固体推进剂用新型Schiff碱类高效键合剂的合成及性能表征

为提高丁羟四组元推进剂和CL-20/GAP推进剂的力学性能,解决新的推进剂填料基体界面“脱湿”问题,设计合成了新型Schiff碱键合剂;采用傅里叶红外光谱仪、扫描电子显微镜及万能材料拉伸机等对键合剂的键合效果和推进剂的力学性能进行了表征。结果表明,合成的新型Schiff碱键合剂包含键合剂必备官能团且在AP表面存在明显键合,新型Schiff碱键合剂有望取代有毒MAPO,可明显提高丁羟四组元推进剂的力学性能,使丁羟四组元推进剂常温拉伸强度达到0.7 MPa,常温延伸率大于55%,高温延伸率大于50%,低温延伸率大于60%,并可以明显改善丁羟四组元推进剂的工艺性能;在CL-20/GAP推进剂中,新型Schiff碱键合剂可同时提高推进剂的拉伸强度和延伸率。

Flexible,thermal processable,self-healing,and fully bio-based starch plastics by constructing dynamic imine network

The serious environmental threat caused by petroleum-based plastics has spurred more researches in developing substitutes from renewable sources.Starch is desirable for fabricating bioplastic due to its abundance and renewable nature.However,limitations such as brittleness,hydrophilicity,and thermal properties restrict its widespread application.To overcome these issues,covalent adaptable network was constructed to fabricate a fully bio-based starch plastic with multiple advantages via Schiff base reactions.This strategy endowed starch plastic with excellent thermal processability,as evidenced by a low glass transition temperature(T_(g)=20.15℃).Through introducing Priamine with long carbon chains,the starch plastic demonstrated superior flexibility(elongation at break=45.2%)and waterproof capability(water contact angle=109.2°).Besides,it possessed a good thermal stability and self-adaptability,as well as solvent resistance and chemical degradability.This work provides a promising method to fabricate fully bio-based plastics as alternative to petroleum-based plastics.

Synthesis,crystal structure,and DNA‑binding of binuclear lanthanide complexes based on a multidentate Schiff base ligand

Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.

一种新型Al^(3+)荧光探针的合成及与DNA的相互作用

以2-羟基-1-萘甲醛、邻氨基苯甲醛为原料,设计合成了一种新型Schiff碱Al^(3+)荧光探针S,并通过1HNMR、^(13)CNMR、ESI-MS、IR对探针S进行结构表征。光谱实验结果表明,探针S在DMSO∶H_(2)O=4∶1(V/V)体系中,对Al^(3+)有良好的荧光和裸眼识别。Al^(3+)浓度在2.0~50μmol/L范围内,体系荧光强度呈现出良好的线性关系,检出限为0.033μmol/L,探针S与Al^(3+)形成1∶1的配合物。通过荧光光谱研究了荧光探针S-Al^(3+)配合物与DNA的相互作用,实验结果表明,探针S-Al^(3+)配合物对DNA的猝灭过程为动态猝灭,同时对不同温度下相互作用的结合点常数、结合位点数及热力学参数进行了计算,推断二者作用力的类型为疏水作用,作用方式为嵌插作用。

Solid-state NMR of the retinal protonated Schiff base in microbial rhodopsins

Rhodopsin is a seven-helical transmembrane protein with a retinal chromophore covalently bound to a conserved lysine in helix G via a retinal protonated Schiff base(RPSB).Microbial rhodopsins absorb light through chromophore and play a fundamental role in optogenetics.Numerous microbial rhodopsins have been discovered,contributing to diverse functions and colors.Solid-state NMR spectroscopy has been instrumental in elucidating the conformation of chromophores and the three-dimensional structure of microbial rhodopsins.This review focuses on the 15N chemical shift values of RPSB and summarizes recent progress in the field.We displayed the correlation between the 15N isotropic chemical shift values of RPSB and the maximum absorption wavelength of rhodopsin using solid-state NMR spectroscopy.

1-苯基-3-(1-环己胺)-丙烯Schiff碱缓蚀剂在盐酸溶液中对J55钢的缓蚀效果

为改善酸化压裂施工造成的腐蚀问题,以肉桂醛和环己胺为原料合成了Schiff碱酸化缓蚀剂1-苯基-3-(1-环己胺)-丙烯(PCP),通过红外光谱和气相色谱-质谱联用对其结构进行表征,并采用失重法、电化学(极化曲线、阻抗谱、噪声)及分子动力学模拟等方法评价了PCP的缓蚀效果。结果表明,合成产物即为目标产物PCP。在15%HCl、90℃的条件下,随着PCP浓度增加,J55钢的失重腐蚀速率及腐蚀电流密度显著减小,缓释率逐渐增大。不同PCP加量下的缓释率均可达到99%以上,缓蚀效果较好。在PCP加量达到0.15%时,腐蚀速率及缓释率随着缓蚀剂浓度的增加整体变化不大,即缓蚀剂在J55钢表面的吸附浓度已达到临界胶束浓度,吸附量不再发生变化。PCP同时抑制了阴极析氢和阳极溶解反应,为混合型缓蚀剂。随着PCP浓度的增加,容抗弧半径、极化电阻及噪声电阻由小到大的排序均为:空白﹤0.05%﹤0.10%﹤0.15%﹤0.20%;低频的白噪声水平在电流PSD图中随着PCP浓度的增加而减小,即J55钢的腐蚀速率不断减小,与失重法及极化曲线反应的规律一致。当PCP分子与金属发生吸附并达到平衡时,整个缓蚀剂分子处于同一平面,平行吸附在J55钢表面,达到完全覆盖,从而有效减缓了腐蚀介质的侵入。

对羟基苯甲醛Schiff碱的合成、表征及生物活性

Schiff是优良配体,并具有抑菌、抗氧化和抗肿瘤等生物活性。以对羟基苯甲醛为原料,分别与4-甲基、5-甲基-2-氨基吡啶反应,合成了2个对羟基苯甲醛Schiff碱,即对羟基苯甲醛缩4-甲基-2-氨基吡啶(1)和对羟基苯甲醛缩5-甲基-2-氨基吡啶(2)。采用熔点、红外光谱、紫外可见光谱、核磁共振氢谱和碳谱以及高分辨质谱等对产物结构进行了全面表征。利用微量肉汤稀释法研究其抑菌活性,结果标明:化合物1和化合物2对大肠杆菌、金黄色葡萄球菌和枯草芽孢杆菌的最小抑菌浓度(MIC)为0.500 mg/mL,对溶藻性弧菌、副溶血性弧菌的MIC为0.250 mg/mL。采用DPPH·法研究了化合物1的抗氧化活性,发现其对DPPH·自由基清除率为68.1%。

Preliminary Investigation of Copper(II) Ion Binding or Complex Coordination in Lysozeme Molecules

Hydrophobic Val derivative Schiff base copper(II) complexes and dipeptide (AlaAla, GlyGly) derivative Schiff base copper(II) complexes were introduced into egg white lysozyme. X-ray crystal structure analysis revealed amino acid derivative Schiff base copper(II) complexes were obtained. Herein we discuss primarily on the binding mode of copper(II) of the complexes obtained with egg white lysozyme. The electron density of copper(II) ions was confirmed by X-ray crystal structure analysis. The Val derivative Schiff base copper(II) complex was weakly bound at Arg114 of egg white lysozyme. In other copper(II) complexes, binding of copper(II) ions with dissociated ligands to various residues was observed. The binding sites of copper(II) ions were compared with computational scientific predictions.

Synthesis and Characterization of Novel Schiff Base for Enhanced Dye-Sensitized Solar Cell Photo-Response Mechanism

The efficient photo-response mechanism is one of the key factors in the commercialization of dye-sensitized solar cells in a bid to satisfy renewable energy demands. Progress in green technology has put solar energy on the front burner as a provider of clean and affordable energy for a sustainable society. We report the synthesis of a novel Schiff base with optical transparency in the visible and near IR region of the solar spectrum that can find application in the DSSCs photo-response mechanism. The synthesized crystal exhibited features that could handle some of the shortcomings of dye-sensitized solar cells which include wide band solar spectrum absorption and capability for swift charge transfer within the photoelectrodes. The synthesized Schiff base was characterized using x-ray diffractometer, UV/Visible spectrometer, Frontier transmission infrared spectrometer and conductometer. XRD data revealed the grown crystal to have an average crystallite size of 2.08 nm with average microstrain value of about 269.43. The FT-IR recorded transmission wave ѵ (CO) at 1207.7 cm−1 while dominant wave occurred at ѵ1654.9 and ѵ1592.3 cm−1 relating to ѵ (CN) stretching and ѵ (NH) bending respectively were observed. The IR spectrum revealed the bonding species and a probable molecular structure of 2,6-bis(benzyloxy)pyridine. The UV/Visible spectra convoluted to maximum peak within the near IR region suggesting that 2,6-bis(benzyloxy)pyridine can absorb both the visible and near IR region while its electrical conductivity was determined to be 4.58 µS/cm. The obtained result of the present study revealed promising characteristics of a photosensitizer that can find application in the photo-response mechanism of DSSCs.

具有植物激素活性的Schiff碱化合物的研究(Ⅲ)——噻二唑类Schiff碱的合成及其生物活性

Twelve new Schiff bases of thiadiazole have been synthesized for the first time. Their physical constants, UV, IR, 1H NMR and elementary analysis were originally characterized, biological activity were originally studied. It is found from the results of biological activity tests that some compounds have a remarkable activity on plant growth hormone. Compounds Ⅲa and Ⅲk have a good activity on cytokinin, compounds Ⅲe and Ⅲj and Ⅲl have an excellent activity on auxin.

Schiff碱铜配合物的生物活性

Schiff碱及其铜配合物以良好的生物活性而被人们广泛地研究.综述了Schiff碱铜配合物作为医药和农药的活性,并就其发展尤其在农药方面进行了展望.

我国Schiff碱稀土配合物的研究进展

本文对近二十年来Schiff碱稀土配合物的类型、合成方法、谱学性质、结构及在催化。

4(3H)-喹唑啉酮类Schiff碱的合成与抗烟草花叶病毒活性

采用邻氨基苯甲酸经醋酐酰化闭环得2-甲基苯并噁嗪-4-酮,水合肼回流合成2-甲基-3-氨基-4(3H)-喹唑啉酮,在无水乙醇中与芳醛反应得4(3H)-喹唑啉酮类Schiff碱.经元素分析,IR,1HNMR,13CNMR对所合成的化合物进行了结构确认和表征.初步生物活性测试表明,化合物3t具有较高的抗烟草花叶病毒活性.

水杨醛型Schiff碱配合物的合成、表征与磁性研究

以乙醇为溶剂、水杨醛缩邻氨基苯酚(L)与过渡金属(M)硝酸盐或醋酸盐作用,制得了6个LM及6个L2M配合物(合成过程中须将反应混合液蒸馏至干才能得到Cr、Fe、Ni的配合物)。对所制备的配合物进行了摩尔电导、磁化率、DTA、SEM、UV、IR等表征。结果表明:LM(M=Cr3+、Mn2+、Fe3+、Co2+)为平面正方形场低自旋型;LNi、LCu及L2M(M=Mn2+,Co2+,Cu2+)为四面体场高自旋型;其余经蒸馏得到的L2M(M=Cr3+,Fe3+,Ni2+)则为八面体场配合物。配合物均为顺磁性,除LCr、LFe、LCu及L2Cu也有电子轨道运动的贡献外,磁性主要是电子自旋运动的贡献,LM分子中有水参与配位,并有分子内氢键形成。

非均相Schiff碱铬(III)配合物催化环己烯环氧化性能的研究

将3种典型的氨基酸-水杨醛Schiff碱铬(III)配合物固载于介孔MCM-41上,制得非均相Schiff碱铬配合物,用傅里叶变换红外光谱、紫外-可见光谱、X射线固体粉末衍射、N2吸附和元素分析对其结构进行了表征,并以30%H2O2为氧化剂,考察该配合物对环己烯环氧化反应的催化性能.结果表明,均相配合物非均相化后,其催化活性明显提高.在较优的反应条件下,环己烯转化率可达52.6%,环氧环己烷选择性为73.5%,且该非均相催化剂重复使用6次后,仍保持较高的催化活性.

Schiff碱类锌(Ⅱ)配合物的合成、晶体结构及发光性能

本文合成了2个新的Schiff碱锌配合物Zn(C13H10NO)2(1)和Zn(C14H12NO)2(2),测定了它们的晶体结构。结果表明,配合物1属三斜晶系,空间群P1,晶胞参数a=0.9495(2)nm,b=1.0758(2)nm,c=1.2343(3)nm,α=68.318(2)°,β=67.882(3)°,γ=78.316(3)°,V=1.0824(4)nm3,Z=2,Dc=1.405Mg·m-3,F(000)=472,μ=1.160mm-1;配合物2属单斜晶系,空间群C2/c,晶胞参数a=2.1845(5)nm,b=0.87905(19)nm,c=1.1988(3)nm,β=96.563(3)°,V=2.2870(9)nm3,Z=4,Dc=1.411Mg·m-3,F(400)=1008,μ=1.102mm-1。研究了它们在甲醇、乙醇溶液中的发光行为,结果表明这两个配合物在溶液中发光为金属离子微扰下配体的n-π*的发光。

2-氨基-5-(4-吡啶基)-1,3,4-噻二唑Schiff碱的合成及其生物活性

含杂环的Schiff碱具有优良的生物活性,有的已被研究开发作为植物生长调节物质[1～4].1,3,4-噻二唑的某些衍生物也因为具有良好的杀菌、除草和植物生长调节等功能倍受关注[5～9].

安息香的绿色催化氧化研究

从绿色化学的理念出发,合成了双水杨醛缩乙二胺合金属配合物[M(Salen)](M=Co,Cu,Zn),研究了用这三种配合物作催化剂,用空气氧化安息香合成苯偶酰的方法,并对催化剂的回收套用作了研究.实验表明,Co(Salen)催化剂的催化性能最高,在80℃下反应进行45 min,苯偶酰的最高收率可达78%以上.三种催化剂都可回收套用三次.该方法降低了生产成本,极大地减少了废液的排放,开辟了一条绿色化合成苯偶酰的新途径.

Zn(Ⅱ)、Ni(Ⅱ)与5-氯水杨醛缩乙二胺Schiff碱单、双核配合物的合成及其对O_2^-的催化歧化作用

A Series of mono and di-nuclear Zn Ni complexes with 5 - chlorosalicylaldehyde -ethylenediamine Schiff base have been synthesized. Theirs compositions and structures were characterized by the elemental analysis.UV.IR spectra and 1H NMR. The Dismutation to O2 free radical has also been investigated.

二正丁基锡三齿酰腙Schiff碱配合物的合成和红外光谱研究

合成了 4种三齿酰腙Schiff碱配体H2 L [H2 L1 :C6 H5C(O)NHN =CHC6 H4OH 2 ,H2 L2 :C6 H5C(O)NHN =CHC6 H3(OH) 2 2 ,4,H2 L3:NC5H4C(O)NHN =CHC6 H4OH 2 ,H2 L4:NC5H4C(O)NHN =CHC6 H3(OH) 2 2 ,4]和它们的二正丁基锡新型配合物 (n Bu) 2 SnL ,通过元素分析确定了这些配合物的组成 ,并对配合物在 4 0 0 0～ 40 0cm- 1范围内的主要红外光谱吸收峰进行了归属和讨论 ,推测出配合物可能的分子结构。