Synthesis and Crystal Structures of Antimony(III) Complexes With a Bis(amino)silane Ligand

Bis(amino)silane bearing bulky substituents on nitrogen, LH₂ [L = Me₂Si(NDipp)₂, Dipp = 2, 6‐diisopropylphenyl] was reacted with nBuLi (ratio 1:1 and 1:2) in toluene. The Me₂Si(LiNDipp)₂ was treated with SbCl₃ in a 1:1 ratio to yield the four‐membered SiN₂Sb ring compound of composition [η²(N,N)‐Me₂Si(NDipp)₂SbCl] ( 1 ). The mono lithiated bis(amino)silane was used to synthesize the monodentate heterotetraatomic complex [(η¹‐Me₂SiNDipp)NHDippSbCl₂] ( 2 ) by the reaction with SbCl₃. The complexes were characterized by ¹H and ¹³C NMR, elemental analysis, IR, and single‐crystal X‐ray structural analysis.     

Design and synthesis of a novel protected mixed ligand siderophore

A novel siderophore analog (4) has been designed to facilitate iron transport-mediated drug delivery and drug release. This mixed ligand siderophore analog includes three bidentate ligands intended to octahedrally coordinate iron (III). The ligands include a 2,3-dihydroxy benzoic acid moiety, N⁵-acetyl-N⁵-hydroxy-l-ornithine, and a β-N-hydroxy-α,β-diaminopropionic acid derivative. The total synthesis of 15, a form of 4 that is suitably protected, yet contains a free carboxylic acid for subsequent drug conjugation, is described.     

Non‐Isothermal Decomposition Kinetics,Specific Heat Capacity and Adiabatic Time‐to‐explosion of a Novel High Energy Material: 1‐Amino‐1‐Methylamino‐2,2‐Dinitroethylene (AMFOX‐7)

A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) $. The critical temperature of thermal explosion of AMFOX‐7 is 244.89°C. The specific heat capacity of AMFOX‐7 was determined with micro‐DSC method and theoretical calculation method, and the standard molar specific heat capacity is 199.39 J·mol^?1·K^?1 at 298.15 K. Adiabatic time‐to‐explosion of AMFOX‐7 was also calculated to be 215.41 s. AMFOX‐7 has higher thermal stability than FOX‐7.     

高活性Cu/SiO2催化剂应用于丙二酸二乙酯加氢制1,3-丙二醇

作为聚对苯二甲酸丙二醇酯(PTT)的不可替代原料,1,3-丙二醇(1,3-PDO)广泛应用于聚酯、树脂、化妆品、润滑剂和制冷剂等领域.采用丙二酸二乙酯(DEM)一步加氢合成1,3-PDO可避免传统化学工艺中醛类副产物的生成和生物法中产品纯度不高的问题,进而满足下游PTT的品质要求. Cu/SiO2催化剂因铜与载体间的强相互作用以及硅胶的弱酸性有利于催化活性中心的建立而被广泛应用于气相加氢反应,可以选择性地活化C?O键而不活化C?C键.因此,本文将Cu/SiO2催化剂应用于DEM加氢反应,重点考察了焙烧温度对催化剂结构与性能影响的本质原因.
　　采用蒸氨法制备Cu/SiO2催化剂,将一定量氨水滴加到硝酸铜水溶液中形成铜氨溶液后滴加JN-30硅溶胶,经老化、过滤、洗涤、烘干、焙烧、压片成型后得到40?60目的催化剂.将不同温度(623?1023 K)焙烧的Cu/SiO2催化剂装填入自制连续高压固定床反应器中进行DEM加氢反应,并采用N2物理吸脱附、电感耦合等离子体发射光谱、N2O化学吸附、X射线衍射、傅里叶红外光谱、H2程序升温还原(TPR)、透射电镜及X射线光电子能谱等手段对不同温度焙烧催化剂进行表征.结果表明,在723 K焙烧的催化剂具有最大的比表面积和最均一的孔径分布,其铜组分分散均匀,活性铜表面积最大,焙烧后可以形成最多的页硅酸铜,导致还原后Cu+/Cu0比例较高.在该催化剂作用下,于473 K、2.0 MPa、氢酯摩尔比330和液体空速1.8 h–1条件下, DEM转化率为90.7%,1,3-PDO选择性为32.3%.
　　焙烧温度对Cu/SiO2催化剂组成、织构、结构、形貌及还原后的价态有较大影响.在焙烧温度为623?1023 K时,低温焙烧有利于生成页硅酸铜,而高温焙烧则有利于形成CuO.在焙烧温度升高的过程中,铜组分形态会发生较大变化,在623?723 K焙烧的催化剂中页硅酸铜含量不断增加;继续升高温度至823 K,页硅酸铜含量减少,但是分散变差,导致铜的比表面积、孔体积和孔径最小;进一步升高温度至923 K,页硅酸铜消失, CuO分散均匀, H2-TPR的还原峰窄且对称;当温度升高到1023 K时,铜晶体迅速长大而较难被还原.     

形态结构和光电特性对纳米TiO2光催化性能的影响

采用sol-gel法制备了系列纳米TiO2光催化剂,运用X射线衍射、BET比表面测定、紫外漫反射吸收光谱和表面光电压谱等手段对催化剂进行表征,并以乙烯作为光催化反应的指标反应分子,研究了TiO2纳米晶的性质对于光催化活性的影响.随着焙烧温度的升高,TiO2的晶粒逐渐增大,比表面积下降,晶相由锐钛矿向金红石转变,其吸收带边与光伏响应阈值向长波方向移动,氧化－还原能力降低,降解乙烯的转化率迅速下降.     

Cr3+水解聚合作用的研究(Ⅷ)-反丁烯二酸存在下的过渡态

本文研究究了Cr(NO₃)₃与四种浓度的反丁烯二酸共存时Cr³⁺在水溶液中的聚合状态,采用LEMIT程序计算了在四种配体浓度下存在的同一粒子(离子或分子),其水解常数不但彼此吻合,且和高、低浓度区的结果一致。     

EuS/Ta异质结的极大磁电阻效应

在铁磁/超导异质结中,铁磁体的交换场通过近邻效应将导致超导体准粒子态密度的塞曼劈裂.基于该效应,在外磁场不强的情况下,通过外加磁场可以有效地调节铁磁/超导界面处的交换作用,从而实现超导体在正常态和超导态之间转换,产生极大磁电阻.本文利用脉冲激光沉积方法制备了EuS/Ta异质结并研究了其电磁特性.Ta在3.6 K以下为超...     

Anion Storage Chemistry of Organic Cathodes for High-Energy and High-Power Density Divalent Metal Batteries

Multivalent batteries show promising prospects for next-generation sustainable energy storage applications. Herein, we report a polytriphenylamine (PTPAn) composite cathode capable of highly reversible storage of tetrakis(hexafluoroisopropyloxy) borate [B(hfip)₄] anions in both Magnesium (Mg) and calcium (Ca) battery systems. Spectroscopic and computational studies reveal the redox reaction mechanism of the PTPAn cathode material. The Mg and Ca cells exhibit a cell voltage >3 V, a high-power density of ∼∼3000 W kg⁻¹ and a high-energy density of ∼∼300 Wh kg⁻¹, respectively. Moreover, the combination of the PTPAn cathode with a calcium-tin (Ca−Sn) alloy anode could enable a long battery-life of 3000 cycles with a capacity retention of 60 %. The anion storage chemistry associated with dual-ion electrochemical concept demonstrates a new feasible pathway towards high-performance divalent ion batteries.     

2,6-二氯-4-乙酰基苯基磷酸的合成

制备了酸性磷酸酶检测底物2，6-二氯-4-乙酰基苯基磷酸酯（DCAP-P）。以2，6-二氯苯酚为原料，经酰化反应、AlCl3催化F-C重排、碱化成盐、磷酯化、水解等5步反应，制备了DCAP-P，并对F-C重排、磷酯化条件进行了改进。     

Effect of polarization on efficiency of volume Bragg grating filter

<正>Diffraction efficiency of volume Bragg grating,whose period is in the same order as the incident wavelength, is related to the polarization direction of the incident linear polarized beam.When two linearly polarized recording beams with the same polarization direction are used for recording volume Bragg gratings in a photopolymer with diffusion amplification,the azimuth of polarization of the reconstruction beam influences the diffraction efficiency of the grating.When the probe beam is linearly polarized and oriented orthogonally to the grating vectors,the±1-order diffraction beams are also linearly polarized with polarization direction parallel to that of the probe beam.According to the results,a two-dimensional nonspatial optical filter consisting of the volume Bragg gratings would achieve significantly higher efficiency.