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1.
Synthesis and single crystal X-ray structures of the first paramagnetic transition metal complexes containing chiral ethylenedithio-tetrathiafulvalene-oxazoline (EDT-TTF-OX) 1a-c and ethylenedithio-tetrathiafulvalene-thiomethyloxazoline 2 (EDT-TTF-(SMe)OX) ligands based on copper (II) and cobalt (II) are described. The racemic [EDT-TTF-OX][Cu(hfac)2] complex 3a crystallizes in the triclinic centrosymmetric space group , whereas the enantiopure counterparts 3b-c crystallize in the triclinic non-centrosymmetric space group P1. Cu(II) adopts a distorted square pyramidal coordination geometry, a much weaker Cu?STTF interaction also being identified. The same coordination pattern around Cu(II) is observed in the complex [(rac)-EDT-TTF-(SMe)OX][Cu(hfac)2] (4) in spite of the bidentate nature of the redox active ligand. DFT theoretical calculations afforded two equilibrium configurations for a corresponding model complex, in which the metal centre establishes secondary coordination either with one STTF or with the SMe group. The same ligand coordinates the cobalt (II) to afford the octahedral complex [(rac)-EDT-TTF-(SMe)OX][Co(hfac)2] (5). In all these novel complexes, the paramagnetic centres are structurally and magnetically isolated. Cyclic voltammetry measurements show the stability of the radical cation species.  相似文献   

2.
Interactions of cationic porphyrins bearing five-membered rings at the meso position, meso-tetrakis(1,2-dimethylpyrazolium-4-yl)porphyrin (MPzP; M is H2, CuII or ZnII), with synthetic polynucleotides poly(dG-dC)2 and poly(dA-dT)2 have been characterized by viscometric, visible absorption, circular dichroisim and magnetic circular dichroism spectroscopic and melting temperature measurements. Both H2PzP and CuPzP are intercalated into poly(dG-dC)2 and are outside-bound to the major groove of poly(dA-dT)2, while ZnPzP is outside-bound to the minor groove of poly(dA-dT)2 and surprisingly is intercalated into poly(dG-dC)2. The binding constants of the porphyrin and poly(dG-dC)2 and poly(dA-dT)2 are on the order of 106 M−1 and are comparable to those of other cationic porphyrins so far reported. The process of the binding of the porphyrin to poly(dG-dC)2 and poly(dA-dT)2 is exothermic and enthalpically driven for H2PzP, whereas it is endothermic and entropically driven for CuPzP and ZnPzP. These results have revealed that the kind of the central metal ion of metalloporphyrins influences the characteristics of the binding of the porphyrins to DNA.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.  相似文献   

3.
Lithioamidines {R′N(Li)C(R)NR′, I; R = CH3, R′ = C6H5, p-CH3,C6H4} react with iron(III) chloride
in monoglyme to produce navy-blue, high spin Fe{R′NC(R)NR′}3 complexes which are extremely air and moisture sensitive. The corresponding reaction when R = R′ = C6H5 produces a soluble red complex and an air-stable green complex, whereas when R = H, R′ = C6H5 and R = R′ = C6H5 and the reaction is started at ca. ?20°, red and green complexes respectively are formed. Though all the complexes are formulated Fe{R′NC(R)NR′}3, their properties reflect association through bridging amidino-groups. Iron(II) chloride reacts with I(R = CH3, R′ = p-CH3C6H4) to form two complexes, one crimson and soluble in organic solvents, and one brown and insoluble, which are fomulated [Fe{R′NC(R)NR′}2]n. The iron(III) complexes failed to react with, or were decomposed by, a variety of reducing, electrophilic and nucleophilic reagents, though blue Fe{p-CH3C6H4NC(CH3)N-p-CH3C6H4}3 reacts readily with nitric oxide to form a purple addition complex from which the N-nitroso-compound p-CH3C6H4NC(CH3)N(NO)-p-CH3C6H4 was obtained in high yield. Treatment of the corresponding brown iron(II) complex with nitric oxide gave no reaction.  相似文献   

4.
The trinuclear [{RuII(bpy)2(bpy-terpy)}2CoII]6+ complex (16+) in which a Co(II)-bis-terpyridine-like centre is covalently linked to two Ru(II)-tris-bipyridine-like moieties by a bridging bipyridine-terpyridine ligand has been synthesised and characterised. Its electrochemical, photophysical and photochemical properties have been investigated in CH3CN. The cyclic voltammetry exhibits two successive reversible oxidation processes, corresponding to the CoIII/CoII and RuIII/RuII redox couples at E1/2 = −0.06 and 0.91 V vs Ag/Ag+ 10 mM, respectively. The one-electron oxidized form of the complex, [{RuII(bpy)2(bpy-terpy)}2CoIII]7+ (17+) obtained after exhaustive electrolysis carried out at 0.2 V is fully stable. 16+ and 17+ are only poorly luminescent, indicating that the covalent linkage of the Ru(II)-tris-bipyridine centre to the cobalt subunit leads to a strong quenching of the RuII excited state by an intramolecular process. Luminescence lifetime experiments carried out at different temperatures indicate that the transfer is more efficient for 17+ compare to 16+ due to lower activation energy. Continuous irradiation of 17+ performed at 405 nm in the presence of P(Ph)3 acting as sacrificial electron donor leads to its quantitative reduction into 16+, whereas similar experiment starting from 16+ with a sulfonium salt as sacrificial electron acceptor converts 16+ into 17+ with a slower rate and a maximum yield of 80%. These photoinduced electron transfers were followed by UV-Visible spectroscopy and compared with those obtained with a simple mixture of both mononuclear parent complexes i.e. [RuII(bpy)3]2+ and [CoII(tolyl-terpy)2]2+ or [CoIII(tolyl-terpy)2]3+ (tolyl-terpy = 4′-(4-methylphenyl)-2,2′:6′,2′′-terpyridine).  相似文献   

5.
Two structurally related vanadium(V) complexes, K3[VO2(C2O4)2]·3H2O and K3[VO(O2)(C2O4)2]·1/2H2O, were thoroughly characterized by infrared, Raman, and electronic spectroscopies. The effect of both complexes on the viability of the human MG-63 osteosarcoma cells was tested using the MTT assay. The monoperoxo complex shows a very strong antiproliferative activity (at 100-μM concentration, this complex diminished the cell viability ca. 80 %), whereas the dioxo complex was inactive.  相似文献   

6.
Xia Z  Zhuang J 《Luminescence》2012,27(5):379-381
A novel blue‐emitting Sr3.5Y6.5O2(PO4)1.5(SiO4)4.5:Eu2+ phosphor was synthesized via a solid‐state reaction. Powder X‐ray diffraction (XRD) analysis demonstrated that the Sr3.5Y6.5O2(PO4)1.5(SiO4)4.5 host had a hexagonal crystal structure in the space group P63/m and unit cell parameters a = 9.418 Å, c = 6.900 Å. The as‐prepared phosphor showed a blue emission and all the main emission peaks were located at around 466 nm for different excitation wavelengths of 297, 333 and 391 nm. The temperature dependence of the photoluminescence property was investigated in the range 20–250 °C, and the emission intensity decreased to 71% of the initial value at room temperature on increasing the temperature to 150 °C. According to the classical theory of fluorescent thermal quenching, the activation energy (ΔE) for the thermal quenching luminescence of the as‐prepared Sr3.45Y6.5O2(PO4)1.5(SiO4)4.5:0.05Eu2+ phosphor was determined to be 0.20 eV. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

7.
The preparation is reported of [(NH3)3Pt(9- MeA)] X2 (9-MeA = 9-methyladenine) with XCl (1a) and XClO4 (1b) and of trans-[(OH)2Pt(NH3)3- (9-MeA)]X2 with XCl (2a) and XClO4 (2b), and the crystal structure of 1b. [(NH3)3Pt(C6H7N5)](ClO4)2 crystallizes in space group P21/n with a = 20.810(7) Å, b = 7.697(3) Å, c = 10.567(4) Å, β = 91.57(6)°, Z = 4. The structure was refined to R = 0.054, Rw = 0.063. In all four compounds Pt coordination is through N7 of 9-MeA, as is evident from 3J coupling between H8 of the adenine ring and 195Pt. Pt(II) and Pt(IV) complexes can be differentiated on the basis of different 3J values, larger for Pt(II) than for Pt(IV) by a factor of 1.57 (av). In Me2SO-d6, hydrogen bonding occurs between Cl? and C(8)H of 9-MeA as weil as between Cl? and the NH3 groups in the case of the Pt(II) complex 1a. Protonation of the 9-MeA ligands was followed using 1H NMR spectroscopy and pKa values for the N1 protonated 9-MeA ligands were determined in D2O. They are 1.9 for 1a and 1.8 for 2a, which compares with 4.5 for the non-platinated 9-MeA. Possible consequences for hydrogen bonding with the complementary bases thymine or uracil are discussed briefly. Protonation of the OH groups in the Pt(IV) complexes has been shown not to occur above pH 1.  相似文献   

8.
R M Wartell 《Biopolymers》1972,11(4):745-759
Helix–coil transition curves are calculated for poly (dA) poly(dT) and poly (dA-dT) poly (dA-dT) using the integral equation approach of Goel and Montroll.5 The transitions are described by the loop entropy model with the exponent of the loop entropy factor, k, remaining an arbitrary constant. The theoretical calculations are compared with experimental transition curves of the two polymers. Results indicate that the stacking energies for these two polymers differ by about 1 kcal/mole of base pairs. Also, a fit between theory and experiment was not possible for k > 1.70.  相似文献   

9.
《Inorganica chimica acta》1987,127(2):153-159
The synthesis and characterization of trans-chloro- (ligand)bis(diphenylglyoximato)cobalt(III) complexes [ligand = pyridine (py), α-, β-, or γ-picoline (α-pic, β-pic, γ-pic), 3,5-lutidine (lut), p-toluidine (p-tol) and PPh3] is presented. X-ray crystal structure determination of the pyridine (1) and p-toluidine (6) derivatives has been carried out. Compound 1 crystallizes in the monoclinic system, space group P21/n, with Z = 4 and unit cell parameters a = 23.124(4), b = 13.009(3) and c = 11.204(3) Å, and β= 93.14(2)°. Compound 6 crystallizes in the monoclinic system, space group P21/n, with Z = 4 and unit cell parameters a = 18.792(3), b = 12.540(2) and c = 15.346(3) Å, and β = 97.54(2)°.  相似文献   

10.
《Inorganica chimica acta》1986,120(2):159-164
The Mo(CO)2(PEt3)2(CF3COO)2 complex, obtained by prolonged reaction of trifluoroacetic acid with Mo(CO)3(PEt3)3 in dichloromethane, was characterized by spectroscopic methods and by X-ray crystal structure determination. The crystals belong to the monoclinic space group Cc, with a = 20.037, b = 10.879, c = 15.176 Å,β/3 = 129.28° and Z = 4. The structure was refined on 2135 observed reflections to R = 0.047. The Mo(II) atom is 7-coordinated and has a capped trigonal prism geometry, the capping position being occupied by a monodentate CF3CO2 ligand. The quadrangular plane contains one CO, one PEt3 and one bidentate CF3CO2 ligand. The remaining CO and PEt3 molecules are found on the opposite edge.  相似文献   

11.
A short review of main cytogenetic features of insects belonging to the sister neuropteran families Myrmeleontidae (antlions) and Ascalaphidae (owlflies) is presented, with a particular focus on their chromosome numbers and sex chromosome systems. Diploid male chromosome numbers are listed for 37 species, 21 genera from 9 subfamilies of the antlions as well as for seven species and five genera of the owlfly subfamily Ascalaphinae. The list includes data on five species whose karyotypes were studied in the present work. It is shown here that antlions and owlflies share a simple sex chromosome system XY/XX; a similar range of chromosome numbers, 2n = 14-26 and 2n = 18-22 respectively; and a peculiar distant pairing of sex chromosomes in male meiosis. Usually the karyotype is particularly stable within a genus but there are some exceptions in both families (in the genera Palpares and Libelloides respectively). The Myrmeleontidae and Ascalaphidae differ in their modal chromosome numbers. Most antlions exhibit 2n = 14 and 16, and Palparinae are the only subfamily characterized by higher numbers, 2n = 22, 24, and 26. The higher numbers, 2n = 20 and 22, are also found in owlflies. Since the Palparinae represent a basal phylogenetic lineage of the Myrmeleontidae, it is hypothesized that higher chromosome numbers are ancestral for antlions and were inherited from the common ancestor of Myrmeleontidae + Ascalaphidae. They were preserved in the Palparinae (Myrmeleontidae), but changed via chromosomal fusions toward lower numbers in other subfamilies.  相似文献   

12.
The preparations of novel platinum and copper metallodendrimers are reported. Surface modified first generation (G0) poly(amidoamine) (PAMAM) dendritic Schiff base, prepared via a condensation reaction was coordinated with platinum chloride and copper chloride yielding [G0-Py4-[PtCl2]4] (4D) and [G0-Py4-[CuCl2]7] (7E) respectively. These functionalized hyper-branched complexes were characterized by IR spectroscopy and CHN analysis. 4D was further characterized through 1H and 13C spectroscopy, while 7E was characterized using matrix-assisted laser desorption ionization time-of-flight (MALDI/TOF) Mass Spectrometer. The cytotoxic effects of the compounds against cells of neoplastic origin (MOLT-4, MCF-7) and cells of benign origin (Chang Liver) were studied. Their cytotoxicities were then compared to their mono-nuclear analogues, [(MeCONHCH2CH2NCHPy)(PtCl2)] (1D) and [(MeCONHCH2CH2NCHPy)(CuCl2)] (1E). The multi-nuclear complexes showed increased cytotoxic activities as compared to their respective mono-nuclear compounds. Most notably, significant inhibitions were observed for 7E on all cell lines, in which its IC50 values were 11.1 ± 0.6, 10.2 ± 1.5 and 8.7 ± 0.7 μM against MOLT-4, MCF-7 and Chang Liver cells respectively. The multi-nuclear copper-based complexes (7E) are therefore most effective against a cancer cell line (MOLT-4) and a cisplatin-resistant cell line (MCF-7).  相似文献   

13.
《Inorganica chimica acta》2001,312(1-2):125-132
Di-organotin(IV)halides R2SnCl2 (R=Me or Ph) react with bis(diphenylphosphine)methane (DPPM) and bis(diphenylphosphine)ethane (DPPE) in ethanol in aerobic conditions yielding 1:1 adducts [R2SnCl2(DPPM–O2)] and [R2SnCl2(DPPE–O2)], respectively, containing the bis(diphenylphosphine) in oxidized form. The 1:1 adduct [SnMe2Cl2(DPPM–O2)] is composed of separate molecules containing six-coordinate tin, with the ligands coordinated in the bidentate O2-fashion, whereas [SnMe2Cl2(DPPE–O2)] is polymeric, with octahedral and centrosymmetric (all trans) tin atoms. In inert atmosphere, the interaction between R2SnCl2 and DPPM or DPPE does not take place. Mono-organotin halides RSnCl3 (R=Me, Bun or Ph) react with DPPM and DPPE yielding 1:1 adducts [RSnCl3(DPPM)] (R=Me, Bun or Ph) and [RSnCl3(DPPE)] (R=Bun or Ph).  相似文献   

14.
Miller JR  Wood BP  Hamilton MB 《Genetics》2008,180(2):1023-1037
A commonly used test for natural selection has been to compare population differentiation for neutral molecular loci estimated by FST and for the additive genetic component of quantitative traits estimated by QST. Past analytical and empirical studies have led to the conclusion that when averaged over replicate evolutionary histories, QST = FST under neutrality. We used analytical and simulation techniques to study the impact of stochastic fluctuation among replicate outcomes of an evolutionary process, or the evolutionary variance, of QST and FST for a neutral quantitative trait determined by n unlinked diallelic loci with additive gene action. We studied analytical models of two scenarios. In one, a pair of demes has recently been formed through subdivision of a panmictic population; in the other, a pair of demes has been evolving in allopatry for a long time. A rigorous analysis of these two models showed that in general, it is not necessarily true that mean QST = FST (across evolutionary replicates) for a neutral, additive quantitative trait. In addition, we used finite-island model simulations to show there is a strong positive correlation between QST and the difference QSTFST because the evolutionary variance of QST is much larger than that of FST. If traits with relatively large QST values are preferentially sampled for study, the difference between QST and FST will also be large and positive because of this correlation. Many recent studies have used tests of the null hypothesis QST = FST to identify diversifying or uniform selection among subpopulations for quantitative traits. Our findings suggest that the distributions of QST and FST under the null hypothesis of neutrality will depend on species-specific biology such as the number of subpopulations and the history of subpopulation divergence. In addition, the manner in which researchers select quantitative traits for study may introduce bias into the tests. As a result, researchers must be cautious before concluding that selection is occurring when QSTFST.  相似文献   

15.
Crystals of Pt(DMSO)4(TFMS)2 have been prepared by dissolution of platinum(II) hydroxide in a solution of CF3SO3H in DMSO and subsequent evaporation. The structure was determined by use of a CAD-4 diffractometer with monochromatic Mo Kα radiation. The space group is P with Z = 2, a = 8.630(2), b = 9.557(3), c = 16.659(3) Å, α = 73.33(2), β = 77.38(2) and γ = 79.19(3)°. The refinement converged to R = 0.056. The coordination around platinum is distorted square-planar with two S- and two O-bonded DMSO ligands in a cis-arrangement. The four donor atoms and the platinum are coplanar within 0.03 Å. There is a severe steric crowding between the two S-bonded DMSO molecules, which gives rise to a distortion of the bond angles around the platinum. The crowding is minimized as much as possible by a staggered arrangement of oxygen atoms and methyl groups of adjacent ligands. Pt---S bond lengths 2.208(3) and 2.205(4) Å are significantly shorter that those in the corresponding palladium complex, in accordance with a much stronger bond in the case of platinum. Bond length comparisons also indicate that ground state transinfluence of S-bonded DMSO probably is about the same in platinum and palladium complexes.  相似文献   

16.
47 names and combinations are published as new, chiefly from the elaboration ofAlchemilla byA. Plocek inL. Bertová (ed.), Flóra Slovenska 4/3, Bratislava (in press). The populations recognized as varieties and species new to science (12 and 29, respectively) come from the summits of W. Beskids (9 taxa), Belianske Tatry (12), other parts of Tatra (8), Fatra (5), elsewhere in the Central Carpathians in Slovakia (4), the Low Beskids in E. Slovakia (1), W. and E. Carpathians (1), N. Moravia (1). In addition, three epithets are published in a new combination, and the names for two new subseries and a new forma are proposed.  相似文献   

17.
Exechia and Bibio have retained several plesiomorphic groundplan features of Diptera and Bibionomorpha, including a fully exposed and sclerotized head capsule, the transverse undivided labrum, the absence of movable premandibles, and undivided mandibles without combs. The fusion of the hypostomal bridge with the head capsule and largely reduced antennae are derived features shared by both taxa. The absence of teeth at the anterior hypostomal margin is a potential autapomorphy of Bibionomorpha. A basal position of Anisopodidae is suggested by a number of plesiomorphies retained in this family. Apomorphies of Bibionomorpha excluding Anisopodidae are the reduction of tentorial elements, the partial fusion of the labrum and clypeus, one-segmented antennae, the absence of a separate submental sclerite, the loss of the labial palpus, and the reduction of the pharyngeal filter apparatus. Head structures of Bibio are largely unmodified. The subprognathous orientation is one of few autapomorphic features. In contrast, the mouthparts of Exechia are highly modified in correlation with the specialized food uptake. The rasping counterrotating movements of maxillae and mandibles with teeth oriented in opposite directions are carried out by strongly developed extensors and flexors of the paired mouthparts. The modified labium mechanically supports the “drill head” formed by the mandibles und maxillae. The necessary stability of the head capsule is provided by the hypostomal bridge which also compensates the far-reaching reduction of the tentorium.  相似文献   

18.
C10H26N10ONiZn, tris(1,2-diaminoethane) zinc(II) tetrakis(cyano)niccolate(II) monohydrate (I), orthorhombic, Pbca, a = 1.1680(4), b = 1.5844(3), c = 1.9981(6) nm, Z = 8 d(meas) = 1.54, d(calc) = 1.53 g cm?3. C10H24N10NiZn, tris(1,2-diaminoethane) zinc(II) terakis(cyano)niccolate(II), (II), monoclinic, P21/n, a = 0.7957(2), b = 1.5170(5), c = 1.4932(4) nm, β = 96.41(2)°, Z = 4, d(meas) = 1.49, d(calc) = 1.51 g cm?3. Both the structures (I) and (II) have been solved by the heavy atom method and refined by full-matrix least-squares to R(I) = 0.086 for 1890 independent reflections and R(II) = 0.058 for 1689 independent reflections, respectively. In the case of (II) the superlattice structure problem was solved. The crystal structure of (I) consists of [Zn(en)3]2+ cations, [Ni(CN)4]2? anions and water molecules. Two of the cyano groups in trans positions are bonded to water molecules by hydrogen bonds, the distances CN?O being 0.289 and 0.291 nm, respectively. The crystal structure of (II) is constituted by [Zn(en)3]2+ cations and [Ni(CN)4]2? anions.  相似文献   

19.
The chelating behavior of 2,6-diacetylpyridine bis(2-aminobenzoylhydrazone) (H2dapa) towards manganese(II), cadmium(II) and oxovanadium(IV) ions has been studied by elemental analyses, conductance measurements, magnetic properties and spectral (IR, 1H NMR, UV-Vis and EPR) studies. The IR spectral studies suggest the pentadentate nature of the ligand with pyridine nitrogen, two azomethine nitrogens and two carbonyl oxygen atoms as the ligating sites. Six coordinate structure for [VO(H2dapa)]SO4 · H2O and seven coordinate structures for [Mn(H2dapa)(Cl)(H2O)]Cl · 2H2O and [Cd(H2dapa)Cl2] · H2O complexes have been proposed. Pentagonal bipyramidal geometry for [Mn(H2dapa)(Cl)(H2O)]Cl · 2H2O and [Cd(H2dapa)(Cl2)] · H2O complexes was confirmed by single crystal analysis. The X-band EPR spectra of the oxovanadium(IV) and manganese(II) complexes in the polycrystalline state at room (300 K) and also at liquid nitrogen temperature (77 K) were recorded and their salient features are reported.  相似文献   

20.
Mitochondria are well-characterized intracellular organelles usually concentrated in locations of high energy consumption. Light microscopic and transmission electron microscopic observations of the internal anatomy of the feather mites Diplaegidia columbae and Falculifer rostratus were conducted. In the anterior half of the bodies of the mites, we found several dozen of distinctive mitochondria-rich (MR) cells filled with abundant, large mitochondria. Mitochondria are placed individually or enclosed in small groups within an elaborated lamellar system forming a mitochondria–lamellae complex (MLC). The role of the MLC as well as the MR cells is not clear at present, but their involvement in heat generation is hypothesized and briefly discussed.  相似文献   

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