Synthesis and Characterization of Two Cyanoxime Ligands, Their Precursors, and Light Insensitive Antimicrobial Silver(I) Cyanoximates.
Synthesis and Characterization of Two Cyanoxime Ligands, Their Precursors, and Light Insensitive Antimicrobial Silver(I) Cyanoximates.
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DOI：
10.1016/j.ica.2013.12.006
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发表时间：
2014-03-01
影响因子：
2.8
通讯作者：
Gerasimchuk N
中科院分区：
文献类型：
--
作者：
Riddles CN;Whited M;Lotlikar SR;Still K;Patrauchan M;Silchenko S;Gerasimchuk N
采用两步制备方法，开发了 N-哌啶-氰基乙酰胺 (1)、N-吗啉基-氰基乙酰胺 (4) 及其肟衍生物 N-哌啶-2-氰基-2-肟基-乙酰胺 (HPiPCO, 2) 和 N-吗啉基-2-氰基-2-肟基-乙酰胺 (HMCO, 5) 的高产率合成方法。首先，纯氰基乙酸酯与相应的环状仲胺（例如哌啶和吗啉）反应得到纯氰基乙酰胺，在室温下使用气态 CH3ONO 进行亚硝化反应将其转化为氰基肟。通过IR、1H、13C和UV-可见光谱对合成的化合物进行了研究。确定了两种起始取代的氰基乙酰胺和两种目标氰肟的晶体结构。以高产率制备了 AgL 组合物（L = PipCO，3；MCO，6）的银（I）配合物。两种金属配合物在 100oC 以上都具有热稳定性，并且对高强度可见光非常稳定。使用漫反射光谱检查了干燥的 AgL 化合物对短波长紫外线辐射（一种常用的杀菌光）的稳定性。两种配合物均在约 3 小时内表现出缓慢的光还原作用，可观察到由于金属银细（纳米级）颗粒的形成而逐渐发生颜色变化和变暗。复合物 Ag(MCO), 6 对紫外线辐射的稳定性比其亲水性类似物 Ag(PipCO), 3 低约 2.6 倍。使用三种人类病原体：铜绿假单胞菌 PAO1（伤口分离物）、金黄色葡萄球菌 NRS70（耐甲氧西林呼吸道细菌），研究了制备的含有嵌入氰肟酸银 (I) 的固体丙烯酸酯基聚合物复合材料的抗菌和生物膜生长抑制特性。分离株）和变形链球菌 UA159（致龋齿分离株）。研究表明，化合物3和化合物6在0.5重量%浓度下完全消除PAO1的生长，在1%浓度下完全消除UA159和NRS70的生长。此外，数据表明复合物3和6还抑制革兰氏阳性和革兰氏阴性细菌病原体的浮游和生物膜生长。两种氰肟酸银（I）所表现出的热稳定性和显着的抗菌活性表明，所研究的复合物具有作为光不敏感抗菌添加剂用于固定留置装置的光固化粘合剂的巨大潜力。
High-yield syntheses of N-piperidine-cyanacetamide (1), N-morpholyl-cyanacetamide (4) and their oxime derivatives N-piperidine-2-cyano-2-oximino-acetamide (HPiPCO, 2) and N-morpholyc-2-cyano-2-oximino-acetamide (HMCO, 5) were developed using two-step preparations. At first, the reactions of neat cyanoacetic acid esters and the respective cyclic secondary amines such as piperideine and morpholine afforded pure cyanacetamides, which were converted into cyanoximes at room temperature using the nitrosation reaction with gaseous CH3ONO. The synthesized compounds were investigated by means of IR, 1H, 13C and UV-visible spectroscopy. Crystal structures of two starting substituted cyan-acetamides and two target cyanoximes were determined. Silver(I) complexes of AgL composition (L = PipCO, 3; MCO, 6) were prepared in high yield. Both metal complexes are thermally stable above 100oC, and remarkably stable to high intensity visible light. The stability of dried AgL compounds towards short wavelength UV-radiation (a frequently used germicidal light) was examined using diffusion reflectance spectroscopy. Both complexes demonstrate slow photoreduction within ~3 hrs, observable as a gradual color change and darkening due to the formation of fine (nano-scale) particles of metallic silver. The complex Ag(MCO), 6, is about 2.6 times less stable towards UV-radiation than its more lypophyllic analog Ag(PipCO), 3. Antimicrobial and biofilm growth inhibition properties of the prepared solid acrylate-based polymeric composites containing embedded silver(I) cyanoximates were investigated using three human pathogens: P. aeruginosa PAO1 (wound isolate), S. aureus NRS70 (methicillin resistant respiratory isolate), and S. mutans UA159 (cariogenic dental isolate). Studies showed that both 3 and 6 compounds completely abolished the growth of PAO1 at 0.5 weight % concentration, and the growth of UA159 and NRS70 at 1% concentration. Moreover, data demonstrates that complexes 3 and 6 also inhibit both planktonic and biofilm growth of Gram-positive and Gram-negative bacterial pathogens. The demonstrated thermal stability and pronounced antimicrobial activity of both silver(I) cyanoximates indicates the strong potential for the studied complexes to be used as light insensitive antimicrobial additives to light-curable adhesives that set indwelling devices in place.
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影响因子：
3.1
作者：
Curtis, Scott;Ilkun, Olesya;Gerasimchuk, Nikolay
通讯作者：
Gerasimchuk, Nikolay
影响因子：
14
作者：
Alt, V;Bechert, T;Schnettler, R
通讯作者：
Schnettler, R
影响因子：
5.2
作者：
Alipour, Misagh;Suntres, Zacharias E.;Omri, Abdelwahab
通讯作者：
Omri, Abdelwahab
影响因子：
4.6
作者：
Bagai, Rashmi;Abboud, Khalil A.;Christou, George
通讯作者：
Christou, George
DOI：
10.1107/s0108768194004179
发表时间：
1994-12-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE
影响因子：
--
作者：
CHERTANOVA, L;PASCARD, C;SHEREMETEV, A
通讯作者：
SHEREMETEV, A