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1.
Chemosphere ; 239: 124825, 2020 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-31527007

RESUMO

Novel Cadmium Oxide-Graphene Nanocomposite Grown on Mesoporous Silica have been successfully prepared using a self-assembly method under the catering of cetyltrimethylammonium bromide (CTAB) as the surfactant template at ambient conditions. The structural and optical properties of the obtained nanocomposites were investigated by many different techniques. The results of photocatalytic measurements revealed that almost 100% of MB organic dye was removed with the presence of SiO2/CdO-graphene composite under visible light irradiation. Moreover, the initial pH also plays an important role in the photodegradation processes. On the other hand, this work opens a way to enhance the photocatalytic activity of gallic acid at ambient conditions without any further different oxidation processes. From the evolutionary aspect, SiO2/CdO-graphene composite revealed better H2 generation than that of binary photocatalyst (CdO-graphene nanocomposite). The results of characterization and photodegradation suggest that SiO2/CdO-graphene material constitutes a new photocatalyst for the degradation of organic contaminants, as well as the development of an efficient hetero-system for hydrogen production.


Assuntos
Compostos de Cádmio/química , Grafite/química , Hidrogênio/química , Nanocompostos/química , Compostos Orgânicos/química , Óxidos/química , Fotólise , Dióxido de Silício/química , Compostos Orgânicos/efeitos da radiação
2.
Biochim Biophys Acta Bioenerg ; 1861(1): 148087, 2020 01 01.
Artigo em Inglês | MEDLINE | ID: mdl-31669490

RESUMO

Electron bifurcating, [FeFe]-hydrogenases are recently described members of the hydrogenase family and catalyze a combination of exergonic and endergonic electron exchanges between three carriers (2 ferredoxinred- + NAD(P)H + 3 H+ = 2 ferredoxinox + NAD(P)+ + 2 H2). A thermodynamic analysis of the bifurcating, [FeFe]-hydrogenase reaction, using electron path-independent variables, quantified potential biological roles of the reaction without requiring enzyme details. The bifurcating [FeFe]-hydrogenase reaction, like all bifurcating reactions, can be written as a sum of two non-bifurcating reactions. Therefore, the thermodynamic properties of the bifurcating reaction can never exceed the properties of the individual, non-bifurcating, reactions. The bifurcating [FeFe]-hydrogenase reaction has three competitive properties: 1) enabling NAD(P)H-driven proton reduction at pH2 higher than the concurrent operation of the two, non-bifurcating reactions, 2) oxidation of NAD(P)H and ferredoxin simultaneously in a 1:1 ratio, both are produced during typical glucose fermentations, and 3) enhanced energy conservation (~10 kJ mol-1 H2) relative to concurrent operation of the two, non-bifurcating reactions. Our analysis demonstrated ferredoxin E°' largely determines the sensitivity of the bifurcating reaction to pH2, modulation of the reduced/oxidized electron carrier ratios contributed less to equilibria shifts. Hydrogenase thermodynamics data were integrated with typical and non-typical glycolysis pathways to evaluate achieving the 'Thauer limit' (4 H2 per glucose) as a function of temperature and pH2. For instance, the bifurcating [FeFe]-hydrogenase reaction permits the Thauer limit at 60 °C if pH 2 ≤ ~10 mbar. The results also predict Archaea, expressing a non-typical glycolysis pathway, would not benefit from a bifurcating [FeFe]-hydrogenase reaction; interestingly, no Archaea have been observed experimentally with a [FeFe]-hydrogenase enzyme.


Assuntos
Proteínas de Bactérias , Hidrogênio , Hidrogenase , Proteínas com Ferro-Enxofre , Thermotoga maritima/enzimologia , Anaerobiose/fisiologia , Proteínas de Bactérias/química , Proteínas de Bactérias/metabolismo , Hidrogênio/química , Hidrogênio/metabolismo , Hidrogenase/química , Hidrogenase/metabolismo , Proteínas com Ferro-Enxofre/química , Proteínas com Ferro-Enxofre/metabolismo , Oxirredução , Termodinâmica
3.
Top Curr Chem (Cham) ; 378(1): 6, 2019 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-31840192

RESUMO

Ferrites are a large class of oxides containing Fe3+ and at least another metal cation that have been investigated for and applied to a wide variety of fields ranging from mature technologies like circuitry, permanent magnets, magnetic recording and microwave devices to the most recent developments in areas like bioimaging, gas sensing and photocatalysis. In the last respect, although ferrites have been less studied than other types of semiconductors, they present interesting properties such as visible light absorption, tuneable optoelectronic properties and high chemical and photochemical stability. The versatility of their chemical composition and of their crystallographic structure opened a playground for developing new catalysts with enhanced efficiency. This article reviews the recent development of the application of ferrites to photoassisted processes for environmental remediation and for the synthesis of solar fuels. Applications in the photocatalytic degradation of pollutants in water and air, photo-Fenton, and solar fuels production, via photocatalytic and photoelectrochemical water splitting and CO2 reduction, are reviewed paying special attention to the relationships between the physico-chemical characteristics of the ferrite materials and their photoactivated performance.


Assuntos
Compostos Férricos/química , Luz Solar , Poluentes Atmosféricos/química , Dióxido de Carbono/química , Dióxido de Carbono/metabolismo , Catálise , Hidrogênio/química , Hidrogênio/metabolismo , Água/química , Purificação da Água
4.
Top Curr Chem (Cham) ; 377(6): 36, 2019 Nov 14.
Artigo em Inglês | MEDLINE | ID: mdl-31728773

RESUMO

Thermochemical lignin conversion processes can be described as complex reaction networks involving not only de-polymerization and re-polymerization reactions, but also chemical transformations of the depolymerized mono-, di-, and oligomeric compounds. They typically result in a product mixture consisting of a gaseous, liquid (i.e., mono-, di-, and oligomeric products), and solid phase. Consequently, researchers have developed a common strategy to simplify this issue by replacing lignin with simpler, but still representative, lignin model compounds. This strategy is typically applied to the elucidation of reaction mechanisms and the exploration of novel lignin conversion approaches. In this review, we present a general overview of the latest advances in the principal thermochemical processes applied for the conversion of lignin model compounds using heterogeneous catalysts. This review focuses on the most representative lignin conversion methods, i.e., reductive, oxidative, pyrolytic, and hydrolytic processes. An additional subchapter on the reforming of pyrolysis oil model compounds has also been included. Special attention will be given to those research papers using "green" reactants (i.e., H2 or renewable hydrogen donor molecules in reductive processes or air/O2 in oxidative processes) and solvents, although less environmentally friendly chemicals will be also considered. Moreover, the scope of the review is limited to those most representative lignin model compounds and to those reaction products that are typically targeted in lignin valorization.


Assuntos
Lignina/química , Biomassa , Catálise , Dimerização , Temperatura Alta , Hidrogênio/química , Hidrogênio/metabolismo , Hidrólise , Oxirredução , Pirólise
5.
Phys Chem Chem Phys ; 21(47): 26049-26057, 2019 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-31746862

RESUMO

A combination of tandem mass spectrometry (MS/MS) and hydrogen attachment dissociation (HAD) is a useful method for peptide sequence analysis. In this study, gas-phase fragmentation induced by the attachment of hydrogen to peptides containing disulfide bonds was investigated. Hydrogen attachment induced the cleavage of either the disulfide or N-Cα bond, which competitively occurred during HAD. The disulfide bond cleavage proceeded through an intermediate, which contains a thiyl radical (-S˙) and a thiol group (-SH). In contrast, N-Cα bond cleavage produced an intermediate containing an enol-imine group and α-carbon radical. The intermediate α-carbon radical then attacked the disulfide bond, resulting in a cyclic [z]+ fragment. The counterpart, [c + H]+˙ with a thiyl radical underwent further hydrogen attachment, producing [c + 2H]+. Because both disulfide and N-Cα bonds were cleaved by a single hydrogen attachment event, HAD-MS/MS can provide sequence information for the backbone region in the disulfide loop.


Assuntos
Dissulfetos/química , Hidrogênio/química , Peptídeos/química , Teoria da Densidade Funcional
6.
Phys Chem Chem Phys ; 21(41): 22849-22856, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31612167

RESUMO

Hyperpolarized metabolites are very attractive contrast agents for in vivo magnetic resonance imaging studies enabling early diagnosis of cancer, for example. Real-time production of concentrated solutions of metabolites is a desired goal that will enable new applications such as the continuous investigation of metabolic changes. To this end, we are introducing two NMR experiments that allow us to deliver high levels of polarization at high concentrations (50 mM) of an acetate precursor (55% 13C polarization) and acetate (17% 13C polarization) utilizing 83% para-state enriched hydrogen within seconds at high magnetic field (7 T). Furthermore, we have translated these experiments to a portable low-field spectrometer with a permanent magnet operating at 1 T. The presented developments pave the way for a rapid and affordable production of hyperpolarized metabolites that can be implemented in e.g. metabolomics labs and for medical diagnosis.


Assuntos
Técnicas de Química Analítica/métodos , Meios de Contraste/síntese química , Campos Magnéticos , Acetatos/química , Acetatos/metabolismo , Meios de Contraste/química , Hidrogênio/química , Imagem por Ressonância Magnética/instrumentação
7.
Nature ; 574(7779): 516-521, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31645723

RESUMO

Methods for selective C-H bond functionalization have provided chemists with versatile and powerful toolboxes for synthesis, such as the late-stage modification of a lead compound without the need for lengthy de novo synthesis1-5. Cleavage of an sp3 C-H bond via hydrogen atom transfer (HAT) is particularly useful, given the large number of available HAT acceptors and the diversity of reaction pathways available to the resulting radical intermediate6-17. Site-selectivity, however, remains a formidable challenge, especially among sp3 C-H bonds with comparable properties. If the intermediate radical could be further trapped enantioselectively, this should enable highly site- and enantioselective functionalization of C-H bonds. Here we report a copper (Cu)-catalysed site- and enantioselective allylic C-H cyanation of complex alkenes, in which a Cu(II)-bound nitrogen (N)-centred radical plays the key role in achieving precise site-specific HAT. This method is shown to be effective for a diverse collection of alkene-containing molecules, including sterically demanding structures and complex natural products and pharmaceuticals.


Assuntos
Carbono/química , Cobre/química , Hidrogênio/química , Alcenos/química , Produtos Biológicos/química , Catálise , Teoria da Densidade Funcional , Nitrogênio/química , Oxirredução , Preparações Farmacêuticas/química , Especificidade por Substrato
8.
Chem Commun (Camb) ; 55(86): 12928-12931, 2019 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-31599273

RESUMO

Herein we report for the first time the site-selective C-H bond arylation of tryptophan and tryptophan residues in proteins in aqueous media at room temperature by using a PdNP bionanohybrid as a heterogeneous catalyst. The reaction proceeds using a stable aryldiazonium salt without a base.


Assuntos
Nanopartículas Metálicas/química , Paládio/química , Proteínas/química , Triptofano/química , Carbono/química , Catálise , Hidrogênio/química , Temperatura Ambiente , Água/química
9.
Phys Chem Chem Phys ; 21(39): 21798-21805, 2019 Oct 09.
Artigo em Inglês | MEDLINE | ID: mdl-31573010

RESUMO

Composites of the noble metal Au supported on MgAl-LDHs were prepared by a simple impregnation-reduction method to be used as thermal- and photocatalysts for the photocatalytic degradation of ciprofloxacin and thermocatalytic decomposition of formic acid to produce hydrogen. A collection of techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) were employed to determine the structure and morphology properties of the as-prepared Au/MgAl-LDHs. The presence of surface Au(0) in Au/MgAl-LDHs was confirmed by TEM and XPS analyses. For the first time, we compared the effect of the surfactant PVP on the catalyst and found that the Au/MgAl-LDH composite with Au particle size of 2-8 nm had better catalytic activity than the (PVP@Au)/MgAl-LDH composite with Au particle size in the range of 1-5 nm. The sizes of Au NPs in the two catalysts were similar but had different effects on the catalytic performance. This indicated that the addition of PVP had an inhibitory effect on the catalytic activity of the catalyst. To evaluate the photostability of Au/MgAl-LDHs, recycle experiments for the photocatalytic degradation of ciprofloxacin were performed, and it was found that Au/MgAl-LDHs had good stability. Finally, we also applied Au/MgAl-LDHs in environmental catalysis and energy catalysis; we hope that they will be useful in practical applications.


Assuntos
Ligas/química , Alumínio/química , Ouro/química , Hidróxidos/química , Magnésio/química , Nanopartículas Metálicas/química , Adsorção , Catálise , Ciprofloxacino/química , Formiatos/química , Hidrogênio/química , Cinética , Oxirredução , Tamanho da Partícula , Processos Fotoquímicos , Propriedades de Superfície , Poluentes Químicos da Água/química
10.
Top Curr Chem (Cham) ; 377(6): 29, 2019 Oct 11.
Artigo em Inglês | MEDLINE | ID: mdl-31605243

RESUMO

Sustainable and high performance energy devices such as solar cells, fuel cells, metal-air batteries, as well as alternative energy conversion and storage systems have been considered as promising technologies to meet the ever-growing demands for clean energy. Hydrogen evolution reaction (HER) is a crucial process for cost-effective hydrogen production; however, functional electrocatalysts are potentially desirable to expedite reaction kinetics and supply high energy density. Thus, the development of inexpensive and catalytically active electrocatalysts is one of the most significant and challenging issues in the field of electrochemical energy storage and conversion. Realizing that advanced nanomaterials could engender many advantageous chemical and physical properties over a wide scale, tremendous efforts have been devoted to the preparation of earth-abundant transition metals as electrocatalysts for HER in both acidic and alkaline environments because of their low processing costs, reasonable catalytic activities, and chemical stability. Among all transition metal-based catalysts, nickel compounds are the most widely investigated, and have exhibited pioneering performances in various electrochemical reactions. Heterostructured nickel phosphide (NixPy) based compounds were introduced as promising candidates of a new category, which often display chemical and electronic characteristics that are distinct from those of non-precious metals counterparts, hence providing an opportunity to construct new catalysts with an improved activity and stability. As a result, the library of NixPy catalysts has been enriched very rapidly, with the possibility of fine-tuning their surface adsorption properties through synergistic coupling with nearby elements or dopants as the basis of future practical implementation. The current review distils recent advancements in NixPy compounds/hybrids and their application for HER, with a robust emphasis on breakthroughs in composition refinement. Future perspectives for modulating the HER activity of NixPy compounds/hybrids, and the challenges that need to be overcome before their practical use in sustainable hydrogen production are also discussed.


Assuntos
Hidrogênio/química , Níquel/química , Água/química , Catálise , Complexos de Coordenação/síntese química , Complexos de Coordenação/química , Técnicas Eletroquímicas , Nanoestruturas/química , Elementos de Transição/química
11.
Top Curr Chem (Cham) ; 377(5): 27, 2019 Sep 26.
Artigo em Inglês | MEDLINE | ID: mdl-31559502

RESUMO

The photocatalytic dehydrogenation of formic acid has recently emerged as an outstanding alternative to the traditional thermal catalysts widely applied in this reaction. The utilization of photocatalytic processes for the production of hydrogen is an appealing strategy that perfectly matches with the idea of a green and sustainable future energy scenario. However, it sounds easier than it is, and great efforts have been needed to design and develop highly efficient photocatalysts for the production of hydrogen from formic acid. In this work, some of the most representative strategies adopted for this application are reviewed, paying particular attention to systems based on TiO2, CdS and C3N4.


Assuntos
Formiatos/química , Hidrogênio/química , Catálise , Hidrogenação , Tamanho da Partícula , Processos Fotoquímicos
12.
Molecules ; 24(18)2019 Sep 12.
Artigo em Inglês | MEDLINE | ID: mdl-31547416

RESUMO

Various types of σ-hole bond complexes were formed with FX, HFY, H2FZ, and H3FT (X = Cl, Br, I; Y = S, Se, Te; Z = P, As, Sb; T = Si, Ge, Sn) as Lewis acid. In order to examine their interactions with a protein, N-methylacetamide (NMA), a model of the peptide linkage was used as the base. These noncovalent bonds were compared by computational means with H-bonds formed by NMA with XH molecules (X = F, Cl, Br, I). In all cases, the A-F bond, which lies opposite the base and is responsible for the σ-hole on the A atom (A refers to the bridging atom), elongates and its stretching frequency undergoes a shift to the red with a band intensification, much as what occurs for the X-H bond in a H-bond (HB). Unlike the NMR shielding decrease seen in the bridging proton of a H-bond, the shielding of the bridging A atom is increased. The spectroscopic changes within NMA are similar for H-bonds and the other noncovalent bonds. The C=O bond of the amide is lengthened and its stretching frequency red-shifted and intensified. The amide II band shifts to higher frequency and undergoes a small band weakening. The NMR shielding of the O atom directly involved in the bond rises, whereas the C and N atoms both undergo a shielding decrease. The frequency shifts of the amide I and II bands of the base as well as the shielding changes of the three pertinent NMA atoms correlate well with the strength of the noncovalent bond.


Assuntos
Calcogênios/química , Halogênios/química , Proteínas/química , Acetamidas/química , Hidrogênio/química , Ligações de Hidrogênio , Ácidos de Lewis/química , Ressonância Magnética Nuclear Biomolecular , Espectrofotometria Infravermelho
13.
Phys Chem Chem Phys ; 21(37): 21038-21048, 2019 Oct 07.
Artigo em Inglês | MEDLINE | ID: mdl-31528920

RESUMO

Dramatically different properties have been observed for two types of osmolytes, i.e., trimethylamine N-oxide (TMAO) and urea, in a protein folding process. Great progress has been made in revealing the potential underlying mechanism of these two osmolyte systems. However, many problems still remain unsolved. In this paper, we propose to use the persistent homology to systematically study the osmolytes' molecular aggregation and their hydrogen-bonding network from a global topological perspective. It has been found that, for the first time, TMAO and urea show two extremely different topological behaviors, i.e., an extensive network and local clusters, respectively. In general, TMAO forms highly consistent large loop or circle structures in high concentrations. In contrast, urea is more tightly aggregated locally. Moreover, the resulting hydrogen-bonding networks also demonstrate distinguishable features. With a concentration increase, TMAO hydrogen-bonding networks vary greatly in their total number of loop structures and large-sized loop structures consistently increase. In contrast, urea hydrogen-bonding networks remain relatively stable with slight reduction of the total loop number. Moreover, the persistent entropy (PE) is, for the first time, used in characterization of the topological information of the aggregation and hydrogen-bonding networks. The average PE systematically increases with the concentration for both TMAO and urea, and decreases in their hydrogen-bonding networks. But their PE variances have totally different behaviors. Finally, topological features of the hydrogen-bonding networks are found to be highly consistent with those from the ion aggregation systems, indicating that our topological invariants can characterize intrinsic features of the "structure making" and "structure breaking" systems.


Assuntos
Metilaminas/química , Ureia/química , Entropia , Hidrogênio/química , Ligações de Hidrogênio , Simulação de Dinâmica Molecular , Agregação Patológica de Proteínas , Homologia Estrutural de Proteína
14.
Photochem Photobiol Sci ; 18(11): 2673-2681, 2019 Nov 06.
Artigo em Inglês | MEDLINE | ID: mdl-31482917

RESUMO

The utilization of the light-harvesting and electron-transferring function of chlorophylls (Chls) has received attention for visible-light driven hydrogen production. In this work, a series of Chl derivatives based on pyropheophorbide-a (Pyro-a) conjugated with a viologen moiety, including a Pyro-a methyl ester directly bonded with the viologen at the 3-position 1, its 31-methylene analog 2 and Pyro-a connected with the viologen in the 17-substituent 3, were synthesized from chemical modification of naturally occurring Chl-a and characterized in terms of their photochemical and photophysical properties. As the photoexcited singlet state of the Pyro-a moiety was strongly quenched by the viologen moiety in a molecule, the effective photoinduced intramolecular electron transfer from Pyro-a to the bonded viologen moiety occurred. Moreover, these molecules were applied as a photosensitizer in the system for visible-light driven hydrogen production with platinum nanoparticles via intramolecular reduction of the bonded viologen moiety. Efficient photoreduction of external methyl viologen and successive hydrogen production on platinum nanoparticles were achieved using the synthetic conjugate of Pyro-a with the viologen moiety as a photosensitizer. In particular, effective visible-light driven hydrogen production was accomplished using 3 and platinum nanoparticles via the reduction of external methyl viologen.


Assuntos
Clorofila/análogos & derivados , Hidrogênio/química , Luz , Nanopartículas Metálicas/química , Platina/química , Clorofila/química , Transporte de Elétrons , Fármacos Fotossensibilizantes/química , Teoria Quântica , Viologênios/química
15.
Chemphyschem ; 20(19): 2408-2412, 2019 10 02.
Artigo em Inglês | MEDLINE | ID: mdl-31479580

RESUMO

Molecular hydrogen has unique nuclear spin properties. Its nuclear spin isomer, parahydrogen (pH2 ), was instrumental in the early days of quantum mechanics and allows to boost the NMR signal by several orders of magnitude. pH2- induced polarization (PHIP) is based on the survival of pH2 spin order in solution, yet its lifetime has not been investigated in aqueous or biological media required for in vivo applications. Herein, we report longitudinal relaxation times (T1 ) and lifetimes of pH2 ( τ P O C ) in methanol and water, with or without O2 , NaCl, rhodium-catalyst or human blood. Furthermore, we present a relaxation model that uses T1 and τ P O C for more precise theoretical predictions of the H2 spin state in PHIP experiments. All measured T1 values were in the range of 1.4-2 s and τ P O C values were of the order of 10-300 minutes. These relatively long lifetimes hold great promise for emerging in vivo implementations and applications of PHIP.


Assuntos
Hidrogênio/sangue , Hidrogênio/química , Humanos , Hidrogênio/análise , Soluções , Água/química
16.
Molecules ; 24(16)2019 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-31398800

RESUMO

Next-generation quantum theory of atoms in molecules (QTAIM) was used to investigate the competition between hydrogen bonding and halogen bonding for the recently proposed (Y = Br, I, At)/halogenabenzene/NH3 complex. Differences between using the SR-ZORA Hamiltonian and effective core potentials (ECPs) to account for relativistic effects with increased atomic mass demonstrated that next-generation QTAIM is a much more responsive tool than conventional QTAIM. Subtle details of the competition between halogen bonding and hydrogen bonding were observed, indicating a mixed chemical character shown in the 3-D paths constructed from the bond-path framework set B. In addition, the use of SR-ZORA reduced or entirely removed spurious features of B on the site of the halogen atoms.


Assuntos
Benzeno/química , Halogênios/química , Hidrogênio/química , Teoria Quântica , Algoritmos , Ligações de Hidrogênio , Modelos Moleculares , Modelos Teóricos , Conformação Molecular
17.
Molecules ; 24(15)2019 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-31370260

RESUMO

Non-metal cation (NMC) pentaborate structures, in which some amino acids (valine, leucine, isoleucine, and threonine) were used as cations, were synthesized. The structural characterization of molecules was carried out by elemental analysis, FT-IR, mass, 11B-NMR, and thermal analysis (TGA/DTA) methods. The hydrogen storage capacity of molecules was also calculated by taking experimental results into consideration. The FT-IR spectra support the similarity of structures. The characteristic peaks attributable to pentaborate rings and amino acids were observed. When thermal analysis data were examined, it was observed that pentaborate salts gave similar degradation steps and degradation products. As a final degradation product of all thermal analysis experiments, a glassy form of B2O3 was observed. The valine pentaborate is the most thermally stable. Also, the amounts of hydrate water outside the coordination sphere of the compounds were determined by thermal analysis curves. The peaks of boric acid, triborate, and pentaborate structures were obtained in ppm with the 11B-NMR results of synthesized pentaborate compounds. With powder X-ray spectroscopy, all structures were found to be crystalline but not suitable for single-crystal X-ray analysis. The molecular cavities of the compounds detected by BET were found to be 3.286, 1.873, 2.309, and 1.860 g/cm3, respectively. A low number of molecular cavities can be interpreted in several existing hydrogen bonds in structures. The hydrogen storage capacities of the molecules were found to be in the range of 0.04 to 0.07% by mass.


Assuntos
Aminoácidos/química , Cátions/química , Hidrogênio/química , Sais/química , Ligações de Hidrogênio , Espectroscopia de Ressonância Magnética , Metais/química , Estrutura Molecular , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura Ambiente , Água/química , Difração de Raios X
18.
Molecules ; 24(15)2019 Jul 31.
Artigo em Inglês | MEDLINE | ID: mdl-31370373

RESUMO

While the overwhelming number of papers on multi-principal-element alloys (MPEAs) focus on the mechanical and microstructural properties, there has been growing interest in these alloys as solid-state hydrogen stores. We report here the synthesis optimization, the physicochemical and the hydrogen sorption properties of Ti0.325V0.275Zr0.125Nb0.275. This alloy was prepared by two methods, high temperature arc melting and ball milling under Ar, and crystallizes into a single-phase bcc structure. This MPEA shows a single transition from the initial bcc phase to a final bct dihydride and a maximum uptake of 1.7 H/M (2.5 wt%). Interestingly, the bct dihydride phase can be directly obtained by reactive ball milling under hydrogen pressure. The hydrogen desorption properties of the hydrides obtained by hydrogenation of the alloy prepared by arc melting or ball milling and by reactive ball milling have been compared. The best hydrogen sorption properties are shown by the material prepared by reactive ball milling. Despite a fading of the capacity for the first cycles, the reversible capacity of the latter material stabilizes around 2 wt%. To complement the experimental approach, a theoretical investigation combining a random distribution technique and first principle calculation was done to estimate the stability of the hydride.


Assuntos
Ligas/química , Hidrogênio/química , Nanoestruturas/química , Adsorção , Ligas/síntese química , Cristalização , Teste de Materiais , Propriedades de Superfície , Vanádio/química
19.
Phys Chem Chem Phys ; 21(34): 18741-18752, 2019 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-31424464

RESUMO

Medical application of nanotechnology implies the development of nanomaterials capable of being functional in different biological environments. In this sense, elongated nanoparticles (e-MNPs) with high-aspect ratio have demonstrated more effective particle cellular internalization, which is favoured by the increased surface area. This paper makes use of an environmentally friendly hydrothermal method to produce magnetic iron oxide e-MNPs, starting from goethite precursors. At high temperatures (Td) goethite transforms into hematite, which subsequently reduces to magnetite when exposed to a hydrogen atmosphere for a certain time. It is shown that by adjusting Td it is possible to obtain Fe3O4 e-MNPs with partially controlled specific surface area and magnetic properties, attributed to different porosity of the samples. The particles' efficiencies for diagnostic and therapeutic purposes (in magnetic resonance imaging and magnetic fluid hyperthermia, respectively) are very good in terms of clinical standards, some samples showing transversal proton nuclear relaxivity r2 (B0 = 1.33 T) = 340 s-1 mM-1 and specific absorption rate SAR > 370 W g-1 at high field amplitudes (B0 = 55 mT). Direct correlations between the SAR, relaxivity, magnetic properties and porosity of the samples are found, and the physico-chemical processes underneath these correlations are investigated. Our results open the possibility of using very efficient high-aspect ratio elongated nanoparticles with optimized chemico-physical properties for biomedical applications.


Assuntos
Nanopartículas de Magnetita/química , Temperatura Alta , Hidrogênio/química , Magnetismo , Conformação Molecular , Fenômenos Físicos , Dióxido de Silício/química , Propriedades de Superfície
20.
Clin Biochem ; 73: 98-104, 2019 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-31425671

RESUMO

Here we validate a GC, Flame Ionization Detection (GC-FID), liquid injection method using hydrogen as a carrier gas combining analysis of toxic volatile alcohols (VA): methanol, ethanol, isopropanol, acetone, as well as glycols, ethylene glycol (EG) and propylene glycol (PG), in a single method. METHODOLOGY: 200 µL of calibrator, QC, or patient specimen were deproteinized with 400 µL of acetonitrile containing internal standards (10 mmol/L N-propyl alcohol for VA and 2.5 mmol/L 1,2-butanediol for glycols). GC-FID analysis using hydrogen carrier gas and nitrogen makeup gas utilized an Agilent 7890 system equipped with Agilent 7683 liquid autosampler on a 30 m × 530 µm RTX-200 fused silica column. Method validation included repeatability, recovery, carryover, linearity, lower limit of quantification (LLOQ), accuracy, selectivity and measurement uncertainty. RESULTS: The 8.3 min from injection to injection reduced time of analysis by 45% over a previously reported method using Helium carrier gas with no loss in resolution. Within-run and Between-run variability were ≤1.4% and ≤6.8% respectively. Recovery was 100% within a 95% confidence interval. Carryover was negligible for all but EG. LLOQ was <1 mmol/L for all analytes. The upper range of linearity was 120 mmol/L for methanol, ethanol and isopropanol, 100 mmol/L for acetone and 50 mmol/L for EG. Analytes demonstrated acceptable accuracy and measurement uncertainty using College of American Pathologists (CAP) criteria. Toluene can cause a false positive EG, while benzene, xylene and 1,3 butanediol can cause false negative EG. CONCLUSIONS: Converting from Helium to Hydrogen carrier gas benefits patient care through a reduction in turnaround time and provides a cost savings to the laboratory.


Assuntos
Etilenoglicol/sangue , Álcoois Graxos/sangue , Hélio/química , Hidrogênio/química , Calibragem , Cromatografia Gasosa , Feminino , Ionização de Chama , Humanos , Masculino
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