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1.
Angew Chem Int Ed Engl ; 63(26): e202404025, 2024 Jun 21.
Article in English | MEDLINE | ID: mdl-38659286

ABSTRACT

Reactive metals hydrolysis offers significant advantages for hydrogen storage and production. However, the regeneration of common reactive metals (e.g., Mg, Al, etc.) is energy-intensive and produces unwanted byproducts such as CO2 and Cl2. Herein, we employ Zn as a reactive mediator that can be easily regenerated by electrolysis of ZnO in an alkaline solution with a Faradaic efficiency of >99.9 %. H2 is produced in the same electrolyte by constructing a Zn-H2O hydrolysis battery consisting of a Zn anode and a Raney-Ni cathode to unlock the Zn-H2O reaction. The entire two-step water splitting reaction with a net energy efficiency of 70.4 % at 80 °C and 50 mA cm-2. Additionally, the Zn-H2O system can be charged using renewable energy to produce H2 on demand and runs for 600 cycles only sacrificing 3.76 % energy efficiency. DFT calculations reveal that the desorption of H* on Raney-Ni (-0.30 eV) is closer to zero compared with that on Zn (-0.87 eV), indicating a faster desorption of H* at low overpotential. Further, a 24 Ah electrolyzer is demonstrated to produce H2 with a net energy efficiency of 65.5 %, which holds promise for its real application.

2.
Chin J Nat Med ; 22(4): 365-374, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38658099

ABSTRACT

Phorbol esters are recognized for their dual role as anti-HIV-1 agents and as activators of protein kinase C (PKC). The efficacy of phorbol esters in binding with PKC is attributed to the presence of oxygen groups at positions C20, C3/C4, and C9 of phorbol. Concurrently, the lipids located at positions C12/C13 are essential for both the anti-HIV-1 activity and the formation of the PKC-ligand complex. The influence of the cyclopropane ring at positions C13 and C14 in phorbol derivatives on their anti-HIV-1 activity requires further exploration. This research entailed the hydrolysis of phorbol, producing seco-cyclic phorbol derivatives. The anti-HIV-1 efficacy of these derivatives was assessed, and the affinity constant (Kd) for PKC-δ protein of selected seco-cyclic phorbol derivatives was determined through isothermal titration calorimetry. The findings suggest that the chemical modification of cyclopropanols could affect both the anti-HIV-1 activity and the PKC binding affinity. Remarkably, compound S11, with an EC50 of 0.27 µmol·L-1 and a CC50 of 153.92 µmol·L-1, demonstrated a potent inhibitory effect on the intermediate products of HIV-1 reverse transcription (ssDNA and 2LTR), likely acting at the viral entry stage, yet showed no affinity for the PKC-δ protein. These results position compound S11 as a potential candidate for further preclinical investigation and for studies aimed at elucidating the pharmacological mechanism underlying its anti-HIV-1 activity.


Subject(s)
Anti-HIV Agents , HIV-1 , HIV-1/drug effects , Humans , Anti-HIV Agents/pharmacology , Anti-HIV Agents/chemistry , Phorbol Esters/pharmacology , Phorbol Esters/chemistry , Molecular Structure , Protein Kinase C/metabolism , Protein Kinase C/chemistry , Structure-Activity Relationship
3.
J Hazard Mater ; 460: 132313, 2023 10 15.
Article in English | MEDLINE | ID: mdl-37619277

ABSTRACT

The degradation of organic pollutants and the adsorption of organic pollutants onto microplastics (MPs) in the environment have recently been intensively studied, but the effects of biocurrents, which are widespread in various soil environments, on the environmental behavior of MPs and antibiotic pollutants have not been reported. In this study, it was found that polylactic acid (PLA) and polyvinyl chloride (PVC) MPs accelerated the mineralization of humic substances in microbial electrochemical systems (MESs). After tetracycline (TC) was introduced into the MESs, the internal resistance of the soil MESs decreased. Additionally, the presence of MPs enhanced the charge output of the soil MESs by 40% (PLA+TC) and 18% (PVC+TC) compared with a control group without MPs (424 C). The loss in MP mass decreased after TC was added, suggesting a promotion of TC degradation rather than MP degradation for charge output. MPs altered the distribution of the highest occupied molecular orbitals and lowest unoccupied molecular orbitals of TC molecules and reduced the energy barrier for the TC hydrolysis reaction. The microbial community of the plastisphere exhibited a greater ability to degrade xenobiotics than the soil microbial community, indicating that MPs were hotspots for TC degradation. This study provides the first glimpse into the influence of MPs on the degradation of TC in MESs, laying a theoretical and methodological foundation for the systematic evaluation of the potential risks of environmental pollutants in the future.


Subject(s)
Environmental Pollutants , Microplastics , Plastics , Soil , Soil Microbiology , Tetracycline , Anti-Bacterial Agents , Polyesters
4.
Polymers (Basel) ; 15(12)2023 Jun 13.
Article in English | MEDLINE | ID: mdl-37376311

ABSTRACT

As a temperature-resistant and salt-resistant polymer, acrylamide and 2-acrylamide-2-methylpropane sulfonic acid (abbreviated as AM-AMPS) copolymer is currently widely used in drilling, water control and oil production stabilization, enhanced oil recovery and other fields, but its stability under high temperature has been less studied. The degradation process of the AM-AMPS copolymer solution was studied by measuring viscosity, the degree of hydrolysis, and weight-average molecular weight at different temperatures and aging time. During the high-temperature aging process, the viscosity of the AM-AMPS copolymer saline solution first increases and then decreases. The combined action of the hydrolysis reaction and the oxidative thermal degradation leads to the change of the viscosity of the AM-AMPS copolymer saline solution. The hydrolysis reaction of the AM-AMPS copolymer mainly affects the structural viscosity of its saline solution through intramolecular and intermolecular electrostatic interactions, while the oxidative thermal degradation mainly reduces its molecular weight by breaking the main chain of the copolymer molecules, reducing the viscosity of the AM-AMPS copolymer saline solution. The content of AM and AMPS groups in the AM-AMPS copolymer solution at various temperatures and aging time was analyzed using liquid nuclear magnetic resonance carbon spectroscopy, demonstrating that the hydrolysis reaction rate constant of AM groups was significantly higher than that of AMPS groups. The contribution values of hydrolysis reaction and oxidative thermal degradation of the AM-AMPS copolymer at different aging time to viscosity were quantitatively calculated at temperatures ranging from 104.5 °C to 140 °C. It was determined that the higher the heat treatment temperature, the smaller the contribution of hydrolysis reaction to viscosity, while the bigger the contribution of oxidative thermal degradation to the viscosity of the AM-AMPS copolymer solution.

5.
Biochem Biophys Res Commun ; 652: 31-34, 2023 04 16.
Article in English | MEDLINE | ID: mdl-36809702

ABSTRACT

Vibrational strong coupling (VSC) has been reported as a polariton-based method for modulating the rate of biochemical reactions. Herein, we studied how VSC modulates the sucrose hydrolysis. By monitoring the refractive index-induced shift of Fabry-Pérot microcavity, in which the catalytic efficiency of sucrose hydrolysis can be increased at least two times, as VSC was tuned to resonate with the stretching vibration of O-H bonds. This research provides new evidence for applying VSC in life sciences, which holds great promise to improving enzymatic industries.


Subject(s)
Biological Science Disciplines , Sucrase , Vibration , Catalysis , Sucrose
6.
Chemistry ; 29(13): e202203207, 2023 Mar 01.
Article in English | MEDLINE | ID: mdl-36469422

ABSTRACT

Developing a highly efficient bifunctional catalyst for hydrolysis of metal hydrides and spontaneous hydrogen evolution reaction (HER) is essential for substituting conventional fuels for H2 production. Herein, Ru-cluster-modified Co3 B-Co(OH)2 supported on nickel foam (Ru/Co3 B-Co(OH)2 @NF) is constructed by electroless deposition, calcination and chemical reduction. The catalyst exhibits an excellent hydrogen generation rate (HGR) of 4989 mL min-1 g c a t a l y s t - 1 ${{{\rm g}}_{catalyst}^{-1}}$ and good reusability, superior to most previously reported catalysts. Besides, Ru/Co3 B-Co(OH)2 @NF displays a prominent hydrogen evolution reaction catalytic capability with a low overpotential of 153.0 mV at 100 mA cm-2 (50.5 mV at 10 mA cm-2 ), a small Tafel slope of 40.0 mV dec-1 and long-term stability (100 h@10 mA cm-2 ) in 1.0 M KOH. The excellent catalytic H2 generation capacity benefits from the rapid charge transfer promoted by metallic Co3 B, the synergistic catalytic effect of Co3 B-Co(OH)2 and Ru clusters, and the unique composite structure favorable for solute transport and gas emission.

7.
Article in Chinese | WPRIM (Western Pacific) | ID: wpr-998176

ABSTRACT

ObjectiveTo investigate the transformation mechanism and content variation of saponins from Polygalae Radix before and after being boiled with licorice juice and water. MethodSimulated licorice juice boiled products and simulated water boiled products of onjisaponin B, onjisaponin Z, onjisaponin F, polygalasaponin ⅩⅩⅧ were prepared by simulated processing technology, and analyzed by ultra-performance liquid chromatography-quadrupole-electrostatic field orbitrap high resolution mass spectrometry(UPLC-Q-Exactive Orbitrap/MS). Then the contents of onjisaponin B, onjisaponin Z, onjisaponin F, polygalasaponin ⅩⅩⅧ and tenuifolin in Polygalae Radix, licorice-boiled Polygalae Radix and water-boiled Polygalae Radix were determined by UPLC-triple quadrupole tandem mass spectrometry(UPLC-QQQ-MS/MS). ResultDuring the boiling process with licorice juice and water, onjisaponin B could be hydrolyzed to produce 4-methoxycinnamic acid, desacylsenegin Ⅲ, polygalasaponin ⅩⅩⅧ and tenuifolin, onjisaponin Z could be hydrolyzed to produce 3,4,5-trimethoxycinnamic acid, onjisaponin TF, polygalasaponin ⅩⅩⅧ and tenuifolin, onjisaponin F could be hydrolyzed to produce 3,4,5-trimethoxycinnamic acid, onjisaponin G, polygalasaponin ⅩⅩⅧ and tenuifolin, and polygalasaponin ⅩⅩⅧ was hydrolyzed to produce tenuifolin. After being boiled with licorice juice or water, the content of onjisaponin B decreased significantly(P<0.05, P<0.01), but the contents of onjisaponin Z, onjisaponin F, polygalasaponin ⅩⅩⅧ and tenuifolin increased significantly(P<0.05, P<0.01) in Polygalae Radix. Compared with the water-boiled products, the contents of onjisaponin Z and tenuifolin increased significantly(P<0.05, P<0.01), and the change of tenuifolin content was the most significant in the licorice-boiled products.However, there was no significant difference in the content of onjisaponin B, onjisaponin F and polygalasaponin ⅩⅩⅧ between the water-boiled products and the licorice-boiled products. ConclusionBeing boiled with licorice juice or water can hydrolyze onjisaponin B, onjisaponin Z, onjisaponin F and polygalasaponin ⅩⅩⅧ, and generate secondary glycosides and aglycones(organic acids) through deglycosylation, which leads to obvious changes in the contents of onjisaponins after Polygalae Radix being processed.It is inferred that licorice juice can promote the hydrolysis of some onjisaponins in Polygalae Radix to onjisaponin Z and tenuifolin.This study provides an experimental basis for revealing processing mechanism of Polygalae Radix.

8.
Nanomaterials (Basel) ; 12(21)2022 Nov 04.
Article in English | MEDLINE | ID: mdl-36364668

ABSTRACT

Recently, as an alternative solution for overcoming the scaling-down limitations of logic devices with design length of less than 3 nm and enhancing DRAM operation performance, 3D heterogeneous packaging technology has been intensively researched, essentially requiring Si wafer polishing at a very high Si polishing rate (500 nm/min) by accelerating the degree of the hydrolysis reaction (i.e., Si-O-H) on the polished Si wafer surface during CMP. Unlike conventional hydrolysis reaction accelerators (i.e., sodium hydroxide and potassium hydroxide), a novel hydrolysis reaction accelerator with amine functional groups (i.e., 552.8 nm/min for ethylenediamine) surprisingly presented an Si wafer polishing rate >3 times higher than that of conventional hydrolysis reaction accelerators (177.1 nm/min for sodium hydroxide). This remarkable enhancement of the Si wafer polishing rate for ethylenediamine was principally the result of (i) the increased hydrolysis reaction, (ii) the enhanced degree of adsorption of the CMP slurry on the polished Si wafer surface during CMP, and (iii) the decreased electrostatic repulsive force between colloidal silica abrasives and the Si wafer surface. A higher ethylenediamine concentration in the Si wafer CMP slurry led to a higher extent of hydrolysis reaction and degree of adsorption for the slurry and a lower electrostatic repulsive force; thus, a higher ethylenediamine concentration resulted in a higher Si wafer polishing rate. With the aim of achieving further improvements to the Si wafer polishing rates using Si wafer CMP slurry including ethylenediamine, the Si wafer polishing rate increased remarkably and root-squarely with the increasing ethylenediamine concentration.

9.
Materials (Basel) ; 15(19)2022 Sep 27.
Article in English | MEDLINE | ID: mdl-36234050

ABSTRACT

Fe additives may play an important role in the preparation of aluminum-based hydrolysis hydrogen powder, with high hydrogen yield, low cost, and good oxidation resistance. Therefore, it is necessary to ascertain the effect of Fe on the hydrogen production performance of Al-Bi-Sn composite powders. According to the calculated vertical cross-section of the Al-10Bi-7Sn-(0~6)Fe (wt.%) quasi-binary system, Al-10Bi-7Sn-xFe (x = 0, 0.5, 1.5, 3) wt.% composite powders for hydrogen production were prepared by the gas-atomization method. The results showed that the Al-10Bi-7Sn-1.5Fe (wt.%) powder exhibited an extremely fast hydrogen generation rate at 50 °C, which reached 1105 mL·g-1 in 27 min in distilled water, 1086 mL·g-1 in 15 min in 0.1 mol·L-1 NaCl solution, and 1086 mL·g-1 in 15 min in 0.1 mol·L-1 CaCl2 solution. In addition, the antioxidant properties of these powders were also investigated. The results showed that the hydrogen production performance of the Al-10Bi-7Sn-1.5Fe (wt.%) powder could retain 91% of its hydrogen production activity, even though the powder was exposed to 25 °C and 60 RH% for 72 h. The addition of Fe not only promoted the hydrogen generation rate of the Al-Bi-Sn composite powders, but also improved their oxidation resistance. The Al-10Bi-7Sn-1.5Fe (wt.%) composite powder shows great potential for mobile hydrogen source scenarios with rapid hydrogen production.

10.
Biochim Biophys Acta Gen Subj ; 1866(6): 130128, 2022 06.
Article in English | MEDLINE | ID: mdl-35278619

ABSTRACT

Haloacid dehalogenase (HAD) superfamily members are mainly phosphomonoesterases, while BT2127 from Bacteroides thetaiotaomicron of the HAD superfamily is identified as an inorganic pyrophosphatase. In this study, to explore the roles of the Lys79 and His23 pair in the hydrolysis reaction of inorganic pyrophosphate (PPi) catalyzed by BT2127, a series of models were designed. Calculations were performed by using the density functional theory (DFT) method with the dispersion energy D3-B3LYP. The His23 and Lys79 pair plays a key role in the high catalytic efficiency of BT2127 with PPi. First, the His23 and Lys79 pair prompts Asp13 to easily provide a proton to the leaving group, which remarkably reduces the energy barrier of the phospho-transfer step; then, Lys79 provides a proton to the first leaving phosphate group via His23, produces a more electrically stabilized phosphate (H3PO4), makes this step exothermal, and further promotes the subsequent phospho-enzyme intermediate hydrolysis. The results suggest that the Lys79-His23 pair helps BT2127 reach high catalytic efficiency by strengthening the acid catalysis. Our study provides detailed chemical insights into the evolution of the inorganic pyrophosphatase function of BT2127 from the phosphomonoesterase of the HAD superfamily and the biomimetic enzyme design.


Subject(s)
Inorganic Pyrophosphatase , Protons , Catalysis , Hydrolases , Inorganic Pyrophosphatase/genetics , Inorganic Pyrophosphatase/metabolism , Phosphates , Phosphoric Monoester Hydrolases
11.
Adv Mater ; 33(11): e2005587, 2021 Mar.
Article in English | MEDLINE | ID: mdl-33569838

ABSTRACT

Layered γ-type iron oxyhydroxide (γ-FeOOH) is a promising material for various applications; however, its sheet-shaped structure often suffers from instability that results in aggregation and leads to inferior performance. Herein, a kinetically controlled hydrolysis strategy is proposed for the scalable synthesis of γ-FeOOH nanosheets arrays (NAs) with enhanced structural stability on diverse substrates at ambient conditions. The underlying mechanisms for the growth of γ-FeOOH NAs associated with their structural evolution are systematically elucidated by alkalinity-controlled synthesis and time-dependent experiments. As a proof-of-concept application, γ-FeOOH NAs are developed as electrocatalysts for the oxygen evolution reaction (OER), where the sample grown on nickel foam (NF) exhibits superior performance of high catalytic current density, small Tafel slope, and exceptional durability, which is among the top level of FeOOH-based electrocatalysts. Density functional theory calculations suggest that γ-NiOOH in situ generated from the electrooxidation of NF would induce charge accumulation on the Fe sites of γ-FeOOH NAs, leading to enhanced OER intermediates adsorption for water splitting. This work affords a new technique to rationally design and synthesize γ-FeOOH NAs for various applications.

12.
J Hazard Mater ; 407: 124546, 2021 04 05.
Article in English | MEDLINE | ID: mdl-33338808

ABSTRACT

Carbonyl sulfide (COS), the organic sulfur generated in the chemical industry, has been receiving more attention due to its environmental and economic influence. In this study N-doped MgAl-LDO catalyst was successfully prepared and tested for the COS hydrolysis reaction at low temperature, it was observed that the N species can be formed both in surface and bulk. Moreover, the basicity property and the H2O adsorption-desorption property were remarkably improved due to the N-doping. Besides, the hydroxyl group can be formed more easily and more abundantly on N modified catalyst surface, which was beneficial to the COS adsorption and the remarkable improvement of catalytic performance. The catalytic hydrolysis performance can proceed for almost 1440 min without any deactivation at 70 °C. However, further increase of temperature was not beneficial to improve the catalytic performance due to the occurrence of H2S oxidation side reaction. Furthermore, it was revealed that the surface hydroxyl groups were responsible for the adsorption of COS and then the formed surface transitional species reacted with the H2O molecules. Hydrogen thiocarbonate and bicarbonate were the main reaction intermediate. The rate-determining step was IM6→IM7 i.e., a type transformation of bicarbonate.

13.
J Environ Sci (China) ; 100: 257-268, 2021 Feb.
Article in English | MEDLINE | ID: mdl-33279038

ABSTRACT

Extracellular polymeric substances (EPS) form a stable gel-like structure to combine with water molecules through steric hindrance, making the mechanical dewatering of wastewater sludge considerably difficult. Coagulation/flocculation has been widely applied in improving the sludge dewatering performance, while sludge properties (organic fraction and solution chemistry conditions) are highly changeable and have important effects on sludge flocculation process. In this work, the alkalinity effects on sludge conditioning with hydroxy-aluminum were comprehensively investigated, and the interaction mechanisms between EPS and hydroxy-aluminum with different speciation were unraveled. The results showed that the effectiveness of hydroxy-aluminum conditioning gradually deteriorated with increase in alkalinity. Meanwhile, the polymeric hydroxy-aluminum (Al13) and highly polymerized hydroxy-aluminum (Al30) were hydrolysed and converted into amorphous aluminum hydroxide (Al(OH)3), which changed the flocculation mechanism from charge neutralization and complexing adsorption to hydrogen bond interaction. Additionally, both Al13 and Al30 showed higher binding capacity for proteins and polysaccharides in EPS than monomeric aluminum and Al(OH)3. Al13 and Al30 coagulation changed the secondary structure of proteins in EPS, which caused a gelation reaction to increase molecular hydrophobicity of proteins and consequently sludge dewaterability. This study provided a guidance for optimizing the hydroxy-aluminum flocculation conditioning of sludge with high solution alkalinity.


Subject(s)
Sewage , Wastewater , Aluminum , Extracellular Polymeric Substance Matrix , Filtration , Flocculation , Polymers , Waste Disposal, Fluid , Water
14.
ChemistryOpen ; 9(9): 967-974, 2020 09.
Article in English | MEDLINE | ID: mdl-33005561

ABSTRACT

Post-polymerization modification (PPM) is one of the most powerful strategy for preparing polymers with functional groups that cannot be synthesized by direct polymerization. So far, numerous experimental efforts have been devoted to the stability issue of monomer structures during the PPM process, but little attention was paid to chemical linkages. However, for hyperbranched polymers, a minor change of linkage unit could lead to a significant influence on the overall stability and performance of polymer materials. In this work, we investigated the chemical stability of long-subchain hyperbranched polystyrenes with ester, aryl ether, and carbon-carbon bonds as branching linkages under a few most popular PPM conditions, including NaOH hydrolysis reaction, TFA-promoted hydrolysis reaction, BBr3-catalyzed methoxy-hydroxyl conversion reaction, and LiAlH4 carbonyl reduction reaction. Related results are summarized into a synthetic route map that can provide practical and intuitive guidance for preparing functional long-subchain hyperbranched polystyrenes and other type of polymers by PPM for future applications.

15.
Chemosphere ; 252: 126292, 2020 Aug.
Article in English | MEDLINE | ID: mdl-32203779

ABSTRACT

New particle formation (NPF) involving amines in the atmosphere is considered an aggregation process, during which stable molecular clusters are formed from amines and sulfuric acid via hydrogen bond interaction. In this work, ab initio dynamics simulations of ammonium bisulfate formation from a series of amines, SO3, and H2O molecules were carried out in the gas phase and at the air-water interface. The results show that reactions between amines and hydrated SO3 molecules in the gas phase are barrierless or nearly barrierless processes. The reaction rate is related to the basicity of gas-phase amines-the stronger the basicity, the faster the reaction. Furthermore, SO3 hydrolysis catalyzed by amines occurs simultaneously with H2SO4-amine cluster formation. At the air-water interface, reactions between amines and SO3 involve multiple water molecules. The reaction center's ring structure (amine-SO3-nH2O) promotes the transfer of protons in the water molecules. The formed ammonium cation (-RNH3+) and the bisulfate anion (HSO4-) are present and stable by means of hydrogen bond interaction. The cluster formation mechanism provides new insights into NPF involving amines, which may play an important role in the formation of aerosols in some heavily polluted areas - e.g., those with a high amine concentration.


Subject(s)
Amines/chemistry , Models, Chemical , Sulfites/chemistry , Aerosols , Atmosphere/chemistry , Catalysis , Hydrogen Bonding , Hydrolysis , Protons , Sulfuric Acids , Water/chemistry
16.
Spectrochim Acta A Mol Biomol Spectrosc ; 228: 117845, 2020 Mar 05.
Article in English | MEDLINE | ID: mdl-31784226

ABSTRACT

A novel quinazolinone based turn-on fluorescence probe for sensitive monitoring hypochlorite was prepared using the mild condensation reaction between 2-(2'-hydroxyphenyl)-4(3H)-quinazolinone derivative and 4-methylbenzenesulfonyl hydrazide. The probe exhibited specific selectivity to ClO- with obvious optical signal changes from weak fluorescence at 560 nm to a strong fluorescence emission at 520 nm and color changes from colorless to yellow, which could be noticed by the naked eye. The detection limit toward hypochlorite is as low as 11.4 nM. Moreover, the probe could sensitively response to ClO- in living cells with satisfying imaging effect and has been successfully applied to the determination of ClO- in practical water samples, which indicated that the probe has certain application potential for hypochlorite monitoring.


Subject(s)
Fluorescent Dyes/chemistry , Hypochlorous Acid/analysis , Quinazolinones/chemistry , Spectrometry, Fluorescence/instrumentation , Carbon Isotopes , Cell Line, Tumor , Coumarins , Humans , Limit of Detection , Magnetic Resonance Spectroscopy , Optical Imaging , Reproducibility of Results , Spectrometry, Fluorescence/methods , Spectrophotometry, Ultraviolet
17.
Materials (Basel) ; 12(20)2019 Oct 12.
Article in English | MEDLINE | ID: mdl-31614803

ABSTRACT

Al-Bi-Sn-Cu composite powders for hydrogen generation were designed from the calculated phase diagram and prepared by the gas atomization process. The morphologies and structures of the composite powders were investigated using X-ray diffraction (XRD) and a scanning electron microscope (SEM) equipped with energy-dispersive X-ray (EDX) spectroscopy, and the results indicate that the Cu additive enhanced the phase separation between the Al-rich phase and the (Bi, Sn)-rich phase. The hydrogen generation performances were investigated by reacting the materials with distilled water. The Al-Bi-Sn-Cu powders reveal a stable hydrogen generation rate, and the Al-10Bi-7Sn-3Cu (wt%) powder exhibits the best hydrogen generation performance in 50 °C distilled water which reaches 856 mL/g in 800 min. In addition, the antioxidation properties of the powders were also studied. The Al-10Bi-7Sn-3Cu (wt%) powder has a good resistance to oxidation and moisture, which shows great potential for being the hydrogen source for fuel cell applications.

18.
Int J Mol Sci ; 20(15)2019 Jul 31.
Article in English | MEDLINE | ID: mdl-31370230

ABSTRACT

Effect of H2O and NH3 on the synergistic oxidation reaction of SO2 and NO2 is investigated by theoretical calculation using the molecule system SO2-2NO2-nH2O (n = 0, 1, 2, 3) and SO2-2NO2-nH2O-mNH3 (n = 0, 1, 2; m = 1, 2). Calculated results show that SO2 is oxidized to SO3 by N2O4 intermediate. The additional H2O in the systems can reduce the energy barrier of oxidation step. The increasing number of H2O molecules in the systems enhances the effect and promotes the production of HONO. When the proportion of H2O to NH3 is 1:1, with NH3 included in the system, the energy barrier is lower than two pure H2O molecules in the oxidation step. The present study indicates that the H2O and NH3 have thermodynamic effects on promoting the oxidation reaction of SO2 and NO2, and NH3 has a more significant role in stabilizing product complexes. In these hydrolysis reactions, nethermost barrier energy (0.29 kcal/mol) can be found in the system SO2-2NO2-H2O. It is obvious that the production of HONO is energetically favorable. A new reaction mechanism about SO2 oxidation in the atmosphere is proposed, which can provide guidance for the further study of aerosol surface reactions.


Subject(s)
Ammonia/chemistry , Nitrogen Dioxide/chemistry , Sulfur Dioxide/chemistry , Water/chemistry , Aerosols , Kinetics , Oxidation-Reduction , Thermodynamics
19.
Angew Chem Int Ed Engl ; 58(29): 9989-9993, 2019 Jul 15.
Article in English | MEDLINE | ID: mdl-31116495

ABSTRACT

Hydrophilic polymer brushes grown via surface-initiated polymerization from silicon oxide surfaces can detach or degraft in aqueous media. Degrafting of these chain end-tethered polymers is believed to involve hydrolysis of bonds at the polymer-substrate interface. Degrafting so far has not been reported for hydrophobic polymer brushes in non-aqueous media. This study has investigated the degrafting and swelling properties of poly(tert-butyl methacrylate) (PtBMA) brushes in different water-miscible, organic solvents, viz. DMF, acetone and THF. In the presence of a sufficient quantity of water in the organic solvent, degrafting was also observed for PtBMA brushes. More importantly, however, the rate of degrafting depended on the nature of the organic solvent and the apparent initial rate constant of the degrafting reaction was found to correlate with the swelling ratio of the polymer brush in the different solvents. This correlation is first, direct evidence in support of the hypothesis that degrafting is facilitated by a tension that acts on the bond(s) that tether the polymer chains to the surface and which is amplified upon swelling of the polymer brush.

20.
Chem Phys Lipids ; 218: 85-90, 2019 01.
Article in English | MEDLINE | ID: mdl-30513281

ABSTRACT

Styrene-maleic acid (SMA) copolymers are increasingly gaining attention in the membrane protein field due to their ability to solubilize lipid membranes into discoidal nanoparticles. The copolymers are synthesized as styrene-maleic anhydride (SMAnh), and need to be converted to the free acid form (SMA) before they are capable of solubilizing membranes. This hydrolysis reaction is traditionally performed under rather cumbersome reflux conditions. Here we report an alternative method for the hydrolysis reaction using simple and readily available equipment found in virtually all biochemical laboratories, namely an autoclave. Based on the results we propose an optimum set of standard conditions for the hydrolysis reaction, that should make the method easily accessible to a wide scope of researchers.


Subject(s)
Maleates/chemistry , Maleic Anhydrides/chemistry , Polymers/chemistry , Styrene/chemistry , Hydrolysis , Molecular Structure
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