Eco-friendly synthesis of 2-substituted benzothiazoles catalyzed by silica sulfuric acid

2-Substituted benzothiazoles have been synthesized via one-pot reaction from aromatic aldehydes and o-aminothiophenol catalyzed by silica sulfuric acid in absolute methanol at room temperature. The remarkable advantages offered by this method are an environmentally friendly and reusable catalyst, a simple procedure, mild conditions, short reaction times, and good to excellent yields of products.     

无镨钕AB5型Mm（Ni,Co,Mn,Al）5合金储氢及电化学性能研究

镍氢电池是目前国内外混合动力汽车的首选电池,但随着稀土价格的不断上涨,稀土元素占其成本的比例约由14%逐步提升到55%,开发无镨、钕的高丰度镧铈稀土元素AB5型储氢材料,有助降低混合动力车用镍氢电池负极材料的成本。采用中频感应熔炼配合快淬甩带工艺制备了LaxCe1-x(NiCoMnAl)5(x=0.8,0.6,0.4)合金,并研究了合金A,B侧各元素的比例以及制备工艺对合金储氢性能及电化学性能的影响。结果表明,随着x的降低,合金的储氢量和放电容量逐渐降低。当x=0.6时,合金电极具有较好的综合电化学性能,最大放电容量达到332.81 mAh.g-1,充放电循环寿命达(715 mA.g-1,80%容量保持率,下同)215次。对该合金B侧Mn,Al含量进行优化后,原材料中的Co含量减少,合金的最高电化学容量可达319.01 mAh.g-1。合金在氩气氛保护下进行退火处理后,结晶度和均匀性上升,电化学容量有所降低,但循环稳定性得到明显改善。其中,经950℃/2 h退火处理的LaxCe1-x(NiCoMnAl)5(x=0.8)合金的最大放电容量达328.07 mAh.g-1,充放电循环寿命达364次。     

基于聚氟乙烯负载四芳基乙烯纳米纤维膜的爆炸物荧光检测

以聚合物纤维负载荧光小分子实现对爆炸物的高灵敏度检测是当前研究的热点之一.本文通过静电纺丝制备了系列聚(偏二氟乙烯-co-六氟丙烯)纤维,当该纤维掺入一定浓度的有机荧光小分子,即双(9-芳胺代芴)联四苯乙烯(TPE-2p TPA),具有聚集诱导增强发光特性.本文研究了复合纤维的表面形貌特征和光物理性能,并应用于荧光化学传感器,对以苦味酸为代表的含氮类爆炸性化合物进行了检查.结果表明,该聚合物复合纤维具有超高的荧光检测灵敏度,可以实现对硝基化合物的超灵敏检测,且具有良好的可重复性,对苦味酸溶液检测可重复利用达9次以上,检测极限达到了10-17g/m L,而对其他含氮类化合物如硝基苯、二硝基苯甲酸也表现出一定的检测特性.同时,在结合实验数据的基础上,我们对检测机理进行了探讨.本研究为爆炸性化合物的选择性检测和高灵敏性检测提供了一种便捷的方法,拓展了荧光传感器的学科内涵.     

Improved conditions for periodate/Schiff's base‐based fluorescent staining of glycoproteins with dansylhydrazine in SDS‐PAGE

An improved periodate/Schiff's base based fluorescent stain with dansylhydrazine (DH) for glycoproteins in 1D and 2D SDS‐PAGE was described. Down to 4–8 ng of glycoproteins can be selectively detected within 2 h, which is approximately 16‐fold higher than that of original protocol, but similar to that of Pro‐Q Emerald 488 stain (Invitrogen, Carlsbad, USA). Furthermore, subsequent study of deglycosylation, glycoprotein affinity isolation, and LC‐MS/MS analysis were performed to confirm the specificity of the improved method. As a result, improved DH stain may provide a new choice for selective, economic, MS compatible, and convenient visualization of gel‐separated glycoproteins.     

Alternative visualization of SDS‐PAGE separated phosphoproteins by alizarin red S‐aluminum (III)‐appended complex

A novel fluorescence detection system using a chemosensor for phosphoprotein in gel electrophoretic analysis has been developed. The system employed the alizarin red S‐aluminum (III)‐appended complex as a fluorescent staining dye to perform the convenient and selective detection of phosphorylated proteins and total proteins in SDS‐PAGE, respectively. Therefore, a full and selective map of proteins can be achieved in the same process without resorting to other compatible detection methods. As low as 62.5 ng of α‐ (seven or eight phosphates) and β‐casein (five phosphates), 125 ng of ovalbumin (two phosphates), and κ‐casein (one phosphate) can be detected in approximately 135 min, with the linear responses of rigorous quantitation of changes over a 125–4000 ng range. As a result, alizarin red S‐aluminum (III) stain may provide a new choice for selective, economic, and convenient visualization of phosphoproteins.     

Double Metal Ions Competitively Control the Guest‐Sensing Process: A Facile Approach to Stimuli‐Responsive Supramolecular Gels

A facile approach to the design of stimuli‐responsive supramolecular gels (SRSGs) termed double‐metal‐ion competitive coordination control is reported. By this means, the fluorescence signals and guest‐selective responsiveness of the SRSGs are controlled by the competitive coordination of two different metal ions with the gelators and the target guest. To demonstrate this approach, a gelator G2 based on multiple self‐assembly driving forces was synthesized. G2 could form Ca²⁺‐coordinated metallogel CaG with strong aggregation‐induced emission (AIE). Doping of CaG with Cu²⁺ results in AIE quenching of CaG and formation of Ca²⁺‐ and Cu²⁺‐based metallogel CaCuG. CaCuG could fluorescently detect CN^? with specific selectivity through the competitive coordination of CN^? with the Cu²⁺ and the coordination of Ca²⁺ with G2 again. This approach may open up routes to novel stimuli‐responsive supramolecular materials.     

Direct Observation of Dynamic Mechanical Regulation of DNA Condensation by Environmental Stimuli

Gene delivery is a promising way to treat hereditary diseases and cancer; however, there is little understanding of DNA:carrier complex mechanical properties, which may be critical for the protection and release of nucleic acids. We applied optical tweezers to directly measure single‐molecule mechanical properties of DNA condensed using 19‐mer poly‐L ‐lysine (PLL) or branched histidine–lysine (HK) peptides. Force–extension profiles indicate that both carriers condense DNA actively, showing force plateaus during stretching and relaxation cycles. As the environment such as carrier concentration, pH, and the presence of zinc ions changes, DNA:HK complexes showed dynamically regulated mechanical properties at multiple force levels. The fundamental knowledge from this study can be applied to design a mechanically tailored complex which may enhance transfection efficiency by controlling the stability of the complex temporally and spatially.     

Control of the Transition between Ni‐C and Ni‐SIa States by the Redox State of the Proximal FeS Cluster in the Catalytic Cycle of [NiFe] Hydrogenase

[NiFe] hydrogenase catalyzes the reversible cleavage of H₂. The electrons produced by the H₂ cleavage pass through three Fe–S clusters in [NiFe] hydrogenase to its redox partner. It has been reported that the Ni‐SI_a, Ni‐C, and Ni‐R states of [NiFe] hydrogenase are involved in the catalytic cycle, although the mechanism and regulation of the transition between the Ni‐C and Ni‐SI_a states remain unrevealed. In this study, the FT‐IR spectra under light irradiation at 138–198 K show that the Ni‐L state of [NiFe] hydrogenase is an intermediate between the transition of the Ni‐C and Ni‐SI_a states. The transition of the Ni‐C state to the Ni‐SI_a state occurred when the proximal [Fe₄S₄]_p^2+/+ cluster was oxidized, but not when it was reduced. These results show that the catalytic cycle of [NiFe] hydrogenase is controlled by the redox state of its [Fe₄S₄]_p^2+/+ cluster, which may function as a gate for the electron flow from the NiFe active site to the redox partner.     

Identification and characterization of the process‐related impurities in fasudil hydrochloride by hyphenated techniques using a quality by design approach

Following the underlying principles of quality by design mentioned in the ICH Q8 guidance, systematic approaches for the control of process‐related impurities have been taken in the manufacturing process of fasudil hydrochloride, a potent Rho‐kinase inhibitor and vasodilator. Three related impurities were found in fasudil hydrochloride lab samples by a newly developed RP‐HPLC with volatile mobile phase gradient elution and UV detection method. The elemental compositions of the impurities were determined by positive ESI high‐resolution TOF‐MS analysis of their [M + H]⁺ ions and their structures were identified through the elucidation of the product mass spectra obtained by a triple quadrupole mass spectrometer. The key impurity was further verified through synthesis and organic spectroscopy including NMR and IR spectroscopy. The origins of these impurities were located and the effective approaches to eliminate them were proposed based on the redesign of the synthetic conditions. The results obtained are important for quality control in the manufacture of fasudil hydrochloride bulk drug substance and injection.     

Gold Nanobone/Carbon Nanotube Hybrids for the Efficient Nonenzymatic Detection of H2O2 and Glucose

We report a facile strategy for the synthesis of gold nanobone/carbon nanotube (CNT@GNB) nanoassemblies, which were prepared through hybridization of CNTs and GNBs mediated by a thiolated pyrene derivative. The SEM images confirmed the successful construction of the CNT@GNB nanoassemblies. Screen printed electrodes modified with the CNT@GNB nanoassemblies exhibited decent electrocatalytic activity, large surface‐to‐volume ratios, high electrochemical reversibility, and efficient electron transport properties, thereby enabling stable and sensitive nonenzymatic detection of H₂O₂ and glucose, with detection limits of 0.8 µM and 0.07 mM, respectively. Moreover, no interference was observed at a potential of +0.38 V for the interfering species, such as ascorbic acid and urea, indicating high selectivity toward the glucose detection.