application of propylsulfonic acid-functionalized mesoporous composites based on natural rubber (NR) and hexagonal mesoporous silica (HMS). In comparison with propylsulfonic acid-functionalized HMS (HMS-SO{sub 3}H), a series of NR/HMS-SO{sub 3}H composites were prepared via an in situ sol–gel process using tetrahydrofuran as the synthesis media. Tetraethylorthosilicate as the silica source, was simultaneously condensed with 3-mercaptopropyltrimethoxysilane in a solution of NR followed by oxidation with hydrogen peroxide to achieve the mesoporous composites containing propylsulfonic acid groups. Fourier-transform infrared spectroscopy and {sup 29}Si MAS nuclear magnetic resonance spectroscopy results verified that the silica surfaces of the NR/HMS-SO{sub 3}H composites were functionalized with propylsulfonic acid groups and covered with NR molecules. After the incorporation of NR and organo-functional group into HMS, the hexagonal mesostructure remained intact concomitantly with an increased framework wall thickness and unit cell size, as evidenced by the X-ray powder diffraction analysis. Scanning electron microscopy analysis indicated a high interparticle porosity of NR/HMS-SO{sub 3}H composites. The textural properties of NR/HMS-SO{sub 3}H were affected by the amount of MPTMS loading to a smaller extent than that of HMS-SO{sub 3}H. NR/HMS-SO{sub 3}H exhibited higher hydrophobicity than HMS-SO{sub 3}H, as revealed by H{sub 2}O adsorption–desorption measurements. Moreover, the NR/HMS-SO{sub 3}H catalysts possessed a superior specific activity to HMS-SO{sub 3}H in the esterification of lauric acid with ethanol, resulting in a higher conversion level. - Highlights: • Acidic NR/HMS-SO{sub 3}H composites were prepared by in situ sol–gel process. • Propylsulfonic acid was functionalized onto HMS surface by direct co-condensation. • NR/HMS-SO{sub 3}H exhibited a hexagonal

Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

International Nuclear Information System (INIS)

Alyoshina, Nonna A.; Parfenyuk, Elena V.

2013-01-01

A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N 2 adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica

Mercury Binding Sites in Thiol-Functionalized Mesostructured Silica

International Nuclear Information System (INIS)

Billinge, Simon J.L.; McKimmey, Emily J.; Shatnawi, Mouath; Kim, HyunJeong; Petkov, Valeri; Wermeille, Didier; Pinnavaia, Thomas J.

2005-01-01

Thiol-functionalized mesostructured silica with anhydrous compositions of (SiO 2 ) 1-x (LSiO 1.5 ) x , where L is a mercaptopropyl group and x is the fraction of functionalized framework silicon centers, are effective trapping agents for the removal of mercuric(II) ions from water. In the present work, we investigate the mercury-binding mechanism for representative thiol-functionalized mesostructures by atomic pair distribution function (PDF) analysis of synchrotron X-ray powder diffraction data and by Raman spectroscopy. The mesostructures with wormhole framework structures and compositions corresponding to x = 0.30 and 0.50 were prepared by direct assembly methods in the presence of a structure-directing amine porogen. PDF analyses of five mercury-loaded compositions with Hg/S ratios of 0.50-1.30 provided evidence for the bridging of thiolate sulfur atoms to two metal ion centers and the formation of chain structures on the pore surfaces. We find no evidence for Hg-O bonds and can rule out oxygen coordination of the mercury at greater than the 10% level. The relative intensities of the PDF peaks corresponding to Hg-S and Hg-Hg atomic pairs indicate that the mercury centers cluster on the functionalized surfaces by virtue of thiolate bridging, regardless of the overall mercury loading. However, the Raman results indicate that the complexation of mercury centers by thiolate depends on the mercury loading. At low mercury loadings (Hg/S (le) 0.5), the dominant species is an electrically neutral complex in which mercury most likely is tetrahedrally coordinated to bridging thiolate ligands, as in Hg(SBu t ) 2 . At higher loadings (Hg/S 1.0-1.3), mercury complex cations predominate, as evidenced by the presence of charge-balancing anions (nitrate) on the surface. This cationic form of bound mercury is assigned a linear coordination to two bridging thiolate ligands.

IR spectroscopy study of SBA-15 silicas functionalized with the ethylthiocarbamidepropyl groups and their interactions with Ag(I) and Hg(II) ions

Science.gov (United States)

Melnyk, Inna V.; Nazarchuk, Galyna I.; Václavíková, Miroslava; Zub, Yuriy L.

2018-04-01

Mesoporous structure of silica is determined by the type of template, but the introduction of functional groups during the synthesis has additional influence. The structure of SBA-15 may be violated by the introduction of long functions, such as ≡Si(CH2)3NHC(=S)NHC2H5. These ethylthiocarbamidepropyl groups can form complexes with metal ions in thiol or thione tautomeric forms. We determined that the 2D hexagonal p6 mm structure is preserved for SBA-15 with thiourea groups at maximal TEOS:trifunctional silane ratio (mol) = 10:2, which was confirmed by TEM and by the presence of an intense reflex in the small-angle region of diffractograms of the final product. It was shown that the obtained sorbents possess high kinetic characteristics. The experimental data fit pseudo-second-order kinetic equation, but the rate constants depend on the content of functional groups in the surface layer. Template Pluronic P-123 defines the porosity of functional mesoporous silica materials even at increasing content of trifunctional silane in the initial solution. Infrared spectroscopy analysis showed that thione form of thiourea ligand is prevalent on the surface of pores of mesoporous samples. However, during the sorption of silver(I) ions, there are both thione and thiol forms on the surface. Thione form is transformed into thiol with increasing concentration of mercury(II) ions in the sorption solution. Adsorption experiments showed that the SBA-15 silicas functionalized with ethylthiocarbamidepropyl groups had high selectivity for silver(I) ions and could concentrate Ag(I) ions from metal ions mixture at pH 2.

Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

Energy Technology Data Exchange (ETDEWEB)

Alyoshina, Nonna A.; Parfenyuk, Elena V., E-mail: evp@iscras.ru

2013-09-15

A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption process of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.

Protein Thiols as an Indication of Oxidative Stress

Directory of Open Access Journals (Sweden)

Yousef Rezaei Chianeh

2014-06-01

Full Text Available Thiol is an organic compound that contain sulphhydryl group that have a critical role in preventing any involvement of oxidative stress in the cell. These defensive functions are generally considered to be carried out by the low molecular weight thiol glutathione and by cysteine residues in the active sites of proteins such as thioredoxin and peroxiredoxin. In addition, there are thiols exposed on protein surfaces that are not directly involved with protein function, although they can interact with the intracellular environment.The process of protection of the cell against an oxidative damage occur by thiol and cystein residue that has a low molecular weight. These residue are present in the active sites of a protein like, peroxiredoxin and thioredoxin. Apart from intracellular antioxidant defense mechanism by protein thiol, there are presence of thiol in outer surface of protein that are not involved with the function of protein, even though they can interact with intracellular part of the cell. [Archives Medical Review Journal 2014; 23(3.000: 443-456

Hydrophobic Coatings by Thiol-Ene Click Functionalization of Silsesquioxanes with Tunable Architecture.

Science.gov (United States)

Dirè, Sandra; Bottone, Davide; Callone, Emanuela; Maniglio, Devid; Génois, Isabelle; Ribot, François

2017-08-08

The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains.

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water

International Nuclear Information System (INIS)

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-01-01

Highlights: ► A novel type of functionalized MOF for heavy metal removal. ► Functionalization of MOF by a facile coordination-based postsynthetic strategy. ► Thiol-functionalization of MOF has been realized for the first time. ► Enhanced removal of Hg 2+ by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu 3 (BTC) 2 (H 2 O) 3 ] n (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu 3 (BTC) 2 ] n samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with –SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N 2 sorption–desorption isothermal. Significantly, the thiol-functionalized [Cu 3 (BTC) 2 ] n exhibited remarkably high adsorption affinity (K d = 4.73 × 10 5 mL g −1 ) and high adsorption capacity (714.29 mg g −1 ) for Hg 2+ adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg 2+ under the same condition.

Differential reactivity of maleimide and bromoacetyl functions with thiols: application to the preparation of liposomal diepitope constructs.

Science.gov (United States)

Schelté, P; Boeckler, C; Frisch, B; Schuber, F

2000-01-01

The comparative reactivity of maleimide and bromoacetyl groups with thiols (2-mercaptoethanol, free cysteine, and cysteine residues present at the N-terminus of peptides) was investigated in aqueous media. These studies were performed (i) with water-soluble functionalized model molecules, i.e., polyoxyethylene-based spacer arms that could also be coupled to lipophilic anchors destined to be incorporated into liposomes, and (ii) with small unilamellar liposomes carrying at their surface these thiol-reactive functions. Our results indicate that an important kinetic discrimination (2-3 orders of magnitude in terms of rate constants) can be achieved between the maleimide and bromoacetyl functions when the reactions with thiols are performed at pH 6.5. The bromoacetyl function which reacts at higher pH values (e.g., pH 9.0) retained a high chemoselectivity; i.e., under conditions where it reacted appreciably with the thiols of, e.g., HS-peptides, it did react with other nucleophilic functions such as alpha- and epsilon-amino groups or imidazole, which could also be present in peptides. This differential reactivity was applied to design chemically defined and highly immunogenic liposomal diepitope constructs as synthetic vaccines, i.e., vesicles carrying at their surface two different peptides conjugated each to a specific amphiphilic anchor. This was realized by coupling sequentially at pH 6.5 and 9.0 two HS-peptides to preformed vesicles containing lipophilic anchors functionalized with maleimide and bromoacetyl groups [Boeckler, C., et al. (1999) Eur. J. Immunol. 29, 2297-2308].

Superhydrophobic and Slippery Lubricant-Infused Flexible Transparent Nanocellulose Films by Photoinduced Thiol-Ene Functionalization.

Science.gov (United States)

Guo, Jiaqi; Fang, Wenwen; Welle, Alexander; Feng, Wenqian; Filpponen, Ilari; Rojas, Orlando J; Levkin, Pavel A

2016-12-14

Films comprising nanofibrillated cellulose (NFC) are suitable substrates for flexible devices in analytical, sensor, diagnostic, and display technologies. However, some major challenges in such developments include their high moisture sensitivity and the complexity of current methods available for functionalization and patterning. In this work, we present a facile process for tailoring the surface wettability and functionality of NFC films by a fast and versatile approach. First, the NFC films were coated with a layer of reactive nanoporous silicone nanofilament by polycondensation of trichlorovinylsilane (TCVS). The TCVS afforded reactive vinyl groups, thereby enabling simple UV-induced functionalization of NFC films with various thiol-containing molecules via the photo "click" thiol-ene reaction. Modification with perfluoroalkyl thiols resulted in robust superhydrophobic surfaces, which could then be further transformed into transparent slippery lubricant-infused NFC films that displayed repellency against both aqueous and organic liquids with surface tensions as low as 18 mN·m -1 . Finally, transparent and flexible NFC films incorporated hydrophilic micropatterns by modification with OH, NH 2 , or COOH surface groups, enabling space-resolved superhydrophobic-hydrophilic domains. Flexibility, transparency, patternability, and perfect superhydrophobicity of the produced nanocellulose substrates warrants their application in biosensing, display protection, and biomedical and diagnostics devices.

Thiol-functionalized silica colloids, grains, and membranes for irreversible adsorption of metal(oxide) nanoparticles

NARCIS (Netherlands)

Claesson, E.M.; Philipse, A.P.

2007-01-01

Thiol-functionalization is described for silica surfaces from diverging origin, including commercial silica nanoparticles and St¨ober silica as well as silica structures provided by porous glasses and novel polymer-templated silica membranes. The functionalization allows in all cases for the

Functional mesoporous silica nanoparticles for bio-imaging applications.

Science.gov (United States)

Cha, Bong Geun; Kim, Jaeyun

2018-03-22

Biomedical investigations using mesoporous silica nanoparticles (MSNs) have received significant attention because of their unique properties including controllable mesoporous structure, high specific surface area, large pore volume, and tunable particle size. These unique features make MSNs suitable for simultaneous diagnosis and therapy with unique advantages to encapsulate and load a variety of therapeutic agents, deliver these agents to the desired location, and release the drugs in a controlled manner. Among various clinical areas, nanomaterials-based bio-imaging techniques have advanced rapidly with the development of diverse functional nanoparticles. Due to the unique features of MSNs, an imaging agent supported by MSNs can be a promising system for developing targeted bio-imaging contrast agents with high structural stability and enhanced functionality that enable imaging of various modalities. Here, we review the recent achievements on the development of functional MSNs for bio-imaging applications, including optical imaging, magnetic resonance imaging (MRI), positron emission tomography (PET), computed tomography (CT), ultrasound imaging, and multimodal imaging for early diagnosis. With further improvement in noninvasive bio-imaging techniques, the MSN-supported imaging agent systems are expected to contribute to clinical applications in the future. This article is categorized under: Diagnostic Tools > In vivo Nanodiagnostics and Imaging Nanotechnology Approaches to Biology > Nanoscale Systems in Biology. © 2018 Wiley Periodicals, Inc.

Designing advanced functional periodic mesoporous organosilicas for biomedical applications

Directory of Open Access Journals (Sweden)

Dolores Esquivel

2014-03-01

Full Text Available Periodic mesoporous organosilicas (PMOs, reported for the first time in 1999, constitute a new branch of organic-inorganic hybrid materials with high-ordered structures, uniform pore size and homogenous distribution of organic bridges into a silica framework. Unlike conventional mesoporous silicas, these materials offer the possibility to adjust the surface (hydrophilicity/hydrophobicity and physical properties (morphology, porosity as well as their mechanical stability through the incorporation of different functional organic moieties in their pore walls. A broad variety of PMOs has been designed for their subsequent application in many fields. More recently, PMOs have attracted growing interest in emerging areas as biology and biomedicine. This review provides a comprehensive overview of the most recent breakthroughs achieved for PMOs in biological and biomedical applications.

Synthesis and Optical Properties of Thiol Functionalized CdSe/ZnS (Core/Shell Quantum Dots by Ligand Exchange

Directory of Open Access Journals (Sweden)

Huaping Zhu

2014-01-01

Full Text Available The colloidal photoluminescent quantum dots (QDs of CdSe (core and CdSe/ZnS (core/shell were synthesized at different temperatures with different growth periods. Optical properties (i.e., UV/Vis spectra and photoluminescent emission spectra of the resulting QDs were investigated. The shell-protected CdSe/ZnS QDs exhibited higher photoluminescent (PL efficiency and stability than their corresponding CdSe core QDs. Ligand exchange with various thiol molecules was performed to replace the initial surface passivation ligands, that is, trioctylphosphine oxide (TOPO and trioctylphosphine (TOP, and the optical properties of the surface-modified QDs were studied. The thiol ligand molecules in this study included 1,4-benzenedimethanethiol, 1,16-hexadecanedithiol, 1,11-undecanedithiol, biphenyl-4,4′-dithiol, 11-mercapto-1-undecanol, and 1,8-octanedithiol. After the thiol functionalization, the CdSe/ZnS QDs exhibited significantly enhanced PL efficiency and storage stability. Besides surface passivation effect, such enhanced performance of thiol-functionalized QDs could be due to cross-linked assembly formation of dimer/trimer clusters, in which QDs are linked by dithiol molecules. Furthermore, effects of ligand concentration, type of ligand, and heating on the thiol stabilization of QDs were also discussed.

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg{sup 2+} from water

Energy Technology Data Exchange (ETDEWEB)

Ke, Fei [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Qiu, Ling-Guang, E-mail: lgqiu@ahu.edu.cn [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Zhu, Jun-Fa [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China)

2011-11-30

Highlights: Black-Right-Pointing-Pointer A novel type of functionalized MOF for heavy metal removal. Black-Right-Pointing-Pointer Functionalization of MOF by a facile coordination-based postsynthetic strategy. Black-Right-Pointing-Pointer Thiol-functionalization of MOF has been realized for the first time. Black-Right-Pointing-Pointer Enhanced removal of Hg{sup 2+} by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu{sub 3}(BTC){sub 2}(H{sub 2}O){sub 3}]{sub n} (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu{sub 3}(BTC){sub 2}]{sub n} samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N{sub 2} sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu{sub 3}(BTC){sub 2}]{sub n} exhibited remarkably high adsorption affinity (K{sub d} = 4.73 Multiplication-Sign 10{sup 5} mL g{sup -1}) and high adsorption capacity (714.29 mg g{sup -1}) for Hg{sup 2+} adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg{sup 2+} under the same condition.

Acid-base equilibria inside amine-functionalized mesoporous silica.

Science.gov (United States)

Yamaguchi, Akira; Namekawa, Manato; Kamijo, Toshio; Itoh, Tetsuji; Teramae, Norio

2011-04-15

Acid-base equilibria and effective proton concentration inside a silica mesopore modified with a trimethyl ammonium (TMAP) layer were studied by steady-state fluorescence experiments. The mesoporous silica with a dense TMAP layer (1.4 molecules/nm(2)) was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at surfactant-templated mesoporous silica (diameter of silica framework =3.1 nm). The resulting TMAP-modified mesoporous silica strongly adsorbed of anionic fluorescence indicator dyes (8-hydroxypyrene-1,3,6-trisulfonate (pyranine), 8-aminopyrene-1,3,6-trisulfonate (APTS), 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid disulfuric acid (TPPS), 2-naphthol-3,6-disulfonate (2NT)) and fluorescence excitation spectra of these dyes within TMAP-modified mesoporous silica were measured by varying the solution pH. The fluorescence experiments revealed that the acid-base equilibrium reactions of all pH indicator dyes within the TMAP-modified silica mesopore were quite different from those in bulk water. From the analysis of the acid-base equilibrium of pyranine, the following relationships between solution pH (pH(bulk)) and the effective proton concentration inside the pore (pH(pore)) were obtained: (1) shift of pH(pore) was 1.8 (ΔpH(pore)=1.8) for the pH(bulk) change from 2.1 to 9.1 (ΔpH(bulk)=7.0); (2) pH(pore) was not simply proportional to pH(bulk); (3) the inside of the TMAP-modified silica mesopore was suggested to be in a weak acidic or neutral condition when pH(bulk) was changed from 2.0 to 9.1. Since these relationships between pH(bulk) and pH(pore) could explain the acid-base equilibria of other pH indicator dyes (APTS, TPPS, 2NT), these relationships were inferred to describe the effective proton concentration inside the TMAP-modified silica mesopore. © 2011 American Chemical Society

Building thiol and metal-thiolate functions into coordination nets: Clues from a simple molecule

International Nuclear Information System (INIS)

He Jun; Yang Chen; Xu Zhengtao; Zeller, Matthias; Hunter, Allen D.; Lin Jianhua

2009-01-01

The simple and easy-to-prepare bifunctional molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid (H 4 DMBD) interacts with the increasingly harder metal ions of Cu + , Pb 2+ and Eu 3+ to form the coordination networks of Cu 6 (DMBD) 3 (en) 4 (Hen) 6 (1), Pb 2 (DMBD)(en) 2 (2) and Eu 2 (H 2 DMBD) 3 (DEF) 4 (3), where the carboxyl and thiol groups bind with distinct preference to the hard and soft metal ions, respectively. Notably, 1 features uncoordinated carboxylate groups and Cu 3 cluster units integrated via the thiolate groups into an extended network with significant interaction between the metal centers and the organic molecules; 2 features a 2D coordination net based on the mercapto and carboxylic groups all bonded to the Pb 2+ ions; 3 features free-standing thiol groups inside the channels of a metal-carboxylate-based network. This study illustrates the rich solid state structural features and potential functions offered by the carboxyl-thiol combination. - Graphical Abstract: Molecule 2,5-dimercapto-1,4-benzenedicarboxylic acid was reacted with Cu + , Pb 2+ and Eu 3+ ions to explore solid state networks with the rich structural features arising from the carboxyl-thiol combination.

Evaluation and Control of Thiol-ene/Thiol-epoxy Hybrid Networks.

Science.gov (United States)

Carioscia, Jacquelyn A; Stansbury, Jeffrey W; Bowman, Christopher N

2007-03-08

The development of thiol-ene/thiol-epoxy hybrid networks offers the advantage of tailorable polymerization kinetics while producing a highly crosslinked, high T(g) polymer that has significantly reduced shrinkage stress. Stoichiometric mixtures of pentaerythritol tetra(3-mercaptopropionate) (PETMP)/triallyl-1,3,5-triazine-2,4,6-trione (TATATO) (thiol-ene, mixture 1) and PETMP/bisphenol a diglycidyl ether (BADGE) (thiol-epoxy, mixture 2) were prepared and hybrid mixtures of 75/25, 50/50, 25/75, and 10/90 w/w of mixtures 1 and 2 were polymerized using a combination of both radical and anionic initiation. The light exposure timing and the relative initiation conditions of the two types were used to control the order and relative rates of the radical and anionic polymerizations. The 50/50 w/w thiol-ene/thiol-epoxy hybrid material exhibited a final stress of only 0.2 MPa, which is 90 % lower than the stress developed in a control dimethacrylate resin. Kinetic analysis indicates composition affects network development in thiol-ene/thiol-epoxy hybrid networks and produces materials with robust mechanical properties.

Evaluation of the influence of sulfur-based functional groups on the embedding of silver nanoparticles into the pores of MCM-41

International Nuclear Information System (INIS)

Oliveira, Roselaine da S.; Camilo, Fernanda F.; Bizeto, Marcos A.

2016-01-01

The incorporation of noble metals in the pores of mesoporous silicas might produce materials with interesting catalytic and sensing capabilities, but the proper control of pore filling and the avoidance of nanoparticles migration to outside the pores are processes not yet completely understood. In this work, we evaluated the role of –SH and –SO_3H groups post-grafted into MCM-41 on the production of silver nanoparticles by using 1-butanol as reducing agent. Thiol groups were the most efficient on promoting the formation of nanoparticles within the pores. Conversely, sulfonic groups establish electrostatic interactions with silver cations that preclude the formation of nanoparticle in yields comparable to thiol groups. MCM-41 without functional groups did not have good affinity to silver and the nanoparticles are produced outside the pores. This study showed the importance on selecting an adequate surface functional group in order to obtain silver nanoparticles filling the pores of MCM-41. - Graphical abstract: Silver nanoparticles formation inside the pores of sulfur-groups functionalized mesoporous silica. - Highlights: • Silver nanoparticles formation inside the pores of mesoporous silica. • n-butanol as reducing agent of impregnated silver cations. • Tuning the silica surface properties by grafting sulfur-based functional groups. • Influence on the loading and distribution of the nanoparticles through the pores.

In situ synthesis of N and Cu functionalized mesoporous FDU-14 resins and carbons for electrochemical hydrogen storage

Energy Technology Data Exchange (ETDEWEB)

Kong, AiGuo; Wang, WenJuan; Yang, Fan; Ding, HanMing; Shan, YongKui [Department of Chemistry, East China Normal University, ShangHai 200062 (China)

2010-07-15

N and Cu cooperatively functionalized mesoporous resin and carbon materials with bicontinuous cubic structure (FDU-14) were obtained by a novel synthesis method. In this method, block copolymers were used as the templates as well as the precursors for the preparation of these modifying mesoporous materials. The CuC{sub 2}O{sub 4} in the channels of mesoporous FDU-14 resins was gotten by in situ oxidation of the templates in a catalytic redox system containing Cu{sup 2+}, Al{sup 3+}, NO{sub 3}{sup -}, PO{sub 4}{sup 3-}, SO{sub 4}{sup 2-} ions. Simultaneously, the phenol-formaldehyde resin frameworks were in situ functionalized by the amine group resulting from the reduction of NO{sub 3}{sup -}, leading to the formation of N and CuC{sub 2}O{sub 4} modified mesoporous FDU-14 resin materials. Its pyrolysis at the different temperatures resulted in the production of N and Cu cooperatively functionalized mesoporous FDU-14 resin and carbon materials. The structure and composition of these materials were characterized by the X-ray power diffraction, transmission electron microscopy, N{sub 2} adsorption-desorption analysis, X-ray photoelectron spectroscopy, infrared spectroscopy, thermogravimetry analysis, and inductive coupled plasma emission spectroscopy. The electrochemical measurement indicated that N and Cu cooperatively functionalized mesoporous FDU-14 carbon materials possessed the enhanced electrochemical hydrogen storage performance. (author)

Fabrication and bonding of thiol-ene-based microfluidic devices

DEFF Research Database (Denmark)

Sikanen, Tiina M; Lafleur, Josiane P.; Moilanen, Maria-Elisa

2013-01-01

In this work, the bonding strength of microchips fabricated by thiol-ene free-radical polymerization was characterized in detail by varying the monomeric thiol/allyl composition from the stoichiometric ratio (1:1) up to 100% excess of thiol (2:1) or allyl (1:2) functional groups. Four different...... properties for each application. Here, a capillary electrophoresis separation is performed to demonstrate the attractive properties of stoichiometric thiol-ene microchips....

Density functional study of a typical thiol tethered on a gold surface: ruptures under normal or parallel stretch

International Nuclear Information System (INIS)

Wang, Guan M; Sandberg, William C; Kenny, Steven D

2006-01-01

The mechanical and dynamical properties of a model Au(111)/thiol surface system were investigated by using localized atomic-type orbital density functional theory in the local density approximation. Relaxing the system gives a configuration where the sulfur atom forms covalent bonds to two adjacent gold atoms as the lowest energy structure. Investigations based on ab initio molecular dynamics simulations at 300, 350 and 370 K show that this tethering system is stable. The rupture behaviour between the thiol and the surface was studied by displacing the free end of the thiol. Calculated energy profiles show a process of multiple successive ruptures that account for experimental observations. The process features successive ruptures of the two Au-S bonds followed by the extraction of one S-bonded Au atom from the surface. The force required to rupture the thiol from the surface was found to be dependent on the direction in which the thiol was displaced, with values comparable with AFM measurements. These results aid the understanding of failure dynamics of Au(111)-thiol-tethered biosurfaces in microfluidic devices where fluidic shear and normal forces are of concern

Alendronate functionalized mesoporous hydroxyapatite nanoparticles for drug delivery

Energy Technology Data Exchange (ETDEWEB)

Li, Dongdong, E-mail: lidongchem@sina.cn [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhu, Yuntao; Liang, Zhiqiang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China)

2013-06-01

Highlights: ► The synthesized mesoporous hydroxyapatite has nanostructure and bioactivity. ► The materials have high surface area and amino group. ► The materials show higher drug loading and slower release rate than pure HAP. - Abstract: Mesoporous nanosized hydroxyapatite (HAP) functionalized by alendronate (ALN) was synthesized using cationic surfactant CTAB as template. The structural, morphological and textural properties were fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and N{sub 2} adsorption/desorption. Then the obtained materials were performed as drug delivery carriers using ibuprofen (IBU) as a model drug to investigate their drug storage/release properties in simulated body fluid (SBF). The materials showed relatively slower release rate compared with HAP due to the ionic interaction between -NH{sub 3}{sup +} on the matrix and -COO{sup −}belongs to IBU. The system provides a new concept for improving the drug loading or slowing down the release rate.

Alendronate functionalized mesoporous hydroxyapatite nanoparticles for drug delivery

International Nuclear Information System (INIS)

Li, Dongdong; Zhu, Yuntao; Liang, Zhiqiang

2013-01-01

Highlights: ► The synthesized mesoporous hydroxyapatite has nanostructure and bioactivity. ► The materials have high surface area and amino group. ► The materials show higher drug loading and slower release rate than pure HAP. - Abstract: Mesoporous nanosized hydroxyapatite (HAP) functionalized by alendronate (ALN) was synthesized using cationic surfactant CTAB as template. The structural, morphological and textural properties were fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and N 2 adsorption/desorption. Then the obtained materials were performed as drug delivery carriers using ibuprofen (IBU) as a model drug to investigate their drug storage/release properties in simulated body fluid (SBF). The materials showed relatively slower release rate compared with HAP due to the ionic interaction between -NH 3 + on the matrix and -COO − belongs to IBU. The system provides a new concept for improving the drug loading or slowing down the release rate

Fluorescent Functionalized Mesoporous Silica for Radioactive Material Extraction

International Nuclear Information System (INIS)

Li, Juan; Zhu, Kake; Shang, Jianying; Wang, Donghai; Nie, Zimin; Guo, Ruisong; Liu, Chongxuan; Wang, Zheming; Li, Xiaolin; Liu, Jun

2012-01-01

Mesoporous silica with covalently bound salicylic acid molecules incorporated in the structure was synthesized with a one-pot, co-condensation reaction at room temperature. The as-synthesized material has a large surface area, uniform particle size, and an ordered pore structure as determined by characterization with transmission electron microscopy, thermal gravimetric analysis, and infrared spectra, etc. Using the strong fluorescence and metal coordination capability of salicylic acid, functionalized mesoporous silica (FMS) was developed to track and extract radionuclide contaminants, such as uranyl (U(VI)) ions encountered in subsurface environments. Adsorption measurements showed a strong affinity of the FMS toward U(VI) with a Kd value of 105 mL/g, which is four orders of magnitude higher than the adsorption of U(VI) onto most of the sediments in natural environments. The new materials have a potential for synergistic environmental monitoring and remediation of the radionuclide U(VI) from contaminated subsurface environments.

Thiol/disulfide redox states in signaling and sensing

Science.gov (United States)

Go, Young-Mi; Jones, Dean P.

2015-01-01

Rapid advances in redox systems biology are creating new opportunities to understand complexities of human disease and contributions of environmental exposures. New understanding of thiol-disulfide systems have occurred during the past decade as a consequence of the discoveries that thiol and disulfide systems are maintained in kinetically controlled steady-states displaced from thermodynamic equilibrium, that a widely distributed family of NADPH oxidases produces oxidants that function in cell signaling, and that a family of peroxiredoxins utilize thioredoxin as a reductant to complement the well-studied glutathione antioxidant system for peroxide elimination and redox regulation. This review focuses on thiol/disulfide redox state in biologic systems and the knowledge base available to support development of integrated redox systems biology models to better understand the function and dysfunction of thiol-disulfide redox systems. In particular, central principles have emerged concerning redox compartmentalization and utility of thiol/disulfide redox measures as indicators of physiologic function. Advances in redox proteomics show that, in addition to functioning in protein active sites and cell signaling, cysteine residues also serve as redox sensors to integrate biologic functions. These advances provide a framework for translation of redox systems biology concepts to practical use in understanding and treating human disease. Biological responses to cadmium, a widespread environmental agent, are used to illustrate the utility of these advances to the understanding of complex pleiotropic toxicities. PMID:23356510

Inhibition of the Vacuolar-like ATPase from Halobacterium saccharovorum by Thiol Reagents: Evidence for Different Functional Thiols

Science.gov (United States)

Hochstein, L. I.; Stanlotter, H.; Emrich, E.; Morrison, David (Technical Monitor)

1994-01-01

N-Ethylmaleimide (NEM) inhibited the vacuolar-like ATPase from Halobacterium saccharovorum (K(sub i) approximately 1 mM) by modifying one or more of the thiols located on the largest of the subunit. ATP protected against inhibition and coincidentally prevented NEM binding which suggested that NEM acts at or near the catalytic site. p-Chloromercuriphenylsulfonate (PCMS) also inhibited this ATPase (K(sub i) approximately 90 microM). ATP did not protect against PCMS inhibition. Dithiothreitol (DTT) partially reversed PCMS inhibition and restored approximately half of the initial activity of 90% inhibited enzyme. DTT did not restore activity of the NEM-inhibited enzyme or the PCMS-inhibited enzyme when it was subsequently incubated with NEM. The failure of ATP to protect against PCMS inhibition and the inability of DTT to restore activity of enzyme incubated in the presence of PCMS and NEM suggests these reagents react with different thiols and that the PCMS-sensitive thiol may have a structural role.

Synthesis of a novel poly-thiolated magnetic nano-platform for heavy metal adsorption. Role of thiol and carboxyl functions

International Nuclear Information System (INIS)

Odio, Oscar F.; Lartundo-Rojas, Luis; Palacios, Elia Guadalupe; Martínez, Ricardo; Reguera, Edilso

2016-01-01

Graphical abstract: Poly-thiols capping of magnetite nanoparticles for Pb(2+) and Cd(2+) adsorption. Display Omitted - Highlights: • A novel magnetic nano-platform containing free thiol and carboxyl groups is reported. • Thiols are protected by disulfide bridges during magnetite functionalization. • Adsorption of Pb"2"+ and Cd"2"+ onto the nano-platform was studied by XPS measurements. • Metal-sulfur interactions dominate if free thiol groups are present. • Metal-carboxyl interactions dominate if thiol groups are depleted by oxidation. - Abstract: We report a novel strategy for the synthesis of magnetic nano-platforms containing free thiol groups. It first involves the synthesis of a poly(acrylic acid) copolymer containing disulfide bridges between the linear chains through di-ester linkages, followed by the anchoring of this new ligand to magnetite nanoparticles using a ligand exchange reaction. Finally, free −SH groups are obtained by treating the resulting disulfide-functionalized magnetic nano-system with tributyl phosphine as reducing agent. The characterization of the resulting 17 nm nanoparticles (Fe_3O_4@PAA-HEDred) by FTIR and TGA confirms the attachment of the copolymer through iron carboxylates. XRD, TEM and magnetic measurements indicate an increase in the inorganic core diameter and the occurrence of strong magnetic inter-particle interactions during the exchange reaction, although coercitivity and remanence drop to near zero at room temperature. Afterwards, Fe_3O_4@PAA-HEDred nanoparticles were tested as sorbent for Pb"2"+ and Cd"2"+ cations in aqueous media. XPS measurements were performed in order to unravel the role of both carboxyl and thiol functions in the adsorption process. For the sake of comparison, the same study was performed using bare Fe_3O_4 nanoparticles and a nanosystem with disulfide groups (Fe_3O_4@DMSA). The joint analysis of the Pb 4f, Cd 3d, Fe 2p and S 2p high resolution spectra for the nanostructured materials

Synthesis of a novel poly-thiolated magnetic nano-platform for heavy metal adsorption. Role of thiol and carboxyl functions

Energy Technology Data Exchange (ETDEWEB)

Odio, Oscar F. [Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, La Habana 10400 (Cuba); Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada-Unidad Legaria, IPN, 11500 México City (Mexico); Lartundo-Rojas, Luis [Centro de Nanociencias y Micro-Nanotecnologías, IPN, 07738 México City (Mexico); Palacios, Elia Guadalupe [Instituto Politécnico Nacional, ESIQIE, UPALM Zacatenco, 07738 México City (Mexico); Martínez, Ricardo [Instituto de Ciencia y Tecnología de Materiales, Universidad de La Habana, La Habana 10400 (Cuba); Reguera, Edilso, E-mail: edilso.reguera@gmail.com [Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada-Unidad Legaria, IPN, 11500 México City (Mexico)

2016-11-15

Graphical abstract: Poly-thiols capping of magnetite nanoparticles for Pb(2+) and Cd(2+) adsorption. Display Omitted - Highlights: • A novel magnetic nano-platform containing free thiol and carboxyl groups is reported. • Thiols are protected by disulfide bridges during magnetite functionalization. • Adsorption of Pb{sup 2+} and Cd{sup 2+} onto the nano-platform was studied by XPS measurements. • Metal-sulfur interactions dominate if free thiol groups are present. • Metal-carboxyl interactions dominate if thiol groups are depleted by oxidation. - Abstract: We report a novel strategy for the synthesis of magnetic nano-platforms containing free thiol groups. It first involves the synthesis of a poly(acrylic acid) copolymer containing disulfide bridges between the linear chains through di-ester linkages, followed by the anchoring of this new ligand to magnetite nanoparticles using a ligand exchange reaction. Finally, free −SH groups are obtained by treating the resulting disulfide-functionalized magnetic nano-system with tributyl phosphine as reducing agent. The characterization of the resulting 17 nm nanoparticles (Fe{sub 3}O{sub 4}@PAA-HEDred) by FTIR and TGA confirms the attachment of the copolymer through iron carboxylates. XRD, TEM and magnetic measurements indicate an increase in the inorganic core diameter and the occurrence of strong magnetic inter-particle interactions during the exchange reaction, although coercitivity and remanence drop to near zero at room temperature. Afterwards, Fe{sub 3}O{sub 4}@PAA-HEDred nanoparticles were tested as sorbent for Pb{sup 2+} and Cd{sup 2+} cations in aqueous media. XPS measurements were performed in order to unravel the role of both carboxyl and thiol functions in the adsorption process. For the sake of comparison, the same study was performed using bare Fe{sub 3}O{sub 4} nanoparticles and a nanosystem with disulfide groups (Fe{sub 3}O{sub 4}@DMSA). The joint analysis of the Pb 4f, Cd 3d, Fe 2p and S 2p high

Synthesis, Characterization, and Catalytic Activity of Pd(II Salen-Functionalized Mesoporous Silica

Directory of Open Access Journals (Sweden)

Rotcharin Sawisai

2017-01-01

Full Text Available Salen ligand synthesized from 2-hydroxybenzaldehyde and 2-hydroxy-1-naphthaldehyde was used as a palladium chelating ligand for the immobilization of the catalytic site. Mesoporous silica supported palladium catalysts were prepared by immobilizing Pd(OAc2 onto a mesoporous silica gel through the coordination of the imine-functionalized mesoporous silica gel. The prepared catalysts were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, energy dispersive X-ray (EDX, inductivity couple plasma (ICP, nitrogen adsorption-desorption, and Fourier transform infrared (FT-IR spectroscopy. The solid catalysts showed higher activity for the hydroamination of C-(tetra-O-acetyl-β-D-galactopyranosylallene with aromatic amines compared with the corresponding homogenous catalyst. The heterogeneous catalytic system can be easily recovered by simple filtration and reused for up to five cycles with no significant loss of catalytic activity.

Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

Science.gov (United States)

Gao, Lin; Sun, Jihong; Li, Yuzhen

2011-08-01

The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N 2 adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation ft= ktn was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties.

Evaluation and Control of Thiol-ene/Thiol-epoxy Hybrid Networks

OpenAIRE

Carioscia, Jacquelyn A.; Stansbury, Jeffrey W.; Bowman, Christopher N.

2007-01-01

The development of thiol-ene/thiol-epoxy hybrid networks offers the advantage of tailorable polymerization kinetics while producing a highly crosslinked, high Tg polymer that has significantly reduced shrinkage stress. Stoichiometric mixtures of pentaerythritol tetra(3-mercaptopropionate) (PETMP)/triallyl-1,3,5-triazine-2,4,6-trione (TATATO) (thiol-ene, mixture 1) and PETMP/bisphenol a diglycidyl ether (BADGE) (thiol-epoxy, mixture 2) were prepared and hybrid mixtures of 75/25, 50/50, 25/75, ...

Functionalized mesoporous silica nanoparticles for stimuli-responsive and targeted

Energy Technology Data Exchange (ETDEWEB)

Knezevic, Nikola [Iowa State Univ., Ames, IA (United States)

2009-12-15

Construction of functional supramolecular nanoassemblies has attracted great deal of attention in recent years for their wide spectrum of practical applications. Mesoporous silica nanoparticles (MSN) in particular were shown to be effective scaffolds for the construction of drug carriers, sensors and catalysts. Herein, we describe the synthesis and characterization of stimuli-responsive, controlled release MSN-based assemblies for drug delivery.

Improved Stabilities of Immobilized Glucoamylase on Functionalized Mesoporous Silica Synthesised using Decane as Swelling Agent

Directory of Open Access Journals (Sweden)

Reni George

2013-06-01

Full Text Available Ordered mesoporous silica, with high porosity was used to immobilize glucoamylase via adsorption and covalent binding. Immobilization of glucoamylase within mesoporous silica was successfully achieved, resulting in catalytically high efficiency during starch hydrolysis. In this study, mesoporous silica was functionalized by co-condensation of tetraethoxysilane (TEOS with organosilane (3-aminopropyl triethoxysilane (APTES in a wide range of molar ratios of APTES: TEOS in the presence of triblock copolymer P123 under acidic hydrothermal conditions. The prepared materials were characterized by Small angle XRD, Nitrogen adsorption – desorption and 29Si MAS solid state NMR. N2 desorption studies showed that pore size distribution decreases due to pore blockage after functionalization and enzyme immobilization. Small angle XRD and 29Si MAS NMR study reveals mesophase formation and Si environment of the materials. The main aim of our work was to study the catalytical activity, effect of pH, temperature storage stability and reusability of covalently bound glucoamylase on mesoporous silica support. The result shows that the stability of enzyme can be enhanced by immobilization.  © 2013 BCREC UNDIP. All rights reservedReceived: 3rd December 2012; Revised: 4th April 2013; Accepted: 20th April 2013[How to Cite: George, R., Gopinath, S., Sugunan, S. (2013. Improved Stabilities of Immobilized Glucoamyl-ase on Functionalized Mesoporous Silica Synthesized using Decane as Swelling Agent. Bulletin of Chemical Reaction Engineering & Catalysis, 8 (1: 70-76. (doi:10.9767/bcrec.8.1.4208.70-76][Permalink/DOI: http://dx.doi.org/10.9767/bcrec.8.1.4208.70-76] | View in  |

Adsorption and Recovery of Polyphenolic Flavonoids Using TiO_2-Functionalized Mesoporous Silica Nanoparticles

International Nuclear Information System (INIS)

Khan, M. Arif; Wallace, William T.; Islam, Syed Z.; Nagpure, Suraj; Strzalka, Joseph

2017-01-01

Exploiting specific interactions with titania (TiO_2) has been proposed for the separation and recovery of a broad range of biomolecules and natural products, including therapeutic polyphenolic flavonoids which are susceptible to degradation, such as quercetin. Functionalizing mesoporous silica with TiO_2 has many potential advantages over bulk and mesoporous TiO_2 as an adsorbent for natural products, including robust synthetic approaches leading to high surface area, stable separation platforms. Here, TiO_2 surface functionalized mesoporous silica nanoparticles (MSNPs) are synthesized and characterized as a function of TiO_2 content (up to 636 mg TiO2/g). The adsorption isotherms of two polyphenolic flavonoids, quercetin and rutin, were determined (0.05-10 mg/ml in ethanol), and a 100-fold increase in the adsorption capacity was observed relative to functionalized nonporous particles with similar TiO_2 surface coverage. An optimum extent of functionalization (approximately 440 mg TiO_2/g particles) is interpreted from characterization techniques including grazing incidence x-ray scattering (GIXS), high resolution transmission electron microscopy (HRTEM) and nitrogen adsorption, which examined the interplay between the extent of TiO_2 functionalization and the accessibility of the porous structures. The recovery of flavonoids is demonstrated using ligand displacement in ethanolic citric acid solution (20% w/v), in which greater than 90% recovery can be achieved in a multistep extraction process. The radical scavenging activity (RSA) of the recovered and particle-bound quercetin as measured by 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging assay demonstrates greater than 80% retention of antioxidant activity by both particle-bound and recovered quercetin. In conclusion, these mesoporous titanosilicate materials can serve as a synthetic platform to isolate, recover, and potentially deliver degradation-sensitive natural products to biological systems.

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template

KAUST Repository

Zhu, Jie

2014-02-12

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules. © 2014 American Chemical Society.

Noncompetitive and Competitive Adsorption of Heavy Metals in Sulfur-Functionalized Ordered Mesoporous Carbon.

Science.gov (United States)

Saha, Dipendu; Barakat, Soukaina; Van Bramer, Scott E; Nelson, Karl A; Hensley, Dale K; Chen, Jihua

2016-12-14

In this work, sulfur-functionalized ordered mesoporous carbons were synthesized by activating the soft-templated mesoporous carbons with sulfur bearing salts that simultaneously enhanced the surface area and introduced sulfur functionalities onto the parent carbon surface. XPS analysis showed that sulfur content within the mesoporous carbons were between 8.2% and 12.9%. The sulfur functionalities include C-S, C═S, -COS, and SO x . SEM images confirmed the ordered mesoporosity within the material. The BET surface areas of the sulfur-functionalized ordered mesoporous carbons range from 837 to 2865 m 2 /g with total pore volume of 0.71-2.3 cm 3 /g. The carbon with highest sulfur functionality was examined for aqueous phase adsorption of mercury (as HgCl 2 ), lead (as Pb(NO 3 ) 2 ), cadmium (as CdCl 2 ), and nickel (as NiCl 2 ) ions in both noncompetitive and competitive mode. Under noncompetitive mode and at a pH greater than 7.0 the affinity of sulfur-functionalized carbons toward heavy metals were in the order of Hg > Pb > Cd > Ni. At lower pH, the adsorbent switched its affinity between Pb and Cd. In the noncompetitive mode, Hg and Pb adsorption showed a strong pH dependency whereas Cd and Ni adsorption did not demonstrate a significant influence of pH. The distribution coefficient for noncompetitive adsorption was in the range of 2448-4000 mL/g for Hg, 290-1990 mL/g for Pb, 550-560 mL/g for Cd, and 115-147 for Ni. The kinetics of adsorption suggested a pseudo-second-order model fits better than other models for all the metals. XPS analysis of metal-adsorption carbons suggested that 7-8% of the adsorbed Hg was converted to HgSO 4 , 14% and 2% of Pb was converted to PbSO 4 and PbS/PbO, respectively, and 5% Cd was converted to CdSO 4 . Ni was below the detection limit for XPS. Overall results suggested these carbon materials might be useful for the separation of heavy metals.

Thermo-responsive polymer-functionalized mesoporous carbon for controlled drug release

Energy Technology Data Exchange (ETDEWEB)

Zhu Shenmin, E-mail: smzhu@sjtu.edu.cn [State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Chen Chenxin [State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China); Chen Zhixin [Faculty of Engineering, University of Wollongong, Wollongong, NSW 2522 (Australia); Liu Xinye; Li Yao; Shi Yang; Zhang Di [State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240 (China)

2011-03-15

Research highlights: {yields} A responsive drug delivery system based on poly(N-isopropyl acrylamide) (PNIPAM) functionalized ordered mesoporous carbon (CMK-3) is developed. {yields} A combination of surface modification of CMK-3 and in situ internal polymerization of PNIPAM was used. {yields} The system exhibited a pronounced transition at around 20-25 deg. C. - Abstract: A novel responsive drug delivery system based on poly(N-isopropyl acrylamide) (PNIPAM) functionalized ordered mesoporous carbon (CMK-3) is developed. The polymer-functionalized CMK-3 was obtained by a combination of simple surface modification of CMK-3 and in situ internal polymerization of PNIPAM. The formation of the PNIPAM inside the CMK-3 was confirmed by thermal gravimetric analysis, Fourier transform-infrared spectroscopy, scanning and transmission electron microscopy and N{sub 2} adsorption/desorption measurements. Controlled drug release tests through the porous network of the PNIPAM functionalized CMK-3 were carried out by measuring the uptake and release of ibuprofen in vitro. The release profiles exhibited a pronounced transition at around 20-25 deg. C. This thermo-sensitive release property of this delivery system was further confirmed by temperature-variable hydrogen nuclear magnetic resonance analysis. The internal PNIPAM layers acted as a storage gate as well as a release switch in response to the stimuli of environment.

Quantification of thiols and disulfides

DEFF Research Database (Denmark)

Winther, Jakob R.; Thorpe, Colin

2014-01-01

lengths to regulate thiol-disulfide bond homeostasis, typically with several, apparently redundant, systems working in parallel. Dissecting the extent of oxidation and reduction of disulfides is an ongoing challenge due, in part, to the facility of thiol/disulfide exchange reactions.......Disulfide bond formation is a key posttranslational modification, with implications for structure, function and stability of numerous proteins. While disulfide bond formation is a necessary and essential process for many proteins, it is deleterious and disruptive for others. Cells go to great...

Total Thiols: Biomedical Importance And Their Alteration In Various Disorders

Directory of Open Access Journals (Sweden)

Mungli Prakash

2009-09-01

Full Text Available Thiols are the organic compounds that contain a sulphydryl group. Among all the antioxidants that are available in the body, thiols constitute the major portion of the total body antioxidants and they play a significant role in defense against reactive oxygen species. Total thiols composed of both intracellular and extracellular thiols either in the free form as oxidized or reduced glutathione, or thiols bound to proteins. Among the thiols that are bound to proteins, albumin makes the major portion of the protein bound thiols, which binds to sufhydryl group at its cysteine-34 portion. Apart from their role in defense against free radicals, thiols share significant role in detoxification, signal transduction, apoptosis and various other functions at molecular level. The thiol status in the body can be assessed easily by determining the serum levels of thiols. Decreased levels of thiols has been noted in various medical disorders including chronic renal failure and other disorders related to kidney, cardiovascular disorders, stroke and other neurological disorders, diabetes mellitus, alcoholic cirrhosis and various other disorders. Therapy using thiols has been under investigation for certain disorders.

Functionalized magnetic mesoporous silica nanoparticles for U removal from low and high pH groundwater

Energy Technology Data Exchange (ETDEWEB)

Li, Dien, E-mail: dien.li@srs.gov [Savannah River National Laboratory, Aiken, SC 29808 (United States); Egodawatte, Shani [Department of Chemistry, University of Iowa, Iowa City, IA 52242 (United States); Kaplan, Daniel I. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Larsen, Sarah C. [Department of Chemistry, University of Iowa, Iowa City, IA 52242 (United States); Serkiz, Steven M. [Savannah River National Laboratory, Aiken, SC 29808 (United States); Department of Physics and Astronomy, Clemson University, Clemson, SC 29634 (United States); Seaman, John C. [Savannah River Ecology Laboratory, University of Georgia, Aiken, SC 29802 (United States)

2016-11-05

Highlights: • Magnetic mesoporous silica nanoparticles were functionalized with organic molecules. • The functionalized nanoparticles had high surface areas and consistent pore sizes. • The functionalized nanoparticles were easily separated due to their magnetism. • They exhibited high capacity for uranium removal from low- or high-pH groundwater. - Abstract: U(VI) species display limited adsorption onto sediment minerals and synthetic sorbents in pH <4 or pH >8 groundwater. In this work, magnetic mesoporous silica nanoparticles (MMSNs) with magnetite nanoparticle cores were functionalized with various organic molecules using post-synthetic methods. The functionalized MMSNs were characterized using N{sub 2} adsorption-desorption isotherms, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), {sup 13}C cross polarization and magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, and powder X-ray diffraction (XRD), which indicated that mesoporous silica (MCM-41) particles of 100–200 nm formed around a core of magnetic iron oxide, and the functional groups were primarily grafted into the mesopores of ∼3.0 nm in size. The functionalized MMSNs were effective for U removal from pH 3.5 and 9.6 artificial groundwater (AGW). Functionalized MMSNs removed U from the pH 3.5 AGW by as much as 6 orders of magnitude more than unfunctionalized nanoparticles or silica and had adsorption capacities as high as 38 mg/g. They removed U from the pH 9.6 AGW as much as 4 orders of magnitude greater than silica and 2 orders of magnitude greater than the unfunctionalized nanoparticles with adsorption capacities as high as 133 mg/g. These results provide an applied solution for treating U contamination that occurs at extreme pH environments and a scientific foundation for solving critical industrial issues related to environmental stewardship and nuclear power production.

Atomistic simulations of thiol-terminated modifiers for hybrid photovoltaic interfaces

International Nuclear Information System (INIS)

Malloci, G.; Petrozza, A.; Mattoni, A.

2014-01-01

Small aromatic molecules such as benzene or pyridine derivatives are often used as interface modifiers (IMs) at polymer/metal oxide hybrid interfaces. We performed a theoretical investigation on prototypical thiol-terminated IMs aimed at improving the photovoltaic performances of poly(3-hexylthiophene)/TiO 2 devices. By means of first-principles calculations in the framework of the density functional theory we investigate 3-furanthiol (3FT), 4-mercaptobenzoicacid (4MB), and 6-isoquinolinethiol (6QT) molecules. We discuss the role of these molecules as modifiers alternative to 4-mercaptopyridine (4MP) which has recently shown to induce a large improvement in the overall power conversion efficiency of mesoporous films of TiO 2 infiltrated by poly(3-hexylthiophene). The IMs investigated are expected to keep the beneficial features of 4MP giving at the same time the possibility to further tune the interlayer properties (e.g., its thickness, stability, and density). Dense interlayers of 6QT turn out to be slightly unstable since the titania substrate induces a compressive strain in the molecular film. On the contrary, we predict very stable films for both 3FT and 4MB molecules, which makes them interesting candidates for future experimental investigations. - Highlights: • We performed a theoretical investigation on thiol-terminated interface modifiers. • We investigate 3-furanthiol (3FT), 4-mercaptobenzoicacid (4MB), and 6-isoquinolinethiol molecules. • We discuss the role of these molecules as modifiers alternative to 4-mercaptopyridine. • Dense interlayers of 6-isoquinolinethiol turn out to be slightly unstable. • We predict very stable self-assembled thin-films for both 3FT and 4MB molecules

Selective oxidation of cyclohexene through gold functionalized silica monolith microreactors

Science.gov (United States)

Alotaibi, Mohammed T.; Taylor, Martin J.; Liu, Dan; Beaumont, Simon K.; Kyriakou, Georgios

2016-04-01

Two simple, reproducible methods of preparing evenly distributed Au nanoparticle containing mesoporous silica monoliths are investigated. These Au nanoparticle containing monoliths are subsequently investigated as flow reactors for the selective oxidation of cyclohexene. In the first strategy, the silica monolith was directly impregnated with Au nanoparticles during the formation of the monolith. The second approach was to pre-functionalize the monolith with thiol groups tethered within the silica mesostructure. These can act as evenly distributed anchors for the Au nanoparticles to be incorporated by flowing a Au nanoparticle solution through the thiol functionalized monolith. Both methods led to successfully achieving even distribution of Au nanoparticles along the length of the monolith as demonstrated by ICP-OES. However, the impregnation method led to strong agglomeration of the Au nanoparticles during subsequent heating steps while the thiol anchoring procedure maintained the nanoparticles in the range of 6.8 ± 1.4 nm. Both Au nanoparticle containing monoliths as well as samples with no Au incorporated were tested for the selective oxidation of cyclohexene under constant flow at 30 °C. The Au free materials were found to be catalytically inactive with Au being the minimum necessary requirement for the reaction to proceed. The impregnated Au-containing monolith was found to be less active than the thiol functionalized Au-containing material, attributable to the low metal surface area of the Au nanoparticles. The reaction on the thiol functionalized Au-containing monolith was found to depend strongly on the type of oxidant used: tert-butyl hydroperoxide (TBHP) was more active than H2O2, likely due to the thiol induced hydrophobicity in the monolith.

Thiol functionalized polymethacrylic acid-based hydrogel microparticles for oral insulin delivery.

Science.gov (United States)

Sajeesh, S; Vauthier, C; Gueutin, C; Ponchel, G; Sharma, Chandra P

2010-08-01

In the present study thiol functionalized polymethacrylic acid-polyethylene glycol-chitosan (PCP)-based hydrogel microparticles were utilized to develop an oral insulin delivery system. Thiol modification was achieved by grafting cysteine to the activated surface carboxyl groups of PCP hydrogels (Cys-PCP). Swelling and insulin loading/release experiments were conducted on these particles. The ability of these particles to inhibit protease enzymes was evaluated under in vitro experimental conditions. Insulin transport experiments were performed on Caco-2 cell monolayers and excised intestinal tissue with an Ussing chamber set-up. Finally, the efficacy of insulin-loaded particles in reducing the blood glucose level in streptozotocin-induced diabetic rats was investigated. Thiolated hydrogel microparticles showed less swelling and had a lower insulin encapsulation efficiency as compared with unmodified PCP particles. PCP and Cys-PCP microparticles were able to inhibit protease enzymes under in vitro conditions. Thiolation was an effective strategy to improve insulin absorption across Caco-2 cell monolayers, however, the effect was reduced in the experiments using excised rat intestinal tissue. Nevertheless, functionalized microparticles were more effective in eliciting a pharmacological response in diabetic animal, as compared with unmodified PCP microparticles. From these studies thiolation of hydrogel microparticles seems to be a promising approach to improve oral delivery of proteins/peptides. Copyright 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

Science.gov (United States)

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-11-30

The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright © 2011 Elsevier B.V. All rights reserved.

Preparation and Preliminary Dielectric Characterization of Structured C60-Thiol-Ene Polymer Nanocomposites Assembled Using the Thiol-Ene Click Reaction

Directory of Open Access Journals (Sweden)

Hanaa M. Ahmed

2015-11-01

Full Text Available Fullerene-containing materials have the ability to store and release electrical energy. Therefore, fullerenes may ultimately find use in high-voltage equipment devices or as super capacitors for high electric energy storage due to this ease of manipulating their excellent dielectric properties and their high volume resistivity. A series of structured fullerene (C60 polymer nanocomposites were assembled using the thiol-ene click reaction, between alkyl thiols and allyl functionalized C60 derivatives. The resulting high-density C60-urethane-thiol-ene (C60-Thiol-Ene networks possessed excellent mechanical properties. These novel networks were characterized using standard techniques, including infrared spectroscopy (FTIR, differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, and thermal gravimetric analysis (TGA. The dielectric spectra for the prepared samples were determined over a broad frequency range at room temperature using a broadband dielectric spectrometer and a semiconductor characterization system. The changes in thermo-mechanical and electrical properties of these novel fullerene-thiol-ene composite films were measured as a function of the C60 content, and samples characterized by high dielectric permittivity and low dielectric loss were produced. In this process, variations in chemical composition of the networks were correlated to performance characteristics.

Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

International Nuclear Information System (INIS)

Gao Lin; Sun Jihong; Li Yuzhen

2011-01-01

The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N 2 adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation f t =kt n was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties. - Graphical abstract: Loading (A) and release profiles (B) of aspirin in N-BMMs and N-MCM-41 indicated that BMMs have more drug loading capacity and faster release rate than that MCM-41. Highlights: → Bimodal mesoporous silicas (BMMs) and MCM-41 modified with amino group via post-treatment procedure. → Loading and release profiles of aspirin in modified BMMs and MCM-41. → Modified BMMs have more drug loading capacity and faster release rate than that modified MCM-41.

Investigations of thiol-modified phenol derivatives for the use in thiol-ene photopolymerizations.

Science.gov (United States)

Reinelt, Sebastian; Tabatabai, Monir; Fischer, Urs Karl; Moszner, Norbert; Utterodt, Andreas; Ritter, Helmut

2014-01-01

Thiol-ene photopolymerizations gain a growing interest in academic research. Coatings and dental restoratives are interesting applications for thiol-ene photopolymerizations due to their unique features. In most studies the relative flexible and hydrophilic ester derivative, namely pentaerythritoltetra(3-mercaptopropionate) (PETMP), is investigated as the thiol component. Thus, in the present study we are encouraged to investigate the performance of more hydrophobic ester-free thiol-modified bis- and trisphenol derivatives in thiol-ene photopolymerizations. For this, six different thiol-modified bis- and trisphenol derivatives exhibiting four to six thiol groups are synthesized via the radical addition of thioacetic acid to suitable allyl-modified precursors and subsequent hydrolysis. Compared to PETMP better flexural strength and modulus of elasticity are achievable in thiol-ene photopolymerizations employing 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) as the ene derivative. Especially, after storage in water, the flexural strength and modulus of elasticity is twice as high compared to the PETMP reference system.

New strategy for surface functionalization of periodic mesoporous silica based on meso-HSiO1.5.

Science.gov (United States)

Xie, Zhuoying; Bai, Ling; Huang, Suwen; Zhu, Cun; Zhao, Yuanjin; Gu, Zhong-Ze

2014-01-29

Organic functionalization of periodic mesoporous silicas (PMSs) offers a way to improve their excellent properties and wide applications owing to their structural superiority. In this study, a new strategy for organic functionalization of PMSs is demonstrated by hydrosilylation of the recently discovered "impossible" periodic mesoporous hydridosilica, meso-HSiO1.5. This method overcomes the disadvantages of present pathways for organic functionalization of PMSs with organosilica. Moreover, compared to the traditional functionalization on the surface of porous silicon by hydrosilylation, the template-synthesized meso-HSiO1.5 is more flexible to access functional-groups-loaded PMSs with adjustable microstructures. The new method and materials will have wider applications based on both the structure and surface superiorities.

Preparation, characterization and photocatalytic applications of amine-functionalized mesoporous silica impregnated with transition-metal-monosubstituted polyoxometalates

International Nuclear Information System (INIS)

Li Li; Liu, Chunming; Geng Aifang; Jiang Chunjie; Guo Yihang; Hu Changwen

2006-01-01

Amine-functionalized mesoporous silica materials impregnated with transition-metal-monosubstituted polyoxometalates, K 5 [M(H 2 O)PW 11 O 39 ]-(EtO) 3 SiCH 2 CH 2 CH 2 NH 2 -MCM-48 (M = Co/Ni), were prepared by coordination of nickel/cobalt centers in the clusters with the amine surface groups in amine-functionalized mesoporous silica supports. The materials obtained were characterized by powder X-ray diffraction (XRD), UV-vis diffuse reflectance spectra (UV-vis-DR), infrared (IR) spectra, magic-angle spinning 31 P MAS NMR, transmission electron microscopy (TEM) and nitrogen adsorption measurements, indicating that the primary Keggin structures remained intact in as-prepared composites, and the composites possessed mesoporous structures. The composites exhibited UV-photocatalytic activity to degrade dye rhodamine B (RB), and the pesticides including hexachlorobenzene (HCB) and methylparathion (MPT). Leakage of K 5 [M(H 2 O)PW 11 O 39 ] from the support was hardly observed during the photocatalytic tests, attributed to strong coordination interactions between the Keggin units and the amine-functionalized silica surface. -- Graphical abstract: The K 5 [M(H 2 O)PW 11 O 39 ]-(EtO) 3 SiCH 2 CH 2 CH 2 NH 2 -SiO 2 composites were prepared by coordination of M centers in the Keggin units with the amine surface groups in amine-functionalized mesoporous silica supports, and the composites exhibited photocatalytic activity to degrade aqueous rhodamine B, hexachlorobenzene and methyl parathion

Role of thiols in cellular response to radiation and drugs. Symposium: thiols

International Nuclear Information System (INIS)

Biaglow, J.E.; Varnes, M.E.; Clark, E.P.; Epp, E.R.

1983-01-01

Cellular nonprotein thiols (NPSH) consist of glutathione (GSH) and other low molecular weight species such as cysteine, cysteamine, and coenzyme. A GSH is usually less than the total cellular NPSH, and with thiol reactive agents, such as diethyl maleate (DEM), its rate of depletion is in part dependent upon the cellular capacity for its resynthesis. If resynthesis is blocked by buthionine-S,R-sulfoximine(BSO), the NPSH, including GSH, is depleted more rapidly, Cellular thiol depletion by diamide, N-ethylmaleimide, and BSO may render oxygenated cells more sensitive to radiation. These cells may or may not show a reduction in the oxygen enhancement ratio (OER). Human A549 lung carcinoma cells depleted of their NPSH either by prolonged culture or by BSO treatment do not show a reduced OER but do show increased aerobic responses to radiation. Other nitrocompounds, such as misonidazole, are activated under hypoxic conditions to radical intermediates. When cellular thiols are depleted peroxide is formed. Under hypoxic conditions thiols are depleted because metabolically reduced intermediates react with GSH instead of oxygen. Thiol depletion, under hypoxic conditions, may be the reason that misonidazole and other nitrocompounds show an extra enhancement ratio with hypoxic cells. Thiol depletion by DEM or BSO alters the radiation response of hypoxic cells to misonidazole. In conclusion, we propose an altered thiol model which includes a mechanism for thiol involvement in the aerobic radiation response of cells

A periodic mixed gaussians-plane waves DFT study on simple thiols on Au(111): adsorbate species, surface reconstruction, and thiols functionalization.

Science.gov (United States)

Rajaraman, Gopalan; Caneschi, Andrea; Gatteschi, Dante; Totti, Federico

2011-03-07

Here we present DFT calculations based on a periodic mixed gaussians/plane waves approach to study the energetics, structure, bonding of SAMs of simple thiols on Au(111). Several open issues such as structure, bonding and the nature of adsorbate are taken into account. We started with methyl thiols (MeSH) on Au(111) to establish the nature of the adsorbate. We have considered several structural models embracing the reconstructed surface scenario along with the MeS˙-Au(ad)-MeS˙ type motif put forward in recent years. Our calculations suggest a clear preference for the homolytic cleavage of the S-H bond leading to a stable MeS˙ on a gold surface. In agreement with the recent literature studies, the reconstructed models of the MeS˙ species are found to be energetically preferred over unreconstructed models. Besides, our calculations reveal that the model with 1:2 Au(ad)/thiols ratio, i.e. MeS˙-Au(ad)-MeS˙, is energetically preferred compared to the clean and 1:1 ratio models, in agreement with the experimental and theoretical evidences. We have also performed Molecular Orbital/Natural Bond Orbital, MO/NBO, analysis to understand the electronic structure and bonding in different structural motifs and many useful insights have been gained. Finally, the studies have then been extended to alkyl thiols of the RSR' (R, R' = Me, Et and Ph) type and here our calculations again reveal a preference for the RS˙ type species adsorption for clean as well as for reconstructed 1:2 Au(ad)/thiols ratio models.

Amine functionalized cubic mesoporous silica nanoparticles as an oral delivery system for curcumin bioavailability enhancement

Science.gov (United States)

Budi Hartono, Sandy; Hadisoewignyo, Lannie; Yang, Yanan; Meka, Anand Kumar; Antaresti; Yu, Chengzhong

2016-12-01

In the present work, a simple method was used to develop composite curcumin-amine functionalized mesoporous silica nanoparticles (MSN). The nanoparticles were used to improve the bioavailability of curcumin in mice through oral administration. We investigated the effect of particle size on the release profile, solubility and oral bioavailability of curcumin in mice, including amine functionalized mesoporous silica micron-sized-particles (MSM) and MSN (100-200 nm). Curcumin loaded within amine functionalized MSN (MSN-A-Cur) had a better release profile and a higher solubility compared to amine MSM (MSM-A-Cur). The bioavailability of MSN-A-Cur and MSM-A-Cur was considerably higher than that of ‘free curcumin’. These results indicate promising features of amine functionalized MSN as a carrier to deliver low solubility drugs with improved bioavailability via the oral route.

Fabrication and bonding of thiol-ene-based microfluidic devices

International Nuclear Information System (INIS)

Sikanen, Tiina M; Moilanen, Maria-Elisa; Lafleur, Josiane P; Zhuang, Guisheng; Jensen, Thomas G; Kutter, Jörg P

2013-01-01

In this work, the bonding strength of microchips fabricated by thiol-ene free-radical polymerization was characterized in detail by varying the monomeric thiol/allyl composition from the stoichiometric ratio (1:1) up to 100% excess of thiol (2:1) or allyl (1:2) functional groups. Four different thiol-ene to thiol-ene bonding combinations were tested by bonding: (i) two stoichiometric layers, (ii) two layers bearing complementary excess of thiols and allyls, (iii) two layers both bearing excess of thiols, or (iv) two layers both bearing excess of allyls. The results showed that the stiffness of the cross-linked polymer plays the most crucial role regarding the bonding strength. The most rigid polymer layers were obtained by using the stoichiometric composition or an excess of allyls, and thus, the bonding combinations (i) and (iv) withstood the highest pressures (up to the cut-off value of 6 bar). On the other hand, excess of thiol monomers yielded more elastic polymer layers and thus decreased the pressure tolerance for bonding combinations (ii) and (iii). By using monomers with more thiol groups (e.g. tetrathiol versus trithiol), a higher cross-linking ratio, and thus, greater stiffness was obtained. Surface characterization by infrared spectroscopy confirmed that the changes in the monomeric thiol/allyl composition were also reflected in the surface chemistry. The flexibility of being able to bond different types of thiol-enes together allows for tuning of the surface chemistry to yield the desired properties for each application. Here, a capillary electrophoresis separation is performed to demonstrate the attractive properties of stoichiometric thiol-ene microchips. (technical note)

Synthesis, characterization, and application of surface-functionalized ordered mesoporous nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Chung, Po-Wen [Iowa State Univ., Ames, IA (United States)

2009-01-01

The dissertation begins with Chapter 1, which is a general introduction of the fundamental synthesis of mesoporous silica materials, the selective functionlization of mesoporous silica materials, and the synthesis of nanostructured porous materials via nanocasting. In Chapter 2, the thermo-responsive polymer coated mesoporous silica nanoparticles (MSN) was synthesized via surface-initated polymerization and exhibited unique partition activities in a biphasic solution with the thermally induced change. In Chapter 3, the monodispersed spherical MSN with different mesoporous structure (MCM-48) was developed and employed as a template for the synthesis of mesoporous carbon nanoparticles (MCN) via nanocasting. MCN was demonstrated for the delivery of membrane impermeable chemical agents inside the cells. The cellular uptake efficiency and biocompabtibility of MCN with human cervical cancer cells were also investigated. In addition to the biocompabtibility of MCN, MCN was demonstrated to support Rh-Mn nanoparticles for catalytic reaction in Chapter 4. Owing to the unique mesoporosity, Rh-Mn nanoparticles can be well distributed inside the mesoporous structure and exhibited interesting catalytic performance on CO hydrogenation. In Chapter 5, the synthesis route of the aforementioned MCM-48 MSN was discussed and investigated in details and other metal oxide nanoparticles were also developed via nanocasting by using MCM-48 MSN as a template. At last, there is a general conclusion summarized in Chapter 6.

High efficiency nanocomposite sorbents for CO2 capture based on amine-functionalized mesoporous capsules

KAUST Repository

Qi, Genggeng; Wang, Yanbing; Estevez, Luis; Duan, Xiaonan; Anako, Nkechi; Park, Ah-Hyung Alissa; Li, Wen; Jones, Christopher W.; Giannelis, Emmanuel P.

2011-01-01

A novel high efficiency nanocomposite sorbent for CO2 capture has been developed based on oligomeric amine (polyethylenimine, PEI, and tetraethylenepentamine, TEPA) functionalized mesoporous silica capsules. The newly synthesized sorbents exhibit extraordinary capture capacity up to 7.9 mmol g-1 under simulated flue gas conditions (pre-humidified 10% CO 2). The CO2 capture kinetics were found to be fast and reached 90% of the total capacities within the first few minutes. The effects of the mesoporous capsule features such as particle size and shell thickness on CO2 capture capacity were investigated. Larger particle size, higher interior void volume and thinner mesoporous shell thickness all improved the CO2 capacity of the sorbents. PEI impregnated sorbents showed good reversibility and stability during cyclic adsorption-regeneration tests (50 cycles). © 2011 The Royal Society of Chemistry.

Functional Carbon Nanotube/Mesoporous Carbon/MnO2 Hybrid Network for High-Performance Supercapacitors

Directory of Open Access Journals (Sweden)

Tao Tao

2014-01-01

Full Text Available A functional carbon nanotube/mesoporous carbon/MnO2 hybrid network has been developed successfully through a facile route. The resulting composites exhibited a high specific capacitance of 351 F/g at 1 A g−1, with intriguing charge/discharge rate performance and cycling stability due to a synergistic combination of large surface area and excellent electron-transport capabilities of MnO2 with the good conductivity of the carbon nanotube/mesoporous carbon networks. Such composite shows great potential to be used as electrodes for supercapacitors.

Thiol/disulphide homeostasis in celiac disease

Science.gov (United States)

Kaplan, Mustafa; Ates, Ihsan; Yuksel, Mahmut; Ozderin Ozin, Yasemin; Alisik, Murat; Erel, Ozcan; Kayacetin, Ertugrul

2017-01-01

AIM To determine dynamic thiol/disulphide homeostasis in celiac disease and to examine the associate with celiac autoantibodies and gluten-free diet. METHODS Seventy three patients with celiac disease and 73 healthy volunteers were enrolled in the study. In both groups, thiol/disulphide homeostasis was examined with a new colorimetric method recently developed by Erel and Neselioglu. RESULTS In patients with celiac disease, native thiol (P = 0.027) and total thiol (P = 0.031) levels were lower, while disulphide (P < 0.001) level, disulphide/native thiol (P < 0.001) and disulphide/total thiol (P < 0.001) ratios were higher compared to the control group. In patients who do not comply with a gluten-free diet, disulphide/native thiol ratio was found higher compared to the patients who comply with the diet (P < 0.001). In patients with any autoantibody-positive, disulphide/native thiol ratio was observed higher compared to the patients with autoantibody-negative (P < 0.05). It is found that there is a negative correlation between celiac autoantibodies, and native thiol, total thiol levels and native thiol/total thiol ratio, while a positive correlation is observed between disulphide, disulphide/native thiol and disulphide/total thiol levels. CONCLUSION This study is first in the literature which found that the patients with celiac disease the dynamic thiol/disulphide balance shifts through disulphide form compared to the control group. PMID:28533921

Tailoring of the Nanotexture of Mesoporous Silica Films and their Functionalized Derivatives for Selectively Harvesting Low Molecular Weight Protein

Science.gov (United States)

Hu, Ye; Bouamrani, Ali; Tasciotti, Ennio; Li, Li; Liu, Xuewu; Ferrari, Mauro

2010-01-01

We present a fast, efficient and reliable system based on mesoporous silica chips to specifically fractionate and enrich the low molecular weight proteome. Mesoporous silica thin films with tunable features at the nanoscale were fabricated using the triblock copolymer template pathway. Using different templates and concentrations in the precursor solution, various pore size distributions, pore structures and connectivity were obtained and applied for selective recovery of low mass proteins. In combination with mass spectrometry and statistic analysis, we demonstrated the correlation between the nanophase characteristics of the mesoporous silica thin films and the specificity and efficacy of low mass proteome harvesting. In addition, to overcome the limitations of the pre-functionalization method in polymer selection, plasma ashing was used for the first time for the treatment of the mesoporous silica surface prior to chemical modification. Surface charge modifications by different functional groups resulted in a selective capture of the low molecular weight proteins from serum sample. In conclusion our study demonstrates that the ability to tune the physico-chemical properties of mesoporous silica surfaces, for a selective enrichment of the low molecular weight proteome from complex biological fluids, has the potential to promote proteomic biomarker discovery. PMID:20014864

Reversible inactivation of CO dehydrogenase with thiol compounds

Energy Technology Data Exchange (ETDEWEB)

Kreß, Oliver [Department of Microbiology, University of Bayreuth, 95440 Bayreuth (Germany); Gnida, Manuel [Department of Chemistry, University of Paderborn, 33098 Paderborn (Germany); Pelzmann, Astrid M. [Department of Microbiology, University of Bayreuth, 95440 Bayreuth (Germany); Marx, Christian [Institute of Biochemistry and Biophysics, Friedrich-Schiller-University of Jena, 07745 Jena (Germany); Meyer-Klaucke, Wolfram [Department of Chemistry, University of Paderborn, 33098 Paderborn (Germany); Meyer, Ortwin, E-mail: Ortwin.Meyer@uni-bayreuth.de [Department of Microbiology, University of Bayreuth, 95440 Bayreuth (Germany)

2014-05-09

Highlights: • Rather large thiols (e.g. coenzyme A) can reach the active site of CO dehydrogenase. • CO- and H{sub 2}-oxidizing activity of CO dehydrogenase is inhibited by thiols. • Inhibition by thiols was reversed by CO or upon lowering the thiol concentration. • Thiols coordinate the Cu ion in the [CuSMo(=O)OH] active site as a third ligand. - Abstract: Carbon monoxide dehydrogenase (CO dehydrogenase) from Oligotropha carboxidovorans is a structurally characterized member of the molybdenum hydroxylase enzyme family. It catalyzes the oxidation of CO (CO + H{sub 2}O → CO{sub 2} + 2e{sup −} + 2H{sup +}) which proceeds at a unique [CuSMo(=O)OH] metal cluster. Because of changing activities of CO dehydrogenase, particularly in subcellular fractions, we speculated whether the enzyme would be subject to regulation by thiols (RSH). Here we establish inhibition of CO dehydrogenase by thiols and report the corresponding K{sub i}-values (mM): L-cysteine (5.2), D-cysteine (9.7), N-acetyl-L-cysteine (8.2), D,L-homocysteine (25.8), L-cysteine–glycine (2.0), dithiothreitol (4.1), coenzyme A (8.3), and 2-mercaptoethanol (9.3). Inhibition of the enzyme was reversed by CO or upon lowering the thiol concentration. Electron paramagnetic resonance spectroscopy (EPR) and X-ray absorption spectroscopy (XAS) of thiol-inhibited CO dehydrogenase revealed a bimetallic site in which the RSH coordinates to the Cu-ion as a third ligand ([Mo{sup VI}(=O)OH{sub (2)}SCu{sup I}(SR)S-Cys]) leaving the redox state of the Cu(I) and the Mo(VI) unchanged. Collectively, our findings establish a regulation of CO dehydrogenase activity by thiols in vitro. They also corroborate the hypothesis that CO interacts with the Cu-ion first. The result that thiol compounds much larger than CO can freely travel through the substrate channel leading to the bimetallic cluster challenges previous concepts involving chaperone function and is of importance for an understanding how the sulfuration step in

Preparation and CO{sub 2} adsorption properties of aminopropyl-functionalized mesoporous silica microspheres

Energy Technology Data Exchange (ETDEWEB)

Araki, S.; Doi, H.; Sano, Y.; Tanaka, S.; Miyake, Y. [Hitachi Zosen Corp., Osaka (Japan). Technical Research Institute

2009-11-15

Aminopropyl-functionalized mesoporous silica microspheres (AF-MSM) were synthesized by a simple one-step modified Stober method. Dodecylamine (DDA) was used as the catalyst for the hydrolysis and condensation of the silica source and as the molecular template to prepare the ordered mesopores. The mesoporous silica surfaces were modified to aminopropyl groups by the co-condensation of tetraethoxysilane (TEOS) with 3-aminopropyltriethoxysilane (APTES), up to a maximum of 20 mol.% APTES content in the silica source. The particle size, Brunauer-Emmet-Teller (BET) specific surface area, and mesoporous regularity decreased with increasing APTES content. It is believed that this result is caused by a decreasing amount of DDA incorporated into AF-MSM with increasing APTES content. It was also confirmed that the spherical shape and the mesostructure were maintained even if 20 mol.% of APTES was added to the silica source. Moreover, AF-MSM was applied to the CO{sub 2} adsorbent. The breakthrough time of the CO{sub 2} and CO{sub 2} adsorption capacities increased with increasing APTES content. The adsorption capacity of CO{sub 2} for AF-MSM, prepared at 20 mol.% APTES, was 0.54 mmol g{sup -1}. Carbon dioxide adsorbed onto AF-MSM was completely desorbed by heating in a N{sub 2} purge at 423 K for 30 min.

Cellular membrane trafficking of mesoporous silica nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Fang, I-Ju [Iowa State Univ., Ames, IA (United States)

2012-01-01

This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulf some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine

Aminopropyl-functionalized ethane-bridged periodic mesoporous organosilica spheres: preparation and application in liquid chromatography.

Science.gov (United States)

Li, Chun; Di, Bin; Hao, Weiqiang; Yan, Fang; Su, Mengxiang

2011-01-21

A synthetic approach for synthesizing spherical aminopropyl-functionalized ethane-bridged periodic mesoporous organosilicas (APEPMOs) is reported. The mesoporous material was prepared by a one-step co-condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) and 3-aminopropyltriethoxysilane (APTES) using cetyltrimethylammonium chlorine (C(18)TACl) as a template with the aid of a co-solvent (methanol) in basic medium. The APEPMOs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis. It was shown that this material exhibited spherical morphology, ordered cubic mesostructure and good mechanical strength. The APEPMOs were tested as a potential stationary phase for liquid chromatography (LC) because the column exhibited reduced back pressure. Moreover, they exhibited good chemical stability in basic mobile phase, which can be ascribed to the ethane groups in the mesoporous framework. Copyright © 2010 Elsevier B.V. All rights reserved.

Hydrogen sulfide deactivates common nitrobenzofurazan-based fluorescent thiol labeling reagents.

Science.gov (United States)

Montoya, Leticia A; Pluth, Michael D

2014-06-17

Sulfhydryl-containing compounds, including thiols and hydrogen sulfide (H2S), play important but differential roles in biological structure and function. One major challenge in separating the biological roles of thiols and H2S is developing tools to effectively separate the reactivity of these sulfhydryl-containing compounds. To address this challenge, we report the differential responses of common electrophilic fluorescent thiol labeling reagents, including nitrobenzofurazan-based scaffolds, maleimides, alkylating agents, and electrophilic aldehydes, toward cysteine and H2S. Although H2S reacted with all of the investigated scaffolds, the photophysical response to each scaffold was significantly different. Maleimide-based, alkylating, and aldehydic thiol labeling reagents provided a diminished fluorescence response when treated with H2S. By contrast, nitrobenzofurazan-based labeling reagents were deactivated by H2S addition. Furthermore, the addition of H2S to thiol-activated nitrobenzofurazan-based reagents reduced the fluorescence signal, thus establishing the incompatibility of nitrobenzofurazan-based thiol labeling reagents in the presence of H2S. Taken together, these studies highlight the differential reactivity of thiols and H2S toward common thiol-labeling reagents and suggest that sufficient care must be taken when labeling or measuring thiols in cellular environments that produce H2S due to the potential for both false-positive and eroded responses.

Proteomic detection of oxidized and reduced thiol proteins in cultured cells.

Science.gov (United States)

Cuddihy, Sarah L; Baty, James W; Brown, Kristin K; Winterbourn, Christine C; Hampton, Mark B

2009-01-01

The oxidation and reduction of cysteine residues is emerging as an important post-translational control of protein function. We describe a method for fluorescent labelling of either reduced or oxidized thiols in combination with two-dimensional sodium dodecyl sulphate polyacrylamide gel electrophoresis (2DE) to detect changes in the redox proteome of cultured cells. Reduced thiols are labelled with the fluorescent compound 5-iodoacetamidofluorescein. To monitor oxidized thiols, the reduced thiols are first blocked with N-ethyl-maleimide, then the oxidized thiols reduced with dithiothreitol and labelled with 5-iodoacetamidofluorescein. The method is illustrated by treating Jurkat T-lymphoma cells with hydrogen peroxide and monitoring increased labelling of oxidized thiol proteins. A decrease in labelling can also be detected, and this is attributed to the formation of higher oxidation states of cysteine that are not reduced by dithiothreitol.

Thiol-ene immobilisation of carbohydrates onto glass slides as a simple alternative to gold-thiol monolayers, amines or lipid binding.

Science.gov (United States)

Biggs, Caroline I; Edmondson, Steve; Gibson, Matthew I

2015-01-01

Carbohydrate arrays are a vital tool in studying infection, probing the mechanisms of bacterial, viral and toxin adhesion and the development of new treatments, by mimicking the structure of the glycocalyx. Current methods rely on the formation of monolayers of carbohydrates that have been chemically modified with a linker to enable interaction with a functionalised surface. This includes amines, biotin, lipids or thiols. Thiol-addition to gold to form self-assembled monolayers is perhaps the simplest method for immobilisation as thiolated glycans are readily accessible from reducing carbohydrates in a single step, but are limited to gold surfaces. Here we have developed a quick and versatile methodology which enables the use of thiolated carbohydrates to be immobilised as monolayers directly onto acrylate-functional glass slides via a 'thiol-ene'/Michael-type reaction. By combining the ease of thiol chemistry with glass slides, which are compatible with microarray scanners this offers a cost effective, but also useful method to assemble arrays.

Investigation of heterogeneous asymmetric dihydroxylation over OsO{sub 4}-(QN){sub 2}PHAL catalysts of functionalized bimodal mesoporous silica with ionic liquid

Energy Technology Data Exchange (ETDEWEB)

Qiu, Shenjie [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Sun, Jihong, E-mail: jhsun@bjut.edu.cn [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China); Li, Yuzhen; Gao, Lin [College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (China)

2011-08-15

Highlights: {yields} Functionalized bimodal mesoporous silica with MTMSPIm{sup +}Cl{sup -}. {yields} Mesoporous catalyst immobilized with OsO{sub 4}-(QN){sub 2}PHAL. {yields} Catalysts for asymmetric dihydroxylation reaction with high yield and enatioselectivity. {yields} Recyclable catalysts. -- Abstract: A novel synthesis of the functionalized bimodal mesoporous silica with ionic liquid (FBMMs) was performed. After grafting 1-methyl-3-(trimethoxysilyl)propylimidazolium chloride onto the surface of bimodal mesoporous silicas, 1,4-bis(9-O-quininyl)phthalazine ((QN){sub 2}-PHAL) and K{sub 2}Os(OH){sub 4}.2H{sub 2}O were immobilized onto the modified FBMMs by adsorption or ionic exchange methods, and then, the asymmetric dihydroxylation reaction was carried out by using solid catalysts. Techniques such as X-ray diffraction, Fourier Transform Infrared spectroscopy, N{sub 2} adsorption and desorption were employed to characterize their structure and properties. The results showed that the mesoporous ordering degree of bimodal mesoporous silica decreased after functionalization and immobilization of OsO{sub 4}-(QN){sub 2}PHAL. Being very effective in asymmetric dihydroxylation with high yield and enantioselectivity, the prepared heterogeneous solid catalyst could be recycled for five times with little loss of enantioselectivity, with comparison of those results obtained in homophase system. Moreover, the effect of Osmium catalyst on asymmetric dihydroxylation was investigated.

Potential of hybrid functionalized meso-porous materials for the separation and immobilization of radionuclides

International Nuclear Information System (INIS)

Luca, V.

2013-01-01

Functionalized meso-porous materials are a class of hybrid organic-inorganic material in which a meso-porous metal oxide framework is functionalized with multifunctional organic molecules. These molecules may contain one or more anchor groups that form strong bonds to the pore surfaces of the metal oxide framework and free functional groups that can impart and or modify the functionality of the material such as for binding metal ions in solution. Such materials have been extensively studied over the past decade and are of particular interest in absorption applications because of the tremendous versatility in choosing the composition and architecture of the metal oxide framework and the nature of the functional organic molecule as well as the efficient mass transfer that can occur through a well-designed hierarchically porous network. A sorbent for nuclear applications would have to be highly selective for particular radio nuclides, it would need to be hydrolytically and radiolytically stable, and it would have to possess reasonable capacity and fast kinetics. The sorbent would also have to be available in a form suitable for use in a column. Finally, it would also be desirable if once saturated with radio nuclides, the sorbent could be recycled or converted directly into a ceramic or glass waste form suitable for direct repository disposal or even converted directly into a material that could be used as a transmutation target. Such a cradle-to- grave strategy could have many benefits in so far as process efficiency and the generation of secondary wastes are concerned.This paper will provide an overview of work done on all of the above mentioned aspects of the development of functionalized meso-porous adsorbent materials for the selective separation of lanthanides and actinides and discuss the prospects for future implementation of a cradle-to-grave strategy with such materials. (author)

Rapid photochemical surface patterning of proteins in thiol-ene based microfluidic devices

DEFF Research Database (Denmark)

Lafleur, Josiane P.; Kwapiszewski, Radoslaw; Jensen, Thomas Glasdam

2012-01-01

” and “ene” monomers present in the microfluidic chip bulk material provides a simple and efficient way of tuning the chip’s surface chemistry. Here, thiol-ene chips displaying an excess of functional thiol groups at their surfaces are functionalized with biotin and streptavidin in a controlled fashion using...

Recent progress in synthesis and surface functionalization of mesoporous acidic heterogeneous catalysts for esterification of free fatty acid feedstocks: A review

International Nuclear Information System (INIS)

Soltani, Soroush; Rashid, Umer; Al-Resayes, Saud Ibrahim; Nehdi, Imededdine Arbi

2017-01-01

Highlights: • Mesoporous catalysts have potential to esterify the wastes feedstocks. • Surface area of mesoporous catalysts depends on materials synthesis methods. • Hydrophobic surface of sulfonated catalyst causes adsorption on FFA particles. • Mesoporous catalysts have large active sites to trap free fatty acids particles. • Recyclability of mesoporous catalyst is a key feature for biodiesel production. - Abstract: Biodiesel is considered as a sulfur free, non-toxic and biodegradable source of energy and its burning provide less pollution than petroleum based fuels. In case of using fried waste oils, animal’s fats and waste cultivated oil which contain high free fatty acid (FFA), esterification is taking place. Through esterification reaction, catalyst is an integral part which accelerates the FFA conversion to the methyl ester (ME) in shorter reaction time. Although, most of the current catalysts have some defect such as poor recyclability, less surface area and poor porosity. Mesoporous materials have been recently attracted remarkable interests because of its desirable properties, such as large and harmonized surface area, tuneable mesoporous channels with flexible pore size, excellent thermal stability, and post-functionalization surface characteristics. The combination of remarkable physico-chemical and textural properties as well as high activity has proposed them as advanced materials. In this review, it has been attempted to present the details of fundamental properties of mesoporous catalysts, various synthetic methods and formation mechanisms, and surface functionalization methodologies. The effects of various factors (such as surface area, porosity, acidity, post-calcination temperature, and reaction parameters) on esterification of different feedstocks are discussed in detail. Furthermore, the kinetic study of esterification reaction in the presence of mesoporous catalysts is also elaborated. At the end, remarkable challenges and outlooks

Hybrid Organic/Inorganic Thiol-ene-Based Photopolymerized Networks.

Science.gov (United States)

Schreck, Kathleen M; Leung, Diana; Bowman, Christopher N

2011-09-15

The thiol-ene reaction serves as a more oxygen tolerant alternative to traditional (meth)acrylate chemistry for forming photopolymerized networks with numerous desirable attributes including energy absorption, optical clarity, and reduced shrinkage stress. However, when utilizing commercially available monomers, many thiol-ene networks also exhibit decreases in properties such as glass transition temperature (T(g)) and crosslink density. In this study, hybrid organic/inorganic thiol-ene resins incorporating silsesquioxane (SSQ) species into the photopolymerized networks were investigated as a route to improve these properties. Thiol- and ene-functionalized SSQs (SH-SSQ and allyl-SSQ, respectively) were synthesized via alkoxysilane hydrolysis/condensation chemistry, using a photopolymerizable monomer [either pentaerythriol tetrakis(3-mercaptopropionate) (PETMP) or 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TATATO)] as the reaction solvent. The resulting SSQ-containing solutions (SSQ-PETMP and SSQ-TATATO) were characterized, and their incorporation into photopolymerized networks was evaluated.

One-step synthesis of mesoporous silica–graphene composites by ...

Indian Academy of Sciences (India)

Silica–graphene oxide composites were synthesized by hydrothermal method with simultaneous functionalization and reduction of graphene oxide (GO) in the presence of mesoporous silica. Two types of silica were used in the study, mesoporous synthetic silica (MSU-F) synthesized by sol-gel method and mesoporous ...

Selenocysteine in thiol/disulfide-like exchange reactions.

Science.gov (United States)

Hondal, Robert J; Marino, Stefano M; Gladyshev, Vadim N

2013-05-01

Among trace elements used as cofactors in enzymes, selenium is unique in that it is incorporated into proteins co-translationally in the form of an amino acid, selenocysteine (Sec). Sec differs from cysteine (Cys) by only one atom (selenium versus sulfur), yet this switch dramatically influences important aspects of enzyme reactivity. The main focus of this review is an updated and critical discussion on how Sec might be used to accelerate thiol/disulfide-like exchange reactions in natural selenoenzymes, compared with their Cys-containing homologs. We discuss in detail three major aspects associated with thiol/disulfide exchange reactions: (i) nucleophilicity of the attacking thiolate (or selenolate); (ii) electrophilicity of the center sulfur (or selenium) atom; and (iii) stability of the leaving group (sulfur or selenium). In all these cases, we analyze the benefits that selenium might provide in these types of reactions. It is the biological thiol oxidoreductase-like function that benefits from the use of Sec, since Sec functions to chemically accelerate the rate of these reactions. We review various hypotheses that could help explain why Sec is used in enzymes, particularly with regard to competitive chemical advantages provided by the presence of the selenium atom in enzymes. Ultimately, these chemical advantages must be connected to biological functions of Sec.

Preparation of thiol-functionalized activated carbon from sewage sludge with coal blending for heavy metal removal from contaminated water.

Science.gov (United States)

Li, Juan; Xing, Xing; Li, Jiao; Shi, Mei; Lin, Aijun; Xu, Congbin; Zheng, Jianzhong; Li, Ronghua

2018-03-01

Sewage sludge produced from wastewater treatment is a pressing environmental issue. Mismanagement of the massive amount of sewage sludge would threat our valuble surface and shallow ground water resources. Use of activated carbon prepared from carbonization of these sludges for heavy metal removal can not only minimize and stabilize these hazardous materials but also realize resources reuse. In this study, thiol-functionalized activated carbon was synthesized from coal-blended sewage sludge, and its capacity was examined for removing Cu(II), Pb(II), Cd(II) and Ni(II) from water. Pyrolysis conditions to prepare activated carbons from the sludge and coal mixture were examined, and the synthesized material was found to achieve the highest BET surface area of 1094 m 2 /g under 500 °C and 30 min. Batch equilibrium tests indicated that the thiol-functionalized activated carbon had a maximum sorption capacity of 238.1, 96.2, 87.7 and 52.4 mg/g for Pb(II), Cd(II), Cu(II) and Ni(II) removal from water, respectively. Findings of this study suggest that thiol-functionalized activated carbon prepared from coal-blended sewage sludge would be a promising sorbent material for heavy metal removal from waters contaminated with Cu(II), Pb(II), Cd(II) and Ni(II). Copyright © 2017 Elsevier Ltd. All rights reserved.

A silica nanoparticle-based sensor for selective fluorescent detection of homocysteine via interaction differences between thiols and particle-surface-bound polymers

International Nuclear Information System (INIS)

Yu Changmin; Zeng Fang; Luo Ming; Wu Shuizhu

2012-01-01

Biothiols play crucial roles in maintaining biological systems; among them, homocysteine (Hcy) has received increasing attention since elevated levels of Hcy have been implicated as an independent risk factor for cardiovascular disease. Hence, the selective detection of this specific biothiol, which is a disease-associated biomarker, is very important. In this paper, we demonstrate a new mesoporous silica nanoparticle-based sensor for selective detection of homocysteine from biothiols and other common amino acids. In this fluorescent sensing system, an anthracene nitroolefin compound was placed inside the mesopores of mesoporous silica nanoparticles (MSNs) and used as a probe for thiols. The hydrophilic polyethylene glycol (PEG 5000) molecules were covalently bound to the MSN surface and used as a selective barrier for Hcy detection via different interactions between biothiols and the PEG polymer chains. The sensor can discriminate Hcy from the two low-molecular mass biothiols (GSH and Cys) and other common amino acids in totally aqueous media as well as in serum, with a detection limit of 0.1 μM. This strategy may offer an approach for designing other MSN-based sensing systems by using polymers as diffusion regulators in sensing assays for other analytes. (paper)

Ionic liquid-functionalized mesoporous sorbents and their use in the capture of polluting gases

Science.gov (United States)

Lee, Jong Suk; Koros, William J.; Bhuwania, Nitesh; Hillesheim, Patrick C.; Dai, Sheng

2016-01-12

A composite structure for capturing a gaseous electrophilic species, the composite structure comprising mesoporous refractory sorbent particles on which an ionic liquid is covalently attached, wherein said ionic liquid includes an accessible functional group that is capable of binding to said gaseous electrophilic species. In particular embodiments, the mesoporous sorbent particles are contained within refractory hollow fibers. Also described is a method for capturing a gaseous electrophilic species by use of the above-described composite structure, wherein the gaseous electrophilic species is contacted with the composite structure. In particular embodiments thereof, cooling water is passed through the refractory hollow fibers containing the IL-functionalized sorbent particles in order to facilitate capture of the gaseous electrophilic species, and then steam is passed through the refractory hollow fibers to facilitate release of the gaseous electrophilic species such that the composite structure can be re-used to capture additional gas.

Functionalized mesoporous silicon for targeted-drug-delivery.

Science.gov (United States)

Tabasi, Ozra; Falamaki, Cavus; Khalaj, Zahra

2012-10-01

The present work concerns a preliminary step in the production of anticancer drug loaded porous silicon (PSi) for targeted-drug-delivery applications. A successful procedure for the covalent attachment of folic acid, polyethylene glycol (PEG) and doxorubicin to hydrophilic mesoporous silicon layers is presented. A systematic approach has been followed to obtain the optimal composition of the N,N'-dicyclohexylcarbodiimide (DCC)/N-hydroxysuccimide (NHS) in dimethylsulfoxide (DMSO) solution for the surface activation process of the undecylenic acid (UD) grafted molecules to take place with minimal undesired byproduct formation. The effect of reactant concentration and kind of solvent (aqueous or DMSO) on the attachment of folic acid to the activated PSi layer has been investigated. The covalent attachment of the doxorubicin molecules to the PSi layer functionalized with folic acid and PEG is discussed. The drug release kinetics as a function of pH has been studied. The functionalized PSi particles show a high cytotoxicity compared to the equivalent amount of free drug. Cell toxicity tests show clearly that the incorporation of folate molecules increases substantially the toxicity of the loaded PSi particles. Accordingly this new functionalized PSi may be considered a proper candidate for targeted drug delivery. Copyright © 2012 Elsevier B.V. All rights reserved.

Functionalization of mesoporous silica membrane with a Schiff base fluorophore for Cu(II) ion sensing

Energy Technology Data Exchange (ETDEWEB)

Chen Xiaotong [Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku 980-8578, Sendai, Miyagi Prefecture (Japan); Department of Chemistry, Tsinghua University, Beijing 100084 (China); Yamaguchi, Akira [College of Science, Ibaraki University, Bunkyo 2-1-1, Mito, Ibaraki 310-8512 (Japan); Frontier Research Center for Applied Atomic Sciences, Ibaraki University, Tokai, Ibaraki 319-1106 (Japan); Namekawa, Manato [Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku 980-8578, Sendai, Miyagi Prefecture (Japan); Kamijo, Toshio [Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku 980-8578, Sendai, Miyagi Prefecture (Japan); Tsuruoka National College of Technology, Aza-Sawada, Tsuruoka 997-8511 (Japan); Teramae, Norio, E-mail: teramae@m.tohoku.ac.jp [Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku 980-8578, Sendai, Miyagi Prefecture (Japan); Tong, Aijun, E-mail: tongaj@mail.tsinghua.edu.cn [Department of Chemistry, Tsinghua University, Beijing 100084 (China)

2011-06-24

Graphical abstract: Highlights: > A hybrid mesoporous membrane (SB-HMM) functionalized by Schiff base fluorophores was fabricated. > SB-HMM showed strong fluorescence with aggregation-induced emission enhancement properties. > SB-HMM was applicable for the detection of Cu(II) in an aqueous solution with good reversibility and reproducibility. - Abstract: A Schiff base (SB) immobilized hybrid mesoporous silica membrane (SB-HMM) was prepared by immobilizing a Schiff base onto the pore surface of mesoporous silica (pore size = 3.1 nm) embedded in the pores of a porous anodic alumina membrane. In contrast to the non-fluorescent analogous SB molecule in homogeneous solutions, SB-HMM exhibited intense fluorescence due to emission enhancement caused by aggregation of SB groups on the pore surface. The high quantum efficiency of the surface SB groups allows SB-HMM to function as a fluorescent sensor for Cu(II) ions in an aqueous solution with good sensitivity, selectivity and reproducibility. Under the optimal conditions described, the linear ranges of fluorescence intensity for Cu(II) are 1.2-13.8 (M (R{sup 2} = 0.993) and 19.4-60 (R{sup 2} = 0.992) (M. The limit of detection for Cu(II) is 0.8 {mu}M on basis of the definition by IUPAC (C{sub LOD} = 3.3S{sub b}/m).

Synthesis, Characterization, and Atenolol Delivery Application of Functionalized Mesoporous Hydroxyapatite Nanoparticles Prepared by Microwave-Assisted Co-precipitation Method.

Science.gov (United States)

Mortazavi-Derazkola, Sobhan; Naimi-Jamal, Mohammad Reza; Ghoreishi, Seyedeh Masoumeh

2016-01-01

Atenolol has been used to treat angina and hypertension, either alone or with other antihypertensives. Despite its usefulness, it shows some side effects such as diarrhea and nausea in some patients. A method for slow release of atenolol in intestine is helpful to prevent such side effects. A facile co-precipitation microwave-assisted method was used to fabricate mesoporous hydroxyapatite nanoparticles (mHAp). It was then functionalized to have SO3H groups. The synthesized material was used for storage/slow release study of atenolol. Atenolol loaded mHAp shows immediate release of atenolol in pH 8, whileafter functionalizing shows up to ca. 30% release at the beginning. In pH 1, 50% of drug was released after 10 h from AT@mHAp and after 18h the drug was almost completely released.The drug release profiles of functionalized HAp at pH value 1 and 8reveals the complete release of atenolol in intestine pH, while no complete release is observed in stomach environment. The aims of this work were synthesis and characterization of mesoporous HAp through the microwave-assisted co-precipitation method and elucidate the underlying drug release capability of mesoporous HAp nanoparticles. The SO3H group was incorporated into the mesoporous HAp and then used as drug delivery carriers using atenolol as a model drug to investigate their drug storage/release properties in simulated body fluid (SBF). Increasing pH value to 8 causes increase in the drug release.

Surface modification of cyclomatrix polyphosphazene microsphere by thiol-ene chemistry and lectin recognition

International Nuclear Information System (INIS)

Chen, Chen; Zhu, Xue-yan; Gao, Qiao-ling; Fang, Fei; Huang, Xiao-jun

2016-01-01

Graphical abstract: A new synthetic route leading to polyphosphazene cyclomatrix microsphere with various functional groups has achieved via thiol-ene click modification. Herein, hexacholorocyclophosphazene (HCCP) crosslinked with bisphenol-S and 4,4′-diallyl bisphenol-S to generate broadly dispersed microspheres. Thiol-ene modification under UV irradiation not only presented high efficiency and flexibility for post-functionalization, but also imposed no harm on global morphology and crosslinked skeleton of such microspheres. - Highlights: • Functional polyphosphazene microspheres with high chemical flexibility were synthesized by thiol-ene modification. • Polyphosphazene microspheres possessed high thermal stability. • Glycosylated polyphosphazene microspheres showed affinity to lectin Con-A, which inferred potential application in biomedicine. - Abstract: A new synthetic route leading to functional polyphosphazene cyclomatrix microsphere has been developed via thiol-ene click modification. Hexacholorocyclophosphazene (HCCP) was crosslinked with both bisphenol-S and 4,4′-diallyl bisphenol-S to obtain vinyl polyphosphazene microspheres (VPZM) in order to ensure high crosslinking degree and introduce vinyl moieties. Compared to the microspheres obtained by HCCP and bisphenol-S, the size of VPZM was broadly dispersed from 400 nm to 1.40 μm. Thiol-ene click reactions were carried out to attach functional groups, such as glucosyl, carboxyl, ester and dodecyl groups onto polyphosphazene microspheres, which demonstrated no change in morphology and size after modification. Solid state NMR (SSNMR) and Fourier transform infrared spectoscopy (FT-IR) results showed that the vinyl moieties were introduced in the period of crosslinking and functionalization was also successful via click reactions. Moreover, the microspheres presented a little difference in thermal properties after modification. Concanavalin A (Con-A) fluorescent adsorption was also observed for

Surface modification of cyclomatrix polyphosphazene microsphere by thiol-ene chemistry and lectin recognition

Energy Technology Data Exchange (ETDEWEB)

Chen, Chen; Zhu, Xue-yan; Gao, Qiao-ling; Fang, Fei; Huang, Xiao-jun, E-mail: hxjzxh@zju.edu.cn

2016-11-30

Graphical abstract: A new synthetic route leading to polyphosphazene cyclomatrix microsphere with various functional groups has achieved via thiol-ene click modification. Herein, hexacholorocyclophosphazene (HCCP) crosslinked with bisphenol-S and 4,4′-diallyl bisphenol-S to generate broadly dispersed microspheres. Thiol-ene modification under UV irradiation not only presented high efficiency and flexibility for post-functionalization, but also imposed no harm on global morphology and crosslinked skeleton of such microspheres. - Highlights: • Functional polyphosphazene microspheres with high chemical flexibility were synthesized by thiol-ene modification. • Polyphosphazene microspheres possessed high thermal stability. • Glycosylated polyphosphazene microspheres showed affinity to lectin Con-A, which inferred potential application in biomedicine. - Abstract: A new synthetic route leading to functional polyphosphazene cyclomatrix microsphere has been developed via thiol-ene click modification. Hexacholorocyclophosphazene (HCCP) was crosslinked with both bisphenol-S and 4,4′-diallyl bisphenol-S to obtain vinyl polyphosphazene microspheres (VPZM) in order to ensure high crosslinking degree and introduce vinyl moieties. Compared to the microspheres obtained by HCCP and bisphenol-S, the size of VPZM was broadly dispersed from 400 nm to 1.40 μm. Thiol-ene click reactions were carried out to attach functional groups, such as glucosyl, carboxyl, ester and dodecyl groups onto polyphosphazene microspheres, which demonstrated no change in morphology and size after modification. Solid state NMR (SSNMR) and Fourier transform infrared spectoscopy (FT-IR) results showed that the vinyl moieties were introduced in the period of crosslinking and functionalization was also successful via click reactions. Moreover, the microspheres presented a little difference in thermal properties after modification. Concanavalin A (Con-A) fluorescent adsorption was also observed for

Highly selective reactions of C(60)Cl(6) with thiols for the synthesis of functionalized [60]fullerene derivatives

OpenAIRE

Khakina, Ekaterina A; Yurkova, Anastasiya A; Peregudov, Alexander S; Troyanov, Sergey I; Trush, Vyacheslav V; Vovk, Andrey I; Mumyatov, Alexander V; Martynenko, Vyacheslav M; Balzarini, Jan; Troshin, Pavel A

2012-01-01

Chlorofullerene C(60)Cl(6) undergoes highly selective reactions with thiols forming compounds C(60)[SR](5)H with high yields. These reactions open up straightforward synthetic routes to many functionalized fullerene derivatives, e.g. water-soluble compounds showing interesting biological activities.

Lignin-Based Materials Through Thiol-Maleimide "Click" Polymerization.

Science.gov (United States)

Buono, Pietro; Duval, Antoine; Averous, Luc; Habibi, Youssef

2017-03-09

In the present report an environmentally friendly approach to transforming renewable feedstocks into value-added materials is proposed. This transformation pathway was conducted under green conditions, without the use of solvents or catalyst. First, controlled modification of lignin, a major biopolymer present in wood and plants, was achieved by esterification with 11-maleimidoundecylenic acid (11-MUA), a derivative from castor oil that contains maleimide groups, following its transformation into 11-maleimidoundecanoyl chloride (11-MUC). Different degrees of substitution were achieved by using various amounts of the 11-MUC, leading to an efficient conversion of lignin hydroxy groups, as demonstrated by 1 H and 31 P NMR analyses. These fully biobased maleimide-lignin derivatives were subjected to an extremely fast (ca. 1 min) thiol-ene "click" polymerization with thiol-containing linkers. Aliphatic and aromatic thiol linkers bearing two to four thiol groups were used to tune the reactivity and crosslink density. The properties of the resulting materials were evaluated by swelling tests and thermal and mechanical analyses, which showed that varying the degree of functionality of the linker and the linker structure allowed accurate tailoring of the thermal and mechanical properties of the final materials, thus providing interesting perspectives for lignin in functional aromatic polymers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic and Thermodynamic Aspects of Cellular Thiol-Disulfide Redox Regulation

DEFF Research Database (Denmark)

Jensen, Kristine Steen; Hansen, Rosa Erritzøe; Winther, Jakob R

2009-01-01

. In the cytosol regulatory disulfide bonds are typically formed in spite of the prevailing reducing conditions and may thereby function as redox switches. Such disulfide bonds are protected from enzymatic reduction by kinetic barriers and are thus allowed to exist long enough to elicit the signal. Factors......Regulation of intracellular thiol-disulfide redox status is an essential part of cellular homeostasis. This involves the regulation of both oxidative and reductive pathways, production of oxidant scavengers and, importantly, the ability of cells to respond to changes in the redox environment...... that affect the rate of thiol-disulfide exchange and stability of disulfide bonds are discussed within the framework of the underlying chemical foundations. This includes the effect of thiol acidity (pKa), the local electrostatic environment, molecular strain and entropy. Even though a thiol-disulfide...

Mesoporous carbon materials

Science.gov (United States)

Dai, Sheng; Fulvio, Pasquale Fernando; Mayes, Richard T.; Wang, Xiqing; Sun, Xiao-Guang; Guo, Bingkun

2014-09-09

A conductive mesoporous carbon composite comprising conductive carbon nanoparticles contained within a mesoporous carbon matrix, wherein the conductive mesoporous carbon composite possesses at least a portion of mesopores having a pore size of at least 10 nm and up to 50 nm, and wherein the mesopores are either within the mesoporous carbon matrix, or are spacings delineated by surfaces of said conductive carbon nanoparticles when said conductive carbon nanoparticles are fused with each other, or both. Methods for producing the above-described composite, devices incorporating them (e.g., lithium batteries), and methods of using them, are also described.

Aminopropyl-functionalized mesoporous silicas as CO{sub 2} adsorbents

Energy Technology Data Exchange (ETDEWEB)

Knowles, Gregory P.; Graham, Jeremy V.; Delaney, Seamus W.; Chaffee, Alan L. [School of Chemistry, PO Box 23, Monash University, Vic 3800 (Australia)

2005-10-15

A range of mesoporous silica substrates were functionalized with 3-aminopropyltrimethoxysilane to form hybrid products suitable for carbon dioxide adsorption. A 'cylindrical pore' model was employed to characterize the extent of surface modification per unit substrate surface area and to permit its comparison on a common basis. The extent of surface functionalisation varied with substrate morphology. Combined DTA/TGA was used to characterise CO{sub 2} adsorption. Substantial reversible CO{sub 2} adsorption capacities were observed under anhydrous conditions (at 20 {sup o}C). In the presence of water, CO{sub 2} capacity was enhanced, but the rate of desorption was diminished. (author)

Combined radiation-protective and radiation-sensitizing agents. III. Radiosensitization by misonidazole as a function of concentrations of endogenous glutathione or exogenous thiols

International Nuclear Information System (INIS)

Koch, C.J.; Stobbe, C.C.; Baer, K.A.

1986-01-01

Radiosensitization of V79 Chinese hamster fibroblasts by 0.5 mM misonidazole is a smooth function of endogenous glutathione (GSH) levels as modulated upwards by pre-incubation in medium containing cysteamine, or downwards by pre-incubation in medium containing buthionine sulfoximine. The enhancement ratio (radiation sensitivity in nitrogen/radiation sensitivity in nitrogen +/- sensitizer or thiol) varies from 1.3 at 12 mM to 2.25 at less than 0.1 mM endogenous GSH. The enhanced radiosensitivity of thiol-depleted hypoxic cells is reversed when exogenous thiols are added, and for equivalent ER, the exogenous thiol concentrations are much lower than the endogenous GSH concentrations. Measurement of intracellular drug concentrations amplified rather than diminished the above discrepancy, since intracellular concentrations of cysteamine were lower and glutathione much lower than the extracellular concentrations. Three possible explanations are addressed: an external membrane component of damage is involved, long-range protection to DNA target radicals is possible from outside the cell (e.g., donation of electrons), and (c) endogenous glutathione is not in a free or exchangeable state (e.g., bound)

Facile synthesis of functionalized ionic surfactant templated mesoporous silica for incorporation of poorly water-soluble drug.

Science.gov (United States)

Li, Jing; Xu, Lu; Yang, Baixue; Wang, Hongyu; Bao, Zhihong; Pan, Weisan; Li, Sanming

2015-08-15

The present paper reported amino group functionalized anionic surfactant templated mesoporous silica (Amino-AMS) for loading and release of poorly water-soluble drug indomethacin (IMC) and carboxyl group functionalized cationic surfactant templated mesoporous silica (Carboxyl-CMS) for loading and release of poorly water-soluble drug famotidine (FMT). Herein, Amino-AMS and Carboxyl-CMS were facilely synthesized using co-condensation method through two types of silane coupling agent. Amino-AMS was spherical nanoparticles, and Carboxyl-CMS was well-formed spherical nanosphere with a thin layer presented at the edge. Drug loading capacity was obviously enhanced when using Amino-AMS and Carboxyl-CMS as drug carriers due to the stronger hydrogen bonding force formed between surface modified carrier and drug. Amino-AMS and Carboxyl-CMS had the ability to transform crystalline state of loaded drug from crystalline phase to amorphous phase. Therefore, IMC loaded Amino-AMS presented obviously faster release than IMC because amorphous phase of IMC favored its dissolution. The application of asymmetric membrane capsule delayed FMT release significantly, and Carboxyl-CMS favored sustained release of FMT due to its long mesoporous channels and strong interaction formed between its carboxyl group and amino group of FMT. Copyright © 2015 Elsevier B.V. All rights reserved.

Thiol Redox Transitions in Cell Signaling: a Lesson from N-Acetylcysteine

Directory of Open Access Journals (Sweden)

Tiziana Parasassi

2010-01-01

Full Text Available The functional status of cells is under the control of external stimuli affecting the function of critical proteins and eventually gene expression. Signal sensing and transduction by messengers to specific effectors operate by post-translational modification of proteins, among which thiol redox switches play a fundamental role that is just beginning to be understood. The maintenance of the redox status is, indeed, crucial for cellular homeostasis and its dysregulation towards a more oxidized intracellular environment is associated with aberrant proliferation, ultimately related to diseases such as cancer, cardiovascular disease, and diabetes. Redox transitions occur in sensitive cysteine residues of regulatory proteins relevant to signaling, their evolution to metastable disulfides accounting for the functional redox switch. N-acetylcysteine (NAC is a thiol-containing compound that is able to interfere with redox transitions of thiols and, thus, in principle, able to modulate redox signaling. We here review the redox chemistry of NAC, then screen possible mechanisms to explain the effects observed in NAC-treated normal and cancer cells; such effects involve a modification of global gene expression, thus of functions and morphology, with a leitmotif of a switch from proliferation to terminal differentiation. The regulation of thiol redox transitions in cell signaling is, therefore, proposed as a new tool, holding promise not only for a deeper explanation of mechanisms, but indeed for innovative pharmacological interventions.

Cooperative functions of manganese and thiol redox system against oxidative stress in human spermatozoa

Directory of Open Access Journals (Sweden)

Amrit Kaur Bansal

2009-01-01

Full Text Available Aims: In this study, the effects of 0.1 mM Mn 2+ on thiol components (total thiols [TSH], glutathione reduced [GSH], glutathione oxidized [GSSG] and redox ratio [GSH/ GSSG] have been determined in human spermatozoa. Settings and Design: The subjects of the study were healthy males having more than 75% motility and 80 x 10 6 sperms/mL. Materials and Methods: Fresh semen was suspended in phosphate-buffered saline (PBS (pH 7.2 and this suspension was divided into eight equal fractions. All fractions, control (containing PBS and experimental (treated/untreated with [ferrous ascorbate, FeAA - 200 FeSO 4 μM, 1000 μM ascorbic acid, nicotine (0.5 mM and FeAA + nicotine], supplemented/unsupplemented with Mn 2+ [0.1 mM], were incubated for 2 h at 378C. These fractions were assessed for determining the thiol components. Statistical Analysis: The data were statistically analyzed by Students " t" test. Results and Conclusions: Ferrous ascorbate, nicotine and ferrous ascorbate + nicotine induced oxidative stress and decreased GSH and redox ratio (GSH/GSSG ratio but increased the TSH and GSSG levels. Mn 2+ supplementation improved TSH, GSH and redox ratio (GSH/GSSG but decreased the GSSG level under normal and oxidative stress conditions. Thiol groups serve as defense mechanisms of sperm cells to fight against oxidative stress induced by stress inducers such as ferrous ascorbate, nicotine and their combination (ferrous ascorbate + nicotine. In addition, Mn 2+ supplementation maintains the thiol level by reducing oxidative stress.

Stretching of BDT-gold molecular junctions: Thiol or thiolate termination?

KAUST Repository

Souza, Amaury De Melo; Rungger, Ivan; Pontes, Renato Borges; Rocha, Alexandre Reily; Da Silva, Antô nio José Roque; Schwingenschlö gl, Udo; Sanvito, S.

2014-01-01

It is often assumed that the hydrogen atoms in the thiol groups of a benzene-1,4-dithiol dissociate when Au-benzene-1,4-dithiol-Au junctions are formed. We demonstrate, by stability and transport property calculations, that this assumption cannot be made. We show that the dissociative adsorption of methanethiol and benzene-1,4-dithiol molecules on a flat Au(111) surface is energetically unfavorable and that the activation barrier for this reaction is as high as 1 eV. For the molecule in the junction, our results show, for all electrode geometries studied, that the thiol junctions are energetically more stable than their thiolate counterparts. Due to the fact that density functional theory (DFT) within the local density approximation (LDA) underestimates the energy difference between the lowest unoccupied molecular orbital and the highest occupied molecular orbital by several electron-volts, and that it does not capture the renormalization of the energy levels due to the image charge effect, the conductance of the Au-benzene-1,4-dithiol-Au junctions is overestimated. After taking into account corrections due to image charge effects by means of constrained-DFT calculations and electrostatic classical models, we apply a scissor operator to correct the DFT energy level positions, and calculate the transport properties of the thiol and thiolate molecular junctions as a function of the electrode separation. For the thiol junctions, we show that the conductance decreases as the electrode separation increases, whereas the opposite trend is found for the thiolate junctions. Both behaviors have been observed in experiments, therefore pointing to the possible coexistence of both thiol and thiolate junctions. Moreover, the corrected conductance values, for both thiol and thiolate, are up to two orders of magnitude smaller than those calculated with DFT-LDA. This brings the theoretical results in quantitatively good agreement with experimental data.

A “Turn-On” thiol functionalized fluorescent carbon quantum dot based chemosensory system for arsenite detection

Energy Technology Data Exchange (ETDEWEB)

Pooja, D., E-mail: poojaiitr@csio.res.in [Academy of Scientific and Innovative Research (AcSIR), Council of Scientific and Industrial Research, New Delhi (India); Central Scientific Instruments Organisation, Sectro-30 C, Chandigarh 160030 (India); Saini, Sonia; Thakur, Anupma; Kumar, Baban; Tyagi, Sachin [Central Scientific Instruments Organisation, Sectro-30 C, Chandigarh 160030 (India); Nayak, Manoj K. [Academy of Scientific and Innovative Research (AcSIR), Council of Scientific and Industrial Research, New Delhi (India); Central Scientific Instruments Organisation, Sectro-30 C, Chandigarh 160030 (India)

2017-04-15

Highlights: • Environmental friendly carbon quantum dots grafted with thiol moieties. • The functionalized CQDs demonstrated for optical detection of arsenite in water. • High analytical performance in terms of sensitivity, selectivity and detection limit (0.086 ppb). - Abstract: Carbon quantum dots (CQDs) have emerged out as promising fluorescent probes for hazardous heavy metals detection in recent past. In this study, water soluble CQDs were synthesized by facile microwave pyrolysis of citric acid & cysteamine, and functionalized with ditheritheritol to impart thiol functionalities at surface for selective detection of toxic arsenite in water. Microscopic analysis reveals that the synthesized CQDs are of uniform size (diameter ∼5 nm) and confirmed to have surface −SH groups by FT-IR. The functionalized probe is then demonstrated for arsenite detection in water by “Turn-On” read out mechanism, which reduces the possibility of false positive signals associated with “turn off’ probes reported earlier. The blue luminescent functionalized CQDs exhibit increase in fluorescence intensity on arsenite addition in 5–100 ppb wide detection range. The probe can be used for sensitive detection of arsenite in environmental water to a theoretical detection limit (3s) of 0.086 ppb (R{sup 2} = 0.9547) with good reproducibility at 2.6% relative standard deviation. The presented reliable, sensitive, rapid fCQDs probe demonstrated to exhibit high selectivity towards arsenite and exemplified for real water samples as well. The analytical performance of the presented probe is comparable to existing organic & semiconductor based optical probes.

Towards thiol functionalization of vanadium pentoxide nanotubes using gold nanoparticles

International Nuclear Information System (INIS)

Lavayen, V.; O'Dwyer, C.; Cardenas, G.; Gonzalez, G.; Sotomayor Torres, C.M.

2007-01-01

Template-directed synthesis is a promising route to realize vanadate-based 1-D nanostructures, an example of which is the formation of vanadium pentoxide nanotubes and associated nanostructures. In this work, we report the interchange of long-chained alkyl amines with alkyl thiols. This reaction was followed using gold nanoparticles prepared by the Chemical Liquid Deposition (CLD) method with an average diameter of ∼0.9nm and a stability of ∼85 days. V 2 O 5 nanotubes (VOx-NTs) with lengths of ∼2μm and internal hollow diameters of 20-100nm were synthesized and functionalized in a Au-acetone colloid with a nominal concentration of ∼4x10 -3 mol dm -3 . The interchange reaction with dodecylamine is found only to occur in polar solvents and incorporation of the gold nanoparticles is not observed in the presence of n-decane

Modification of porous silicon rugate filters through thiol-yne photochemistry

International Nuclear Information System (INIS)

Soeriyadi, Alexander H.; Zhu, Ying; Gooding, J. Justin; Reece, Peter

2014-01-01

Porous silicon (PSi) has a considerable potential as biosensor platform. In particular, the ability to modify the surface chemistry of porous silicon is of interest. Here we present a generic method to modify the surface of porous silicon through thiol-yne photochemistry initiated by a radical initiator. Firstly, a freshly etched porous silicon substrate is modified through thermal hydrosilylation with 1,8-nonadiyne to passivate the surface and introduce alkyne functionalities. The alkyne functional surface could then be further reacted with thiol species in the presence of a radical initiator and UV light. Functionalization of the PSi rugate filter is followed with optical reflectivity measurements as well as high resolution X-ray photoelectron spectroscopy (XPS)

Magnetic Fe3O4@MCM-41 core-shell nanoparticles functionalized with thiol silane for efficient l-asparaginase immobilization.

Science.gov (United States)

Ulu, Ahmet; Noma, Samir Abbas Ali; Koytepe, Suleyman; Ates, Burhan

2018-06-06

l-Asparaginase (l-ASNase) is a vital enzyme for medical treatment and food industry. Here, we assessed the use of Fe 3 O 4 @Mobil Composition of Matter No. 41 (MCM-41) magnetic nanoparticles as carrier matrix for l-ASNase immobilization. In addition, surface of Fe 3 O 4 @MCM-41 magnetic nanoparticles was functionalized with 3-mercaptopropyltrimethoxysilane (MPTMS) to enhance stability of l-ASNase. The chemical structure, thermal properties, magnetic profile and morphology of the thiol-functionalized Fe 3 O 4 @MCM-41 magnetic nanoparticles were characterized with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning calorimetry (DSC), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), energy dispersive X-ray (EDX) spectroscopy and zeta-potential measurement. l-ASNase was covalently immobilized onto the thiol-functionalized Fe 3 O 4 @MCM-41 magnetic nanoparticles. The properties of the immobilized enzyme, including optimum pH, temperature, kinetic parameters, thermal stability, reusability and storage stability were investigated and compared to free one. Immobilized enzyme was found to be stable over a wide range of pH and temperature range than free enzyme. The immobilized l-ASNase also showed higher thermal stability after 180 min incubation at 50 °C. The immobilized enzyme still retained 63% of its original activity after 16 times of reuse. The Km value for the immobilized enzyme was 1.15-fold lower than the free enzyme, which indicates increased affinity for the substrate. Additionally, the immobilized enzyme was active over 65% and 53% after 30 days of storage at 4 °C and room temperature (∼25 °C), respectively. Thereby, the results confirmed that thiol-functionalized Fe 3 O 4 @MCM-41 magnetic nanoparticles had high efficiency for l-ASNase immobilization and improved stability of L-ASNase.

Impaired Thiol-Disulfide Balance in Acute Brucellosis.

Science.gov (United States)

Kolgelier, Servet; Ergin, Merve; Demir, Lutfi Saltuk; Inkaya, Ahmet Cagkan; Aktug Demir, Nazlim; Alisik, Murat; Erel, Ozcan

2017-05-24

The objective of this study was to examine a novel profile: thiol-disulfide homeostasis in acute brucellosis. The study included 90 patients with acute brucellosis, and 27 healthy controls. Thiol-disulfide profile tests were analyzed by a recently developed method, and ceruloplasmin levels were determined. Native thiol levels were 256.72 ± 48.20 μmol/L in the acute brucellosis group and 461.13 ± 45.37 μmol/L in the healthy group, and total thiol levels were 298.58 ± 51.78 μmol/L in the acute brucellosis group and 504.83 ± 51.05 μmol/L in the healthy group (p brucellosis than in the healthy controls (p brucellosis. The strong associations between thiol-disulfide parameters and a positive acute-phase reactant reflected the disruption of the balance between the antioxidant and oxidant systems. Since thiol groups act as anti-inflammatory mediators, the alteration in the thiol-disulfide homeostasis may be involved in brucellosis.

Toward Anhydrous Proton Conductivity Based on Imidazole Functionalized Mesoporous Silica/Nafion Composite Membranes

International Nuclear Information System (INIS)

Amiinu, Ibrahim Saana; Li, Wei; Wang, Guangjin; Tu, Zhengkai; Tang, Haolin; Pan, Mu; Zhang, Haining

2015-01-01

Highlights: • Imidazole-functionalized mesoporous silica/Nafion composite is formed. • Electrostatic interaction between ionic clusters leads to enhanced molecular rigidity and T g . • Charge transfer resistance decreases with increase in temperature up to 130 °C. • The composite membrane exhibited considerable stability over 70 h at 130 °C. - Abstract: Although Nafion is regarded as the most preferred electrolyte membrane and often used as a benchmark for comparative evaluation of other electrolyte membranes, its wide spread for commercial PEM fuel cells is limited by the poor electrochemical properties at elevated temperatures and low relative humidity conditions. Herein, sol–gel synthesized mesoporous silica functionalized with a protogenic molecule (imidazole) is introduced into the Nafion matrix via a colloid mediated process. The formation of a stable colloid enables homogeneous dispersion of the silica-imidazole nanoparticles without aggregation. Under non-humidified conditions, the amphoteric and self-dissociative character of the tethered imidazole within the matrix functions as a transporting medium to facilitate proton conductivity. The structural and chemical phases are characterized, and qualitatively evaluated by XRD, TEM, FT-IR, TGA, and DMA. The results show that the average proton conductivity of the composite membrane with the optimal amount of functionalized nanoparticles increases progressively to 1.06 × 10 −2 S cm −1 at 130 °C, corresponding to an activation energy of 6.95 kJ mol −1 under non-humidified conditions. The mechanism governing the dynamics of proton conductivity and structural limitations as a function of temperature is discussed

Facile synthesis of thiol-polyethylene glycol functionalized magnetic titania nanomaterials for highly efficient enrichment of N-linked glycopeptides.

Science.gov (United States)

Wang, Jiawen; Yao, Jizong; Sun, Nianrong; Deng, Chunhui

2017-08-25

As protein N-glycosylation involved in generation and development of various cancers and diseases, it is vital to capture glycopeptides from complex biological samples for biomarker discovery. In this work, by taking advantages of the interaction between titania and thiol groups, thiol-polyethylene glycol functionalized magnetic titania nanomaterials (denoted as Fe 3 O 4 @TiO 2 @PEG) were firstly fabricated as an excellent hydrophilic adsorbent of N-linked glycopeptides. On one hand, the special interaction of titanium-thiol makes the synthetic manipulation simple and provides a new idea for design and synthesis of novel nanomaterials; on the other hand, strong magnetic response could realize rapid separation and the outstanding hydrophilicity of polyethylene glycol makes Fe 3 O 4 @TiO 2 @PEG nanomaterials show superior performance for glycopeptides enrichment with ultralow limit of detection (0.1mol/μL) and high selectivity (1:100). As a result, 24 and 33 glycopeptides enriched from HRP and IgG digests were identified respectively by MALDI-TOF MS, and 300 glycopeptides corresponding to 106 glycoproteins were recognized from merely 2μL human serum, indicating a great potential of Fe 3 O 4 @TiO 2 @PEG nanomaterials for glycoproteomic research. Copyright © 2017 Elsevier B.V. All rights reserved.

Electronic structure, magnetic properties, and microstructural analysis of thiol-functionalized Au nanoparticles: role of chemical and structural parameters in the ferromagnetic behaviour

Energy Technology Data Exchange (ETDEWEB)

Guerrero, Estefania; Munoz-Marquez, Miguel A., E-mail: miguel.angel@icmse.csic.e [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) (Spain); Fernandez-Pinel, Enrique; Crespo, Patricia; Hernando, Antonio [Instituto de Magnetismo Aplicado (UCM-ADIF-CSIC) (Spain); Fernandez, Asuncion [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) (Spain)

2008-12-15

Gold nanoparticles (NPs) have been stabilized with a variety of thiol-containing molecules in order to change their chemical and physical properties; among the possible capping systems, alkane chains with different lengths, a carboxylic acid and a thiol-containing biomolecule (tiopronin) have been selected as protecting shells for the synthesized NPs; the NPs solubility in water or organic solvents is determined by the protecting molecule. A full microstructural characterization of these NPs is presented in the current research work. It has been shown that NPs capped with alkanethiol chains have a marked ferromagnetic behaviour which might also be dependent on the chain length. The simultaneous presence of Au-Au and Au-S bonds together with a reduced particle diameter, and the formation of an ordered monolayer protective shell, have proved to be key parameters for the ferromagnetic-like behaviour exhibited by thiol-functionalized gold NPs.

Surface analysis of gold nanoparticles functionalized with thiol-modified glucose SAMs for biosensor applications.

Directory of Open Access Journals (Sweden)

Valentina eSpampinato

2016-02-01

Full Text Available In this work, Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS, Principal Component Analysis (PCA and X-ray Photoelectron Spectroscopy (XPS have been used to characterize the surface chemistry of gold substrates before and after functionalization with thiol-modified glucose self-assembled monolayers and subsequent biochemical specific recognition of maltose binding protein (MBP.The results indicate that the surface functionalization is achieved both on flat and nanoparticles gold substrates thus showing the potential of the developed system as biodetection platform. Moreover, the method presented here has been found to be a sound and valid approach to characterize the surface chemistry of nanoparticles functionalized with large molecules.Both techniques were proved to be very useful tools for monitoring all the functionalization steps, including the investigation of the biological behaviour of the glucose-modified particles in presence of the maltose binding protein.

Quantifying the global cellular thiol-disulfide status

DEFF Research Database (Denmark)

Hansen, Rosa E; Roth, Doris; Winther, Jakob R

2009-01-01

It is widely accepted that the redox status of protein thiols is of central importance to protein structure and folding and that glutathione is an important low-molecular-mass redox regulator. However, the total cellular pools of thiols and disulfides and their relative abundance have never been...... determined. In this study, we have assembled a global picture of the cellular thiol-disulfide status in cultured mammalian cells. We have quantified the absolute levels of protein thiols, protein disulfides, and glutathionylated protein (PSSG) in all cellular protein, including membrane proteins. These data...... cell types. However, when cells are exposed to a sublethal dose of the thiol-specific oxidant diamide, PSSG levels increase to >15% of all protein cysteine. Glutathione is typically characterized as the "cellular redox buffer"; nevertheless, our data show that protein thiols represent a larger active...

Novel thermal curing of cycloaliphatic resins by thiol-epoxy click process with several multifunctional thiols

OpenAIRE

Guzman, Dailyn; Mateu, Blai; Fernández Francos, Xavier; Ramis Juan, Xavier; Serra Albet, Àngels

2017-01-01

Novel thermosets were prepared by the base-catalysed reaction between a cycloaliphatic resin (ECC) and various thiol crosslinkers. 4-(N,N-Dimethylaminopyridine) (DMAP) was used as base catalyst for the thiol–epoxy reaction. A commercial tetrathiol (PETMP) and three different thiols synthesized by us, 6SH-SQ, 3SH-EU and 3SH-ISO, were tested. 6SH-SQ and 3SH-EU were prepared from vinyl or allyl compounds from renewable resources such as squalene and eugenol, respectively. Thiol 3SH-ISO was prepa...

Mesoporous Carbon Produced from Tri-constituent Mesoporous Carbon-silica Composite for Water Purification

KAUST Repository

Yu, Yanjie

2012-01-01

Highly ordered mesoporous carbon-silica nanocomposites with interpenetrating carbon and silica networks were synthesized by the evaporation-induced tri-constituent co- assembly approach. The removal of silica by concentrated NaOH solution produced mesoporous carbons, which contained not only the primary large pores, but also the secondary mesopores in the carbon walls. The thus synthesized mesoporous carbon was further activated by using ZnCl2. The activated mesoporous carbon showed an improved surface area and pore volume. The synthesized mesoporous carbon was tested for diuron removal from water and the results showed that the carbon gave a fast diuron adsorption kinetics and a high diuron removal capacity, which was attributable to the primary mesopore channels being the highway for mass transfer, which led to short diffusion path length and easy accessibility of the interpenetrated secondary mesopores. The optimal adsorption capacity of the porous carbon was determined to be 390 mg/g, the highest values ever reported for diuron adsorption on carbon-based materials.

Mesoporous Carbon Produced from Tri-constituent Mesoporous Carbon-silica Composite for Water Purification

KAUST Repository

Yu, Yanjie

2012-05-01

Highly ordered mesoporous carbon-silica nanocomposites with interpenetrating carbon and silica networks were synthesized by the evaporation-induced tri-constituent co- assembly approach. The removal of silica by concentrated NaOH solution produced mesoporous carbons, which contained not only the primary large pores, but also the secondary mesopores in the carbon walls. The thus synthesized mesoporous carbon was further activated by using ZnCl2. The activated mesoporous carbon showed an improved surface area and pore volume. The synthesized mesoporous carbon was tested for diuron removal from water and the results showed that the carbon gave a fast diuron adsorption kinetics and a high diuron removal capacity, which was attributable to the primary mesopore channels being the highway for mass transfer, which led to short diffusion path length and easy accessibility of the interpenetrated secondary mesopores. The optimal adsorption capacity of the porous carbon was determined to be 390 mg/g, the highest values ever reported for diuron adsorption on carbon-based materials.

Ion-Exchange-Induced Selective Etching for the Synthesis of Amino-Functionalized Hollow Mesoporous Silica for Elevated-High-Temperature Fuel Cells.

Science.gov (United States)

Zhang, Jin; Liu, Jian; Lu, Shanfu; Zhu, Haijin; Aili, David; De Marco, Roland; Xiang, Yan; Forsyth, Maria; Li, Qingfeng; Jiang, San Ping

2017-09-20

As differentiated from conventional synthetic processes, amino-functionalized hollow mesoporous silica (NH 2 -HMS) has been synthesized using a new and facile strategy of ion-exchange-induced selective etching of amino-functionalized mesoporous silica (NH 2 -meso-silica) by an alkaline solution. Nuclear magnetic resonance (NMR) spectroscopy and in situ time-resolved small-angle X-ray scattering (SAXS) reveal that ion-exchange-induced selective etching arises from the gradient distribution of OH - in the NH 2 -meso-silica nanospheres. Moreover, the ion-exchange-induced selective etching mechanism is verified through a successful synthesis of hollow mesoporous silica. After infiltration with phosphotungstic acid (PWA), PWA-NH 2 -HMS nanoparticles are dispersed in the poly(ether sulfone)-polyvinylpyrrolidone (PES-PVP) matrix, forming a hybrid PWA-NH 2 -HMS/PES-PVP nanocomposite membrane. The resultant nanocomposite membrane with an optimum loading of 10 wt % of PWA-NH 2 -HMS showed an enhanced proton conductivity of 0.175 S cm -1 and peak power density of 420 mW cm -2 at 180 °C under anhydrous conditions. Excellent durability of the hybrid composite membrane fuel cell has been demonstrated at 200 °C. The results of this study demonstrated the potential of the facile synthetic strategy in the fabrication of NH 2 -HMS with controlled mesoporous structure for application in nanocomposite membranes as a technology platform for elevated-temperature proton exchange membrane fuel cells.

Research Update: Mesoporous sensor nanoarchitectonics

Directory of Open Access Journals (Sweden)

Katsuhiko Ariga

2014-03-01

Full Text Available In this short review, we have selected three main subjects: (i mesoporous materials, (ii sensing applications, and (iii the concept of nanoarchitectonics, as examples of recent hot topics in nanomaterials research. Mesoporous materials satisfy the conditions necessary not only for a wide range of applications but also for ease of production, by a variety of simple processes, which yield bulk quantities of materials without loss of their well-defined nanometric structural features. Sensing applications are of general importance because many events arise from interaction with external stimuli. In addition to these important features, nanoarchitectonics is a concept aimed at production of novel functionality of whole units according to concerted interactions within nanostructures. For the combined subject of mesoporous sensor nanoarchitectonics, we present recent examples of research in the corresponding fields categorized according to mechanism of detection including optical, electrical, and piezoelectric sensing.

Oriented Decoration in Metal-Functionalized Ordered Mesoporous Silicas and Their Catalytic Applications in the Oxidation of Aromatic Compounds

Directory of Open Access Journals (Sweden)

Shijian Zhou

2018-02-01

Full Text Available Ordered mesoporous silicas (OMSs attract considerable attention due to their advanced structural properties. However, for the pristine silica materials, the inert property greatly inhibits their catalytic applications. Thus, to contribute to the versatile surface of OMSs, different metal active sites, including acidic/basic sites and redox sites, have been introduced into specific locations (mesoporous channels and framework of OMSs and the metal-functionalized ordered mesoporous silicas (MOMSs show great potential in the catalytic applications. In this review, we first present the categories of metal active sites. Then, the synthesized processes of MOMSs are thoroughly discussed, in which the metal active sites would be introduced with the assistance of organic groups into the specific locations of OMSs. In addition, the structural morphologies of OMSs are elaborated and the catalytic applications of MOMSs in the oxidation of aromatic compounds are illustrated in detail. Finally, the prospects for the future development in this field are proposed.

Interface chemistry of nanostructured materials: ion adsorption on mesoporous alumina.

Science.gov (United States)

Wang, Yifeng; Bryan, Charles; Xu, Huifang; Pohl, Phil; Yang, Yi; Brinker, C Jeffrey

2002-10-01

This paper presents a part of our work on understanding the effect of nanoscale pore space confinement on ion sorption by mesoporous materials. Acid-base titration experiments were performed on both mesoporous alumina and alumina particles under various ionic strengths. The point of zero charge (PZC) for mesoporous alumina was measured to be approximately 9.1, similar to that for nonmesoporous alumina materials, indicating that nanoscale pore space confinement does not have a significant effect on the PZC of pore surfaces. However, for a given pH deviation from the PZC, (pH-PZC), the surface charge per mass on mesoporous alumina was as much as 45 times higher than that on alumina particles. This difference cannot be fully explained by the surface area difference between the two materials. Our titration data have demonstrated that nanoscale confinement has a significant effect, most likely via the overlap of the electric double layer (EDL), on ion sorption onto mesopore surfaces. This effect cannot be adequately modeled by existing surface complexation models, which were developed mostly for an unconfined solid-water interface. Our titration data have also indicated that the rate of ion uptake by mesoporous alumina is relatively slow, probably due to diffusion into mesopores, and complete equilibration for sorption could take 4-5 min. A molecular simulation using a density functional theory was performed to calculate ion adsorption coefficients as a function of pore size. The calculation has shown that as pore size is reduced to nanoscales (<10 nm), the adsorption coefficients of ions can vary by more than two orders of magnitude relative to those for unconfined interfaces. The prediction is supported by our experimental data on Zn sorption onto mesoporous alumina. Owing to their unique surface chemistry, mesoporous materials can potentially be used as effective ion adsorbents for separation processes and environmental cleanup.

o-Vanillin functionalized mesoporous silica – coated magnetite nanoparticles for efficient removal of Pb(II) from water

Energy Technology Data Exchange (ETDEWEB)

Culita, Daniela C., E-mail: danaculita@yahoo.co.uk [“Ilie Murgulescu” Institute of Physical Chemistry, Splaiul Independentei 202, Bucharest (Romania); Simonescu, Claudia Maria; Patescu, Rodica-Elena [Politehnica University, Faculty of Applied Chemistry and Materials Science, Bucharest (Romania); Dragne, Mioara [S.C. KEMCRISTAL S.R.L., Muncii Str., No. 51, Fundulea, Călăraşi (Romania); Stanica, Nicolae [“Ilie Murgulescu” Institute of Physical Chemistry, Splaiul Independentei 202, Bucharest (Romania); Oprea, Ovidiu [Politehnica University, Faculty of Applied Chemistry and Materials Science, Bucharest (Romania)

2016-06-15

o-Vanillin functionalized mesoporous silica – coated magnetite (Fe{sub 3}O{sub 4}@MCM-41-N-oVan) was synthesized and fully characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N{sub 2} adsorption–desorption technique and magnetic measurements. The capacity of Fe{sub 3}O{sub 4}@MCM-41-N-oVan to adsorb Pb(II) from aqueous solutions was evaluated in comparison with raw mesoporous silica – coated magnetite (Fe{sub 3}O{sub 4}@MCM-41) and amino – modified mesoporous silica coated magnetite (Fe{sub 3}O{sub 4}@MCM-41-NH{sub 2}). The effect of adsorption process parameters such us pH, contact time, initial Pb(II) concentration was also investigated. The adsorption data were successfully fitted with the Langmuir model, exhibiting a maximum adsorption capacity of 155.71 mg/g at pH=4.4 and T=298 K. The results revealed that the adsorption rate was very high at the beginning of the adsorption process, 80–90% of the total amount of Pb(II) being removed within the first 60 min, depending on the initial concentration. The results of the present work suggest that Fe{sub 3}O{sub 4}@MCM-41-N-oVan is a suitable candidate for the separation of Pb(II) from contaminated water. - Graphical abstract: A novel magnetic adsorbent based on o-vanillin functionalized mesoporous silica – coated magnetite was synthesized and fully characterized and its adsorption capacity for Pb(II) ions in aqueous solutions was evaluated. The maximum adsorption capacity for Pb(II) ions was determined to be 155.71 mg g{sup −1}. The adsorption rate was very high at the beginning of the adsorption process, 90% of the total amount of Pb(II) being removed within the first 60 min. Display Omitted.

o-Vanillin functionalized mesoporous silica – coated magnetite nanoparticles for efficient removal of Pb(II) from water

International Nuclear Information System (INIS)

Culita, Daniela C.; Simonescu, Claudia Maria; Patescu, Rodica-Elena; Dragne, Mioara; Stanica, Nicolae; Oprea, Ovidiu

2016-01-01

o-Vanillin functionalized mesoporous silica – coated magnetite (Fe 3 O 4 @MCM-41-N-oVan) was synthesized and fully characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N 2 adsorption–desorption technique and magnetic measurements. The capacity of Fe 3 O 4 @MCM-41-N-oVan to adsorb Pb(II) from aqueous solutions was evaluated in comparison with raw mesoporous silica – coated magnetite (Fe 3 O 4 @MCM-41) and amino – modified mesoporous silica coated magnetite (Fe 3 O 4 @MCM-41-NH 2 ). The effect of adsorption process parameters such us pH, contact time, initial Pb(II) concentration was also investigated. The adsorption data were successfully fitted with the Langmuir model, exhibiting a maximum adsorption capacity of 155.71 mg/g at pH=4.4 and T=298 K. The results revealed that the adsorption rate was very high at the beginning of the adsorption process, 80–90% of the total amount of Pb(II) being removed within the first 60 min, depending on the initial concentration. The results of the present work suggest that Fe 3 O 4 @MCM-41-N-oVan is a suitable candidate for the separation of Pb(II) from contaminated water. - Graphical abstract: A novel magnetic adsorbent based on o-vanillin functionalized mesoporous silica – coated magnetite was synthesized and fully characterized and its adsorption capacity for Pb(II) ions in aqueous solutions was evaluated. The maximum adsorption capacity for Pb(II) ions was determined to be 155.71 mg g −1 . The adsorption rate was very high at the beginning of the adsorption process, 90% of the total amount of Pb(II) being removed within the first 60 min. Display Omitted

Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H2O2

International Nuclear Information System (INIS)

Dong, Xinbo; Wang, Danjun; Li, Kebin; Zhen, Yanzhong; Hu, Huaiming; Xue, Ganglin

2014-01-01

Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H 2 O 2 , featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH 2 ) are prepared and characterized by FT-IR, XRD, N 2 adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H 2 O 2 as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H 5 [PV 2 W 10 O 40 ] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H 2 O 2

Vapor phase versus liquid phase grafting of meso-porous alumina

NARCIS (Netherlands)

Sripathi, V.G.P.; Mojet, Barbara; Nijmeijer, Arian; Benes, Nieck Edwin

2013-01-01

Functionalization of meso-porous c-alumina has been performed by grafting of 3-Aminopropyltrimethoxysilane (3APTMS) simultaneously from either the liquid phase or from the vapor phase. In both cases, after grafting nitrogen physisorption indicates that the materials remain meso-porous with

Selective Preparation of Furfural from Xylose over Sulfonic Acid Functionalized Mesoporous Sba-15 Materials

Directory of Open Access Journals (Sweden)

Panpan Li

2011-04-01

Full Text Available Sulfonic acid functionalized mesoporous SBA-15 materials were prepared using the co-condensation and grafting methods, respectively, and their catalytic performance in the dehydration of xylose to furfural was examined. SBA-15-SO3H(C prepared by the co-condensation method showed 92–95% xylose conversion and 74% furfural selectivity, and 68–70% furfural yield under the given reaction conditions. The deactivation and regeneration of the SBA-15-SO3H(C catalyst for the dehydration of xylose was also investigated. The results indicate that the used and regeneration catalysts retained the SBA-15 mesoporous structure, and the S content of SBA-15-SO3H(C almost did not change. The deactivation of the catalysts is proposed to be associated with the accumulation of byproducts, which is caused by the loss reaction of furfural. After regeneration by H2O2, the catalytic activity of the catalyst almost recovered.

Thiol-yne/thiol-epoxy hybrid crosslinked materials based on propargyl modified hyperbranched poly(ethyleneimine) and diglycidylether of bisphenol A resins

OpenAIRE

Acebo Gorostiza, Cristina; Fernández Francos, Xavier; Ramis Juan, Xavier; Serra Albet, Àngels

2016-01-01

A novel curing methodology based on the combination of thiol-yne and thiol-epoxy click reactions has been developed. The curing process consists of a first photoinitiated thiol-yne reaction, followed by a thermal thiol-epoxy process. As alkyne substrate a new propargyl terminated hyperbranched poly(ethyleneimine) (PEIyne) has been synthesized from the reaction of commercial poly(ethylenimine) (PEI) and glycidyl propargyl ether. The evolution of the curing of different mixtures of PEIyne and d...

Mesoporous Silicate Materials in Sensing

Directory of Open Access Journals (Sweden)

Paul T. Charles

2008-08-01

Full Text Available Mesoporous silicas, especially those exhibiting ordered pore systems and uniform pore diameters, have shown great potential for sensing applications in recent years. Morphological control grants them versatility in the method of deployment whether as bulk powders, monoliths, thin films, or embedded in coatings. High surface areas and pore sizes greater than 2 nm make them effective as adsorbent coatings for humidity sensors. The pore networks also provide the potential for immobilization of enzymes within the materials. Functionalization of materials by silane grafting or through cocondensation of silicate precursors can be used to provide mesoporous materials with a variety of fluorescent probes as well as surface properties that aid in selective detection of specific analytes. This review will illustrate how mesoporous silicas have been applied to sensing changes in relative humidity, changes in pH, metal cations, toxic industrial compounds, volatile organic compounds, small molecules and ions, nitroenergetic compounds, and biologically relevant molecules.

Studies on alterations of the 86-rubidium efflux from rat pancreatic islets caused by thiol and thiol oxidants

International Nuclear Information System (INIS)

Wahl, M.A.

1983-01-01

The following findings were revealed by this study: 1) Oxidation-reduction (redox) of the intracellular system of glutathione influences the potassium efflux by way of an increase in the 86-rubidium efflux brought about by the oxidation of intracellular thiols. 2) The 86-rubidium efflux is not subject to change by oxidation of extracellular thiols located in the membrane, nor can it in any way be influenced by reduced glutathione of exogenous origin. 3) The potassium efflux from rat pancreatic islets, being generally known to trigger the electric activities of the beta-cell, is controlled by the oxidation-reduction of intracellular thiols rather than by that of extracellular thiols. (TRV) [de

Cytoplasmic glutathione redox status determines survival upon exposure to the thiol-oxidant 4,4'-dipyridyl disulfide

DEFF Research Database (Denmark)

López-Mirabal, H Reynaldo; Thorsen, Michael; Kielland-Brandt, Morten C

2007-01-01

Dipyridyl disulfide (DPS) is a highly reactive thiol oxidant that functions as electron acceptor in thiol-disulfide exchange reactions. DPS is very toxic to yeasts, impairing growth at low micromolar concentrations. The genes TRX2 (thioredoxin), SOD1 (superoxide dismutase), GSH1 (gamma-glutamyl-c......Dipyridyl disulfide (DPS) is a highly reactive thiol oxidant that functions as electron acceptor in thiol-disulfide exchange reactions. DPS is very toxic to yeasts, impairing growth at low micromolar concentrations. The genes TRX2 (thioredoxin), SOD1 (superoxide dismutase), GSH1 (gamma...... antioxidant pools of glutathione (GSH) and thioredoxin are required for resistance to DPS. We found that DPS-sensitive mutants display increases in the disulfide form of GSH (GSSG) during DPS exposure that roughly correlate with their more oxidizing GSH redox potential in the cytosol and their degree of DPS...

Modulating the physicochemical and structural properties of gold-functionalized protein nanotubes through thiol surface modification.

Science.gov (United States)

Carreño-Fuentes, Liliana; Plascencia-Villa, Germán; Palomares, Laura A; Moya, Sergio E; Ramírez, Octavio T

2014-12-16

Biomolecules are advantageous scaffolds for the synthesis and ordering of metallic nanoparticles. Rotavirus VP6 nanotubes possess intrinsic affinity to metal ions, a property that has been exploited to synthesize gold nanoparticles over them. The resulting nanobiomaterials have unique properties useful for novel applications. However, the formed nanobiomaterials lack of colloidal stability and flocculate, limiting their functionality. Here we demonstrate that it is possible to synthesize thiol-protected gold nanoparticles over VP6 nanotubes, which resulted in soluble nanobiomaterials. With this strategy, it was possible to modulate the size, colloidal stability, and surface plasmon resonance of the synthesized nanoparticles by controlling the content of the thiolated ligands. Two types of water-soluble ligands were tested, a small linear ligand, sodium 3-mercapto-1-propanesulfonate (MPS), and a bulky ligand, 5-mercaptopentyl β-D-glucopyranoside (GlcC5SH). The synthesized nanobiomaterials had a higher stability in suspension, as determined by Z-potential measurements. To the extent of our knowledge, this is the first time that a rational strategy is developed to modulate the particular properties of metal nanoparticles in situ synthesized over a protein bioscaffold through thiol coating, achieving a high spatial and structural organization of nanoparticles in a single integrative hybrid structure.

Composite hydrogel based on surface modified mesoporous silica and poly[(2-acryloyloxy)ethyl trimethylammonium chloride

International Nuclear Information System (INIS)

Torres, Cecilia C.; Urbano, Bruno F.; Campos, Cristian H.; Rivas, Bernabé L.; Reyes, Patricio

2015-01-01

This work focused on the synthesis, characterization and water absorbency of a composite hydrogel based on poly[(2-acryloyloxy)ethyl trimethylammonium chloride] and mesoporous silica, MCM-41. The MCM-41 was synthesized and later surface functionalized with triethoxyvinylsilane (VTES) and 3-trimethoxysilylpropylmethacrylate (TMSPM) by a post-grafting procedure. The composite hydrogels were obtained by in-situ polymerization using a mixture of monomer, crosslinker and initiator in the presence of functionalized MCM-41. Diverse characterization techniques were used at the different stages of synthesis, namely, FT-IR, TEM, SEM, DRX, 29 Si and 13 C solid state NMR, and N 2 adsorption isotherms at 77 K. Finally, the water uptake performance of the composites was tested as a function of time, mesoporous silica loading and coupling agent used at the functionalization. The composites using non-functionalized MCM-41 reached the highest water uptake, whereas those composite with MCM-41 TMSPM exhibited the lowest sorption. - Highlights: • Hydrophilic crosslinked polymer-mesoporous silica was obtained. • Mesoporous silica MCM-41 was synthesized and functionalized with organosilane. • Functionalization of MCM-41 affects the water uptake of composite. • Mesoporous silica is covalently bound to the polymer acting as crosslinked point

o-Vanillin functionalized mesoporous silica - coated magnetite nanoparticles for efficient removal of Pb(II) from water

Science.gov (United States)

Culita, Daniela C.; Simonescu, Claudia Maria; Patescu, Rodica-Elena; Dragne, Mioara; Stanica, Nicolae; Oprea, Ovidiu

2016-06-01

o-Vanillin functionalized mesoporous silica - coated magnetite (Fe3O4@MCM-41-N-oVan) was synthesized and fully characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N2 adsorption-desorption technique and magnetic measurements. The capacity of Fe3O4@MCM-41-N-oVan to adsorb Pb(II) from aqueous solutions was evaluated in comparison with raw mesoporous silica - coated magnetite (Fe3O4@MCM-41) and amino - modified mesoporous silica coated magnetite (Fe3O4@MCM-41-NH2). The effect of adsorption process parameters such us pH, contact time, initial Pb(II) concentration was also investigated. The adsorption data were successfully fitted with the Langmuir model, exhibiting a maximum adsorption capacity of 155.71 mg/g at pH=4.4 and T=298 K. The results revealed that the adsorption rate was very high at the beginning of the adsorption process, 80-90% of the total amount of Pb(II) being removed within the first 60 min, depending on the initial concentration. The results of the present work suggest that Fe3O4@MCM-41-N-oVan is a suitable candidate for the separation of Pb(II) from contaminated water.

Synthesis of Single-walled Carbon Nanotubes Coated with Thiol-reactive Gel via Emulsion Polymerization.

Science.gov (United States)

Nagai, Yukiko; Tsutsumi, Yusuke; Nakashima, Naotoshi; Fujigaya, Tsuyohiko

2018-06-15

Single-walled carbon nanotubes (SWNTs) have unique near-infrared absorption and photoemission properties that are attractive for in vivo biological applications such as photothermal cancer treatment and bioimaging. Therefore, a smart functionalization strategy for SWNTs to create biocompatible surfaces and introduce various ligands to target active cancer cells without losing the unique optical properties of the SWNTs is strongly desired. This paper reports the de-sign and synthesis of a SWNT/gel hybrid containing maleimide groups, which react with various thiol compounds through Michael addition reactions. In this hybrid, the method called carbon nanotube micelle polymerization was used to non-covalently modify the surface of SWNTs with a cross-linked polymer gel layer. This method can form an extremely stable gel layer on SWNTs; such stability is essential for in vivo biological applications. The monomer used to form the gel layer contained a maleimide group, which was protected with furan in endo-form. The resulting hybrid was treated in water to induce deprotection via retro Diels-Alder reaction and then functionalized with thiol com-pounds through Michael addition. The functionalization of the hybrid was explored using a thiol-containing fluores-cent dye as a model thiol and the formation of the SWNT-dye conjugate was confirmed by energy transfer from the dye to SWNTs. Our strategy offers a promising SWNT-based platform for biological functionalization for cancer targeting, imaging, and treatment.

Imprint-coating synthesis of selective functionalized ordered mesoporous sorbents for separation and sensors

Science.gov (United States)

Dai, Sheng; Burleigh, Mark C.; Shin, Yongsoon

2001-01-01

The present invention relates generally to mesoporous sorbent materials having high capacity, high selectivity, fast kinetics, and molecular recognition capability. The invention also relates to a process for preparing these mesoporous substrates through molecular imprinting techniques which differ from convention techniques in that a template molecule is bound to one end of bifunctional ligands to form a complex prior to binding of the bifunctional ligands to the substrate. The present invention also relates to methods of using the mesoporous sorbent materials, for example, in the separation of toxic metals from process effluents, paints, and other samples; detection of target molecules, such as amino acids, drugs, herbicides, fertilizers, and TNT, in samples; separation and/or detection of substances using chromatography; imaging agents; sensors; coatings; and composites.

Dynamic thiol/disulphide homeostasis in patients with basal cell carcinoma.

Science.gov (United States)

Demirseren, Duriye Deniz; Cicek, Cagla; Alisik, Murat; Demirseren, Mustafa Erol; Aktaş, Akın; Erel, Ozcan

2017-09-01

The aim of this study is to measure and compare the dynamic thiol/disulphide homeostasis of patients with basal cell carcinoma and healthy subjects with a newly developed and original method. Thirty four patients attending our outpatient clinic and clinically and histopathologically diagnosed as nodular basal cell carcinoma, and age and gender matched 30 healthy individuals have been involved in the study. Thiol/disulphide homeostasis tests have been measured with a novel automatic spectrophotometric method developed and the results have been compared statistically. Serum native thiol and disulphide levels in the patient and control group show a considerable variance statistically (p = 0.028, 0.039, respectively). Total thiol levels do not reveal a considerable variation (p = 0.094). Disulphide/native thiol ratios and native thiol/total thiol ratios also show a considerable variance statistically (p = 0.012, 0.013, 0.010, respectively). Thiol disulphide homeostasis in patients with basal cell carcinoma alters in the way that disulphide gets lower and thiols get higher. Thiol/disulphide level is likely to have a role in basal cell carcinoma pathogenesis.

Catalytic Activity and Photophysical Properties of Biomolecules Immobilized on Mesoporous Silica

DEFF Research Database (Denmark)

Ikemoto, Hideki

Mesoporous silicas, based on Santa Barbara Amorphous-15 (SBA-15), with different morphology, structure, pore size and functional groups have been synthesized. Two metalloenzymes and a photosynthetic membrane protein were immobilized on or confined in the pores of the mesoporous silicas to prepare...

Redox-Triggered Bonding-Induced Emission of Thiol-Functionalized Gold Nanoclusters for Luminescence Turn-On Detection of Molecular Oxygen.

Science.gov (United States)

Ao, Hang; Feng, Hui; Zhao, Mengting; Zhao, Meizhi; Chen, Jianrong; Qian, Zhaosheng

2017-11-22

Most optical sensors for molecular oxygen were developed based on the quenching effect of the luminescence of oxygen-sensitive probes; however, the signal turn-off mode of these probes is undesirable to quantify and visualize molecular oxygen. Herein, we report a novel luminescence turn-on detection strategy for molecular oxygen via the specific oxygen-triggered bonding-induced emission of thiol-functionalized gold nanoclusters. Thiol-functionalized gold nanoclusters were prepared by a facile one-step synthesis, and as-prepared gold nanoclusters possess significant aggregation-induced emission (AIE) property. It is the first time to discover the oxygen-triggered bonding-induced emission (BIE) behavior of gold nanoclusters, which results in disulfide-linked covalent bonding assemblies with intensely red luminescence. This specific redox-triggered BIE is capable of quantitatively detecting dissolved oxygen in aqueous solution in a light-up manner, and trace amount of dissolved oxygen at ppb level is achieved based on this detection method. A facile and convenient test strip for oxygen detection was also developed to monitor molecular oxygen in a gas matrix. Covalent bonding-induced emission is proven to be a more efficient way to attain high brightness of AIEgens than a physical aggregation-induced emission process, and provides a more convenient and desirable detection method for molecular oxygen than the previous sensors.

Low molecular weight thiols and thioredoxins are important players in Hg(II) resistance in Thermus thermophilus HB27.

Science.gov (United States)

Norambuena, J; Wang, Y; Hanson, T; Boyd, J M; Barkay, T

2017-11-17

known about how mer systems interact with cellular thiol systems. Thermus spp. possess a simple mer operon in which a low molecular weight thiol biosynthesis gene is present, along with merR and merA In this study, we present experimental evidence for the role of thiol systems in mercury resistance. Our data suggest that in T. thermophilus thiolated compounds may function side-by-side with mer genes to detoxify mercury. Thus, thiol systems function in consort with mer -mediated resistance to mercury, suggesting exciting new questions for future research. Copyright © 2017 American Society for Microbiology.

Folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell composite particles: synthesis and application in drug release.

Science.gov (United States)

Yang, Dandan; Wei, Kaiwei; Liu, Qi; Yang, Yong; Guo, Xue; Rong, Hongren; Cheng, Mei-Ling; Wang, Guoxiu

2013-07-01

A drug delivery system was designed by deliberately combining the useful functions into one entity, which was composed of magnetic ZnFe2O4 hollow microsphere as the core, and mesoporous silica with folic acid molecules as the outer shell. Amine groups coated magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NH2) composite particles were first synthesized by a one-pot direct co-condensation method. Subsequently a novel kind of folic acid-functionalized magnetic ZnFe2O4 hollow microsphere core/mesoporous silica shell (MZHM-MSS-NHFA) composite particles were synthesized by conjugating folic acid as targeted molecule to MZHM-MSS-NH2. Ibuprofen, a well-known antiphlogistic drug, was used as a model drug to assess the loading and releasing behavior of the composite microspheres. The results show that the MZHM-MSS-NHFA system has the higher capacity of drug storage and good sustained drug-release property. Copyright © 2013 Elsevier B.V. All rights reserved.

Involvement of thiol-based mechanisms in plant development.

Science.gov (United States)

Rouhier, Nicolas; Cerveau, Delphine; Couturier, Jérémy; Reichheld, Jean-Philippe; Rey, Pascal

2015-08-01

Increasing knowledge has been recently gained regarding the redox regulation of plant developmental stages. The current state of knowledge concerning the involvement of glutathione, glutaredoxins and thioredoxins in plant development is reviewed. The control of the thiol redox status is mainly ensured by glutathione (GSH), a cysteine-containing tripeptide and by reductases sharing redox-active cysteines, glutaredoxins (GRXs) and thioredoxins (TRXs). Indeed, thiol groups present in many regulatory proteins and metabolic enzymes are prone to oxidation, ultimately leading to post-translational modifications such as disulfide bond formation or glutathionylation. This review focuses on the involvement of GSH, GRXs and TRXs in plant development. Recent studies showed that the proper functioning of root and shoot apical meristems depends on glutathione content and redox status, which regulate, among others, cell cycle and hormone-related processes. A critical role of GRXs in the formation of floral organs has been uncovered, likely through the redox regulation of TGA transcription factor activity. TRXs fulfill many functions in plant development via the regulation of embryo formation, the control of cell-to-cell communication, the mobilization of seed reserves, the biogenesis of chloroplastic structures, the metabolism of carbon and the maintenance of cell redox homeostasis. This review also highlights the tight relationships between thiols, hormones and carbon metabolism, allowing a proper development of plants in relation with the varying environment and the energy availability. GSH, GRXs and TRXs play key roles during the whole plant developmental cycle via their antioxidant functions and the redox-regulation of signaling pathways. This article is part of a Special Issue entitled Redox regulation of differentiation and de-differentiation. Copyright © 2015 Elsevier B.V. All rights reserved.

Novel thiols of prokaryotes.

Science.gov (United States)

Fahey, R C

2001-01-01

Glutathione metabolism is associated with oxygenic cyanobacteria and the oxygen-utilizing purple bacteria, but is absent in many other prokaryotes. This review focuses on novel thiols found in those bacteria lacking glutathione. Included are glutathione amide and its perthiol, produced by phototrophic purple sulfur bacteria and apparently involved in their sulfide metabolism. Among archaebacteria, coenzyme M (2-mercaptoethanesulfonic acid) and coenzyme B (7-mercaptoheptanoylthreonine phosphate) play central roles in the anaerobic production of CH4 and associated energy conversion by methanogens, whereas the major thiol in the aerobic phototrophic halobacteria is gamma-glutamylcysteine. The highly aerobic actinomycetes produce mycothiol, a conjugate of N-acetylcysteine with a pseudodisaccharide of glucosamine and myo-inositol, AcCys-GlcNalpha(1 --> 1)Ins, which appears to play an antioxidant role similar to glutathione. Ergothioneine, also produced by actinomycetes, remains a mystery despite many years of study. Available data on the biosynthesis and metabolism of these and other novel thiols is summarized and key areas for additional study are identified.

Vanadium-substituted heteropolyacids immobilized on amine- functionalized mesoporous MCM-41: A recyclable catalyst for selective oxidation of alcohols with H{sub 2}O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Dong, Xinbo [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Wang, Danjun [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Li, Kebin [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Zhen, Yanzhong [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); College of Chemistry Chemical Engineering, Yanan University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan' an 716000 (China); Hu, Huaiming [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China); Xue, Ganglin, E-mail: xglin707@163.com [Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Department of Chemistry (Ministry of Education), Northwest University, Xi' an 710069 (China)

2014-09-15

Graphical abstract: Vanadium-substituted phosphotungstic acids are immobilized on amine- functionalized mesoporous MCM-41 and the hybrid catalyst is proved to be a highly efficient solid catalyst for the oxidation of aromatic alcohols to the corresponding carbonyl compounds with H{sub 2}O{sub 2}, featured by the high conversion and selectivity, easy recovery, and quite steady reuse. - Highlights: • Vanadium-substituted phosphotungstic acid immobilized on amine-functionalized mesoporous MCM-41 are prepared. • HPAs were fixed on the inner surface of mesoporous MCM-41 by chemical bonding to aminosilane groups. • The hybrid catalyst showed much higher catalytic activity than the pure HPAs. • The hybrid catalyst is a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols. - Abstract: New hybrid materials of vanadium-substituted phosphotungstic acids (VHPW) immobilized on amine-functionalized mesoporous MCM-41 (VHPW/MCM-41/NH{sub 2}) are prepared and characterized by FT-IR, XRD, N{sub 2} adsorption, elemental analysis, SEM and TEM for their structural integrity and physicochemical properties. It is found that the structure of the heteropolyacids is retained upon immobilization over mesoporous materials. The catalytic activities of these hybrid materials are tested in the selective oxidation of alcohols to the carbonyl products with 30% aqueous H{sub 2}O{sub 2} as oxidant in toluene. The catalytic activities of different number of vanadium-substituted phosphotungstic acid are investigated, and among the catalysts, H{sub 5}[PV{sub 2}W{sub 10}O{sub 40}] immobilized on amine-functionalized MCM-41 exhibits the highest activity with 97% conversion and 99% selectivity in the oxidation of benzyl alcohol to benzaldehyde. The hybrid catalyst is proved to be a highly efficient recyclable solid catalyst for the selective oxidation of aromatic alcohols to the corresponding aldehydes with H{sub 2}O{sub 2}.

Ordered mesoporous silica (OMS) as an adsorbent and membrane for separation of carbon dioxide (CO2).

Science.gov (United States)

Chew, Thiam-Leng; Ahmad, Abdul L; Bhatia, Subhash

2010-01-15

Separation of carbon dioxide (CO(2)) from gaseous mixture is an important issue for the removal of CO(2) in natural gas processing and power plants. The ordered mesoporous silicas (OMS) with uniform pore structure and high density of silanol groups, have attracted the interest of researchers for separation of carbon dioxide (CO(2)) using adsorption process. These mesoporous silicas after functionalization with amino groups have been studied for the removal of CO(2). The potential of functionalized ordered mesoporous silica membrane for separation of CO(2) is also recognized. The present paper reviews the synthesis of mesoporous silicas and important issues related to the development of mesoporous silicas. Recent studies on the CO(2) separation using ordered mesoporous silicas (OMS) as adsorbent and membrane are highlighted. The future prospectives of mesoporous silica membrane for CO(2) adsorption and separation are also presented and discussed. Copyright 2009 Elsevier B.V. All rights reserved.

Composite hydrogel based on surface modified mesoporous silica and poly[(2-acryloyloxy)ethyl trimethylammonium chloride

Energy Technology Data Exchange (ETDEWEB)

Torres, Cecilia C. [Department of Organic Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Urbano, Bruno F., E-mail: burbano@udec.cl [Department of Polymer Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Campos, Cristian H. [Department of Organic Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Rivas, Bernabé L. [Department of Polymer Chemistry, Faculty of Chemical Science, University of Concepción (Chile); Reyes, Patricio [Department of Physical Chemistry, Faculty of Chemical Science, University of Concepción (Chile)

2015-02-15

This work focused on the synthesis, characterization and water absorbency of a composite hydrogel based on poly[(2-acryloyloxy)ethyl trimethylammonium chloride] and mesoporous silica, MCM-41. The MCM-41 was synthesized and later surface functionalized with triethoxyvinylsilane (VTES) and 3-trimethoxysilylpropylmethacrylate (TMSPM) by a post-grafting procedure. The composite hydrogels were obtained by in-situ polymerization using a mixture of monomer, crosslinker and initiator in the presence of functionalized MCM-41. Diverse characterization techniques were used at the different stages of synthesis, namely, FT-IR, TEM, SEM, DRX, {sup 29}Si and {sup 13}C solid state NMR, and N{sub 2} adsorption isotherms at 77 K. Finally, the water uptake performance of the composites was tested as a function of time, mesoporous silica loading and coupling agent used at the functionalization. The composites using non-functionalized MCM-41 reached the highest water uptake, whereas those composite with MCM-41 TMSPM exhibited the lowest sorption. - Highlights: • Hydrophilic crosslinked polymer-mesoporous silica was obtained. • Mesoporous silica MCM-41 was synthesized and functionalized with organosilane. • Functionalization of MCM-41 affects the water uptake of composite. • Mesoporous silica is covalently bound to the polymer acting as crosslinked point.

Thioredoxin Selectivity for Thiol-based Redox Regulation of Target Proteins in Chloroplasts*

Science.gov (United States)

Yoshida, Keisuke; Hara, Satoshi; Hisabori, Toru

2015-01-01

Redox regulation based on the thioredoxin (Trx) system is believed to ensure light-responsive control of various functions in chloroplasts. Five Trx subtypes have been reported to reside in chloroplasts, but their functional diversity in the redox regulation of Trx target proteins remains poorly clarified. To directly address this issue, we studied the Trx-dependent redox shifts of several chloroplast thiol-modulated enzymes in vitro and in vivo. In vitro assays using a series of Arabidopsis recombinant proteins provided new insights into Trx selectivity for the redox regulation as well as the underpinning for previous suggestions. Most notably, by combining the discrimination of thiol status with mass spectrometry and activity measurement, we identified an uncharacterized aspect of the reductive activation of NADP-malate dehydrogenase; two redox-active Cys pairs harbored in this enzyme were reduced via distinct utilization of Trxs even within a single polypeptide. In our in vitro assays, Trx-f was effective in reducing all thiol-modulated enzymes analyzed here. We then investigated the in vivo physiological relevance of these in vitro findings, using Arabidopsis wild-type and Trx-f-deficient plants. Photoreduction of fructose-1,6-bisphosphatase was partially impaired in Trx-f-deficient plants, but the global impact of Trx-f deficiency on the redox behaviors of thiol-modulated enzymes was not as striking as expected from the in vitro data. Our results provide support for the in vivo functionality of the Trx system and also highlight the complexity and plasticity of the chloroplast redox network. PMID:25878252

Noncovalently functionalized graphitic mesoporous carbon as a stable support of Pt nanoparticles for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Shao, Yuyan; Zhang, Sheng; Kou, Rong; Wang, Chongmin; Viswanathan, Vilayanur; Liu, Jun; Wang, Yong; Lin, Yuehe [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Wang, Xiqing; Dai, Sheng [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

2010-04-02

We report a durable electrocatalyst support, highly graphitized mesoporous carbon (GMPC), for oxygen reduction in polymer electrolyte membrane (PEM) fuel cells. GMPC is prepared through graphitizing the self-assembled soft-template mesoporous carbon (MPC) under high temperature. Heat-treatment at 2800 C greatly improves the degree of graphitization while most of the mesoporous structures and the specific surface area of MPC are retained. GMPC is then noncovalently functionalized with poly(diallyldimethylammonium chloride) (PDDA) and loaded with Pt nanoparticles by reducing Pt precursor (H{sub 2}PtCl{sub 6}) in ethylene glycol. Pt nanoparticles of {proportional_to}3.0 nm in diameter are uniformly dispersed on GMPC. Compared to Pt supported on Vulcan XC-72 carbon black (Pt/XC-72), Pt/GMPC exhibits a higher mass activity towards oxygen reduction reaction (ORR) and the mass activity retention (in percentage) is improved by a factor of {proportional_to}2 after 44 h accelerated degradation test under the potential step (1.4-0.85 V) electrochemical stressing condition which focuses on support corrosion. The enhanced activity and durability of Pt/GMPC are attributed to the graphitic structure of GMPC which is more resistant to corrosion. These findings demonstrate that GMPC is a promising oxygen reduction electrocatalyst support for PEM fuel cells. The approach reported in this work provides a facile, eco-friendly promising strategy for synthesizing stable metal nanoparticles on hydrophobic support materials. (author)

Novel one-pot synthesis and characterization of bioactive thiol-silicate nanoparticles for biocatalytic and biosensor applications

International Nuclear Information System (INIS)

Neville, Frances; Pchelintsev, Nikolay A; Broderick, Michael J F; Gibson, Tim; Millner, Paul A

2009-01-01

A novel one-pot neutral synthesis using bioinspired polymers to fabricate thiol-nanoparticles is presented. The thiol-particles may be directly tethered to metal surfaces such as gold, allowing the production of self-assembled nanostructured biocatalytic or biosensor surfaces. This one-pot method has also been used to entrap enzymes within the thiol-nanoparticles; it is apparent that once enzyme entrapment is carried out a bimodal distribution of particles is formed, with particles of one mode being very similar in size to thiol-nanoparticles without enzyme entrapped, and particles of the other mode being much larger in size. To this end, efforts have been made to separate the two modes of particles for the sample containing enzyme and it has been observed that the larger mode thiol-nanoparticles do indeed contain significant amounts of enzyme in comparison to the smaller mode ones. As the enzyme-containing thiol-nanoparticles can now be isolated, this means that there are many future possibilities for the use of thiol-particles containing enzyme, as they may be used in a wide range of processes and devices which require catalytic functionalized surfaces, such as biosensors and biocatalytic reactors.

Amine-functionalized magnetic mesoporous silica nanoparticles for DNA separation

Energy Technology Data Exchange (ETDEWEB)

Sheng, Wei; Wei, Wei; Li, Junjian; Qi, Xiaoliang; Zuo, Gancheng; Chen, Qi; Pan, Xihao; Dong, Wei, E-mail: weidong@njust.edu.cn

2016-11-30

Highlights: • Fe{sub 3}O{sub 4}@SiO{sub 2}@EDPS with uniform size and good dispersity is prepared. • We fabricated MMSN@EDPS with distinct core-shell–shell triple-layer composition. • DNA adsorption capacity of MMSN@EDPS is considerable. - Abstract: We report a modified approach for the functionalized magnetic mesoporous silica nanoparticles (MMSN) using polymer microspheres incorporated with magnetic nanoparticles in the presence of cetyltrimethylammonium bromide (CTAB) and the core-shell magnetic silica nanoparticles (MSN). These particles were functionalized with amino groups via the addition of aminosilane directly to the particle sol. We then evaluate their DNA separation abilities and find the capacity of DNA binding significantly increased (210.22 μg/mg) compared with normal magnetic silica spheres (138.44 μg/mg) by using an ultraviolet and visible spectrophotometer (UV). The morphologies, magnetic properties, particle size, pore size, core-shell structure and Zeta potential are characterized by Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometer (VSM), Transmission electron microscopy (TEM), Powder X-ray diffraction (XRD), and dynamic light scattering (DLS). This work demonstrates that our MMSN own an excellent potential application in bioseparation and drug delivery.

Chemiluminescence immunoassay based on dual signal amplification strategy of Au/mesoporous silica and multienzyme functionalized mesoporous silica

Energy Technology Data Exchange (ETDEWEB)

Lin Jiehua, E-mail: linjiehua@qust.edu.cn [Key Laboratory of Eco-chemical Engineering, Ministry of Education, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China); Zhao Yue; Wei Zhijing; Wang Wei [Key Laboratory of Eco-chemical Engineering, Ministry of Education, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 (China)

2011-11-15

Highlights: > The increased amount of monoclonal antibody in Au/SiO{sub 2} led to a wider linear range. > Due to the increased HRP tags in HRP-Ab{sub 2}/SiO{sub 2}, signal amplification achieved. > A simple dual amplification immunoassay achieved with flow injection analysis. - Abstract: A chemiluminescent dual signal amplification strategy for the determination of {alpha}-fetoprotein (AFP) was proposed based on a sandwich immunoassay format. Monoclonal antibody of AFP immobilized on the gold nanoparticles doped mesoporous SiO{sub 2} (Au/SiO{sub 2}) were prepared and used as a primary antibody. Horseradish peroxidase (HRP) and HRP-labeled secondary antibody (Ab{sub 2}) co-immobilized into the mesoporous SiO{sub 2} nanoparticles (HRP-Ab{sub 2}/SiO{sub 2}) were used as the labeled immunological probe. Due to the high ratio surface areas and pore volumes of the mesoporous SiO{sub 2}, not only the amount of AFP monoclonal antibody but also the amount of the modified HRP and Ab{sub 2} in HRP-Ab{sub 2}/SiO{sub 2} were largely increased. Thus the chemiluminescent signal was amplified by using the system of luminol and H{sub 2}O{sub 2} under the catalysis of HRP. Under the optimal conditions, two linear ranges for AFP were obtained from 0.01 to 0.5 ng mL{sup -1} and 0.5 to 100 ng mL{sup -1} with a detection limit of 0.005 ng mL{sup -1} (3{sigma}). The fabricated signal amplification strategy showed an excellent promise for sensitive detection of AFP and other tumor markers.

Synthesis and characterization of mesoporous NaY zeolite from natural Blitar’s kaolin

Science.gov (United States)

Khalifah, S. N.; aini, Z. N.; Hayati, E. K.; Aini, N.; Prasetyo, A.

2018-03-01

Mesoporous NaY Zeolite has been synthesized from calcined natural Blitar’s kaolin with the addition of NaOH and CTABr surfactant as mesoporous template by hydrothermal method. Natural kaolin was calcinated with different time and temperature to change kaolin to metakaolin. X-ray diffraction data showed that mesoporous NaY zeolite was formed with impurities compound of sodalite, kaolin and quartz phases. The BET analysis resulted that the pore of NaY Zeolite belongs to mesoporous type with pore size 9,421 nm. Characterization from FTIR confirmed about the functional group of zeolites (988, 776, 663, 464 cm-1). Scanning electron microscopy characterization showed that the morphological of mesoporous NaY zeolites have uniform and crystalline particles formed.

One-step fabrication of PEGylated fluorescent nanodiamonds through the thiol-ene click reaction and their potential for biological imaging

Science.gov (United States)

Huang, Hongye; Liu, Meiying; Tuo, Xun; Chen, Junyu; Mao, Liucheng; Wen, Yuanqing; Tian, Jianwen; Zhou, Naigen; Zhang, Xiaoyong; Wei, Yen

2018-05-01

Over the past years, fluorescent carbon nanoparticles have got growing interest for biological imaging. Fluorescent nanodiamonds (FNDs) are novel fluorescent carbon nanoparticles with multitudinous useful properties, including remarkable fluorescence properties, extremely low toxicity and high refractive index. However, facile preparation of FNDs with designable properties and functions from non-fluorescent detonation nanodiamonds (DNDs) has demonstrated to be challengeable. In this work, we reported for the first time that preparation of Polyethylene glycol (PEG) functionalized FNDs through a one-step thiol-ene click reaction using thiol containing PEG (PEG-SH) as the coating agent. Based on the characterization results, we demonstrated that PEG-SH could be efficiently introduced on DNDs to obtain FNDs through the thiol-ene click chemistry. The resultant FND-PEG composites showed high water dispersibility, strong fluorescence and low cytotoxicity. Moreover, FND-PEG composites could be internalized by cells and displayed good cell dyeing performance. All of these features implied that FND-PEG composites are of great potential for biological imaging. Taken together, a facile one-step strategy based on the one-step thiol-ene click reaction has been developed for efficient preparation of FND-PEG composites from non-fluorescent DNDs. The strategy should be also useful for fabrication of many other functional FNDs via using different thiol containing compounds for the universality of thiol-ene click reaction.

Synthesis and Physicochemical Characterization of Mesoporous SiO2 Nanoparticles

Directory of Open Access Journals (Sweden)

Dharani Das

2014-01-01

Full Text Available There exists a knowledge gap in understanding potential toxicity of mesoporous silica nanoparticles. A critical step in assessing toxicity of these particles is to have a wide size range with different chemistries and physicochemical properties. There are several challenges when synthesizing mesoporous silica nanoparticles over a wide range of sizes including (1 nonuniform synthesis protocols using the same starting materials, (2 the low material yield in a single batch synthesis (especially for particles below 60–70 nm, and (3 morphological instability during surfactant removal process and surface modifications. In this study, we synthesized a library of mesoporous silica nanoparticles with approximate particle sizes of 25, 70, 100, 170, and 600 nm. Surfaces of the silica nanoparticles were modified with hydrophilic-CH2–(CH22–COOH and relatively hydrophobic-CH2–(CH210–COOH functional groups. All silica nanoparticles were analysed for morphology, surface functionality, surface area/pore volume, surface organic content, and dispersion characteristics in liquid media. Our analysis revealed the synthesis of a spectrum of monodisperse bare and surface modified mesoporous silica nanoparticles with a narrow particle size distribution and devoid of cocontaminants critical for toxicity studies. Complete physicochemical characterization of these synthetic mesoporous silica nanoparticles will permit systematic toxicology studies for investigation of structure-activity relationships.

Mesoporous silica nanoparticles functionalized with folic acid/methionine for active targeted delivery of docetaxel

Directory of Open Access Journals (Sweden)

Khosravian P

2016-12-01

Full Text Available Pegah Khosravian,1 Mehdi Shafiee Ardestani,2 Mehdi Khoobi,3 Seyed Naser Ostad,4 Farid Abedin Dorkoosh,1 Hamid Akbari Javar,1,* Massoud Amanlou5,6,* 1Department of Pharmaceutics, 2Department of Radiopharmacy, 3Department of Pharmaceutical Biomaterials, 4Department of Pharmacology and Toxicology, 5Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, 6Drug Design and Development Research Center, Tehran University of Medical Sciences, Tehran, Iran *These authors contributed equally to this work Abstract: Mesoporous silica nanoparticles (MSNs are known as carriers with high loading capacity and large functionalizable surface area for target-directed delivery. In this study, a series of docetaxel-loaded folic acid- or methionine-functionalized mesoporous silica nanoparticles (DTX/MSN-FA or DTX/MSN-Met with large pores and amine groups at inner pore surface properties were prepared. The results showed that the MSNs were successfully synthesized, having good pay load and pH-sensitive drug release kinetics. The cellular investigation on MCF-7 cells showed better performance of cytotoxicity and cell apoptosis and an increase in cellular uptake of targeted nanoparticles. In vivo fluorescent imaging on healthy BALB/c mice proved that bare MSN-NH2 are mostly accumulated in the liver but MSN-FA or MSN-Met are more concentrated in the kidney. Importantly, ex vivo fluorescent images of tumor-induced BALB/c mice organs revealed the ability of MSN-FA to reach the tumor tissues. In conclusion, DTX/MSNs exhibited a good anticancer activity and enhanced the possibility of targeted drug delivery for breast cancer. Keywords: targeted delivery, mesoporous silica nanoparticle, folic acid, methionine, docetaxel

Biomimetic synthesized chiral mesoporous silica: Structures and controlled release functions as drug carrier

Energy Technology Data Exchange (ETDEWEB)

Li, Jing; Xu, Lu, E-mail: xl2013109@163.com; Yang, Baixue; Bao, Zhihong; Pan, Weisan; Li, Sanming, E-mail: li_sanming2013@163.com

2015-10-01

This work initially illustrated the formation mechanism of chiral mesoporous silica (CMS) in a brand new insight named biomimetic synthesis. Three kinds of biomimetic synthesized CMS (B-CMS, including B-CMS1, B-CMS2 and B-CMS3) were prepared using different pH or stirring rate condition, and their characteristics were tested with transmission electron microscope and small angle X-ray diffraction. The model drug indomethacin was loaded into B-CMS and drug loading content was measured using ultraviolet spectroscopy. The result suggested that pH condition influenced energetics of self-assembly process, mainly packing energetics of the surfactant, while stirring rate was the more dominant factor to determine particle length. In application, indomethacin loading content was measured to be 35.3%, 34.8% and 35.1% for indomethacin loaded B-CMS1, indomethacin loaded B-CMS2 and indomethacin loaded B-CMS3. After loading indomethacin into B-CMS carriers, surface area, pore volume and pore diameter of B-CMS carriers were reduced. B-CMS converted crystalline state of indomethacin to amorphous state, leading to the improved indomethacin dissolution. B-CMS1 controlled drug release without burst-release, while B-CMS2 and B-CMS3 released indomethacin faster than B-CMS1, demonstrating that the particle length, the ordered lever of multiple helixes, the curvature degree of helical channels and pore diameter greatly contributed to the release behavior of indomethacin loaded B-CMS. - Highlights: • Chiral mesoporous silica was synthesized using biomimetic method. • pH influenced energetics of self-assembly process of chiral mesoporous silica. • Stirring rate determined the particle length of chiral mesoporous silica. • Controlled release behaviors of chiral mesoporous silica varied based on structures.

Biomimetic synthesized chiral mesoporous silica: Structures and controlled release functions as drug carrier

International Nuclear Information System (INIS)

Li, Jing; Xu, Lu; Yang, Baixue; Bao, Zhihong; Pan, Weisan; Li, Sanming

2015-01-01

This work initially illustrated the formation mechanism of chiral mesoporous silica (CMS) in a brand new insight named biomimetic synthesis. Three kinds of biomimetic synthesized CMS (B-CMS, including B-CMS1, B-CMS2 and B-CMS3) were prepared using different pH or stirring rate condition, and their characteristics were tested with transmission electron microscope and small angle X-ray diffraction. The model drug indomethacin was loaded into B-CMS and drug loading content was measured using ultraviolet spectroscopy. The result suggested that pH condition influenced energetics of self-assembly process, mainly packing energetics of the surfactant, while stirring rate was the more dominant factor to determine particle length. In application, indomethacin loading content was measured to be 35.3%, 34.8% and 35.1% for indomethacin loaded B-CMS1, indomethacin loaded B-CMS2 and indomethacin loaded B-CMS3. After loading indomethacin into B-CMS carriers, surface area, pore volume and pore diameter of B-CMS carriers were reduced. B-CMS converted crystalline state of indomethacin to amorphous state, leading to the improved indomethacin dissolution. B-CMS1 controlled drug release without burst-release, while B-CMS2 and B-CMS3 released indomethacin faster than B-CMS1, demonstrating that the particle length, the ordered lever of multiple helixes, the curvature degree of helical channels and pore diameter greatly contributed to the release behavior of indomethacin loaded B-CMS. - Highlights: • Chiral mesoporous silica was synthesized using biomimetic method. • pH influenced energetics of self-assembly process of chiral mesoporous silica. • Stirring rate determined the particle length of chiral mesoporous silica. • Controlled release behaviors of chiral mesoporous silica varied based on structures

Cisplatin impairs rat liver mitochondrial functions by inducing changes on membrane ion permeability: Prevention by thiol group protecting agents

International Nuclear Information System (INIS)

Custodio, Jose B.A.; Cardoso, Carla M.P.; Santos, Maria S.; Almeida, Leonor M.; Vicente, Joaquim A.F.; Fernandes, Maria A.S.

2009-01-01

Cisplatin (CisPt) is the most important platinum anticancer drug widely used in the treatment of head, neck, ovarian and testicular cancers. However, the mechanisms by which CisPt induces cytotoxicity, namely hepatotoxicity, are not completely understood. The goal of this study was to investigate the influence of CisPt on rat liver mitochondrial functions (Ca 2+ -induced mitochondrial permeability transition (MPT), mitochondrial bioenergetics, and mitochondrial oxidative stress) to better understand the mechanism underlying its hepatotoxicity. The effect of thiol group protecting agents and some antioxidants against CisPt-induced mitochondrial damage was also investigated. Treatment of rat liver mitochondria with CisPt (20 nmol/mg protein) induced Ca 2+ -dependent mitochondrial swelling, depolarization of membrane potential (ΔΨ), Ca 2+ release, and NAD(P)H fluorescence intensity decay. These effects were prevented by cyclosporine A (CyA), a potent and specific inhibitor of the MPT. In the concentration range of up to 40 nmol/mg protein, CisPt slightly inhibited state 3 and stimulated state 2 and state 4 respiration rates using succinate as respiratory substrate. The respiratory indexes, respiratory control ratio (RCR) and ADP/O ratios, the ΔΨ, and the ADP phosphorylation rate were also depressed. CisPt induced mitochondrial inner membrane permeabilization to protons (proton leak) but did not induce significant changes on mitochondrial H 2 O 2 generation. All the effects induced by CisPt on rat liver mitochondria were prevented by thiol group protecting agents namely, glutathione (GSH), dithiothreitol (DTT), N-acetyl-L-cysteine (NAC) and cysteine (CYS), whereas superoxide-dismutase (SOD), catalase (CAT) and ascorbate (ASC) were without effect. In conclusion, the anticancer drug CisPt: (1) increases the sensitivity of mitochondria to Ca 2+ -induced MPT; (2) interferes with mitochondrial bioenergetics by increasing mitochondrial inner membrane permeabilization to

Contribution of mesopores in MgO-templated mesoporous carbons to capacitance in non-aqueous electrolytes

Science.gov (United States)

Kado, Yuya; Soneda, Yasushi; Yoshizawa, Noriko

2015-02-01

MgO-templated mesoporous carbons were fabricated by annealing trimagnesium dicitrate nonahydrate at various temperatures from 700 to 1000 °C with subsequent acid leaching of MgO. The obtained carbons contained a large amount of mesopores. Performances of electric double-layer capacitors using these carbons were examined for propylene carbonate electrolyte containing 1 M tetraethylammonium tetrafluoroborate. The mesoporous carbons synthesized at higher temperatures showed better rate capabilities. AC impedance measurements indicated that high-temperature annealing of the carbon precursors and the presence of mesopores were important for high rate performance. In addition, the contribution of mesopores to capacitance was more significant at higher current densities of 30 A g-1.

Synthesis of non-siliceous mesoporous oxides.

Science.gov (United States)

Gu, Dong; Schüth, Ferdi

2014-01-07

Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

Functionalization of mesoporous materials for lanthanide and actinide extraction.

Science.gov (United States)

Florek, Justyna; Giret, Simon; Juère, Estelle; Larivière, Dominic; Kleitz, Freddy

2016-10-14

Among the energy sources currently available that could address our insatiable appetite for energy and minimize our CO2 emission, solar, wind, and nuclear energy currently occupy an increasing portion of our energy portfolio. The energy associated with these sources can however only be harnessed after mineral resources containing valuable constituents such as actinides (Ac) and rare earth elements (REEs) are extracted, purified and transformed into components necessary for the conversion of energy into electricity. Unfortunately, the environmental impacts resulting from their manufacture including the generation of undesirable and, sometimes, radioactive wastes and the non-renewable nature of the mineral resources, to name a few, have emerged as challenges that should be addressed by the scientific community. In this perspective, the recent development of functionalized solid materials dedicated to selective elemental separation/pre-concentration could provide answers to several of the above-mentioned challenges. This review focuses on recent advances in the field of mesoporous solid-phase (SP) sorbents designed for REEs and Ac liquid-solid extraction. Particular attention will be devoted to silica and carbon sorbents functionalized with commonly known ligands, such as phosphorus or amide-containing functionalities. The extraction performances of these new systems are discussed in terms of sorption capacity and selectivity. In order to support potential industrial applications of the silica and carbon-based sorbents, their main drawbacks and advantages are highlighted and discussed.

A Search for Interstellar Monohydric Thiols

Energy Technology Data Exchange (ETDEWEB)

Gorai, Prasanta; Das, Ankan; Das, Amaresh; Chakrabarti, Sandip K. [Indian Centre for Space Physics, 43 Chalantika, Garia Station Rd., Kolkata, 700084 (India); Sivaraman, Bhalamurugan [Atomic Molecular and Optical Physics Division, Physical Research Laboratory, Ahmedabad, 380009 (India); Etim, Emmanuel E., E-mail: ankan.das@gmail.com [Indian Institute of Science Bangalore, 560012 (India)

2017-02-10

It has been pointed out by various astronomers that a very interesting relationship exists between interstellar alcohols and the corresponding thiols (sulfur analog of alcohols) as far as the spectroscopic properties and chemical abundances are concerned. Monohydric alcohols such as methanol and ethanol are widely observed and 1-propanol was recently claimed to have been seen in Orion KL. Among the monohydric thiols, methanethiol (chemical analog of methanol) has been firmly detected in Orion KL and Sgr B2(N2) and ethanethiol (chemical analog of ethanol) has been observed in Sgr B2(N2), though the confirmation of this detection is yet to come. It is very likely that higher order thiols could be observed in these regions. In this paper, we study the formation of monohydric alcohols and their thiol analogs. Based on our quantum chemical calculation and chemical modeling, we find that the Tg conformer of 1-propanethiol is a good candidate of astronomical interest. We present various spectroscopically relevant parameters of this molecule to assist in its future detection in the interstellar medium.

Hybrid Organic/Inorganic Thiol-ene-Based Photopolymerized Networks

OpenAIRE

Schreck, Kathleen M.; Leung, Diana; Bowman, Christopher N.

2011-01-01

The thiol-ene reaction serves as a more oxygen tolerant alternative to traditional (meth)acrylate chemistry for forming photopolymerized networks with numerous desirable attributes including energy absorption, optical clarity, and reduced shrinkage stress. However, when utilizing commercially available monomers, many thiol-ene networks also exhibit decreases in properties such as glass transition temperature (Tg) and crosslink density. In this study, hybrid organic/inorganic thiol-ene resins ...

Hydrangea-like magneto-fluorescent nanoparticles through thiol-inducing assembly

Science.gov (United States)

Chen, Shun; Zhang, Junjun; Song, Shaokun; Xiong, Chuanxi; Dong, Lijie

2017-01-01

Magneto-fluorescent nanoparticles (NPs), recognized as an emerging class of materials, have drawn much attention because of their potential applications. Due to surface functionalization and thiol-metal bonds, a simple method has been put forward for fabricating hydrangea-like magneto-fluorescent Fe3O4-SH@QD NPs, through assembling thiol-modified Fe3O4 NPs with sub-size multi-layer core/shell CdSe/CdS/ZnS QDs. After a refined but controllable silane hydrolysis process, thiol-modified Fe3O4 was fabricated, resulting in Fe3O4-SH@QD NPs with QDs, while preventing the quenching of the QDs. As a result, the core Fe3O4 NPs were 18 nm in diameter, while the scattered CdSe/CdS/ZnS QDs were 7 nm in diameter. The resultant magneto-fluorescent Fe3O4-SH@QD NPs exhibit efficient fluorescence, superparamagnetism at room temperature, and rapid response to the external field, which make them ideal candidates for difunctional probes in MRI and bio-labels, targeting and photodynamic therapy, and cell tracking and separation.

Energy down converting organic fluorophore functionalized mesoporous silica hybrids for monolith-coated light emitting diodes

Directory of Open Access Journals (Sweden)

Markus Börgardts

2017-04-01

Full Text Available The covalent attachment of organic fluorophores in mesoporous silica matrices for usage as energy down converting phosphors without employing inorganic transition or rare earth metals is reported in this article. Triethoxysilylpropyl-substituted derivatives of the blue emitting perylene, green emitting benzofurazane, and red emitting Nile red were synthesized and applied in the synthesis of mesoporous hybrid materials by postsynthetic grafting to commercially available MCM-41. These individually dye-functionalized hybrid materials are mixed in variable ratios to furnish a powder capable of emitting white light with CIE chromaticity coordinates of x = 0.33, y = 0.33 and an external quantum yield of 4.6% upon irradiation at 410 nm. Furthermore, as a proof of concept two different device setups of commercially available UV light emitting diodes, are coated with silica monoliths containing the three triethoxysilylpropyl-substituted fluorophore derivatives. These coatings are able to convert the emitted UV light into light with correlated color temperatures of very cold white (41100 K, 10700 K as well as a greenish white emission with correlated color temperatures of about 5500 K.

Multiplexed Thiol Reactivity Profiling for Target Discovery of Electrophilic Natural Products.

Science.gov (United States)

Tian, Caiping; Sun, Rui; Liu, Keke; Fu, Ling; Liu, Xiaoyu; Zhou, Wanqi; Yang, Yong; Yang, Jing

2017-11-16

Electrophilic groups, such as Michael acceptors, expoxides, are common motifs in natural products (NPs). Electrophilic NPs can act through covalent modification of cysteinyl thiols on functional proteins, and exhibit potent cytotoxicity and anti-inflammatory/cancer activities. Here we describe a new chemoproteomic strategy, termed multiplexed thiol reactivity profiling (MTRP), and its use in target discovery of electrophilic NPs. We demonstrate the utility of MTRP by identifying cellular targets of gambogic acid, an electrophilic NP that is currently under evaluation in clinical trials as anticancer agent. Moreover, MTRP enables simultaneous comparison of seven structurally diversified α,β-unsaturated γ-lactones, which provides insights into the relative proteomic reactivity and target preference of diverse structural scaffolds coupled to a common electrophilic motif and reveals various potential druggable targets with liganded cysteines. We anticipate that this new method for thiol reactivity profiling in a multiplexed manner will find broad application in redox biology and drug discovery. Copyright © 2017 Elsevier Ltd. All rights reserved.

Contrasting bonding behavior of thiol molecules on carbon fullerene structures

International Nuclear Information System (INIS)

Mixteco-Sanchez, J.C.; Guirado-Lopez, R.A.

2003-01-01

We have performed semiempirical as well as ab initio density-functional theory (DFT) calculations at T=0 to analyze the equilibrium configurations and electronic properties of spheroidal C 60 as well as of cylindrical armchair (5,5) and (8,8) fullerenes passivated with SCH 3 and S(CH 2 ) 2 CH 3 thiols. Our structural results reveal that the lowest-energy configurations of the adsorbates strongly depend on their chain length and on the structure of the underlying substrate. In the low-coverage regime, both SCH 3 and S(CH 2 ) 2 CH 3 molecules prefer to organize into a molecular cluster on one side of the C 60 surface, providing thus a less protective organic coating for the carbon structure. However, with increasing the number of adsorbed thiols, a transition to a more uniform distribution is obtained, which actually takes place for six and eight adsorbed molecules when using S(CH 2 ) 2 CH 3 and SCH 3 chains, respectively. In contrast, for the tubelike arrangements at the low-coverage regime, a quasi-one-dimensional zigzag organization of the adsorbates along the tubes is always preferred. The sulfur-fullerene bond is considerably strong and is at the origin of outward and lateral displacements of the carbon atoms, leading to the stabilization of three-membered rings on the surface (spheroidal structures) as well as to sizable nonuniform radial deformations (cylindrical configurations). The electronic spectrum of our thiol-passivated fullerenes shows strong variations in the energy difference between the highest occupied and lowest unoccupied molecular orbitals as a function of the number and distribution of adsorbed thiols, opening thus the possibility to manipulate the transport properties of these compounds by means of selective adsorption mechanisms

Covalent immobilization of lipase onto chitosan-mesoporous silica hybrid nanomaterials by carboxyl functionalized ionic liquids as the coupling agent.

Science.gov (United States)

Xiang, Xinran; Suo, Hongbo; Xu, Chao; Hu, Yi

2018-05-01

Chitosan-mesoporous silica SBA-15 hybrid nanomaterials (CTS-SBA-15) were synthesized by means of carboxyl functionalized ionic liquids as the coupling agent. The as-prepared CTS-SBA-15 support was characterized by TEM, FTIR, TG and nitrogen adsorption-desorption techniques. Porcine pancreas lipase (PPL) was then bound to the hybrid nanomaterials by using the cross-linking reagent glutaraldehyde (GA). Further, the parameters like cross-linking concentration, time and ratio of supports to enzyme were optimized. The property of immobilized lipase were tested in detail by enzyme activity assays. The results indicated that the hybrid nanomaterials could form three-dimensional (3D) structure with homogeneous mesoporous structures and immobilized PPL revealed excellent enzymatic performance. Copyright © 2018 Elsevier B.V. All rights reserved.

Mesoporous aluminium organophosphonates: a reusable chemsensor for the detection of explosives

International Nuclear Information System (INIS)

Li, Dongdong; Yu, Xiang

2016-01-01

Rapid and sensitive detection of explosives is in high demand for homeland security and public safety. In this work, electron-rich of anthracene functionalized mesoporous aluminium organophosphonates (En-AlPs) were synthesized by a one-pot condensation process. The mesoporous structure and strong blue emission of En-AlPs were confirmed by the N 2 adsorption-desorption isotherms, transmission electron microscopy images and fluorescence spectra. The materials En-AlPs can serve as sensitive chemosensors for various electron deficient nitroderivatives, with the quenching constant and the detection limit up to 1.5×10 6 M −1 and 0.3 ppm in water solution. More importantly, the materials can be recycled for many times by simply washed with ethanol, showing potential applications in explosives detection. - Graphical abstract: Electron-rich of anthracene functionalized mesoporous aluminium organophosphonates can serve as sensitive and recycled chemosensors for nitroderivatives with the quenching constant up to 1.5×10 6 M −1 in water solution. Display Omitted - Highlights: • Anthracene functionalized mesoporous aluminium organophosphonates were synthesized. • The materials serve as sensitive chemosensors for nitroderivatives. • The materials can be recycled for many times by simply washed with ethanol. • The materials show potential applications in explosives detection.

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

Science.gov (United States)

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Near-field radiative heat transfer in mesoporous alumina

International Nuclear Information System (INIS)

Li Jing; Feng Yan-Hui; Zhang Xin-Xin; Huang Cong-Liang; Wang Ge

2015-01-01

The thermal conductivity of mesoporous material has aroused the great interest of scholars due to its wide applications such as insulation, catalyst, etc. Mesoporous alumina substrate consists of uniformly distributed, unconnected cylindrical pores. Near-field radiative heat transfer cannot be ignored, when the diameters of the pores are less than the characteristic wavelength of thermal radiation. In this paper, near-field radiation across a cylindrical pore is simulated by employing the fluctuation dissipation theorem and Green function. Such factors as the diameter of the pore, and the temperature of the material are further analyzed. The research results show that the radiative heat transfer on a mesoscale is 2∼4 orders higher than on a macroscale. The heat flux and equivalent thermal conductivity of radiation across a cylindrical pore decrease exponentially with pore diameter increasing, while increase with temperature increasing. The calculated equivalent thermal conductivity of radiation is further developed to modify the thermal conductivity of the mesoporous alumina. The combined thermal conductivity of the mesoporous alumina is obtained by using porosity weighted dilute medium and compared with the measurement. The combined thermal conductivity of mesoporous silica decreases gradually with pore diameter increasing, while increases smoothly with temperature increasing, which is in good agreement with the experimental data. The larger the porosity, the more significant the near-field effect is, which cannot be ignored. (paper)

Immobilization of mesoporous silica particles on stainless steel plates

International Nuclear Information System (INIS)

Pasqua, Luigi; Morra, Marco

2017-01-01

A preliminary study aimed to the nano-engineering of stainless steel surface is presented. Aminopropyl-functionalized mesoporous silica is covalently and electrostatically anchored on the surface of stainless steel plates. The anchoring is carried out through the use of a nanometric spacer, and two different spacers are proposed (both below 2 nm in size). The first sample is obtained by anchoring to the stainless steel amino functionalized, a glutaryl dichloride spacer. This specie forms an amide linkage with the amino group while the unreacted acyl groups undergo hydrolysis giving a free carboxylic group. The so-obtained functionalized stainless steel plate is used as substrate for anchoring derivatized mesoporous silica particles. The second sample is prepared using 2-bromo-methyl propionic acid as spacer (BMPA). Successively, the carboxylic group of propionic acid is condensed to the aminopropyl derivatization on the external surface of the mesoporous silica particle through covalent bond. In both cases, a continuous deposition (coating thickness is around 10 μm) is obtained, in fact, XPS data do not reveal the metal elements constituting the plate. The nano-engineering of metal surfaces can represent an intriguing opportunity for producing long-term drug release or biomimetic surface.

Immobilization of mesoporous silica particles on stainless steel plates

Energy Technology Data Exchange (ETDEWEB)

Pasqua, Luigi, E-mail: luigi.pasqua@unical.it [University of Calabria, Department of Environmental and Chemical Engineering (Italy); Morra, Marco, E-mail: mmorra@nobilbio.com [Via Valcastellana 26 (Italy)

2017-03-15

A preliminary study aimed to the nano-engineering of stainless steel surface is presented. Aminopropyl-functionalized mesoporous silica is covalently and electrostatically anchored on the surface of stainless steel plates. The anchoring is carried out through the use of a nanometric spacer, and two different spacers are proposed (both below 2 nm in size). The first sample is obtained by anchoring to the stainless steel amino functionalized, a glutaryl dichloride spacer. This specie forms an amide linkage with the amino group while the unreacted acyl groups undergo hydrolysis giving a free carboxylic group. The so-obtained functionalized stainless steel plate is used as substrate for anchoring derivatized mesoporous silica particles. The second sample is prepared using 2-bromo-methyl propionic acid as spacer (BMPA). Successively, the carboxylic group of propionic acid is condensed to the aminopropyl derivatization on the external surface of the mesoporous silica particle through covalent bond. In both cases, a continuous deposition (coating thickness is around 10 μm) is obtained, in fact, XPS data do not reveal the metal elements constituting the plate. The nano-engineering of metal surfaces can represent an intriguing opportunity for producing long-term drug release or biomimetic surface.

Replacement of Poly(vinyl pyrrolidone) by Thiols: A Systematic Study of Ag Nanocube Functionalization by Surface-Enhanced Raman Scattering.

Science.gov (United States)

Moran, Christine H; Rycenga, Matthew; Zhang, Qiang; Xia, Younan

2011-11-10

In this work, we used surface-enhanced Raman scattering (SERS) to monitor the replacement of poly(vinyl pyrrolidone) (PVP) on Ag nanocubes by cysteamine, thiol-terminated PEG, and benzenedithiol. PVP is widely used as a colloidal stabilizer and capping agent to control the shape of Ag (as well as many other noble metals) nanocrystals during synthesis, and to stabilize the final colloidal suspension. However, the surface chemistry of Ag nanocrystals often needs to be tailored for specific applications, so the PVP coating must be removed and/or replaced by other ligands. By monitoring the signature peak from the carbonyl groups of PVP, we show, for the first time, that the PVP adsorbed on the surface of Ag nanocubes was completely replaced by the thiol molecules at room temperature over the course of a few hours. We observed the same trend no matter if the Ag nanocubes were suspended in an aqueous solution of the thiol or supported on a silicon substrate and then immersed in the thiol solution.

Heterofunctional Glycopolypeptides by Combination of Thiol-Ene Chemistry and NCA Polymerization.

Science.gov (United States)

Krannig, Kai-Steffen; Schlaad, Helmut

2016-01-01

Glycopolypeptides are prepared either by the polymerization of glycosylated amino acid N-carboxyanhydrides (NCAs) or by the post-polymerization functionalization of polypeptides with suitable functional groups. Here we present a method for the in-situ functionalization and (co-) polymerization of allylglycine N-carboxyanhydride in a facile one-pot procedure, combining radical thiol-ene photochemistry and nucleophilic ring-opening polymerization techniques, to yield well-defined heterofunctional glycopolypeptides.

Investigation of thiol-disulphide balance in patients with acute urticaria and chronic spontaneous urticaria.

Science.gov (United States)

Akbas, Ayse; Kilinc, Fadime; Sener, Sertac; Aktaş, Akın; Baran, Pervin; Ergin, Merve

2017-09-01

Thiol-disulphide balance plays a major role in health and diseases. This balance may be disrupted by various diseases. We aimed to determine status of the effect of thiol-disulphide balance in urticaria. We aimed to investigate the thiol-disulphide balance in patients with acute urticaria (AUP) and chronic spontaneous urticaria (CSU). Study included 53 AUP and 47 healthy controls plus 57 patients with chronic spontaneous urticaria (CSUP) and 57 healthy controls. Levels of native thiols, disulphides and total thiols were evaluated in plasma using a new and automated spectrophotometric method. Ratios of disulphides/total thiols, disulphides/native thiols and native thiols/total thiols were calculated. For AU, there was no statistical difference compared to control group in levels of native thiols, disulphides and total thiols. For CSU, however, there was an increase in levels of native thiols, disulphides and total thiols and the ratio of thiol/disulphide in favour of disulphide. Thiol-disulphide balance was not affected by AU but shifted towards to disulphide in CSU indicating the presence of oxidative stress (OS).

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template

KAUST Repository

Zhu, Jie; Zhu, Yihan; Zhu, Liangkui; Rigutto, Marcello S.; Van Der Made, Alexander W.; Yang, Chengguang; Pan, Shuxiang; Wang, Liang; Zhu, Longfeng; Jin, Yinying; Sun, Qi; Wu, Qinming; Meng, Xiangju; Zhang, Daliang; Han, Yu; Li, Jixue; Chu, Yueying; Zheng, Anmin; Qiu, Shilun; Zheng, Xiaoming; Xiao, Fengshou

2014-01-01

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a

Fast and Selective Modification of Thiol Proteins/Peptides by N-(Phenylseleno)phthalimide

Science.gov (United States)

Wang, Zhengfang; Zhang, Yun; Zhang, Hao; Harrington, Peter B.; Chen, Hao

2012-03-01

We previously reported that selenamide reagents such as ebselen and N-(phenylseleno)phthalimide (NPSP) can be used to selectively derivatize thiols for mass spectrometric analysis, and the introduced selenium tags are useful as they could survive or removed with collision-induced dissociation (CID). Described herein is the further study of the reactivity of various protein/peptide thiols toward NPSP and its application to derivatize thiol peptides in protein digests. With a modified protocol (i.e., dissolving NPSP in acetonitrile instead of aqueous solvent), we found that quantitative conversion of thiols can be obtained in seconds, using NPSP in a slight excess amount (NPSP:thiol of 1.1-2:1). Further investigation shows that the thiol reactivity toward NPSP reflects its chemical environment and accessibility in proteins/peptides. For instance, adjacent basic amino acid residues increase the thiol reactivity, probably because they could stabilize the thiolate form to facilitate the nucleophilic attack of thiol on NPSP. In the case of creatine phosphokinase, the native protein predominately has one thiol reacted with NPSP while all of four thiol groups of the denatured protein can be derivatized, in accordance with the corresponding protein conformation. In addition, thiol peptides in protein/peptide enzymatic digests can be quickly and effectively tagged by NPSP following tri- n-butylphosphine (TBP) reduction. Notably, all three thiols of the peptide QCCASVCSL in the insulin peptic digest can be modified simultaneously by NPSP. These results suggest a novel and selective method for protecting thiols in the bottom-up approach for protein structure analysis.

Templating mesoporous zeolites

DEFF Research Database (Denmark)

Egeblad, Kresten; Christensen, Christina Hviid; Kustova, Marina

2008-01-01

The application of templating methods to produce zeolite materials with hierarchical bi- or trimodal pore size distributions is reviewed with emphasis on mesoporous materials. Hierarchical zeolite materials are categorized into three distinctly different types of materials: hierarchical zeolite...... crystals, nanosized zeolite crystals, and supported zeolite crystals. For the pure zeolite materials in the first two categories, the additional meso- or macroporosity can be classified as being either intracrystalline or intercrystalline, whereas for supported zeolite materials, the additional porosity...... originates almost exclusively from the support material. The methods for introducing mesopores into zeolite materials are discussed and categorized. In general, mesopores can be templated in zeolite materials by use of solid templating, supramolecular templating, or indirect templating...

Quaternary ammonium-functionalized MCM-48 mesoporous silica as a sorbent for the dispersive solid-phase extraction of endocrine disrupting compounds in water.

Science.gov (United States)

Zhang, Shijuan; Lu, Fengli; Ma, Xiaoyun; Yue, Mingbo; Li, Yanxin; Liu, Jiammin; You, Jinmao

2018-07-06

MCM-48 mesoporous silica was functionalized with dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, a quaternary ammonium salt with a long hydrophobic chain, to prepare a new sorbent for the dispersive solid-phase extraction (DSPE) of seven endocrine disrupting compounds (EDCs) including 4-hexylphenol, 4-octylphenol, 4-nonylphenol, bisphenol A, estrone, 17β-estradiol and estriol in water. A series of differently functionalized MCM-48 materials were also synthesized, and they served as reference materials to study the mechanism. The developed DSPE method was combined with HPLC with fluorescence detection to evaluate the adsorption performance. The results indicated that the quaternary ammonium-functionalized MCM-48 mesoporous silica can be used as ideal sorbent for EDCs in water with recoveries of higher than 95% due to the electrostatic interactions and hydrophobic effect. Hydrogen bonding and π-π interactions in other synthesized materials could lead to about 25-30% increase in recoveries, but the results for polyhydroxy compounds were still not satisfying. The quaternary ammonium-functionalized MCM-48 mesoporous silica was successfully applied to the DSPE of EDCs in real water samples. The optimum extraction conditions were sorbent amount, 15 mg; desorption time; 5 min; elution volume, 0.8 mL; sample pH 3.0; and salt addition, 5 g/L. The limits of detection were in the range of 1.2-2.6 ng/L, while the limits of quantitation were in the range of 4.3-8.3 ng/L. Copyright © 2018 Elsevier B.V. All rights reserved.

Structure of water in mesoporous organosilica by calorimetry and inelastic neutron scattering

Science.gov (United States)

Levy, Esthy; Kolesnikov, Alexander I.; Li, Jichen; Mastai, Yitzhak

2009-01-01

In this paper, we describe the preparation of mesoporous organosilica samples with hydrophilic or hydrophobic organic functionality inside the silica channel. We synthesized mesoporous organosilica of identical pore sizes based on two different organic surface functionality namely hydrophobic (based on octyltriethoxysilane OTES) and hydrophilic (3-aminopropyltriethoxysilane ATES) and MCM-41 was used as a reference system. The structure of water/ice in those porous silica samples have been investigated over a range temperatures by differential scanning calorimetry (DSC) and inelastic neutron scattering (INS). INS study revealed that water confined in hydrophobic mesoporous organosilica shows vibrational behavior strongly different than bulk water. It consists of two states: water with strong and weak hydrogen bonds (with ratio 1:2.65, respectively), compared to ice-Ih. The corresponding O-O distances in these water states are 2.67 and 2.87 Ǻ, which strongly differ compared to ice-Ih (2.76 Ǻ). INS spectra for water in hydrophilic mesoporous organosilica ATES show behavior similar to bulk water, but with greater degree of disorder.

Efficiency enhancement in dye sensitized solar cells using dual function mesoporous silica as scatterer and back recombination inhibitor

Science.gov (United States)

Tanvi; Mahajan, Aman; Bedi, R. K.; Kumar, Subodh; Saxena, Vibha; Aswal, D. K.

2016-08-01

In the present work, we report the usage of mesoporous silica for improving light harvesting as well as for suppression of back recombination without affecting the extent of dye loading on TiO2 films. Synthesized mesoporous SiO2 was characterized by X-ray photoelectron spectroscopy, X-ray diffraction, Brunauer Emmett and Teller measurement, Scanning electron microscopy and Transmission electron microscopy. DSSCs were fabricated by incorporating different wt% of mesoporous SiO2 in TiO2 paste. An improvement of 50% was observed for devices fabricated using 0.75 wt% of mesoporous SiO2. The mechanism behind the improvement was investigated using electrochemical impedance spectroscopy and UV-Vis spectroscopy.

Mesoporous aluminum phosphite

International Nuclear Information System (INIS)

El Haskouri, Jamal; Perez-Cabero, Monica; Guillem, Carmen; Latorre, Julio; Beltran, Aurelio; Beltran, Daniel; Amoros, Pedro

2009-01-01

High surface area pure mesoporous aluminum-phosphorus oxide-based derivatives have been synthesized through an S + I - surfactant-assisted cooperative mechanism by means of a one-pot preparative procedure from aqueous solution and starting from aluminum atrane complexes and phosphoric and/or phosphorous acids. A soft chemical extraction procedure allows opening the pore system of the parent as-prepared materials by exchanging the surfactant without mesostructure collapse. The nature of the pore wall can be modulated from mesoporous aluminum phosphate (ALPO) up to total incorporation of phosphite entities (mesoporous aluminum phosphite), which results in a gradual evolution of the acidic properties of the final materials. While phosphate groups in ALPO act as network building blocks (bridging Al atoms), the phosphite entities become basically attached to the pore surface, what gives practically empty channels. The mesoporous nature of the final materials is confirmed by X-ray diffraction (XRD), transmission electron microscopy (TEM) and N 2 adsorption-desorption isotherms. The materials present regular unimodal pore systems whose order decreases as the phosphite content increases. NMR spectroscopic results confirm the incorporation of oxo-phosphorus entities to the framework of these materials and also provide us useful information concerning the mechanism through which they are formed. - Abstract: TEM image of the mesoporous aluminum phosphite showing the hexagonal disordered pore array that is generated by using surfactant micelles as template. Also a scheme emphasizing the presence of an alumina-rich core and an ALPO-like pore surface is presented.

Thiol synthesis and arsenic hyperaccumulation in Pteris vittata (Chinese brake fern)

International Nuclear Information System (INIS)

Zhang Weihua; Cai Yong; Downum, Kelsey R.; Ma, Lena Q.

2004-01-01

Pteris vittata (Chinese brake fern) has potential for phytoremediation of As-contaminated sites. In this study, the synthesis of total thiols and acid-soluble thiols in P. vittata was investigated under arsenic exposure. The strong and positive correlation between As concentration and acid-soluble thiols in plant leaflets suggests that acid-soluble thiols may play a role in As detoxification. A major As-induced thiol was purified and characterized. A molecular ion (M+1) of 540 m/z suggests that the thiol was a phytochelatin (PC) with two base units (PC 2 ). However, the ratios of acid-soluble thiols to As in leaflets exposed to As ranged from 0.012 to 0.026, suggesting that only a very small part of As is complexed by PC 2 . PCs could play a minor detoxification role in this hyperaccumulator. A PC-independent mechanism appears to be mainly involved in As tolerance, while PC-dependent detoxification seems to be a supplement

Thiol synthesis and arsenic hyperaccumulation in Pteris vittata (Chinese brake fern)

Energy Technology Data Exchange (ETDEWEB)

Zhang Weihua; Cai Yong; Downum, Kelsey R.; Ma, Lena Q

2004-10-01

Pteris vittata (Chinese brake fern) has potential for phytoremediation of As-contaminated sites. In this study, the synthesis of total thiols and acid-soluble thiols in P. vittata was investigated under arsenic exposure. The strong and positive correlation between As concentration and acid-soluble thiols in plant leaflets suggests that acid-soluble thiols may play a role in As detoxification. A major As-induced thiol was purified and characterized. A molecular ion (M+1) of 540 m/z suggests that the thiol was a phytochelatin (PC) with two base units (PC{sub 2}). However, the ratios of acid-soluble thiols to As in leaflets exposed to As ranged from 0.012 to 0.026, suggesting that only a very small part of As is complexed by PC{sub 2}. PCs could play a minor detoxification role in this hyperaccumulator. A PC-independent mechanism appears to be mainly involved in As tolerance, while PC-dependent detoxification seems to be a supplement.

Rod-shaped silica particles derivatized with elongated silver nanoparticles immobilized within mesopores

Energy Technology Data Exchange (ETDEWEB)

Mnasri, Najib [Institut Charles Gerhardt de Montpellier, CNRS UMR 5253, Université Montpellier, Place Eugène Bataillon, 34095 Montpellier Cedex 5 (France); Materials, Environment and Energy Laboratory (UR14ES26), Faculty of Science, University of Gafsa, 2112 Gafsa (Tunisia); Charnay, Clarence; Ménorval, Louis-Charles de [Institut Charles Gerhardt de Montpellier, CNRS UMR 5253, Université Montpellier, Place Eugène Bataillon, 34095 Montpellier Cedex 5 (France); Elaloui, Elimame [Materials, Environment and Energy Laboratory (UR14ES26), Faculty of Science, University of Gafsa, 2112 Gafsa (Tunisia); Zajac, Jerzy, E-mail: jerzy.zajac@umontpellier.fr [Institut Charles Gerhardt de Montpellier, CNRS UMR 5253, Université Montpellier, Place Eugène Bataillon, 34095 Montpellier Cedex 5 (France)

2016-11-15

Silver-derivatized silica particles possessing a non-spherical morphology and surface plasmon resonance properties have been achieved. Nanometer-sized silica rods with uniformly sized mesopore channels were prepared first making use of alkyltrimethyl ammonium surfactants as porogens and the 1:0.10 tetraethyl orthosilicate (TEOS) : 3-aminopropyltriethoxysilane (APTES) mixture as a silicon source. Silica rods were subsequently functionalized by introducing elongated silver nanoparticles within the intra-particle mesopores thanks to the AgNO{sub 3} reduction procedure based on the action of hemiaminal groups previously located on the mesopore walls. The textural and structural features of the samples were inferred from the combined characterization studies including SEM and TEM microscopy, nitrogen adsorption-desorption at 77 K, powder XRD in the small- and wide-angle region, as well as UV–visible spectroscopy. {sup 129}Xe NMR spectroscopy appeared particularly useful to obtain a correct information about the porous structure of rod-shaped silica particles and the silver incorporation within their intra-particle mesopores. - Highlights: • Mesoporous monodisperse submicron-sized silica rods were achieved. • Silver nanoparticles were located lengthwise within the intra-particle mesopores. • Textural and plasmonic properties of particles studied by {sup 129}Xe NMR and UV–Vis.

Thiol-ene thermosets exploiting surface reactivity for layer-by-layer structures and control of penetration depth for selective surface reactivity

DEFF Research Database (Denmark)

Daugaard, Anders Egede; Westh, Andreas; Pereira Rosinha Grundtvig, Ines

Thiol-ene thermosets have been shown to be an efficient platform for preparation of functional polymer surfaces. Especially the effectiveness and versatility of the system has enabled a large variety of network properties to be obtained in a simple and straight-forward way. Due to its selectivity......, various thiols and allyl or other vinyl reactants can be used to obtain either soft and flexible1 or more rigid functional thermosets 2. The methodology permits use of etiher thermal or photochemical conditions both for matrix preparation as well as for surface functionalization. Due to excess reactive...... groups in thµe surface of thiol-ene thermosets, it is possible to prepare surface functional thermosets or to exploit the reactive groups for modular construction and subsequent chemical bonding. Here a different approach preparing monolithic layer-by-layer structures with controlled mechanical...

Surface Properties of Al-Functionalized Mesoporous MCM-41 and the Melting Behavior of Water in Al-MCM-41 Nanopores.

Science.gov (United States)

Sterczyńska, Angelina; Deryło-Marczewska, Anna; Zienkiewicz-Strzałka, Małgorzata; Śliwińska-Bartkowiak, Małgorzata; Domin, Kamila

2017-10-24

We report an experimental investigation of structural and adhesive properties for Al-containing mesoporous MCM-41 and MCM-41 surfaces. In this work, highly ordered hexagonal mesoporous structures of aluminosilica with two different Si/Al molar ratios equal to 50 and 80 and silica samples were studied; Al was incorporated into the MCM-41 structures using the direct synthesis method, with CTAB as a surfactant. The incorporation of aluminum was evidenced simultaneously without any change in the hexagonal arrangement of cylindrical mesopores. The porous materials were examined by techniques such as low-temperature nitrogen sorption, energy-dispersive spectroscopy, and scanning and transmission electron microscopy. Surface properties were determined through X-ray photoelectron spectroscopy, potentiometric titration, and static contact angle measurements. It was shown that an increase in surface acidity leads to an increase in the wetting energy of the surface. To investigate the influence of acidity on the confinement effects, the melting behavior of water in Al-MCM-41 and MCM-41 with the same pore size was determined by using dielectric relaxation spectroscopy and differential scanning calorimetry methods. We found that the melting-point depression of water in pores is larger in the functionalized pores than in pure silica pores of the same pore diameter.

Synthesis and characterization of triflic acid-functionalized mesoporous Zr-TMS catalysts: heterogenization of CF3SO3H over Zr-TMS and its catalytic activity

NARCIS (Netherlands)

Chidambaram, M.; Curulla Ferre, D.; Singh, A.P.; Anderson, B.G.

2003-01-01

Triflic acid-functionalized Zr-TMS (zirconium oxide with a mesostructured framework; TMS, transition metal oxide mesoporous molecular sieves) catalysts have been synthesized by functionalizing triflic acid onto the walls of Zr-TMS via post synthesis method. The synthesized materials were

Synthesis and structure of pyridine-functionalized mesoporous SBA-15 organosilicas and their application for sorption of diclofenac

Science.gov (United States)

Barczak, Mariusz

2018-02-01

A series of pyridine-functionalized mesoporous silicas have been prepared for the first time via direct co-condensation of tetraethoxysilane (TEOS) and 2-(2-pyridyl)ethyltrimethoxysilane (PETS) using the block copolymer Pluronic P123 as a structure-directing agent. The obtained materials were fully characterized by a wide range of instrumental techniques and employed as adsorbents for the removal of a diclofenac which is considered a priority hazardous drug. The synthesized materials exhibit a high adsorption capacities and rapid adsorption rates. The structural and adsorption properties depend largely on the relative amount of PETS/TEOS ratio: the gradual degradation of ordered structure and porosity was observed with the increasing amount of PETS. However due to the highest loading of pyridine units the most structurally degraded material had the highest adsorption uptake (631 mg g-1) indicating that the surface chemistry plays - along with porosity - an important role in governing the adsorption process. The experimental adsorption data were modelled using the Langmuir, Freundlich and Langmuir-Freundlich isotherms - among them the Langmuir-Freundlich model turned out to be the most suitable for describing adsorption behaviour of diclofenac onto the materials. The collected data show that the pyridine-functionalized mesoporous silicas can be a promising absorbent of pharmaceuticals.

2-Hydroxy-naphthyl functionalized mesoporous silica for fluorescence sensing and removal of aluminum ions.

Science.gov (United States)

Das, Trisha; Roy, Ankita; Uyama, Hiroshi; Roy, Partha; Nandi, Mahasweta

2017-06-06

Mesoporous silica functionalized with a 2-hydroxy-naphthyl moiety has been synthesized and characterized by standard techniques like powder X-ray diffraction, N 2 adsorption/desorption studies, transmission electron microscopy and spectral studies like FT-IR, UV-visible, fluorescence and 13 C and 29 Si solid state NMR. The functionalized silica material showed significant enhancement in its emission intensity in the presence of Al 3+ ions whereas other metal ions could not bring about any increase in its emission intensity. They either quench the emission or do not alter the intensity significantly making the functionalized material a fluorescence chemosensor for Al 3+ . The sensitivity of the probe towards Al 3+ has been determined to be high with a low limit of detection value. As functionalized silica is not soluble in common solvents, it has been effectively used to bind and remove Al 3+ from a solution. Theoretical calculations on a model system have been performed to investigate the electronic spectral transitions.

Low-cost route for synthesis of mesoporous silica materials with high silanol groups and their application for Cu(II) removal

International Nuclear Information System (INIS)

Wang Yangang; Huang Sujun; Kang Shifei; Zhang Chengli; Li Xi

2012-01-01

Graphical abstract: A simple and low-cost route to synthesize mesoporous silica materials with high silanol groups has been demonstrated by means of a sol–gel process using citric acid as the template and acid catalyst, further studies on the adsorption of Cu(II) onto the representative amine-functionalized mesoporous silica showed that it had a high Cu(II) removal efficiency. Highlights: ► A low-cost route to synthesize mesoporous silica with high silanol groups was demonstrated. ► Citric acid as the template and acid catalyst for the reaction of tetraethylorthosilicate. ► Water extraction method was an effective technique to remove template which can be recycled. ► The mesoporous silica with high silanol groups was easily modified by functional groups. ► A high Cu(II) removal efficiency on the amine-functionalized mesoporous silica. - Abstract: We report a simple and low-cost route for the synthesis of mesoporous silica materials with high silanol groups by means of a sol–gel process using citric acid as the template, tetraethylorthosilicate (TEOS) as the silica source under aqueous solution system. The citric acid can directly work as an acid catalyst for the hydrolysis of TEOS besides the function as a pore-forming agent in the synthesis. It was found that by using a water extraction method the citric acid template in as-prepared mesoporous silica composite can be easily removed and a high degree of silanol groups were retained in the mesopores, moreover, the citric acid template in the filtrate can be recycled after being dried. The structural properties of the obtained mesoporous silica materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and nitrogen adsorption–desorption analysis. Furthermore, an adsorption of Cu(II) from aqueous solution on the representative amine-functionalized mesoporous silica was investigated

Biological Applications and Transmission Electron Microscopy Investigations of Mesoporous Silica Nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Trewyn, Brian G. [Iowa State Univ., Ames, IA (United States)

2006-01-01

The research presented and discussed within involves the development of novel biological applications of mesoporous silica nanoparticles (MSN) and an investigation of mesoporous material by transmission electron microscopy (TEM). Mesoporous silica nanoparticles organically functionalized shown to undergo endocytosis in cancer cells and drug release from the pores was controlled intracellularly and intercellularly. Transmission electron microscopy investigations demonstrated the variety of morphologies produced in this field of mesoporous silica nanomaterial synthesis. A series of room-temperature ionic liquid (RTIL) containing mesoporous silica nanoparticle (MSN) materials with various particle morphologies, including spheres, ellipsoids, rods, and tubes, were synthesized. By changing the RTIL template, the pore morphology was tuned from the MCM-41 type of hexagonal mesopores to rotational moire type of helical channels, and to wormhole-like porous structures. These materials were used as controlled release delivery nanodevices to deliver antibacterial ionic liquids against Escherichia coli K12. The involvement of a specific organosiloxane function group, covalently attached to the exterior of fluorescein doped mesoporous silica nanoparticles (FITC-MSN), on the degree and kinetics of endocytosis in cancer and plant cells was investigated. The kinetics of endocystosis of TEG coated FITC-MSN is significantly quicker than FITC-MSN as determined by flow cytometry experiments. The fluorescence confocal microscopy investigation showed the endocytosis of TEG coated-FITC MSN triethylene glycol grafted fluorescein doped MSN (TEG coated-FITC MSN) into both KeLa cells and Tobacco root protoplasts. Once the synthesis of a controlled-release delivery system based on MCM-41-type mesoporous silica nanorods capped by disulfide bonds with superparamagnetic iron oxide nanoparticles was completed. The material was characterized by general methods and the dosage and kinetics of the

Bone tissue engineering using silica-based mesoporous nanobiomaterials:Recent progress.

Science.gov (United States)

Shadjou, Nasrin; Hasanzadeh, Mohammad

2015-10-01

Bone disorders are of significant concern due to increase in the median age of our population. It is in this context that tissue engineering has been emerging as a valid approach to the current therapies for bone regeneration/substitution. Tissue-engineered bone constructs have the potential to alleviate the demand arising from the shortage of suitable autograft and allograft materials for augmenting bone healing. Silica based mesostructured nanomaterials possessing pore sizes in the range 2-50 nm and surface reactive functionalities have elicited immense interest due to their exciting prospects in bone tissue engineering. In this review we describe application of silica-based mesoporous nanomaterials for bone tissue engineering. We summarize the preparation methods, the effect of mesopore templates and composition on the mesopore-structure characteristics, and different forms of these materials, including particles, fibers, spheres, scaffolds and composites. Also, the effect of structural and textural properties of mesoporous materials on development of new biomaterials for production of bone implants and bone cements was discussed. Also, application of different mesoporous materials on construction of manufacture 3-dimensional scaffolds for bone tissue engineering was discussed. It begins by giving the reader a brief background on tissue engineering, followed by a comprehensive description of all the relevant components of silica-based mesoporous biomaterials on bone tissue engineering, going from materials to scaffolds and from cells to tissue engineering strategies that will lead to "engineered" bone. Copyright © 2015 Elsevier B.V. All rights reserved.

Gyroidal mesoporous carbon materials and methods thereof

Energy Technology Data Exchange (ETDEWEB)

Wiesner, Ulrich B.; Werner, Joerg G.

2017-07-25

The present invention relates to, inter alia, gyroidal mesoporous carbon materials and methods of use and manufacture thereof. In one embodiment, the present invention relates to a mesoporous carbon composition comprising a gyroidal mesoporous carbon having an ordered gyroidal structure and mesopores having a pore size of greater than 2 nanometers (nm) in diameter, and more particularly greater than 11 nm in diameter.

In-situ functionalization of mesoporous hexagonal ZnO synthesized in task specific ionic liquid as a photocatalyst for elimination of SO2, NOx, and CO

Science.gov (United States)

Kowsari, Elaheh; Abdpour, Soheil

2017-12-01

A novel mesoporous structure of zinc oxide was synthesized in hydrothermal autocalve in the presence of a functional ionic liquid (FIL) {[CH2CH2] O2 (mm)2}. This FIL with ether groups was used simultaneously as a designer templating agent and a source of the hydroxyl radical. The presence of this ionic liquid led to producing ethylene glycol in the reaction media, which adsorb on the surface of mesoporous hexagonal ZnO plates. These mesoporous structures can adsorb pollutant gases and increase photocatalytic oxidation of pollutant gases in compare with commercial ZnO nanoparticles and agglomerated nanoparticles synthesized in this work. XPS data confirmed ethylene glycol production by the ionic liquid, which could prove a role for ionic liquids as designers. The estimated BET surface area values of ZnO hexagonal mesoporous plates and agglomerated particles were 84 m2/g and 12 m2/g respectively. Optical properties of the mesoporous structures were analyzed by photoluminescence spectroscopy and diffuse reflectance UV-visible spectroscopy. The performance of these structures as efficient photocatalysts was further demonstrated by their removal of NOx, SO2, and CO under UV irradiation. The removal of NOx, SO2, and CO under UV irradiation was 56%, 81%, and 35% respectively, after 40 min of irradiation time. Reusability of the photocatalyst was determined; the results show no significant decrease of activity of photocatalyst. after five cycles.

Efficient epoxidation over cyanocobalamine containing SBA-15 organic-inorganic nanohybrids

Energy Technology Data Exchange (ETDEWEB)

Karimi, Z. [Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mahjoub, A.R., E-mail: mahjouba@modares.ac.ir [Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

2010-05-01

SBA-15 mesoporous silica is synthesized using triblock copolymer P123 surfactant and chemically modified by aminopropyl, thiol, ammonium and sulfonic acid functional groups. Functionalization is performed via post synthesize method using 3-aminopropyltriethoxysilane (APTES) or 3-mercatopropyl trimethoxysilane (MPTMS) precursor. The as synthesized mesoporous systems are applied for immobilization of cyanocobalamine. Functionalization effectively improves sorption properties of the supports, while different functional groups exert different effects. The organic-inorganic mesoporous materials are characterized via X-ray diffraction (XRD), nitrogen adsorption and desorption, transmission electron microscopy (TEM), FT-IR and inductively coupled plasma-optical emission (ICP). The newly synthesized systems exhibit high catalytic activity for heterogeneous epoxidation of cyclooctene in presence of hydrogen peroxide. Reaction conditions are optimized, effect of functional groups on performance of the catalysts is taken into consideration and reusability of the designed heterogeneous systems is studied. Systems with chemically modified supports are shown to be more efficient and stable catalysts however; chemical nature of functional groups plays a crucial role.

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

Energy Technology Data Exchange (ETDEWEB)

Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

2007-11-27

Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

Soft-Templating Synthesis of Mesoporous Silica-Based Materials for Environmental Applications

Science.gov (United States)

Gunathilake, Chamila Asanka

Dissertation research is mainly focus on: 1) the development of mesoporous silica materials with organic pendant and bridging groups (isocyanurate, amidoxime, benzene) and incorporated metal (aluminum, zirconium, calcium, and magnesium) species for high temperature carbon dioxide (CO2) sorption, 2) phosphorous-hydroxy functionalized mesoporous silica materials for water treatment, and 3) amidoxime-modified ordered mesoporous silica materials for uranium sorption under seawater conditions. The goal is to design composite materials for environmental applications with desired porosity, surface area, and functionality by selecting proper metal oxide precursors, organosilanes, tetraethylorthosilicate, (TEOS), and block copolymer templates and by adjusting synthesis conditions. The first part of dissertation presents experimental studies on the merge of aluminum, zirconium, calcium, and magnesium oxides with mesoporous silica materials containing organic pendant (amidoxime) and bridging groups (isocyanurate, benzene) to obtain composite sorbents for CO2 sorption at ambient (0-25 °C) and elevated (60-120 °C) temperatures. These studies indicate that the aforementioned composite sorbents are fairly good for CO2 capture at 25 °C via physisorption mechanism and show a remarkably high affinity toward CO2 chemisorption at 60-120 °C. The second part of dissertation is devoted to silica-based materials with organic functionalities for removal of heavy metal ions such as lead from contaminated water and for recovery of metal ions such as uranium from seawater. First, ordered mesoporous organosilica (OMO) materials with diethylphosphatoethyl and hydroxyphosphatoethyl surface groups were examined for Pb2+ adsorption and showed unprecedented adsorption capacities up to 272 mg/g and 202 mg/g, respectively However, the amidoxime-modified OMO materials were explored for uranium extraction under seawater conditions and showed remarkable capacities reaching 57 mg of uranium per gram

Synthesis and Characterization of Hyaluronic Acid Modified Colloidal Mesoporous Silica Nanoparticles

Science.gov (United States)

Zhang, Wenbiao; Wang, Yu; Li, Zhen; Wang, Wanxia; Sun, Honghao; Liu, Mingxing

2017-12-01

The colloidal mesoporous silica nanoparticles functionalized with hyaluronic acid (CMS-HA) were successfully synthesized by grafting hyaluronic acid onto the external surface of the amino-functionalized mesoporous silica nanoparticles (CMS-NH2). Moreover, the paticle properties of CMS-HA were characterized by fourier transform infrared spectroscopy (FT-IR), dynamic light scattering (DLS) and transmission electron microscopy (TEM). The nanomaterials were negatively charged and had a relatively uniform spherical morphology with about 100 nm in diameter, which could make it more compatible with blood. So the results suggested that the CMS-HA might be a critical nanomaterial for applying in target drug delivery system.

Modification of the mitochondrial sulfonylurea receptor by thiol reagents.

Science.gov (United States)

Szewczyk, A; Wójcik, G; Lobanov, N A; Nalecz, M J

1999-08-19

The purpose of this study was to investigate the effects exerted by thiol-modifying reagents on themitochondrial sulfonylurea receptor. The thiol-oxidizing agents (timerosal and 5, 5'-dithio-bis(2-nitrobenzoic acid)) were found to produce a large inhibition (70% to 80%) of specific binding of [(3)H]glibenclamide to the beef heart mitochondrial membrane. Similar effects were observed with membrane permeable (N-ethylmaleimide) and non-permeable (mersalyl) thiol modifying agents. Glibenclamide binding was also decreased by oxidizing agents (hydrogen peroxide) but not by reducing agents (reduced gluthatione, dithiothreitol and the 2,3-dihydroxy-1,4-dithiolbutane). The results suggest that intact thiol groups, facing the mitochondrial matrix, are essential for glibenclamide binding to the mitochondrial sulfonylurea receptor. Copyright 1999 Academic Press.

Ordered mesoporous carbon for electrochemical sensing: A review

Energy Technology Data Exchange (ETDEWEB)

Ndamanisha, Jean Chrysostome [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Universite du Burundi, Institut de pedagogie appliquee, B.P. 5223, Bujumbura (Burundi); Guo Liping, E-mail: guolp078@nenu.edu.cn [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China)

2012-10-17

Highlights: Black-Right-Pointing-Pointer The preparation and functionalization of ordered mesoporous carbon. Black-Right-Pointing-Pointer Their applications as electrochemical sensors with high electrocatalytic activity. Black-Right-Pointing-Pointer A promising electrode material based on its interesting properties. - Abstract: With its well-ordered pore structure, high specific surface area and tunable pore diameters in the mesopore range, ordered mesoporous carbon (OMC) is suitable for applications in catalysis and sensing. We report recent applications of OMC in electrochemical sensors and biosensors. After a brief description of the electrochemical properties, the functionalization of the OMC for improvement of the electrocatalytic properties is then presented. We show how the ordered mesostructure of OMC is very important in those applications. The high density of edge plane-like defective sites (EDSs), oxygen-containing groups and a large surface area on OMC may provide many favorable sites for electron transfer to compounds, which makes OMC a potential novel material for an investigation of the electrochemical behavior of substances. Moreover, the structural capabilities of OMC at the scale of a few nanometers agree with immobilization of other electrocataytic substances. Interesting properties of this material may open up a new approach to study the electrochemical determination of other biomolecules.

Large pore bi-functionalised mesoporous silica for metal ion pollution treatment

International Nuclear Information System (INIS)

Burke, Aoife M.; Hanrahan, John P.; Healy, David A.; Sodeau, John R.; Holmes, Justin D.; Morris, Michael A.

2009-01-01

Here we demonstrate aminopropyl and mercatopropyl functionalised and bi-functionalised large pore mesoporous silica spheres to extract various metal ions from aqueous solutions towards providing active sorbents for mitigation of metal ion pollution. Elemental analysis (EA) and FTIR techniques were used to quantify the attachment of the aminopropyl and mercatopropyl functional groups to the mesoporous silica pore wall. Functionalisation was achieved by post-synthesis reflux procedures. For all functionalised silicas the functionalisation refluxing does not alter particle morphology/agglomeration of the particles. It was found that sorptive capacities of the mesoporous silica towards the functional groups were unaffected by co-functionalisation. Powder X-ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameters, packing of the pores and specific surface areas of the modified mesoporous silica spheres. Atomic absorption (AA) spectroscopy and inductively coupled plasma-atomic emission spectrometry (ICP-AES) techniques were used to measure the extraction efficiencies of each metal ion species from solution at varying pHs. Maximum sorptive capacities (as metal ions) were determined to be 384 μmol g -1 for Cr, 340 μmol g -1 for Ni, 358 μmol g -1 for Fe, 364 μmol g -1 for Mn and 188 μmol g -1 for Pd

Large pore bi-functionalised mesoporous silica for metal ion pollution treatment

Energy Technology Data Exchange (ETDEWEB)

Burke, Aoife M.; Hanrahan, John P. [Department of Chemistry, Materials Section and Supercritical Fluid Centre, University College Cork, Cork (Ireland); Environmental Research Institute (ERI), Lee Road, Cork (Ireland); Healy, David A.; Sodeau, John R. [Department of Chemistry, Centre of Research in Atmospheric Chemistry, University College Cork, Cork (Ireland); Holmes, Justin D. [Department of Chemistry, Materials Section and Supercritical Fluid Centre, University College Cork, Cork (Ireland); Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2 (Ireland); Morris, Michael A. [Department of Chemistry, Materials Section and Supercritical Fluid Centre, University College Cork, Cork (Ireland); Environmental Research Institute (ERI), Lee Road, Cork (Ireland); Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin, Dublin 2 (Ireland)], E-mail: m.morris@ucc.ie

2009-05-15

Here we demonstrate aminopropyl and mercatopropyl functionalised and bi-functionalised large pore mesoporous silica spheres to extract various metal ions from aqueous solutions towards providing active sorbents for mitigation of metal ion pollution. Elemental analysis (EA) and FTIR techniques were used to quantify the attachment of the aminopropyl and mercatopropyl functional groups to the mesoporous silica pore wall. Functionalisation was achieved by post-synthesis reflux procedures. For all functionalised silicas the functionalisation refluxing does not alter particle morphology/agglomeration of the particles. It was found that sorptive capacities of the mesoporous silica towards the functional groups were unaffected by co-functionalisation. Powder X-ray diffraction (PXRD) and nitrogen adsorption techniques were used to establish the pore diameters, packing of the pores and specific surface areas of the modified mesoporous silica spheres. Atomic absorption (AA) spectroscopy and inductively coupled plasma-atomic emission spectrometry (ICP-AES) techniques were used to measure the extraction efficiencies of each metal ion species from solution at varying pHs. Maximum sorptive capacities (as metal ions) were determined to be 384 {mu}mol g{sup -1} for Cr, 340 {mu}mol g{sup -1} for Ni, 358 {mu}mol g{sup -1} for Fe, 364 {mu}mol g{sup -1} for Mn and 188 {mu}mol g{sup -1} for Pd.

Adsorption characteristics of self-assembled thiol and dithiol layer on gold

International Nuclear Information System (INIS)

Tlili, A.; Abdelghani, A.; Aguir, K.; Gillet, M.; Jaffrezic-Renault, N.

2007-01-01

Monolayers of functional proteins are important in many fields related to pure and applied biochemistry and biophysics. The formation of extended uniform protein monolayers by single- or multiple-step self-chemisorption depends on the quality of the functionalized gold surface. The optical and the electrical properties of the 1-nonanethiol and 1,9-nonanedithiol deposited on gold with the self-assembled technique were investigated. We use cyclic voltammetry and impedance spectroscopy to characterize the insulating properties of the two layers. The analysis of the impedance spectra in terms of equivalent circuit of the gold/electrolyte and gold/SAM/electrolyte interface allows defining the thickness of the two thiols and the percentage of coverage area. Atomic force microscopy, contact angle measurement and Fourier transform infra-red spectroscopy have been used for homogeneity, hydrophobic properties and molecular structure of the formed thiols layer, respectively. The measured thickness with impedance spectroscopy fit well the results found with atomic force microscopy

Thiols in the alphaIIbbeta3 integrin are necessary for platelet aggregation.

Science.gov (United States)

Manickam, Nagaraj; Sun, Xiuhua; Hakala, Kevin W; Weintraub, Susan T; Essex, David W

2008-07-01

Sulfhydryl groups of platelet surface proteins are important in platelet aggregation. While p-chloromercuribenzene sulphonate (pCMBS) has been used in most studies on platelet surface thiols, the specific thiol-proteins that pCMBS reacts with to inhibit aggregation have not been well defined. Since the thiol-containing P2Y(12) ADP receptor is involved in most types of platelet aggregation, we used the ADP scavenger apyrase and the P2Y(12) receptor antagonist 2-MeSAMP to examine thiol-dependent reactions in the absence of contributions from this receptor. We provide evidence for a non-P2Y(12) thiol-dependent reaction near the final alphaIIbbeta3-dependent events of aggregation. We then used 3-(N-maleimidylpropionyl)biocytin (MPB) and pCMBS to study thiols in alphaIIbbeta3. As previously reported, disruption of the receptor was required to obtain labelling of thiols with MPB. Specificity of labelling for thiols in the alphaIIb and beta3 subunits was confirmed by identification of the purified proteins by mass spectrometry and by inhibition of labelling with 5,5'-dithiobis-(2-nitrobenzoic acid). In contrast to MPB, pCMBS preferentially reacted with thiols in alphaIIbbeta3 and blocked aggregation under physiological conditions. Similarly, pCMBS preferentially inhibited signalling-independent activation of alphaIIbbeta3 by Mn(2+). Our results suggest that the thiols in alphaIIbbeta3 that are blocked by pCMBS are important in the activation of this integrin.

Quantification of protein-derived thiols during atmosphere-controlled brewing in laboratory scale

DEFF Research Database (Denmark)

Murmann, Anne Nordmark; Andersen, Preben; Mauch, Alexander

2016-01-01

. Fermentation caused an increase in free thiols, and the balance between free and total thiols was shifted toward a higher degree of free thiols. This was explained by either a reducing effect of fermentation or secretion of thiol-containing compounds from yeast. The efficiency of sulfite to reduce reversibly...... was more pronounced at longer incubation times. However, the reduction of the pool of oxidized thiols by sulfite was inefficient for sulfite concentrations typically found in beer, and the reaction was found to be relatively slow compared with reduction by tris(carboxyethyl)phosphine....

Ordered hierarchical mesoporous/microporous carbon derived from mesoporous titanium-carbide/carbon composites and its electrochemical performance in supercapacitor

Energy Technology Data Exchange (ETDEWEB)

Liu, Hai-Jing; Wang, Jie; Wang, Cong-Xiao; Xia, Yong-Yao [Department of Chemistry and Shanghai Key Laboratory of Molecular, Catalysis and Innovative Materials, Institute of New Energy, Fudan University, Shanghai (China)

2011-11-15

Novel ordered hierarchical mesoporous/microporous carbon (OHMMC) derived from mesoporous titanium-carbide/carbon composites was prepared for the first time by synthesizing ordered mesoporous nanocrystalline titanium-carbide/carbon composites, followed by chlorination of titanium carbides. The mesostructure and microstructure can be conveniently tuned by controlling the TiC contents of mesoporous TiC/C composite precursor, and chlorination temperature. By optimal condition, the OHMMC has a high surface area (1917 m{sup 2}g{sup -1}), large pore volumes (1.24 cm{sup 3}g{sup -1}), narrow mesopore-size distributions (centered at about 3 nm), and micropore size of 0.69 and 1.25 nm, and shows a great potential as electrode for supercapacitor applications: it exhibits a high capacitance of 146 Fg{sup -1} in noaqueous electrolyte and excellent rate capability. The ordered mesoporous channel pores are favorable for retention and immersion of the electrolyte, providing a more favorable path for electrolyte penetration and transportation to achieve promising rate capability performance. Meanwhile, the micropores drilled on the mesopore-walls can increase the specific surface area to provide more sites for charge storage. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Actinide Sequestration Using Self-Assembled Monolayers on Mesoporous Supports

International Nuclear Information System (INIS)

Fryxell, Glen E.; Lin, Yuehe; Fiskum, Sandra K.; Birnbaum, Jerome C.; Wu, Hong; Kemner, K. M.; Kelly, Shelley

2005-01-01

Surfactant templated synthesis of mesoporous ceramics provides a versatile foundation upon which to create high efficiency environmental sorbents. These nanoporous ceramic oxides condense a huge amount of surface area into a very small volume. The ceramic oxide interface is receptive to surface functionalization through molecular self-assembly. The marriage of mesoporous ceramics with self-assembled monolayer chemistry creates a powerful new class of environmental sorbent materials called self-assembled monolayers on mesoporous supports (SAMMS). These SAMMS materials are highly efficient sorbents, whose interfacial chemistry can be fine-tuned to selectively sequester a specific target species, such as heavy metals, tetrahedral oxometallate anions and radionuclides. Details addressing the design, synthesis and characterization of SAMMS materials specifically designed to sequester actinides, of central importance to the environmental clean-up necessary after 40 years of weapons grade plutonium production, as well as evaluation of their binding affinities and kinetics are presented

Electrical resistivity of nanoporous gold modified with thiol self-assembled monolayers

Energy Technology Data Exchange (ETDEWEB)

Hakamada, Masataka, E-mail: hakamada.masataka.3x@kyoto-u.ac.jp; Kato, Naoki, E-mail: katou.naoki.75w@st.kyoto-u.ac.jp; Mabuchi, Mamoru, E-mail: mabuchi@energy.kyoto-u.ac.jp

2016-11-30

Highlights: • Nanoporous gold is modified with thiol-containing self-assembled monolayers. • The electrical resistivity of the thiol-modified nanoporous gold increases. • The electrical resistivity increases with increasing thiol concentration. • Monolayer tail groups enhance the atmosphere dependence of electrical resistivity. - Abstract: The electrical resistivity of nanoporous gold (NPG) modified with thiol self-assembled monolayers (SAMs) has been measured at 298 K using a four-probe method. We found that the adsorption of thiol SAMs increases the electrical resistivity of NPG by up to 22.2%. Dependence of the electrical resistivity on the atmosphere (air or water) was also observed in SAMs-modified NPG, suggesting that the electronic states of the tail groups affect the electrons of the binding sulfur and adjacent surface gold atoms. The present results suggest that adsorption of thiol molecules can influence the behavior of the conducting electrons in NPG and that modification of NPG with SAMs may be useful for environmental sensing.

Mesoporous silica nanoparticles supported copper(II) and nickel(II) Schiff base complexes: Synthesis, characterization, antibacterial activity and enzyme immobilization

Science.gov (United States)

Tahmasbi, Leila; Sedaghat, Tahereh; Motamedi, Hossein; Kooti, Mohammad

2018-02-01

Mesoporous silica nanoparticles (MSNs) were prepared by sol-gel method and functionalized with 3-aminopropyltriethoxysilane. Schiff base grafted mesoporous silica nanoparticle was synthesized by the condensation of 2-hydroxy-3-methoxybenzaldehyde and amine-functionalized MSNs. The latter material was then treated with Cu(II) and Ni(II) salts separately to obtain copper and nickel complexes anchored mesoporous composites. The newly prepared hybrid organic-inorganic nanocomposites have been characterized by several techniques such as FT-IR, LA-XRD, FE-SEM, TEM, EDS, BET and TGA. The results showed all samples have MCM-41 type ordered mesoporous structure and functionalization occurs mainly inside the mesopore channel. The presence of all elements in synthesized nanocomposites and the coordination of Schiff base via imine nitrogen and phenolate oxygen were confirmed. MSNs and all functionalized MSNs have uniform spherical nanoparticles with a mean diameter less than 100 nm. The as-synthesized mesoporous nanocomposites were investigated for antibacterial activity against Gram-positive (B. subtilis and S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacteria, as carrier for gentamicin and also for immobilization of DNase, coagulase and amylase enzymes. MSN-SB-Ni indicated bacteriocidal effect against S.aureus and all compounds were found to be good carrier for gentamicin. Results of enzyme immobilization for DNase and coagulase and α-amylase revealed that supported metal complexes efficiently immobilized enzymes.

Cadmium(II) and lead(II) adsorption onto hetero-atom functional mesoporous silica and activated carbon

Science.gov (United States)

Machida, Motoi; Fotoohi, Babak; Amamo, Yoshimasa; Mercier, Louis

2012-07-01

Adsorption of cadmium(II) and lead(II) on amino-, mercapto-functionalized mesoporous silica (HMS) and carboxylic-functionalized activated carbon (AC) were examined. The resultant isotherms fitted the Langmuir model and amino-functionalized HMS exhibited the highest adsorption capacity for both cadmium(II) and lead(II). Adsorption affinities for cadmium(II) were always greater than those for lead(II) in all three adsorbent types, while the difference between the two values was the largest for mercapto-functionalized HMS indicating a selective adsorption of cadmium(II). Influence of equilibrium solution pH on adsorption of cadmium(II), lead(II) and their binary mixtures was also studied. Carboxylic-functionalized AC adsorbed cadmium(II) and lead(II) in a wide pH range than conditions for the mercapto-functionalized HMS. It was concluded that each functional group had its own characteristics and advantages for adsorption of heavy metal ions; amino-groups showed high adsorption capacity, while mercapto-groups had good selectivity toward cadmium(II) adsorption and a wide solution pH in adsorption by carboxylic-groups were established in this study.

Cadmium(II) and lead(II) adsorption onto hetero-atom functional mesoporous silica and activated carbon

International Nuclear Information System (INIS)

Machida, Motoi; Fotoohi, Babak; Amamo, Yoshimasa; Mercier, Louis

2012-01-01

Adsorption of cadmium(II) and lead(II) on amino-, mercapto-functionalized mesoporous silica (HMS) and carboxylic-functionalized activated carbon (AC) were examined. The resultant isotherms fitted the Langmuir model and amino-functionalized HMS exhibited the highest adsorption capacity for both cadmium(II) and lead(II). Adsorption affinities for cadmium(II) were always greater than those for lead(II) in all three adsorbent types, while the difference between the two values was the largest for mercapto-functionalized HMS indicating a selective adsorption of cadmium(II). Influence of equilibrium solution pH on adsorption of cadmium(II), lead(II) and their binary mixtures was also studied. Carboxylic-functionalized AC adsorbed cadmium(II) and lead(II) in a wide pH range than conditions for the mercapto-functionalized HMS. It was concluded that each functional group had its own characteristics and advantages for adsorption of heavy metal ions; amino-groups showed high adsorption capacity, while mercapto-groups had good selectivity toward cadmium(II) adsorption and a wide solution pH in adsorption by carboxylic-groups were established in this study.

The Role of Follicular Fluid Thiol/Disulphide Homeostasis in Polycystic Ovary Syndrome.

Science.gov (United States)

Tola, Esra Nur; Köroğlu, Nadiye; Ergin, Merve; Oral, Hilmi Baha; Turgut, Abdülkadir; Erel, Özcan

2018-04-04

Oxidative stress is suggested as a potential triggering factor in the etiopathogenesis of Polycystic ovary syndrome related infertility. Thiol/disulphide homeostasis, a recently oxidative stress marker, is one of the antioxidant mechanism in human which have critical roles in folliculogenesis and ovulation. The aim of our study is to investigate follicular fluid thiol/disulphide homeostasis in the etiopathogenesis of Polycystic ovary syndrome and to determine its' association with in vitro fertilization outcome. The study procedures were approved by local ethic committee. Cross sectional design Methods: Follicular fluid of twenty-two Polycystic ovary syndrome women and twenty ovulatory controls undergoing in vitro fertilization treatment were recruited. Thiol/disulphide homeostasis was analyzed via a novel spectrophotometric method. Follicular native thiol levels were found to be lower in Polycystic ovary syndrome group than non- Polycystic ovary syndrome group (p=0.041) as well as native thiol/total thiol ratio (pPolycystic ovary syndrome group (pPolycystic ovary syndrome patients was found. A positive predictive effect of native thiol on fertilization rate among Polycystic ovary syndrome group was also found (p=0.03, β=0.45, 95% CI=0.031-0.643). Deterioration in thiol/disulphide homeostasis, especially elevated disulphide levels could be one of the etiopathogenetic mechanism in Polycystic ovary syndrome. Increased native thiol levels is related to fertilization rate among Polycystic ovary syndrome patients and also positive predictor marker of fertilization rate among Polycystic ovary syndrome patients. Improvement of thiol/disulphide homeostasis could be of importance in the treatment of Polycystic ovary syndrome to increase in vitro fertilization success in Polycystic ovary syndrome.

Chitosan scaffold modified with D-(+) raffinose and enriched with thiol-modified gelatin for improved osteoblast adhesion

International Nuclear Information System (INIS)

Galli, C; Parisi, L; Smerieri, A; Lumetti, S; Manfredi, E; Macaluso, G M; Elviri, L; Bianchera, A; Bettini, R; Lagonegro, P

2016-01-01

The aim of the present study was to investigate whether chitosan-based scaffolds modified with D-(+) raffinose and enriched with thiol-modified gelatin could selectively improve osteoblast adhesion and proliferation. 2, 3 and 4.5% chitosan films were prepared. Chitosan suitability for tissue engineering was confirmed by protein adsorption assay. Scaffolds were incubated with a 2.5 mg ml −1 BSA solution and the decrease of protein content in the supernatants was measured by spectrophotometry. Chitosan films were then enriched with thiol-modified gelatin and their ability to bind BSA was also measured. Then, 2% chitosan discs with or without thiol-modified gelatin were used as culture substrates for MC3T3-E1 cells. After 72 h cells were stained with trypan blue or with calcein AM and propidium iodide for morphology, viability and proliferation assays. Moreover, cell viability was measured at 48, 72, 96 and 168 h to obtain a growth curve. Chitosan films efficiently bound and retained BSA proportionally to the concentration of chitosan discs. The amount of protein retained was higher on chitosan enriched with thiol-modified gelatin. Moreover, chitosan discs allowed the adhesion and the viability of cells, but inhibited their proliferation. The functionalization of chitosan with thiol-modified gelatin enhanced cell spreading and proliferation. Our data confirm that chitosan is a suitable material for tissue engineering. Moreover, our data show that the enrichment of chitosan with thiol-modified gelatin enhances its biological properties. (paper)

Dynamic thiol/disulfide homeostasis and effects of smoking on homeostasis parameters in patients with psoriasis.

Science.gov (United States)

Emre, Selma; Demirseren, Duriye Deniz; Alisik, Murat; Aktas, Akin; Neselioglu, Salim; Erel, Ozcan

2017-12-01

Recently, increased reactive oxygen species (ROS), reduced antioxidant capacity, and oxidative stress have been suggested in the pathogenesis of psoriasis. The aim of this study to evaluate the thiol/disulfide homeostasis in patients with psoriasis. Ninety patients with psoriasis who did not receive any systemic treatment in the last six  months were included in the study. Seventy-six age and gender-matched healthy volunteers served as control group. Thiol/disulfide homeostasis was measured in venous blood samples obtained from patient and control groups. Native thiol and total thiol levels were significantly higher in patients than in control group. When thiol/disulfide hemostasis parameters and clinical and demographic characteristics were compared, a negative correlation was detected between native thiol and total thiol with age. The levels of total thiols had also negative correlation with PASI and duration of the disease. When we divided the patients into smokers and non-smokers, native thiol and total thiol levels were significantly higher in smokers than in controls, whereas native thiol and total thiol levels were comparable in non-smoker patients and controls. Thiol/disulfide balance shifted towards thiol in psoriasis patients and this may be responsible for increased keratinocyte proliferation in the pathogenesis of psoriasis.

The role of thiols in cellular response to radiation and drugs

International Nuclear Information System (INIS)

Biaglow, J.E.; Varnes, M.E.; Clark, E.P.; Epp, E.R.

1983-01-01

Cellular nonprotein thiols (NPSH) consist of glutathione (GSH) and other low molecular weight species such as cysteine, cysteamine, and coenzyme A. GSH is usually less than the total cellular NPSH, and with thiol reactive agents, such as diethyl maleate (DEM), its rate of depletion is in part dependent upon the cellular capacity for its resynthesis. If resynthesis is blocked by buthionine-S,R-sulfoximine(BSO), the NPSH, including GSH, is depleted more rapidly, Cellular thiol depletion by diamide, N-ethylmaleimide, and BSO may render oxygenated cells more sensitive to radiation. These cells may or may not show a reduction in the oxygen enhancement ratio (OER). Human A549 lung carcinoma cells depleted of their NPSH either by prolonged culture or by BSO treatment do not show a reduced OER but do show increased aerobic responses to radiation. Some nitroheterocyclic radiosensitizing drugs also deplete cellular thiols under aerobic conditions. Such reactivity may be the reason that they show anomalous radiation sensitization (i.e., better than predicted on the basis of electron affinity). Other nitrocompounds, such as misonidazole, are activated under hypoxic conditions to radical intermediates. When cellular thiols are depleted peroxide is formed. Under hypoxic conditions thiols are depleted because metabolically reduced intermediates react with GSH instead of oxygen. Thiol depletion, under hypoxic conditions, may be the reason that misonidazole and other nitrocompounds show an extra enhancement ratio with hypoxic cells. Thiol depletion by DEM or BSO alters the radiation response of hypoxic cells to misonidazole

Protection by thiols against poisoning by radiomimetic agents. Chapter 8

International Nuclear Information System (INIS)

Bacq, Z.M.

1975-01-01

A review is presented of reports of studies aimed at detecting a protective effect of thiols against radiomimetic alkylating agents such as those used in cancer therapy (nitrogen mustards (HN2), sarcolysine, busulfan, etc.). Protection by thiols against alkylating agents has been observed in mammals, plant cells, bacteria, isolated mammalian cells and in model systems. The lack of correlation between the protective power of various thiols against radiomimetic agents and ionizing radiations indicates that different mechanisms are involved. Studies have been made of the toxicity of the protector and the competition factor, increased excretion of detoxication products of alkylating agents, decreased alkylation of DNA and RNA both in vivo and in vitro, the protection of hematopoietic tissues, tumours and the adrenal cortex, and the modification of the effects of nitrosoalkylamines, carbon tetrachloride and fungistatics by thiols. The restriction of DNA alkylation by the competitive removal of radiomimetic agents is thought to account for the protective effect of thiols against radiomimetic agents. (U.K.)

Antioxidant activity of selenenamide-based mimic as a function of the aromatic thiols nucleophilicity, a DFT-SAPE model.

Science.gov (United States)

Kheirabadi, Ramesh; Izadyar, Mohammad

2018-05-18

The mechanism of action of the selenenamide 1 as a mimic of the glutathione peroxidase (GPx) was investigated by the density functional theory. The solvent-assisted proton exchange procedure was applied to model the catalytic behavior and antioxidant activity of this mimic. To have an insight into the charge transfer effect, different aromatic thiols, including electron donating substituents on the phenyl ring were considered. The catalytic behavior of the selenenamide was modeled in a four-step mechanism, described by the oxidation of the mimic, the reduction of the obtained product, selenoxide, the reduction of the selenenylsulfide and dehydration of selenenic acid. On the basis of the activation parameters, the final step of the proposed mechanism is the rate determining states of the catalytic cycle. Turnover frequency (TOF) analysis showed that the electron donating groups at the para-position of the phenyl ring of the PhSH do not affect the catalytic activity of the selenenamide in contrast to p-methyl thiophenol which indicates the highest nucleophilicity. The evaluation of the electronic contribution of the various donating groups on the phenyl ring of the aromatic thiols shows that the antioxidant activity of the selenenamide sufficiently increases in the presence of the electron-donating substitutions. Finally, the charge transfer process at the rate-determining state was investigated based on the natural bond orbital analysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

In Situ Growth of Mesoporous Silica with Drugs on Titanium Surface and Its Biomedical Applications.

Science.gov (United States)

Wan, Mimi; Zhang, Jin; Wang, Qi; Zhan, Shuyue; Chen, Xudong; Mao, Chun; Liu, Yuhong; Shen, Jian

2017-06-07

Mesoporous silica has been developed for the modification of titanium surfaces that are used as implant materials. Yet, the traditional modification methods failed to effectively construct mesoporous silica on the titanium surface evenly and firmly, in which the interaction between mesoporous silica and titanium was mainly physical. Here, in situ growth of mesoporous silica on a titanium surface was performed using a simple evaporation-induced self-assembly strategy. Meantime, in situ introduction of drugs (heparin and vancomycin) to mesoporous silica was also adopted to improve the drug-loading amount. Both the above-mentioned processes were completed at the same time. Transmission electron microscopy, N 2 adsorption-desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy, and water contact angle measurements were used to characterize the structure of the mesoporous silica film. Results indicated that the mesoporous silica film that in situ grew on the titanium surface was smooth, thin, transparent, and stable. Cytotoxicity, proliferation performance of osteoblast cells, and in vitro and in vivo studies of the antibacterial activity of the coating were tested. This is the first study to modify the titanium surface by the in situ growth of a mesoporous silica coating with two kinds of drugs. The stability of the mesoporous silica coating can be attributed to the chemical bonding between dopamine and silicon hydroxyl of the mesoporous silica coating, and the smooth surface of mesoporous silica is a result of the method of in situ growth. The large amount of drug-loading also could be ascribed to the in situ introduction of drugs during the synthetic process. The strategy proposed in this work will bring more possibilities for the preparation of advanced functional materials based on the combination of mesoporous structure and metallic materials.

Enhanced electrochromic and energy storage performance in mesoporous WO3 film and its application in a bi-functional smart window.

Science.gov (United States)

Wang, Wei-Qi; Wang, Xiu-Li; Xia, Xin-Hui; Yao, Zhu-Jun; Zhong, Yu; Tu, Jiang-Ping

2018-05-03

Construction of multifunctional photoelectrochemical energy devices is of great importance to energy saving. In this study, we have successfully prepared a mesoporous WO3 film on FTO glass via a facile dip-coating sol-gel method; the designed mesoporous WO3 film exhibited advantages including high transparency, good adhesion and high porosity. Also, multifunctional integrated energy storage and optical modulation ability are simultaneously achieved by the mesoporous WO3 film. Impressively, the mesoporous WO3 film exhibits a noticeable electrochromic energy storage performance with a large optical modulation up to 75.6% at 633 nm, accompanied by energy storage with a specific capacity of 75.3 mA h g-1. Furthermore, a full electrochromic energy storage window assembled with the mesoporous WO3 anode and PANI nanoparticle cathode is demonstrated with large optical modulation and good long-term stability. Our research provides a new route to realize the coincident utilization of optical-electrochemical energy.

Functionalized mesoporous silicas with crown ether moieties for selective adsorption of lithium ions in artificial sea water.

Science.gov (United States)

Sung, Soo Park; Moorthy, Madhappan Santha; Song, Hyun-Jin; Ha, Chang-Sik

2014-11-01

Lithium ion has been increasingly recognized in a wide range of industrial applications. In this work, we studied on the adsorption of Li+ in the artificial seawater with high selectivity using methyl-crown ether (AC-SBA-15) and aza-crown ether (HMC-SBA-15) moieties-functionalized mesoporous silica materials. First, methyl-crown ether and aza-crown ether moieties-functionalized mesoporous silica materials were synthesized via two-step post-synthesis process using a grafting method. The functionalized materials were employed to the metal ion adsorption from aqueous solution (artificial seawater) containing Li+, Co2+, Cr3+ and Hg2+. The prepared hybrid material showed high selectivity for Li+ ion in the artificial seawater at pH 8.0. The absorbed amount of Li+ was 73 times higher than Cr3+ for aza-crown ether containing AC-SBA-15 as an absorbent. The absorbed amount of Co2+ (4.5 x 10(-5) mol/g), Cr3+ (1.5 x 10(-5) mol/g) and Hg2+ (2.25 x 10(-4) mol/g) were remarkably lower than the case of Li+. On the other hand, the absorbed amount of various metal ions of HMC-SBA-15 with amine groups in alky chains and crown ether moieties were 1.1 x 10(-3) mol/g for Li+, 5.0 x 10(-5) mol/g for Co2+, 2.9 x 10(-4) mol/g for Cr3+, 2.8 x 10(-4) mol/g for Hg2+ mol/g, respectively.

Enzymatic Conversion of CO2 to Bicarbonate in Functionalized Mesoporous Silica

Energy Technology Data Exchange (ETDEWEB)

Yu, Yuehua; Chen, Baowei; Qi, Wen N.; Li, Xiaolin; Shin, Yongsoon; Lei, Chenghong; Liu, Jun

2012-05-01

We report here that carbonic anhydrase (CA), the fastest enzyme that can covert carbon dioxide to bicarbonate, can be spontaneously entrapped in functionalized mesoporous silica (FMS) with super-high loading density (up to 0.5 mg of protein/mg of FMS) due to the dominant electrostatic interaction. The binding of CA to HOOC-FMS can result in the protein’s conformational change comparing to the enzyme free in solution, but can be overcome with increased protein loading density. The higher the protein loading density, the less conformational change, hence the higher enzymatic activity and the higher enzyme immobilization efficiency. The electrostatically bound CA can be released by changing pH. The released enzyme still displayed the native conformational structure and the same high enzymatic activity as that prior to the enzyme entrapment. This work opens up a new approach converting carbon dioxide to biocarbonate in a biomimetic nanoconfiguration that can be integrated with the other part of biosynthesis process for the assimilation of carbon dioxide.

Gold Nanoparticles Protected with Thiol-Derivatized Amphiphilic Poly(epsilon-caprolactone)-b-poly(acrylic acid)

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Hvilsted, Søren

2009-01-01

) of tent-butyl acrylate (tBA) in a controlled fashion by use of NiBr2(PPh3)(2) catalyst to produce Prot-PCL-b-PtBA with narrow polydispersities (1.17-1.39). Subsequent mild deprotection protocols provided HS-PCL-b-PAA. Reduction of a gold salt in the presence of this macroligand under thiol......Amphiphilic poly(epsilon-caprolactone)-b-poly(acrylic acid) (HS-PCL-b-PAA) with a thiol functionality in the PCL terminal has been prepared in a novel synthetic cascade. Initially, living anionic ring-opening polymerization (ROP) of epsilon-caprolactone (epsilon-CL) employing the difunctional...

Direct esterification of olive-pomace oil using mesoporous silica supported sulfonic acids

Directory of Open Access Journals (Sweden)

F. Alrouh

2017-02-01

Full Text Available Mesoporous silica MCM-41 and SBA-15 containing propyl sulfonic acid groups were synthesized according to the literature and were characterized by X-ray diffraction, N2 adsorption and the H+ exchange capacities of the sulfonic acid groups were titrated. The esterification reaction of glycerol with olive-pomace oil has been carried out by using prepared functionalized mesoporous silica (MCM-41 and SBA-15 as catalysts. It has been monitored by GC two fatty acids (palmitic and oleic acids as reactants in olive-pomace oil and their related monoacylglycerols (Glycerol monopalmitate GMP and monooleate GMO as reaction product. The catalytic activities of the functionalized mesoporous silica were compared with commercial catalysts, these included homogeneous catalysts (p-toluenesulfonic acid and heterogeneous catalysts (Amberlyst-15. The total yield of monoacylglycerols (GMO + GMP was nearly 40%. Remarkably, we found that MCM-41-SO3H was recycled at least 3 times without any loss of activity.

Incorporation of Znq2 complexes into mesoporous silica and their transparent polymer luminescent nanocomposites

International Nuclear Information System (INIS)

Du Yaying; Fu Yuqin; Shi Yongli; Lue Xiaodan; Lue Changli; Su Zhongmin

2009-01-01

Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent nanocomposites were prepared by in situ bulk polymerization. CMS nanoparticles or nanorods with hydroxyl-, mercapto- and sulfonic-functionalized interiors were obtained by different synthetic routes in the nanosize dimensions between 50 and 500 nm. The luminescent Znq 2 complex was successfully introduced in the pores of different mesoporous silicas by chemical adsorption as the driving force. The different internal circumstances of mesoporous silicas had an obvious effect on the luminescence and lifetime of Znq 2 complex. The transparent fluorescent nanocomposites were fabricated from different Znq 2 -CMS and suitable monomers. The Znq 2 -CMS were uniformly dispersed in the polymer matrix without evident aggregation. The photoluminescence properties of Znq 2 -CMS in the transparent matrix exhibited a dependence on the inner surrounding of CMS due to the interaction between Znq 2 -CMS and polymers. The maximum emission peak of the nanocomposites had a red-shift of 28 nm as compared to pure Znq 2 -CMS. - Graphical abstract: Znq 2 -functionalized colloidal mesoporous silicas (Znq 2 -CMS)/polymer transparent fluorescent nanocomposites were prepared by in situ bulk polymerization. The figure shows the synthetic scheme for the Znq 2 -CMS and their transparent bulk nanocomposites.

“Oxygen sensing” by Na,K-ATPase: these miraculous thiols

Directory of Open Access Journals (Sweden)

Anna Bogdanova

2016-08-01

Full Text Available Control over the Na,K-ATPase function plays a central role in adaptation of the organisms to hypoxic and anoxic conditions. As the enzyme itself does not possess O2 binding sites its oxygen-sensitivity is mediated by a variety of redox-sensitive modifications including S-glutathionylation, S-nitrosylation and redox-sensitive phosphorylation. This is an overview of the current knowledge on the plethora of molecular mechanisms tuning the activity of the ATP-consuming Na,K-ATPase to the cellular metabolic activity. Recent findings suggest that oxygen-derived free radicals and H2O2, NO, and oxidised glutathione are the signalling messengers that make the Na,K-ATPase oxygen-sensitive. This very ancient signalling pathway targeting thiols of all three subunits of the Na,K-ATPase as well as redox-sensitive kinases sustains the enzyme activity at the optimal level avoiding terminal ATP depletion and maintaining the transmembrane ion gradients in cells of anoxia-tolerant species. We acknowledge the complexity of the underlying processes as we characterise the sources of reactive oxygen and nitrogen species production in hypoxic cells, and identify their targets, the reactive thiol groups which, upon modification, impact the enzyme activity. Structured accordingly, this review presents a summery on (i the sources of free radical production in hypoxic cells, (ii localisation of regulatory thiols within the Na,K-ATPase and the role reversible thiol modifications play in responses of the enzymes to a variety of stimuli (hypoxia, receptors’ activation control of the enzyme activity (iii redox-sensitive regulatory phosphorylation, and (iv the role of fine modulation of the Na,K-ATPase function in survival success under hypoxic conditions. The co-authors attempted to cover all the contradictions and standing hypotheses in the field and propose the possible future developments in this dynamic area of research, the importance of which is hard to overestimate

Mesoporous metal oxides and processes for preparation thereof

Energy Technology Data Exchange (ETDEWEB)

Suib, Steven L.; Poyraz, Altug Suleyman

2018-03-06

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.

A simple large-scale synthesis of mesoporous In2O3 for gas sensing applications

Science.gov (United States)

Zhang, Su; Song, Peng; Yan, Huihui; Yang, Zhongxi; Wang, Qi

2016-08-01

In this paper, large-scale mesoporous In2O3 nanostructures were synthesized by a facile Lewis acid catalytic the furfural alcohol resin (FAR) template route for the high-yield. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG) and the Brunauer-Emmett-Teller (BET) approach. The as-obtained mesoporous In2O3 nanostructures possess excellent mesoporous and network structure, which increases the contact area with the gases, it is conducive for adsorption-desorption of gas on the surface of In2O3. The In2O3 particles and pores were both about 15 nm and very uniform. In gas-sensing measurements with target gases, the gas sensor based on mesoporous In2O3 nanostructures showed a good response, short response-recovery time, good selectivity and stability to ethanol. These properties are due to the large specific surface area of mesoporous structure. This synthetic method could use as a new design concept for functional mesoporous nanomaterials and for mass production.

Functionalization of Fe3O4 NPs by Silanization: Use of Amine (APTES and Thiol (MPTMS Silanes and Their Physical Characterization

Directory of Open Access Journals (Sweden)

Silvia Villa

2016-10-01

Full Text Available In this paper the results concerning the synthesis of magnetite (Fe3O4 nanoparticles (NPs, their functionalization using silane derivatives, such as (3-Aminopropyltriethoxysilane (APTES and (3-mercaptopropyltrimethoxysilane (MPTMS, and their exhaustive morphological and physical characterization by field emission scanning electron microscopy (FE-SEM with energy dispersion X-ray spectrometer (EDX analysis, AC magnetic susceptibility, UV-VIS and IR spectroscopy, and thermogravimetric (TGA analyses are reported. Two different paths were adopted to achieve the desired functionalization: (1 the direct reaction between the functionalized organo-silane molecule and the surface of the magnetite nanoparticle; and (2 the use of an intermediate silica coating. Finally, the occurrence of both the functionalization with amino and thiol groups has been demonstrated by the reaction with ninhydrin and the capture of Au NPs, respectively.

[Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

Science.gov (United States)

Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

2014-08-01

Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

Enhancing Electrophoretic Display Lifetime: Thiol-Polybutadiene Evaporation Barrier Property Response to Network Microstructure

Energy Technology Data Exchange (ETDEWEB)

Cook, Caitlyn Christian [California State Polytechnic State Univ., San Luis Obispo, CA (United States)

2017-02-27

An evaporation barrier is required to enhance the lifetime of electrophoretic deposition (EPD) displays. As EPD functions on the basis of reversible deposition and resuspension of colloids suspended in a solvent, evaporation of the solvent ultimately leads to device failure. Incorporation of a thiol-polybutadiene elastomer into EPD displays enabled display lifetime surpassing six months in counting and catalyzed rigid display transition into a flexible package. Final flexible display transition to mass production compels an electronic-ink approach to encapsulate display suspension within an elastomer shell. Final thiol-polybutadiene photosensitive resin network microstructure was idealized to be dense, homogeneous, and expose an elastic response to deformation. Research at hand details an approach to understanding microstructural change within display elastomers. Polybutadiene-based resin properties are modified via polymer chain structure, with and without added aromatic urethane methacrylate difunctionality, and in measuring network response to variation in thiol and initiator concentration. Dynamic mechanical analysis results signify that cross-linked segments within a difunctionalized polybutadiene network were on average eight times more elastically active than that of linked segments within a non-functionalized polybutadiene network. Difunctionalized polybutadiene samples also showed a 2.5 times greater maximum elastic modulus than non-functionalized samples. Hybrid polymer composed of both polybutadiene chains encompassed TE-2000 stiffness and B-1000 elasticity for use in encapsulating display suspension. Later experiments measured kinetic and rheological response due to alteration in dithiol cross-linker chain length via real time Fourier transform infrared spectroscopy and real-time dynamic rheology. Distinct differences were discovered between dithiol resin systems, as maximum thiol conversion achieved in short and long chain length dithiols was 86% and

Resistivity of thiol-modified gold thin films

International Nuclear Information System (INIS)

Correa-Puerta, Jonathan; Del Campo, Valeria; Henríquez, Ricardo; Häberle, Patricio

2014-01-01

In this work, we study the effect of thiol self assembled monolayers on the electrical resistivity of metallic thin films. The analysis is based on the Fuchs–Sondheimer–Lucas theory and on electrical transport measurements. We determined resistivity change due to dodecanethiol adsorption on gold thin films. For this purpose, we controlled the deposition and annealing temperatures of the films to change the surface topography and to diminish the effect of electron grain boundary scattering. Results show that the electrical response to the absorption of thiols strongly depends on the initial topography of the surface. - Highlights: • We study the effect of self assembled monolayers on the resistivity of thin films. • Fuchs–Sondheimer theory reproduces the resistivity increase due to thiol deposition. • We determined resistivity change due to dodecanethiol deposition on gold thin films. • The electrical response strongly depends on the substrate surface topography

Resistivity of thiol-modified gold thin films

Energy Technology Data Exchange (ETDEWEB)

Correa-Puerta, Jonathan [Instituto de Física, Pontificia Universidad Católica de Valparaíso, Av. Universidad 330, Curauma, Valparaíso (Chile); Del Campo, Valeria [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaiso 2390123 (Chile); Henríquez, Ricardo, E-mail: ricardo.henriquez@usm.cl [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaiso 2390123 (Chile); Häberle, Patricio [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaiso 2390123 (Chile)

2014-11-03

In this work, we study the effect of thiol self assembled monolayers on the electrical resistivity of metallic thin films. The analysis is based on the Fuchs–Sondheimer–Lucas theory and on electrical transport measurements. We determined resistivity change due to dodecanethiol adsorption on gold thin films. For this purpose, we controlled the deposition and annealing temperatures of the films to change the surface topography and to diminish the effect of electron grain boundary scattering. Results show that the electrical response to the absorption of thiols strongly depends on the initial topography of the surface. - Highlights: • We study the effect of self assembled monolayers on the resistivity of thin films. • Fuchs–Sondheimer theory reproduces the resistivity increase due to thiol deposition. • We determined resistivity change due to dodecanethiol deposition on gold thin films. • The electrical response strongly depends on the substrate surface topography.

Biodegradable Oxamide-Phenylene-Based Mesoporous Organosilica Nanoparticles with Unprecedented Drug Payloads for Delivery in Cells

KAUST Repository

Croissant, Jonas

2016-06-03

We describe biodegradable mesoporous hybrid NPs in the presence of proteins, and its application for drug delivery. We synthesized oxamide-phenylene-based mesoporous organosilica nanoparticles (MON) in the absence of silica source which had a remarkably high organic content with a high surface area. Oxamide functions provided biodegradability in the presence of trypsin model proteins. MON displayed exceptionally high payloads of hydrophilic and hydrophobic drugs (up to 84 wt%), and a unique zero premature leakage without the pore capping, unlike mesoporous silica. MON were biocompatible and internalized into cancer cells for drug delivery.

Magnetic mesoporous material for the sequestration of algae

Science.gov (United States)

Trewyn, Brian G.; Kandel, Kapil; Slowing, Igor Ivan; Lee, Show-Ling

2014-09-09

The present invention provides a magnetic mesoporous nanoparticle that includes a mesoporous silicate nanoparticle and iron oxide. The present invention also provides a method of using magnetic mesoporous nanoparticles to sequester microorganisms from a media.

Multi-chamber and multi-layer thiol-ene microchip for cell culture

DEFF Research Database (Denmark)

Tan, H. Y.; Hemmingsen, Mette; Lafleur, Josiane P.

2014-01-01

We present a multi-layer and multi-chamber microfluidic chip fabricated using two different thiol-ene mixtures. Sandwiched between the thiol-ene chip layers is a commercially available membrane whose morphology has been altered with coatings of thiol-ene mixtures. Experiments have been conducted ...... with the microchip and shown that the fabricated microchip is suitable for long term cell culture....

Mesoporous block-copolymer nanospheres prepared by selective swelling.

Science.gov (United States)

Mei, Shilin; Jin, Zhaoxia

2013-01-28

Block-copolymer (BCP) nanospheres with hierarchical inner structure are of great interest and importance due to their possible applications in nanotechnology and biomedical engineering. Mesoporous BCP nanospheres with multilayered inner channels are considered as potential drug-delivery systems and templates for multifunctional nanomaterials. Selective swelling is a facile pore-making strategy for BCP materials. Herein, the selective swelling-induced reconstruction of BCP nanospheres is reported. Two poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) samples with different compositions (PS(23600)-b-P2VP(10400) and PS(27700)-b-P2VP(4300)) are used as model systems. The swelling reconstruction of PS-b-P2VP in ethanol, 1-pyrenebutyric acid (PBA)/ethanol, or HCl/ethanol (pH = 2.61) is characterized by scanning electron microscopy and transmission electron microscopy. It is observed that the length of the swellable block in BCP is a critical factor in determining the behavior and nanostructures of mesoporous BCP nanospheres in selective swelling. Moreover, it is demonstrated that the addition of PBA modifies the swelling structure of PS(23600)-b-P2VP(10400) through the interaction between PBA and P2VP blocks, which results in BCP nanospheres with patterned pores of controllable size. The patterned pores can be reversibly closed by annealing the mesoporous BCP nanospheres in different selective solvents. The controllable and reversible open/closed reconstruction of BCP nanospheres can be used to enclose functional nanoparticles or drugs inside the nanospheres. These mesoporous BCP nanospheres are further decorated with gold nanoparticles by UV photoreduction. The enlarged decoration area in mesoporous BCP nanospheres will enhance their activity and sensitivity as a catalyst and electrochemical sensor. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ordered mesoporous crystalline gamma-Al2O3 with variable architecture and porosity from a single hard template.

Science.gov (United States)

Wu, Zhangxiong; Li, Qiang; Feng, Dan; Webley, Paul A; Zhao, Dongyuan

2010-09-01

In this paper, an efficient route is developed for controllable synthesis of ordered mesoporous alumina (OMA) materials with variable pore architectures and high mesoporosity, as well as crystalline framework. The route is based on the nanocasting pathway with bimodal mesoporous carbon as the hard template. In contrast to conventional reports, we first realize the possibility of creating two ordered mesopore architectures by using a single carbon hard template obtained from organic-organic self-assembly, which is also the first time such carbon materials are adopted to replicate ordered mesoporous materials. The mesopore architecture and surface property of the carbon template are rationally designed in order to obtain ordered alumina mesostructures. We found that the key factors rely on the unique bimodal mesopore architecture and surface functionalization of the carbon hard template. Namely, the bimodal mesopores (2.3 and 5.9 nm) and the surface functionalities make it possible to selectively load alumina into the small mesopores dominantly and/or with a layer of alumina coated on the inner surface of the large primary mesopores with different thicknesses until full loading is achieved. Thus, OMA materials with variable pore architectures (similar and reverse mesostructures relative to the carbon template) and controllable mesoporosity in a wide range are achieved. Meanwhile, in situ ammonia hydrolysis for conversion of the metal precursor to its hydroxide is helpful for easy crystallization (as low as approximately 500 degrees C). Well-crystallized alumina frameworks composed of gamma-Al(2)O(3) nanocrystals with sizes of 6-7 nm are obtained after burning out the carbon template at 600 degrees C, which is advantageous over soft-templated aluminas. The effects of synthesis factors are demonstrated and discussed relative to control experiments. Furthermore, our method is versatile enough to be used for general synthesis of other important but difficult

Preparation of mesoporous zirconia microspheres as inert matrix

Energy Technology Data Exchange (ETDEWEB)

Guo, Ting [State Key Laboratory of New Ceramics and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, 100084 (China); Wang, Chen; Lv, Jinlong [Beijing Key Laboratory of Fine Ceramics, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, 100084 (China); Liang, Tongxiang, E-mail: txliang@tsinghua.edu.cn [State Key Laboratory of New Ceramics and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing, 100084 (China)

2016-12-01

Mesoporous zirconia microspheres, with a diameter of 900 μm, were prepared as an inert accelerator driven system (ADS) transmutation element matrix by the sol-gel method. The purpose of mesopores is to improve the adsorption capacity of inert matrix fuel (IMF) for minor actinides. The study indicated that the mesoporous zirconia performance was improved after the microspheres were hydrothermally treated at 150 °C, the specific surface area increased from 28.29 m{sup 2}/g to 61.28 m{sup 2}/g, and hydrothermal treatment avoided the cracking of the microspheres. Pre-decomposition of the organics during the hydrothermal process stabilized the mesoporous structure. The average pore diameter of mesoporous microsphere was 14.3 nm. - Highlights: • Mesoporous zirconia microspheres with a diameter of 900 μm were prepared as ADS transmutation element inert matrix. • The mesoporous performance was improved after the microspheres were hydrothermally treated at 150 °C. • The specific surface area increased from 28.29 m{sup 2}/g to 61.28 m{sup 2}/g. • The hydrothermal treatment could avoid the cracking of the microspheres. • The specific surface area of mesoporous microsphere was 61.28 m{sup 2}/g and the average pore diameter was 14.3 nm.

Gold Nanoparticles Protected with Thiol-Derivatized Amphiphilic Poly( -caprolactone)-b-poly(acrylic acid)

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Hvilsted, Søren

2008-01-01

Amphiphilic poly(c-caprolactone)-b-poly(acrylic acid) (HS-PCL-b-PAA) bearing thiol functionality at the PCL terminal has been synthesized by a combination of ring-opening polymerization (ROP) of c-caprolactone (c-CL), esterification of hydroxy chain end with protected mercaptoacetic acid, subsequ....... As a result stable, aggregation-free nanopaticles with moderate dispersity as estimated from UV-visible spectroscopy and transmission electron microscopy (TEM) data were obtained....... chromatography (SEC), nuclear magnetic resonance eR NMR) and infrared (FT IR) spectroscopy. The capacity of the resulting block copolymer in preparation of monolayer-protected gold nanoparticles has been examined by reduction of a gold salt in the presence of this macroligand under thiol-deficient conditions...

Aminopropyl-functionalized mesoporous carbon (APTMS-CMK-3) as effective phosphate adsorbent

Science.gov (United States)

Yang, Yanju; Wang, Juanjuan; Qian, Xiaoqing; Shan, Yuhua; Zhang, Haipeng

2018-01-01

Excess phosphate discharge into water bodies can lead to severe eutrophication. Adsorption has been considered as one of the most effective approaches for phosphate removal and recovery. A new aminopropyl-functionalized mesoporous carbon CMK-3 (denoted as APTMS-CMK-3) was prepared and the materials were used as adsorbents for the removal of phosphate in water. The structure, functional groups and surface charge of the materials were characterized by X-ray powder diffraction, transmission electron microscope, N2 adsorption-desorption, elemental analysis, Fourier transform infrared spectra, X-ray photoelectron spectroscopy and zeta potential measurements. The effects of contact time, initial phosphate concentration, solution pH, coexisting anions and dissolved humic acid were studied. The adsorption capacity of APTMS-CMK-3 was 38.09 mg g-1 at the equilibrium concentration of 49.06 mg L-1, and the adsorption data were well fitted with the Freundlich model. As for the reuse of APTMS-CMK-3, a relatively stable adsorption performance was observed after five adsorption-desorption cycles. Therefore, the way of grafting aminopropyl groups on the CMK-3 efficiently enhanced the capability for phosphate adsorption, indicating that it could be used as potential adsorbents for the removal of phosphate in water.

Ordered mesoporous silica materials with complicated structures

KAUST Repository

Han, Yu

2012-05-01

Periodically ordered mesoporous silicas constitute one of the most important branches of porous materials that are extensively employed in various chemical engineering applications including adsorption, separation and catalysis. This short review gives an introduction to recently developed mesoporous silicas with emphasis on their complicated structures and synthesis mechanisms. In addition, two powerful techniques for solving complex mesoporous structures, electron crystallography and electron tomography, are compared to elucidate their respective strength and limitations. Some critical issues and challenges regarding the development of novel mesoporous structures as well as their applications are also discussed. © 2011 Elsevier Ltd.

General strategy for fabricating thoroughly mesoporous nanofibers

KAUST Repository

Hou, Huilin

2014-12-03

Recently, preparation of mesoporous fibers has attracted extensive attentions because of their unique and broad applications in photocatalysis, optoelectronics, and biomaterials. However, it remains a great challenge to fabricate thoroughly mesoporous nanofibers with high purity and uniformity. Here, we report a general, simple and cost-effective strategy, namely, foaming-assisted electrospinning, for producing mesoporous nanofibers with high purity and enhanced specific surface areas. As a proof of concept, the as-fabricated mesoporous TiO2 fibers exhibit much higher photocatalytic activity and stability than both the conventional solid counterparts and the commercially available P25. The abundant vapors released from the introduced foaming agents are responsible for the creation of pores with uniform spatial distribution in the spun precursor fibers. The present work represents a critically important step in advancing the electrospinning technique for generating mesoporous fibers in a facile and universal manner.

Amphiphilic silicone architectures via anaerobic thiol-ene chemistry.

Science.gov (United States)

Keddie, Daniel J; Grande, John B; Gonzaga, Ferdinand; Brook, Michael A; Dargaville, Tim R

2011-11-18

Despite broad application, few silicone-based surfactants of known structure or, therefore, surfactancy have been prepared because of an absence of selective routes and instability of silicones to acid and base. Herein the synthesis of a library of explicit silicone-poly(ethylene glycol) (PEG) materials is reported. Pure silicone fragments were generated by the B(C(6)F(5))(3)-catalyzed condensation of alkoxysilanes and vinyl-functionalized hydrosilanes. The resulting pure products were coupled to thiol-terminated PEG materials using photogenerated radicals under anaerobic conditions.

Spectrophotometric Determination of Phenolic Antioxidants in the Presence of Thiols and Proteins

Directory of Open Access Journals (Sweden)

Aslı Neslihan Avan

2016-08-01

Full Text Available Development of easy, practical, and low-cost spectrophotometric methods is required for the selective determination of phenolic antioxidants in the presence of other similar substances. As electron transfer (ET-based total antioxidant capacity (TAC assays generally measure the reducing ability of antioxidant compounds, thiols and phenols cannot be differentiated since they are both responsive to the probe reagent. In this study, three of the most common TAC determination methods, namely cupric ion reducing antioxidant capacity (CUPRAC, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid diammonium salt/trolox equivalent antioxidant capacity (ABTS/TEAC, and ferric reducing antioxidant power (FRAP, were tested for the assay of phenolics in the presence of selected thiol and protein compounds. Although the FRAP method is almost non-responsive to thiol compounds individually, surprising overoxidations with large positive deviations from additivity were observed when using this method for (phenols + thiols mixtures. Among the tested TAC methods, CUPRAC gave the most additive results for all studied (phenol + thiol and (phenol + protein mixtures with minimal relative error. As ABTS/TEAC and FRAP methods gave small and large deviations, respectively, from additivity of absorbances arising from these components in mixtures, mercury(II compounds were added to stabilize the thiol components in the form of Hg(II-thiol complexes so as to enable selective spectrophotometric determination of phenolic components. This error compensation was most efficient for the FRAP method in testing (thiols + phenols mixtures.

Highly tailorable thiol-ene based emulsion-templated monoliths

DEFF Research Database (Denmark)

Lafleur, J. P.; Kutter, J. P.

2014-01-01

The attractive surface properties of thiol-ene polymers combined with their ease of processing make them ideal substrates in many bioanalytical applications. We report the synthesis of highly tailorable emulsion-templated porous polymers and beads in microfluidic devices based on off-stoichiometr......The attractive surface properties of thiol-ene polymers combined with their ease of processing make them ideal substrates in many bioanalytical applications. We report the synthesis of highly tailorable emulsion-templated porous polymers and beads in microfluidic devices based on off......-stoichiometry thiolene chemistry. The method allows monolith synthesis and anchoring inside thiol-ene microchannels in a single step. Variations in the monomer stoichiometric ratios and/or amount of porogen used allow for the creation of extremely varied polymer morphologies, from foam-like materials to dense networks...

Liquid Photonic Crystals for Mesopore Detection.

Science.gov (United States)

Zhu, Biting; Fu, Qianqian; Chen, Ke; Ge, Jianping

2018-01-02

Nitrogen adsorption-desorption for mesopore characterization requires the using of expensive instrumentation, time-consuming processes, and the consumption of liquid nitrogen. Herein, a new method is developed to measure the pore parameters through mixing a mesoporous substance with a supersaturated SiO 2 colloidal solution at different temperatures, and subsequent rapid measurement of reflection changes of the precipitated liquid photonic crystals. The pore volumes and diameters of mesoporous silica were measured according to the positive correlation between unit mass reflection change (Δλ/m) and pore volume (V), and the negative correlation between average absorption temperature (T) and pore diameter (D). This new approach may provide an alternative method for fast, convenient and economical characterization of mesoporous materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Reducing Capacity of Thioredoxin on Oxidized Thiols in Boiled Wort

DEFF Research Database (Denmark)

Murmann, Anne N.; Hägglund, Per; Svensson, Birte

2017-01-01

system was also capable of increasing the free thiol concentration, although with lower efficiency to 187 and 170 μM, respectively. The presence of sulfite, an important antioxidant in beer secreted by the yeast during fermentation, was found to inactivate thioredoxin by sulfitolysis. Reduction......Free thiol-containing proteins are suggested to work as antioxidants in beer, but the majority of thiols in wort are present in their oxidized form as disulfides and are therefore not active as antioxidants. Thioredoxin, a disulfide-reducing protein, is released into the wort from some yeast...... and fluorescence detection of thiol-derivatives. When boiled wort was incubated with all components of the thioredoxin system at pH 7.0 and 25 °C for 60 min under anaerobic conditions, the free thiol concentration increased from 25 to 224 μM. At pH values similar to wort (pH 5.7) and beer (pH 4.5), the thioredoxin...

Identification of novel aroma-active thiols in pan-roasted white sesame seeds.

Science.gov (United States)

Tamura, Hitoshi; Fujita, Akira; Steinhaus, Martin; Takahisa, Eisuke; Watanabe, Hiroyuki; Schieberle, Peter

2010-06-23

Screening for aroma-active compounds in an aroma distillate obtained from freshly pan-roasted sesame seeds by aroma extract dilution analysis revealed 32 odorants in the FD factor range of 2-2048, 29 of which could be identified. The highest FD factors were found for the coffee-like smelling 2-furfurylthiol, the caramel-like smelling 4-hydroxy-2,5-dimethyl-3(2H)-furanone, the coffee-like smelling 2-thenylthiol (thiophen-2-yl-methylthiol), and the clove-like smelling 2-methoxy-4-vinylphenol. In addition, 9 odor-active thiols with sulfurous, meaty, and/or catty, black-currant-like odors were identified for the first time in roasted sesame seeds. Among them, 2-methyl-1-propene-1-thiol, (Z)-3-methyl-1-butene-1-thiol, (E)-3-methyl-1-butene-1-thiol, (Z)-2-methyl-1-butene-1-thiol, (E)-2-methyl-1-butene-1-thiol, and 4-mercapto-3-hexanone were previously unknown as food constituents. Their structures were confirmed by comparing their mass spectra and retention indices as well as their sensory properties with those of synthesized reference compounds. The relatively unstable 1-alkene-1-thiols represent a new class of food odorants and are suggested as the key contributors to the characteristic, but quickly vanishing, aroma of freshly ground roasted sesame seeds.

Recent progress of ordered mesoporous silica-supported chiral metallic catalysts

Directory of Open Access Journals (Sweden)

LIU Rui

2013-02-01

Full Text Available Recently,ordered silica-based mesoporous chiral organometallics-functionalized heterogeneous catalysts have attracted extensive research interest due to their excellent properties,such as easy preparation,high activity and convenient recycle.This review mainly summarizesthe generally prepared strategy and the silica-based organometallics-functionalized heterogeneous catalysts reported in the literatures.

Amine-Functionalized Mesoporous Silica Nanoparticles: A New Nanoantibiotic for Bone Infection Treatment

Directory of Open Access Journals (Sweden)

Pedraza Daniel

2018-01-01

Full Text Available This manuscript reports an effective new alternative for the management of bone infection by the development of an antibiotic nanocarrier able to penetrate bacterial biofilm, thus enhancing antimicrobial effectiveness. This nanosystem, also denoted as “nanoantibiotic”, consists in mesoporous silica nanoparticles (MSNs loaded with an antimicrobial agent (levofloxacin, LEVO and externally functionalized with N-(2-aminoethyl-3- aminopropyltrimethoxysilane (DAMO as targeting agent. This amine functionalization provides MSNs of positive charges, which improves the affinity towards the negatively charged bacteria wall and biofilm. Physical and chemical properties of the nanoantibiotic were studied using different characterization techniques, including Xray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption porosimetry, elemental chemical analysis, dynamic light scattering (DLS, zeta (ζ-potential and solid-state nuclear magnetic resonance (NMR. “In vial” LEVO release profiles and the in vitro antimicrobial effectiveness of the different released doses were investigated. The efficacy of the nanoantibiotic against a S. aureus biofilm was also determined, showing the practically total destruction of the biofilm due to the high penetration ability of the developed nanosystem. These findings open up promising expectations in the field of bone infection treatment.

Amine-Functionalized Mesoporous Silica Nanoparticles: A New Nanoantibiotic for Bone Infection Treatment

Directory of Open Access Journals (Sweden)

Pedraza Daniel

2017-12-01

Full Text Available This manuscript reports an effective new alternative for the management of bone infection by the development of an antibiotic nanocarrier able to penetrate bacterial biofilm, thus enhancing antimicrobial effectiveness. This nanosystem, also denoted as “nanoantibiotic”, consists in mesoporous silica nanoparticles (MSNs loaded with an antimicrobial agent (levofloxacin, LEVO and externally functionalized with N-(2-aminoethyl-3-aminopropyltrimethoxysilane (DAMO as targeting agent. This amine functionalization provides MSNs of positive charges, which improves the affinity towards the negatively charged bacteria wall and biofilm. Physical and chemical properties of the nanoantibiotic were studied using different characterization techniques, including Xray diffraction (XRD, transmission electron microscopy (TEM, N2 adsorption porosimetry, elemental chemical analysis, dynamic light scattering (DLS, zeta (ζ -potential and solid-state nuclear magnetic resonance (NMR. “In vial” LEVO release profiles and the in vitro antimicrobial effectiveness of the different released doses were investigated. The efficacy of the nanoantibiotic against a S. aureus biofilm was also determined, showing the practically total destruction of the biofilm due to the high penetration ability of the developed nanosystem. These findings open up promising expectations in the field of bone infection treatment.

Mesoporous tungsten titanate as matrix for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of biomolecules

International Nuclear Information System (INIS)

Shan Zhe; Han Lu; Yuan Minjia; Deng Chunhui; Zhao Dongyuan; Tu Bo; Yang Pengyuan

2007-01-01

In this paper, mesoporous tungsten titanate (WTiO) with different nano-pore structures was utilized as matrix for the analysis of short peptides by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). Effect of characteristic features of mesoporous matrices on laser desorption/ionization process was investigated. Experiments showed that the ordered two-dimensional and three-dimensional mesoporous matrices were superior in performance to the non-ordered WTiO matrix. The dramatic enhancement of signal sensitivity by the ordered mesoporous matrices can be reasonably attributed to the ordered structure, which facilitated the understanding on structure-function relationship in mesoporous cavity for laser desorption process of adsorbed biomolecules. With the ordered mesoporous matrix, the short peptides are successfully detected. The presence of trace alkali metal salt effectively increased the analyte ion yields and the MALDI-TOFMS using the inorganic mesoporous matrices displayed a high salt tolerance. The developed technique also showed a satisfactory performance in peptide-mapping and amino-acid sequencing analysis

Preparation and characterization of multifunctional magnetic mesoporous calcium silicate materials

International Nuclear Information System (INIS)

Zhang, Jianhua; Tao, Cuilian; Zhu, Yufang; Zhu, Min; Li, Jie; Hanagata, Nobutaka

2013-01-01

We have prepared multifunctional magnetic mesoporous Fe–CaSiO 3 materials using triblock copolymer (P123) as a structure-directing agent. The effects of Fe substitution on the mesoporous structure, in vitro bioactivity, magnetic heating ability and drug delivery property of mesoporous CaSiO 3 materials were investigated. Mesoporous Fe–CaSiO 3 materials had similar mesoporous channels (5–6 nm) with different Fe substitution. When 5 and 10% Fe were substituted for Ca in mesoporous CaSiO 3 materials, mesoporous Fe–CaSiO 3 materials still showed good apatite-formation ability and had no cytotoxic effect on osteoblast-like MC3T3-E1 cells evaluated by the elution cell culture assay. On the other hand, mesoporous Fe–CaSiO 3 materials could generate heat to raise the temperature of the surrounding environment in an alternating magnetic field due to their superparamagnetic property. When we use gentamicin (GS) as a model drug, mesoporous Fe–CaSiO 3 materials release GS in a sustained manner. Therefore, magnetic mesoporous Fe–CaSiO 3 materials would be a promising multifunctional platform with bone regeneration, local drug delivery and magnetic hyperthermia. (paper)

A simple three step method for selective placement of organic groups in mesoporous silica thin films

Energy Technology Data Exchange (ETDEWEB)

Franceschini, Esteban A. [Gerencia Química, Centro Atómico Constituyentes, Comisión Nacional de Energía Atómica, Av. Gral Paz 1499 (B1650KNA) San Martín, Buenos Aires (Argentina); Llave, Ezequiel de la; Williams, Federico J. [Departamento de Química Inorgánica, Analítica y Química Física and INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, C1428EHA Buenos Aires (Argentina); Soler-Illia, Galo J.A.A., E-mail: galo.soler.illia@gmail.com [Departamento de Química Inorgánica, Analítica y Química Física and INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, C1428EHA Buenos Aires (Argentina); Instituto de Nanosistemas, Universidad Nacional de General San Martín, 25 de Mayo y Francia (1650) San Martín, Buenos Aires (Argentina)

2016-02-01

Selective functionalization of mesoporous silica thin films was achieved using a three step method. The first step consists in an outer surface functionalization, followed by washing off the structuring agent (second step), leaving the inner surface of the pores free to be functionalized in the third step. This reproducible method permits to anchor a volatile silane group in the outer film surface, and a second type of silane group in the inner surface of the pores. As a concept test we modified the outer surface of a mesoporous silica film with trimethylsilane (–Si–(CH{sub 3}){sub 3}) groups and the inner pore surface with propylamino (–Si–(CH{sub 2}){sub 3}–NH{sub 2}) groups. The obtained silica films were characterized by Environmental Ellipsometric Porosimetry (EEP), EDS, XPS, contact angle and electron microscopy. The selectively functionalized silica (SF) shows an amount of surface amino functions 4.3 times lower than the one-step functionalized (OSF) silica samples. The method presented here can be extended to a combination of silane chlorides and alkoxides as functional groups, opening up a new route toward the synthesis of multifunctional mesoporous thin films with precisely localized organic functions. - Highlights: • Selective functionalization of mesoporous silica thin films was achieved using a three step method. • A volatile silane group is anchored by evaporation on the outer film surface. • A second silane is deposited in the inner surface of the pores by post-grafting. • Contact angle, EDS and XPS measurements show different proportions of amino groups on both surfaces. • This method can be extended to a combination of silane chlorides and alkoxides functional groups.

Investigations of step-growth thiol-ene polymerizations for novel dental restoratives.

Science.gov (United States)

Lu, Hui; Carioscia, Jacquelyn A; Stansbury, Jeffery W; Bowman, Christopher N

2005-12-01

The goal of this work was to investigate the feasibility of formulating novel dental restorative materials that utilize a step-growth thiol-ene photopolymerization. Particularly, we are aiming to significantly reduce the polymerization shrinkage and shrinkage stress while retaining adequate physical properties as compared to current dimethacrylatre-based systems. The thiol-ene system is composed of a 4:3 molar mixture of triallyl-1,3,5-triazine-2,4,6-trione (TATATO) and pentaerythritol tetramercaptopropionate (PETMP). The simultaneous measurement of shrinkage stress and functional group conversion was performed. Solvent extraction of unreacted monomers and dynamic mechanical analysis on the polymer networks that were formed were also studied. Flexural strength was measured for both filled and unfilled PETMP/TATATO and Bis-GMA/TEGDMA systems. Photopolymerization of PETMP/TATATO occurs at a much higher rate, with the maximum polymerization rate six times faster, than Bis-GMA/TEGDMA cured under the identical conditions. The results from the simultaneous measurement of shrinkage stress and conversion showed that the onset of shrinkage stress coincides with the delayed gel point conversion, which is predicted to be 41% for the 3:4 stoichiometric PETMP/TATATO resin composition. The maximum shrinkage stress developed for PETMP/TATATO was about 0.4 MPa, which was only approximately 14% of the maximum shrinkage stress of the Bis-GMA/TEGDMA system. Adequate flexural strength and flexural modulus values were obtained for both filled and unfilled PETMP/TATATO systems. The dramatically reduced shrinkage stress, increased polymerization rate, significance increased functional group conversion, and decreased leachable species are all benefits for the use-of thiol-ene systems as potential dental restorative materials.

Relationship of non-protein thiol pools and accumulated Cd or Hg in the marine macrophyte Posidonia oceanica (L.) Delile

International Nuclear Information System (INIS)

Maserti, B.E.; Ferrillo, V.; Avdis, O.; Nesti, U.; Di Garbo, A.; Catsiki, A.; Maestrini, P.L.

2005-01-01

The accumulation of cadmium or mercury and the effect of these elements on the levels of non-protein thiols in the blades of the marine macrophyte Posidonia oceanica were investigated. A significant accumulation of cadmium or mercury, dependent on metal concentration supplied, was observed in metal-treated blades. In the blades treated either with cadmium or mercury, a significant increase in the levels of non-protein thiols (other than glutathione) and a marked depletion of the reduced glutathione content as a function of the metal, exposure time and metal concentration supplied were found. This investigation provides first experimental report on the relationship between non-protein thiol pools and accumulated cadmium or mercury in P. oceanica

A simple large-scale synthesis of mesoporous In_2O_3 for gas sensing applications

International Nuclear Information System (INIS)

Zhang, Su; Song, Peng; Yan, Huihui; Yang, Zhongxi; Wang, Qi

2016-01-01

Graphical abstract: Large-scale mesoporous In_2O_3 nanostructures for gas-sensing applications were successfully fabricated via a facile Lewis acid catalytic the furfural alcohol resin template route. - Highlights: • Mesoporous In_2O_3 nanostructures with high-yield have been successfully fabricated via a facile strategy. • The microstructure and formation mechanism of mesoporous In_2O_3 nanostructures were discussed based on the experimental results. • The as-prepared In_2O_3 samples exhibited high response, short response-recovery times and good selectivity to ethanol gas. - Abstract: In this paper, large-scale mesoporous In_2O_3 nanostructures were synthesized by a facile Lewis acid catalytic the furfural alcohol resin (FAR) template route for the high-yield. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG) and the Brunauer-Emmett-Teller (BET) approach. The as-obtained mesoporous In_2O_3 nanostructures possess excellent mesoporous and network structure, which increases the contact area with the gases, it is conducive for adsorption-desorption of gas on the surface of In_2O_3. The In_2O_3 particles and pores were both about 15 nm and very uniform. In gas-sensing measurements with target gases, the gas sensor based on mesoporous In_2O_3 nanostructures showed a good response, short response-recovery time, good selectivity and stability to ethanol. These properties are due to the large specific surface area of mesoporous structure. This synthetic method could use as a new design concept for functional mesoporous nanomaterials and for mass production.

Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

Science.gov (United States)

Devi, J Meena

2017-06-01

The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

[Study on absorbing volatile oil with mesoporous carbon].

Science.gov (United States)

Yan, Hong-mei; Jia, Xiao-bin; Zhang, Zhen-hai; Sun, E; Yang Nan

2014-11-01

Clove oil and turmeric oil were absorbed by mesoporous carbon. The absorption ratio of mesoporous carbon to volatile oil was optimized with the eugenol yield and curcumol yield as criteria Curing powder was characterized by scanning electron microscopy (SEM) and differential scanning calorietry (DSC). The effects of mesoporous carbon on dissolution in vitro and thermal stability of active components were studied. They reached high adsorption rate when the absorption ratio of mesoporous carbon to volatile oil was 1:1. When volatile oil was absorbed, dissolution rate of active components had a little improvement and their thermal stability improved after volatile oil was absorbed by the loss rate decreasing more than 50%. Absorbing herbal volatile oil with mesoporous carbon deserves further studying.

Iron and thiols as two major players in carcinogenesis: friends or foes?

Science.gov (United States)

Toyokuni, Shinya

2014-01-01

Iron is the most abundant metal in the human body and mainly works as a cofactor for proteins such as hemoglobin and various enzymes. No independent life forms on earth can survive without iron. However, excess iron is intimately associated with carcinogenesis by increasing oxidative stress via its catalytic activity to generate hydroxyl radicals. Biomolecules with redox-active sulfhydryl function(s) (thiol compounds) are necessary for the maintenance of mildly reductive cellular environments to counteract oxidative stress, and for the execution of redox reactions for metabolism and detoxification. Involvement of glutathione S-transferase and thioredoxin has long attracted the attention of cancer researchers. Here, I update recent findings on the involvement of iron and thiol compounds during carcinogenesis and in cancer cells. It is now recognized that the cystine/glutamate transporter (antiporter) is intimately associated with ferroptosis, an iron-dependent, non-apoptotic form of cell death, observed in cancer cells, and also with cancer stem cells; the former with transporter blockage but the latter with its stabilization. Excess iron in the presence of oxygen appears the most common known mutagen. Ironically, the persistent activation of antioxidant systems via genetic alterations in Nrf2 and Keap1 also contributes to carcinogenesis. Therefore, it is difficult to conclude the role of iron and thiol compounds as friends or foes, which depends on the quantity/distribution and induction/flexibility, respectively. Avoiding further mutation would be the most helpful strategy for cancer prevention, and myriad of efforts are being made to sort out the weaknesses of cancer cells.

Formation of Micro and Mesoporous Amorphous Silica-Based Materials from Single Source Precursors

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Mohd Nazri Mohd Sokri

2016-03-01

Full Text Available Polysilazanes functionalized with alkoxy groups were designed and synthesized as single source precursors for fabrication of micro and mesoporous amorphous silica-based materials. The pyrolytic behaviors during the polymer to ceramic conversion were studied by the simultaneous thermogravimetry-mass spectrometry (TG-MS analysis. The porosity of the resulting ceramics was characterized by the N2 adsorption/desorption isotherm measurements. The Fourier transform infrared spectroscopy (FT-IR and Raman spectroscopic analyses as well as elemental composition analysis were performed on the polymer-derived amorphous silica-based materials, and the role of the alkoxy group as a sacrificial template for the micro and mesopore formations was discussed from a viewpoint to establish novel micro and mesoporous structure controlling technologies through the polymer-derived ceramics (PDCs route.

Live-cell imaging of biothiols via thiol/disulfide exchange to trigger the photoinduced electron transfer of gold-nanodot sensor

International Nuclear Information System (INIS)

Liu, Ching-Ping; Wu, Te-Haw; Liu, Chia-Yeh; Lin, Shu-Yi

2014-01-01

Highlights: • The ultrasmall size, PAMAM dendrimer-entrapped Au 8 -clusters were synthesized. • Thiol/disulfide exchange with biothiols to release 2-PyT resulted in quenching. • The sensing platform can detect both low and high molecular weight thiols. • Capable of imaging biothiols including protein thiols in living cells. - Abstract: Biothiols have been reported to involve in intracellular redox-homeostasis against oxidative stress. In this study, a highly selective and sensitive fluorescent probe for sensing biothiols is explored by using an ultrasmall gold nanodot (AuND), the dendrimer-entrapped Au 8 -cluster. This strategy relies upon a thiol/disulfide exchange to trigger the fluorescence change through a photoinduced electron transfer (PET) process between the Au 8 -cluster (as an electron donor) and 2-pyridinethiol (2-PyT) (as an electron acceptor) for sensing biothiols. When 2-PyT is released via the cleavage of disulfide bonds by biothiols, the PET process from the Au 8 -cluster to 2-PyT is initiated, resulting in fluorescence quenching. The fluorescence intensity was found to decrease linearly with glutathione (GSH) concentration (0–1500 μM) at physiological relevant levels and the limit of detection for GSH was 15.4 μM. Compared to most nanoparticle-based fluorescent probes that are limited to detect low molecular weight thiols (LMWTs; i.e., GSH and cysteine), the ultrasmall Au 8 -cluster-based probe exhibited less steric hindrance and can be directly applied in selectively and sensitively detecting both LMWTs and high molecular weight thiols (HMWTs; i.e., protein thiols). Based on such sensing platform, the surface-functionalized Au 8 -cluster has significant promise for use as an efficient nanoprobe for intracellular fluorescence imaging of biothiols including protein thiols in living cells whereas other nanoparticle-based fluorescent probes cannot

Live-cell imaging of biothiols via thiol/disulfide exchange to trigger the photoinduced electron transfer of gold-nanodot sensor

Energy Technology Data Exchange (ETDEWEB)

Liu, Ching-Ping; Wu, Te-Haw; Liu, Chia-Yeh; Lin, Shu-Yi, E-mail: shuyi@nhri.org.tw

2014-11-07

Highlights: • The ultrasmall size, PAMAM dendrimer-entrapped Au{sub 8}-clusters were synthesized. • Thiol/disulfide exchange with biothiols to release 2-PyT resulted in quenching. • The sensing platform can detect both low and high molecular weight thiols. • Capable of imaging biothiols including protein thiols in living cells. - Abstract: Biothiols have been reported to involve in intracellular redox-homeostasis against oxidative stress. In this study, a highly selective and sensitive fluorescent probe for sensing biothiols is explored by using an ultrasmall gold nanodot (AuND), the dendrimer-entrapped Au{sub 8}-cluster. This strategy relies upon a thiol/disulfide exchange to trigger the fluorescence change through a photoinduced electron transfer (PET) process between the Au{sub 8}-cluster (as an electron donor) and 2-pyridinethiol (2-PyT) (as an electron acceptor) for sensing biothiols. When 2-PyT is released via the cleavage of disulfide bonds by biothiols, the PET process from the Au{sub 8}-cluster to 2-PyT is initiated, resulting in fluorescence quenching. The fluorescence intensity was found to decrease linearly with glutathione (GSH) concentration (0–1500 μM) at physiological relevant levels and the limit of detection for GSH was 15.4 μM. Compared to most nanoparticle-based fluorescent probes that are limited to detect low molecular weight thiols (LMWTs; i.e., GSH and cysteine), the ultrasmall Au{sub 8}-cluster-based probe exhibited less steric hindrance and can be directly applied in selectively and sensitively detecting both LMWTs and high molecular weight thiols (HMWTs; i.e., protein thiols). Based on such sensing platform, the surface-functionalized Au{sub 8}-cluster has significant promise for use as an efficient nanoprobe for intracellular fluorescence imaging of biothiols including protein thiols in living cells whereas other nanoparticle-based fluorescent probes cannot.

Evaluation of Dynamic Disulphide/Thiol Homeostasis in Silica Exposed Workers

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Meşide Gündüzöz

2017-04-01

Full Text Available Background: Oxidative stress is implicated as one of the main molecular mechanism underlying silicosis. Aims: In this study, our aim was to asses the redox status in occupationally silica-exposed workers, by evaluating the dynamic thiol-disulphide homeostasis. Study Design: Case-control study. Methods: Thirty-six male workers occupationally exposed to silica particles and 30 healthy volunteers, working as office workers were included to the study. Posteroanterior chest radiographs and pulmonary function tests of both groups were evaluated. Also serum thiol disulphide levels were measured using the spectrophotometric method described by Erel and Neşelioğlu. Results: Among the 36 workers that underwent pulmonary function tests 6 (17% had obstructive, 7 (19% had restrictive, 6 (17% had obstructive and restrictive signs whereas 17 (47% had no signs. The mean PFTs results of silica-exposed workers were significantly lower than control subjects. The serum disulphide levels of silica-exposed workers were significantly higher than control subjects (23.84±5.89 μmol/L and 21.18±3.44 μmol/L, respectively p=0.02. Conclusion: The serum disulphide levels, a biomarker of oxidative stress, are found to be higher in silica-exposed workers

Orented immobilization of farnesylated proteins by the thiol-ene reaction

NARCIS (Netherlands)

Weinrich, Dirk; Lin, Po-Chiao; Jonkheijm, Pascal; Nguyen, Uyen T.T.; Schröder, Hendrik; Niemeyer, Christof M.; Alexandrov, Kirill; Goody, Roger; Waldmann, Herbert

2010-01-01

Anchoring the protein: Proteins were immobilized rapidly under mild conditions by thiol-ene photocoupling between S-farnesyl groups attached to a genetically encodable “CAAX-box” tetrapeptide sequence (A is aliphatic) at the C terminus of the protein and surface-exposed thiols (see scheme). This

Intercalation of gaseous thiols and sulfides into Ag+ ion-exchanged aluminum dihydrogen triphosphate.

Science.gov (United States)

Hayashi, Aki; Saimen, Hiroki; Watanabe, Nobuaki; Kimura, Hitomi; Kobayashi, Ayumi; Nakayama, Hirokazu; Tsuhako, Mitsutomo

2005-08-02

Ag(+) ion-exchanged layered aluminum dihydrogen triphosphate (AlP) with the interlayer distance of 0.85 nm was synthesized by the ion-exchange of proton in triphosphate with Ag(+) ion. The amount of exchanged Ag(+) ion depended on the concentration of AgNO(3) aqueous solution. Ag(+) ion-exchanged AlP adsorbed gaseous thiols and sulfides into the interlayer region. The adsorption amounts of thiols were more than those of sulfides, thiols with one mercapto group > thiol with two mercapto groups > sulfides, and depended on the amount of exchanged Ag(+) ion in the interlayer region. The thiols with one mercapto group were intercalated to expand the interlayer distance of Ag(+) ion-exchanged AlP, whereas there was no expansion in the adsorption of sulfide. In the case of thiol with two mercapto groups, there was observed contraction of the interlayer distance through the bridging with Ag(+) ions of the upper and lower sides of the interlayer region.

Kinetics and mechanisms of thiol-disulfide exchange covering direct substitution and thiol oxidation-mediated pathways.

Science.gov (United States)

Nagy, Péter

2013-05-01

Disulfides are important building blocks in the secondary and tertiary structures of proteins, serving as inter- and intra-subunit cross links. Disulfides are also the major products of thiol oxidation, a process that has primary roles in defense mechanisms against oxidative stress and in redox regulation of cell signaling. Although disulfides are relatively stable, their reduction, isomerisation, and interconversion as well as their production reactions are catalyzed by delicate enzyme machineries, providing a dynamic system in biology. Redox homeostasis, a thermodynamic parameter that determines which reactions can occur in cellular compartments, is also balanced by the thiol-disulfide pool. However, it is the kinetic properties of the reactions that best represent cell dynamics, because the partitioning of the possible reactions depends on kinetic parameters. This review is focused on the kinetics and mechanisms of thiol-disulfide substitution and redox reactions. It summarizes the challenges and advances that are associated with kinetic investigations in small molecular and enzymatic systems from a rigorous chemical perspective using biological examples. The most important parameters that influence reaction rates are discussed in detail. Kinetic studies of proteins are more challenging than small molecules, and quite often investigators are forced to sacrifice the rigor of the experimental approach to obtain the important kinetic and mechanistic information. However, recent technological advances allow a more comprehensive analysis of enzymatic systems via using the systematic kinetics apparatus that was developed for small molecule reactions, which is expected to provide further insight into the cell's machinery.

Mesoporous material grafted with luminescent molecules for the design of selective metal ion chemosensor

International Nuclear Information System (INIS)

Zhang Huidong; Zhang Ping; Ye Kaiqi; Sun Yinghui; Jiang Shimei; Wang Yue; Pang Wenqin

2006-01-01

Luminescent Schiff-base groups have been successfully grafted on the surface of mesoporous material MCM-48. The grafted Schiff-base groups were employed to prepare luminescent Schiff-base-Zn complex that was covalently bound to the MCM-48 surface. These luminescent mesoporous materials were characterized with X-ray, UV-VIS and emission spectroscopic methods. Experimental results demonstrated that MCM-48 modified with functional groups exhibited novel luminescent property. The chemosensing property of modified MCM-48 sample was investigated. It was demonstrated that the fluorescence of MCM-48 solid with Schiff-base groups could be completely quenched by Cu 2+ cation and this mesoporous material was suitable for sensing Cu 2+ cation in aqueous media

Mesoporous tin-doped indium oxide thin films: effect of mesostructure on electrical conductivity

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Till von Graberg, Pascal Hartmann, Alexander Rein, Silvia Gross, Britta Seelandt, Cornelia Röger, Roman Zieba, Alexander Traut, Michael Wark, Jürgen Janek and Bernd M Smarsly

2011-01-01

Full Text Available We present a versatile method for the preparation of mesoporous tin-doped indium oxide (ITO thin films via dip-coating. Two poly(isobutylene-b-poly(ethyleneoxide (PIB-PEO copolymers of significantly different molecular weight (denoted as PIB-PEO 3000 and PIB-PEO 20000 are used as templates and are compared with non-templated films to clarify the effect of the template size on the crystallization and, thus, on the electrochemical properties of mesoporous ITO films. Transparent, mesoporous, conductive coatings are obtained after annealing at 500 °C; these coatings have a specific resistance of 0.5 Ω cm at a thickness of about 100 nm. Electrical conductivity is improved by one order of magnitude by annealing under a reducing atmosphere. The two types of PIB-PEO block copolymers create mesopores with in-plane diameters of 20–25 and 35–45 nm, the latter also possessing correspondingly thicker pore walls. Impedance measurements reveal that the conductivity is significantly higher for films prepared with the template generating larger mesopores. Because of the same size of the primary nanoparticles, the enhanced conductivity is attributed to a higher conduction path cross section. Prussian blue was deposited electrochemically within the films, thus confirming the accessibility of their pores and their functionality as electrode material.

Cubic mesoporous Ag@CN: a high performance humidity sensor.

Science.gov (United States)

Tomer, Vijay K; Thangaraj, Nishanthi; Gahlot, Sweta; Kailasam, Kamalakannan

2016-12-01

The fabrication of highly responsive, rapid response/recovery and durable relative humidity (%RH) sensors that can precisely monitor humidity levels still remains a considerable challenge for realizing the next generation humidity sensing applications. Herein, we report a remarkably sensitive and rapid %RH sensor having a reversible response using a nanocasting route for synthesizing mesoporous g-CN (commonly known as g-C 3 N 4 ). The 3D replicated cubic mesostructure provides a high surface area thereby increasing the adsorption, transmission of charge carriers and desorption of water molecules across the sensor surfaces. Owing to its unique structure, the mesoporous g-CN functionalized with well dispersed catalytic Ag nanoparticles exhibits excellent sensitivity in the 11-98% RH range while retaining high stability, negligible hysteresis and superior real time %RH detection performances. Compared to conventional resistive sensors based on metal oxides, a rapid response time (3 s) and recovery time (1.4 s) were observed in the 11-98% RH range. Such impressive features originate from the planar morphology of g-CN as well as unique physical affinity and favourable electronic band positions of this material that facilitate water adsorption and charge transportation. Mesoporous g-CN with Ag nanoparticles is demonstrated to provide an effective strategy in designing high performance %RH sensors and show great promise for utilization of mesoporous 2D layered materials in the Internet of Things and next generation humidity sensing applications.

Detoxification of Atrazine by Low Molecular Weight Thiols in Alfalfa (Medicago sativa).

Science.gov (United States)

Zhang, Jing Jing; Xu, Jiang Yan; Lu, Feng Fan; Jin, She Feng; Yang, Hong

2017-10-16

Low molecular weight (LMW) thiols in higher plants are a group of sulfur-rich nonprotein compounds and play primary and multiple roles in cellular redox homeostasis, enzyme activities, and xenobiotics detoxification. This study focused on identifying thiols-related protein genes from the legume alfalfa exposed to the herbicide atrazine (ATZ) residues in environment. Using high-throughput RNA-sequencing, a set of ATZ-responsive thiols-related protein genes highly up-regulated and differentially expressed in alfalfa was identified. Most of the differentially expressed genes (DEGs) were involved in regulation of biotic and abiotic stress responses. By analyzing the genes involved in thiols-mediated redox homeostasis, we found that many of them were thiols-synthetic enzymes such as γ-glutamylcysteine synthase (γECS), homoglutathione synthetase (hGSHS), and glutathione synthetase (GSHS). Using liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS), we further characterized a group of ATZ-thiols conjugates, which are the detoxified forms of ATZ in plants. Cysteine S-conjugate ATZ-HCl+Cys was the most important metabolite detected by MS. Several other ATZ-conjugates were also examined as ATZ-detoxified metabolites. Such results were validated by characterizing their analogs in rice. Our data showed that some conjugates under ATZ stress were detected in both plants, indicating that some detoxified mechanisms and pathways can be shared by the two plant species. Overall, these results indicate that LMW thiols play critical roles in detoxification of ATZ in the plants.

Operation of trans-thylakoid thiol-metabolizing pathways in photosynthesis

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Mohamed eKaramoko

2013-11-01

Full Text Available Thiol oxidation to disulfides and the reverse reaction, i.e. disulfide reduction to free thiols, are under the control of catalysts in vivo. Enzymatically assisted thiol-disulfide chemistry is required for the biogenesis of all energy-transducing membrane systems. However, until recently, this had only been demonstrated for the bacterial plasma membrane. Long considered to be vacant, the thylakoid lumen has now moved to the forefront of photosynthesis research with the realization that its proteome is far more complicated than initially anticipated. Several lumenal proteins are known to be disulfide bonded in Arabidopsis, highlighting the importance of sulfhydryl oxidation in the thylakoid lumen. While disulfide reduction in the plastid stroma is known to activate several enzymatic activities, it appears that it is the reverse reaction, i.e. thiol oxidation that is required for the activity of several lumen-resident proteins. This paradigm for redox regulation in the thylakoid lumen has opened a new frontier for research in the field of photosynthesis. Of particular significance in this context is the discovery of trans-thylakoid redox pathways controlling disulfide bond formation and reduction, which are required for photosynthesis.

Mesoporous Silica: A Suitable Adsorbent for Amines

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Abdollahzadeh-Ghom Sara

2009-01-01

Full Text Available Abstract Mesoporous silica with KIT-6 structure was investigated as a preconcentrating material in chromatographic systems for ammonia and trimethylamine. Its adsorption capacity was compared to that of existing commercial materials, showing its increased adsorption power. In addition, KIT-6 mesoporous silica efficiently adsorbs both gases, while none of the employed commercial adsorbents did. This means that KIT-6 Mesoporous silica may be a good choice for integrated chromatography/gas sensing micro-devices.

Mesoporous Transition Metal Oxides for Supercapacitors.

Science.gov (United States)

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Tunable conductivity in mesoporous germanium

Science.gov (United States)

Beattie, Meghan N.; Bioud, Youcef A.; Hobson, David G.; Boucherif, Abderraouf; Valdivia, Christopher E.; Drouin, Dominique; Arès, Richard; Hinzer, Karin

2018-05-01

Germanium-based nanostructures have attracted increasing attention due to favourable electrical and optical properties, which are tunable on the nanoscale. High densities of germanium nanocrystals are synthesized via electrochemical etching, making porous germanium an appealing nanostructured material for a variety of applications. In this work, we have demonstrated highly tunable electrical conductivity in mesoporous germanium layers by conducting a systematic study varying crystallite size using thermal annealing, with experimental conductivities ranging from 0.6 to 33 (×10‑3) Ω‑1 cm‑1. The conductivity of as-prepared mesoporous germanium with 70% porosity and crystallite size between 4 and 10 nm is shown to be ∼0.9 × 10‑3 Ω‑1 cm‑1, 5 orders of magnitude smaller than that of bulk p-type germanium. Thermal annealing for 10 min at 400 °C further reduced the conductivity; however, annealing at 450 °C caused a morphological transformation from columnar crystallites to interconnecting granular crystallites and an increase in conductivity by two orders of magnitude relative to as-prepared mesoporous germanium caused by reduced influence of surface states. We developed an electrostatic model relating the carrier concentration and mobility of p-type mesoporous germanium to the nanoscale morphology. Correlation within an order of magnitude was found between modelled and experimental conductivities, limited by variation in sample uniformity and uncertainty in void size and fraction after annealing. Furthermore, theoretical results suggest that mesoporous germanium conductivity could be tuned over four orders of magnitude, leading to optimized hybrid devices.

Oxidative stress and pathology in muscular dystrophies: focus on protein thiol oxidation and dysferlinopathies.

Science.gov (United States)

Terrill, Jessica R; Radley-Crabb, Hannah G; Iwasaki, Tomohito; Lemckert, Frances A; Arthur, Peter G; Grounds, Miranda D

2013-09-01

The muscular dystrophies comprise more than 30 clinical disorders that are characterized by progressive skeletal muscle wasting and degeneration. Although the genetic basis for many of these disorders has been identified, the exact mechanism for pathogenesis generally remains unknown. It is considered that disturbed levels of reactive oxygen species (ROS) contribute to the pathology of many muscular dystrophies. Reactive oxygen species and oxidative stress may cause cellular damage by directly and irreversibly damaging macromolecules such as proteins, membrane lipids and DNA; another major cellular consequence of reactive oxygen species is the reversible modification of protein thiol side chains that may affect many aspects of molecular function. Irreversible oxidative damage of protein and lipids has been widely studied in Duchenne muscular dystrophy, and we have recently identified increased protein thiol oxidation in dystrophic muscles of the mdx mouse model for Duchenne muscular dystrophy. This review evaluates the role of elevated oxidative stress in Duchenne muscular dystrophy and other forms of muscular dystrophies, and presents new data that show significantly increased protein thiol oxidation and high levels of lipofuscin (a measure of cumulative oxidative damage) in dysferlin-deficient muscles of A/J mice at various ages. The significance of this elevated oxidative stress and high levels of reversible thiol oxidation, but minimal myofibre necrosis, is discussed in the context of the disease mechanism for dysferlinopathies, and compared with the situation for dystrophin-deficient mdx mice. © 2013 The Authors Journal compilation © 2013 FEBS.

Electrochemistry behavior of endogenous thiols on fluorine doped tin oxide electrodes

Energy Technology Data Exchange (ETDEWEB)

Rojas, Luciana; Molero, Leonard; Tapia, Ricardo A.; Rio, Rodrigo del; Valle, M. Angelica del; Antilen, Monica [Departamento de Quimica Inorganica, Facultad de Quimica, Pontificia Universidad Catolica de Chile, Av Vicuna Mackenna 4860, Casilla 306, Correo 22, Macul, Santiago (Chile); Armijo, Francisco, E-mail: jarmijom@uc.cl [Departamento de Quimica Inorganica, Facultad de Quimica, Pontificia Universidad Catolica de Chile, Av Vicuna Mackenna 4860, Casilla 306, Correo 22, Macul, Santiago (Chile)

2011-10-01

Highlights: > The first time that fluorine doped tin oxide electrodes are used for the electrooxidation of endogenous thiols. > Low potentials of electrooxidation were obtained for the different thiols. > The electrochemical behavior of thiols depends on the pH and the ionic electroactive species, the electrooxidation proceeds for a process of adsorption of electroactive species on FTO and high values the heterogeneous electron tranfer rate constant of the reaction were obtained. - Abstract: In this work the electrochemical behavior of different thiols on fluorine doped tin oxide (FTO) electrodes is reported. To this end, the mechanism of electrochemical oxidation of glutathione (GSH), cysteine (Cys), homocysteine (HCys) and acetyl-cysteine (ACys) at different pH was investigated. FTO showed electroactivity for the oxidation of the first three thiols at pH between 2.0 and 4.0, but under these conditions no acetyl-cysteine oxidation was observed on FTO. Voltammetric studies of the electro-oxidation of GSH, Cys and HCys showed peaks at about 0.35, 0.29, and 0.28 V at optimum pH 2.4, 2.8 and 3.4, respectively. In addition, this study demonstrated that GSH, Cys and HCys oxidation occurs when the zwitterion is the electro-active species that interact by adsorption on FTO electrodes. The overall reaction involves 4e{sup -}/4H{sup +} and 2e{sup -}/2H{sup +}, respectively, for HCys and for GSH and Cys and high heterogeneous electron transfer rate constants. Besides, the use of FTO for the determination of different thiols was evaluated. Experimental square wave voltammetry shows a linear current vs. concentrations response between 0.1 and 1.0 mM was found for HCys and GSH, indicating that these FTO electrodes are promising candidates for the efficient electrochemical determination of these endogenous thiols.

A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.

Science.gov (United States)

Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y

2018-08-01

Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.

“Turn-on” fluorescence probe integrated polymer nanoparticles for sensing biological thiol molecules

Science.gov (United States)

Ang, Chung Yen; Tan, Si Yu; Lu, Yunpeng; Bai, Linyi; Li, Menghuan; Li, Peizhou; Zhang, Quan; Selvan, Subramanian Tamil; Zhao, Yanli

2014-11-01

A ``turn-on'' thiol-responsive fluorescence probe was synthesized and integrated into polymeric nanoparticles for sensing intracellular thiols. There is a photo-induced electron transfer process in the off state of the probe, and this process is terminated upon the reaction with thiol compounds. Configuration interaction singles (CIS) calculation was performed to confirm the mechanism of this process. A series of sensing studies were carried out, showing that the probe-integrated nanoparticles were highly selective towards biological thiol compounds over non-thiolated amino acids. Kinetic studies were also performed to investigate the relative reaction rate between the probe and the thiolated amino acids. Subsequently, the Gibbs free energy of the reactions was explored by means of the electrochemical method. Finally, the detection system was employed for sensing intracellular thiols in cancer cells, and the sensing selectivity could be further enhanced with the use of a cancer cell-targeting ligand in the nanoparticles. This development paves a path for the sensing and detection of biological thiols, serving as a potential diagnostic tool in the future.

Thiol-disulfide exchange in peptides derived from human growth hormone.

Science.gov (United States)

Chandrasekhar, Saradha; Epling, Daniel E; Sophocleous, Andreas M; Topp, Elizabeth M

2014-04-01

Disulfide bonds stabilize proteins by cross-linking distant regions into a compact three-dimensional structure. They can also participate in hydrolytic and oxidative pathways to form nonnative disulfide bonds and other reactive species. Such covalent modifications can contribute to protein aggregation. Here, we present experimental data for the mechanism of thiol-disulfide exchange in tryptic peptides derived from human growth hormone in aqueous solution. Reaction kinetics was monitored to investigate the effect of pH (6.0-10.0), temperature (4-50°C), oxidation suppressants [ethylenediaminetetraacetic acid (EDTA) and N2 sparging], and peptide secondary structure (amide cyclized vs. open form). The concentrations of free thiol containing peptides, scrambled disulfides, and native disulfide-linked peptides generated via thiol-disulfide exchange and oxidation reactions were determined using reverse-phase HPLC and liquid chromatography-mass spectrometry. Concentration versus time data were fitted to a mathematical model using nonlinear least squares regression analysis. At all pH values, the model was able to fit the data with R(2) ≥ 0.95. Excluding oxidation suppressants (EDTA and N2 sparging) resulted in an increase in the formation of scrambled disulfides via oxidative pathways but did not influence the intrinsic rate of thiol-disulfide exchange. In addition, peptide secondary structure was found to influence the rate of thiol-disulfide exchange. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Carboxylic acid-grafted mesoporous material and its high catalytic activity in one-pot three-component coupling reaction

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Ruth Gomes

2014-11-01

Full Text Available A new carboxylic acid functionalized mesoporous organic polymer has been synthesized via in situ radical polymerization of divinylbenzene and acrylic acid using a mesoporous silica as a seed during the polymerization process under solvothermal conditions. The mesoporous material MPDVAA-1 has been thoroughly characterized employing powder XRD, solid state 13C cross polarization magic angle spinning-nuclear magnetic resonance, FT-IR spectroscopy, N2 sorption, HR-TEM, and NH3 temperature programmed desorption-thermal conductivity detector (TPD-TCD analysis to understand its porosity, chemical environment, bonding, and surface properties. The mesoporous polymer was used as a catalyst for a three comp onent Biginelli condensation between various aldehydes, β-keto esters, and urea/thioureas to give 3,4-dihydropyrimidine-2(1H-ones. The reactions were carried out under conventional heating as well as solvent-free microwave irradiation of solid components, and in both the cases, the mesoporous polymer MPDVAA-1 proved to be a powerful, robust, and reusable catalyst with high catalytic efficiency.

Protection against ionising radiation and synergism with thiols by zinc aspartate

International Nuclear Information System (INIS)

Floersheim, G.L.; Floersheim, P.

1986-01-01

Pre-treatment with zinc aspartate protected mice against the lethal effects of radiation and raised the LD 50 from 8 gy to 12.2 Gy. Zinc chloride and zinc sulphate were clearly less active. The radioprotective effect of zinc aspartate was equivalent to cysteamine and slightly inferior to S,2-aminoethylisothiourea (AET). Zinc aspartate displayed a similar therapeutic index to the thiols but could be applied at an earlier time before irradiation. Synergistic effects occurred with the combined administration of zinc aspartate and thiols. By giving zinc aspartate with cysteamine, the LD 50 was increased to 13.25 Gy and, by combining it in the optimal protocol with AET, to 17.3 Gy. The radioprotection by zinc and its synergism with thiols is explained by the stabilisation of thiols through the formation of zinc complexes. (author)

Evaluation of dynamic serum thiol/disulfide homeostasis in locally advanced and metastatic gastric cancer

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Mutlu Hizal

2018-04-01

Full Text Available Background: Gastric cancer is one the most diagnosed cancer and the third leading cause of death from cancer worldwide. As an indicator of antioxidant capacity thiol/disulfide homeostasis regulates detoxification, cell signal mechanisms, apoptosis, transcription and antioxidant defense mechanisms. Disregulation of thiol/disulfide homeostasis identified in other cancer types by recent data. In this study, we aimed to evaluate the thiol/disulfide homeostasis in advanced gastric cancer patients. Methods: The patients who diagnosed with gastric cancer and healthy control subjects were included to study. Serum samples for the thiol-disulphide test were obtained at the time of diagnosis. Thiol-disulphide homeostasis tests were measured by the automated spectrophotometric method. Thiol-disulphide homeostasis was also measured according to clinical and laboratory features. Results: Thirty newly diagnosed advanced gastric adenocarcinoma patients and 28 healthy controls were enrolled in the study. The native thiol (NT and total thiol (TT levels of patients' group were significantly lower compared with controls (p = 0.001 and p < 0.001. In the CEA high (≥5.4 ng/ml group, DS/NT ratio were higher compared with CEA low (<5.4 ng/ml group (p = 0.024. In CA.19-9 high (≥28.3 kU/L group, both DS and DS/NT ratio were significantly higher compared with a CA19-9 low(<28.3 kU/L group (p < 0.05 both. The correlation between CEA and DS levels was also significant (p = 0.02. There was also a positive correlation between CEA levels and DS/NT ratio (p = 0.01. Conclusion: Derangements of thiol/disulfide homeostasis may have a role in gastric cancer pathogenesis and the higher level of oxidative stress may relate to extensive and aggressiveness of the advanced disease. The diagnostic and prognostic values of thiol/disulfide products need to identify with further studies. Keywords: Thiol, Disulfide, Oxidative stress, Gastric cancer, Metastatic

General strategy for fabricating thoroughly mesoporous nanofibers

KAUST Repository

Hou, Huilin; Wang, Lin; Gao, Fengmei; Wei, Guodong; Tang, Bin; Yang, Weiyou; Wu, Tao

2014-01-01

mesoporous nanofibers with high purity and uniformity. Here, we report a general, simple and cost-effective strategy, namely, foaming-assisted electrospinning, for producing mesoporous nanofibers with high purity and enhanced specific surface areas. As a

CD44-engineered mesoporous silica nanoparticles for overcoming multidrug resistance in breast cancer

International Nuclear Information System (INIS)

Wang, Xin; Liu, Ying; Wang, Shouju; Shi, Donghong; Zhou, Xianguang; Wang, Chunyan; Wu, Jiang; Zeng, Zhiyong; Li, Yanjun; Sun, Jing; Wang, Jiandong; Zhang, Longjiang; Teng, Zhaogang; Lu, Guangming

2015-01-01

Graphical abstract: - Highlights: • CD44-engineered mesoporous silica nanoparticles are synthesized. • The mechanism of CD44-engineered mesoporous silica nanoparticles is revealed. • This new delivery system increased the drug accumulation in vitro and in vivo. • This new delivery system offers an effective approach to treat multidrug resistance. - Abstract: Multidrug resistance is a major impediment for the successful chemotherapy in breast cancer. CD44 is over-expressed in multidrug resistant human breast cancer cells. CD44 monoclonal antibody exhibits anticancer potential by inhibiting proliferation and regulating P-glycoprotein-mediated drug efflux activity in multidrug resistant cells. Thereby, CD44 monoclonal antibody in combination with chemotherapeutic drug might be result in enhancing chemosensitivity and overcoming multidrug resistance. The purpose of this study is to investigate the effects of the CD44 monoclonal antibody functionalized mesoporous silica nanoparticles containing doxorubicin on human breast resistant cancer MCF-7 cells. The data showed that CD44-modified mesoporous silica nanoparticles increased cytotoxicity and enhanced the downregulation of P-glycoprotein in comparison to CD44 antibody. Moreover, CD44-engineered mesoporous silica nanoparticles provided active target, which promoted more cellular uptake of DOX in the resistant cells and more retention of DOX in tumor tissues than unengineered counterpart. Animal studies of the resistant breast cancer xenografts demonstrated that CD44-engineered drug delivery system remarkably induced apoptosis and inhibited the tumor growth. Our results indicated that the CD44-engineered mesoporous silica nanoparticle-based drug delivery system offers an effective approach to overcome multidrug resistance in human breast cancer

Hybrid inorganic-organic adsorbents Part 1: Synthesis and characterization of mesoporous zirconium titanate frameworks containing coordinating organic functionalities.

Science.gov (United States)

Griffith, Christopher S; De Los Reyes, Massey; Scales, Nicholas; Hanna, John V; Luca, Vittorio

2010-12-01

A series of functional hybrid inorganic-organic adsorbent materials have been prepared through postsynthetic grafting of mesoporous zirconium titanate xerogel powders using a range of synthesized and commercial mono-, bis-, and tris-phosphonic acids, many of which have never before been investigated for the preparation of hybrid phases. The hybrid materials have been characterized using thermogravimetric analysis, diffuse reflectance infrared (DRIFT) and 31P MAS NMR spectroscopic techniques and their adsorption properties studied using a 153Gd radiotracer. The highest level of surface functionalization (molecules/nm2) was observed for methylphosphonic acid (∼3 molecules/nm2). The level of functionalization decreased with an increase in the number of potential surface coordinating groups of the phosphonic acids. Spectral decomposition of the DRIFT and 31P MAS NMR spectra showed that each of the phosphonic acid molecules coordinated strongly to the metal oxide surface but that for the 1,1-bis-phosphonic acids and tris-phosphonic acids the coordination was highly variable resulting in a proportion of free or loosely coordinated phosphonic acid groups. Functionalization of a porous mixed metal oxide framework with the tris-methylenephosphonic acid (ATMP-ZrTi-0.33) resulted in a hybrid with the highest affinity for 153Gd3+ in nitric acid solutions across a wide range of acid concentrations. The ATMP-ZrTi-0.33 hybrid material extracted 153Gd3+ with a Kd value of 1×10(4) in 0.01 M HNO3 far exceeding that of the other hybrid phases. The unfunctionalized mesoporous mixed metal oxide had negligible affinity for Gd3+ (KdATMP-ZrTi-0.33 hybrid phase for Gd3+ has been determined to be about 0.005 mmol/g in 0.01 M HNO3. This behavior and that of the other hybrid phases suggests that the surface-bound ATMP ligand functions as a chelating ligand toward 153Gd3+ under these acidic conditions.

Changes in Thiol-Disulfide Homeostasis of the Body to Surgical Trauma in Laparoscopic Cholecystectomy Patients.

Science.gov (United States)

Polat, Murat; Ozcan, Onder; Sahan, Leyla; Üstündag-Budak, Yasemin; Alisik, Murat; Yilmaz, Nigar; Erel, Özcan

2016-12-01

We aimed to investigate the short-term effect of laparoscopic surgery on serum thiol-disulfide homeostasis levels as a marker of oxidant stress of surgical trauma in elective laparoscopic cholecystectomy patients. Venous blood samples were collected, and levels of native thiols, total thiols, and disulfides were determined with a novel automated assay. Total antioxidant capacity (measured as the ferric-reducing ability of plasma) and serum ischemia modified albumin, expressed as absorbance units assayed by the albumin cobalt binding test, were determined. The major findings of the present study were that native thiol (283 ± 45 versus 241 ± 61 μmol/L), total thiol (313 ± 49 versus 263 ± 67 μmol/L), and disulfide (14.9 ± 4.6 versus 11.0 ± 6.1 μmol/L) levels were decreased significantly during operation and although they increased, they did not return to preoperation levels 24 hours after laparoscopic surgery compared to the levels at baseline. Disulfide/native thiol and disulfide/total thiol levels did not change during laparoscopic surgery. The decrease in plasma level of native and total thiol groups suggests impairment of the antioxidant capacity of plasma; however, the delicate balance between the different redox forms of thiols was maintained during surgery.

Mesoporous Silica Supported Au Nanoparticles with Controlled Size as Efficient Heterogeneous Catalyst for Aerobic Oxidation of Alcohols

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Xuefeng Chu

2015-01-01

Full Text Available A series of Au catalysts with different sizes were synthesized and employed on amine group functionalized ordered mesoporous silica solid supports as catalyst for the aerobic oxidation of various alcohols. The mesoporous silica of MCM-41 supported Au nanoparticles (Au-1 exhibited the smallest particle size at ~1.8 nm with superior catalytic activities owing to the confinement effect of the mesoporous channels. Au-1 catalyst is also very stable and reusable under aerobic condition. Therefore, this presented work would obviously provide us a platform for synthesizing more size-controlled metal catalysts to improve the catalytic performances.

A novel method for preparation of 8-hydroxyquinoline functionalized mesoporous silica: Aluminum complexes and photoluminescence studies

Energy Technology Data Exchange (ETDEWEB)

Badiei, Alireza, E-mail: abadiei@khayam.ut.ac.ir [School of Chemistry, College of Science, University of Tehran, P.O. Box 14155-6455, Tehran (Iran, Islamic Republic of); Goldooz, Hassan [Department of Chemistry, Tarbiat Modares University, Tehran (Iran, Islamic Republic of); Ziarani, Ghodsi Mohammadi [Department of Chemistry, Faculty of Science, Alzahra University, Tehran (Iran, Islamic Republic of)

2011-03-15

8-Hydroxyquinoline (8-HQ) was attached to mesoporous silica by sulfonamide bond formation between 8-hydroxyquinoline-5-sulfonyl chloride (8-HQ-SO{sub 2}Cl) and aminopropyl functionalized SBA-15 (designated as SBA-SPS-Q) and then aluminum complexes of 8-HQ was covalently bonded to SBA-SPS-Q using coordinating ability of grafted 8-HQ.The prepared materials were characterized by powder X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FT-IR), thermal analysis (TGA-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), elemental analysis and fluorescence spectra. The environmental effects on the emission spectra of grafted 8-HQ and its complexes were studied and discussed in details.

Incorporating allylated lignin-derivatives in thiol-ene gel-polymer electrolytes.

Science.gov (United States)

Baroncini, Elyse A; Stanzione, Joseph F

2018-07-01

Growing environmental and economic concerns as well as the uncertainty that accompanies finite petrochemical resources contributes to the increase in research and development of bio-based, renewable polymers. Concurrently, industrial and consumer demand for smaller, safer, and more flexible technologies motivates a global research effort to improve electrolytic polymer separators in lithium-ion batteries. To incorporate the aromatic structural advantages of lignin, a highly abundant and renewable resource, into gel-polymer electrolytes, lignin-derived molecules, vanillyl alcohol and gastrodigenin are functionalized and UV-polymerized with multi-functional thiol monomers. The resulting thin, flexible, polymer films possess glass transition temperatures ranging from -42.1°C to 0.3°C and storage moduli at 25°C ranging from 1.90MPa to 10.08MPa. The crosslinked polymer films swollen with electrolyte solution impart conductivities in the range of 7.04×10 -7 to 102.73×10 -7 Scm -1 . Thiol molecular weight has the most impact on the thermo-mechanical properties of the resulting films while polymer crosslink density has the largest effect on conductivity. The conducting abilities of the bio-based gel-polymer electrolytes in this study prove the viability of lignin-derived feedstock for use in lithium-ion battery applications and reveal structurally and thermally desirable traits for future work. Copyright © 2018 Elsevier B.V. All rights reserved.

Conferring specificity in redox pathways by enzymatic thiol/disulfide exchange reactions.

Science.gov (United States)

Netto, Luis Eduardo S; de Oliveira, Marcos Antonio; Tairum, Carlos A; da Silva Neto, José Freire

2016-01-01

Thiol-disulfide exchange reactions are highly reversible, displaying nucleophilic substitutions mechanism (S(N)2 type). For aliphatic, low molecular thiols, these reactions are slow, but can attain million times faster rates in enzymatic processes. Thioredoxin (Trx) proteins were the first enzymes described to accelerate thiol-disulfide exchange reactions and their high reactivity is related to the high nucleophilicity of the attacking thiol. Substrate specificity in Trx is achieved by several factors, including polar, hydrophobic, and topological interactions through a groove in the active site. Glutaredoxin (Grx) enzymes also contain the Trx fold, but they do not share amino acid sequence similarity with Trx. A conserved glutathione binding site is a typical feature of Grx that can reduce substrates by two mechanisms (mono and dithiol). The high reactivity of Grx enzymes is related to the very acid pK(a) values of reactive Cys that plays roles as good leaving groups. Therefore, although distinct oxidoreductases catalyze similar thiol–disulfide exchange reactions, their enzymatic mechanisms vary. PDI and DsbA are two other oxidoreductases, but they are involved in disulfide bond formation, instead of disulfide reduction, which is related to the oxidative environment where they are found. PDI enzymes and DsbC are endowed with disulfide isomerase activity, which is related with their tetra-domain architecture. As illustrative description of specificity in thiol-disulfide exchange, redox aspects of transcription activation in bacteria, yeast, and mammals are presented in an evolutionary perspective. Therefore, thiol-disulfide exchange reactions play important roles in conferring specificity to pathways, a required feature for signaling.

Immobilization of Thiadiazole Derivatives on Magnetite Mesoporous Silica Shell Nanoparticles in Application to Heavy Metal Removal from Biological Samples

International Nuclear Information System (INIS)

Emadi, Masoomeh; Shams, Esmaeil

2010-01-01

In this report magnetite was synthesized by a coprecipitation method, then coated with a layer of silica. Another layer of mesoporous silica was added by a sol-gel method, then 5-amino-1,3,4-thiadiazole-thiol (ATT) was immobilized onto the synthesized nanoparticles with a simple procedure. This was followed by a series of characterizations, including transmission electron microscopy (TEM), FT-IR spectrum, elemental analysis and XRD. Heavy metal uptake of the modified nanoparticles was examined by atomic absorption spectroscopy. For further investigation we chose Cu 2+ as the preferred heavy metal to evaluate the amount of adsorption, as well as the kinetics and mechanism of adsorption. Finally, the capacity of our nanoparticles for the heavy metal removal from blood was shown. We found that the kinetic rate of Cu 2+ adsorption was 0.05 g/mg/min, and the best binding model was the Freundlich isotherm.

Catalytic hydrodeoxygenation of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolites

International Nuclear Information System (INIS)

Lee, Hyung Won; Jun, Bo Ram; Kim, Hannah; Kim, Do Heui; Jeon, Jong-Ki; Park, Sung Hoon; Ko, Chang Hyun; Kim, Tae-Wan; Park, Young-Kwon

2015-01-01

The hydrodeoxygenation of 2-methoxy phenol and dibenzofuran, which are representative model compounds of bio-oil, was performed using two different Pt/mesoporous zeolite catalysts, Pt/mesoporous Y and Pt/mesoporous MFI. The reforming of 2-methoxy phenol and dibenzofuran via catalytic hydrodeoxygenation was investigated using a batch reactor at 40 bar and 250 °C. The characteristics of the catalysts were analyzed by N 2 adsorption-desorption, X-ray diffraction, and NH 3 temperature programmed desorption. Pt/mesoporous zeolite catalysts containing both strong acid sites and mesopores showed the higher conversion of 2-methoxy phenol than Pt/SiO 2 and Pt/Si-MCM-48 with no acid sites, Pt/γ-Al 2 O 3 , and a mixture of mesoporous Y and Pt/SiO 2 , indicating the importance of both Pt and strong acid sites for high catalytic activity. Among the two Pt/mesoporous zeolite catalysts tested, the conversion of 2-methoxy phenol to cyclohexane over Pt/mesoporous Y was much higher than that over the Pt/mesoporous MFI. This was attributed to the better textural properties, such as surface area, pore volume and micropore size, compared to those of Pt/mesoporous MFI. The catalytic conversions of dibenzofuran obtained using two Pt/mesoporous zeolite catalysts were similar and the main products were 1,1′-bicyclohexyl, cyclopentylmethyl-cyclohexane and cyclohexane. In addition, the reaction mechanisms of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolite were suggested. - Highlights: • HDO of 2-methoxy phenol and dibenzofuran was performed over Pt/mesoporous zeolites. • Pt/mesoporous zeolites have mesopores and strong acid sites. • Main product of HDO of 2-methoxy phenol was cyclohexane. • Main products of HDO of dibenzofuran were bicyclohexyl (BCH), i-BCH, and cyclohexane

Oxidative stress and decreased thiol level in patients with migraine: cross-sectional study.

Science.gov (United States)

Eren, Yasemin; Dirik, Ebru; Neşelioğlu, Salim; Erel, Özcan

2015-12-01

Although migraine is a neurological disorder known since long, its physiopathology remains unclear. Recent studies suggest that migraine is associated with oxidative stress; however, they report divergent results. The aim of the present study was to evaluate total antioxidant status (TAS), total oxidant status (TOS), oxidative stress index (OSI), and serum thiol level in migraine patients with or without aura. The study group consisted of 141 migraine patients. The control group included 70 healthy subjects. TAS, TOS, OSI were evaluated using a method developed by Erel. Serum thiol level was measured using the Hu method. No difference was found in TAS, TOS, OSI between the patients and controls. The level of thiol was significantly lower in patients than in controls. Negative correlations were detected between thiol level and Migraine Disability Assessment score in patients. Although TAS, TOS, and OSI were similar to those of the control group, serum thiol level, an important marker of antioxidant capacity, was significantly lower in migraines compared with controls, and caused more serious disability. Novel treatment approaches may be developed based on these data, and compounds containing thiol, such as alpha lipoic acid and N-acetyl cysteine, may be used in prophylaxis.

Mesoporous Transition Metal Oxides for Supercapacitors

Science.gov (United States)

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

Mesoporous Transition Metal Oxides for Supercapacitors

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Yan Wang

2015-10-01

Full Text Available Recently, transition metal oxides, such as ruthenium oxide (RuO2, manganese dioxide (MnO2, nickel oxides (NiO and cobalt oxide (Co3O4, have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4, and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Ultrasound-driven design of new mesoporous metal catalysts

Energy Technology Data Exchange (ETDEWEB)

Schaeferhans, Jana; Pazos Perez, Nicolas; Andreeva, Daria [Physikalische Chemie II, Univ. Bayreuth (Germany); Skorb, Ekaterina [Max-Planck-Institut fuer Kolloid- und Grenzflaechenforschung, Golm (Germany)

2011-07-01

Mesoporous metal nanocomposites were formed by a ''green chemistry'' method with ultrasound irradiation. The sonication technique combines the fabrication of a mesoporous support consisting of metallic particles (Al, Mg) several tens of micrometers in size and the subsequent incorporation of metal (Ag, Au, Pt etc.) nanoparticles into its pores. Next to filling the mesoporous support with particles we are also able to form mesoporous alloys e.g. AlNi or CoAlFe. The resulting material is analyzed by transmission electron microscopy, powder X-ray diffraction, small-angle neutron scattering and the Brunauer-Emmett-Teller and the Barrett-Joyner-Halenda method. Surface areas up to 200 m{sup 2}/g with a narrow pore size distribution around 3 nm can be achieved. The mesoporous structures are analyzed by confocal light microscopy after coloring the particles with dye. We explain the formation of the mesoporous inner structures by the following mechanism: Thermal etching and recrystallization of metals by ultrasound-stimulated high-speed jets of liquid form the porous structure that is stabilized by surface oxidation through free radicals generated during cavitation. We expect this approach to be universal and opening perspectives for a whole new class of catalytic materials that can be prepared in a fairly easy and cost effective way.

Synthesis and catalytic applications of combined zeolitic/mesoporous materials

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Jarian Vernimmen

2011-11-01

Full Text Available In the last decade, research concerning nanoporous siliceous materials has been focused on mesoporous materials with intrinsic zeolitic features. These materials are thought to be superior, because they are able to combine (i the enhanced diffusion and accessibility for larger molecules and viscous fluids typical of mesoporous materials with (ii the remarkable stability, catalytic activity and selectivity of zeolites. This review gives an overview of the state of the art concerning combined zeolitic/mesoporous materials. Focus is put on the synthesis and the applications of the combined zeolitic/mesoporous materials. The different synthesis approaches and formation mechanisms leading to these materials are comprehensively discussed and compared. Moreover, Ti-containing nanoporous materials as redox catalysts are discussed to illustrate a potential implementation of combined zeolitic/mesoporous materials.

Mesoporous carbonates and method of making

Science.gov (United States)

Fryxell, Glen; Liu, Jun; Zemanian, Thomas S.

2004-06-15

Mesoporous metal carbonate structures are formed by providing a solution containing a non-ionic surfactant and a calcium acetate salt, adding sufficient base to react with the acidic byproducts to be formed by the addition of carbon dioxide, and adding carbon dioxide, thereby forming a mesoporous metal carbonate structure containing the metal from said metal salt.

Insight into the adsorption of tetracycline onto amino and amino-Fe3+ gunctionalized mesoporous silica: Effect of functionalized groups.

Science.gov (United States)

Zhang, Ziyang; Li, Haiyan; Liu, Huijuan

2018-03-01

In order to study the influences of functionalized groups onto the adsorption of tetracycline, we prepared a series of amino and amino-Fe 3+ complex mesoporous silica adsorbents with diverse content of amino and Fe 3+ groups (named N,N-SBA15 and Fe-N,N-SBA15). The resulting mesoporous silica adsorbents were fully characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectrometer (FTIR) and N 2 adsorption/desorption isotherms. Furthermore, the effects of functionalized groups on the removal of TC were investigated. The results showed that the periodic ordered structure of SBA-15 was maintained after modification of amino/Fe 3+ groups. The functionalized amino groups decreased the adsorption capacity while the coordinated Fe 3+ increased the adsorption capacity. The adsorption kinetics of TC fitted pseudo-second-order model well and the equilibrium was achieved quickly. The adsorption isotherms fitted the Langmuir model well and with the Fe 3+ content increased from 3.93% to 8.26%, the Q max of the adsorbents increased from 102 to 188mmol/kg. The solution pH affected the adsorption of TC onto amino complex adsorbents slightly while influenced the adsorption onto Fe-amine complex adsorbents greatly. The adsorption of TC on SBA15 and N,N-SBA15 may be related to the formation of outer-sphere surface complexes, while the adsorption of TC onto Fe-N,N-SBA15 was mainly attributed to the inner-sphere surface complexes. This study could offer potential materials that have excellent adsorption behavior for environmental remediation and suggested useful information for the preparing other adsorbents in environmental applications. Copyright © 2017. Published by Elsevier B.V.

A chromenoquinoline-based fluorescent off-on thiol probe for bioimaging.

Science.gov (United States)

Kand, Dnyaneshwar; Kalle, Arunasree Marasanapalli; Varma, Sreejith Jayasree; Talukdar, Pinaki

2012-03-11

A new chromenoquinoline-based fluorescent off-on thiol probe 2 is reported. In aqueous buffer solutions at physiological pH, the probe exhibited 223-fold enhancement in fluorescence intensity by a Michael addition of cysteine to the maleimide appended to a chromenoquinoline. Cell permeability and live cell imaging of thiols are also demonstrated. This journal is © The Royal Society of Chemistry 2012

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

Energy Technology Data Exchange (ETDEWEB)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

2016-11-15

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

International Nuclear Information System (INIS)

Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

2016-01-01

Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH 2 ) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

Reactivities of some thiol collectors and their interactions with Ag (+1) ion by molecular modeling

International Nuclear Information System (INIS)

Yekeler, Hulya; Yekeler, Meftuni

2004-01-01

The most commonly used collectors for sulfide minerals in the mining industry are the thiol collectors for the recovery of these minerals from their associated gangues by froth flotation. For this reason, a great deal of attention has been paid to understand the attachment mechanism of thiol collectors to metal sulfide surfaces. The density functional theory (DFT) calculations at the B3LYP/3-21G* and B3LYP/6-31++G** levels were employed to propose the flotation responses of these thiol collectors, namely, diethyl dithiocarbamate, ethyl dithiocarbamate, ethyl dithiocarbonate, ethyl trithiocarbonate and ethyl dithiophosphate ions, and to study the interaction energies of these collectors with Ag (+1) ion in connection to acanthite (Ag 2 S) mineral. The calculated interaction energies, ΔE, were interpreted in terms of the highest occupied molecular orbital (HOMO) energies of the isolated collector ions. The results show that the HOMOs are strongly localized to the sulfur atoms and the HOMO energies can be used as a reactivity descriptor for the flotation ability of the thiol collectors. Using the HOMO and ΔE energies, the reactivity order of the collectors is found to be (C 2 H 5 ) 2 NCS 2 - > C 2 H 5 NHCS 2 - > C 2 H 5 OCS 2 - > C 2 H 5 SCS 2 - > (C 2 H 5 O)(OH)PS 2 - . The theoretically obtained results are in good agreement with the experimental data reported

Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance.

Science.gov (United States)

Podgórski, Maciej; Becka, Eftalda; Chatani, Shunsuke; Claudino, Mauro; Bowman, Christopher N

A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercaptopropionate-based thiol-ene or thiol-Michael networks. For polymers with no hydrolytically degradable esters, glass transition temperatures (T g 's) as high as 100 °C were achieved. Importantly, solvent resistance tests demonstrated enhanced stability of ester-free formulations over PETMP-based polymers, especially in concentrated basic solutions. Kinetic analysis showed that glassy step-growth polymers are readily formed at ambient conditions with conversions reaching 80% and higher.

A study of mesoporous silica-encapsulated gold nanorods as enhanced light scattering probes for cancer cell imaging

Energy Technology Data Exchange (ETDEWEB)

Zhan Qiuqiang; Qian Jun; Li Xin; He Sailing, E-mail: qianjun@coer.zju.edu.cn [Centre for Optical and Electromagnetic Research, State Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou 310058 (China)

2010-02-05

Mesoporous encapsulation of gold nanorods (GNRs) in a silica shell of controllable thickness (4.5-25.5 nm) was realized through a single-step coating method without any intermediary coating. The dependence of localized surface plasmon resonance (LSPR) extinction spectra of the coated GNRs on the thickness of the silica shell was investigated with both simulation and experiments, which agreed well with each other. It was found that cetyltrimethyl ammonium bromide (CTAB) molecules, which act as surfactants for the GNRs and dissociate in the solution, greatly affect the silica coating. Mesoporous silica-encapsulated GNRs were also shown to be highly biocompatible and stable in bio-environments. Based on LSPR enhanced scattering, mesoporous silica-encapsulated GNRs were utilized for dark field scattering imaging of cancer cells. Biomolecule-conjugated mesoporous silica-encapsulated GNRs were specifically taken up by cancer cells in vitro, justifying their use as effective optical probes for early cancer diagnosis. Mesoporous silica can also be modified with functional groups and conjugated with certain biomolecules for specific labeling on mammalian cells as well as carrying drugs or biomolecules into biological cells.

Application of mesoporous carbon and modified mesoporous carbon for treatment of DMF sewage

Energy Technology Data Exchange (ETDEWEB)

Liu, Fang, E-mail: liufangfw@163.com; Gao, Ya; Zhang, Shuang; Yan, Xi; Fan, Fengtao; Zhao, Chaocheng; Sun, Juan [China University of Petroleum(East China), Department of Chemical Engineering (China)

2016-02-15

Mesoporous carbon (MC) was prepared in soft template, and potassium ferricyanide was added into MC to prepare the modified mesoporous carbon (MMC). TEM, SEM, FT-IR, and N{sub 2} adsorption–desorption were used to characterize the textural properties of mesoporous materials. The BET specific surface area, pore volume, and the pore size of MC and MMC were 607.6321 and 304.7475 m{sup 2}/g, 0.313552 and 0.603573 cm{sup 3}/g, and 5.4356 and 7.9227 nm, respectively. The adsorption capabilities of MC and MMC were compared with the silica mesoporous material MCM-41. The influences of different adsorption conditions were optimized. For MC, the optimums of adsorbent dose, DMF initial concentration, rotating speed, and pH were 0.002 mg/50 mL, 200 mg/L, 200 r/min, and 4, respectively. MMC showed the highest DMF adsorption capacity at adsorbent dose 0.002 g/50 mL, DMF initial concentration 1000 mg/L, rotating speed 1000 r/min, pH more than 9, and contact time of less than 20 min. Meanwhile for MC, MMC, Pseudo-second-order equation was used to fit adsorption kinetics data. And adsorption process could be well fitted by Langmuir and Freundlich adsorption isotherms of MC, MMC. The results showed that MMC was a perfect adsorbent for DMF, and it was easy to separation and recycle. The recycling property of MMC was still relatively better than other two adsorbents.

Kinetic Resolution of sec-Thiols via Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase

NARCIS (Netherlands)

Pickl, Mathias; Swoboda, Alexander; Romero, Elvira; Winkler, Christoph; Binda, Claudia; Mattevi, Andrea; Faber, Kurt; Fraaije, Marco

2018-01-01

Various flavoprotein oxidases were recently shown to oxidize prim-thiols. Here we extend this reactivity towards sec-thiols via structure-guided engineering of 5-(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of rac-sec-thiols

Nanostructured Mesoporous Silicas for Bone Tissue Regeneration

Directory of Open Access Journals (Sweden)

Isabel Izquierdo-Barba

2008-01-01

Full Text Available The research on the development of new biomaterials that promote bone tissue regeneration is receiving great interest by the biomedical scientific community. Recent advances in nanotechnology have allowed the design of materials with nanostructure similar to that of natural bone. These materials can promote new bone formation by inducing the formation of nanocrystalline apatites analogous to the mineral phase of natural bone onto their surfaces, i.e. they are bioactive. They also stimulate osteoblast proliferation and differentiation and, therefore, accelerate the healing processes. Silica-based ordered mesoporous materials are excellent candidates to be used as third generation bioceramics that enable the adsorption and local control release of biological active agents that promote bone regeneration. This local delivery capability together with the bioactive behavior of mesoporous silicas opens up promising expectations in the bioclinical field. In this review, the last advances in nanochemistry aimed at designing and tailoring the chemical and textural properties of mesoporous silicas for biomedical applications are described. The recent developed strategies to synthesize bioactive glasses with ordered mesopore arrangements are also summarized. Finally, a deep discussion about the influence of the textural parameters and organic modification of mesoporous silicas on molecules adsorption and controlled release is performed.

Thiol Modification of Psyllium Husk Mucilage and Evaluation of Its Mucoadhesive Applications

Directory of Open Access Journals (Sweden)

Meenakshi Bhatia

2013-01-01

Full Text Available Thiol functionalization of psyllium was carried out to enhance its mucoadhesive potential. Thiolation of psyllium was achieved by esterification with thioglycolic acid. Thiolation was observed to change the surface morphology of psyllium from fibrous to granular and result in a slight increase in the crystallinity and swelling. Thiolated psyllium was found to contain 3.282 m moles of thiol groups/g of the polymer. Mucoadhesive applications of thiolated psylium were explored by formulating gels using metronidazole as the model drug. On comparative evaluation thiolated psyllium gels showed 3-fold higher mucoadhesive strength than the psyllium gels as determined by modified physical balance using chicken buccal pouch. The results of in vitro release study revealed that thiolated psyllium gels provided a prolonged release of metronidazole. Further, the psyllium and thiolated psyllium gels were found to release the drug following first-order kinetics by combination of polymer relaxation and diffusion through the matrix.

Thiol Modification of Psyllium Husk Mucilage and Evaluation of Its Mucoadhesive Applications

Science.gov (United States)

Bhatia, Meenakshi

2013-01-01

Thiol functionalization of psyllium was carried out to enhance its mucoadhesive potential. Thiolation of psyllium was achieved by esterification with thioglycolic acid. Thiolation was observed to change the surface morphology of psyllium from fibrous to granular and result in a slight increase in the crystallinity and swelling. Thiolated psyllium was found to contain 3.282 m moles of thiol groups/g of the polymer. Mucoadhesive applications of thiolated psylium were explored by formulating gels using metronidazole as the model drug. On comparative evaluation thiolated psyllium gels showed 3-fold higher mucoadhesive strength than the psyllium gels as determined by modified physical balance using chicken buccal pouch. The results of in vitro release study revealed that thiolated psyllium gels provided a prolonged release of metronidazole. Further, the psyllium and thiolated psyllium gels were found to release the drug following first-order kinetics by combination of polymer relaxation and diffusion through the matrix. PMID:24348147

Thermomechanical characterization of thiol-epoxy shape memory thermosets for mechanical actuators design

Science.gov (United States)

Belmonte, Alberto; Fernández-Francos, Xavier; De la Flor, Silvia

2018-02-01

In this paper, shape-memory "thiol-epoxy" polymers are synthesized and characterized as potential thermomechanical actuators. Their thermomechanical properties are investigated through dynamo mechanical and tensile analyses and related to their network structural properties by using "thiol" and "epoxy" compounds of different functionality and structure. Their mechanical properties (resistance at break, elongation limits and strain energy) are related to their shape-memory response under free-recovery conditions and partially-constrained conditions, thus, establishing the connection between network relaxation (free-recovery) with the work output capabilities (partially-constrained). Results show high mechanical performance, achieving high elongation at break values (up to 100%) and stress at break values (up to 50 MPa). The shape-memory experiments reveal strong dependence of the programming conditions and network structure on the recovery efficiency at free-conditions, whereas under partially-constrained conditions, the controlling factors are the mechanical limits at high temperature. Moreover, some recommendations to achieve the maximum work output efficiency for a given operational design of a thermomechanical actuator are deduced.

Recent development, applications, and perspectives of mesoporous silica particles in medicine and biotechnology.

Science.gov (United States)

Pasqua, Luigi; Cundari, Sante; Ceresa, Cecilia; Cavaletti, Guido

2009-01-01

Mesoporous silica particles (MSP) are a new development in nanotechnology. Covalent modification of the surface of the silica is possible both on the internal pore and on the external particle surface. It allows the design of functional nanostructured materials with properties of organic, biological and inorganic components. Research and development are ongoing on the MSP, which have applications in catalysis, drug delivery and imaging. The most recent and interesting advancements in size, morphology control and surface functionalization of MSP have enhanced the biocompatibility of these materials with high surface areas and pore volumes. In the last 5 years several reports have demonstrated that MSP can be efficiently internalized using in vitro and animal models. The functionalization of MSP with organic moieties or other nanostructures brings controlled release and molecular recognition capabilities to these mesoporous materials for drug/gene delivery and sensing applications, respectively. Herein, we review recent research progress on the design of functional MSP materials with various mechanisms of targeting and controlled release.

A simple large-scale synthesis of mesoporous In{sub 2}O{sub 3} for gas sensing applications

Energy Technology Data Exchange (ETDEWEB)

Zhang, Su; Song, Peng, E-mail: mse_songp@ujn.edu.cn; Yan, Huihui; Yang, Zhongxi; Wang, Qi, E-mail: mse_wangq@ujn.edu.cn

2016-08-15

Graphical abstract: Large-scale mesoporous In{sub 2}O{sub 3} nanostructures for gas-sensing applications were successfully fabricated via a facile Lewis acid catalytic the furfural alcohol resin template route. - Highlights: • Mesoporous In{sub 2}O{sub 3} nanostructures with high-yield have been successfully fabricated via a facile strategy. • The microstructure and formation mechanism of mesoporous In{sub 2}O{sub 3} nanostructures were discussed based on the experimental results. • The as-prepared In{sub 2}O{sub 3} samples exhibited high response, short response-recovery times and good selectivity to ethanol gas. - Abstract: In this paper, large-scale mesoporous In{sub 2}O{sub 3} nanostructures were synthesized by a facile Lewis acid catalytic the furfural alcohol resin (FAR) template route for the high-yield. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG) and the Brunauer-Emmett-Teller (BET) approach. The as-obtained mesoporous In{sub 2}O{sub 3} nanostructures possess excellent mesoporous and network structure, which increases the contact area with the gases, it is conducive for adsorption-desorption of gas on the surface of In{sub 2}O{sub 3}. The In{sub 2}O{sub 3} particles and pores were both about 15 nm and very uniform. In gas-sensing measurements with target gases, the gas sensor based on mesoporous In{sub 2}O{sub 3} nanostructures showed a good response, short response-recovery time, good selectivity and stability to ethanol. These properties are due to the large specific surface area of mesoporous structure. This synthetic method could use as a new design concept for functional mesoporous nanomaterials and for mass production.

Shape-Enhanced Photocatalytic Activities of Thoroughly Mesoporous ZnO Nanofibers

KAUST Repository

Ren, Xiaolong

2016-06-24

1D mesoporous materials have attracted extensive interest recently, owning to their fascinating properties and versatile applications. However, it remains as a grand challenge to develop a simple and efficient technique to produce oxide nanofibers with mesoporous architectures, controlled morphologies, large surface areas, and optimal performances. In this work, a facile foaming-assisted electrospinning strategy with foaming agent of tea saponin is used to produce thoroughly mesoporous ZnO nanofibers with high purity and controlled morphology. Interestingly, mesoporous fibers with elliptical cross-section exhibit the significantly enhanced photocatalytic activity for hydrogen production, as compared to the counterparts with circular and rectangular cross-sections, and they also perform better than the commercial ZnO nanopowders. The unexpected shape dependence of photocatalytic activities is attributed to the different stacking modes of the mesoporous fibers, and a geometrical model is developed to account for the shape dependence. This work represents an important step toward producing thoroughly mesoporous ZnO nanofibers with tailored morphologies, and the discovery that fibers with elliptical cross-section render the best performance provides a valuable guideline for improving the photocatalytic performance of such mesoporous nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

"Bricks and mortar" self-assembly approach to graphitic mesoporous carbon nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Fulvio, P. F.; Mayes, R.; Wang, X. Q.; Mahurin, S., M.; Bauer, J. C.; Presser, V.; McDonough, J.; Gogotsi, Y.; Dai, S.

2011-04-20

Mesoporous carbon materials do not have sufficient ordering at the atomic scale to exhibit good electronic conductivity. To date, mesoporous carbons having uniform mesopores and high surface areas have been prepared from partially-graphitizable precursors in the presence of templates. High temperature thermal treatments above 2000 °C, which are usually required to increase conductivity, result in a partial or total collapse of the mesoporous structures and reduced surface areas induced by growth of graphitic domains, limiting their applications in electric double layer capacitors and lithium-ion batteries. In this work, we successfully implemented a “brick-and-mortar” approach to obtain ordered graphitic mesoporous carbon nanocomposites with tunable mesopore sizes below 850 °C without using graphitization catalysts or high temperature thermal treatments. Phenolic resin-based mesoporous carbons act as mortar to highly conductive carbon blacks and carbon onions (bricks). The capacitance and resistivity of final materials can be tailored by changing the mortar to brick ratios.

Functionalisation of mesoporous materials for application as additives in high temperature PEM fuel cell membranes

Energy Technology Data Exchange (ETDEWEB)

Sharifi, Monir

2012-03-06

The presented thesis contains six original research articles dedicated to the preparation and characterization of organic-inorganic mesoporous materials as additives for polymer electroly1e membrane fuel cells (PEMFCs). The mesoporous materials Si-MCM-41 and benzene-PMO (periodic mesoporous organosilica) were chosen for the investigations. These materials were modified with functional groups for enhanced proton conductivity and water-keeping properties. In order to improve these materials Broenstedt acidic groups were introduced in the framework of mesoporous Si-MCM-41. Therefore, some silicium atoms in the framework were substituted by aluminium using different aluminium sources. Here NaAlO{sub 2} exhibits clearly the best results because the entire aluminium incorporated within the framework is tetragonally coordinated as observed by {sup 2}7AI MAS NMR. The increase of the proton conductivities results from an improved hydrophilicity, a decreased particle size, and newly introduced Broenstedt acidity in the mesoporous Al-MCM-41. However, mesoporous Si-MCM-41 materials functionalised by co-condensation with sulphonic acid groups exhibit the best results concerning proton conductivity, compared to those prepared by grafting. Hence, these materials where characterized in more detail by SANS and by MAS NMR measurements. The first one indicated that by co-condensation the entire inner pore surface is altered by functional groups which are, thus, distributed much more homogeneously than samples functionalised by grafting. This result explains the improved proton conductivities. Additionally, {sup 2}9Si NMR spectra proved that samples prepared by co-condensation lead to a successful and almost complete incorporation of mercaptopropyltrimethoxysilan (MPMS) into the mesoporous framework. Furthermore, it was shown by {sup 1}3C MAS NMR spectroscopy that the majority of the organic functional groups remained intact after H{sub 2}0{sub 2}-oxidation. However, proton

Cysteine 893 is a target of regulatory thiol modifications of GluA1 AMPA receptors.

Directory of Open Access Journals (Sweden)

Lotta von Ossowski

Full Text Available Recent studies indicate that glutamatergic signaling involves, and is regulated by, thiol modifying and redox-active compounds. In this study, we examined the role of a reactive cysteine residue, Cys-893, in the cytosolic C-terminal tail of GluA1 AMPA receptor as a potential regulatory target. Elimination of the thiol function by substitution of serine for Cys-893 led to increased steady-state expression level and strongly reduced interaction with SAP97, a major cytosolic interaction partner of GluA1 C-terminus. Moreover, we found that of the three cysteine residues in GluA1 C-terminal tail, Cys-893 is the predominant target for S-nitrosylation induced by exogenous nitric oxide donors in cultured cells and lysates. Co-precipitation experiments provided evidence for native association of SAP97 with neuronal nitric oxide synthase (nNOS and for the potential coupling of Ca2+-permeable GluA1 receptors with nNOS via SAP97. Our results show that Cys-893 can serve as a molecular target for regulatory thiol modifications of GluA1 receptors, including the effects of nitric oxide.

Mesoporous Zeolite Single Crystals for Catalytic Hydrocarbon Conversion

DEFF Research Database (Denmark)

Schmidt, I.; Christensen, Claus H.; Kustova, Marina

2005-01-01

Recently, mesoporous zeolite single crystals were discovered. They constitute a novel family of materials that features a combined micropore and mesopore architecture within each individual crystal. Here, we briefly summarize recent catalytic results from cracking and isomerization of alkalies......, alkylation of aromatics and present new results on isomerization of aromatics. Specifically, the shape-selective isomerization of meta-xylenc into para-xylene and ortho-xylene is studied. In all these reactions, rnesoporous zeolite single crystals prove to be unique catalysts since they provide easy...... transport to and from active sites and at the same time maintain the shape-selectivity required. Thus, all these results support the idea that the beneficial effect of the mesopores system in the mesoporous zeolite single crystals call be solely attributed to enhanced mass transport....

Thiol/disulfide homeostasis in pregnant women with obstructive sleep apnea syndrome.

Science.gov (United States)

Üstündağ, Yasemin; Demirci, Hakan; Balık, Rifat; Erel, Ozcan; Özaydın, Fahri; Kücük, Bilgen; Ertaş, Dilber; Ustunyurt, Emin

2017-11-27

Repetitive episodes of hypoxia and reoxygenation during sleep in patients with obstructive sleep apnea syndrome (OSAS) resemble an ischemia-reperfusion injury. We aimed to test the hypothesis that oxidative stress occurs in pregnant women with OSAS. We also aimed to compare thiol/disulfide homeostasis with ischemia-modified albumin (IMA) and total antioxidant capacity (TAC) as markers of ischemia-reperfusion injury in pregnant women with and without OSAS and healthy control. This study included 29 pregnant women with OSAS, 30 women without OSAS in the third trimester applying for periodic examinations, and 30 healthy women. Serum IMA and TAC (using the ferric reducing power of plasma method) were measured. Serum thiol/disulfide homeostasis was determined by a novel automated method. The mean age of the pregnant women with OSAS was 31.0 ± 4.7 years with a mean gestational age of 36.5 ± 3.0 weeks. The mean age of pregnant women without OSAS was 29.8 ± 4.9 years with a mean gestational age of 36.9 ± 2.7 weeks. The mean age of the nonpregnant control group was 29.7 ± 6.4 years. Both native thiol (291 ± 29 μmol/L versus 314 ± 30 μmol/L; p = .018) and total thiol (325 ± 32 versus 350 ± 32, p = .025) levels were lower in pregnant women with OSAS compared to pregnant women without OSAS, respectively (p total thiol levels were lower in pregnant women with OSAS compared to those without OSAS. However, dynamic thiol/disulfide homeostasis parameters cannot provide valuable information to discriminate OSAS in pregnant women.

Diffusion Study by IR Micro-Imaging of Molecular Uptake and Release on Mesoporous Zeolites of Structure Type CHA and LTA

Directory of Open Access Journals (Sweden)

Jörg Kärger

2013-07-01

Full Text Available The presence of mesopores in the interior of microporous particles may significantly improve their transport properties. Complementing previous macroscopic transient sorption experiments and pulsed field gradient NMR self-diffusion studies with such materials, the present study is dedicated to an in-depth study of molecular uptake and release on the individual particles of mesoporous zeolitic specimens, notably with samples of the narrow-pore structure types, CHA and LTA. The investigations are focused on determining the time constants and functional dependences of uptake and release. They include a systematic variation of the architecture of the mesopores and of the guest molecules under study as well as a comparison of transient uptake with blocked and un-blocked mesopores. In addition to accelerating intracrystalline mass transfer, transport enhancement by mesopores is found to be, possibly, also caused by a reduction of transport resistances on the particle surfaces.

One-Pot Fabrication of Antireflective/Antibacterial Dual-Function Ag NP-Containing Mesoporous Silica Thin Films.

Science.gov (United States)

Wang, Kaikai; He, Junhui

2018-04-04

Thin films that integrate antireflective and antibacterial dual functions are not only scientifically interesting but also highly desired in many practical applications. Unfortunately, very few studies have been devoted to the preparation of thin films with both antireflective and antibacterial properties. In this study, mesoporous silica (MSiO 2 ) thin films with uniformly dispersed Ag nanoparticles (Ag NPs) were prepared through a one-pot process, which simultaneously shows high transmittance, excellent antibacterial activity, and mechanical robustness. The optimal thin-film-coated glass substrate demonstrates a maximum transmittance of 98.8% and an average transmittance of 97.1%, respectively, in the spectral range of 400-800 nm. The growth and multiplication of typical bacteria, Escherichia coli ( E. coli), were effectively inhibited on the coated glass. Pencil hardness test, tape adhesion test, and sponge washing test showed favorable mechanical robustness with 5H pencil hardness, 5A grade adhesion, and functional durability of the coating, which promises great potential for applications in various touch screens, windows for hygiene environments, and optical apparatuses for medical uses such as endoscope, and so on.

Toposelective electrochemical desorption of thiol SAMs from neighboring polycrystalline gold surfaces.

Science.gov (United States)

Tencer, Michal; Berini, Pierre

2008-11-04

We describe a method for the selective desorption of thiol self-assembled monolayers from gold surfaces having micrometer-scale separations on a substrate. In an electrolyte solution, the electrical resistance between the adjacent areas can be much lower than the resistance between a surface and the counter electrode. Also, both reductive and oxidative thiol desorption may occur. Therefore, the potentials of the surfaces must be independently controlled with a multichannel potentiostat and operating windows for a given thiol/electrolyte system must be established. In this study operating windows were established for 1-dodecanethiol-based SAMs in phosphate buffer, phosphate-buffered saline, and sodium hydroxide solution, and selective SAM removal was successfully performed in a four-electrode configuration.

Effect of thiol group on the curing process of alkaline developable photo-resists

International Nuclear Information System (INIS)

Hidetaka Oka; Masaki Ohwa; Hisatoshi Kura

1999-01-01

Photosensitivity of a conventional radical photo-initiator in an alkaline developable photoresist is boosted by substitution with a thiol group. Evidence is presented that the thiol group acts via chain transfer mechanism

Generalized synthesis of mesoporous shells on zeolite crystals

KAUST Repository

Han, Yu; Pitukmanorom, Pemakorn; Zhao, L. J.; Ying, Jackie

2010-01-01

A simple and generalized synthetic approach is developed for creating mesoporous shells on zeolite crystals. This method allows for the tailoring of thickness, pore size, and composition of the mesoporous shell, and can be applied to zeolites

Ester-free Thiol-X Resins: New Materials with Enhanced Mechanical Behavior and Solvent Resistance

OpenAIRE

Podgórski, Maciej; Becka, Eftalda; Chatani, Shunsuke; Claudino, Mauro; Bowman, Christopher N.

2015-01-01

A series of thiol-Michael and radical thiol-ene network polymers were successfully prepared from ester-free as well as ester-containing monomer formulations. Polymerization reaction rates, dynamic mechanical analysis, and solvent resistance experiments were performed and compared between compositions with varied ester loading. The incorporation of ester-free alkyl thiol, vinyl sulfone and allylic monomers significantly improved the mechanical properties when compared with commercial, mercapto...

Preparation and Characterization of Fluorinated Hydrophobic UV-Crosslinkable Thiol-Ene Polyurethane Coatings

Directory of Open Access Journals (Sweden)

Wenjing Xia

2017-08-01

Full Text Available The polyurethane prepolymer terminated with a double bond was synthesized using isophorone diisocyanate (IPDI, hydroxyl terminated polybutadiene (HTPB, 1,4-butanediol (BDO, and 2-hydroxyethyl acrylate (HEA. Then, a series of innovative UV-curable polyurethane coatings were prepared by blending ene-terminated polyurethane, fluoroacrylate monomer, and multifunctional thiol crosslinker upon UV exposure. The incorporation of fluoroacrylate monomer and multifunctional thiols into polyurethane coatings significantly enhanced the hydrophobic property, mechanical property, pencil hardness, and glossiness of the polyurethane coatings. This method of preparing UV crosslinkable, hydrophobic polyurethane coatings based on thiol-ene chemistry exhibited numerous advantages over other UV photocuring systems.

Carbon Paste Electrode Modified with Carbamoylphosphonic Acid Functionalized Mesoporous Silica: A New Mercury-Free Sensor for Uranium Detection

International Nuclear Information System (INIS)

Yantasee, Wassana; Lin, Yuehe; Fryxell, Glen E.; Wang, Zheming

2004-01-01

This study reports a new approach for developing a uranium (U(VI)) electrochemical sensor that is mercury-free, solid-state, and has less chance for ligand depletion than existing sensors. A carbon-paste electrode modified with carbamoylphosphonic acid self-assembled monolayer on mesoporous silica was developed for uranium detection based on an adsorptive square-wave stripping voltammetry technique. Voltammetric responses for U(VI) detection are reported as a function of pH, preconcentration time, and aqueous phase U(VI) concentration. The uranium detection limit is 25 ppb after 5 minutes preconcentration and improved to 1 ppb after 20 minutes preconcentration. The relative standard deviations are normally less than 5%

Reactivities of some thiol collectors and their interactions with Ag (+1) ion by molecular modeling

Energy Technology Data Exchange (ETDEWEB)

Yekeler, Hulya; Yekeler, Meftuni

2004-09-15

The most commonly used collectors for sulfide minerals in the mining industry are the thiol collectors for the recovery of these minerals from their associated gangues by froth flotation. For this reason, a great deal of attention has been paid to understand the attachment mechanism of thiol collectors to metal sulfide surfaces. The density functional theory (DFT) calculations at the B3LYP/3-21G* and B3LYP/6-31++G** levels were employed to propose the flotation responses of these thiol collectors, namely, diethyl dithiocarbamate, ethyl dithiocarbamate, ethyl dithiocarbonate, ethyl trithiocarbonate and ethyl dithiophosphate ions, and to study the interaction energies of these collectors with Ag (+1) ion in connection to acanthite (Ag{sub 2}S) mineral. The calculated interaction energies, {delta}E, were interpreted in terms of the highest occupied molecular orbital (HOMO) energies of the isolated collector ions. The results show that the HOMOs are strongly localized to the sulfur atoms and the HOMO energies can be used as a reactivity descriptor for the flotation ability of the thiol collectors. Using the HOMO and {delta}E energies, the reactivity order of the collectors is found to be (C{sub 2}H{sub 5}){sub 2}NCS{sub 2}{sup -} > C{sub 2}H{sub 5}NHCS{sub 2}{sup -} > C{sub 2}H{sub 5}OCS{sub 2}{sup -} > C{sub 2}H{sub 5}SCS{sub 2}{sup -} > (C{sub 2}H{sub 5}O)(OH)PS{sub 2}{sup -}. The theoretically obtained results are in good agreement with the experimental data reported.

Pharmacological aspects of application of 1,2,4-triazole-3-thiol furan derivatives

Directory of Open Access Journals (Sweden)

O. A. Bihdan

2016-12-01

Full Text Available Introduction. Nowadays 1,2,4-triazole-3-thiol furan derivatives have established themselves as a separate class of promising bioactive compounds. Presented substance is practically non-toxic and exhibits various kinds of pharmacological activity. New original drug «Tryfuzol» in two dosage forms (1% injectable solution and 1% solution for oral administration triumphantly entered the practice of the national veterinary. The most attractive in pharmacological aspects are water-soluble compounds 5-(furan-2-yl-4R-1,2,4-triazole-3-thiols. Other classes of 1,2,4-triazole-3-thiol furan derivatives are also in considerable scientific interest. However, despite the presence of a sufficiently large number of publications, the issue of pharmacological tests systematization of the 1,2,4-triazole-3-thiol furan derivatives is still open. In this way the aim of our work was the systematization of the available sources of domestic authors. Materials and methods. Our work presents the results of systematic analysis of the available domestic literature related to the study of pharmacological properties of 1,2,4-triazole-3-thiol furan derivatives. Research results. It is known that 1,2,4-triazole-3-thiol furan derivatives have wide range of properties and biological activities. Thioacetate salts of corresponding acids show the highest results. The authors investigated the properties of water-soluble compounds of 1,2,4-triazole-3-thiol furan derivatives. Another group of compounds was investigated on hypoglycemic activity. It was established that the most active were piperidine 2-(5-(furan-2-yl-4-(3-methylphenyl-1,2,4-triazol-3-ylthio acetate and piperidine 2-(5-(furan-2-yl-4-phenyl-1,2,4-triazol-3-ylthio acetate. Conclusion. The scientific potential of the domestic pharmaceutical industry has no doubts for today. The literature analysis of Russian authors proves the obvious prospect of further research of biologically active compounds among 1,2,4-triazole-3-thiol

Aluminum-rich mesoporous MFI - type zeolite single crystals

DEFF Research Database (Denmark)

Kustova, Marina; Kustov, Arkadii; Christensen, Christina Hviid

2005-01-01

Zeolitcs are crystalline materials, which are widely used as solid acid catalysts and supports in many industrial processes. Recently, mesoporous MFI-type zeolite single crystals were synthesized by use of carbon particles as a mesopore template and sodium aluminate as the aluminum Source....... With this technique, only zeolites with relatively low Al contents were reported (Si/Al ratio about 100). In this work, the preparation of aluminum-rich mesoporous MFI-type zeolite single crystals (Si/Al similar to 16-50) using aluminum isopropoxide as the aluminum Source is reported for the first time. All samples...... are characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), ammonia temperature programmed desorption (NH3-TPD), and N-2 adsorption measurements. The obtained zeolites combine the high crystallinity and the characteristic micropores of zeolites with an intracrystalline mesopore system...

Pathways to Mesoporous Resin/Carbon Thin Films with Alternating Gyroid Morphology

Energy Technology Data Exchange (ETDEWEB)

Zhang, Qi [Department; Matsuoka, Fumiaki [Department; Suh, Hyo Seon [Institute; Materials; Beaucage, Peter A. [Department; Xiong, Shisheng [Institute; Materials; Smilgies, Detlef-M. [Cornell; Tan, Kwan Wee [Department; School; Werner, Jörg G. [Department; Nealey, Paul F. [Institute; Materials; Wiesner, Ulrich B. [Department

2017-12-19

Three-dimensional (3D) mesoporous thin films with sub-100 nm periodic lattices are of increasing interest as templates for a number of nanotechnology applications, yet are hard to achieve with conventional top-down fabrication methods. Block copolymer self-assembly derived mesoscale structures provide a toolbox for such 3D template formation. In this work, single (alternating) gyroidal and double gyroidal mesoporous thin-film structures are achieved via solvent vapor annealing assisted co-assembly of poly(isoprene-block-styrene-block-ethylene oxide) (PI-b-PS-b-PEO, ISO) and resorcinol/phenol formaldehyde resols. In particular, the alternating gyroid thin-film morphology is highly desirable for potential template backfilling processes as a result of the large pore volume fraction. In situ grazing-incidence small-angle X-ray scattering during solvent annealing is employed as a tool to elucidate and navigate the pathway complexity of the structure formation processes. The resulting network structures are resistant to high temperatures provided an inert atmosphere. The thin films have tunable hydrophilicity from pyrolysis at different temperatures, while pore sizes can be tailored by varying ISO molar mass. A transfer technique between substrates is demonstrated for alternating gyroidal mesoporous thin films, circumventing the need to re-optimize film formation protocols for different substrates. Increased conductivity after pyrolysis at high temperatures demonstrates that these gyroidal mesoporous resin/carbon thin films have potential as functional 3D templates for a number of nanomaterials applications.

Mesoporous zeolite and zeotype single crystals synthesized in fluoride media

DEFF Research Database (Denmark)

Egeblad, Kresten; Kustova, Marina; Klitgaard, Søren Kegnæs

2007-01-01

We report the synthesis and characterization of a series of new mesoporous zeolite and zeotype materials made available by combining new and improved procedures for directly introducing carbon into reaction mixtures with the fluoride route for conventional zeolite synthesis. The mesoporous...... materials were all prepared by hydrothermal crystallization of gels adsorbed on carbon matrices which were subsequently removed by combustion. The procedures presented here resulted in mesoporous zeolite and zeotypes materials with MFI, MEL, BEA, AFI and CHA framework structures. All samples were...... characterized by XRPD, SEM, TEM and N-2 physisorption measurements. For the zeolite materials it A as found that mesoporous MFI and MEL structured single crystals could indeed be crystallized from fluoride media using an improved carbon-templating approach. More importantly, it was found that mesoporous BEA...

Kinetic Resolution of sec-Thiols by Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase.

Science.gov (United States)

Pickl, Mathias; Swoboda, Alexander; Romero, Elvira; Winkler, Christoph K; Binda, Claudia; Mattevi, Andrea; Faber, Kurt; Fraaije, Marco W

2018-03-05

Various flavoprotein oxidases were recently shown to oxidize primary thiols. Herein, this reactivity is extended to sec-thiols by using structure-guided engineering of 5-(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of racemic sec-thiols, thus yielding the corresponding thioketones and nonreacted R-configured thiols with excellent enantioselectivities (E≥200). The engineering strategy applied went beyond the classic approach of replacing bulky amino acid residues with smaller ones, as the active site was additionally enlarged by a newly introduced Thr residue. This residue established a hydrogen-bonding interaction with the substrates, as verified in the crystal structure of the variant. These strategies unlocked HMFO variants for the enantioselective oxidation of a range of sec-thiols. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

International Nuclear Information System (INIS)

Paul, Manidipa; Pal, Nabanita; Bhaumik, Asim

2012-01-01

Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6–7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate–adsorbent interaction at the surfaces. - Graphical abstract: Highly ordered 2D-hexagonal mesoporous borosilicate materials have been synthesized by using Pluronic P123 as template. The materials show very good adsorption and release of organic cationic dye molecules under physiological conditions. Highlights: ► Highly ordered 2D-hexagonal mesoporous borosilicate. ► Nonionic Pluoronic P123 templated mesoporous material. ► Adsorption of organic dyes at the mesopore surface. ► Controlled release of dyes under physiological pH and temperature. ► Release of safranine T (ST) and malachite green (MG) dyes in simulated body fluids.

The impact of framework organic functional groups on the hydrophobicity and overall stability of mesoporous silica materials

International Nuclear Information System (INIS)

Smeulders, Geert; Meynen, Vera; Silvestre-Albero, Ana; Houthoofd, Kristof; Mertens, Myrjam; Silvestre-Albero, Joaquin; Martens, Johan A.; Cool, Pegie

2012-01-01

Graphical abstract: The stability (hydrothermal, mechanical and chemical) of PMOs is studied in a systematic way and ranks them between classic and other hybrid mesoporous silica materials. Highlights: ► The stability (hydrothermal, mechanical and chemical) of PMOs is studied. ► Compared stability of PMOs with classic and other hybrid mesoporous silica materials. ► Immersion calorimetry to study the effect of hydrophobicity. ► PMOs show superior stability. - Abstract: The hydrothermal, mechanical and chemical stability of various mesoporous materials have been studied in detail, using X-ray diffraction and nitrogen sorption. Pure siliceous nanoporous powders (MCM-41 and SBA-15) are evaluated against their hybrid counterparts; namely 2 types of periodic mesoporous organosilicas (benzene and ethane bridged PMOs) and an organosilane grafted MCM-41 material. In primary tests, the stability of the hybrid materials is found to be superior compared to that of the pure siliceous ones. The stability of the materials was correlated to their hydrophobicity via immersion calorimetry, applied for the first time in this context. Based on these results, a clear correlation between the hydrophobicity of a material and its stability has been revealed. In addition, with 29 Si-MAS-NMR and vacuum experiments, the mechanism of the structural deterioration in the three different stability treatments could be unambiguously identified as the hydrolyzation of the siloxane bonds. The homogeneity of the hydrophobic groups throughout the entire network was found to be of great importance, irrespective of the hydrophobic nature at the surface as determined by calorimetric measurements. The results reveal that the most stable material can withstand (a) a pressure of 740 MPa during 5 min, (b) a 2 h stirring in a 2 M NaOH solution and (c) a 3 day steaming treatment at 393 K.

The impact of framework organic functional groups on the hydrophobicity and overall stability of mesoporous silica materials

Energy Technology Data Exchange (ETDEWEB)

Smeulders, Geert, E-mail: geert.smeulders@ua.ac.be [University of Antwerpen (Ukraine), Laboratory of Adsorption and Catalysis, Universiteitsplein 1, 2610 Wilrijk (Belgium); Meynen, Vera [University of Antwerpen (Ukraine), Laboratory of Adsorption and Catalysis, Universiteitsplein 1, 2610 Wilrijk (Belgium); Silvestre-Albero, Ana [Universidad de Alicante, Laboratorio de Materiales Avanzados, Apartado 99, 03080 Alicante (Spain); Houthoofd, Kristof [KULeuven, Centre for Surface Chemistry and Catalysis, Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Mertens, Myrjam [Flemish Institute for Technological Research (VITO N.V.), Boeretang 200, 2400 Mol (Belgium); Silvestre-Albero, Joaquin [Universidad de Alicante, Laboratorio de Materiales Avanzados, Apartado 99, 03080 Alicante (Spain); Martens, Johan A. [KULeuven, Centre for Surface Chemistry and Catalysis, Kasteelpark Arenberg 23, 3001 Heverlee (Belgium); Cool, Pegie [University of Antwerpen (Ukraine), Laboratory of Adsorption and Catalysis, Universiteitsplein 1, 2610 Wilrijk (Belgium)

2012-02-15

Graphical abstract: The stability (hydrothermal, mechanical and chemical) of PMOs is studied in a systematic way and ranks them between classic and other hybrid mesoporous silica materials. Highlights: Black-Right-Pointing-Pointer The stability (hydrothermal, mechanical and chemical) of PMOs is studied. Black-Right-Pointing-Pointer Compared stability of PMOs with classic and other hybrid mesoporous silica materials. Black-Right-Pointing-Pointer Immersion calorimetry to study the effect of hydrophobicity. Black-Right-Pointing-Pointer PMOs show superior stability. - Abstract: The hydrothermal, mechanical and chemical stability of various mesoporous materials have been studied in detail, using X-ray diffraction and nitrogen sorption. Pure siliceous nanoporous powders (MCM-41 and SBA-15) are evaluated against their hybrid counterparts; namely 2 types of periodic mesoporous organosilicas (benzene and ethane bridged PMOs) and an organosilane grafted MCM-41 material. In primary tests, the stability of the hybrid materials is found to be superior compared to that of the pure siliceous ones. The stability of the materials was correlated to their hydrophobicity via immersion calorimetry, applied for the first time in this context. Based on these results, a clear correlation between the hydrophobicity of a material and its stability has been revealed. In addition, with {sup 29}Si-MAS-NMR and vacuum experiments, the mechanism of the structural deterioration in the three different stability treatments could be unambiguously identified as the hydrolyzation of the siloxane bonds. The homogeneity of the hydrophobic groups throughout the entire network was found to be of great importance, irrespective of the hydrophobic nature at the surface as determined by calorimetric measurements. The results reveal that the most stable material can withstand (a) a pressure of 740 MPa during 5 min, (b) a 2 h stirring in a 2 M NaOH solution and (c) a 3 day steaming treatment at 393 K.

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants

International Nuclear Information System (INIS)

Min, Sa Hoon; Jang, Jyongsik; Lee, Kyung Jin; Bae, Joonwon

2013-01-01

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol–gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant. (paper)

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants

Energy Technology Data Exchange (ETDEWEB)

Min, Sa Hoon; Jang, Jyongsik; Lee, Kyung Jin [School of Chemical and Biological Engineering, College of Engineering, Seoul National University, Shinlimdong 56-1, Seoul, 151-742 (Korea, Republic of); Bae, Joonwon [Department of Applied Chemistry, Dongduk Women' s University, Seoul 136-714 (Korea, Republic of)

2013-06-28

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol-gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant. (paper)

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants

Science.gov (United States)

Min, Sa Hoon; Bae, Joonwon; Jang, Jyongsik; Lee, Kyung Jin

2013-06-01

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol-gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant.

Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

Energy Technology Data Exchange (ETDEWEB)

Zhang, Jinyu; Zhou, Guowei, E-mail: guoweizhou@hotmail.com; Jiang, Bin; Zhao, Minnan; Zhang, Yan

2014-05-01

Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d{sub 100}), and cell parameter (a{sub 0}) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d{sub 100} and a{sub 0} continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%. - Graphical abstract: Curved rod-shaped mesoporous silica can be obtained at low and the highest PVP concentration, while straight rod-shaped mesoporous silica can be obtained at higher PVP concentration. - Highlights: • Mesoporous silica with morphology evolution from CRMS to SRMS were prepared. • Effects of PVP molecular weight and concentration on silica morphology were studied. • A possible mechanism for the formation of morphology evolution SiO{sub 2} was proposed. • Esterification of lauric acid with 1-butanol catalyzed by immobilized PPL.

Thiol-ene/methacrylate systems for mechanical damping

Science.gov (United States)

McNair, Olivia; Senyurt, Askim; Wei, Huanyu; Gould, Trent; Piland, Scott; Hoyle, Charles; Savin, Daniel

2010-03-01

Ternary thiol-ene-methacrylate (TEMA) networks as materials for mechanical energy damping are unique to the sports world. Using a photoinitiation process, TEMA systems are formed via an initial thiol-ene step-growth mechanism along with traditional radical polymerization of acrylate and ene monomers. Final networks have two-part morphologies: acrylate homopolymer sectors imbedded in a multi-component mesh. Several (TEMA) systems have been synthesized and analyzed via thermal and mechanical probing. Initial studies on these ternary systems have shown excellent properties compared to traditional ethylene vinyl alcohol (EVA) copolymers. For example, PEMA networks exhibit glass transition temperatures 33 K higher than EVA, resulting in improved damping at room temperature. This research will help develop relationships between tan delta, glass transition and their effects on mechanical energy damping for ternary (TEMA) systems.

Irreversible bonding of polyimide and polydimethylsiloxane (PDMS) based on a thiol-epoxy click reaction

International Nuclear Information System (INIS)

Hoang, Michelle V; Chung, Hyun-Joong; Elias, Anastasia L

2016-01-01

Polyimide is one of the most popular substrate materials for the microfabrication of flexible electronics, while polydimethylsiloxane (PDMS) is the most widely used stretchable substrate/encapsulant material. These two polymers are essential in fabricating devices for microfluidics, bioelectronics, and the internet of things; bonding these materials together is a crucial challenge. In this work, we employ click chemistry at room temperature to irreversibly bond polyimide and PDMS through thiol-epoxy bonds using two different methods. In the first method, we functionalize the surfaces of the PDMS and polyimide substrates with mercaptosilanes and epoxysilanes, respectively, for the formation of a thiol-epoxy bond in the click reaction. In the second method, we functionalize one or both surfaces with mercaptosilane and introduce an epoxy adhesive layer between the two surfaces. When the surfaces are bonded using the epoxy adhesive without any surface functionalization, an extremely small peel strength (<0.01 N mm −1 ) is measured with a peel test, and adhesive failure occurs at the PDMS surface. With surface functionalization, however, remarkably higher peel strengths of ∼0.2 N mm −1 (method 1) and  >0.3 N mm −1 (method 2) are observed, and failure occurs by tearing of the PDMS layer. We envision that the novel processing route employing click chemistry can be utilized in various cases of stretchable and flexible device fabrication. (paper)

Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis

Science.gov (United States)

Li, Keyan; Zhao, Yongqin; Song, Chunshan; Guo, Xinwen

2017-12-01

Magnetic Fe3O4/CeO2 composites with highly ordered mesoporous structure and large surface area were synthesized by impregnation-calcination method, and the mesoporous CeO2 as support was synthesized via the hard template approach. The composition, morphology and physicochemical properties of the materials were characterized by XRD, SEM, TEM, XPS, Raman spectra and N2 adsorption/desorption analysis. The mesoporous Fe3O4/CeO2 composite played a dual-function role as both adsorbent and Fenton-like catalyst for removal of organic dye. The methylene blue (MB) removal efficiency of mesoporous Fe3O4/CeO2 was much higher than that of irregular porous Fe3O4/CeO2. The superior adsorption ability of mesoporous materials was attributed to the abundant oxygen vacancies on the surface of CeO2, high surface area and ordered mesoporous channels. The good oxidative degradation resulted from high Ce3+ content and the synergistic effect between Fe and Ce. The mesoporous Fe3O4/CeO2 composite presented low metal leaching (iron 0.22 mg L-1 and cerium 0.63 mg L-1), which could be ascribed to the strong metal-support interactions for dispersion and stabilization of Fe species. In addition, the composite can be easily separated from reaction solution with an external magnetic field due to its magnetic property, which is important to its practical applications.

Mesoporous silica as carrier of antioxidant for food packaging materials

Science.gov (United States)

Buonocore, Giovanna Giuliana; Gargiulo, Nicola; Verdolotti, Letizia; Liguori, Barbara; Lavorgna, Marino; Caputo, Domenico

2014-05-01

Mesoporous silicas have been long recognized as very promising materials for the preparation of drug delivery systems. In this work SBA-15 mesoporous silica has been functionalized with amino-silane to be used as carrier of antioxidant compound in the preparation of active food packaging materials exhibiting tailored release properties. Active films have been prepared by loading the antioxidant tocopherol, the purely siliceous SBA-15 and the aminofunctionalized SBA-15 loaded with tocopherol into LDPE matrix trough a two-step process (mixing+extrusion). The aim of the present work is the study of the effect of the pore size and of the chemical functionality of the internal walls of the mesophase on the migration of tocopherol from active LDPE polymer films. Moreover, it has been proved that the addition of the active compound do not worsen the properties of the film such as optical characteristic and water vapor permeability, thus leading to the development of a material which could be favorably used mainly, but not exclusively, in the sector of food packaging.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

Science.gov (United States)

Parans Paranthaman, Mariappan; Bi, Zhonghe; Bridges, Craig A.; Brown, Gilbert M.

2017-04-11

Compositions and methods of making are provided for treated mesoporous metal oxide microspheres electrodes. The compositions include microspheres with an average diameter between about 200 nanometers and about 10 micrometers and mesopores on the surface and interior of the microspheres. The methods of making include forming a mesoporous metal oxide microsphere composition and treating the mesoporous metal oxide microspheres by at least annealing in a reducing atmosphere, doping with an aliovalent element, and coating with a coating composition.

Mesoporous silica formulation strategies for drug dissolution enhancement: a review.

Science.gov (United States)

McCarthy, Carol A; Ahern, Robert J; Dontireddy, Rakesh; Ryan, Katie B; Crean, Abina M

2016-01-01

Silica materials, in particular mesoporous silicas, have demonstrated excellent properties to enhance the oral bioavailability of poorly water-soluble drugs. Current research in this area is focused on investigating the kinetic profile of drug release from these carriers and manufacturing approaches to scale-up production for commercial manufacture. This review provides an overview of different methods utilized to load drugs onto mesoporous silica carriers. The influence of silica properties and silica pore architecture on drug loading and release are discussed. The kinetics of drug release from mesoporous silica systems is examined and the manufacturability and stability of these formulations are reviewed. Finally, the future prospects of mesoporous silica drug delivery systems are considered. Substantial progress has been made in the characterization and development of mesoporous drug delivery systems for drug dissolution enhancement. However, more research is required to fully understand the drug release kinetic profile from mesoporous silica materials. Incomplete drug release from the carrier and the possibility of drug re-adsorption onto the silica surface need to be investigated. Issues to be addressed include the manufacturability and regulation status of formulation approaches employing mesoporous silica to enhance drug dissolution. While more research is needed to support the move of this technology from the bench to a commercial medicinal product, it is a realistic prospect for the near future.

Contact-Engineered Electrical Properties of MoS2 Field-Effect Transistors via Selectively Deposited Thiol-Molecules.

Science.gov (United States)

Cho, Kyungjune; Pak, Jinsu; Kim, Jae-Keun; Kang, Keehoon; Kim, Tae-Young; Shin, Jiwon; Choi, Barbara Yuri; Chung, Seungjun; Lee, Takhee

2018-05-01

Although 2D molybdenum disulfide (MoS 2 ) has gained much attention due to its unique electrical and optical properties, the limited electrical contact to 2D semiconductors still impedes the realization of high-performance 2D MoS 2 -based devices. In this regard, many studies have been conducted to improve the carrier-injection properties by inserting functional paths, such as graphene or hexagonal boron nitride, between the electrodes and 2D semiconductors. The reported strategies, however, require relatively time-consuming and low-yield transfer processes on sub-micrometer MoS 2 flakes. Here, a simple contact-engineering method is suggested, introducing chemically adsorbed thiol-molecules as thin tunneling barriers between the metal electrodes and MoS 2 channels. The selectively deposited thiol-molecules via the vapor-deposition process provide additional tunneling paths at the contact regions, improving the carrier-injection properties with lower activation energies in MoS 2 field-effect transistors. Additionally, by inserting thiol-molecules at the only one contact region, asymmetric carrier-injection is feasible depending on the temperature and gate bias. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption removal of acid black 1 from aqueous solution using ordered mesoporous carbon

Energy Technology Data Exchange (ETDEWEB)

Peng, Xiaoming, E-mail: pengxiaoming70@126.com [School of Civil Engineering, Southeast University, Nanjing 210096 (China); Hu, Xijun [Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong,China (China); Fu, Dafang, E-mail: fdf@seu.edu.cn [School of Civil Engineering, Southeast University, Nanjing 210096 (China); Lam, Frank L.Y. [Department of Chemical and Biomolecular Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong,China (China)

2014-03-01

Highlights: • Ordered mesoporous carbon was prepared using template. • Ordered mesoporous carbon was introduced of N-containing group by Chemical vapor deposition method. • Modified CMK-3 have better adsorption capacity and efficiency than virgin CMK-3 to removal AB1 dye. - Abstract: A novel ordered mesoporous carbon CMK-3 and synthetic CMK-3 containing nitrogen functional groups by ammonia-treated were applied for acid black 1(AB1) dye adsorption. The ammonia-treated(chemical vapor deposition method) before and after CMK-3 were characterized by using a Micrometitics ASAP 2020 surface area analyzer (ASAP 2020), Fourier transform infrared spectrophotometer (FT–IR), X-ray Photoelectron Spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM) and equilibrium studies. This result indicates that the prepared CMK-3 and modified CMK-3 were almost uniform, as rope-like domains and their uniform mesopore with diameter centered at 3.2 nm and 3.7 nm. The FIIR analysis depicted that the presence of a variety of new basic functional groups on the modified CMK-3 surface. Several effect variables of pH, dye concentration and temperature were studied. The pseudo second-order model showed the fitter well to agree with the kinetic data. The experimental data were analyzed by the Langmuir and Freundlich models, with the latter found to closely the isotherm model. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The results show that CMK-3 using ammonia gas modified by thermal treatment system is an effective method to improvement capacity as it shows the highest adsorption capacity of AB1, as compared to the unmodified CMK-3 and the bamboo-based carbon, respectively.

Thiol-based redox signaling in the nitrogen-fixing symbiosis

Directory of Open Access Journals (Sweden)

Pierre eFrendo

2013-09-01

Full Text Available In nitrogen poor soils legumes establish a symbiotic interaction with rhizobia that results in the formation of root nodules. These are unique plant organs where bacteria differentiate into bacteroids, which express the nitrogenase enzyme complex that reduces atmospheric N2 to ammonia. Nodule metabolism requires a tight control of the concentrations of reactive oxygen and nitrogen species (RONS so that they can perform useful signaling roles while avoiding nitro-oxidative damage. In nodules a thiol-dependent regulatory network that senses, transmits and responds to redox changes is starting to be elucidated. A combination of enzymatic, immunological, pharmacological and molecular analyses has allowed to conclude that glutathione and its legume-specific homolog, homoglutathione, are abundant in meristematic and infected cells, their spatio-temporally distribution is correlated with the corresponding (homoglutathione synthetase activities, and are crucial for nodule development and function. Glutathione is at high concentrations in the bacteroids and at moderate amounts in the mitochondria, cytosol and nuclei. Less information is available on other components of the network. The expression of multiple isoforms of glutathione peroxidases, peroxiredoxins, thioredoxins, glutaredoxins and NADPH-thioredoxin reductases has been detected in nodule cells using antibodies and proteomics. Peroxiredoxins and thioredoxins are essential to regulate and in some cases to detoxify RONS in nodules. Further research is necessary to clarify the regulation of the expression and activity of thiol redox-active proteins in response to abiotic, biotic and developmental cues, their interactions with downstream targets by disulfide-exchange reactions, and their participation in signaling cascades. The availability of mutants and transgenic lines will be crucial to facilitate systematic investigations into the function of the various proteins in the legume

Magnetic solid-phase extraction based on mesoporous silica-coated magnetic nanoparticles for analysis of oral antidiabetic drugs in human plasma

Energy Technology Data Exchange (ETDEWEB)

Souza, Karynne Cristina de; Andrade, Gracielle Ferreira [Centro de Desenvolvimento da Tecnologia Nuclear, CDTN/CNEN, Rua Professor Mário Werneck, s/n. Campus Universitário, Belo Horizonte, MG CEP 30.123-970 (Brazil); Vasconcelos, Ingrid; Oliveira Viana, Iara Maíra de; Fernandes, Christian [Departamento de Produtos Farmacêuticos, Faculdade de Farmácia, Universidade Federal de Minas Gerais, Belo Horizonte, MG (Brazil); Martins Barros de Sousa, Edésia, E-mail: sousaem@cdtn.br [Centro de Desenvolvimento da Tecnologia Nuclear, CDTN/CNEN, Rua Professor Mário Werneck, s/n. Campus Universitário, Belo Horizonte, MG CEP 30.123-970 (Brazil)

2014-07-01

In the present work, magnetic nanoparticles embedded into mesoporous silica were prepared in two steps: first, magnetite was synthesized by oxidation–precipitation method, and next, the magnetic nanoparticles were coated with mesoporous silica by using nonionic block copolymer surfactants as structure-directing agents. The mesoporous SiO{sub 2}-coated Fe{sub 3}O{sub 4} samples were functionalized using octadecyltrimethoxysilane as silanizing agent. The pure and functionalized silica nanoparticles were physicochemically and morphologically characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N{sub 2} adsorption, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The resultant magnetic silica nanoparticles were applied as sorbents for magnetic solid-phase extraction (MSPE) of oral antidiabetic drugs in human plasma. Our results revealed that the magnetite nanoparticles were completely coated by well-ordered mesoporous silica with free pores and stable pore walls, and that the structural and magnetic properties of the Fe{sub 3}O{sub 4} nanoparticles were preserved in the applied synthesis route. Indeed, the sorbent material was capable of extracting the antidiabetic drugs from human plasma, being useful for the sample preparation in biological matrices. - Highlights: • SBA-15/Fe{sub 3}O{sub 4} was synthesized and functionalized with octadecyltrimethoxysilane. • Magnetite nanoparticles were completely coated by well-ordered mesoporous silica. • The samples were used as sorbent for magnetic solid-phase extraction (MSPE). • The sorbent material was capable of extracting drugs from human plasma. • The extraction ability makes the material a candidate to be employed as MSPE.

Synthesis and characterization of mesoporous silica core-shell particles

Directory of Open Access Journals (Sweden)

Milan Nikolić

2010-06-01

Full Text Available Core-shell particles were formed by deposition of primary silica particles synthesized from sodium silicate solution on functionalized silica core particles (having size of ~0.5 µm prepared by hydrolysis and condensation of tetraethylortosilicate. The obtained mesoporous shell has thickness of about 60 nm and consists of primary silica particles with average size of ~21 nm. Scanning electron microscopy and zeta potential measurements showed that continuous silica shell exists around functionalized core particles which was additionally proved by FTIR and TEM results.

Rapid and simple preparation of thiol-ene emulsion-templated monoliths and their application as enzymatic microreactors

DEFF Research Database (Denmark)

Lafleur, Josiane P; Senkbeil, Silja; Novotny, Jakub

2015-01-01

A novel, rapid and simple method for the preparation of emulsion-templated monoliths in microfluidic channels based on thiol-ene chemistry is presented. The method allows monolith synthesis and anchoring inside thiol-ene microchannels in a single photoinitiated step. Characterization by scanning...... electron microscopy showed that the methanol-based emulsion templating process resulted in a network of highly interconnected and regular thiol-ene beads anchored solidly inside thiol-ene microchannels. Surface area measurements indicate that the monoliths are macroporous, with no or little micro...

Recent progress in mesoporous titania materials: adjusting morphology for innovative applications

Directory of Open Access Journals (Sweden)

Juan L Vivero-Escoto, Ya-Dong Chiang, Kevin C-W Wu and Yusuke Yamauchi

2012-01-01

Full Text Available This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.

Mesoporous Transition Metal Oxides for Supercapacitors

OpenAIRE

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are result...

Mesoporous silica nanoparticles for biomedical and catalytical applications

Energy Technology Data Exchange (ETDEWEB)

Sun, Xiaoxing [Iowa State Univ., Ames, IA (United States)

2011-01-01

Mesoporous silica materials, discovered in 1992 by the Mobile Oil Corporation, have received considerable attention in the chemical industry due to their superior textual properties such as high surface area, large pore volume, tunable pore diameter, and narrow pore size distribution. Among those materials, MCM-41, referred to Mobile Composition of Matter NO. 41, contains honeycomb liked porous structure that is the most common mesoporous molecular sieve studied. Applications of MCM-41 type mesoporous silica material in biomedical field as well as catalytical field have been developed and discussed in this thesis. The unique features of mesoporous silica nanoparticles were utilized for the design of delivery system for multiple biomolecules as described in chapter 2. We loaded luciferin into the hexagonal channels of MSN and capped the pore ends with gold nanoparticles to prevent premature release. Luciferase was adsorbed onto the outer surface of the MSN. Both the MSN and the gold nanoparticles were protected by poly-ethylene glycol to minimize nonspecific interaction of luciferase and keep it from denaturating. Controlled release of luciferin was triggered within the cells and the enzymatic reaction was detected by a luminometer. Further developments by varying enzyme/substrate pairs may provide opportunities to control cell behavior and manipulate intracellular reactions. MSN was also served as a noble metal catalyst support due to its large surface area and its stability with active metals. We prepared MSN with pore diameter of 10 nm (LP10-MSN) which can facilitate mass transfer. And we successfully synthesized an organo silane, 2,2'-Bipyridine-amide-triethoxylsilane (Bpy-amide-TES). Then we were able to functionalize LP10-MSN with bipyridinyl group by both post-grafting method and co-condensation method. Future research of this material would be platinum complexation. This Pt (II) complex catalyst has been reported for a C-H bond activation reaction as an

Transdermal thiol-acrylate polyethylene glycol hydrogel synthesis using near infrared light

Science.gov (United States)

Chung, Solchan; Lee, Hwangjae; Kim, Hyung-Seok; Kim, Min-Gon; Lee, Luke P.; Lee, Jae Young

2016-07-01

Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm-2) could induce gelation via a mixed-mode reaction with a small increase in temperature (~5 °C) under the optimized conditions. We also achieved successful transdermal gelation via the NIR-assisted photothermal thiol-acryl reactions. This new type of NIR-assisted thiol-acrylate polymerization provides new opportunities for in situ hydrogel formation for injectable hydrogels and delivery of drugs/cells for various biomedical applications.Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm-2) could induce gelation

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

Science.gov (United States)

Wilgosz, Karolina; Chen, Xuecheng; Kierzek, Krzysztof; Machnikowski, Jacek; Kalenczuk, Ryszard J.; Mijowska, Ewa

2012-05-01

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors.

Purification, Characterization, and Effect of Thiol Compounds on Activity of the Erwinia carotovora L-Asparaginase

Directory of Open Access Journals (Sweden)

Suchita C. Warangkar

2010-01-01

Full Text Available L-asparaginase was extracted from Erwinia carotovora and purified by ammonium sulfate fractionation (60–70%, Sephadex G-100, CM cellulose, and DEAE sephadex chromatography. The apparent Mr of enzyme under nondenaturing and denaturing conditions was 150 kDa and 37±0.5 kDa, respectively. L-asparaginase activity was studied in presence of thiols, namely, L-cystine (Cys, L-methionine (Met, N-acetyl cysteine (NAC, and reduced glutathione (GSH. Kinetic parameters in presence of thiols (10–400 M showed an increase in Vmax values (2000, 2223, 2380, 2500, and control 1666.7 moles mg−1min−1 and a decrease in K values (0.086, 0.076, 0.062, 0.055 and control 0.098 mM indicating nonessential mode of activation. KA values displayed propensity to bind thiols. A decrease in Vmax/K ratio in concentration plots showed inverse relationship between free thiol groups (NAC and GSH and bound thiol group (Cys and Met. Enzyme activity was enhanced in presence of thiol protecting reagents like dithiothreitol (DTT, 2-mercaptoethanol (2-ME, and GSH, but inhibited by p-chloromercurybenzoate (PCMB and iodoacetamide (IA.

Single-Crystal Mesoporous ZnO Thin Films Composed of Nanowalls

KAUST Repository

Wang, Xudong

2009-02-05

This paper presents a controlled, large scale fabrication of mesoporous ZnO thin films. The entire ZnO mesoporous film is one piece of a single crystal, while high porosity made of nanowalls is present. The growth mechanism was proposed in comparison with the growth of ZnO nanowires. The ZnO mesoporous film was successfully applied as a gas sensor. The fabrication and growth analysis of the mesoporous ZnO thin film gi ve general guidance for the controlled growth of nanostructures. It also pro vides a unique structure with a superhigh surface-to-volume ratio for surface-related applications. © 2009 American Chemical Society.

Preparation of carbon-functionalized magnetic graphene/mesoporous silica composites for selective extraction of miglitol and voglibose in rat plasma.

Science.gov (United States)

Liu, Xiaodan; Feng, Jianan; Li, Yan

2018-05-15

In this work, magnetic graphene/mesoporous silica composites with carbon-functionalized pore-walls (denoted as MG@mSiO 2 -C composites) were synthesized and applied as restricted access matrix solid phase extraction (RAM-SPE) adsorbents for the determination of miglitol and voglibose in rat plasma by LC-MS/MS. The MG@mSiO 2 -C composites were synthesized by using the template (Cetyltrimethyl Ammonium Bromide, CTAB) as carbon source with sulfuric acid pretreated. The obtained nano-composites were proven to have many unique properties such as large specific surface area of 277.1 cm 2 g -1 , uniform mesopores with average pore size of 3.35 nm, and carbon-functionalized pore-walls. Taking advantage of the hydrophilic interaction between carbon and glycans, α-glucosidase inhibitors (miglitol and voglibose) could be directly extracted from rat plasma with no need of other pre-treatment procedures. The SPE conditions such as the adsorbent amount, elution solvent type, adsorption time and elution time were optimized. For both miglitol and voglibose, good linearities of 10-2000 ng mL -1 were obtained with determination coefficients (R 2 ) > 0.99. The intra-day and inter-day RSDs were 3.3-6.9% (n = 6) and 6.0-8.0% (n = 6), respectively. The recoveries were in the range of 99.9-100.4% and the sensitivities were as low as 2-2.5 ng mL -1 (LOD). This MG@mSiO 2 -C composites-based RAM-SPE method offers high extraction efficiency for the determination of α-glucosidase inhibitor in plasma. Copyright © 2018 Elsevier B.V. All rights reserved.

Biocompatibility of Soft-Templated Mesoporous Carbons

Energy Technology Data Exchange (ETDEWEB)

Gencoglu, Maria F. [Michigan Technological Univ., Houghton, MI (United States). Dept. of Chemical Engineering; Spurri, Amanda [Widener Univ., Chester, PA (United States). Dept. of Chemical Engineering; Franko, Mitchell [Widener Univ., Chester, PA (United States). Dept. of Chemical Engineering; Chen, Jihua [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Hensley, Dale K. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS); Heldt, Caryn L. [Michigan Technological Univ., Houghton, MI (United States). Dept. of Chemical Engineering; Saha, Dipendu [Widener Univ., Chester, PA (United States). Dept. of Chemical Engineering

2014-08-21

We report that soft-templated mesoporous carbon is morphologically a non-nano type of carbon. It is a relatively newer variety of biomaterial, which has already demonstrated its successful role in drug delivery applications. To investigate the toxicity and biocompatibility, we introduced three types of mesoporous carbons with varying synthesis conditions and pore textural properties. We compared the Brunauer–Emmett–Teller (BET) surface area and pore width and performed cytotoxicity experiments with HeLa cells, cell viability studies with fibroblast cells and hemocomapatibility studies. Cytotoxicity tests reveal that two of the carbons are not cytotoxic, with cell survival over 90%. The mesoporous carbon with the highest surface area showed slight toxicity (~70% cell survival) at the highest carbon concentration of 500 μg/mL. Fibroblast cell viability assays suggested high and constant viability of over 98% after 3 days with no apparent relation with materials property and good visible cell-carbon compatibility. No hemolysis (<1%) was confirmed for all the carbon materials. Protein adsorption experiments with bovine serum albumin (BSA) and fibrinogen revealed a lower protein binding capacity of 0.2–0.6 mg/m² and 2–4 mg/m² for BSA and fibrinogen, respectively, with lower binding associated with an increase in surface area. The results of this study confirm the biocompatibility of soft-templated mesoporous carbons.

Aroma extraction dilution analysis of Sauternes wines. Key role of polyfunctional thiols.

Science.gov (United States)

Bailly, Sabine; Jerkovic, Vesna; Marchand-Brynaert, Jacqueline; Collin, Sonia

2006-09-20

The aim of the present work was to investigate Sauternes wine aromas. In all wine extracts, polyfunctional thiols were revealed to have a huge impact. A very strong bacon-petroleum odor emerged at RI = 845 from a CP-Sil5-CB column. Two thiols proved to participate in this perception: 3-methyl-3-sulfanylbutanal and 2-methylfuran-3-thiol. A strong synergetic effect was evidenced between the two compounds. The former, never mentioned before in wines, and not found in the musts of this study, is most probably synthesized during fermentation. 3-Methylbut-2-ene-1-thiol, 3-sulfanylpropyl acetate, 3-sulfanylhexan-1-ol, and 3-sulfanylheptanal also contribute to the global aromas of Sauternes wines. Among other key odorants, the presence of a varietal aroma (alpha-terpineol), sotolon, fermentation alcohols (3-methylbutan-1-ol and 2-phenylethanol) and esters (ethyl butyrate, ethyl hexanoate, and ethyl isovalerate), carbonyls (trans-non-2-enal and beta-damascenone), and wood flavors (guaiacol, vanillin, eugenol, beta-methyl-gamma-octalactone, and Furaneol) is worth stressing.

Aminopropyl-modified mesoporous molecular sieves as efficient adsorbents for removal of auxins

Energy Technology Data Exchange (ETDEWEB)

Moritz, Michał, E-mail: michal.moritz@put.poznan.pl [Poznan University of Technology, Faculty of Chemical Technology, Institute of Chemistry and Technical Electrochemistry, Berdychowo 4, 60-965 Poznań (Poland); Geszke-Moritz, Małgorzata, E-mail: Malgorzata.Geszke-Moritz@amu.edu.pl [NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)

2015-03-15

Graphical abstract: Adsorption of indole-3-acetic acid (IAA) on aminopropyl-modified mesoporous sieves. - Highlights: • Four types of mesoporous molecular sieves were used as sorbents for removal of auxins. • SBA-15, MCF, PHTS and SBA-16 were grafted with (3-aminopropyl)triethoxysilane. • The adsorption capacity of modified materials was higher as compared to pure silicas. • Surface modification and pore volume play important role in adsorption process. - Abstract: In the present study, mesoporous siliceous materials grafted with 3-aminopropyltriethoxysilane (APTES) were examined as sorbents for removal of chosen plant growth factors (auxins) such as 1-naphthaleneacetic acid (NAA), indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA). Four different types of mesoporous molecular sieves including SBA-15, PHTS, SBA-16 and MCF have been prepared via non-ionic surfactant-assisted soft templating method. Silica molecular sieves were thoroughly characterized by nitrogen adsorption–desorption analysis, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FT-IR). The maximum adsorption capacity (Q{sub max}) for NAA, IAA and IBA was in the range from 51.0 to 140.8 mg/g and from 4.3 to 7.3 mg/g for aminopropyl-modified adsorbents and pure silicas, respectively. The best adsorption performance was observed for IAA entrapment using both APTES-functionalized SBA-15 and MCF matrices (Q{sub max} of 140.8 and 137.0 mg/g, respectively) which can be ascribed to their larger pore volumes and pore diameters. Moreover, these silicas were characterized by the highest adsorption efficiency exceeding 90% at low pollutant concentration. The experimental points for adsorption of plant growth factors onto aminopropyl-modified mesoporous molecular sieves fitted well to the Langmuir equation.

Aminopropyl-modified mesoporous molecular sieves as efficient adsorbents for removal of auxins

International Nuclear Information System (INIS)

Moritz, Michał; Geszke-Moritz, Małgorzata

2015-01-01

Graphical abstract: Adsorption of indole-3-acetic acid (IAA) on aminopropyl-modified mesoporous sieves. - Highlights: • Four types of mesoporous molecular sieves were used as sorbents for removal of auxins. • SBA-15, MCF, PHTS and SBA-16 were grafted with (3-aminopropyl)triethoxysilane. • The adsorption capacity of modified materials was higher as compared to pure silicas. • Surface modification and pore volume play important role in adsorption process. - Abstract: In the present study, mesoporous siliceous materials grafted with 3-aminopropyltriethoxysilane (APTES) were examined as sorbents for removal of chosen plant growth factors (auxins) such as 1-naphthaleneacetic acid (NAA), indole-3-acetic acid (IAA) and indole-3-butyric acid (IBA). Four different types of mesoporous molecular sieves including SBA-15, PHTS, SBA-16 and MCF have been prepared via non-ionic surfactant-assisted soft templating method. Silica molecular sieves were thoroughly characterized by nitrogen adsorption–desorption analysis, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), and Fourier-transform infrared spectroscopy (FT-IR). The maximum adsorption capacity (Q max ) for NAA, IAA and IBA was in the range from 51.0 to 140.8 mg/g and from 4.3 to 7.3 mg/g for aminopropyl-modified adsorbents and pure silicas, respectively. The best adsorption performance was observed for IAA entrapment using both APTES-functionalized SBA-15 and MCF matrices (Q max of 140.8 and 137.0 mg/g, respectively) which can be ascribed to their larger pore volumes and pore diameters. Moreover, these silicas were characterized by the highest adsorption efficiency exceeding 90% at low pollutant concentration. The experimental points for adsorption of plant growth factors onto aminopropyl-modified mesoporous molecular sieves fitted well to the Langmuir equation

Equilibrium mercury isotope fractionation between dissolved Hg(II) species and thiol-bound Hg

NARCIS (Netherlands)

Wiederhold, Jan G.; Cramer, Christopher J.; Daniel, Kelly; Infante, Ivan; Bourdon, Bernard; Kretzschmar, Ruben

2010-01-01

Stable Hg isotope ratios provide a new tool to trace environmental Hg cycling. Thiols (-SH) are the dominant Hg-binding groups in natural organic matter. Here, we report experimental and computational results on equilibrium Hg isotope fractionation between dissolved Hg(II) species and thiol-bound

Preparation of Mesoporous SBA-16 Silica-Supported Biscinchona Alkaloid Ligand for the Asymmetric Dihydroxylation of Olefins

Directory of Open Access Journals (Sweden)

Shaheen M. Sarkar

2014-01-01

Full Text Available Optically active cinchona alkaloid was anchored onto mesoporous SBA-16 silica and the as-prepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. The prepared catalytic system provided 90–93% yield of vicinal diol with 92–99% enantioselectivity. The ordered mesoporous SBA-16 silica was found to be a valuable support for the cinchona alkaloid liganded osmium catalyst system which is frequently used in chemical industries and research laboratories for olefin functionalization.

Mesoporous structured MIPs@CDs fluorescence sensor for highly sensitive detection of TNT.

Science.gov (United States)

Xu, Shoufang; Lu, Hongzhi

2016-11-15

A facile strategy was developed to prepare mesoporous structured molecularly imprinted polymers capped carbon dots (M-MIPs@CDs) fluorescence sensor for highly sensitive and selective determination of TNT. The strategy using amino-CDs directly as "functional monomer" for imprinting simplify the imprinting process and provide well recognition sites accessibility. The as-prepared M-MIPs@CDs sensor, using periodic mesoporous silica as imprinting matrix, and amino-CDs directly as "functional monomer", exhibited excellent selectivity and sensitivity toward TNT with detection limit of 17nM. The recycling process was sustainable for 10 times without obvious efficiency decrease. The feasibility of the developed method in real samples was successfully evaluated through the analysis of TNT in soil and water samples with satisfactory recoveries of 88.6-95.7%. The method proposed in this work was proved to be a convenient and practical way to prepare high sensitive and selective fluorescence MIPs@CDs sensors. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced microwave absorption properties of Ni-doped ordered mesoporous carbon/polyaniline nanocomposites

International Nuclear Information System (INIS)

Wang, Liuding; Wu, Hongjing; Shen, Zhongyuan; Guo, Shaoli; Wang, Yiming

2012-01-01

Highlights: ► OMC-Ni/PANI nanocomposites were prepared by in situ polymerization method. ► The effective absorption bandwidth was 4.7 GHz for OMC-Ni0.15/PANI. ► OMC-Ni/PANI showed excellent microwave absorption with respect to OMC-Ni. ► This effect could be mainly attributed to the improvement of impendence matching. - Abstract: We propose and demonstrate a new scheme to improve microwave absorption property through polyaniline (PANI)-functionalized Ni-doped ordered mesoporous carbon (OMC) by in situ polymerization method. The polymer-functionalized nanocomposites, embedding polyaniline within ordered mesoporous carbon, exhibit strong and broadband microwave absorption due to its better dielectric loss characteristic. OMC-Ni0.15/PANI exhibits an effective absorption bandwidth (i.e., reflection loss (RL) ≤ −10 dB) of 4.7 GHz and an absorption peak of −51 dB at 9.0 GHz. The absorption peak intensity and position can be tuned by controlling the thickness of the coating.

Mesoporous zeolite single crystal catalysts: Diffusion and catalysis in hierarchical zeolites

DEFF Research Database (Denmark)

Christensen, Christina Hviid; Johannsen, Kim; Toernqvist, Eric

2007-01-01

During the last years, several new routes to produce zeolites with controlled mesoporosity have appeared. Moreover, an improved catalytic performance of the resulting mesoporous zeolites over conventional zeolites has been demonstrated in several reactions. In most cases, the mesoporous zeolites...... exhibit higher catalytic activity, but in some cases also improved selectivity and longer catalyst lifetime has been reported. The beneficial effects of introducing mesopores into the zeolites has in most instances been attributed to improved mass transport to and from the active sites located...... in the zeolite micropores. Here, we briefly discuss the most important ways of introducing mesopores into zeolites and, for the first time, we show experimentally that the presence of mesopores dramatically increases the rate of diffusion in zeolite catalysts. This is done by studying the elution of iso...

Mesoporous Silica Nanomaterials for Applications in Catalysis, Sensing, Drug Delivery and Gene Transfection

Energy Technology Data Exchange (ETDEWEB)

Radu, Daniela Rodica [Iowa State Univ., Ames, IA (United States)

2004-01-01

The central theme of this dissertation is represented by the versatility of mesoporous silica nanomaterials in various applications such as catalysis and bio-applications, with main focus on biological applications of Mesoporous Silica Nanospheres (MSN). The metamorphosis that we impose to these materials from catalysis to sensing and to drug and gene delivery is detailed in this dissertation. First, we developed a synthetic method that can fine tune the amount of chemically accessible organic functional groups on the pores surface of MSN by exploiting electrostatic and size matching between the cationic alkylammonium head group of the cetyltrimethylammonium bromide (CTAB) surfactant and various anionic organoalkoxysilane precursors at the micelle-water interface in a base-catalyzed condensation reaction of silicate. Aiming nature imitation, we demonstrated the catalytic abilities of the MSNs, We utilized an ethylenediamine functional group for chelating Cu²⁺ as a catalytic functional group anchored inside the mesopores. Thus, a polyalkynylene-based conducting polymer (molecular wire) was synthesized within the Cu-functionalized MSNs silica catalyst. For sensing applications, we have synthesized a poly(lactic acid) coated mesoporous silica nanosphere (PLA-MSN) material that serves as a fluorescence sensor system for detection of amino-containing neurotransmitters in neutral aqueous buffer. We exploited the mesoporosity of MSNs for encapsulating pharmaceutical drugs. We examined bio-friendly capping molecules such as polyamidoamine dendrimers of generations G2 to G4, to prevent the drug leaching. Next, the drug delivery system employed MSNs loaded with Doxorubicin, an anticancer drug. The results demonstrated that these nano-Trojan horses have ability to deliver Doxorubicin to cancer cells and induce their death. Finally, to demonstrate the potential of MSN as an universal cellular transmembrane nanovehicle, we anchored positively charged dendrimers on

Periodic mesoporous organosilica-doped nanocomposite membranes and systems including same

KAUST Repository

Hammami, Mohamed Amen

2017-12-28

A periodic mesoporous organosilica (PMO) nanoparticle functionalized nanocomposite membrane (NCM) for membrane distillation, the NCM including: polymer fibers such as polyetherimide fibers aggregated into a matrix; and hydrophobic PMO nanoparticles disposed on the polymer fibers. The PMO nanoparticles include a framework connected by organic groups and pentafluorophenyl groups. Good membrane flux and anti-fouling was demonstrated. Membranes can be prepared by electrospinning.

Periodic mesoporous organosilica-doped nanocomposite membranes and systems including same

KAUST Repository

Hammami, Mohamed Amen; Francis, Lijo; Croissant, Jonas; Ghaffour, NorEddine; Alsaiari, Shahad; Khashab, Niveen M.

2017-01-01

A periodic mesoporous organosilica (PMO) nanoparticle functionalized nanocomposite membrane (NCM) for membrane distillation, the NCM including: polymer fibers such as polyetherimide fibers aggregated into a matrix; and hydrophobic PMO nanoparticles disposed on the polymer fibers. The PMO nanoparticles include a framework connected by organic groups and pentafluorophenyl groups. Good membrane flux and anti-fouling was demonstrated. Membranes can be prepared by electrospinning.

Investigations of thiol-modified phenol derivatives for the use in thiol–ene photopolymerizations

Science.gov (United States)

Reinelt, Sebastian; Tabatabai, Monir; Fischer, Urs Karl; Moszner, Norbert; Utterodt, Andreas

2014-01-01

Summary Thiol–ene photopolymerizations gain a growing interest in academic research. Coatings and dental restoratives are interesting applications for thiol–ene photopolymerizations due to their unique features. In most studies the relative flexible and hydrophilic ester derivative, namely pentaerythritoltetra(3-mercaptopropionate) (PETMP), is investigated as the thiol component. Thus, in the present study we are encouraged to investigate the performance of more hydrophobic ester-free thiol-modified bis- and trisphenol derivatives in thiol–ene photopolymerizations. For this, six different thiol-modified bis- and trisphenol derivatives exhibiting four to six thiol groups are synthesized via the radical addition of thioacetic acid to suitable allyl-modified precursors and subsequent hydrolysis. Compared to PETMP better flexural strength and modulus of elasticity are achievable in thiol–ene photopolymerizations employing 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO) as the ene derivative. Especially, after storage in water, the flexural strength and modulus of elasticity is twice as high compared to the PETMP reference system. PMID:25161731

Investigations of thiol-modified phenol derivatives for the use in thiol–ene photopolymerizations

Directory of Open Access Journals (Sweden)

Sebastian Reinelt

2014-07-01

Full Text Available Thiol–ene photopolymerizations gain a growing interest in academic research. Coatings and dental restoratives are interesting applications for thiol–ene photopolymerizations due to their unique features. In most studies the relative flexible and hydrophilic ester derivative, namely pentaerythritoltetra(3-mercaptopropionate (PETMP, is investigated as the thiol component. Thus, in the present study we are encouraged to investigate the performance of more hydrophobic ester-free thiol-modified bis- and trisphenol derivatives in thiol–ene photopolymerizations. For this, six different thiol-modified bis- and trisphenol derivatives exhibiting four to six thiol groups are synthesized via the radical addition of thioacetic acid to suitable allyl-modified precursors and subsequent hydrolysis. Compared to PETMP better flexural strength and modulus of elasticity are achievable in thiol–ene photopolymerizations employing 1,3,5-triallyl-1,3,5-triazine-2,4,6-trione (TATATO as the ene derivative. Especially, after storage in water, the flexural strength and modulus of elasticity is twice as high compared to the PETMP reference system.

Manganese oxide-based multifunctionalized mesoporous silica nanoparticles for pH-responsive MRI, ultrasonography and circumvention of MDR in cancer cells.

Science.gov (United States)

Chen, Yu; Yin, Qi; Ji, Xiufeng; Zhang, Shengjian; Chen, Hangrong; Zheng, Yuanyi; Sun, Yang; Qu, Haiyun; Wang, Zheng; Li, Yaping; Wang, Xia; Zhang, Kun; Zhang, Linlin; Shi, Jianlin

2012-10-01

Nano-biotechnology has been introduced into cancer theranostics by engineering a new generation of highly versatile hybrid mesoporous composite nanocapsules (HMCNs) for manganese-based pH-responsive dynamic T(1)-weighted magnetic resonance imaging (MRI) to efficiently respond and detect the tumor acidic microenvironment, which was further integrated with ultrasonographic function based on the intrinsic unique hollow nanostructures of HMCNs for potentially in vitro and in vivo dual-modality cancer imaging. The manganese oxide-based multifunctionalization of hollow mesoporous silica nanoparticles was achieved by an in situ redox reaction using mesopores as the nanoreactors. Due to the dissolution nature of manganese oxide nanoparticles under weak acidic conditions, the relaxation rate r(1) of manganese-based mesoporous MRI-T(1) contrast agents (CAs) could reach 8.81 mM(-1)s(-1), which is a 11-fold magnitude increase compared to the neutral condition, and is almost two times higher than commercial Gd(III)-based complex agents. This is also the highest r(1) value ever reported for manganese oxide nanoparticles-based MRI-T(1) CAs. In addition, the hollow interiors and thin mesoporous silica shells endow HMCNs with the functions of CAs for efficient in vitro and in vivo ultrasonography under both harmonic- and B-modes. Importantly, the well-defined mesopores and large hollow interiors of HMCNs could encapsulate and deliver anticancer agents (doxorubicin) intracellularly to circumvent the multidrug resistance (MDR) of cancer cells and restore the anti-proliferative effect of drugs by nanoparticle-mediated endocytosis process, intracellular drug release and P-gp inhibition/ATP depletion in cancer cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

Role of efflux pumps and intracellular thiols in natural antimony resistant isolates of Leishmania donovani.

Directory of Open Access Journals (Sweden)

Smita Rai

Full Text Available BACKGROUND: In view of the recent upsurge in the phenomenon of therapeutic failure, drug resistance in Leishmania, developed under natural field conditions, has become a great concern yet little understood. Accordingly, the study of determinants of antimony resistance is urgently warranted. Efflux transporters have been reported in Leishmania but their role in clinical resistance is still unknown. The present study was designed to elucidate the mechanism of natural antimony resistance in L. donovani field isolates by analyzing the functionality of efflux pump(s and expression profiles of known genes involved in transport and thiol based redox metabolism. METHODOLOGY/PRINCIPAL FINDINGS: We selected 7 clinical isolates (2 sensitive and 5 resistant in addition to laboratory sensitive reference and SbIII resistant mutant strains for the present study. Functional characterization using flow cytometry identified efflux pumps that transported substrates of both P-gp and MRPA and were inhibited by the calmodulin antagonist trifluoperazine. For the first time, verapamil sensitive efflux pumps for rhodamine 123 were observed in L. donovani that were differentially active in resistant isolates. RT-PCR confirmed the over-expression of MRPA in isolates with high resistance index only. Resistant isolates also exhibited consistent down regulation of AQP1 and elevated intracellular thiol levels which were accompanied with increased expression of ODC and TR genes. Interestingly, γ-GCS is not implicated in clinical resistance in L. donovani isolates. CONCLUSIONS/SIGNIFICANCE: Here we demonstrate for the first time, the role of P-gp type plasma membrane efflux transporter(s in antimony resistance in L. donovani field isolates. Further, decreased levels of AQP1 and elevated thiols levels have emerged as biomarkers for clinical resistance.

A fluorescent probe which allows highly specific thiol labeling at low pH

DEFF Research Database (Denmark)

Nielsen, Jonas W.; Jensen, Kristine Steen; Hansen, Rosa E.

2012-01-01

and properties of a thiol-specific reagent, fluorescent cyclic activated disulfide (FCAD), which includes the fluorescein moiety as fluorophore and utilizes a variation of thiol-disulfide exchange chemistry. The leaving-group character of FCAD makes it reactive at pH 3, allowing modification at low pH, limiting...

Preparation and Characterization of Fluorinated Hydrophobic UV-Crosslinkable Thiol-Ene Polyurethane Coatings

OpenAIRE

Wenjing Xia; Nianqing Zhu; Rongjie Hou; Wengui Zhong; Mingqing Chen

2017-01-01

The polyurethane prepolymer terminated with a double bond was synthesized using isophorone diisocyanate (IPDI), hydroxyl terminated polybutadiene (HTPB), 1,4-butanediol (BDO), and 2-hydroxyethyl acrylate (HEA). Then, a series of innovative UV-curable polyurethane coatings were prepared by blending ene-terminated polyurethane, fluoroacrylate monomer, and multifunctional thiol crosslinker upon UV exposure. The incorporation of fluoroacrylate monomer and multifunctional thiols into polyurethane ...

Novel strategy for the preparation of graphene-encapsulated mesoporous metal oxides with enhanced lithium storage

International Nuclear Information System (INIS)

Lin, Rong; Yue, Wenbo; Niu, Fangzhou; Ma, Jie

2016-01-01

As potential anode materials for lithium-ion batteries, mesoporous metal oxides show high reversible capacities but relatively poor cycle stability due to the structural collapse during cycles. Graphene-encapsulated mesoporous metal oxides may increase the electronic conductivity of the composite as well as stabilize the mesostructure of metal oxides, thereby enhancing the electrochemical performance of mesoporous metal oxides. Herein we describe a novel strategy for the preparation of graphene-encapsulated mesoporous metal oxides (SnO_2, Mn_3O_4), which exhibit superior electrochemical performance compared to pure mesoporous metal oxides. Moreover, some mesoporous metal oxides may be further reduced to low-valence metal oxides when calcined in presence of graphene. Mesoporous metal oxides with high isoelectric points are not essential for this synthesis method since metal oxides are connected with graphene through mesoporous silica template, thus expanding the types of graphene-encapsulated mesoporous metal oxides.

A general soft-enveloping strategy in the templating synthesis of mesoporous metal nanostructures.

Science.gov (United States)

Fang, Jixiang; Zhang, Lingling; Li, Jiang; Lu, Lu; Ma, Chuansheng; Cheng, Shaodong; Li, Zhiyuan; Xiong, Qihua; You, Hongjun

2018-02-06

Metal species have a relatively high mobility inside mesoporous silica; thus, it is difficult to introduce the metal precursors into silica mesopores and suppress the migration of metal species during a reduction process. Therefore, until now, the controlled growth of metal nanocrystals in a confined space, i.e., mesoporous channels, has been very challenging. Here, by using a soft-enveloping reaction at the interfaces of the solid, liquid, and solution phases, we successfully control the growth of metallic nanocrystals inside a mesoporous silica template. Diverse monodispersed nanostructures with well-defined sizes and shapes, including Ag nanowires, 3D mesoporous Au, AuAg alloys, Pt networks, and Au nanoparticle superlattices are successfully obtained. The 3D mesoporous AuAg networks exhibit enhanced catalytic activities in an electrochemical methanol oxidation reaction. The current soft-enveloping synthetic strategy offers a robust approach to synthesize diverse mesoporous metal nanostructures that can be utilized in catalysis, optics, and biomedicine applications.

Quantification of protein thiols and dithiols in the picomolar range using sodium borohydride and 4,4'-dithiodipyridine

DEFF Research Database (Denmark)

Hansen, Rosa E; Østergaard, Henrik; Nørgaard, Per

2007-01-01

Experimental determination of the number of thiols in a protein requires methodology that combines high sensitivity and reproducibility with low intrinsic thiol oxidation disposition. In detection of disulfide bonds, it is also necessary to efficiently reduce disulfides and to quantify...... the liberated thiols. Ellman's reagent (5,5'-dithiobis-[2-nitrobenzoic acid], DTNB) is the most widely used reagent for quantification of protein thiols, whereas dithiothreitol (DTT) is commonly used for disulfide reduction. DTNB suffers from a relatively low sensitivity, whereas DTT reduction is inconvenient...... sodium borohydride and the thiol reagent 4,4'-dithiodipyridine (4-DPS). Because borohydride is efficiently destroyed by the addition of acid, the complete reduction and quantification can be performed conveniently in one tube without desalting steps. Furthermore, the use of reverse-phase high...

Quinoline-2-thiol Derivatives as Fluorescent Sensors for Metals, pH and HNO

Directory of Open Access Journals (Sweden)

Naphtali A. O’Connor

2014-06-01

Full Text Available A tautomeric equilibrium exists for quinoline-2-thiol and quinoline-2(1H-thione. Quantum mechanical calculations predict the thione is the major tautomer and this is confirmed by the absorption spectra. The utility of quinolone-2-thiol/quinoline-2(1H-thione as a chromophore for developing fluorescent sensors is explored. No fluorescence is observed when excited at absorption maxima, however a fluorescence increase is observed when exposed to HNO, a molecule of import as a cardiovascular therapeutic. Alkylated quinoline-2-thiol derivatives are found to be fluorescent and show a reduction in fluorescence when exposed to metals and changes in pH.

Enzymatic Continuous Flow Synthesis of Thiol-Terminated Poly(δ-Valerolactone) and Block Copolymers.

Science.gov (United States)

Zhu, Ning; Huang, Weijun; Hu, Xin; Liu, Yihuan; Fang, Zheng; Guo, Kai

2018-04-01

Thiol-terminated poly(δ-valerolactone) is directly synthesized via enzymatic 6-mercapto-1-hexanol initiated ring-opening polymerization in both batch and microreactor. By using Candida antartica Lipase B immobilized tubular reactor, narrowly dispersed poly(δ-valerolactone) with higher thiol fidelity is more efficiently prepared in contrast to the batch reactor. Moreover, the integrated enzyme packed tubular reactor system is established to perform the chain extension experiments. Thiol-terminated poly(δ-valerolactone)-block-poly(ε-caprolactone) and poly(ε-caprolactone)-block-poly(δ-valerolactone) are easily prepared by modulating the monomer introduction sequence. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of mesoporous silica microsphere from dual surfactant

Directory of Open Access Journals (Sweden)

Venkatathri Narayanan

2008-12-01

Full Text Available A new procedure is reported to synthesis mesoporous silica micro sphere for the first time. In these method two surfactants namely Span 80 and Tween 80 were used. Small angle X ray diffraction and N2 adsorption analysis shows the synthesized material has mesoporous property. The material has spherical morphology with 1-10 µm particle size. Beside the material found to have microcapsule property as observed from the Transmission electron microscopy. The Fourier transform Infrared spectroscopic analysis reveals that the materials are similar to other mesoporous materials. We also encapsulated an UV-absorber Ibuprofen inside the microcapsule, by mixing it before the synthesis. This shows a possibility of the materials in cosmetic applications.

Advances in Multicompartment Mesoporous Silica Micro/Nanoparticles for Theranostic Applications.

Science.gov (United States)

Liu, Jian; Liu, Tingting; Pan, Jian; Liu, Shaomin; Lu, G Q Max

2018-04-04

Mesoporous silica nanoparticles (MSNs) are promising functional nanomaterials for a variety of biomedical applications, such as bioimaging, drug/gene delivery, and cancer therapy. This is due to their low density, low toxicity, high biocompatibility, large specific surface areas, and excellent thermal and mechanical stability. The past decade has seen rapid advances in the development of MSNs with multiple compartments. These include hierarchical porous structures and core-shell, yolk-shell, and Janus structured particles for efficient diagnosis and therapeutic applications. We review advances in this area, covering the categories of multicompartment MSNs and their synthesis methods, with an emphasis on hierarchical structures and the incorporation of multiple functions. We classify multicompartment mesoporous silica micro/nanostructures, ranging from core-shell and yolk-shell structures to Janus and raspberry-like nanoparticles, and discuss their synthesis methods. We review applications of these multicompartment MSNs, including bioimaging, targeted drug/gene delivery, chemotherapy, phototherapy, and in vitro diagnostics. We also highlight the latest trends and new opportunities. Expected final online publication date for the Annual Review of Chemical and Biomolecular Engineering Volume 9 is June 7, 2018. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Aspirin degradation in surface-charged TEMPO-oxidized mesoporous crystalline nanocellulose.

Science.gov (United States)

Carlsson, Daniel O; Hua, Kai; Forsgren, Johan; Mihranyan, Albert

2014-01-30

TEMPO-mediated surface oxidation of mesoporous highly crystalline Cladophora cellulose was used to introduce negative surface charges onto cellulose nanofibrils without significantly altering other structural characteristics. This enabled the investigation of the influence of mesoporous nanocellulose surface charges on aspirin chemical stability to be conducted. The negative surface charges (carboxylate content 0.44±0.01 mmol/g) introduced on the mesoporous crystalline nanocellulose significantly accelerated aspirin degradation, compared to the starting material which had significantly less surface charge (0.06±0.01 mmol/g). This effect followed from an increased aspirin amorphisation ability in mesopores of the oxidized nanocellulose. These results highlight the importance of surface charges in formulating nanocellulose for drug delivery. Copyright © 2013 Elsevier B.V. All rights reserved.

TiO2-coated mesoporous carbon: conventional vs. microwave-annealing process.

Science.gov (United States)

Coromelci-Pastravanu, Cristina; Ignat, Maria; Popovici, Evelini; Harabagiu, Valeria

2014-08-15

The study of coating mesoporous carbon materials with titanium oxide nanoparticles is now becoming a promising and challenging area of research. To optimize the use of carbon materials in various applications, it is necessary to attach functional groups or other nanostructures to their surface. The combination of the distinctive properties of mesoporous carbon materials and titanium oxide is expected to be applied in field emission displays, nanoelectronic devices, novel catalysts, and polymer or ceramic reinforcement. But, their synthesis is still largely based on conventional techniques, such as wet impregnation followed by chemical reduction of the metal nanoparticle precursors, which takes time and money. The thermal heating based techniques are time consuming and often lack control of particle size and morphology. Hence, since there is a growing interest in microwave technology, an alternative way of power input into chemical reactions through dielectric heating is the use of microwaves. This work is focused on the advantages of microwave-assisted synthesis of TiO2-coated mesoporous carbon over conventional thermal heating method. The reviewed studies showed that the microwave-assisted synthesis of such composites allows processes to be completed within a shorter reaction time allowing the nanoparticles formation with superior properties than that obtained by conventional method. Copyright © 2014 Elsevier B.V. All rights reserved.

Mesoporous carbon incorporated metal oxide nanomaterials as supercapacitor electrodes

Energy Technology Data Exchange (ETDEWEB)

Jiang, Hao [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China); School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Ma, Jan [School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Li, Chunzhong [Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237 (China)

2012-08-08

Supercapacitors have attracted huge attention in recent years as they have the potential to satisfy the demand of both huge energy and power density in many advanced technologies. However, poor conductivity and cycling stability remains to be the major challenge for its widespread application. Various strategies have been developed for meeting the ever-increasing energy and power demands in supercapacitors. This Research News article aims to review recent progress in the development of mesoporous carbon incorporated metal oxide nanomaterials, especially metal oxide nanoparticles confined in ordered mesoporous carbon and 1D metal oxides coated with a layer of mesoporous carbon for high-performance supercapacitor applications. In addition, a recent trend in supercapacitor development - hierarchical porous graphitic carbons (HPGC) combining macroporous cores, mesoporous walls, and micropores as an excellent support for metal oxides - is also discussed. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Importance of thiol-functionalized molecules for the structure and properties of compression-molded glassy wheat gluten bioplastics.

Science.gov (United States)

Jansens, Koen J A; Lagrain, Bert; Brijs, Kristof; Goderis, Bart; Smet, Mario; Delcour, Jan A

2013-11-06

High-temperature compression molding of wheat gluten at low water levels yields a rigid plastic-like material. We performed a systematic study to determine the effect of additives with multiple thiol (SH) groups on gluten network formation during processing and investigate the impact of the resulting gluten network on the mechanical properties of the glassy end product. To this end, a fraction of the hydroxyl groups of different polyols was converted into SH functionalities by esterifying with 3-mercaptopropionic acid (MPA). The monofunctional additive MPA was evaluated as well. During low-temperature mixing SH-containing additives decreased the gluten molecular weight, whereas protein cross-linking occurred during high-temperature compression molding. The extent of both processes depended on the molecular architecture of the additives and their concentration. After molding, the material strength and failure strain increased without affecting the modulus, provided the additive concentration was low. The strength decreased again at too high concentrations for polyols with low SH functionalization. Attributing these effects solely to the interplay of plasticization and the SH-facilitated introduction of cross-links is inadequate, since an improvement in both strength and failure strain was also observed in the presence of high levels of MPA. It is hypothesized that, regardless of the molecular structure of the additive, the presence of SH-containing groups induces conformational changes which contribute to the mechanical properties of glassy gluten materials.

Dinitrosyl iron complexes with thiol-containing ligands as a "working form" of endogenous nitric oxide.

Science.gov (United States)

Vanin, Anatoly F

2016-04-01

The material presented herein is an overview of the results obtained by our research team during the many years' study of biological activities and occurrence of dinitrosyl iron complexes (DNIC) with thiol-containing ligands in human and animal organisms. With regard to their dose dependence and vast diversity of biological activities, DNIC are similar to the system of endogenous NO, one of the most universal regulators of biological processes. The role of biologically active components in DNIC is played by their iron-dinitrosyl fragments, [Fe(NO)2], endowed with the ability to generate neutral NO molecules and nitrosonium ions (NO(+)). Their release is effected by heme-and thiol-containing proteins, which fulfill the function of biological targets and acceptors of NO and NO(+). Beneficial regulatory effects of DNIC on physiological and metabolic processes are numerous and diverse and include, among other things, lowering of arterial pressure and accelerated healing of skin wounds. In the course of fast decomposition of their Fe(NO)2 fragments (e.g., in the presence of iron chelators), DNIC produce adverse (cytotoxic) effects, which can best be exemplified by their ability to suppress the development of experimental endometriosis in animals. In animal tissues, DNIC with thiol-containing ligands are predominantly represented by the binuclear form, which, contrary to mononuclear DNIC detectable by the 2.03 signal, is EPR-silent. The ample body of evidence on biological activities and occurrence of DNIC gained so far clearly demonstrates that in human and animal organisms DNIC with thiol-containing ligands represent a "working form" of the system of endogenous NO responsible for its accumulation and stabilization in animal tissues as well as its further transfer to its biological targets. Copyright © 2016 Elsevier Inc. All rights reserved.

Characterization of an engineered cellulose based membrane by thiol dendrimer for heavy metals removal

OpenAIRE

Algarra, Manuel; Vázquez, María Isabel; Alonso, Beatriz S.; Casado, Carmen Mª.; Casado, Juan; Benavente, Juana

2014-01-01

Diaminobutane based poly(propyleneimine) dendrimer functionalized with sixteen thiol groups, DAB-3-(SH)16, was successfully embeded in a swollen cellulosic support in order to achieve an easily handle engineered membrane. The membrane was characterised by physicochemical, electrical and transport measurements, and the effect of the dendrimer was established by comparing these results with those obtained for the original cellulosic support. Results show that dendrimer inclusion improves the me...

Integration of the thiol redox status with cytokine response to physical training in professional basketball players.

Science.gov (United States)

Zembron-Lacny, A; Slowinska-Lisowska, M; Ziemba, A

2010-01-01

The present study was designed to evaluate the plasma markers of reactive oxygen species (ROS) activity and cytokines, and their relationship with thiol redox status of basketball players during training. Sixteen professional players of the Polish Basketball Extraleague participated in the study. The study was performed during the preparatory period and the play-off round. Markers of ROS activity (lipid peroxidation TBARS, protein carbonylation PC) and reduced glutathione (GSH) demonstrated regularity over time, i.e. TBARS, PC and GSH were elevated at the beginning and decreased at the end of training periods. Oxidized glutathione (GSSG) was not affected by exercise training. Thiol redox status (GSH(total)-2GSSG/GSSG) correlated with TBARS and PC in both training periods. The level of interleukin-6 (IL-6) was increased and positively correlated with thiol redox (r=0.423) in the preparatory period, whereas tumor necrosis factor alpha (TNFalpha) was increased and inversely correlated with thiol redox (r= 0.509) in the play-off round. The present study showed significant shifts in markers of ROS activity, thiol redox status and inflammatory mediators (IL-6, TNFalpha) following professional sport training as well as correlation between changes in thiol redox and cytokine response.

Generalized synthesis of mesoporous shells on zeolite crystals

KAUST Repository

Han, Yu

2010-12-30

A simple and generalized synthetic approach is developed for creating mesoporous shells on zeolite crystals. This method allows for the tailoring of thickness, pore size, and composition of the mesoporous shell, and can be applied to zeolites of various structures, compositions, and crystal sizes. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hierarchical zeolites: progress on synthesis and characterization of mesoporous zeolite single crystal catalysts

DEFF Research Database (Denmark)

Kustova, Marina; Egeblad, Kresten; Christensen, Claus H.

2007-01-01

Recently, a new family of crystalline zeolitic materials was reported, the so-called mesoporous zeolite single crystals featuring individual zeolite single crystals with an additional noncrystalline mesopore system interconnected with the usual micropore system of the zeolite, resulting...... measurements. Additionally, the results of diffusion of n-hexadecane in conventional and mesoporous zeolites are presented. Isomerization and cracking of n-hexadecane was chosen as model test reaction for these materials. All results support that mesoporous zeolites are superior catalysts due to improved mass...... transport. Importantly, the mesoporous zeolites show significant improved resistance to poisoning by carbon formation....

Thiol peroxidases mediate specific genome-wide regulation of gene expression in response to hydrogen peroxide

Science.gov (United States)

Fomenko, Dmitri E.; Koc, Ahmet; Agisheva, Natalia; Jacobsen, Michael; Kaya, Alaattin; Malinouski, Mikalai; Rutherford, Julian C.; Siu, Kam-Leung; Jin, Dong-Yan; Winge, Dennis R.; Gladyshev, Vadim N.

2011-01-01

Hydrogen peroxide is thought to regulate cellular processes by direct oxidation of numerous cellular proteins, whereas antioxidants, most notably thiol peroxidases, are thought to reduce peroxides and inhibit H2O2 response. However, thiol peroxidases have also been implicated in activation of transcription factors and signaling. It remains unclear if these enzymes stimulate or inhibit redox regulation and whether this regulation is widespread or limited to a few cellular components. Herein, we found that Saccharomyces cerevisiae cells lacking all eight thiol peroxidases were viable and withstood redox stresses. They transcriptionally responded to various redox treatments, but were unable to activate and repress gene expression in response to H2O2. Further studies involving redox transcription factors suggested that thiol peroxidases are major regulators of global gene expression in response to H2O2. The data suggest that thiol peroxidases sense and transfer oxidative signals to the signaling proteins and regulate transcription, whereas a direct interaction between H2O2 and other cellular proteins plays a secondary role. PMID:21282621

Thermal and hydrothermal stability of ZrMCM-41 mesoporous ...

Indian Academy of Sciences (India)

Administrator

The mesoporous structure of the ZrMCM-41 mesoporous molecular sieve still retains after calcination at 750°C for 3 h or ... adsorption, sensor and petrochemical industry. 2–5. However, the ... the pH value of the mixed solution was adjusted to.

Chromenoquinoline-based thiol probes: a study on the quencher position for controlling fluorescent Off-On characteristics.

Science.gov (United States)

Kand, Dnyaneshwar; Kalle, Arunasree Marasanapalli; Talukdar, Pinaki

2013-02-13

The design, synthesis and thiol sensing ability of chromenoquinoline-based fluorescent probes 4, 5 and 6 and are reported here. The relative position of the maleimide moiety was varied along the chromenoquinoline fluorophore to decrease the background fluorescence. Lower background fluorescence in probes 4 and 6 was rationalized by the smaller k(r)/k(nr) values compared to that of probe 5. An intramolecular charge transfer (ICT) mechanism was proposed for quenching and the extent was dependent on the position of the maleimide quencher. Fluorescent Off-On characteristics were evaluated by theoretical calculations. All probes were selective only towards thiol containing amino acids. Thiol sensing by probes 4 and 6 were much better compared to 5. Probe 4 displayed a better fluorescence response for less hindered thiol (185-, 223- and 156-fold for Hcy, Cys and GSH, respectively), while for probe 6, a higher enhancement in fluorescence was observed with more hindered thiols (180-, 205- and 245-fold for Hcy, Cys and GSH, respectively). The better response to bulkier thiol, GSH by probe 6 was attributed to the steric crowding at the C-4 position and bulkiness of the GSH group which force the succinimide unit to be in a nearly orthogonal conformation. This spatial arrangement was important in reducing the fluorescence quenching ability of the succinimide moiety. The application of probes 4, 5 and 6 was demonstrated by naked eye detection thiols using a 96-well plate system as well as by live-cell imaging.

Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons.

Science.gov (United States)

Lorenc-Grabowska, Ewa; Gryglewicz, Grazyna

2005-04-15

The adsorption by a coal-based mesoporous activated carbon of humic acids (HAs) isolated from two Polish lignites was studied. For comparison, a commercial Aldrich humic acid was also included into this study. The differences in chemical structure and functional groups of HAs were determined by elemental analysis and infrared spectroscopy DRIFT. Two activated carbons used differed in terms of mesopore volume, mesopore size distribution, and chemical properties of the surface. The kinetics of adsorption of HAs have been discussed using three kinetic models, i.e., the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. It was found that the adsorption of HAs from alkaline solution on mesoporous activated carbon proceeds according to the pseudo-second-order model. The correlation coefficients were close to 1. The intraparticle diffusion of HA molecules within the carbon particle was identified to be the rate-limiting step. Comparing the two activated carbons, the carbon with a higher volume of pores with widths of 10-50 nm showed a greater removal efficiency of HA. An increase in the Freundlich adsorption capacity with decreasing carbon content of HA was observed. Among the HAs studied, S-HA shows characteristics indicating the highest contribution of small-size fraction. The S-HA was removed by both activated carbons to the highest extent. The effect of pH solution on the adsorption of HA was examined over the range pH 5.4-12.2. It was found that the extent of adsorption decreased with decreasing pH of the solution.

NMR studies of organic liquids confined in mesoporous materials: (1) Pore size distribution and (2) Phase behaviour and dynamic studies in restricted geometry

International Nuclear Information System (INIS)

Foerland, Kjersti

2005-01-01

In the thesis NMR spectroscopy is used for studying liquids confined in various porous materials. In the first part, pore size distributions of mesoporous silicas and controlled pore glasses were determined by measuring the 1H NMR signal from the non-frozen fraction of the confined liquid as a function of temperature, using benzene, acetonitrile and HMDS as probe molecules. In the second part, the molecular dynamics of acetonitrile, hexamethyldisilane, cyclohexane and cyclopentane confined in mesoporous materials were studied as a function of temperature. 6 papers are included with titles: 1) Pore-size determination of mesoporous materials by 1H NMR spectroscopy. 2) Pore-size distribution in mesoporous materials as studied by 1H NMR. 3) Dynamic 1H and 2H NMR investigations of acetonitrile confined in porous silica. 4) NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies. 5) 1H and 2H NMR studies of cyclohexane nano crystals in controlled pore glasses. 6) 1H NMR relaxation and diffusion studies of cyclohexane and cyclopentane confined in MCM-41

NMR studies of organic liquids confined in mesoporous materials: (1) Pore size distribution and (2) Phase behaviour and dynamic studies in restricted geometry

Energy Technology Data Exchange (ETDEWEB)

Foerland, Kjersti

2005-07-01

In the thesis NMR spectroscopy is used for studying liquids confined in various porous materials. In the first part, pore size distributions of mesoporous silicas and controlled pore glasses were determined by measuring the 1H NMR signal from the non-frozen fraction of the confined liquid as a function of temperature, using benzene, acetonitrile and HMDS as probe molecules. In the second part, the molecular dynamics of acetonitrile, hexamethyldisilane, cyclohexane and cyclopentane confined in mesoporous materials were studied as a function of temperature. 6 papers are included with titles: 1) Pore-size determination of mesoporous materials by 1H NMR spectroscopy. 2) Pore-size distribution in mesoporous materials as studied by 1H NMR. 3) Dynamic 1H and 2H NMR investigations of acetonitrile confined in porous silica. 4) NMR investigations of hexamethyldisilane confined in controlled pore glasses: Pore size distribution and molecular dynamics studies. 5) 1H and 2H NMR studies of cyclohexane nano crystals in controlled pore glasses. 6) 1H NMR relaxation and diffusion studies of cyclohexane and cyclopentane confined in MCM-41.

Soft templating strategies for the synthesis of mesoporous materials: inorganic, organic-inorganic hybrid and purely organic solids.

Science.gov (United States)

Pal, Nabanita; Bhaumik, Asim

2013-03-01

With the discovery of MCM-41 by Mobil researchers in 1992 the journey of the research on mesoporous materials started and in the 21st century this area of scientific investigation have extended into numerous branches, many of which contribute significantly in emerging areas like catalysis, energy, environment and biomedical research. As a consequence thousands of publications came out in large varieties of national and international journals. In this review, we have tried to summarize the published works on various synthetic pathways and formation mechanisms of different mesoporous materials viz. inorganic, organic-inorganic hybrid and purely organic solids via soft templating pathways. Generation of nanoscale porosity in a solid material usually requires participation of organic template (more specifically surfactants and their supramolecular assemblies) called structure-directing agent (SDA) in the bottom-up chemical reaction process. Different techniques employed for the syntheses of inorganic mesoporous solids, like silicas, metal doped silicas, transition and non-transition metal oxides, mixed oxides, metallophosphates, organic-inorganic hybrids as well as purely organic mesoporous materials like carbons, polymers etc. using surfactants are depicted schematically and elaborately in this paper. Moreover, some of the frontline applications of these mesoporous solids, which are directly related to their functionality, composition and surface properties are discussed at the appropriate places. Copyright © 2012 Elsevier B.V. All rights reserved.

Monodisperse metal nanoparticle catalysts on silica mesoporous supports: synthesis, characterizations, and catalytic reactions

Energy Technology Data Exchange (ETDEWEB)

Somorjai, G.A.

2009-09-14

addition, Pt-mesoporous silica core-shell structured NPs (Pt{at}mSiO{sub 2}) were prepared, where the individual Pt NP is encapsulated by the mesoporous silica layer. The Pt{at}mSiO{sub 2} catalysts showed promising catalytic activity in high temperature CO oxidation. The design of catalytic structures with tunable parameters by rational synthetic methods presents a major advance in the field of catalyst synthesis, which would lead to uncover the structure-function relationships in heterogeneous catalytic reactions.

Surface PEGylation of mesoporous silica materials via surface-initiated chain transfer free radical polymerization: Characterization and controlled drug release.

Science.gov (United States)

Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Wan, Qing; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-12-01

As a new type of mesoporous silica materials with large pore diameter (pore size between 2 and 50nm) and high specific surface areas, SBA-15 has been widely explored for different applications especially in the biomedical fields. The surface modification of SBA-15 with functional polymers has demonstrated to be an effective way for improving its properties and performance. In this work, we reported the preparation of PEGylated SBA-15 polymer composites through surface-initiated chain transfer free radical polymerization for the first time. The thiol group was first introduced on SBA-15 via co-condensation with γ-mercaptopropyltrimethoxysilane (MPTS), that were utilized to initiate the chain transfer free radical polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and itaconic acid (IA) as the monomers. The successful modification of SBA-15 with poly(PEGMA-co-IA) copolymers was evidenced by a series of characterization techniques, including 1 H NMR, FT-IR, TGA and XPS. The final SBA-15-SH- poly(PEGMA-co-IA) composites display well water dispersity and high loading capability towards cisplatin (CDDP) owing to the introduction of hydrophilic PEGMA and carboxyl groups. Furthermore, the CDDP could be released from SBA-15-SH-poly(PEGMA-co-IA)-CDDP complexes in a pH dependent behavior, suggesting the potential controlled drug delivery of SBA-15-SH-poly(PEGMA-co-IA). More importantly, the strategy should be also useful for fabrication of many other functional materials for biomedical applications owing to the advantages of SBA-15 and well monomer adoptability of chain transfer free radical polymerization. Copyright © 2017 Elsevier B.V. All rights reserved.

Rational design of mesoporous metals and related nanomaterials by a soft-template approach.

Science.gov (United States)

Yamauchi, Yusuke; Kuroda, Kazuyuki

2008-04-07

We review recent developments in the preparation of mesoporous metals and related metal-based nanomaterials. Among the many types of mesoporous materials, mesoporous metals hold promise for a wide range of potential applications, such as in electronic devices, magnetic recording media, and metal catalysts, owing to their metallic frameworks. Mesoporous metals with highly ordered networks and narrow pore-size distributions have traditionally been produced by using mesoporous silica as a hard template. This method involves the formation of an original template followed by deposition of metals within the mesopores and subsequent removal of the template. Another synthetic method is the direct-template approach from lyotropic liquid crystals (LLCs) made of nonionic surfactants at high concentrations. Direct-template synthesis creates a novel avenue for the production of mesoporous metals as well as related metal-based nanomaterials. Many mesoporous metals have been prepared by the chemical or electrochemical reduction of metal salts dissolved in aqueous LLC domains. As a soft template, LLCs are more versatile and therefore more advantageous than hard templates. It is possible to produce various nanostructures (e.g., lamellar, 2D hexagonal (p6mm), and 3D cubic (Ia\\3d)), nanoparticles, and nanotubes simply by controlling the composition of the reaction bath.

The chemical foundations of nitroalkene fatty acid signaling through addition reactions with thiols.

Science.gov (United States)

Turell, Lucía; Steglich, Martina; Alvarez, Beatriz

2018-03-22

Nitroalkene fatty acids can be formed in vivo and administered exogenously. They exert pleiotropic signaling actions with cytoprotective and antiinflammatory effects. The presence of the potent electron withdrawing nitro group confers electrophilicity to the adjacent β-carbon. Thiols (precisely, thiolates) are strong nucleophiles and can react with nitroalkene fatty acids through reversible Michael addition reactions. In addition, nitroalkene fatty acids can undergo several other processes including metabolic oxidation, reduction, esterification, nitric oxide release and partition into hydrophobic compartments. The signaling actions of nitroalkenes are mainly mediated by reactions with critical thiols in regulatory proteins. Thus, the thio-Michael addition reaction provides a framework for understanding the molecular basis of the biological effects of nitroalkene fatty acids at the crossroads of thiol signaling and electrophilic lipid signaling. In this review, we describe the reactions of nitroalkene fatty acids in biological contexts. We focus on the Michael addition-elimination reaction with thiols and its mechanism, and extrapolate kinetic and thermodynamic considerations to in vivo settings. Copyright © 2018 Elsevier Inc. All rights reserved.

Thiol-ene reaction as tool for crosslinking of polynorbornene micelles in the nanoscale

Science.gov (United States)

Rupp, Barbara; Bauer, Thomas; Slugovc, Christian

2009-08-01

The thiol-ene reaction is a established photoreaction of multifunctional thiols and enes. Virtually any type of ene will participate in a free radical polymerisation process with a thiol. An advantage over many other photochemical reactions is that the reaction proceeds almost as rapidly in ambient conditions as in inert atmosphere. In this work we introduce the UV-crosslinking of polynorbornenes made by ring opening metathesis polymerization making use of the residual double bond in the polymer backbone. The crosslinking experiments were done in thin films and were followed by FTIR measurements, to proof the accessibility of double-bonds in the polymers for the addition of the thiols. As a result of these pre-experiments we created flexible and light transmitting films. To further increase the scope of this reaction, amphiphilic block copolymers were prepared and used to form block copolymer micelles in a selective solvent, which were subsequently crosslinked with pentaerythritol tetra(3-mercaptopropionate) (PETMP). FT-IR, DLS and SEM-measurements were used to prove the successful crosslinking and thus nanoparticle formation.

Facially amphiphilic thiol capped gold and silver nanoparticles

Indian Academy of Sciences (India)

Abstract. A series of bile acid-derived facially amphiphilic thiols have been used to cap sliver and gold nanoparticles. The self-assembling properties of these steroid-capped nanoparticles have been investigated and reported in this article.

Selective chromogenic detection of thiol-containing biomolecules using carbonaceous nanospheres loaded with silver nanoparticles as carrier.

Science.gov (United States)

Hu, Bo; Zhao, Yang; Zhu, Hai-Zhou; Yu, Shu-Hong

2011-04-26

Thiol-containing biomolecules show strong affinity with noble metal nanostructures and could not only stably protect them but also control the self-assembly process of these special nanostructures. A highly selective and sensitive chromogenic detection method has been designed for the low and high molecular weight thiol-containing biomolecules, including cysteine, glutathione, dithiothreitol, and bovine serum albumin, using a new type of carbonaceous nanospheres loaded with silver nanoparticles (Ag NPs) as carrier. This strategy relies upon the place-exchange process between the reporter dyes on the surface of Ag NPs and the thiol groups of thiol-containing biomolecules. The concentration of biomolecules can be determined by monitoring with the fluorescence intensity of reporter dyes dispersed in solution. This new chromogenic assay method could selectively detect these biomolecules in the presence of various other amino acids and monosaccharides and even sensitively detect the thiol-containing biomolecules with different molecular weight, even including proteins.

Studies of Aqueous U(IV) Complexation under Thiol-rich Conditions

International Nuclear Information System (INIS)

Cha, Wansik; Cho, Hyeryun; Jung, Euo Chang

2013-01-01

Organic thiol compounds and hydrogen sulfide (H 2 S) are electron donors and metabolic products of sulfate reducing bacteria. In addition, they are among redox potential (Eh) determinants of groundwater systems due to their redox characteristics. The low values of acid dissociation constants for .SH (pK a , 7-9) compared to those of aliphatic or phenolic .OH, impart greater anionic and metal-binding properties to the molecules. Recently, we demonstrated that a thiol compound (i. e., thiosalicylate) enhances the solubility of U(VI) at higher pH levels ( 2 nanoparticles may explain the observed solubility increase

Near-infrared emission from mesoporous crystalline germanium

Energy Technology Data Exchange (ETDEWEB)

Boucherif, Abderraouf; Aimez, Vincent; Arès, Richard, E-mail: richard.ares@usherbrooke.ca [Institut Interdisciplinaire d’Innovation Technologique (3IT), Université de Sherbrooke, 3000 Boulevard Université, Sherbrooke, J1K OA5, Québec (Canada); Laboratoire Nanotechnologies Nanosystèmes (LN2)-CNRS UMI-3463, Université de Sherbrooke, 3000 Boulevard Université, Sherbrooke, J1K OA5, Québec (Canada); Korinek, Andreas [Canadian Centre for Electron Microscopy, Brockhouse Institute for Materials Research, McMaster University, Hamilton, Ontario, L8S 4M1 (Canada)

2014-10-15

Mesoporous crystalline germanium was fabricated by bipolar electrochemical etching of Ge wafer in HF-based electrolyte. It yields uniform mesoporous germanium layers composed of high density of crystallites with an average size 5-7 nm. Subsequent extended chemical etching allows tuning of crystallites size while preserving the same chemical composition. This highly controllable nanostructure exhibits photoluminescence emission above the bulk Ge bandgap, in the near-infrared range (1095-1360nm) with strong evidence of quantum confinement within the crystallites.

Pharmacokinetic and toxicological evaluation of multi-functional thiol-6-fluoro-6-deoxy-d-glucose gold nanoparticles in vivo

Science.gov (United States)

Roa, Wilson; Xiong, Yeping; Chen, Jie; Yang, Xiaoyan; Song, Kun; Yang, Xiaohong; Kong, Beihua; Wilson, John; Xing, James Z.

2012-09-01

We synthesized a novel, multi-functional, radiosensitizing agent by covalently linking 6-fluoro-6-deoxy-d-glucose (6-FDG) to gold nanoparticles (6-FDG-GNPs) via a thiol functional group. We then assessed the bio-distribution and pharmacokinetic properties of 6-FDG-GNPs in vivo using a murine model. At 2 h, following intravenous injection of 6-FDG-GNPs into the murine model, approximately 30% of the 6-FDG-GNPs were distributed to three major organs: the liver, the spleen and the kidney. PEGylation of the 6-FDG-GNPs was found to significantly improve the bio-distribution of 6-FDG-GNPs by avoiding unintentional uptake into these organs, while simultaneously doubling the cellular uptake of GNPs in implanted breast MCF-7 adenocarcinoma. When combined with radiation, PEG-6-FDG-GNPs were found to increase the apoptosis of the MCF-7 breast adenocarinoma cells by radiation both in vitro and in vivo. Pharmacokinetic data indicate that GNPs reach their maximal concentrations at a time window of two to four hours post-injection, during which optimal radiation efficiency can be achieved. PEG-6-FDG-GNPs are thus novel nanoparticles that preferentially accumulate in targeted cancer cells where they act as potent radiosensitizing agents. Future research will aim to substitute the 18F atom into the 6-FDG molecule so that the PEG-6-FDG-GNPs can also function as radiotracers for use in positron emission tomography scanning to aid cancer diagnosis and image guided radiation therapy planning.

Ordered mesoporous silica-based inorganic nanocomposites

International Nuclear Information System (INIS)

Wang Qingqing; Shantz, Daniel F.

2008-01-01

This article reviews the synthesis and characterization of nanoparticles and nanowires grown in ordered mesoporous silicas (OMS). Summarizing work performed over the last 4 years, this article highlights the material properties of the final nanocomposite in the context of the synthesis methodology employed. While certain metal-OMS systems (e.g. gold in MCM-41) have been extensively studied this article highlights that there is a rich set of chemistries that have yet to be explored. The article concludes with some thoughts on future developments and challenges in this area. - Graphical abstract: HAADF TEM image of gold nanoparticles in amine-functionalized MCM-41 (from Ref. [22])

Structurally stabilized organosilane-templated thermostable mesoporous titania.

Science.gov (United States)

Amoli, Vipin; Tiwari, Rashmi; Dutta, Arghya; Bhaumik, Asim; Sinha, Anil Kumar

2014-01-13

Structurally thermostable mesoporous anatase TiO2 (m-TiO2) nanoparticles, uniquely decorated with atomically dispersed SiO2, is reported for the first time. The inorganic Si portion of the novel organosilane template, used as a mesopores-directing agent, is found to be incorporated in the pore walls of the titania aggregates, mainly as isolated sites. This is evident by transmission electron microscopy and high-angle annular dark field scanning transmission electron microscopy, combined with electron dispersive X-ray spectroscopy. This type of unique structure provides exceptional stability to this new material against thermal collapse of the mesoporous structure, which is reflected in its high surface area (the highest known for anatase titania), even after high-temperature (550 °C) calcination. Control of crystallite size, pore diameter, and surface area is achieved by varying the molar ratios of the titanium precursor and the template during synthesis. These mesoporous materials retain their porosity and high surface area after template removal and further NaOH/HCl treatment to remove silica. We investigate their performance for dye-sensitized solar cells (DSSCs) with bilayer TiO2 electrodes, which are prepared by applying a coating of m-TiO2 onto a commercial titania (P25) film. The high surface area of the upper mesoporous layer in the P25-m-TiO2 DSSC significantly increases the dye loading ability of the photoanode. The photocurrent and fill factor for the DSSC with the bilayer TiO2 electrode are greatly improved. The large increase in photocurrent current (ca. 56%) in the P25-m-TiO2 DSSC is believed to play a significant role in achieving a remarkable increase in the photovoltaic efficiency (60%) of the device, compared to DSSCs with a monolayer of P25 as the electrode. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multifunctional Mesoporous Carbon Capsules and their Robust Coatings for Encapsulation of Actives: Antimicrobial and Anti-bioadhesion Functions.

Science.gov (United States)

Mishra, Gargi; Mittal, Nitesh; Sharma, Ashutosh

2017-06-14

We present the synthesis and applications of multifunctional hollow porous carbon spheres with well-ordered pore architecture and ability to encapsulate functional nanoparticles. In the present work, the applications of hollow mesoporous carbon capsules (HMCCs) are illustrated in two different contexts. In the first approach, the hollow capsule core is used to encapsulate silver nanoparticles to impart antimicrobial characteristics. It is shown that silver-loaded HMCCs (concentration ∼100 μg/mL) inhibit the growth and multiplication of bacterial colonies of Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) up to 96% and 83%, respectively. In the second part, the fabrication of hierarchical micro- and nanostructured superhydrophobic coatings of HMCCs (without encapsulation with silver nanoparticles) is evaluated for anti-bioadhesion properties. Studies of protein adsorption and microorganism and platelet adhesion have shown a significant reduction (up to 100%) for the HMCC-based superhydrophobic surfaces compared with the control surfaces. Therefore, this unique architecture of HMCCs and their coatings with the ability to encapsulate functional materials make them a promising candidate for a variety of applications.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

Science.gov (United States)

Sachtler, W.M.H.; Huang, Y.Y.

1998-07-28

Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

Preparation of mesoporous carbon from fructose using zinc-based activators

Directory of Open Access Journals (Sweden)

Tutik Setianingsih

2015-07-01

Full Text Available Mesoporous carbons were synthesized from fructose using activators of zinc silicate (ZS, zinc borate (ZB, and zinc borosilicate (ZBS. The synthesis involves 3 steps, including caramelization of sugar, carbonization of caramel, and washing of carbon to separate the activator from the carbon. The solid products were characterized by N2 gas adsorption-desorption, X-ray diffraction, FTIR spectrophotometry, and Transmission Electron Microscopy. The pore characterizations of the carbons indicate that in ZBS system, ZB may have the role as mesopore size controller, whereas silica component may improve porosity created by ZB without changing the size. This role of ZB may be connected to it’s performance as catalyst of caramelization and it’s crystalinity, as supported by measurement of caramel intermediete and characterization of the activators with X-ray diffraction. The infrared spectra confirms that the carbons’s surfaces have C=O, C-O, and O-H functional groups. The XRD patterns of the carbons show that all activators create the turbotratic carbons.

Fast and efficient mesoporous adsorbents for the separation of toxic compounds from aqueous media.

Science.gov (United States)

Anbia, Mansoor; Mohammadi, Nourali; Mohammadi, Kaveh

2010-04-15

The effect of cationic template on the adsorption of chromium (VI), furfural and copperphthalocyanine-3,4',4'',4'''-tetrasulfonic acid tetrasodium salt (CuPc) in MCM-41 and MCM-48 mesoporous materials was investigated in this work. We used cetyltrimethylammonium bromide (CTAB) as the cationic template and sodiummetasilicate (for MCM-41) and tetraethyl-orthosilicon (for MCM-48) as the silica source for the synthesis of mesoporous materials. The properties of synthesized samples were characterized with XRD-low angle, SEM, N(2) adsorption-desorption and TG-DT analysis. The extent of adsorption was investigated as a function of solution pH, shaking speed, contact time, analyte concentration, reaction temperature and supporting electrolyte (sodium chloride) concentration. Langmuir and Freundlich isotherms were used to model the adsorption equilibrium data. The as-synthesized mesoporous samples showed very high adsorption capacity for the analytes and adsorption uptakes were rapid on the adsorbents reaching equilibrium in less than 2 h. The materials without surfactant did not show significant affinity for the analytes. 2009 Elsevier B.V. All rights reserved.

Systematically controlled pore system of ordered mesoporous carbons using phosphoric acid as the in situ generated catalysts for carbonization and activation

Energy Technology Data Exchange (ETDEWEB)

Jin, Xing; Lee, Chang Hyun; Kim, Jin Hoe; You, Dae Jong; Shon, Jeong Kuk; Kim, Ji Man [Dept. of Chemistry, Sungkyunkwan University, Suwon (Korea, Republic of); Pak, Chan Ho [Fuel Cell Group, Corporate R and D Center, Samsung SDI Co. Ltd., Yongin (Korea, Republic of)

2015-08-15

We report on a facile synthesis of the ordered mesoporous carbon (OMC) materials with systematically controlled microporosity and mesoporosity simultaneously through the nano-replication route using phosphoric acid as the acid catalyst and activation agent. The use of phosphoric acid affects the pore structures of OMC materials, such as the formation of numerous micropores by activation of the carbon framework and the enlargement of mesopores by spontaneous phase separation during the carbonization. The mesopore sizes, surface areas, total pore volumes, and micropore volumes of the OMC materials are highly dependent on the phosphoric acid content and can be systematically controlled in the range 3.7–7.5 nm, 1027–2782 m{sup 2} g{sup -1}, 1.12–3.53 cm{sup 3} g{sup -1} and 0.34–0.95 cm{sup 3} g{sup -1}, respectively. OMC materials with systematically controlled pore structures were successfully synthesized using phosphoric acid as the carbonization catalyst and mesoporous silica materials with cubic Ia3d and 2-D hexagonal mesostructures as the templates. The phosphoric acid in the synthesis of ordered mesoporous carbon materials acts as the chemical activating agent for micropore generation of the carbon framework and pore-expanding agent for controlling of mesopore size, in addition to functioning as the acid catalyst. The present synthesis pathway is very useful for preparing OMC materials with tunable mesopore sizes and well-developed microporosities at the same time.

Aromatization of alkanes over Pt promoted conventional and mesoporous gallosilicates of MEL zeolite

KAUST Repository

Akhtar, M. N.; Al-Yassir, N.; Al-Khattaf, S.; Čejka, Jiří

2012-01-01

Aromatization of hexane and propane was investigated over Pt promoted mesoporous gallium-containing HZSM-11 with controlled mesoporosity generated by desilication. Prepared catalysts were characterized by nitrogen adsorption, X-ray powder diffraction, scanning electron microscopy, Fourier transform infrared of chemisorbed pyridine, and NH 3 temperature programmed desorption confirming the development of intracrystalline mesoporosity of Ga-containing HZSM-11. The catalytic activities, which were compared in the aromatization of n-hexane and propane, increased upon desilication. The aromatization of n-hexane decreased in the following order, Pt/mesoporous GaZSM-11 Pt/conventional GaZSM-11 mesoporous GaZSM-11 > conventional GaZSM-11. Hexane conversion reached 70.1% over mesoporous Pt/GaZSM-11 with Si/Ga of 61, as compared with 29.6 and 24.9% for corresponding mesoporous and conventional GaZSM-11 (Si/Ga = 94), respectively, for experiments at liquid hour space velocity of 3.6 h -1, and 540 °C. Comparison of BTX (benzene-toluene-xylene) selectivity at the conversion level of ∼21.0% revealed that Pt/mesoporous GaZSM-11 is more selective than corresponding mesoporous and conventional GaZSM-11. The BTX selectivity over Pt/mesoporous GaZSM-11 (Si/Ga = 94), which showed strong dependence on the conversion, reached 28.2%, whereas over corresponding mesoporous and conventional GaZSM-11catalysts reached 19.1% and 5.5%, respectively. A higher conversion and better selectivity can be attributed to the improved accessibility to the active extra-framework Ga species owing to the generation of mesopores inside the zeolite particles and shortening the contact time. It is worth mentioning that the prepared catalysts exhibited quite low activity in propane aromatization but exhibiting similar trends as for hexane aromatization. © 2011 Elsevier B.V. All rights reserved.

Synthesis of mesoporous hollow silica nanospheres using polymeric micelles as template and their application as a drug-delivery carrier.

Science.gov (United States)

Sasidharan, Manickam; Zenibana, Haruna; Nandi, Mahasweta; Bhaumik, Asim; Nakashima, Kenichi

2013-10-07

Mesoporous hollow silica nanospheres with uniform particle sizes of 31-33 nm have been successfully synthesized by cocondensation of tetramethoxysilane (TMOS) and alkyltrimethoxysilanes [RSi(OR)3], where the latter also acts as a porogen. ABC triblock copolymer micelles of poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) with a core-shell-corona architecture have been employed as a soft template at pH 4. The cationic shell block with 2-vinyl pyridine groups facilitates the condensation of silica precursors under the sol-gel reaction conditions. Phenyltrimethoxysilane, octyltriethoxysilane, and octadecyltriethoxysilanes were used as porogens for generating mesopores in the shell matrix of hollow silica and the octadecyl precursor produced the largest mesopore among the different porogens, of dimension ca. 4.1 nm. The mesoporous hollow particles were thoroughly characterized by small-angle X-ray diffraction (SXRD), thermal (TG/DTA) and nitrogen sorption analyses, infra-red (FTIR) and nuclear magnetic resonance ((13)C-CP MAS NMR and (29)Si MAS NMR) spectroscopies, and transmission electron microscopy (TEM). The mesoporous hollow silica nanospheres have been investigated for drug-delivery application by an in vitro method using ibuprofen as a model drug. The hollow silica nanospheres exhibited higher storage capacity than the well-known mesoporous silica MCM-41. Propylamine functionalized hollow particles show a more sustained release pattern than their unfunctionalized counterparts, suggesting a huge potential of hollow silica nanospheres in the controlled delivery of small drug molecules.

Recent Advances in Catalysis Over Mesoporous Molecular Sieves

Czech Academy of Sciences Publication Activity Database

Martín-Aranda, R. M.; Čejka, Jiří

2010-01-01

Roč. 53, 3-4 (2010), s. 141-153 ISSN 1022-5528 R&D Projects: GA AV ČR KAN100400701; GA AV ČR IAA400400805; GA ČR GA104/09/0561 Institutional research plan: CEZ:AV0Z40400503 Keywords : mesoporous molecular sieves * MCM-41 * SBA-15 * mesoporous alumina Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.359, year: 2010

Chemical Design of Functional Nanomaterials

DEFF Research Database (Denmark)

Egeblad, Kresten

This thesis deals with a very specific class of functional nanomaterials known as mesoporous zeolites. Zeolites are a class of crystalline aluminosilicate minerals characterized by featuring pores or cavities of molecular dimensions as part of their crystal structure. Mesoporous zeolites are zeol...

Adsorption of vitamin E on mesoporous titania nanocrystals

International Nuclear Information System (INIS)

Shih, C.J.; Lin, C.T.; Wu, S.M.

2010-01-01

Tri-block nonionic surfactant and titanium chloride were used as starting materials for the synthesis of mesoporous titania nanocrystallite powders. The main objective of the present study was to examine the synthesis of mesoporous titania nanocrystals and the adsorption of vitamin E on those nanocrystals using X-ray diffraction (XRD), transmission electron microscopy, and nitrogen adsorption and desorption isotherms. When the calcination temperature was increased to 300 o C, the reflection peaks in the XRD pattern indicated the presence of an anatase phase. The crystallinity of the nanocrystallites increased from 80% to 98.6% with increasing calcination temperature from 465 o C to 500 o C. The N 2 adsorption data and XRD data taken after vitamin E adsorption revealed that the vitamin E molecules were adsorbed in the mesopores of the titania nanocrystals.

Single-Crystal Mesoporous ZnO Thin Films Composed of Nanowalls

KAUST Repository

Wang, Xudong; Ding, Yong; Li, Zhou; Song, Jinhui; Wang, Zhong Lin

2009-01-01

This paper presents a controlled, large scale fabrication of mesoporous ZnO thin films. The entire ZnO mesoporous film is one piece of a single crystal, while high porosity made of nanowalls is present. The growth mechanism was proposed

Nitroolefin-based BODIPY as a novel water-soluble ratiometric fluorescent probe for detection of endogenous thiols

Science.gov (United States)

Kang, Jin; Huo, Fangjun; Chao, Jianbin; Yin, Caixia

2018-04-01

Small molecule biothiols, including cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), play many crucial roles in physiological processes. In this work, we have prepared a nitroolefin-based BODIPY fluorescent probe with excellent water solubility for detection thiols, which displayed ratiometric fluorescent signal for thiols. Incorporation of a nitroolefin unit to the BODIPY dye would transform it into a strong Michael acceptor, which would be highly susceptible to sulfhydryl nucleophiles. This probe shows an obvious ratio change upon response with thiols, an increase of the emission at 517 nm along with a concomitant decrease of fluorescence peak at 573 nm. Moreover, these successes of intracellular imaging experiments in A549 cells indicated that this probe is suitable for imaging of ex-/endogenous thiols in living cells.

Conductivity of liquid lithium electrolytes with dispersed mesoporous silica particles

International Nuclear Information System (INIS)

Sann, K.; Roggenbuck, J.; Krawczyk, N.; Buschmann, H.; Luerßen, B.; Fröba, M.; Janek, J.

2012-01-01

Highlights: ► The conductivity of disperse lithium electrolytes with mesoporous fillers is studied. ► In contrast to other investigations in literature, no conductivity enhancement could be observed for standard battery electrolytes and typical mesoporous fillers in various combinations. ► Disperse electrolytes can become relevant in terms of battery safety. ► Dispersions of silicas and electrolyte with LiPF 6 as conducting salt are not stable, although the silicas were dried prior to preparation and the electrolyte water content was controlled. Surface modification of the fillers improved the stability. ► The observed conductivity decrease varied considerably for various fillers. - Abstract: The electrical conductivity of disperse electrolytes was systematically measured as a function of temperature (0 °C to 60 °C) and filler content for different types of fillers with a range of pore geometry, pore structure and specific surface area. As fillers mesoporous silicas SBA-15, MCM-41 and KIT-6 with pore ranges between 3 nm and 15 nm were dispersed in commercially available liquid lithium electrolytes. As electrolytes 1 M of lithium hexafluorophosphate (LiPF 6 ) in a mixture of ethylene carbonate (EC) and diethylene carbonate (DEC) at the ratio 3:7 (wt/wt) and the same solvent mixture with 0.96 M lithium bis(trifluoromethanesulfon)imide (LiTFSI) were used. No conductivity enhancement could be observed, but with respect to safety aspects the highly viscous disperse pastes might be useful. The conductivity decrease varied considerably for the different fillers.

Thiol/Disulfide system plays a crucial role in redox protection in the acidophilic iron-oxidizing bacterium Leptospirillum ferriphilum.

Directory of Open Access Journals (Sweden)

Javiera Norambuena

Full Text Available Thiol/disulfide systems are involved in the maintenance of the redox status of proteins and other molecules that contain thiol/disulfide groups. Leptospirillum ferriphilum DSM14647, an acidophilic bacterium that uses Fe(2+ as electron donor, and withstands very high concentrations of iron and other redox active metals, is a good model to study how acidophiles preserve the thiol/disulfide balance. We studied the composition of thiol/disulfide systems and their role in the oxidative stress response in this extremophile bacterium. Bioinformatic analysis using genomic data and enzymatic assays using protein extracts from cells grown under oxidative stress revealed that the major thiol/disulfide system from L. ferriphilum are a cytoplasmic thioredoxin system (composed by thioredoxins Trx and thioredoxin reductase TR, periplasmic thiol oxidation system (DsbA/DsbB and a c-type cytochrome maturation system (DsbD/DsbE. Upon exposure of L. ferriphilum to reactive oxygen species (ROS-generating compounds, transcriptional activation of the genes encoding Trxs and the TR enzyme, which results in an increase of the corresponding activity, was observed. Altogether these data suggest that the thioredoxin-based thiol/disulfide system plays an important role in redox protection of L. ferriphilum favoring the survival of this microorganism under extreme environmental oxidative conditions.

Mesoporous yttria-zirconia and metal-yttria-zirconia solid solutions for fuel cells

Energy Technology Data Exchange (ETDEWEB)

Mamak, M.; Coombs, N.; Ozin, G. [Toronto Univ., ON (Canada). Dept. of Chemistry

2000-02-03

A new class of binary mesoporous yttria-zirconia (YZ) and ternary mesoporous metal-YZ materials (M = electroactive Ni/Pt) is presented here that displays the highest surface area of any known form of yttria-stabilized zirconia. These mesoporous materials form as solid solutions and retain their structural integrity to 800 C, which bodes well for their possible utilization in fuel cells. (orig.)

Mesoporous silica obtained with methyltriethoxysilane as co-precursor in alkaline medium

Science.gov (United States)

Putz, Ana-Maria; Wang, Kunzhou; Len, Adél; Plocek, Jiri; Bezdicka, Petr; Kopitsa, Gennady P.; Khamova, Tamara V.; Ianăşi, Cătălin; Săcărescu, Liviu; Mitróová, Zuzana; Savii, Cecilia; Yan, Minhao; Almásy, László

2017-12-01

Mesoporous silica particles have been synthesized by sol-gel method from tetraethoxysilane (tetraethylorthosilicate, TEOS) and methyltriethoxysilane (MTES), in ethanol and water mixture, at different ratios of the of the silica precursors. Ammonia was used as catalyst at room temperature and hexadecyltrimethylammonium bromide (cetyltrimethylammonium bromide, CTAB) as the structure directing agent. Nitrogen sorption, X-ray diffraction and small-angle neutron scattering gave information on the evolution of the gel structure and pore morphologies in the function of MTES/TEOS molar ratio. Thermogravimetric and differential thermal analysis showed that with addition of MTES the exothermic peak indicating the oxidation of the low molecular weight organic fragments shift to higher temperature. A room-temperature, one-pot synthesis of MCM-41 type materials is presented, in which the variation of the MTES concentration allows to change the hydrophobicity, preserving the specific properties materials, like the ordered pore structure, large specific surface area and high porosity. Specifically, the obtained materials had cylindrical pores, specific surface areas up to 1101 m2/g and total pore volumes up to 0.473 cm3/g. The obtained mesoporous materials are susceptible for further functionalization to improve their selective uptake of guest species in drug delivery applications.