NICKEL(II) AND ZINC(II) COMPLEXES OF β-ALANINEHYDROXAMIC ACID

Abstract

Potentiometric and spectrophotometric studies of Ni(II) coordination to β-alaninehydroxamix acid (β-Alaha) have shown 4N coordination of β-Alaha for 1:2 species and their planar geometry. The geometry of the species formed in the nickel(II)-β-Alaha below ca. pH 7 is octahedral. The differences between the stabilities of zinc(II)-β-Alaha and zinc(II)-α-alaninehydroxamic acid complexes can be explained by the terdentate coordination of the β-alaninehydroxamic acid.     

THE CHEMICAL CONSTITUENTS OF COLEUS ESQUIROLII(II)

Three new diterpenoids,named esquirolin B(1),C(2),D(3)respectively,and two known cemocundseariocal(4)and taraxerol were isolated from Coleus esquirolii(Levl).The structure elucidation was achieved byspectroscopic means     

THE PHOTOCHEMICAL SYNTHESIS OF THE PYRIDINE ADDUCT OF TETRAPHENYLPORPHYRINATORHODIUM(Ⅱ)AND THE MECHANISM OF PHOTOCHEMICAL REACTION

A new rhodium(Ⅱ)porphyrin complex was isolated by chromatography from the photochemical reac-tion of(μ—tetraphenylporphyrinato)bis[dicarbonylrhodium(Ⅰ)]with pyridine in benzene and has been charac-terized.From the results,the reaction mechanism is proposed.     

INVESTIGATION OF THE SOLUTION STRUCTURE OF Cu(II) MIXED-LIGAND COMPLEXES OF ADENOSINE 5′-MONOPHOSPHATE AND CYTIDINE 5′-MONOPHOSPHATE AND POLYAMINES

Abstract

The coordination mode of complexes formed in the systems Cu(II)/NMP/PA; (NMP =adenosine 5′-monophosphate, cytidine 5′-monophosphate; PA = 1,4-diaminopropane (putrescine, Put), 1,7-diamino-4-azaheptane (3,3-tri) and 1,11-diamino-4,8-diazaundekane (3,3,3-tet)) was determined on the basis of the equilibrium and spectroscopic studies. The presence of the following mixed complexes was established: Cu(CMP)H(Put), Cu(AMP)H₂(3,3-tri) and Cu(CMP)H₂(3,3-tri), Cu(CMP)H₄(3,3-tri) and coordination compounds of MLL′ type-Cu(CMP)(3,3,3-tet), Cu(AMP)(3,3,3-tet). A significant influence of the polyamine length on the solution structure of the complexes was observed. In mixed-ligand complexes Cu(NMP)(3,3,3-tet) a {N4, O} chromophore is formed, and metallation involves all nitrogen atoms from 3,3,3-tet. In the analogous system with 3,3-tri, protonated complexes occur. Non-covalent intramolecular interaction between the protonated amine groups and donor atoms from the purine ring from the nucleotide results in an increase of complex stability.     

~(10)BE AND THE ACCUMULATIONEVOLUTION OF LOESS

We report here a first series of ~(10)Be measurements on loess samples covering the last 750,000 years. The close correlation of the ~(10)Be data with δ~(18)O variations from deep sea cores allows for establishing a preliminary time scale. Based on this time scale accumulation rates and ~(10)Be fluxes can be calculated. The accumulation-evolution of loess is also discussed in terms of a simple qualitative model of ~(10)Be.     

COMPLEXES OF 4,5-DIAZAFLUORENE AND 9,9′-BIS(4,5-DIAZAFLUORENYL) WITH NICKEL(II), COPPER(II) AND ZINC(II)

Abstract

Complexes having the compositions [LMCl₂], [L₂MCl₂], [L₂Cu][PF₆], [L′MCl₂] and [L′(MCl₂)₂] of 4,5-diazafluorene, L, and 9,9′-bis(4,5-diazafluorenyl), L′, have been prepared from MCl₂ (M = Ni, Cu, Zn) and characterised. Steric strain or the bite angle of the pro-ligand has no recognisable effect on its coordination chemistry with smaller 3d-metals.     

SPECTROSCOPIC DETERMINATION OF THE AVERAGE NUMBER OF COAGGREGATES (Nco) OF CHOLESTERYL ESTERS AND THE FLUORESCENCE PROBE

Average aggregate number of coaggregates(N_co)of CE-n or BL-n and the fluoresc-ence probe(Np-16)have been determined by using time-resolved fluorescence spectroscopy.Chain-length,hydroxy-group and chain-foldability effects on the N_co have been discussed.     

ANALYSIS AND MODELLING OF TROPICAL CYCLONE MOTION(Ⅰ)——THE AXIASYMMETRIC STRUCTURE AND THE SUDDEN CHANGE OF TRACKS

The impact of axiasymmetric structure of tropical cyclone, beta effect and the environmentalflow field on tropical cyclone motion have been investigated in terms of theoretical analysisand numerical modelling. The sudden change of tropical cyclone (TC) motion has also beenstudied. The analysis and modelling results indicate that the impact of axiasymmetric struc-ture of TC on its motion cannot be underestimated in the certain stage of TC development.Under the specified conditions, it may lead to snakelike or loop motion of TC. The movingdirection and speed of TC will change suddenly when the interaction of environmental flowfield, beta effect and axiasymmetric wind and pressure fields reach a critical state.     

THE STUDY OF THE SYNTHESES OF THE DERIVATIVES OF POLYPHENYLENE AND THEIR CONDUCTIVITY

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THE GROWTH OF SINGLE CRYSTAL AND THE DETERMINATION OF CRYSTALLOGRAPHIC PA RAMETERS OF (L-TRYPTOPHAN)~(A1)-INSULIN AND (D-TRYPTOPHAN)~(A1)-INSULIN

The crystal-growing conditions and the results of preliminary X-ray crystallographic analysis of (L-Try)~(A1)-insulin and (D-Try)~(A1)-insulin are reported. The single crystals of this pair of insulin analogue suitable for X-ray diffraction analysis have been grown in the citrate buffer system by still-setting method. They both belong to the trigonal system with space group R3. The parameters of the unit cell (L-Trp)~(A1)-insulin are αH= 80.31, cH= 37.45 and those of (D-Trp)~(A1)-insulin αH = 79.48, cH = 43.81. There are two molecules in an asymmetric unit. The obtained results are discussed.     

THE SYNTHESIS AND CHARACTERIZATION OF THE COORDINATION COMPOUNDS OF Pt(Ⅱ)AND Ir(Ⅲ)WITH 2-MERCAPTOPYRIDINE-1-OXIDE AND ITS METHYL DERIVATIVES

Six coordination compounds of Pt(Ⅱ)L_2 and Ir(Ⅲ)L_3 type(where L is PT~-,3Me-PT~-or 4Me-PT~-)are reported here.Four coordination compounds of the lattertwo ligands have never been reported before,while PT~-'s were synthesized withH_2PtCl_6 and(NH_4)_3IrCl_6 respectively,which were different from the methods ofDavidson et al.~1 and Sterinbrech~2.They were characterized by elemental analysis,UV,IR,~1HNMR and molar conductance.Their structural formulas have beendetermined,and the mechanism of synthetic reaction has been discussed.     

A NEW METHOD OF PREPARATION OF IRON(II) PORPHYRIN COMPLEXES — ISOLATION AND CHARACTERIZATION OF BIS(N-BUTYLAMINE) IRON(II) PORPHYRIN

Abstract

Fe(II)T(p-X)PP(NH₂Bu ⁿ )₂ (X = H, Cl, CH₃, OCH₃, TPP = dianion of meso-tetraphenylporphyrin) complexes have been prepared by the reduction of Fe(III) porphrins with n-butylamine in antiformin/dichloromethane in air, and by sodium borohydride reduction. The complexes were characterized by electronic and IR spectra and elemental analysis.     

THE DEVELOPMENT OF THE THEORY OF MOLECULAR STRUCTURE AND THE NATURE OF THE CHEMICAL BOND

THE development of the theory of molecular structure and thenature of the chemical bond are discussed.Particular atten-tion is given to the theory of hybrid bond orbitals.     

THE INFRARED SPECTRA (4000 - 50 cm−1) OF COMPLEXES OF QUINOLINE N-OXIDE AND ITS PERDEUTERATED ANALOGUE WITH METAL(II) PERCHLORATES OF THE FIRST TRANSITION SERIES

Abstract

Infrared assignments (4000 - 50 cm^?1) are presented for the complexes [M(quinO)_n](ClO₄)₂(quinO = quinoline N-oxide; n = 6 for Mn, Co, Ni; n = 5 for Zn, and n = 4 for Cu) and their perdeuterated analogues. The spectra are consistent with octahedral structures for the 6-coordinate complexes, a trigonal bipyramidal structure for the Zn(II) complex and a square planar structure for the Cu(II) complex, with some distortion from idealised symmetry evident for each complex. In the Mn(II) complex, strong coupling occurs between the vM-O of lowest frequency and the ligand vibration, xN-O (mode 45). In the Cu(II) complex, the single vCu-O is strongly coupled with the ring torsion (mode 28).     

ROLE AND IMPORTANCE OF RADIUS OF GYRATION OF CHAINS IN THE MELT IN THE CRYSTALIZATION OF POLY(1-BUTENE)

Crystallization in polymer systems actually is a process that transfers the entangled melts into a semi-crystallinelayered structure. Whether or not a chain disentangles may result in different crystallization mechanism. When compared tothe crystal thickness (d_c), the volume occupied by the chain in the melt, i.e., the radius of gyration (R_g), plays a veryimportant role in polymer crystallization. When d_c≤R_g, crystallization does not necessitate a chain disentangling. Theentanglements are just shifted into the amorphous regions. However, as d_c>R_g, i.e., as the crystal thickness ges larger thanthe radius of gyration of the chain in the melt, it becomes necessary for a chain to disentangle. Then a change ofcrystallization mechanism occurs. Such change has been experimentally observed in the crystallization of poly(1-butene). Achange in the crystal morphologies from spherulite to quadrangle, is seen via PLM, as crystalliation temperatures increase.Even more, such a change is molecular weigh dependent and shifts to lower temperature as molecular weigh decreases.There exists a jump of crystal thickness and crystallinity associated with morphological change, as seen via SAXS. A changeof crystallization kinetics and crystallinity is further evidenced via dilatometry. The unique feature of P1b crystallization hasbeen discussed based on the radius of gyration of chain in the melt (R_g), and very good agreement is obtained.     

A PRELIMINARY STUDY ON THE IMMUNODIAGNOSIS OF PARAGONIMIASIS——THE PHYSICO-CHEMICAL AND IMMUNOLOGICAL CHARACTERISTICS OF THE CRUDE AND PARTIALLY PURIFIED ANTIGENS OF THE PARAGONIMUS WESTERMANI (LIAONING)

We have now succeeded in preparing a partially purified antigen (Fr. 1). The positive rates of the indirect ELISA were 100% both for sera of proved human cases and dogs infected with Paragonimus westermani when Fr. 1 was used, whereas the positive rates of the test were 71.4% and 75% on sera from patients and infected dogs respectively when crude antigen was used. Moreover, it is also better than the crude antigen in specificity, so a more reliable test in immunodiagnosis of paragonimiasis is available in our laboratory.     

THE HYDROSILATION REACTION OF LADDERLIKE POLYALLYLSILSESQUIOXANE(ALLYL-T)AND POLYHYDROSILSESQUIOXANE(H-T)

The one plus one (1 + 1) mode of hydrosilation reaction of ladderlike cis-isotatic polyallylsilsesquioxane (Allyl-T)and polyhydrosilsesquioxane (H-T) using dicyclopentadienylplatinumdichloride (Cp_2PtCl_2) as the catalyst leads to theformation of a new polyorganosiloxane (POS). The presence of nanoscale tubular structure in the product POS waspreliminarily proved by IR, ~1H-NMR, differential scanning calorimetry (DSC), X-ray diffraction (XRD), gel permeationchromatography (GPC), atomic force microscopy (AFM) and molecular simulation.     

PRECURSORS OF HEXA-AZAMACROCYCLES. SYNTHESIS AND X-RAY STRUCTURE OF 2,9-DIAMINOPHENANTHROLINEBISACETATE-Co(II) AND 6,6′-DIAMINOBIPYRIDINE-BISACETATE-M(II) (M = Ni,Cu)

Abstract

The synthesis, conventional characterisations and x-ray structures of the following monomeric complexes are given for 2,9-diaminophenanthroline-bisacetate-cobalt(II) ( A ) and 6,6′-diaminobipyridine-bisacetate-M(II) (M = nickel( C ) and copper( B )). Complex A crystalizes in the monoclinic, C2/c space group with a=12.813(6), b = 10.218(3), c= 13.811(5), Å; β= 118.17(2)°; Z=4; V=1549(2) ų. A total of 1787 unique reflections with F > 6σ(F) were refined to values of R and R_w 0.0461 and 0.0774, respectively. Complex B crystallizes in the triclinic, P-1 space group with a=10.099(5), b=10.257(5), c=8.015(11), Å; α=112.98(2), β=93.13(2), γ=92.960(2),°; Z=2; V = 761(1), ų. A total of 2603 unique reflections with F > 3.00σ(F) were refined to values of R and R_w 0.0764 and 0.1022, respectively. Complex C crystallizes in the monoclinic, P2₁/n space group with a=8.124(5), b=10.343(6), c=18.724(11), β=98.36(2),°; Z=4; V=1556(1), ų. A total of 2537 unique reflections with F > 3.00σ(F) were refined to values of R and R_w 0.0689 and 0.0975, respectively. The structures consist of six-coordinate [M(CH₃COO)₂(L)] (L=2,9-diaminophenanthroline or 6,6′-diaminobipyridine) discrete monomeric neutral species, although in the Cu(II) compound the elongation of two long Cu—O bonds, due to the Jahn-Teller effect, makes the metal essentially four-coordinate. In the Ni and Co compounds the acetate acts as a bidentate ligand. The diamino ligands are coordinated by the pyridine nitrogen atoms. The IR spectra of the complexes have been recorded and are discussed in relation to the crystal structure and the acetate coordination mode.     

HEAT FLOW ON THE QINGHAI-XIZANG(TIBETAN) PLATEAU AND THE MODELING OF THE TECTONO-THERMAL EVOLUTION

Thirteen observed heat flow values in combination with relevant geological and geophysical information are employed in the current paper to conduct a model study by means of direct inversion. The modeling demonstrates the tectono-thermal evolution of the Tibetan Plateau during the last 40 Ma since the continent-continent collision. The authors stress the fact that the tectonic deformations of terranes are usually the inducing factors for the deep-seated thermal activities in the crust and upper mantle. On this basis a series of kinematic equations of 3-D deformations of terranes in forms of shortening-thickening-uplifting-erosion-mass sliding were deduced using the principle of plate kinematics. These equations are further used as systematically defined initial and boundary conditions for simulating the integrated processes of tectono-thermal evolution, The results of the model study suggest that there exist sharp differences in the tectono-thermal evolution between the old northern terranes and the new     

THE STACKING INERACTION OF TERNARY COMPLEXES OF Zn(ATP)~(2-)AND PYRIDINE-LIKELIGANDS

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