6-氨基己酸及2-氨基乙磺酸C60加成物的合成及溶解性

水溶性Fullerenes (C₆₀)衍生物的制备对于C₆₀的生物学研究具有十分重要的意义. 氨基酸与C₆₀的胺化反应可得到水溶性的氨基酸C₆₀衍生物. 以C₆₀与过量6-氨基己酸或2-氨基乙磺酸(摩尔比为1∶10)于80 ℃搅拌反应24 h, 分别得到加成度为5和4的氨基酸C₆₀主产物, 产率按加入的C₆₀计算分别为30%, 28%. 氨基酸碳链的长度及加成产物在反应体系中能否及时沉淀析出影响和控制着加成度的大小. C₆₀[NH(CH₂)₅COOH]₅H₅ (3a), C₆₀(NHCH₂CH₂SO₃H)₄H₄ (6a)用柱层析进一步纯化, 其结构组成经元素分析, ¹H NMR, ¹³C NMR, IR所证实. 6a的水溶性受溶液pH的影响较小, 3a在不同pH缓冲溶液中的溶解性用光谱法测定, 分别为: pH＝10.25时为71.81 mg•mL^－1, pH＝7时为23.68 mg•mL^－1, pH＝3.36时为10.12 mg•mL^－1. 在波长273 nm处, 3a的摩尔消光系数为ε＝3.43×10⁴ L•mol^－1•cm^－1.     

C60-吡咯烷衍生物的合成及非线性光学性质的研究

通过富勒烯C₆₀与肌氨酸和有机醛化合物的1,3-偶极环加成反应, 获得了九种含不同有机功能基团的C₆₀吡咯烷衍生物1～9, 用¹H NMR, ¹³C NMR, FTIR, UV-vis和FAB-MS进行了结构表征; 利用皮秒激光光源, 采用z扫描技术测定了分子的三阶非线性超极化率γ⁽³⁾, 结果显示: 化合物3 (γ⁽³⁾＝4.14×10^－33 esu)具有最大的三阶非线性光学系数, 说明增加噻吩共轭链的长度, 使三阶非线性活性增加; 对具有相同共轭链的C₆₀-噻吩吡咯烷衍生物(2, 5, 1和4), 吸电子取代基减小了三阶光学非线性活性, 给电子基增大了三阶光学非线性活性; 同时发现喹啉环2-位键联(7)比4-位(8)有更好的三阶光学非线性活性.     

C59XH (X＝N, B)自由基加成区域选择性的理论研究

用半经验的AM1方法, 对C₅₉XHCl_2n (X＝N, B; n＝1～2)和C₆₀H₂Cl_2n (n＝1～2)的异构体进行几何构型全优化和振动频率计算, 结合密度泛函B3LYP/6-31G*单点能计算确定各异构体的相对稳定性. 对比C₅₉XH (X＝N, B)和C₆₀H₂的H₂加成方式, 计算结果表明H₂或Cl₂加在碳笼官能化部分的邻近位置在能量上都是有利的; C₅₉NH和C₅₉BH自由基多加成物区域选择性的差别可归因于N原子和B原子电子性质的不同; 立体效应是导致H₂和Cl₂加成方式不同的主要原因.     

两个含铁、钴、硫金属异核羰基取代簇合物的合成及结构

Two novel substituted derivatives ( μ3-S)( μ-H)Fe₂Co(CO)₇L_n (n=2, L=AsPh₃ (3) n=1, L=dppm (4)) have been synthesized and characterized by IR, ¹H NMR, ³¹P NMR, MS and X-ray crystallography . The cluster 4 crystallizes in monoclinic space group C2/c, with a=1.589 1(7), b=1.814 9(8), c=2.277 8(11) nm, β=96.861(8), V=6.522(5) nm³, Z=8, D_c=1.552 g·cm^-3, F(000)=3 094, μ=12.95 cm^-1. Final R indices [i>2σ(I)]: R₁=0.054 3, wR₂=0.101 1. The cyclic voltammetric behavior for the parent cluster 1 and its substituted derivatives were investigated, the results show that the order of σ-donator ability is CO < PPh₃ < AsPh₃ < dppm. CCDC: 221867.     

具有C2对称的氮磷-氧磷配体双噁唑啉磷乙烷的合成及在不对称催化加氢中的应用

利用易得的光学纯N-甲基氨基醇与1,2-双(二氯磷)乙烷缩合合成了一类新的具有C₂对称轴的氮磷-氧磷配体(R,R)-双噁唑啉磷乙烷(BOAPE) 1～4. 该类配体不仅具有C₂对称结构和刚性五元环, 还具有富电子特性, 利用500 MHz进行了¹H NMR, ³¹P NMR, ¹³C NMR表征. 与这些配体配位形成的Rh配合物用于N-苯甲酰基脱氢丙氨酸衍生物和α-功能化酮不对称加氢, 分别可以得到99%和98%的ee. 这类配体比它们相对应的非C₂对称的氮磷-氧磷化合物(AMPP)配体具有更高的对映选择性. 在这四个新的配体中配体(R,R)-Ph-BOAPE (2)的催化性能最优. 催化剂[Rh(COD)(R,R)-Ph-BOAPE]BF₄的半反应周期t_1/2和周转频率(TOF)在N-苯甲酰基肉桂酸甲酯的不对称加氢反应中分别为12 min和6.5 min^－1.     

酰腙类Schiff碱汞(Ⅱ)配合物的合成及晶体结构

合成了Schiff碱配体3-乙酰吡啶缩邻氨基苯甲酰腙(L¹)及4-乙酰吡啶缩邻氨基苯甲酰腙(L²),并分别与HgCl₂进行了配位反应,得到2个配位聚合物{[Hg(L¹)Cl₂]·CH₃OH}_n (1)和[Hg(L²)Cl₂]_n (2),采用¹H NMR、FTIR和元素分析等手段对化合物进行了表征,并对配合物的热稳定性进行了考察。通过X射线单晶体衍射技术测定了2个配合物的单晶结构,结构解析表明,配合物1属于三斜晶系,P1空间群,配合物2属于单斜晶系,P2₁/n空间群。     

有机锡联苯乙酸酯的合成、结构表征和体外抗癌活性

合成了4个新的有机锡联苯乙酸酯{[(n-C₄H₉)₄Sn(O₂CCH₂C₆H₄C₆H₅-4)]₂O}₂ (1)和R₃SnO₂CCH₂C₆H₄C₆H₅-4(R=C₄H₅，2；c-C₆H₁₁，3；C₆H₅C(CH₃)₂CH₂，4)，利用元素分析、IR、 ¹H和 ¹³C NMR表征了其结构。通过X-射线单晶衍射测定了1和4的晶体结构。化合物1和化合物4均属三斜晶系，空间群P1。化合物1为具有Sn₂O₂四元环的中心对称二聚体结构，4为畸变的四面体结构。生物活性测试结果表明，化合物1和4对3种人癌细胞HeLa、CoLo205和MCF-7具有较好的体外抑制活性。     

二维大环网状结构的双(三环已基锡)二元酸酯的合成、结构及生物活性

三环己基氢氧化锡分别与辛二酸和壬二酸进行甲醇溶剂热反应,合成了2个双(三环已基锡)二元酸酯(CH₂)_n(CO₂SnCy₃)₂[(n:6(1),7(2)],并用IR、¹H和¹³C NMR、元素分析和X射线单晶衍射表征结构。化合物1、2均属单斜晶系,空间群分别为P2₁/n和P2₁/c,在化合物的晶体中,1通过Sn-O共价键,2通过Sn-O和Sn…O弱作用,分别形成了四锡核30元(1)和32元(2)二维大环网状结构。化合物1、2对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有良好的体外抑制活性,对S. Aureus、B. Subtilis、E. Coli和S. Typhi具有选择性的抑菌作用。     

含硅铁键环状化合物[Me2Si-η5-C5H4Fe(CO)(PPh3)][Me2Si-η5-C5H4Fe- (CO)2－n(PPh3)n] (n＝0或1)的合成与结构

鉴于含硅-过渡金属键化合物作为催化剂具有重要的应用价值, 在我们最近发现的化合物(η⁵,η⁵-C₅H₄Me₂SiSi-Me₂C₅H₄)Fe₂(CO)₄ (1)的硅硅键和铁铁键复分解重排反应可以有效地合成含有两个硅铁键的环状化合物[Me₂Si-η⁵-C₅H₄- Fe(CO)₂]₂ (2)的基础上, 对该硅铁键环状化合物的三苯基膦取代衍生物[Me₂Si-η⁵-C₅H₄-Fe(CO)(PPh₃)][Me₂Si-η⁵-C₅H₄Fe(CO)_2－n(PPh₃)_n] (3: n＝0, 5: n＝1)的合成方法进行了研究. 发现化合物1在三苯基膦存在下的复分解重排反应是合成单三苯基膦取代产物3的最好方法; 而双三苯基膦取代化合物5则可通过光照条件下2与三苯基膦发生羰基取代反应而得到, 产物中含有的顺反异构体可利用制备薄层色谱法分离. 利用X射线衍射法测定了化合物3的分子结构, 考察了三苯基膦配体的存在对分子结构的影响以及三苯基膦与铁形成的配位键的稳定性.     

二维大环网状结构的双(三环已基锡)二元酸酯的合成、结构及生物活性

三环己基氢氧化锡分别与辛二酸和壬二酸进行甲醇溶剂热反应,合成了2个双(三环已基锡)二元酸酯(CH₂)_n(CO₂SnCy₃)₂[(n:6(1),7(2)],并用IR、¹H和¹³C NMR、元素分析和X射线单晶衍射表征结构。化合物1、2均属单斜晶系,空间群分别为P2₁/n和P2₁/c,在化合物的晶体中,1通过Sn-O共价键,2通过Sn-O和Sn…O弱作用,分别形成了四锡核30元(1)和32元(2)二维大环网状结构。化合物1、2对人癌细胞Colo205、HepG2、MCF-7、Hela、NCI-H460均具有良好的体外抑制活性,对S. Aureus、B. Subtilis、E. Coli和S. Typhi具有选择性的抑菌作用。     

Synthesis of water-soluble cystine C60 derivative with catalyst and its active oxygen radical scavenging ability

A novel water-soluble cystine C_(60)derivative was synthesized in the presence of the catalyst,tetrabutylammonium hydroxide (TBAH).The product was characterized by FT-IR,UV,~1H NMR,~(13)C NMR,MS and elemental analysis.Furthermore,the scavenging ability to superoxygen anion radical O_2~(·-)and hydroxyl radical ~·OH was studied by chemiluminescence.It was found that cystine C_(60)derivative showed an excellent efficiency in eliminating superoxygen anion radical and hydroxyl radical.The 50% inhibition concentration(IC_(50))for superoxygen anion radical and hydroxyl radical were 0.167 and 0.008 mg/mL,respectively.     

Laser flash photolysis of fullerols of C60 and of C70 in aqueous solutions

Fullerols of C₆₀ and of C₇₀ [C₆₀(OH)_n, C₇₀(OH)_m], water-soluble fullerene derivatives, unlike some other fullerene derivatives (such as C₆₀ (C₄H₆O), C₆₀ (C₃H₇N) and C₆₀ [C(COOEt)₂]_x), do not result in excited triplet state but in ionization via monophotonic process in aqueous solutions with 248 nm laser. The quantum yields of formation of hydrated electron (Φ_e ⁻) are determined to be 0.08 and 0.11 for fullerols of C₆₀ and of C₇₀ respectively at room temperature (ca. 15°C) with KI solution used as reference. By laser flash photolysis and oxidation of sulfate radical anion SO₄ ⁻, the fullerol radical cation or neutral radical of C₆₀ is confirmed to be existent and the transient absorption spectra of fullerol radical cation of C₇₀ are observed for the first time. Project supported by the National Natural Science Foundation of China     

BIS(DITHIOSQUARAMIDE) LIGANDS AND THEIR COMPLEXES WITH DIVALENT NICKEL: THERMOCHROMIC BEHAVIOUR AND UNANTICIPATED FORMATION OF 2:2 SPECIES

Abstract

Reaction of two equivalents of N-mono- or di-substituted 3-amino-4-(n-butoxy)-3-cyclobutene-1,2-diones with a 1,2-diaminoethane gave N-mono- or di-substituted 1,2-bis((2-amino-1-cyclobutene-3,4-dione)amino)-ethane derivatives (bis(squaramides)). Reaction of the bis(squaramides) with excess P₄S₁₀ gave the analogous tetrathio derivatives (bis(dithiosquaramides), LH₂) of formula (NR¹R²)C₄S₂(NHCH₂CH₂NH)-C₄S₂(NR¹R²) (R¹=n-Bu, R²=H; R¹=R²=Et, n-Bu). The new bis(dithiosquaramide) ligands were characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR, electronic, and mass spectroscopic methods. The complexes of these ligands with nickel(II) were prepared, isolated and characterized. The isolated complexes are neutral 2:2 species of formula Ni₂L₂, as evidenced by results from mass spectrometry, and they exhibit thermochromic behaviour in pyridine solution. Additional spectroscopic data (IR, NMR) are consistent with the ligands being coordinated only through sulfur donor atoms and a structure for the complexes is proposed.     

Synthesis,spectroscopic/electrochemical characterization and DNA interaction study of novel ferrocenyl‐substituted porphyrins

We report the synthesis and characterization of two new meso‐ferrocenylporphyrins, with the ferrocenyl unit attached at the para position of a C₆F₄ group by a C? N bond with ? NH(CH₂)₂NH? ( 2a ) and ? NH(CH₂)₄NH? ( 2b ) spacers. Compounds 2a and 2b were characterized through elemental analyses, electrospray ionization high‐resolution mass spectrometry, ¹H NMR, UV–visible and fluorescence spectroscopies, electrochemistry and spectroelectrochemistry. The free base porphyrin 2 was included for comparison purposes. The binding ability of 2 and the porphyrin derivatives 2a and 2b with calf thymus DNA was determined using UV–visible and fluorescence spectroscopies. The results suggest that the interaction of these systems most probably occurs through π‐stacking by non‐classical modes involving the partial insertion of the C₆F₅ ring between adjacent base pairs on DNA and possible hydrogen interaction with the aliphatic ? NH(CH₂)_nNH? (n = 2 or 4) groups with calf thymus DNA. Moreover, we also demonstrate that porphyrins generate singlet oxygen species and show good photostability after irradiation.     

Magnetic field and magnetic isotope effects on the recombination kinetics of covalently-linked ketyl-phenoxyl triplet radical pairs

The recombination kinetics of three photogenerated covalently-linked ketyl-phenoxyl triplet radical pairs,³[PhC^.(OD)C₆H₄O(CH₂) _n OC₆H₄C₆H₄O^.] (n=3, 6, and 10), and of the corresponding deuterated derivatives were examined by the laser flash technique under an external magnetic field (up to 0.2 T) in a CDCl₃/CD₃OD (21) mixture. In zero magnetic field, radical pairs (RPs) with small exchange interactions (n=6 and 10) are characterized by high values of the magnetic isotope effect (MIE), which reach 3 for pairs withn=10. Under strong magnetic fields (up to 0.2 T), the values of MIE decrease to 1.2 to 1.1. The photochemical behavior of covalently-linked RPs is compared with that of similar unlinked RPs in micelles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 442–446, March, 1995.The authors are grateful to V. F. Tarasov, A. I. Shushin (N. N. Semenov Institute of Chemical Physics, RAS) and V. A. Nadtochenko (Institute of Chemical Physics in Chernogolovka, RAS) for helpful discussions.     

High‐Potential Perfluorinated Phthalocyanine–Fullerene Dyads for Generation of High‐Energy Charge‐Separated States: Formation and Photoinduced Electron‐Transfer Studies

High oxidation potential perfluorinated zinc phthalocyanines (ZnF_nPcs) are synthesised and their spectroscopic, redox, and light‐induced electron‐transfer properties investigated systematically by forming donor–acceptor dyads through metal–ligand axial coordination of fullerene (C₆₀) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine‐ (Py) and phenylimidazole‐functionalised fullerene (C₆₀Im) derivatives to the zinc centre of the F_nPcs. The determined binding constants, K, in o‐dichlorobenzene for the 1:1 complexes are in the order of 10⁴ to 10⁵ M ^?1; nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6‐31G* method. The HOMO and LUMO levels are located on the Pc and C₆₀ entities, respectively; this suggests the formation of ZnF_nPc^.+–C₆₀Im^.? and ZnF_nPc^.+–C₆₀Py^.? (n=0, 8 or 16) intra‐supramolecular charge‐separated states during electron transfer. Electrochemical studies on the ZnPc–C₆₀ dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge‐separated states. The energy of the charge‐separated state for dyads composed of ZnF_nPc is higher than that of normal ZnPc–C₆₀ dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar‐energy harvesting and optoelectronic device building applications.     

Crystal structures,electrochemical properties,antioxidant screening and in vitro cytotoxic studies on four novel Cu(II) complexes of bidentate Schiff base ligands derived from 2-methoxyethylamine

Four novel Schiff base ligands and their copper(II) complexes, [Cu(L¹)₂] (1), [Cu(L²)₂] (2), [Cu(L³)₂] (3), and [Cu(L⁴)₂] (4), were synthesized and characterized by elemental analyses, FT-IR, and UV–Vis spectroscopy. The ligands were synthesized from the condensation of 2-methoxyethylamine with various salicylaldehyde derivatives (x-salicylaldehyde for HLⁿ, x = H (n = 1), 5-Br (n = 2), 3-OMe (n = 3), and 4-OMe (n = 4)). The molecular structures of 1, 2, and 3 were determined by the single crystal X-ray diffraction technique. The redox behavior studies of the complexes in acetonitrile display the electronic effects of the groups on the redox potential. The antioxidant activity of the Schiff base ligands and their Cu(II) complexes was evaluated using the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method and FRAP assay. Furthermore, the in vitro anticancer activity of compounds was screened, including MTT and migration assays against gastric cancer cell line (MKN-45). The results show that all ligands and complexes have antioxidant and anticancer activity in a concentration-dependent way.     

THE B.A.S.I.C. (BINO-ANSA-SPIRO-IN-CYCLOPHOSPHAZENES) SYSTEM. PART I: NEW DERIVATIVES OF THE BIS-(TETRACHLORO-CYCLOTRIPHOSPHAZENYL)-SPERMINE

Abstract

The synthesis of new derivatives of bis-(tetrachlorocyclotriphosphazenyl)-spermine was achieved upon reaction of some MONOSPIRO–N₃P₃Cl₄[HN–(CH₂) _n –NH] (n = 2,3,4) derivatives and of the gem–N₃P₃Az₂Cl₄ with spermine. All compounds were obtained in the monomeric state. ³¹P and ¹³C high-resolution NMR were used, together with IR spectroscopy and mass spectrometry, to assign molecular structures and to reveal conformational equilibria, if any.     

2,4,4'-三羟基脱氧安息香-3'-磺酸钴的合成、晶体结构表征及性质研究

合成了未见文献报道的水溶性很好的2,4,4'-三羟基脱氧安息香-3'-磺酸钴, 采用IR, UV, ¹H NMR和元素分析对其进行了表征, 并利用X射线单晶衍射仪测定了该化合物的晶体结构. 使用荧光光谱法检测了化合物对羟基自由基的清除作用, 紫外光谱法检测其对超氧自由基的清除作用. 实验结果表明, 2,4,4'-三羟基脱氧安息香-3'-磺酸钴[C₂₈H₄₆CoO₂₆S₂]属于单斜晶系, 空间群C2/c, a＝3.3937(3) nm, b＝0.85180(7) nm, c＝1.37455(11) nm, α＝90°, β＝97.8200(10)°, γ＝90°, Z＝4, V＝3.9365(5) nm³, D_c＝1.555 g/cm³, F(000)＝1924, R₁＝0.0329, wR₂＝0.0852, 具有较好的清除羟基自由基和超氧自由基的作用.