Synthesis and Anti-Candida Activity of Cobalt(II) Complexes of Benzene-1,2-Dioxyacetic Acid (bdoaH(2)). X-Ray Crystal Structures of [Co(bdoa)(H(2)O)(3)] 3.5H(2)O and {[CO(phen)(3)](bdoa)}(2)24H(2)O (phen = 1,10-Phenanthroline)

Co(CH(3)CO(2))(2)4H(2)O reacts with benzene-1,2-dioxyacetic acid (bdoaH(2)) to give the Co(2+) complexes [Co(bdoa)(H(2)O)(3)]H(2)O (1a) and [Co(bdoa)(H(2)O)(3)] 3.5H(2)O (1b). Subsequent reaction of 1a with 1,10- phenanthroline produces [CO(phen)(3)] bdoa10H(2)O (2a) and {[CO(phen)(3)](bdoa)}(2)24H(2)O (2b). Molecular structures of 1b and 2b were determined crystallographically. In 1b the bdoa(2-)- ligates the metal by two carboxylate oxygens and two ethereal oxygens, whereas in 2b the bdoa(2-) is uncoordinated. The Mn(2+) and Cu(2+) complexes [Mn(bdoa)(phen)(2)]H(2)O (3) and [Cu(pdoa)(imid)(2)] (4) were also synthesised, 1a-4 and other metal complexes of bdoa H(2) (metal = Mn(2+), Co(2+) ,Cu(2+), Cu(+) ) were screened for their ability to inhibit the growth ofhe yeast Candida albicans. Complexes incorporating the 1,10-phenanthroline ligand were the most active.     

Interaction of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] and [Rh(2)(O(2)CCH(OH)Ph)(2)(phen)(2)(H(2)O)(2)](O(2)C-CH(OH)Ph)(2) With Sulfhydryl Compounds and Ceruloplasmin

The interaction of binuclear rhodium(II) complexes [Rh(2)(OOCCH(3))(4)(H(2)O)(2)], [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] {OOCCH(OH)Ph}(2), [Rh(2)(OOCCH(3))(2)(bpy)(2)(H(2)O)(2)](OOCCH(3))(2) and [Rh(2)Cl(2)(OOCMe)(2)(bpy)(2)](3H(2)O) with ceruloplasmin, cysteine, glutathione and coenzyme A have been investigated using. UV-Vis and CD spectroscopies. The complexes containing phen or bpy at pH = 7.4 and 4.0 are readily reduced with sulfhydryl compounds, while rhodium(II) acetate is relatively stable in these conditions. Complex [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] strongly changes structure of ceruloplasmin leading to the decrease of of alpha-helix content and loss of oxidase activity.     

Properties of Binuclear Rhodium(II) Complexes and Their Antibacterial Activity

Binuclear rhodium(II) complexes [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)], [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) and [Rh(2)Cl(2)(mu-OOCCH(3))(terpy)(2)](H(3)O)Cl(2).9H(2)O (R = H, Me, Bu(n), ph, PhCHOH; N-N = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp) and 6,7-dimethyl-2,3- di(2-pyridyl)quinoxaline (dmpq); terpy 2,2':6',2'-terpyridine) have been synthesized and their structure and properties have been studied by electronic, IR and (1)H NMR spectroscopy. Antibacterial activity of these complexes against Staphylococcus aureus and Escherichia coli has been investigated. The most active antibacterial agents against S. aureus were [Rh(2)(OOCPh)(2)(phen)(2)(H(2)O)(2)](2+), [Rh(2)(OOCPh)(2)(dmpq)(2)(H(2)O)(2)](2+), [Rh(2)(OOCBu)(2)(phen)(2)(H(2)O)(2)](2+) and [Rh(2)-(OOCBu)(2)(bpy)(2)(H(2)O)(2)](2+) which were considerably more active than the appropriate nitrogen ligands. The complexes show rather low activity against E. coli.     

Synthesis and Crystal Structure of Diaqua(1,10-Phenanthroline-N,N')(Thiosulfato-O,S)Manganese(II). Biological Properties

The synthesis of diaqua(1,10-phenanthroline-N,N')(thiosulfato-O,S)manganese(ll) [Mn(phen)(S(2)O(3))(H(2)O)(2)] was investigated. Its structure was determined by single crystal X-ray diffraction from 2418 reflections (I > 3 sigma(I)) to a final value of R = 0.047 and Rw = 0.054. Crystal data are as follows : space group P(2) (1); a = 10.356(3), b = 7.097(3), c = 20.316(2) A, beta = 94.29(2) degrees , V = 1489.1(8) , A(3), Z = 2. There are two independent title compounds in the asymetric unit. Each manganese atom has a distorted octahedral Mn(SO)N(2)O(2) geometry with the S and O atoms (from two neighbouring thiosulfate ligands) mutually trans, two N atoms from the 1,10-phenanthroline ligand and two water oxygen. The thiosulfate group behaves as a bridging ligand, connecting, through sulfur and oxygen, Mn atoms related by the binary b translation, thus forming infinite chains running parallel to this axis. Infrared and electronic spectra are reported.     

三元钴配合物[Co（thy）（phen）（H2O）2]的合成、表征及荧光性能研究

用溶液法合成了钴的配合物[Co（thy）（phen）（H2O）2],对它进行了元素分析、红外光谱表征。其中硫代水杨酸和1,10-邻菲啰啉为双齿配位,分别与Co^2＋形成稳定的六,五元螯合环。并进一步研究了配合物和配体硫代水杨酸的荧光性质。     

配位聚合物[Zn(phen)(H_2O)_2SO_4]_n的合成与晶体结构

通过扩散法得到了一个新的配位聚合物[Zn(phen)(H2O)2SO4]n[phen=邻菲啰啉]。通过X-ray单晶衍射对配合物的结构进行了表征。配合物属单斜晶系,Cc空间群,晶胞参数:a=15.1399(10),b=14.1420(10),c=6.6994(5),α=90°,β=103.458(1)°,γ=90°,V=1395.01(17)3,Z=2,μ=0.752 mm-1,R1=0.0214,wR2=0.0602。     

Chiral platinum(II) metallointercalators with potent in vitro cytotoxic activity

Four platinum(II) metallointercalating complexes of 1,10-phenanthroline (phen) with the chiral ancillary ligands trans-R,R- and trans-S,S-1,2-diaminocyclohexane (R,R- and S,S-dach, respectively), and N,N'-dimethyl-R,R- and N,N'-dimethyl-S,S-1,2-diaminocyclohexane (Me(2)-R,R-dach and Me(2)-S,S-dach, respectively) have been synthesised and characterised. The crystal structure of [Pt(Me(2)-S,S-dach)(phen)](ClO(4))(2)1.5 H(2)O (C(20)H(26)Cl(2)N(4)O(9.5)Pt) has been determined; orthorhombic, space group P2(1)2(1)2(1)(No. 19), a=23.194(8), b=25.131(9), c=8.522(3) A. In vitro cytotoxic assays (IC(50)) in the human bladder cancer cell line 5637 and in the murine leukemia L1210 cell line revealed that [Pt(S,S-dach)(phen)](ClO(4))(2) (0.091 and 0.13 microM, respectively) and [Pt(R,R-dach)(phen)](ClO(4))(2) (0.54 and 1.50 microM, respectively) were more cytotoxic than cisplatin (0.31 and 0.50 microM, respectively) and considerably more cytotoxic than their methylated counterparts, [Pt(Me(2)-R,R-dach)(phen)](ClO(4))(2) and [Pt(Me(2)-S,S-dach)(phen)](ClO(4))(2) (both>23 microM). Chiral discrimination for [Pt(S,S-dach)(phen)](ClO(4))(2) over its R,R-enantiomer was observed in all 13 cancer cell lines investigated. Moreover, [Pt(S,S-dach)(phen)](ClO(4))(2) was more active than cisplatin in all cell lines tested and shows only partial cross-resistance to cisplatin in two cisplatin resistant cell lines.     

Facile Routes to Manganese(II) Triflate Complexes

Manganese(II) chloride reacts with trimethylsilyl triflate (TMS(OTf) where OTf = (-)OSO(2)CF(3)) in a 1:1 mixture of acetonitrile and tetrahydrofuran, and after recrystallization affords the linear coordination polymer [Mn(II)(CH(3)CN)(2)(OTf)(2)](n). Each distorted octahedral manganese(II) center in the polymeric chain has trans-acetonitriles and the remaining equatorial coordination positions are occupied by the bridging triflate anions. Dissolving [Mn(II)(CH(3)CN)(2)(OTf)(2)](n) in equal volumes of acetonitrile and pyridine followed by recrystallization with diethyl ether yields trans-[Mn(II)(C(5)H(5)N)(4)(OTf)(2)]. The distorted octahedral geometry of the manganese center features monodentate trans-triflate anions and four equatorial pyridines. Exposure of either [Mn(II)(CH(3)CN)(2)(OTf)(2)](n) or [Mn(II)(C(5)H(5)N)(4)(OTf)(2)] to water readily gives [Mn(II)(H(2)O)(6)](OTf)(2). XRD reveals hydrogen-bonding interactions between the [Mn(II)(H(2)O)(6)](2+) cation and the triflate anion. All three of these species are easily crystallized and provide convenient sources of manganese(II) for further synthetic elaboration.     

Binuclear Rhodium(II) Complexes With Selective Antibacterial Activity

Binuclear rhodium(II) complexes [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)] {R = H, Me; N-N = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen)} and [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) (R = Me, Et;) have been synthesized and their structure and properties have been studied by electronic, IR and (1)H NMR spectroscopy. Antibacterial activity of these complexes against Escherichia coli and Staphylococcus aureus has been investigated. The most active antibacterial agents against E. coli were [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)] and [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) {R = H and Me} which were considerably more active than the appropriate nitrogen ligands. The complexes show low activity against S. aureus. The activity of the complexes [Rh(2)(OOCR)(2)(N-N)(2)(H(2)O)(2)](OOCR)(2) against E. coli decreases in the series: R=H congruent withCH(3)>C(2)H(5)>C(3)H(7) congruent withC(4)H(9). The reverse order was found in the case of S. aureus.     

Synthesis and structure of a dimeric scandium bis(μ-methoxy) complex

Reaction of hydrated scandium nitrate with 1,10-phenanthroline (phen) in methanol leads to formation of the unusual dimeric complex [(phen)(NO₃)₂Sc(μ-OMe)₂Sc(NO₃)₂(phen)], in which the scandium centres are eight co-ordinate. The complex features two bridging methoxy ligands, as well as bidentate nitrates and chelating 1,10-phenanthroline ligands.     

配合物La（C6H5CHOHC00）3（phen）（H2O）的合成

用苯羟基乙酸、邻菲罗啉与稀土的硝酸盐为原料合成了配合物La(C_6H_5CHOHCOO)_3(phen)(H_2O),通过元素分析、红外光谱、核磁共振等测试手段,确定了配合物的组成和结构,并通过热重分析对其热性质进行了表征。结果表明,配合物中邻菲罗啉以双齿螯合方式配位,而苯羟乙酸则以桥联或单齿方式参与配位。     

Cooperative Effect of 3,3′,4,4′-Benzophenonetetracarboxylic Acid and 1,10-Phenanthroline under Solvothermal Conditions to Afford Two Novel Zinc(II) and Cadmium(II) Complexes

Rational self-assembly of a flexible ligand 3,3′,4,4′-benzophenonetetracarboxylic acid and d¹⁰ transition metal salts in the presence of rigid bidentate ligand 1,10-phenanthroline yields two novel helical coordination polymers with different structural motifs; i.e., [Zn(H₂bbtc)(phen)₂ · 2H₂O] _n (1) and [Cd₂(bbtc)(phen)₄ · 2.25H₂O] _n (2) (H₄bbtc = 3,3′,4,4′-benzophenonetetracarboxylic acid, phen = 1,10-phenanthroline), under solvothermal condition. One is hydrogen bonded and π–π stacked together into a network, and the other is a covalently coordinated 3D framework. The coordination polymers were characterized by FT-IR, UV/VIS and fluorescent spectroscopy, single crystal X-ray diffraction, elemental analysis and differential thermal analysis/thermogravimetry (DTA/TG). The most intriguing structural feature is that each complex exhibits novel helical-spaced chains by reason of two different ligands coordinating to the metal centers. Additionally, compounds 1 and 2 showed good fluorescence properties compared to the free ligands.     

5-硝基苯并三唑-1-乙酸镝与1,10-邻菲啰啉配合物的合成和性质研究

采用溶液合成法,合成了标题化合物,通过元素分析、摩尔电导率、紫外光谱、红外光谱和热分析法确定配合物的组成为Dy(L)3phen.1.5H2O(HL=5-硝基苯并三唑-1-乙酸;phen=1,10-邻菲啰啉)。荧光光谱表明:镝配合物的荧光强度较强,说明配体5-硝基苯并三唑-1-乙酸和1,10-邻菲啰啉是很好的敏化剂。     

稀土配合物[Ln(C_3H_7NO_2)_x(C_3H_4N_2)(H_2O)](ClO_4)_3(Ln=La,x=3;Ln=Pr,Nd,Sm,x=2)的合成、表征与热分析

合成了稀土高氯酸盐与咪唑、DL α 丙氨酸的4种配合物晶体。经傅里叶变换红外光谱(FTIR)、元素分析和化学分析测定后确定其组成为[Ln(C3H7NO2)x(C3H4N2)(H2O)](ClO4)3(Ln=La,x=3;Ln=Pr,Nd,Sm,x=2)。用差示扫描量热法(DSC)测定了4种配合物的热分解数据,4个配合物开始熔化分解的温度分别为502 5K,532 4K,495 7K,516 7K,配合物有较高的热稳定性。     

Single crystal structure of a heterometallic one-dimensional polymer: [{Cu(1,10-phen)}2(V2O4)(O3PCH2CH2CH2CH2PO3H)2(H2O)]n

A heterometallic one-dimensional polymer [{Cu(1,10-phen)}₂(V₂O₄)(O₃PCH₂CH₂CH₂CH₂PO₃H)₂(H₂O)]_n 1 (1,10-phen=1,10-phenanthroline) has been synthesized under hydrothermal conditions. The structure of 1 shows a stepped chain with two parallel 1,4-butylenediphosphonate ligands as linking units.     

Relationship between Antioxidant Activity and Ligand Basicity in the Dipicolinate Series of Oxovanadium(IV) and Dioxovanadium(V) Complexes

Oxidative stress plays an important role in the pathogenesis of many serious diseases, including cancer, atherosclerosis, coronary artery disease, Parkinson’s disease, Alzheimer’s disease, stroke and myocardial infarction. In the body’s natural biochemical processes, harmful free radicals are formed, which can be removed with the help of appropriate enzymes, a balanced diet or the supply of synthetic antioxidant substances such as flavonoids, vitamins or anthocyanins to the body. Due to the growing demand for antioxidant substances, new complex compounds of transition metal ions with potential antioxidant activity are constantly being sought. In this study, four oxovanadium(IV) and dioxovanadium(V) dipicolinate (dipic) complexes with 1,10-phenanthroline (phen), 2,2′-bipyridyl (bipy) and the protonated form of 2-phenylpyridine (2-phephyH): (1) [VO(dipic)(H₂O)₂]·2 H₂O, (2) [VO(dipic)(phen)]·3 H₂O, (3) [VO(dipic)(bipy)]·H₂O and (4) [VOO(dipic)](2-phepyH)·H₂O were synthesized including one new complex, so far unknown and not described in the literature, i.e., [VOO(dipic)](2-phepyH)·H₂O. The oxovanadium(IV) dipicolinate complexes with 1,10-phenanthroline and 2,2′-bipyridyl have been characterized by several physicochemical methods: NMR, MALDI-TOF-MS, IR, but new complex [VOO(dipic)](2-phepyH)·H₂O has been examined by XRD to confirm its structure. The antioxidant activities of four complexes have been examined by the nitrotetrazolium blue (NBT) method towards superoxide anion. All complexes exhibit high reactivity with superoxide anion and [VOO(dipic)](2-phepyH)·H₂O has higher antioxidant activity than L-ascorbic acid. Our studies confirmed that high basicity of the auxiliary ligand increases the reactivity of the complex with the superoxide radical.     

Heterometallic Supramolecular Architecture Based on a Trinuclear [Mn(H2O)4(NiL)2] Unit: Crystal Structure and Magnetic Properties

A heterometallic supramolecular structure, [Mn(H₂O)₄(NiL)₂]·7H₂O (H₃L = glycylglycine, N-[1-(2-hydroxy, phenyl)-propylidene]) was constructed based on a trinuclear unit. This unit consists of one Mn(H₂O) ₄ ²⁺ group and two symmetric groups [NiL]^? connected by carboxylate oxygen atoms. Magnetic studies suggest a weak antiferromagnetic interaction between Mn(II) ions, whereas the Ni(II) ions are diamagnetic in the trinuclear unit.     

2,2′-二喹啉-4,4′-二羧酸构筑的锰配合物的合成、结构及性质

利用2,2′-二喹啉-4,4′-二羧酸(2,2′-bca)为主配体,1,10-邻菲罗啉(1,10-phen)为辅配体,与四水合醋酸锰通过溶剂热反应得到配合物1([Mn(2,2′-bca)(1,10-phen)(H₂O)2]_n)和配合物2([Mn(2,2′-bca)(H₂O)]_n),并使用X-射线单晶衍射、傅里叶红外光谱、元素分析、紫外光谱、荧光光谱、热重分析等测试手段对其结构进行表征与性质研究。单晶结构分析表明配合物1由一个2,2′-bca配体、一个1,10-phen和两个配位水分子组成,通过主配体2,2′-bca的桥联作用连接Mn²⁺形成一维链结构,并通过氢键相互作用与π-π堆积,进一步有序堆积形成三维网络结构;配合物2是由一个2,2′-bca配体和一个配位水分子组成,通过2,2′-bca配体的两个羧酸基团桥联Mn²⁺形成无限三维框架结构。两种配合物均有良好的荧光性能和热稳定性。     

Supramolecular Coordination Assemblies Using 2-Aminodiacetic Terephthalic Acid Ligands: K[NiII(Hadta)(H2O)2]·H2O and K[Cu 1.5 II (adta)(H2O)1.5]·H2O

Two new network structures, K[Ni^II(Hadta)(H₂O)₂]·H₂O (1) and K[Cu_1.5^II(adta)(H₂O)_1.5]·H₂O (2) which are stabilized by 2-aminodiacetic terephthalic acid ligands have been synthesized and structurally characterized. Supplemental analyses include infrared spectroscopy and CHN analysis. 1 contains mononuclear secondary building units that are linked through potassium counterions and H-bonds to form a 3D network structure. 2 contains a 1D coordination polymer containing Cu^II ions with two different coordination environments. Potassium counterions further network these 1D chain structures.     

Down-Regulation of Porcine Heart Diaphorase Reactivity by Trimanganese Hexakis(3,5-Diisopropylsalicylate), Mn(3)(3,5-DIPS)6, and Down-Regulation of Nitric Oxide Synthase Reactivity by Mn(3)(3,5-DIPS)(6) and Cu(II)(2)(3,5-DIPS)(4)

Purposes of this work were to examine the plausible down-regulation of porcine heart diaphorase (PHD) enzyme reactivity and nitric oxide synthase (NOS) enzyme reactivity by trimanganese hexakis(3,5-diisopropylsalicylate), [Mn(3)(3,5-DIPS)(6)] as well as dicopper tetrakis(3,5- diisopropylsalicylate, [Cu(II)(2)(3,5-DIPS)(4)] as a mechanistic accounting for their pharmacological activities.Porcine heart disease was found to oxidize 114 muM reduced nicotinamide-adenine- dinucleotide-'(3)-phosphate (NADPH) with a corresponding reduction of an equivalent concentration of 2,6-dichlorophenolindophenol (DCPIP). As reported for Cu(II)(2) (3,5-DIPS)(4), addition of Mn(3)(3,5-DIPS)(6) to this reaction mixture decreased the reduction of DCPIP without significantly affecting the oxidation of NADPH. The concentration of Mn(3)(3,5-DIPS)(6) that produced a 50% decrease in DCPIP reduction (IC(50)) was found to be 5muM. Mechanistically, this inhibition of DCPIP reduction with ongoing NADPH oxidation by PHD was found to be due to the ability of Mn(3)(3,5-DIPS)(6) to serve as a catalytic electron acceptor for reduced PHD as had been reported for Cu(II)(2)(3,5-DIPS)(4). This catalytic decrease in reduction of DCPIP by Mn(3)(3,5-DIPS)(6) was enhanced by the presence of a large concentration of DCPIP and decreased by the presence of a large concentration of NADPH, consistent with what had been observed for the activity of Cu(II)(2)(3,5-DIPS)(4)Oxidation of NADPH by PHD in the presence of Mn(3)(3,5-DIPS)(6) and the absence of DCPIP was linearly related to the concentration of added Mn(3)(3,5-DIPS)(6) through the concentration range of 2.4 muM to 38muM with a 50% recovery of NADPH oxidation by PHD at a concentration of 6 muM Mn(3)(3,5-DIPS)(6)Conversion of [(3)H] L-Arginine to [(3)H] L-Citrulline by purified rat brain nitric oxide synthase (NOS) was decreased in a concentrated related fashion with the addition of Mn(3)(3,5-DIPS)(6) as well as Cu(II)(2)(3,5-DIPS)(4) which is an extention of results reported earlier for Cu(II)(2)(3,5-DIPS)(4). The concentration of these two compounds required to produce a 50% decrease in L-Citrulline synthesis by NOS, which may be due to down-regulation of NOS, were 0.1 mM and 8muM respectively, consistent with the relative potencies of these two complexes in preventing the reduction of Cytochrome c by NOS.It is concluded that Mn(3)(3,5-DIPS)(6), as has been reported for Cu(II)(2) (3,5-DIPS)(4) , serves as an electron acceptor in down-regulating PHD and both of these complexes down-regulate rat brain NOS reactivity. A decrease in NO synthesis in animal models of seizure and radiation injury may account for the anticonvulsant, radioprotectant, and radiorecovery activities of Mn(3)(3,5-DIPS)(6) and Cu(II)(2)(3,5-DIPS)(4).