Chiral Aggregates of Triphenylamine‐Based Dyes for Depleting the Production of Hydrogen Peroxide in the Photochemical Water‐Splitting Process

Recent studies on water‐splitting photoelectrochemical cells (PECs) have demonstrated the intriguing possibility of controlling the spin state in this chemical reaction to form H₂ and O₂ by exploiting the chirality of organic π‐conjugated supramolecular polymers. Although this fascinating phenomenon has been disclosed, the chiral supramolecular materials reported thus far are not optimized for acting as efficient photosensitizer for dye‐sensitized PECs. In this work we report on the design, synthesis, and characterization of chiral supramolecular aggregates based on C₃‐symmetric triphenylamine‐based dyes that are able to both absorb visible light and control the spin state of the process. Variable temperature‐dependent spectroscopic measurements reveal the assembly process of the dyes and confirm the formation of chiral aggregates, both in solution as well as on solid supports. Photoelectrochemical measurements on TiO₂‐based anodes validate the advantage of using chiral supramolecular aggregates as photosensitizer displaying higher photocurrent compared to achiral analogues. Moreover, fluorimetric tests for the quantification of the hydrogen peroxide produced, confirm the possibility of controlling the spin of the reaction exerting spin‐selection with chiral supramolecular polymers. These results represent a further step towards the next‐generation of organic‐based water‐splitting solar cells.     

Molecular Dynamics Simulation of the Binding Interaction between Hormone Glucagon Protein and Self-Assembled Monolayer Molecules

Restrained molecular dynamics simulations were performed to study the binding affinity of the peptide with alkanethiols of different tail-groups, S（CH2）7CH3, S（CH2）7OH and S（CH2）7COOH, which self-assembled on Au（111） surface in the presence of water molecules. The curves of binding affinity were calculated by fixing the center of mass of the peptide at various distances from the assembling surface. Simulation results show that the binding affin- ity is in the order as COOH-SAMs〉OH-SAMs〉CH3-SAMs, while 100% COOH-SAMs〉5% COOH-SAMS in concentration. The effects on binding affinity by different tail-groups were also studied. Results show that the binding affinity between COOH-SAMs and the peptide is bigger than those of the others and increasing the acidity of COOH-SAMs will result in stronger attractive power.     

多壁碳纳米管固载金鸡纳生物碱季铵盐类手性相转移催化剂的制备及其催化烷基化反应性能

制备了多壁碳纳米管(MWCNTs)固载的金鸡纳生物碱季铵盐类手性相转移催化剂PTC-1/MWCNTs,并用于催化N-二苯亚甲基-甘氨酸叔丁酯的不对称烷基化反应中.采用紫外-可见光谱系统研究了五种有机溶剂对PTC-1在MWCNTs上吸附和脱附的影响.结果表明,在甲苯中,MWCNTs对PTC-1的吸附率最高(53%),而在三氯甲烷中PTC-1的脱附率最低(仅为0.75%).PTC-1/MWCNTs催化剂在催化N-二苯亚甲基-甘氨酸叔丁酯和不同卤代烃的不对称烷基化反应中,所得产物的收率和对映体选择性都较高,而且该催化剂可回收循环使用,说明PTC-1经MWCNTs固载后,仍能够有效地催化多种卤代烃的不对称烷基化反应.     

Correlation between the bath composition and nanoporosity of DC-electrodeposited Ni-Fe alloy

The outstanding mechanical strength of as-deposited DC-electrodeposited nanocrystalline (nc) Ni-Fe alloys has been the subject of numerous researches in view of their scientific and practical interest. However, recent studies have reported a dramatic drop in ductility upon annealing above 350°C, associated with a concomitant abnormal rapid grain growth. The inherent cause has been ascribed to the presence of a detrimental product or by product in the bath, which affects either the microstructure or causes defects in the concentration and/or distribution of the as-deposited films. The present work has been inspired by the observed abnormal behaviour of annealed electrodeposited nc Ni-Fe alloy, which has here been addressed by considering the relationship between the composition of the bath (iron-chloride, nickel-sulphate solution, saccharin and ascorbic acid) and deposition defects (e.g. grain boundary pores) in the case of an nc Ni-Fe (Fe 48 wt%) alloy. The current investigations have included X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) in both as-deposited and post-annealed conditions (300°C–400°C). XPS depth profiling with Ar ion sputtering showed a significant amount of C and O impurities entrapped in the foils during deposition. As such impurities are often overlooked in common analytical techniques, new scenarios may need to be rationalised to explain the observed drop in tensile ductility of the as-deposited Ni-Fe alloys.     

Direct Observation of the Electroadsorptive Effect on Ultrathin Films for Microsensor and Catalytic‐Surface Control

Microchemical sensors and catalytic reactors make use of gases during adsorption in specific ways on selected materials. Fine‐tuning is normally achieved by morphological control and material doping. The latter relates surface properties to the electronic structure of the bulk, and this suggests the possibility of electronic control. Although unusual for catalytic surfaces, such phenomena are sometimes reported for microsensors, but with little understanding of the underlying mechanisms. Herein, direct observation of the electroadsorptive effect by a combination of X‐ray photoelectron spectroscopy and conductivity analysis on nanometre‐thick semiconductor films on buried control electrodes is reported. For the SnO₂/NO₂ model system, NO₃ surface species, which normally decay at the latest within minutes, can be kept stable for 1.5 h with a high coverage of 15 % under appropriate electric fields. This includes uncharged states, too, and implies that nanoelectronic structures provide control over the predominant adsorbate conformation on exterior surfaces and thus opens the field for chemically reactive interfaces with in situ tunability.