Reaction of 2-methyl-3-morpholino-1-phenylprop-2-en-1-one with Ru3(CO)12

The reaction of Ru₃(CO)₁₂ with 2-methyl-3-morpholino-1-phenylprop-2-en-1-one (1) produced the Ru₆(CO)₁₆(μ₄-η¹:η¹:η²:η²-PhC(O)-C(Me)=C)₂ (2), Ru₂O₂(CO)₄(η³-OC(Ph)C(Me)C(H)C(Me)₂C(Ph))₂ (3), and [Ru(CO)₂(PhCO₂)(O(CH₂-CH₂)₂NH]₂ (4) complexes, which were characterized by IR and NMR spectroscopy. The structures of the complexes were established by X-ray diffraction. The formation of the complexes is accompanied by deamination of ligand 1. Complexes 2 and 3 bearing the vinyl ketone groups contain five-membered oxaruthenacycles and dihydropyran rings. Morpholine is not removed from the reaction mixture and leads to the formation of complex 4. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2063–2068, December, 2006.     

基于3-羟基沙利度胺的比率型荧光探针对过氧化氢的检测

药物分子3-羟基沙利度胺作为分子胶水因其良好的生物相容性、 明确的代谢途径以及与CRBN 蛋白的特异性结合而备受关注, 但其在分析化学领域的应用却鲜有报道. 本文基于3-羟基沙利度胺的特殊荧光性能, 研究了其在化学传感器领域的新应用. 以3-羟基沙利度胺为荧光核, 设计合成了显现荧光的过氧化氢探针沙利度胺基频哪醇硼酸酯. 基于激发态分子内质子转移机理, 该探针对过氧化氢显示出特异选择性和超高灵敏度, 检出限为9.8 nmo/L, 可应用于化学实验废水、 污水及化妆品中过氧化氢的检测. 此外, 通过光谱技术和理论计算揭示了该荧光探针的识别机制.     

Michael reactions withtrans-3-isopropenyl-2-phenylthiocyclopentan-1-one andtrans-3-isopropenyl-2-phenylsulfonylcyclopentan-1-one

The condensation of methyl acrylate with the title -ketosulfide and -ketosulfone was studied. The primary adduct of -ketosulfone with acrolein readily undergoes intramolecular aldolization to give bicyclo[3.2.1]octane derivatives. The molecular structure of one of them was elucidated by X-ray analysis.Deceased Nov., 1, 1992.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 118–122, January, 1993.     

Synthesis of 1-Bromo-3-butyn-2-one and 1,3-Dibromo-3-buten-2-one

Synthetic procedures for the preparation of 1-bromo-3-butyn-2-one and 1,3-dibromo-3-buten-2-one are given. These compounds are prepared from 2-bromomethyl-2-vinyl-1,3-dioxolane, which can readily be prepared from 2-ethyl- 2-methyl-1,3-dioxolane. The synthetic routes are as follows: 2-bromomethyl-2-vinyl-1,3-dioxolane is converted to 2-(1,2-dibromoethyl)-2-bromomethyl-1,3-dioxolane. Double dehydrobromination with ^tBuOK affords 2-ethynyl-2-bromomethyl-1,3-dioxolane. Formolysis with formic acid gives 1-bromo-3-butyn-2-one. Deacetalized 2-bromoethyl-2-vinyl-1,3-dioxolane was treated with Br₂ and Li₂CO₃/12-crown-4 in tetrahydrofuran to give 1,3-dibrom-3-buten-2-one in moderate yield.     

一种新型Zn2＋近红外荧光探针的研究

Zn^2＋是多种酶和转录因子的必要成分, 在生物体内起着重要的作用, 检测Zn²⁺具有十分重要的生物学意义. 我们合成了一种新型近红外荧光探针TAEA-IR-780, 该探针通过配位作用与Zn^2＋结合后, 荧光显著增强. 通过质谱和氢谱对该探针进行了表征, 并探讨了pH值、其它金属离子对Zn^2＋检测的影响. 该探针的激发波长为683 nm, 发射波长为750 nm, 可避免对生物活体的损伤, 同时生物体内常见的金属离子对其干扰较小. 该探针对Zn^2＋的检测下限达1.0× 10^－9 mol•L^－1, 具有较高的检测灵敏度.     

肿瘤乏氧靶向响应的罗丹明荧光探针及其成像介导手术治疗

基于罗丹明的良好荧光性能, 经化学偶联反应制备并表征了一个偶氮乏氧特异响应的“Off-On”型荧光成像探针(FY-4). 从分子层面证实了其荧光“Off-On”性能和响应机制; 在L02正常细胞及4T1, HeLa和A549肿瘤细胞层面考察了其对受试细胞株的毒性和不同乏氧时间的荧光成像性能; 再利用4T1肿瘤模型, 分别以肿瘤原位注射和尾静脉注射的方式考察了其荧光成像性能, 并探究了其荧光成像介导切除肿瘤性能, 最后还考察了FY-4的生物安全性. 结果表明, FY-4有高的肿瘤乏氧靶向特异“关-开”响应的荧光成像差异显影及荧光成像介导切除肿瘤的潜能, 结合其良好的光物理性能、 生物安全性和明晰的给药时间等特性, 有望为生物医学荧光成像介导肿瘤切除提供新的研究工具.     

Photolysis of 2-piperidino- and 2-morpholino-3-methoxy-1,4-naphthoquinones

PMR and¹³C NMR spectroscopy was used to establish the structure of the primary products of the photolysis of 2-piperidino- and 2-morpholino-3-methoxy-l, 4-naph-thoquinones. A scheme for the subsequent dark transformations of these compounds is proposed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 709–713, March, 1991.     

Tb~(3+)配合物修饰的磁性纳米荧光探针对水中Cu~(2+)的超灵敏检测

合成了一种Tb~(3+)配合物修饰的磁性纳米荧光探针cs124-DTPA-NH-PEGDBI-Fe3O4∶Tb。该复合荧光探针与Cu~(2+)有很强的结合能力,Cu~(2+)对Tb~(3+)配合物修饰的磁性纳米荧光探针具有荧光猝灭作用。实验表明,该复合荧光探针稳定性良好且有很好的水溶性,可在较宽的pH范围(5.0~10.0)快速检测Cu~(2+)。此外,在竞争实验中发现,该纳米荧光探针能够实现对溶液中Cu~(2+)的超灵敏和选择性检测而对其他多种常见离子响应较小,对Cu~(2+)的检测限甚至可达到1nmol/L。     

反应型次氯酸荧光探针

生物体内的次氯酸是氯离子和过氧化氢(H2O2)由髓过氧化物酶(MPO)催化生成的,是生物体内最重要的活性氧(ROS)之一,在生理过程中发挥了至关重要的作用.但是,过量的次氯酸会导致一系列生理疾病,因此有效的识别和检测次氯酸备受研究者们的青睐.与传统检测方法相比,荧光探针具有选择性好、灵敏度高、可实时监测等诸多优势,因此...     

以苯并咪唑萘酰亚胺为荧光团高选择快速检测H2S的荧光探针

以1,8-萘二甲酸酐为起始原料合成一种萘酰亚胺衍生物3-叠氮基-7H-苯并[de]苯并[4,5]咪唑[2,1-a]异喹啉(DBNG),利用傅里叶变换红外光谱(FT-IR)和核磁共振波谱(NMR)等测试手段确定其结构,并将其作为小分子荧光探针用于检测H2S,系统研究了其荧光特性,结合理论计算,探究其可能的检测机制.结果表...     

Synthesis of 3-(4-bromophenyl)-1-morpholino-2-phenylalkan-3-ol hydrochlorides

Reactions of 1-(4-bromophenyl)-3-morpholino-2-phenylpropan-1-one with various Grignard compounds in diethyl ether gave a broad series of tertiary amino alcohols, 3-(4-bromophenyl)-1-morpholino-2-phenylalkan-3-ol hydrochlorides, that can be regarded as Trihexyphenidyl analogs.     

Synthesis of 1-Methyl-3-pyrrolin-2-one

The synthesis of 1-methyl-3-pyrrolin-2-one from the oxidative-elimination of 1-methyl-3-phenylselenenyl-2-pyrrolidinone and from the pyrolysis of 3-phenylsulfinyl-2-pyrrolidinone is reported.     

Synthesis of chalcogeno lactones. II. 3, 4-dihydro-1 H-2-benzothiin-3-one, 3,4-dihydro-1H-2-benzoselenin-3-one and 3,4-dihydro-1H-2-benzotellurin-3-one

The synthesis of 3, 4-dihydro-1H-benzothiin-3-one and its selenium and tellurium analogs is reported from o-bromomethylphenylacetyl chloride and sodium hydrogen chalcogenates, via phase-transfer catalysis.     

Non-Ionic Water-Soluble Crown-Ether-Substituted Polyfluorene as Fluorescent Probe for Lead Ion Assays

A new non-ionic water-soluble polyfluorene that contains two benzo-18-crown-6 side chains per repeat unit (PFDC) is synthesized and characterized. Upon addition of Pb²⁺ ions to a solution of PFDC, the PFDC fluorescence is strongly quenched. The minor interference from other metal ions, especial from Cu²⁺ and Hg²⁺ions, clearly shows that the PFDC can be used to detect Pb²⁺ ions with high selectivity. The fluorescence quenching of PFDC in solution originates from the multivalent coordination of the crown-ether moieties to Pb²⁺ ions followed by precipitation. In comparison to ionic conjugated polymers, the pH of the medium shows less effect on the binding of non-ionic PFDC to Pb²⁺ ions.

     

6-氯-2(1 H)-喹喔酮合成方法的改进

设计了以对氯苯胺和氯乙酰氯为原料,经缩合、硝化、还原、环合、氧化五步制得6-氯-2(1H)-喹喔酮的位置选择性合成方法,并对以氯乙酰氯作为苯胺的氨基保护试剂进行硝化的反应和对含活泼氯的硝基化合物进行还原的反应进行了研究.研究结果表明以氯乙酰氯作为苯胺的氨基保护试剂进行硝化的反应符合一般的硝化定位规则,而含活泼氯的硝基化合物的还原在优化条件下以铁粉为还原剂可以高选择性获得目标产物.