一些含硫、含氮化合物在卤化银成像过程中的作用

采用在曝光前后用不同浓度的化合物溶液分别处理硫增感立方乳剂样品方法,观察它们在感光特性上的差别,从而判断这些化合物在卤化银成像过程的不同阶段各自所起的作用.本工作中所选用的化合物有-1-苯基-5-巯基四氮唑(PMT),6-硝基苯并咪唑-(硝酸盐-),5-硝基苯并咪唑,5-硝基吲唑,4-羟基-6-甲基-1,3,3a,7-四氮茚-(TAI)和硫代乙酰胺.结果表明:PMT在一定的浓度范围内对潜影的形成有促进作用,但对显影有抑制作用;6-硝基苯并咪唑和-5-硝基苯并咪唑的情况相似,对潜影的形成无显著影响,而对显影的抑制作用明显;5-硝基吲唑不仅对潜影的形成有明显阻滞作用,而且对显影也有抑制作用;TAI则对潜影的形成有明显的促进作用,对显影的影响较小;硫代乙酰胺在弱酸性介质中对潜影的形成有显著阻滞作用,对显影也有一定的抑制作用,但对灰雾的增长十分显著.     

高分子介质对银盐扩散转移过程的影响

分散在高分子介质中的物理显影核层作为影像接受层,是CTP版材的重要组成部分.本文采用线阵CCD及银量测定法研究了三种高分子作为物理显影核的介质对物理显影过程及版材性能的影响.结果表明,PVA-Ⅰ、PVA-Ⅱ减慢扩散转移过程并降低版材的反差,而PVP对扩散转移过程有轻微促进作用.此外还用扫描电镜方法观察了物理显影银的表面堆积状态,发现银堆积状态与介质的种类及涂布量有关.     

添加剂在KOH溶液中对锌电极枝晶的影响

采用电流-时间曲线研究了6-硝基苯并咪唑、苯并咪唑和Pb2+在KOH（4 mol/L）溶液中对锌枝晶的影响。 结果表明,6-硝基苯并咪唑、苯并咪唑以及Pb2+能有效抑制锌枝晶的形成,从而提高锌电极的充电性能;当0.05 g/L Pb2+分别与6-硝基苯并咪唑和苯并咪唑在阴极过电位η=-200 mV进行充电实验时,具有较高的充电效率并能有效的抑制锌枝晶的生长。     

银盐CTP版材物理显影过程及银堆积形态的研究

银盐扩散型CTP(Computer-To-Plate)版材基于银盐扩散转移原理.本文利用高分辨率的场效应扫描电子显微镜及CCD等手段研究了几种因素对该类版材物理显影银堆积状态及物理显影过程的影响.清晰地观察到不同曝光区物理显影银的堆积状态,在弱曝光区,银颗粒堆积紧密,是版材具有亲油性的主要原因.使用不同类型络合剂分别得到了颗粒状、树枝状等各种形态的物理显影银,表明络合剂对银颗粒形态有显著影响.通过CCD装置对版材上物理显影过程的实时原位监测,从动力学的角度解释了络合剂、显影温度对物理显影银堆积状态的影响.     

酰基苯肼的感染显影及反差促进剂的作用

研究了六种结构不同的酰基苯肼化合物(通式:R—PhNH—NH—COR′)对卤化银乳剂感光性能的影响。结果表明,感染显影作用程度与酰基苯肼的结构有密切的关系。另外本文还就反差促进剂(醇类化合物和胺类衍生物)的作用及其机理进行了较深入的研究。事实说明,显影液中加入反差促进剂,不但能消除单独使用酰基苯肼时出现的“自阻”效应,而且还大大促进了感染显影的进行,提高了乳剂的反差和感光度。同时,本实验在应用高压液相色谱、色-质联仪、顺磁共振等方法对酰基苯胼的还原反应产物及反应中间物进行分析的基础上,更加明确地解释了感染显影和反差促进的作用机理。     

不同离子液体中硝基苯的电化学还原

研究了硝基苯在N-甲基咪唑对甲基苯磺酸([Mim][PhSO3])和1-丁基-3-甲基咪唑六氟磷酸([Bmim][PF6])两种离子液体中的电化学还原反应.循环伏安法测试显示,硝基苯在[Mim][PhSO3]中只出现一个还原峰,是一个受扩散控制的不可逆电化学反应,而在[Bmim][PF6]中出现两对氧化还原峰,表明其还原产物随离子液体性质的不同而异.     

硫醇化合物在银盐CTP版材上的疏水作用

本文采用线形CCD(ChargeCoupledDevice)技术、接触角等方法研究了一种长链硫醇化合物对计算机直接制版材料物理显影动力学及疏水性能的影响。结果表明,该化合物是物理显影过程的抑制剂,在显定合一的加工液中添加该化合物可以显著提高版材物理显影银区的疏水性能。同时,通过表面显微拉曼光谱进一步证明了硫醇化合物在物理显影银表面的吸附增加了版材的亲油性。     

由抑制剂引起的高反差机理研究

本文利用吸附曲线及电化学的方法,研究了一系列抑制剂在银及溴化银上的吸附行为,将这些吸附性质与显影过程中相应的抑制剂存在时的显影结果对比,实验表明:只有当抑制剂在银上为中等的吸附,而在溴化银上吸附很小时,才可能利用抑制剂达到高反差。相应的机理及抑制剂在银上的吸附性质在文中也作了讨论。     

Ni-Co-B非晶态合金催化剂用于氯代硝基苯液相加氢制氯代苯胺

 用化学还原法制备了 Ni-Co-B 非晶态合金催化剂,并采用透射电子显微镜、扫描电子显微镜、选区电子衍射、X射线衍射、X射线能谱和差热-热重分析等表征手段研究了催化剂的非晶性质和原子组成等. 将此催化剂用于邻氯硝基苯和 3,4-二氯硝基苯的液相催化加氢反应,结果表明,当Co/(Co+Ni)=0.5 (摩尔比)时, Ni-Co-B 催化剂具有较好的加氢性能和较高的抑制脱卤性能. 在不加脱卤抑制剂的情况下,两种氯代硝基苯的转化率均接近100%, 脱卤率分别为1.12%和0.42%, 优于使用 Ni-B 和 Co-B 非晶态合金催化剂时的结果. 还讨论了将Co引入到 Ni-B 非晶态合金催化剂时对其性能的影响.     

离子液体中硝基苯的扩散系数与量子化学参数的相关研究

采用量子化学半经验AM1方法,分别对[CMIM]+(1,3-二甲基咪唑离子)、[C2MIM]+(1-甲基-3-乙基咪唑离子)、[C4MIM]+(1-甲基-3-丁基咪唑离子)、[C6MIM]+(1-甲基-3-己基咪唑离子)和硝基苯,以及它们1∶1复合物构象进行优化,在此基础上以DFT(B3LYP/6-31+G)计算它们的...     

Electronic effects in dianion radicals of nitro derivatives of 2-phenylbenzimidazole

The EPR spectra of the dianion radicals of 5(6)-nitro-2-(4-aminophenyl)benzimidazole (I), 5(6)-nitro-2-phenylbenzimidazole (II), 5(6)-nitro-2-(4-nitrophenyl)benzimidazole (III), 5(6)-nitro-2-(3-nitrophenyl)benzimidazole (IV), and 2-(4-nitrophenyl) benzimidazole (V), obtained by electrochemical reduction in dimethylformamide (DMF) in a Bu₄NClO₄ -base electrolyte in the presence of Bu₄NOH (VI), were studied. Under the influence of VI, these compounds split out a proton from the imidazole ring and give anions I–V, which are capable of adding an electron reversibly. It was shown that the unpaired electron in I and II is localized in the benzimidazole system and that the splitting of the nitrogen atom of the nitro group does not depend significantly on the substituent in the phenyl ring. The introduction of a nitro group in the phenyl ring (III–V) leads to localization of the unpaired electron on it. The nature of the substituent in the benzimidazole system has a significant effect on the splitting constant for the nitrogen atom of the nitro group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 530–531, April, 1979.We thank T. A. Maslennikova for kindly providing us with the compounds for the investigation.     

Synthesis of [13C6]3,4-diaminobenzoic acid as a precursor for stable isotope labeled benzimidazoles

The synthesis of [¹³C₆]3,4-diaminobenzoic acid from commercially available [¹³C₆]aniline is described in six steps. Salient features of this route include the preparation of a differentially protected 3,4-diaminobenzonitrile, hydrogen gas free aromatic nitro group reduction with ammonium formate and facile benzimidazole ring closure of the ortho-arylenediamine with triethylorthoformate. This stable-labeled 3,4-diaminobenzoic acid is an ideal [M+6]isotopomer to synthesize complex benzimidazole fragments for mass spectrometry internal assays.     

Electrochemical and Theoretical Studies of 1-Alkyl-2-substituted Benzimidazoles as Corrosion Inhibitors for Carbon Steel Surface in HCl Medium

The inhibition efficiencies of newly synthesized four 1-alkyl-2-substituted benzimidazole compounds(a~d) have been studied for the corrosion of carbon steel in 1.0 M HCl by using potentiodynamic polarization measurement. The four inhibitors act as mixed-type inhibitors,which mainly inhibit cathodes. The inhibition efficiency of these compounds enhanced when the concentration of the inhibitors increased. A theoretical study of the corrosion inhibition efficiency of these compounds was carried out by using the B3 LYP level with the 6-31+G* basis set. Considering the solvent effect,the IEFPCM model was selected. Furthermore,the adsorption energies of the inhibitors with the iron(001) surface were studied by using molecular dynamic(MD) simulations. The theoretical results show that these inhibitors all exhibit several adsorption active-centers. Meanwhile,the MD simulations indicate that the adsorption occurs mostly through benzene ring and the lone pair electrons of the nitro atoms. These results demonstrated that the theoretical studies and MD simulations are reliable and promising methods for analyzing the inhibition efficiency of organic inhibitors.     

A new sequence isomer of AB‐polybenzimidazole for high‐temperature PEM fuel cells

A new sequence isomer of AB‐polybenzimidazole (AB‐PBI) was developed as a candidate for high‐temperature polymer electrolyte membrane fuel cells. A diacid monomer, 2,2′‐bisbenzimidazole‐5,5′‐dicarboxylic acid, was synthesized and polymerized with 3,3′,4,4′‐tetraaminobiphenyl to prepare a polymer that was composed of repeating 2,5‐benzimidazole units. In contrast to previously prepared AB‐PBI, which contains only head‐to‐tail benzimidazole sequences, the new polymer also contains head‐to‐head and tail‐to‐tail benzimidazole sequences. The polymer was prepared in polyphosphoric acid (PPA) and cast into membranes using the sol–gel PPA process. Membranes formed from the new AB‐PBI were found to be mechanically stronger, possessed higher acid doping levels, and showed improved fuel cell performance, when compared to the previously known AB‐PBI. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A fluorine scan of non-peptidic inhibitors of neprilysin: Fluorophobic and fluorophilic regions in an enzyme active site

This article describes the synthesis and in vitro biological affinities of (poly)fluorinated neprilysin inhibitors. Two series of inhibitors with F-substitution of the central benzimidazole platform of the ligands and the benzylic vector to fill the S1’ pocket of NEP were investigated. The S1’ pocket was found to be highly fluorophobic, and F-substitution led to significantly decreased binding affinities of inhibitors. This result is explained by electrostatically unfavorable close contacts of organic fluorine with the negatively polarized π-surfaces of surrounding aromatic amino acid side chains. In contrast, the protein environment around the benzimidazole platform, with three electropositive guanidinium side chains of Arg residues, was found to provide a fluorophilic environment. Overall, the data support that organic fluorine, with its high negative charge density prefers to orient into electropositive regions of receptor sites. pK_a measurements of fluorinated ligands provided several simple patterns for the prediction of pK_a values of benzimidazoles, important building blocks in medicinal chemistry.     

HPLC analysis of thimerosal and its degradation products in ophthalmic solutions with electrochemical detection

A reverse-phase high-performance liquid chromatographic assay using amperometric detection on a glassy-carbon electrode has been developed for analysis of thimerosal and its main degradation products, thiosalicylic acid and dithiodibenzoic acid, in ophthalmic formulations. A potential value of 0.9 V vs. Ag/AgCl was chosen for simultaneous detection of thimerosal and thiosalicylic acid, obtaining limits of detection of 1.0 and 0.2 ng injected, respectively. A potential value of 1.2V was applied for simultaneous determination of all three compounds studied, obtaining in this case limits of detection of 3,4 and 4 ng injected for thimerosal, thiosalicylic acid and dithiodibenzoic acid, respectively. The results obtained reveal the utility of the HPLC method in quality control of commercial products containing thimerosal with good detectability.     

Combinatorial liquid-phase synthesis of structurally diverse benzimidazole libraries

An expedient liquid-phase synthesis for construction of the diverse benzimidazole libraries is described. Nucleophilic aryl substitution of poly(ethylene glycol)-supported 4-fluoro-3-nitrobenzoic acid 3 with several primary amines under basic conditions, followed by Zn/NH(4)Cl mediated nitro group reduction, gave the PEG bound diamines 5. Subsequent cyclization of immobilized o-phenylenediamine 5 using thiocarbonyldiimidazole (TCD) or thiophosgene in dichloromethane furnished benzimidazole-2-thiones 6. Treatment of 6 with alkyl halides and benzylic halides in the presence of triethylamine provided 1-substituted-2-alkylthio-5-carbamoylbenzimidazoles on the support. The desired products 8 were severed from the PEG under mild conditions in high yield and high purity.     

Suzuki–Miyaura Cross‐Coupling of Potassium Organoborates with 6‐Sulfonate Benzimidazoles Using Microwave Irradiation

This article focuses on the utility of organotrifluoroborate salts as coupling partners for Suzuki–Miyaura cross‐coupling with 4‐nitro‐6‐triflyl benzimidazoles using microwave irradiation. The C–C bond formation at the 6‐position of the electron‐rich 1‐,4‐,6‐trisubstituted benzimidazole core is challenging and was not achievable via Kumada, Negishi, Stille, or Heck coupling strategies. Yields of 37–70% could be obtained via palladium coupling strategies utilizing potassium benzyl trifluoroborates as the organometallic coupling partner.     

Dimerization of biradicaloid heterocyclic compounds. Nitro derivatives of pyrrolo[1, 2-a]benzimidazole

A new type of easily dimerized heterocyclic compound, viz., nitro derivatives of 2-phenylpyrrolo[1,2-a]benzimidazole, was discovered. The reaction proceeds by heating the latter in acetic acid. A radical mechanism for the dimerization that takes into account partial protonation of the starting compound is discussed on the basis of electrochemical data, the high -donor capacity of 2-phenyl-4-methylpyrrolo[1,2-a]benzimidazole, the coloration that is characteristic for selfcomplexes, and EPR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 188–196, February, 1984.     

Biological Activity of Newly Synthesized Benzimidazole and Benzothizole 2,5-Disubstituted Furane Derivatives

Newly designed and synthesized cyano, amidino and acrylonitrile 2,5-disubstituted furane derivatives with either benzimidazole/benzothiazole nuclei have been evaluated for antitumor and antimicrobial activity. For potential antitumor activity, the compounds were tested in 2D and 3D cell culture methods on three human lung cancer cell lines, A549, HCC827 and NCI-H358, with MTS cytotoxicity and BrdU proliferation assays in vitro. Compounds 5, 6, 8, 9 and 15 have been proven to be compounds with potential antitumor activity with high potential to stop the proliferation of cells. In general, benzothiazole derivatives were more active in comparison to benzimidazole derivatives. Antimicrobial activity was evaluated with Broth microdilution testing (according to CLSI (Clinical Laboratory Standards Institute) guidelines) on Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Additionally, Saccharomyces cerevisiae was included in testing as a eukaryotic model organism. Compounds 5, 6, 8, 9 and 15 showed the most promising antibacterial activity. In general, the compounds showed antitumor activity, higher in 2D assays in comparison with 3D assays, on all three cell lines in both assays. In natural conditions, compounds with such an activity profile (less toxic but still effective against tumor growth) could be promising new antitumor drugs. Some of the tested compounds showed antimicrobial activity. In contrast to ctDNA, the presence of nitro group or chlorine in selected furane-benzothiazole structures did not influence the binding mode with AT-DNA. All compounds dominantly bound inside the minor groove of AT-DNA either in form of monomers or dimer and higher-order aggregates.