新型双腙基喹唑啉类衍生物的合成及其抑菌活性

以邻氨基苯甲酸为起始原料,设计并合成了17个新型的双腙基喹唑啉类衍生物,其结构经1H NMR,13C NMR,IR,MS和元素分析表征.初步生物活性测试结果表明,部分化合物对小麦赤霉菌、辣椒枯萎菌和苹果腐烂菌有一定的抑制活性.     

含4(3H)-喹唑啉酮结构的取代1,3,4-噁二唑(噻二唑)化合物的合成及抗菌活性研究

以2-胺基苯甲酸为原料,通过环化、缩合、肼解、环化、硫醚化和氧化等步骤,合成了10个含喹唑啉酮取代1,3,4-噁二唑(噻二唑)化合物。通过1H NMR、13C NMR、MS 和元素分析进行确证其结构。初步抑菌活性测试表明,化合物浓度在50 μg/mL时,对葡萄座腔菌(Botryosphaeria dothidea)、拟茎点霉菌(Phomopsis sp.)和灰霉菌(B. cinerea)具有中等抑制活性。另外,目标化合物对猕猴桃溃疡病(Pseudomonas syringae pv. actinidia)均具有一定的抑制活性,其中化合物6a和6b对猕猴桃溃疡病的EC50值为11.7 μg/mL和20.5 μg/mL,优于对照药剂叶枯唑(24.5 μg/mL)。这类化合物具有较好抗菌的生物活性,在此基础上进行结构优化,有望发现较高活性化合物。     

二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee99%)。     

新型乙酰腙类化合物的合成与抗菌活性研究

以邻氨基苯甲酸甲酯为原料,经过甲基化、取代、关环、肼解反应制得含有喹唑啉二酮的中间体乙酰肼,进一步与多种取代醛和酮反应制得目标化合物9a-9t,所有化合物结构均经₁H NMR、₁₃C NMR、MS确证,并进行了体外抗菌活性测试,初步测试结果表明所有化合物均对测试菌株有一定的抗菌活性,且部分化合物对部分测试菌株的抑制活性接近甚至优于现有药物硫酸链霉素和多抗霉素B。     

双酰胺类衍生物的合成及抑菌活性

以对氯苯甲酸和取代邻氨基苯甲酸为起始原料,设计并合成9个未见文献报道的含苯并噻唑基双酰胺类化合物,其结构经1H NMR、13C NMR、IR及元素分析确证。初步生物活性测试结果表明,部份化合物具有一定的抑菌活性。     

新型喹唑啉二酮乙酰腙类化合物的合成与抗菌活性研究（英文）

以邻氨基苯甲酸甲酯为原料,经过甲基化、取代、关环、肼解反应制得含有喹唑啉二酮的中间体乙酰肼,进一步与多种取代醛和酮反应得到目标化合物9a~9t,所有化合物结构均经~1H NMR、~(13)C NMR和MS确证,并进行了体外抗菌活性测试。初步测试结果表明,所有化合物均对测试菌株有一定的抗菌活性,且部分化合物对测试菌株的抑制活性接近甚至优于现有药物硫酸链霉素和多抗霉素B。     

2,4-二氨基喹唑啉和2,4-二氨基吡啶并[2,3-d]嘧啶衍生物的合成

以6-氯-5-氰基烟酸、3-氰基-4-氟苯甲酸、4-氰基-3-氟苯甲酸和6-氯-5氰基-2-吡啶甲酸为原料,经过酰胺化和关环两步反应合成了2,4-二氨基喹唑啉和2,4-二氨基吡啶并[2,3-d]嘧啶衍生物,该方法操作简便,除6-氯-5-氰基-2-吡啶甲酸外,其它三种酸的反应收率可达65%以上.采用氢核磁(1H NMR)、碳核磁(13C NMR)和高效液质联用(LC-MS)分析对目标产物进行了表征.采用四甲基偶氮唑盐(MTT)法考察所合成化合物的体外抗肿瘤活性测性,结果表明部分化合物对所选肿瘤细胞的增殖有一定的抑制活性,化合物4c,4d,4e和4f对人白血病细胞(K562)和人肝癌细胞(HepG2)的抑制活性强于阳性对照药5-氟尿嘧啶(5-Fu).     

1,3-二取代-1H-1,2,4-三唑-5-胺类化合物的合成、结构表征及抑菌活性

以硝基胍、醛和卤代烷烃为原料,通过肼解、缩合、烷基化和酸催化分子内环化等反应,合成了一系列结构新颖的1,3-二取代-1H-1,2,4-三唑-5-胺类化合物,其结构经~1H NMR、~(13)C NMR、IR以及HRMS等方法确证.初步离体抑菌活性测定表明,在50 mg/L药剂浓度下,大部分化合物均具有一定的抑菌活性.相对于其他目标化合物,1-正丁基-3-(4-氯苯基)-1H-1,2,4-三唑-5-胺(6y)表现出较广谱的抑菌活性,对五种病原菌的抑菌活性均在53%以上.该类化合物合成简单,易于衍生化,可作为抑菌先导化合物进行优化.     

2-芳氨基-3-羟乙基喹唑啉-4(3H)-酮衍生物的合成及生物活性

以取代2-氨基苯甲酸(1)为原料,经系列反应合成关键中间体β-乙氧酰基膦亚胺(4),再与芳基异氰酸酯、乙醇胺进行三组份串联的氮杂-Wittig反应,合成了一系列2-芳氨基-3-羟乙基-4(3H)-喹唑啉酮衍生物6.目标分子的结构通过IR,1H NMR,MS和元素分析确证,并进一步测试了目标化合物对烟草青枯菌的室内抑菌活性.结果表明,虽然所有化合物的抗菌活性抑制率均低于参照药物噻菌铜,但若喹唑啉酮母环附加有取代基时,化合物的抑菌活性得到显著的提高.由此可见,对喹唑啉酮母环进行修饰也不乏是一种改进其生物活性的有效途径.     

含嘧啶取代1,3,4-噁二唑(噻二唑)硫醚化合物的合成及抗菌活性研究

以2-甲基-4-氨基-5-氰基嘧啶为原料,通过水解、酯化、肼解、环化和醚化等步骤,合成了12个含1,3,4-噁二唑(噻二唑)取代嘧啶化合物。通过₁H NMR,₁₃C NMR,MS 和元素分析进行确证其结构。初步抑菌活性测试标明,化合物浓度在50 μg/mL时,化合物6f和6f′对油菜菌核病菌(S. sclerotiorum)、马铃薯晚疫病菌(P. infestans)、水稻纹枯病(T. cucumeris)、小麦赤霉病菌(G. zeae)具有中等抑制率,其活性与对照药剂醚菌酯相当。     

应用先进光谱技术研究无机离子的环境界面化学

发生在环境界面的吸附-解吸和氧化-还原等反应对于污染物在环境介质间传输、转化以及归趋起着重要的调控作用。传统的研究方法虽然可以在实验室模拟并进而描述污染物环境界面过程,但是不能揭示界面反应机制,限制了对污染物环境界面行为的认识。近二十年来,各种谱学技术(例如X射线吸收精细结构和傅里叶红外光谱等)应用于环境界面反应的研究,推动了这一领域研究的发展,特别是在分子水平研究污染物的环境界面过程。通过现代光/波谱技术原位分析,可以实时获取界面反应的定量与结构信息,从而更准确地判断反应机制,极大促进了对污染物在多介质环境界面迁移转化规律的认识。本文将在概述环境界面化学反应的基础上,针对无机离子在环境界面的反应过程,重点介绍几种关键光/波谱技术(X射线吸收精细结构光谱、傅里叶红外光谱、拉曼光谱、核磁共振谱和穆斯堡尔谱等)在环境界面化学研究中的应用,并展望其在环境界面过程研究中的应用前景。     

ICP-MS的KED模式测定磷酸加王水复溶土壤样品中的二十种金属元素

在研究锗测定时,磷酸先溶解样品,后加入王水复溶,可同时测定锂、铍、钪、钒、铬、钴、镍、铜、锌、锗、钼、镉、钡、镧、铈、钨、铊、铅、钍和铀元素。研究ICP-MS的最佳测量模式、最佳工作状态,以铑为内标校正仪器的漂移。通过选择高、中、低几个国家一级水系沉积物和土壤标准物质随同样品一起实验溶解建立标准曲线,消除消解、分取、定容中带来的不确定误差和基体干扰,选择8个土壤标准物质为实验样本。最终结果表明,该实验方法准确度(ΔlgC)小于0.1,精密度(RSD)小于8%,该方法满足测定要求,适用于地质普通样品的多金属检测。#$NL     

Transition Metal–(μ-Cl)–Aluminum Bonding in α-Olefin and Diene Chemistry

Olefin and diene transformations, catalyzed by organoaluminum-activated metal complexes, are widely used in synthetic organic chemistry and form the basis of major petrochemical processes. However, the role of M–(μ-Cl)–Al bonding, being proven for certain >C=C< functionalization reactions, remains unclear and debated for essentially more important industrial processes such as oligomerization and polymerization of α-olefins and conjugated dienes. Numerous publications indirectly point at the significance of M–(μ-Cl)–Al bonding in Ziegler–Natta and related transformations, but only a few studies contain experimental or at least theoretical evidence of the involvement of M–(μ-Cl)–Al species into catalytic cycles. In the present review, we have compiled data on the formation of M–(μ-Cl)–Al complexes (M = Ti, Zr, V, Cr, Ni), their molecular structure, and reactivity towards olefins and dienes. The possible role of similar complexes in the functionalization, oligomerization and polymerization of α-olefins and dienes is discussed in the present review through the prism of the further development of Ziegler–Natta processes and beyond.     

中文化学名词醇醛酮醚酯之由来

1932年民国教育部颁布的《化学命名原则》为中文化学名词确立了统一的标准,并对于"元素及化合物定名取字"提出"取字应以谐声为主,会意次之,不重象形"的定名总则.它确立的中文化学名词醇、醛、酮、醚、酯是意译名,这似乎与其音译为主的命名原则相悖.本文讨论了醇、醛、酮、醚、酯的各种历史译名,并分析了它们被《原则》采纳的原因.     

Bestimmung von Fe, Co, Cu, Zn, Se, Rb und Cs in NBS-Ochsenleber, Blutplasma und Erythrocyten durch INAA und AAS

Zusammenfassung Der Gehalt von Fe, Co, Cu, Zn, Se, Rb und Cs wurde in Blutplasma und in Erythrocyten von sechs Normalpersonen mittels der instrumentellen Neutronenaktivierungsanalyse und der flammenlosen Absorptionsspektrometrie (Cu) bestimmt. Zur Überprüfung der Richtigkeit wurde der NBS-Standard 1577, Ochsenleber, verwendet. Die erhaltenen Resultate für Elemente mit höheren Gehalten (Fe, Cu, Zn) liegen weitgehend im Bereich der bisher veröffentlichten Daten. Bei Elementen mit kleineren Gehalten (Co, Se, Rb, Cs) liegen unsere Werte in dem unteren Bereich oder darunter. Für diese Elemente wurden in Blutplasma und in Erythrocyten (hier bezogen auf Trockenmasse) die folgenden Mittelwerte ermittelt: Für Co 0,22 ±0,14 ng/ml, 0,59±0,23 ng/g, für Se 103±18 ng/ml, 401±29 ng/g, für Rb 167±36 ng/ml, 12,1±2,5 g/g und für Cs 0,88±0,18 ng/ml, 13,0±5,7 ng/g.

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Determination of Fe, Co, Cu, Zn, Se, Rb and Cs in NBS Bovine Liver, blood plasma and erythrocytes by INAA and AAS

Summary The content of the above elements has been determined in blood plasma and in erythrocytes of six normal persons by instrumental neutron activation analysis and flameless atomic absorption spectrometry (Cu). The over-all accuracy of these techniques was checked by using the NBS standard 1577, Bovine Liver. The results obtained for elements of higher content (Fe, Cu, Zn) are essentially in the range of other published data. However, our results for elements occurring with lower contents (Co, Se, Rb, Cs) are in agreement with the lowest values of the published data and in some cases they are even significantly below these. For these elements, the following contents have been determined in blood plasma and in erythrocytes (here related to dry weight): for Co 0.22±0.14 ng/ml and 0.59±0.23 ng/g, for Se 103±18 ng/ml and 401±29 ng/g, for Rb 167 ±36 ng/ml and 12.1±2.5 g/g and for Cs 0.88 ±0.18 ng/ml and 13.0±5.7 ng/g, respectively.

Diese Arbeit wurde durch die Deutsche Forschungsgemeinschaft gefördert.Dem Kernforschungszentrum danken wir für den Erlaß der Bestrahlungskosten.Herrn Dr. med. K. Spenger sind wir für die Mitwirkung bei der Blutentnahme und für wertvolle Diskussion dankbar.     

Attenuation of Scopolamine-Induced Amnesia via Cholinergic Modulation in Mice by Synthetic Curcumin Analogs

Alzheimer’s disease is an emerging health disorder associated with cognitive decline and memory loss. In this study, six curcumin analogs (1a–1f) were synthesized and screened for in vitro cholinesterase inhibitory potential. On the basis of promising results, they were further investigated for in vivo analysis using elevated plus maze (EPM), Y-maze, and novel object recognition (NOR) behavioral models. The binding mode of the synthesized compounds with the active sites of cholinesterases, and the involvement of the cholinergic system in brain hippocampus was determined. The synthesized curcumin analog 1d (p < 0.001, n = 6), and 1c (p < 0.01, n = 6) showed promising results by decreasing retention time in EPM, significantly increasing % SAP in Y-maze, while significantly (p < 0.001) enhancing the % discrimination index (DI) and the time exploring the novel objects in NORT mice behavioral models. A molecular docking study using MOE software was used for validation of the inhibition of cholinesterase(s). It has been indicated from the current research work that the synthesized curcumin analogs enhanced memory functions in mice models and could be used as valuable therapeutic molecules against neurodegenerative disorders. To determine their exact mechanism of action, further studies are suggested.     

Phosphorescence of aromatic molecules in complexes with crystalline β-cyclodextrin at room temperature

The rate constants for the quenching by oxygen of triplet states of aromatic molecules (naphthalenes-d₈ and-h₈, phenanthrene) forming inclusion complexes with crystalline β-cyclodextrin in water at 290 K are equal to 900–1300 L mol⁻¹s⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1450–1453, August, 1997.     

Direct benzylic functionalization of pyridines:Palladium-catalyzed mono-α-arylation of α-(2-pyridinyl)acetates with heteroaryl halides

Herein,we report a Pd-catalyzed mono-a-arylation reaction for pyridine benzylic functionalization.This approach serves as an efficient alternative to synthesize di-heteroaryl acetates in good yields and selectivities.Moreover,the method is applicable to heteroa ryl substrate combinations,and exhibits great functional group tolerance.A streamlined protocol also enables the rapid synthesis of diheteroaryl ketones.The synthetic value was also demonstrated by scale-up experiments.     

Unveiling Antimicrobial and Antioxidant Compositional Differences between Dukkah and Za’atar via SPME-GCMS and HPLC-DAD

Interest in plant-based diets has been on the rise in recent years owing to the potential health benefits of their individual components and the notion that plant-based diets might reduce the incidence of several diseases. Egyptian dukkah and Syrian za’atar are two of the most historic and famous Middle Eastern herbal blends used for their anti-inflammatory, hypolipidemic, and antidiabetic effects. Headspace SPME-GCMS and HPLC-DAD were adopted for characterizing the aroma profile and phenolic compounds of both herbal blends, respectively. Further, vapor-phase minimum inhibitory concentration was employed for assessing each blend’s antibacterial potential, while their antioxidant potential was estimated via in vitro antioxidant assays. SPME headspace analysis indicated the abundance of ethers and monoterpene hydrocarbons, while HPLC revealed the presence of several phenolics including rosmarinic acid, ferulic acid, and rutin. Biological investigations affirmed that vapor-phase of the tested blends exhibited antibacterial activities against Gram-positive and Gram-negative pathogens, while the antioxidant potential of the blends was investigated and expressed as Trolox (125.15 ± 5.92 to 337.26 ± 13.84 μM T eq/mg) and EDTA (18.08 ± 1.62 to 51.69 41 ± 5.33 μM EDTA eq/mg) equivalent. The presented study offers the first insight into the chemical profile and biological activities of both dukkah and za’atar.