High-performance photocatalysts for the selective oxidation of alcohols to carbonyl compounds

With an increase in awareness about the need for green chemistry, there is a shift in focus towards identifying eco-compatible technologies that can improve product yield and eliminate the use or generation of hazardous compounds. An immediate practical example of such an approach is the development of sustainable methods for alcohol oxidation as alternatives to the current processes that are energy intensive and rely on ecotoxic chemicals. In this regard, heterogeneous photocatalysis has been identified as a robust technique to catalyze reactions under benign conditions, which would otherwise require harsh synthesis routes. With the advent of materials sciences and nanotechnology, there has been a tremendous increase in the scope of applicability of photocatalysis in fine chemicals synthesis. Though an attractive choice, much of the fundamental information pertaining to catalyst activity, selectivity and reaction conditions for optimum conversion are still to be investigated for most of these systems. To this end, this review will encompass recent achievements in the selective photocatalytic oxidation of alcohols by harnessing solar radiation as a viable source of energy. The discussion will be arranged based on common types of photocatalysts reported in literature, namely metal oxides (eg, TiO₂ and ZnO, Nb₂O₅), sulphides (eg, CdS, CuS, and Bi₂S₃), and carbonaceous photocatalysts (eg, g-C₃N₄). Several such candidates for photocatalysts will be discussed critically with the aim of providing useful insight into developing selective photocatalysts that can oxidize alcohols via eco-friendly pathways along with high yields.     

分级加载电压下考虑有效电势变化的软黏土电渗固结理论

分级加载电压技术能够有效延长电渗处理的时间,改善地基的处理效果并能有效降低能耗。在利用分级加载电压技术开展电渗试验时,随着土体的排水固结,土体各点的电势会发生明显的变化,这与现有的电渗固结理论假设土体各点电势保持不变有所差异。利用自主设计的电渗试验仪器开展了分级加载电压下的电渗室内试验,分析了电渗过程中土体有效电势变化的规律。基于该规律并结合Esrig固结理论建立了在阳极处不排水、阴极处排水条件下考虑土体有效电势变化的电渗固结理论,得到了分级加载电压条件下考虑土体有效电势变化的超静孔隙水压力和平均固结度的解析表达式。研究表明,在电压分级加载过程中,土体有效电势变化规律表现为随时间先基本保持不变,后呈抛物线状先增后减。通过试验案例验证了考虑土体有效电势变化所求得解析解的合理性,且该数值计算结果相较于Esrig数值计算结果,前者更加接近实测值,该固结方程的建立为后续分级加载电压技术的推广应用提供了理论依据,也为实际工程提供了参考。     

Three-dimensional thermal analysis of the repository for high-level radioactive nuclear waste

One of the key issues of the dimensioning design and safety assessment of the repository for deposing the high-level radioactive nuclear waste is the temperature distribution. A three-dimensional layered model was established for analyzing the heat conduction near single waste canister. Applying the Laplace transform and finite Fourier Sine transform upon the governing equations of heat conduction, the solutions in the Laplace domain were obtained. The solutions in the Laplace domain were numerically inverted into semi-analytical solutions in the time domain by the Crump method, and the temperature distribution was obtained near the canister at the center of one disposal panel. The initially estimated value of the canister spacing was determined according to the temperature distribution and design criterion. Finally, the obtained temperature distribution was used to investigate the influence of relevant parameters on the canister surface temperature. The results show that the present model is reliable by comparing with the existing analytical model. The peak canister surface temperature is significantly affected by the tunnel spacing, canister spacing, thickness of buffer layer, and thermal conductivities of buffer material and surrounding rock.     

Electrodes based on nano-tree-like vanadium nitride and carbon nanotubes for micro-supercapacitors

Vanadium nitride(VN) was deposited by DC-sputtering on a vertically aligned carbon nanotube(CNTs)template for the purpose of nano-structuration. This led to the fabrication of hierarchically composite electrodes consisting of porous and nanostructured VN grown on vertically aligned CNTs in a nano-treelike configuration for micro-supercapacitor application. The electrodes show excellent performance with an areal capacitance as high as 37.5 m F cm~(-2) at a scan rate of 2 mV s~(-1) in a 0.5 MK_2SO_4 mild electrolyte solution. Furthermore, the capacitance decay was only 15% after 20,000 consecutive cycles. Moreover,the capacitance was found to increase with VN deposit thickness. The X-ray photoelectron spectroscopy analyses of the electrodes before and after cycling suggest that the oxide layers that form at the VN surface is the responsible for the redox energy storage in this material. Such electrodes can compete with other transition metal nitride based electrodes for micro-supercapacitors.     

Heterogeneous oxidation of indoor surfaces by gas‐phase hydroxyl radicals

We investigate heterogeneous oxidation kinetics of monolayer‐thick, surface‐sorbed organics, namely di‐n‐octyl phthalate (DnOP) and palmitic acid (PA), with gas‐phase OH. The pseudo‐first order rate constants for organic loss at OH concentrations of 1.6 × 10⁸ molecules/cm³ are: (2.3 ± 0.1) × 10^?4 to (4.8 ± 0.8) × 10^?4 s^?1, and (1.3 ± 0.5) × 10^?4 s^?1 for DnOP and PA, respectively. Films developed in indoor office environments over a few weeks are also oxidized using the same OH concentration. Heterogeneous decay rate constants of mass signals from these films, attributed to phthalates (MW = 390.6) and to PA, are similar to those for the single‐component films, ie, (1.9 ± 0.4) × 10^?4 to (3.4 ± 0.5) × 10^?4 s^?1, and (1.1 ± 0.4) × 10^?4 s^?1, respectively. These results suggest that the lifetimes for OH heterogeneous oxidation of monolayer‐thick indoor organic films will be on the timescale of weeks to months. To support this argument, we present the first analysis of the mass transfer processes that occur when short‐lived gas‐phase molecules, such as OH, are taken up by reactive indoor surfaces. Due to rapid chemical production, the diffusion limitation to mass transfer is less important for short‐lived molecules than for molecules with little chemical production, such as ozone.     

三维圆弧型井眼轨道设计模型的拟解析解

为了研究三维圆弧型井眼轨道设计方程组是否存在解析解以及如何有效求解，使用消去法从多元非线性方程组中推导出其中的某个未知数满足一个特征多项式方程，并且证明了该方程组的拟解析解可以由特征多项式方程的实数根和已知设计参数构成的解析公式计算得到；如果极点多项式非恒等于0，则当特征多项式次数不超过5时，如果有解则为解析解，否则为数值解。通过使用C++类实现多项式加减法、乘法的计算方法，提出了多项式实数根的分隔算法、并用二分法快速求解出多项式全部实数根的计算方案。该方法在数学上经严格推导，计算方案简洁、稳健，在三维井眼轨道设计、智能钻井定向控制中具有应用价值。     

Analysis of flame structure using detailed chemistry and applicability of flamelet/progress variable model in the laminar counter-flow diffusion flames of pulverized coals

Pulverized coal is still found in many practical devices even though it is recognized as “dirty fuel” because of its CO₂ and pollutant emissions. To overcome this problem, advanced coal utilization technologies have been developed using numerical simulations. In this study, the structures of the laminar counter-flow diffusion flames of pulverized coals were investigated by performing simulations based on detailed chemistry. The high-temperature region became narrower as the coal/air ratio increased, because of the departure from the stoichiometric mixture and local quenching by the heat transfer between the gas and solid phases. Further, the applicability of the flamelet/progress-variable (FPV) model was investigated through a priori and a posteriori tests. The a priori test confirmed that the FPV model is capable of reproducing the numerical solutions obtained using the detailed chemistry, including the mass fractions of minor species. In the a posteriori test, there was a slight difference between the FPV model and detailed chemistry results due to overestimation of the progress of the chemical reactions. Given the sufficiently high accuracy of the FPV model in various numerical conditions, it can be concluded that the extended FPV model has potential for use in turbulent coal combustion simulations.     

Cyclodextrin-Based Multistimuli-Responsive Supramolecular Assemblies and Their Biological Functions

Cyclodextrins (CDs), which are a class of cyclic oligosaccharides extracted from the enzymatic degradation of starch, are often utilized in molecular recognition and assembly constructs, primarily via host–guest interactions in water. In this review, recent progress in CD-based supramolecular nanoassemblies that are sensitive to chemical, biological, and physical stimuli is updated and reviewed, and intriguing examples of the biological functions of these nanoassemblies are presented, including pH- and redox-responsive drug and gene delivery, enzyme-activated specific cargo release, photoswitchable morphological interconversion, microtubular aggregation, and cell–cell communication, as well as a geomagnetism-controlled nanosystem for the suppression of tumor invasion and metastasis. Moreover, future perspectives and challenges in the fabrication of intelligent CD-based biofunctional materials are also discussed at the end of this review, which is expected to promote the translational development of these nanomaterials in the biomedical field.     

Switchable Fluorescence of Doxorubicin for Label-Free Imaging of Bioorthogonal Drug Release

Monitoring the release and activation of prodrug formulations provides essential information about the outcome of a therapy. While the prodrug delivery can be confirmed by using different imaging techniques, confirming the release of active payload by using imaging is a challenge. Here, we have discovered that the switchable fluorescence of doxorubicin can validate drug release upon its uncaging reaction with a highly specific chemical partner. We have observed that the conjugation of doxorubicin with a trans-cyclooctene (TCO) diminishes its fluorescence at 595 nm. This quenched fluorescence of the doxorubicin prodrug is recovered upon its bond-cleaving reaction with tetrazine. Clinically assessed iron oxide nanoparticles were used to formulate a doxorubicin nanodrug. The release of doxorubicin from the nanodrug was studied under various experimental conditions. A fivefold increase in doxorubicin fluorescence is observed after complete release. The studies were carried out in vitro in MDA-MB-231 breast cancer cells. An increase in Dox signal was observed upon tetrazine administration. This switchable fluorescence mechanism of Dox could be employed for fundamental studies, that is, the reactivity of various tetrazine and TCO linker types under different experimental conditions. In addition, the system could be instrumental for translational research where the release and activation of doxorubicin prodrug payloads can be monitored by using optical imaging systems.