具有其模块特性(氨基硫脲+羰基化合物)的硫代氨基脲(TSC)允许在主要R1R2C=N(1)-NH-C(S)-N(4)R3R4核心上最多四个取代基的广泛变化,因此是形成缀合物或纳米颗粒(NP)官能化的有趣工具。在这项工作中,引入二-2-吡啶基酮以配位金属和9-蒽醛以作为R1和R2发光至TSC。改变R3和R4取代基以形成缀合物。在N4位置引入氨基酸以产生[R1R2TSC-间隔区-氨基酸]缀合物。Further,官能团,例如膦酸(R-P(O)(OH)2),D-葡萄糖,邻-氢醌,OH,在N4位置引入硫醇(SH),产生用于直接NP锚定的[R1R2TSC-间隔基-锚定基团]缀合物。苯基,环己基,苄基,乙基和甲基用作间隔单元。作为直接NP锚定的第一个实例,两种苯基膦酸TSC衍生物都结合在TiO2NP上。[R1R2TSC-间隔-端基]缀合物,包括OH,S-Bn(Bn=苄基),NH-Boc(Boc=叔丁氧羰基),COOtBu,C=CH,或N3端基被合成用于通过酰胺与功能分子或官能化NP的潜在共价结合,酯,或三唑功能。从胺开始合成氨基硫脲H2NNH-C(S)-NR3R4,包括氨基酸,SCCl2或CS2,以及肼及其与联吡啶酮和蒽醛的缩合产生了34种新的TSC衍生物。它们在多达六个步骤中合成,总产率在10%至85%之间,并通过核磁共振波谱和质谱的组合进行了表征。UV-vis吸收和光致发光光谱使我们能够轻松地追踪联吡啶亚胺和蒽发色团。
Thiosemicarbazones (TSCs) with their modular character (thiosemicarbazides + carbonyl compound) allow broad variation of up to four substituents on the main R1R2C=N(1)-NH-C(S)-N(4)R3R4 core and are thus interesting tools for the formation of conjugates or the
functionalization of nanoparticles (NPs). In this work, di-2-pyridyl ketone was introduced for the coordination of metals and 9-anthraldehyde for luminescence as R1 and R2 to TSCs. R3 and R4 substituents were varied for the formation of conjugates. Amino acids were introduced at the N4 position to produce [R1R2TSC-spacer-amino acid] conjugates. Further, functions such as phosphonic acid (R-P(O)(OH)2), D-glucose, o-hydroquinone, OH, and thiol (SH) were introduced at the N4 position producing [R1R2TSC-spacer-anchor group] conjugates for direct NP anchoring. Phenyl, cyclohexyl, benzyl, ethyl and methyl were used as spacer units. Both phenyl phosphonic acid TSC derivatives were bound on TiO2 NPs as a first example of direct NP anchoring. [R1R2TSC-spacer-end group] conjugates including OH, S-Bn (Bn = benzyl), NH-Boc (Boc = tert-butyloxycarbonyl), COOtBu, C≡CH, or N3 end groups were synthesized for potential covalent binding to functional molecules or functionalized NPs through amide, ester, or triazole functions. The synthesis of the thiosemicarbazides H2NNH-C(S)-NR3R4 starting from amines, including amino acids, SCCl2 or CS2, and hydrazine and their condensation with dipyridyl ketone and anthraldehyde led to 34 new TSC derivatives. They were synthesized in up to six steps with overall yields ranging from 10 to 85% and were characterized by a combination of nuclear magnetic resonance spectroscopy and mass spectrometry. UV-vis absorption and photoluminescence spectroscopy allowed us to easily trace the dipyridyl imine and anthracene chromophores.