Crystal Structures of Urokinase-type Plasminogen Activator in Complex with 4-(Aminomethyl) Benzoic Acid and 4-(Aminomethyl-phenyl)-methanol

Urokinase-type plasminogen activator （uPA） is a trypsin-like serine protease and plays a key role in several biological processes, including tissue remodeling, cell migration, and matrix degradation. The inhibitors of uPA have been shown to prevent the spread of metastasis and tumor growth, and accordingly uPA is widely recognized as a target for the treatment of cancer. In this work, we report the crystal structures of the complexes of uPA with its inhibitors： 4- （aminomethyl）-benzoic acid （AMBA） and 4-（aminomethyl-phenyl）-methanol （AMPM）, both at a resolution of 2.35 А. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that AMBA is a better inhibitor for uPA （Ki = 2.68 mM） than AMPM （Ki = 13.99 mM）. The structural study shows that the binding mode of inhibitor AMBA on uPA is similar to that of AMPM on uPA, both docked into the active site S1 pocket of uPA. Structural details of these complexes are provided to explain the difference of inhibitory constants.

Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Synthesis of Aminomethyl Arylsulfides via Novel Synthetic Auxiliary Benzotriazole Promoted by Samarium Diiodide

Aminomethyl arylsulfides are synthesized through nucleophilic substitution of a benzotriazolate anion by thiolates promoted by samarium diiodide.

Convenient synthesis of (4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolane

A convenient approach for the preparation of （4R,5R）-4,5-bis（aminomethyl）-2-isopropyl-l,3-dioxolane is described. The target compound via two steps is synthesized from diethyl-2,3-O-isobutylidene-D-tartrate, through ammonolysis and reduction.

Synthesis and Crystal Structure of N,N′-4-aminomethyl-pyromellitic diimide

The title compound N,N′-4-aminomethyl-pyromellitic diimide （4-pmpmd） crystallizes in monoclinic, space group P21/c with a = 4.785（1）, b = 6.200（1）, c = 29.907（2） A, β = 93.583（11）°, V= 885.5（2） A^3, Dc = 1.494 g/cm^3, Z= 2, C22H14N4O4, Mr = 398.37,/t（MoKα） = 0.106 mm^-1 and F（000） = 412, and its structure was refined to R = 0.0469 and wR = 0.1017 for 1194 observed reflections （F0 〉 4σ（F0））. The X-ray diffraction shows the existence of the staggered strong intermolecular C-H…O （DA） hydrogen bonds between adjacent molecules, the intermo- lecular C-H…π hydrogen bonds and the weak π…π stacking interactions, leading to the formation of multi-dimensional supramolecular network based on the Z-mode conformation of the title compound.

Palladium-Catalyzed Cascade Double C--N Bond Activation： A New Strategy for Aminomethylation of 1,3-Dienes with Aminals

A new palladium-catalyzed selective aminomethylation of conjugated 1,3-dienes with aminais via double C-N bond activation is described. This simple method provides an effective and rapid approach for the synthesis of linear a,13-unsaturated allylic amines with perfect regioselectivity. Mechanistic studies disclosed that one palladium catalyst cleaved two distinct C-N bond to furnish a cascade double C-N bond activation, in which an allylic 1,3-diamine and allylic 1,2-diamine were initially formed as key intermediates through the palladium-catalyzed C-N bond activation of aminal and the α,β-unsaturated allylic amine was subsequently produced via palladium-catalyzed C-N bond activation of the allylic diamines.

Copper-Catalyzed Asymmetric Formal Hydroaminomethylation of Alkenes with N,O-Acetals to Access Chiral β-Stereogenic Amines: Dual Functions of the Copper Catalyst

Chiral amines are synthetically versatile intermedi-ates used for the preparation of a wide range of biologically active compounds and drugs.Compared with the well-developed synthesis ofα-stereogenic amines,the establishment of enantioselective protocols to accessβ-stereogenic amines are very limited.

Synthesis of FER Zeolite Using 4-(Aminomethyl)pyridine as Structure-directing Agent

This paper describes the synthesis of FER zeolite using commercially available 4-(aminomethyl)pyridine as organic structure-directing agent(OSDA). FER zeolites were prepared in mixtures with SiO2/Al2O3 molar ratios in a narrow range and the resultant products possessed a typical flake-shaped morphology. The crystallization of FER zeolite was tracked in order to better understand the formation mechanism and the products obtained at different crystallization time were systematically characterized using multiple techniques. It showed that a majority of Si atoms and nearly all the Al atoms transformed into the solid phase during the hydrothermal synthesis. The rearrangement of inorganic species gave rise to zeolitic 5-membered rings(5-MRs) and 6-membered rings(6-MRs). Consequently, FER zeolite crystals were formed by the consumption of amorphous bulky gel/solid matrix. Tracking the synthesis process of FER can help.

The Influence of Pore Structures and Degree of Cross-Linking on Catalytic Properties of Aminomethyl Polystyrene Resin Supported Dendritic Copper Complexes

1 Introduction Immobilization of homogeneous catalysts onto polymer supports through covalent attachment has received wide attention because these materials offer advantage features of heterogeneous catalysis to homogeneous systems.The polymer-supported catalysts enhance their thermal stability,selectivity,recyclability and easy separation from reaction products leading to the operationally flexible[1-2].Such behaviour prompted us to know the effect of pore structures of polymer supporters on catalytic ...

3-氨甲基吡啶合成烟酰胺的方法研究

本文主要介绍了一种用3-氨甲基吡啶为原料合成烟酰胺的方法。此方法使用了二氧化锰和高锰酸钾为混合催化剂,乙醇作为反应的溶剂,反应条件相对温和,分离工艺简单。这个方法的优点在于操作简单、安全、产率高。本文对反应催化剂的种类和用量、溶剂的种类、反应的温度和反应时间进行了优化,并且最终优化的结果可以使得烟酰胺的产率达到95%以上。

Palladium-Catalyzed Aminomethylation of Nitrodienes and Dienones via Double C-N Bond Activation

Main observation and conclusion A new strategy for the generation of the active Pd-alkyl species from aminal via C-N bond activation has been established,in which the formation of zwitterionic intermediate through aza-Michael addition of aminal to nitrodienes or dienones is identified as a key step for the activation of the C-N bond.The efficient strategy has enabled a new palladium-catalyzed a-aminomethylation of nitro-dienes and dienones via double C-N bond activation.The scope and versatility of the reaction were demonstrated and a broad range of substrates bearing electron-donating and-withdrawing groups on the aromatic rings were all compatible with this reaction to furnish the desired a-aminomethylated products in moderate to good yields with excellent regioselectivities and E/Z selectivities.

Electrosynthesis and Characterization of Aminomethyl Functionalized PEDOT with Electrochromic Property

We herein report the electrosynthesis of an aminomethyl functionalized poly（3,4-ethylenedioxythiophene）（PEDOT） derivative, poly（2＇-aminomethyl-3,4-ethylenedioxythiophene）（PEDOT-Me NH2）, in CH2Cl2-Bu4NPF6（0.1 mol·L^-1） system containing 2% boron trifluoride diethyl etherate（BFEE）. The electrochemical behavior, structure characterization, thermal properties and surface morphology of this novel polymer were systematically investigated by cyclic voltammetry（CV）, Fourier-transform infrared spectroscopy（FTIR）, thermogravimetry（TG） and scanning electron microscopy（SEM）, respectively. Electrochemistry results demonstrated that PEDOT-Me NH2 film displayed good redox properties and high electrochemical stability. Besides, PEDOT-Me NH2 films exhibited the electrochromic nature with obvious color changing from purple in the reduced form to blue upon oxidation. By further investigation, kinetic studies revealed that PEDOT-Me NH2 film had decent contrast ratio（41.8%）, favorable coloration efficiency（152.1 cm^2·C^-1）, low switching voltages and moderate response time（2.4 s）. Satisfactory results implied that the obtained PEDOT-Me NH2 film is a promising optoelectronic material and holds promise for electrochromic devices and display applications.

茶叶中草甘膦及其代谢产物氨甲基膦酸残留量液相色谱-串联质谱法的研究

研究了茶叶中草甘膦及其代谢产物氨甲基膦酸残留量的液相色谱-串联质谱测定方法。样品用水提取,MCX固相萃取柱净化,采用MRM监测正离子模式进行定性及内标法定量分析。结果表明,草甘膦及其代谢产物氨甲基膦酸的相关系数均大于0.999,定量限均为0.03 mg/kg,草甘膦加标回收率为106.0%~111.3%,氨甲基膦酸加标回收率为96.0%~106.3%。该方法灵敏度高、准确性好,更加合理,有利于操作,适用于茶叶中草甘膦及其代谢物氨甲基膦酸残留量的检测。

改良QuEChERS方法与UPLC-MS/MS联用测定茶叶中草甘膦、草铵膦及氨甲基膦酸

建立了改良QuEChERS-超高液相色谱-串联质谱法(UPLC-MS/MS)快速检测红茶和绿茶中草甘膦、草铵膦及氨甲基膦酸残留的分析方法。样品经纯净水提取2次,提取液采用MWCNT、C18、PVPP和CNT-OH吸附剂分散固相萃取净化,质谱以多反应监测模式(MRM)进行测定,外标法定量。结果表明,红茶和绿茶基质中,草甘膦、草铵膦和氨甲基膦酸在一定浓度范围内线性良好,相关系数(R^(2))为0.999 3~1.000 0,方法的检出限(LOD)分别为0.005 0、0.030、0.030 mg·kg^(-1),定量限(LOQ)分别为0.050、0.10、0.10 mg·kg^(-1),平均加标回收率在81.6%~120.0%,相对标准偏差(RSD)在0.6%~13.6%。该方法前处理简单、成本低、重复性好、灵敏度高,适用于红茶和绿茶中草甘膦、草铵膦及氨甲基膦酸的检测。

非衍生-离子色谱-三重四极杆质谱测定环境水样中有机磷

建立了一种非衍生-离子色谱-三重四极杆质谱法测定环境水样中有机磷(草甘膦、氨甲基膦酸、草铵膦、杀木膦和乙烯利)的方法。环境水样经RP-C18固相萃取柱和Ba柱除去杂质后,滤液无须衍生化,可直接进行定量分析。有机磷通过AS 19阴离子色谱柱分离,在负离子模式下以多反应监测方式(MRM)进行检测。结果表明,草甘膦、氨甲基膦酸和草铵膦在0.10~10.0μg/L范围内的线性相关系数(r)均>0.999,检出限分别为0.02,0.03和0.03μg/L,相对标准偏差(RSD)分别为2.8%~4.7%,5.4%~11.7%和5.1%~7.4%。杀木膦和乙烯利在0.02~2.00μg/L范围内的r值均>0.999,检出限分别为0.007和0.004μg/L,RSD分别为3.7%~5.8%和2.1%~13.2%。对实际水样进行测定,各目标物的加标回收率为70.0%~120%。该方法操作简便,精密度好,准确度高,适用于环境水样中5种极性有机磷的测定。

环己烷二甲胺合成技术的研究进展

环己烷二甲胺是一种重要的有机和精细化工中间体,在高端塑料和橡胶行业具有关键应用,但我国的核心生产技术却长期被国外垄断,开发高效的生产工艺可满足我国石油化工产业向高端精细化方向发展的需求。综述了环己烷二甲胺传统的加氢合成路线以及新兴的技术路线。结合当前市场需求的调研情况,分析了每条合成技术路线的优劣势及应用前景。从催化剂复配和有机反应过程的角度,重点剖析了环己烷二甲醇氨化制环己烷二甲胺全路线的技术难点。提出开发低成本高效的氨化催化剂和连续化生产的反应工艺是未来研究的热点方向,展望了二元醇氨化反应路线有拓展至其他二元胺关键单体的潜力。

ω-氨甲基长叶烯的合成、表征及其抑菌活性

采用Gabriel合成法,由ω-氯甲基长叶烯(3)经中间体N-取代邻苯二甲酰亚胺衍生物(4)合成了目标化合物ω-氨甲基长叶烯(5)。化合物4和5的结构经高分辨质谱(HRMS)、傅里叶红外光谱(FT-IR)、核磁共振氢谱(1 H NMR)、核磁共振碳谱(13 C NMR)和单晶X射线衍射(SC-XRD)进行表征确证,化合物5的绝对构型由合成的化合物4的晶体结构推断。在化合物4的水解反应中,采用添加氢氧化钠在无溶剂下加热回流肼解的方法,能提高化合物5的产率,简化分离提纯工艺。单因素试验结果表明:较佳的肼解反应工艺条件为n(水合肼)∶n(化合物4)=23∶1、10%氢氧化钠溶液5 g、反应温度120℃、反应时间6 h,此条件下化合物5的产率为94.1%,纯度为99.98%。体外抗菌活性测定结果表明:化合物5对4种细菌(金黄色葡萄球菌、枯草芽孢杆菌、大肠杆菌和肺炎克雷伯菌)和3种真菌(白色念珠菌、热带念珠菌和黑曲霉)的生长有明显的抑制作用,其最低抑制质量浓度(MIC)分别为1.95、1.95、7.81、3.91、3.91、1.95和15.63 mg/L。其中化合物5对白色念珠菌和热带念珠菌的抑制活性强于阳性对照酮康唑。

Synthesis of bis(amino)furans from biomass based 5-hydroxymethyl furfural

In this study we report a new reaction pathway in which the hydroxyl and the aldehyde groups of 5-hydroxymethyl furfural were aminated respectively. Hydroxyl group was aminated via Ritter reaction followed by direct reductive amination of aldehyde group. For the Ritter reaction of 5-hydroxymethyl furfural, mixture of trifluoromethane sulfonic acid and phosphoric anhydride showed good performance and the intermediate N-acyl-5-aminomethyl furfural with the highest yield of 89.1 wt% was obtained.Optimization of direct reductive amination of 2,5-bis（aminomethyl） furan was conducted and a yield of45.7 wt% was achieved. This study presents a simple way for preparing bis（amino）furans from renewable biomass based 5-hydroxymethyl furfural, which enriches the biorefinery concept from biomass.

超高效液相色谱-串联质谱法测定不同茶叶中草甘膦、氨甲基膦酸及草铵膦的残留

建立了超高效液相色谱-串联质谱同时快速测定不同茶叶中草甘膦、氨甲基膦酸及草铵膦的方法。样品用0.05 mol/L NaOH提取,并以HCl调节pH值, Oasis HLB小柱净化除杂,氯甲酸-9-芴基甲酯（ FMOC-Cl）柱前衍生反应后,超高效液相色谱-串联质谱法测定。本方法在5~1000μg/L浓度范围内,不同茶叶基质中草甘膦、氨甲基膦酸、草铵膦线性关系良好（R^2〉0.99）。在0.1,0.4和4 mg/kg添加水平下,不同茶叶（绿茶、红茶、乌龙茶、普洱茶）中3种化合物回收率均介于72.1%~109.9%之间,相对标准偏差RSD在0.5%~9.8%之间（n=6）,方法定量限（LOQ）在0.03~0.08 mg/kg之间（S/N=10）。本方法稳定,简便,灵敏,能够满足检测需求。

3-[二(羧甲基)氨甲基]-1,2-二羟基蒽醌与蛋白质作用的研究

在pH4.1的缓冲溶液中,研究3-[二(羧甲基)氨甲基]-1,2-二羟基蒽醌(AFB)与牛血清蛋白(BSA)结合反应,相互生成紫色的配合物.采用UV光谱法,测得此配合物的最大吸收峰值为510nm,与试剂本身相比较红移90nm.表观摩尔吸光系数ε=1.2474×10~4mol^(-1)·cm^(-1)·L,最大结合数n=7,表观结合常数K_C=3.85×l0~6.研究发现,AFB与BSA之间主要是以分子之间的静电引力结合,认为该反应符合Scatchard模型.离子强度对结合反应有显著的影响.