New organoruthenium metallates containing ferrocenecarboxalidine thiosemicarbazones and their nucleic acid/albumin binding and in vitro cytotoxicity

A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh₃]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh₃]Cl was the most active on HT-29 cells.     

Salen–Mg-doped NH2–MIL-101(Cr) for effective CO2 adsorption under ambient conditions

A novel metal-doped metal–organic framework (MOF) was developed by incorporating salen–Mg into NH₂–MIL-101(Cr) structure under ambient conditions. The Schiff base complex was successfully prepared by condensing salicylaldehyde with a free amino group and then coordinating metal ions. Such a structure can endow the sample with higher CO₂ adsorption performance. At 0°C and 1 bar, the salen–Mg-modified sample achieves the maximum adsorption capacity of 2.18 mmol g⁻¹ for CO₂, which was 5.8% higher than the pristine salen–MOF under the same conditions. Notably, the Freundlich model indicates that the CO₂ adsorption process of all samples conforms to reversible adsorption. However, the correlation coefficients (R²) of the Mg-doped sample are lower than that of the pristine sample. Besides, the CO₂/N₂ adsorption selectivity and isosteric heat also show a similar trend. These results indicate that the salen–Mg can enhance the interaction between the material and CO₂ molecules.     

Crystalline Boragermenes

Boragermene 3 featuring a double bond between the Ge and dicoordinate B atoms has been synthesized for the first time by reacting the cyclic (alkyl)(boryl)germylene–PMe₃ adduct 1 with Cl₂BN(SiMe₃)₂ followed by reductive dehalogenation with KC₈. Addition of a Lewis base (^MeNHC) to 3 leads to the formation of the corresponding adduct 4 , which shows double bond character between the Ge and tricoordinate B atoms. Compound 3 undergoes hydrogenation with H₂ concomitant with a complete scission of the Ge=B bond.     

基于Ni-SnO2纳米颗粒的GS-PUF设计

气敏传感器具有气体识别、探测和监测等功能, 广泛应用于工业生产等领域, 但在泄漏预警时缺乏迅速识别和定位等功能. 本文基于传感器制备工艺偏差分析, 通过对传感器气敏机制的研究, 提出一种基于Ni-SnO2纳米颗粒的气敏传感器物理不可克隆函数(Gas Sensor-Physical Unclonable Function, GS-PUF)设计方案. 该方案利用掺杂Ni元素的方法, 结合静电喷雾沉积技术制备Ni-SnO2气敏传感器, 以获取更加稳定可靠的物理特征值, 然后采集气敏传感器对不同浓度下气体的响应数据, 最后利用随机阻值多位平衡算法比较不同组气敏传感器响应电信号值, 实现PUF数据输出. 制备每组样本可产生128位二进制数据的多组PUF样本, 进行对比实验. 结果表明, 所设计的GS-PUF具有气体泄漏源头识别定位的功能, 且随机性提升至99%, 唯一性达49.80%.     

基于碳化硅衬底的宽禁带半导体外延

宽禁带半导体具备禁带宽度大、电子饱和飘移速度高、击穿场强大等优势,是制备高功率密度、高频率、低损耗电子器件的理想材料。碳化硅(SiC)材料具有热导率高、化学稳定性好、耐高温等优点,在SiC衬底上外延宽禁带半导体材料,对充分发挥宽禁带半导体材料的优势,并提升宽禁带半导体电子器件的性能具有重要意义。得益于SiC衬底质量持续提升及成本不断降低,基于SiC衬底的宽禁带半导体电子市场占比呈现逐年增加的态势。在SiC衬底上外延生长高质量的宽禁带半导体材料是提高宽禁带半导体电子器件性能及可靠性的关键瓶颈。本文综述了近年来国内外研究者们在SiC衬底上外延SiC、氮化镓(GaN)、氧化镓(Ga₂O₃)所取得的研究进展,并展望了SiC衬底上宽禁带半导体外延的发展及应用前景。     

Mechanism and Stereoselectivity of the Elementometalation Process of Activated Alkyne RCCR(RCO2Me) by Cp2TaH3

The elementometalation process is a fundamental chemical step in several catalytic cycles. In this work, density functional theory computations have elucidated the detailed elementometalation mechanism of activated alkyne RCCR(RCO₂Me) by Cp₂TaH₃ and rationalized the selectivity in experimental findings. The calculated results show that in the formation process of (E)-olefin monohydride((E)-Pro), the Gibbs free energy barrier is low and the entire reaction is spontaneous and exothermic; thus, (E)-Pro can be formed easily. The formation of (Z)-η²-olefin monohydride complex ((Z)-Pro) is difficult due to its high Gibbs free energy barrier. The formation process (E)-Pro consists of the following five steps: hydride H1-shift, conformational isomerism 1, hydride H2-shift, conformational isomerism 2, and olefin coordination process. Topological analysis shows that there is a five-membered ring plane structure in the reaction pathway and that the final product (E)-Pro belongs to a typical η²-olefin monohydride complex. Our calculated results provide an explanation for experimental observations and useful insights for further development of olefin functionalization. © 2019 Wiley Periodicals, Inc.     

Influence of counter-anion on the coordination geometry of manganese(II) complexes with methyl-2-pyrazinecarboximidate ligand

Two new complexes of [Mn(2-MPyzCI)₂Cl₂].H²O (1) and [Mn(2-MPyzCI)₂(H₂O)₂](NO₃)₂ (2) were synthesized from the reaction of MnX₂.4H₂O (X=Cl^? and NO₃^?) with 2-cyanopyrazine in methanolic solution. The chelating methyl pyrazine-2-carboximidate (2-MPyzCI) ligand is formed via the methanolysis of 2-cyanopyrazine. Although coordination environment around manganes(II) ions is similar, but these complexes are different in geometrical position of 2-MPyzCI ligands. As both compounds are synthesized under the same reaction conditions, the only difference between these two complexes are counter ions and changing of geometrical position of ligands can be considered as a result of influence of the counter-anions on the molecular structures.     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

Synthesis,crystal structure and conformational analysis of an unexpected [1,5]dithiocine product of aminopyridine and thiovanillin

The condensation reaction of 2‐mercapto‐3‐methoxybenzaldehyde with 3‐aminopyridine afforded an unexpected N‐alkylated [1,5]dithiocine instead of the N‐salicylideneaniline. The proposed mechanism for this condensation involves a strong intramolecular hydrogen bond between the thiol and the amine groups, leading to a second condensation. The corresponding product, i.e. 4,10‐dimethoxy‐13‐(pyridin‐3‐yl)‐6H,12H‐6,12‐epiminodibenzo[b,f][1,5]dithiocine methanol 0.463‐solvate, C₂₁H₁₈N₂O₂S₂·0.463CH₃OH, was characterized by single‐crystal X‐ray diffraction analysis. The supramolecular structure shows π–π stacking and S…S interactions in the crystal packing. Within the asymmetric unit, two geometries of the N atom are observed. Although a planar geometry should be expected, a pyramidal one is observed due to the crystal packing. The presence of the two geometries was further supported by density functional theory (DFT) calculations that show an electronic energy difference of less than 2 kJ mol^?1 between the two conformers.