生物化学中酶促"不可逆"反应及其相关问题辨析

在生物化学教学和研究中,一些酶促反应被归类为不可逆反应。然而,此处的"不可逆"与物理化学中的"不可逆"有所不同,这一表述本身常导致学生的困惑。不仅如此,"不可逆"的实际含义及其衍生的观念可能进一步使学生产生很多对基本生化反应过程的严重误解。本文以物理化学所定义的"不可逆"为准,重新讨论生物化学中所指"不可逆"的准确含义,并举例讨论了包括"速控步""限速酶""高能磷酸键"在内的若干因生物化学中"不可逆"的不准确定义造成的认知误区。     

In situ Deposition of ‘Naked’ Gold Nanoparticles Supported on Silica Spheres as Recyclable Catalysts in Styrene Epoxidation

Tlie rational designs of particle size, morphology and surface states of the Au nanoparticles(AuNPs) are crucial for Au nanocatalyst. We herein report a method to synthesize the silica microspheres supported AuNPs(ca.1 nm) and their application in controlling the reaction conversion and selectivity in styrene epoxidation. Surfactant-ftee AuNPs deposited on silica microspheres were in situ fabricated with aid of the Ag nanoparticles (AgNPs) as sacrificial template by galvanic replacement reaction, leading to AuNPs/SiO2 catalyst directly without any post-treatment to expose crystal facets.A high conversion of 46.7% and selectivity of 91.7% to styrene oxide was achieved with H2O2 as oxidant in ethanol. The solid catalyst could be reused at least 10 reaction cycles without significant decrease in activity and selectivity. This study not only supplies an active, recoverable catalyst for styrene oxidation with green oxidant and solvent, but also demonstrates that the silica microspheres functionalized with thiol groups have a superior ability in stabilizing noble metal nanoparticles even without any surfactant.     

Self-cleaning Anti-fouling TiO2/Poly(aryl ether sulfone) Composite Ultrafiltration Membranes

A series of novel TiO2/poly(aryl ether sulfone) ultrafiltration membranes with anti-fouling and self-cleaning properties was designed and prepared. First, anti-photocatalytic degraded fluorine contained polv(aryl ether sulfone) matrix(PAES-F) was synthesized. Then the composite membranes were prepared via TiO2 nanopartides and PAES-F polymer matrix by solution blending and non-solvent induced phase inversion methods. Further, separation efficiency, fouling behavior and self-cleaning property of the composite ultrafiltration(UF) membranes were investigated by dead-end filtration experiments using a polyacn lamide solution. The composite UF membranes exhibited outstanding self-cleaning efficiency and anti-photocatalytic degraded property after exposure to simulated sunliglit irradiation.The water flux recovery ratios(FRR)of the optimal composite UF membranes could reach 74.24%, which was attributable to photocatalytic degradation of the organic contaminant by TiO2. And the retention rates of the composite UF membranes could maintain over 97%, which indicated the excellent photocatalytic degradation resistance of the fluorine contained PAES-F matrix. The novel high perfomiance composite UF membranes have a broad application prospect in water treatment.     

Simultaneous Visualization of Endogenous Homocysteine,Cysteine, Glutathione,and their Transformation through Different Fluorescence Channels

Studying numerous biologically important species simultaneously is crucial to understanding cellular functions and the root causes of related diseases. Direct visualization of endogenous biothiols in biological systems is of great value to understanding their biological roles. Herein, a novel multi‐signal fluorescent probe was rationally designed and exploited for the simultaneous sensing of homocysteine (Hcy), cysteine (Cys), and glutathione (GSH) using different emission channels. This probe was successfully applied to the simultaneous discrimination between and visualization of endogenous Hcy, Cys, GSH, and their transformation in living cells.     

Improved thermal model and its application in UV high-power pulsed laser ablation of metal target

An improved thermal model describing UV high-power nanosecond laser ablation of metal target is presented. The vaporization effect, the plasma shielding effect, as well as the absorption coefficient and absorptivity dependence of temperature are considered in this model. Take iron target as an example, the numerical solutions are obtained from the heat flow equations (before and after melting) using a finite difference method. The space and time dependence of temperature of the target, the time dependence of temperature at two different positions for a certain laser fluence, and the ablation rate as a function of laser fluence are also presented. The numerical results that agreed well with the experimental data are much better than the one without, which indicates that the above two effects and the temperature dependence of absorption coefficient and absorptivity in UV high-power laser ablation of metal target should not be neglected. We hope the present model will be useful for further experimental investigation of metal thin films prepared by pulsed laser deposition.     

Direct gem-Difluoroalkenylation of X−H Bonds with Trifluoromethyl Ketone N-Triftosylhydrazones for Synthesis of Tetrasubstituted Heteroatomic gem-Difluoroalkenes

The direct gem-difluoroalkenylation of X−H bonds represents the most straightforward approach to access heteroatomic gem-difluoroalkenes that, as the isostere of the carbonyl group, have great potency in drug discovery. However, the construction of tetrasubstituted heteroatomic gem-difluoroalkenes by this strategy is still an unsolved problem. Here, we report the first direct X−H bond gem-difluoroalkenylation of amines and alcohols with trifluoromethyl ketone N-triftosylhydrazones under silver (for (hetero)aryl hydrazones) or rhodium (for alkyl hydrazones), thereby providing a most powerful method for the synthesis of tetrasubstituted heteroatomic gem-difluoroalkenes. This method features a broad substrate scope, high product yield, excellent functional group tolerance, and operational simplicity (open air conditions). Moreover, the site-specific replacement of the carbonyl group with a gem-difluorovinyl ether bioisostere in drug Trimebutine and the post-modification of bioactive molecules demonstrates potential use in medicinal research. Finally, the reaction mechanism was investigated by combining experiments and DFT calculations, and disclosed that the key step of HF elimination occurred via five-membered ring transition state, and the difference in the electrophilicity of Ag- and Rh-carbenes as well as the multiple intermolecular interactions rendered the effectiveness of Rh catalyst selectively for alkyl hydrazones.     

Proton conductivity study on three CS/IL@fle-MOF membranes

The low-cost, high specific surface area and porosity, controlled pore size, and chemical properties of metal–organic framework (MOF) materials have attracted much attention in the exploration of proton conduction. The method of chemically modifying MOF structures or introducing conductive medium into the holes can effectively improve the proton conductivities of the materials. Here, the structural tunability of ionic liquid (IL) and flexible MOF (fle-MOF) materials are matched to give full play to the conductivity of IL, the framework support, and the microporous effect of MOFs, which achieves the synergistic effect of performance and expands the temperature range of proton transfer. Three kinds of CS/IL@fle-MOF membranes were prepared by combining three fle-MOFs with 1-carboxymethyl-3-methylimidazole (CMMIM) in different proportions to obtain 15 pieces of membranes. The comparative analyses show that CS/IL@fle-MOF membranes have excellent proton conduction performance at a wider temperature range (263–353 K) and lower relative humidity (75% RH). Among them, the proton conductivities of CS/CMMIM@MIL-88A-25% and CS/CMMIM@MIL-88B-125% are up to 1.33 and 1.42 S cm⁻¹ at 75% RH and 353 K, respectively; whereas those of CS/CMMIM@MIL-53(Fe)-75% and CS/CMMIM@MIL-88B-125% reach up to 2.1 × 10⁻³ and 1.28 × 10⁻³ S cm⁻¹ at 75% RH and 263 K, respectively. The E_a of CS/CMMIM@fle-MOFs is in the range of 0.1–0.5 eV, suggesting that the proton transport follows predominantly the typical Grotthuss transfer mechanism. The results of this study indicate that the CS/CMMIM@fle-MOF membranes combinations offer great potential for the design of composite porous proton-conducting materials.     

Development of efficient and accurate skeletal mechanisms for hydrocarbon fuels and kerosene surrogate

In this paper,the methodology of the directed relation graph with error propagation and sensitivity analysis(DRGEPSA),proposed by Niemeyer et al.(Combust Flame 157:1760-1770.2010).and its differences to the original directed relation graph method are described.Using DRGEPSA,the detailed mechanism of ethylene containing 71 species and 395 reaction steps is reduced to several skeletal mechanisms with different error thresholds.The 25-species and 131-step mechanism and the 24-species and115-step mechanism are found to be accurate for the predictions of ignition delay time and laminar flame speed.Although further reduction leads to a smaller skeletal mechanism with 19 species and 68 steps,it is no longer able to represent the correct reaction processes.With the DRGEPSA method,a detailed mechanism for n-dodecane considering low-temperature chemistry and containing 2115 species and8157 steps is reduced to a much smaller mechanism with249 species and 910 steps while retaining good accuracy.If considering only high-temperature(higher than 1000 K)applications,the detailed mechanism can be simplified to even smaller mechanisms with 65 species and 340 steps or48 species and 220 steps.Furthermore,a detailed mechanism for a kerosene surrogate having 207 species and 1592 steps is reduced with various error thresholds and the results show that the 72-species and 429-step mechanism and the66-species and 392-step mechanism are capable of predicting correct combustion properties compared to those of the detailed mechanism.It is well recognized that kinetic mechanisms can be effectively used in computations only after they are reduced to an acceptable size level for computation capacity and at the same time retaining accuracy.Thus,the skeletal mechanisms generated from the present work are expected to be useful for the application of kinetic mechanisms of hydrocarbons to numerical simulations of turbulent or supersonic combustion.     

Regulating Phase Junction and Oxygen Vacancies of TiO2 Nanoarrays for Boosted Photoelectrochemical Water Oxidation

In this study, we have provided a facile solution to synthesize well-aligned titanium dioxide nanorods by using hydrothermal reaction. By calcining the materials under different atmospheres and temperatures, a batch of titanium dioxides with excellent oxygen evolution reaction(OER) catalytic efficiency were obtained. This new structured TiO₂ photoanode material yields a high photocurrent density of 5.69 mA/cm² at 1.23 V vs. reversible hydrogen electrode(RHE) under simulated solar light(100 mW/cm²). Surface photovoltage techniques and other measurements were carried out to confirm that the enhanced photoelectrochemical performances were attributed to the synergistic effect of the phase junction and a certain content of surface states, which accelerate the separation and transmission of the photogenerated charges. This material with phase junction and surface states promises a potential application in the field of photoelectric catalysis under solar light.