Trapped interfacial redox introduces reversibility in the oxygen reduction reaction in a non-aqueous Ca2+ electrolyte

Electrochemical investigations of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have been conducted in a Ca²⁺-containing dimethyl sulfoxide electrolyte. While the ORR appears irreversible, the introduction of a tetrabutylammonium perchlorate (TBAClO₄) co-salt in excess concentrations results in the gradual appearance of a quasi-reversible OER process. Combining the results of systematic cyclic voltammetry investigations, the degree of reversibility depends on the ion pair competition between Ca²⁺ and TBA⁺ cations to interact with generated superoxide (O₂⁻). When TBA⁺ is in larger concentrations, and large reductive overpotentials are applied, a quasi-reversible OER peak emerges with repeated cycling (characteristic of formulations without Ca²⁺ cations). In situ Raman microscopy and rotating ring-disc electrode (RRDE) experiments revealed more about the nature of species formed at the electrode surface and indicated the progressive evolution of a charge storage mechanism based upon trapped interfacial redox. The first electrochemical step involves generation of O₂⁻, followed primarily by partial passivation of the surface by Ca_xO_y product formation (the dominant initial reaction). Once this product matrix develops, the subsequent formation of TBA⁺--O₂⁻ is contained within the Ca_xO_y product interlayer at the electrode surface and, consequently, undergoes a facile oxidation reaction to regenerate O₂.

An interlayer product of oxygen reduction with Ca²⁺/TBA⁺ yields a quasi-reversible oxygen evolution reaction by inducing a trapped interfacial redox process.     

A Review of Bacteriochlorophyllides: Chemical Structures and Applications

Generally, bacteriochlorophyllides were responsible for the photosynthesis in bacteria. Seven types of bacteriochlorophyllides have been disclosed. Bacteriochlorophyllides a/b/g could be synthesized from divinyl chlorophyllide a. The other bacteriochlorophyllides c/d/e/f could be synthesized from chlorophyllide a. The chemical structure and synthetic route of bacteriochlorophyllides were summarized in this review. Furthermore, the potential applications of bacteriochlorophyllides in photosensitizers, immunosensors, influence on bacteriochlorophyll aggregation, dye-sensitized solar cell, heme synthesis and for light energy harvesting simulation were discussed.     

Ba0.6Sr0.4TiO3/聚偏氟乙烯-聚甲基丙烯酸甲酯复合材料的制备及其介电性能

采用流延热压工艺制备Ba_0.6Sr_0.4TiO₃(BST)/聚偏氟乙烯(PVDF)?聚甲基丙烯酸甲酯(PMMA)复合薄膜,研究了PMMA含量对复合材料微观组织结构和介电性能的影响规律。结果表明,BST相能够均匀分散在聚合物基体中,归因于PMMA与PVDF良好的相容性,2种聚合物之间的界面不分明;随着PMMA含量的增加,复合材料的介电常数先降低后升高,耐击穿强度和介电可调性先增加后减少。PMMA含量(体积分数)为15%的BST/PVDF?PMMA₁₅复合材料的综合性能最佳:介电常数为23.2,介电损耗为0.07,耐击穿强度为1412 kV·cm^-1,在550 kV·cm^-1偏压场下,介电可调性为26.2%。     

High Efficiency Multi-kW Diode-Side-Pumped Nd：YAG Laser with Reduced Thermal Effect

We demonstrate a high efficiency multi-kW diode-side-pumped Nd：YAG laser. High cooling efficiency of the diode-side-pumped module in the laser is achieved. The middle portion of the Nd：YAG rod in the module is cooled by a coolant jet with screwed side surface, and the end-caps of the rod without screwed side surface are cooled by Au coated on the surface. The thermal effect of the laser rod is reduced, which leads to high output power with high optical-optical conversion efficiency. By using three identical Nd：YAG laser modules, an output power of 4.2 kW and beam quality of 58 mm＆#12539;mrad with an optical-optical efficiency of 35% at 1064 nm is obtained in a laser oscillator. By using four identical Nd：YAG laser modules, an output power of 3.1 kW and beam quality of 17 mm＆#12539;mrad with an optical-optical efficiency of 25.8% is demonstrated in a master oscillator power-amplifier system.     

还原氧化石墨烯/介孔TiO2复合材料的合成及其光解水制氢性能

采用溶胶凝胶法,以钛酸四异丙酯(TTIP)为钛源,十六烷基三甲基溴化铵(CTAB)为模板剂合成了介孔二氧化钛样品mTiO_2,考察了合成温度、水量、模板剂用量和焙烧温度对其在紫外光条件下光催化产氢活性的影响。结果显示,在350℃下焙烧后,样品由无定形结构转变为锐钛矿相;随着焙烧温度的提高,锐钛矿相结构产物的结晶度提高,当焙烧温度超过550℃后,样品大部分转变为金红石相。以合成温度为30℃,模板剂用量(nCTAB/nTiO_2)为0.2,水量(nH2O/nTiO_2)为100,焙烧温度为450℃条件下合成的m-TiO_2样品为催化剂,当催化剂用量为0.4 g·L-1,体系中甲醇浓度高于20%(V/V)时,其紫外光条件下的光催化产氢活性达170 mmol·g-1·h-1。采用水热法将氧化石墨烯(GO)与m-TiO_2复合制备了一系列还原氧化石墨烯/介孔TiO_2复合材料(rGO/m-TiO_2),其晶相结构为锐钛矿相。当r GO复合量(wGO/wTiO_2)为0.01时,样品在紫外光下的产氢活性为241 mmol·g-1·h-1,能量转化效率达7.4%,较未复合样品提高了42.3%;在可见光条件下,其产氢活性达9 mmol·g-1·h-1。     

Efficient acid catalytic synthesis of pyrazolopyrimidines from 1H-pyrazol-5-yl-N,N-dimethylformamidines with cyanamide

The efficient acid catalytic synthesis of pyrazolo [3,4-d]pyrimidine was developed by treating 1H-pyrazol-5-yl-N,N-dimethylformamidine with various aminating agents including N,O-bis(trimethylsilyl)hydroxylamine (NHSiMe₃(OSiMe₃)), cyanamide (NH₂CN), hydroxylamine (NH₂OH), methoxyamine (NH₂OMe), hydrazine (NH₂NH₂), and urea (NH₂C(O)NH₂) in acidic solution at reflux. Based on the experimental result, cyanamide (NH₂CN) and methanesulfonic acid were indicated the best aminating agent and acid mediated solvent. On the other hands, the reactivity tendency was involved the activity of original leaving species grafting on the aminating agents, such as –OH, –OMe, –OSiMe₃, –NH₂, –OSiMe₃, –C(O)NH₂, and –CN, in acid catalytic heterocyclic reaction.     

Determination of calcium in complex samples using functional magnetic beads combined with electrodeless/sheathless electrospray ionization mass spectrometry

Conventionally, electrospray ionization ion trap mass spectrometry (ESI-ITMS) is not used for the analysis of metal ions because metal ions may be of too low mass to be trapped by the mass analyzer. Furthermore, metal ions can easily precipitate during ESI processes because of their poor volatilities. We present an approach for solving these two problems using milk as the sample to demonstrate the feasibility of using ESI-ITMS as the detection method for metal ions. Iron oxide magnetic beads with nitrilotriacetic acid (NTA) immobilized on their surface were used as affinity probes for calcium ions from dairy drinks. Ethylenediaminetetraacetic acid (EDTA) was used for the elution of the metal ions chelated by NTA on the beads. The EDTA eluent was analyzed by electrodeless/sheathless ESI-ITMS. The use of functional magnetic beads to trap metal ions from complex samples can effectively reduce the interference from sample matrix. Using the EDTA eluent as the sample avoids the problem of the low volatility of metal ions during ESI-ITMS analysis. This method gives measurements of calcium ions in dairy drinks quantitatively very close to the true values (<4% error).     

一种在线测量微机械薄膜残余应力的新结构

提出了一种利用临界屈曲法在线测量微机械薄膜残余应力的新结构，并采用表面微加工技术制作了两种测试样品.搭建了在线观测实验装置来实时监控释放过程中结构出现的临界屈曲变形模态，由此判断出结构内部的应力状态，同时在测得临界刻蚀深度的情况下，采用有限元方法计算出残余应力大小.借助有限元方法，先研究了多个参数对临界屈曲应力的影响，然后利用这种新结构对薄膜残余应力进行了实际测量，所得结果与微旋转结构的应力测量结果基本吻合.分析及实验表明，新结构在测量薄膜残余应力方面有许多优点，具有较高的实用价值，不仅能满足大量程的应力检测要求，而且只用一个结构就可以同时测量压应力和拉应力，从而极大提高了器件版图空间的利用率.     

Development of a matrix-assisted laser desorption ionization mass spectrometric method for rapid process-monitoring of phthalocyanine compounds

Phthalocyanines (PCs), an important class of chemicals widely used in many industrial sectors, are macrocyclic compounds possessing a heteroaromatic π-electron system with optical properties influenced by chemical structures and impurities or by-products introduced during the synthesis process. Analytical tools allowing for rapid monitoring of the synthesis processes are of significance for the development of new PCs with improved performance in many application areas. In this work, we report a matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry (TOFMS) method for rapid and convenient monitoring of PC synthesis reactions. For this class of compounds, intact molecular ions could be detected by MALDI using retinoic acid as matrix. It was shown that relative quantification results of two PC compounds could be generated by MALDI MS. This method was applied to monitor the bromination reactions of nickel- and copper-containing PCs. It was demonstrated that, compared to the traditional UV–visible method, the MALDI MS method offers the advantage of higher sensitivity while providing chemical species and relative quantification information on the reactants and products, which are crucial to process monitoring.     

Insulator, semiclassical oscillations and quantum Hall liquids at low magnetic fields

Magneto-transport measurements are performed on two-dimensional GaAs electron systems to probe the quantum Hall (QH) effect at low magnetic fields. Oscillations following the Shubnikov-de Haas (SdH) formula are observed in the transition from the insulator to QH liquid when the observed almost temperature-independent Hall slope indicates insignificant interaction correction. Our study shows that the existence of SdH oscillations in such a transition can be understood based on the non-interacting model.