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1989 Volume 6 Issue 5
1989, 6(5): 1-10
Abstract:
The developing aspects of synthetic chemistry of cluster compounds of transition metals are reviewed. The two general rules on bonding between metal atoms in cluster compounds and main synthetic routes for three classes of clusters, i.e. metal carbonyl clusters, iron-sulfur clusters and molybdenum-iron-sulfur clusters, are given.
The developing aspects of synthetic chemistry of cluster compounds of transition metals are reviewed. The two general rules on bonding between metal atoms in cluster compounds and main synthetic routes for three classes of clusters, i.e. metal carbonyl clusters, iron-sulfur clusters and molybdenum-iron-sulfur clusters, are given.
1989, 6(5): 11-15
Abstract:
Using the widely accepted combination-chemotherapeutic antitumor drug amethopterin (abbreviated mtxH2) as ligand, seven complexes with the composition of VO(mtx)·5H2O,Mn(mtx)·5H2O,(Femtx)2O·10H2O, Co(mtx)·51/2H2O, Ni(mtx)·61/2H2O, Cu(mtx)·4H2O, and Zn (mtx)·4H2O, were prepared. The structures of the complexes were characterized and discussed by the thermogravimetric, infrared, magnetic susceptibility, Mössbauer (for ferric complex) and electron paramagnetic resonance (for cupric and vanadyl complexes) measurements.
Using the widely accepted combination-chemotherapeutic antitumor drug amethopterin (abbreviated mtxH2) as ligand, seven complexes with the composition of VO(mtx)·5H2O,Mn(mtx)·5H2O,(Femtx)2O·10H2O, Co(mtx)·51/2H2O, Ni(mtx)·61/2H2O, Cu(mtx)·4H2O, and Zn (mtx)·4H2O, were prepared. The structures of the complexes were characterized and discussed by the thermogravimetric, infrared, magnetic susceptibility, Mössbauer (for ferric complex) and electron paramagnetic resonance (for cupric and vanadyl complexes) measurements.
1989, 6(5): 16-20
Abstract:
The crystal structure of K8H(BW11O39)·13H2O has been determined by X-ray diffractometry on the four-circle diffractometer. The ctystal is cubic with the space group P43m and a=10.710(1)Å,V=1228.58Å3,Do=4.39gcm-3,Dc=4.42gcm-3 for Z=1.The structure of (BW11O39)9- anion belongs to an unsaturated α-Keggin type, with B atom being on the center of O. tetrahedron. The IR and Raman spectra of the compound have also been measured and discussed.
The crystal structure of K8H(BW11O39)·13H2O has been determined by X-ray diffractometry on the four-circle diffractometer. The ctystal is cubic with the space group P43m and a=10.710(1)Å,V=1228.58Å3,Do=4.39gcm-3,Dc=4.42gcm-3 for Z=1.The structure of (BW11O39)9- anion belongs to an unsaturated α-Keggin type, with B atom being on the center of O. tetrahedron. The IR and Raman spectra of the compound have also been measured and discussed.
1989, 6(5): 21-25
Abstract:
EPR spetra of eight paramagnetic binuclear clusters have been measured and classified into two kinds. One is similar to those of mononuclear compound and is called "piece mode",the other manifests characters of spectra of binuclear cluster and is called "cluster mode", Under effect of the temperature and solvent,the two kinds of spectra show normal paramagnetic and unnormal paramagnetic properties respectively. Some information provided by EPR spectra are discussed.
EPR spetra of eight paramagnetic binuclear clusters have been measured and classified into two kinds. One is similar to those of mononuclear compound and is called "piece mode",the other manifests characters of spectra of binuclear cluster and is called "cluster mode", Under effect of the temperature and solvent,the two kinds of spectra show normal paramagnetic and unnormal paramagnetic properties respectively. Some information provided by EPR spectra are discussed.
1989, 6(5): 26-30
Abstract:
In present paper luminescent characteristics of Eu (Ⅱ) and Ce(Ⅲ) and their concentration quenching in BaYF5 are studied. Both ions show d-f excitation and emission. By comparison with the values reported before,the quenching concentrations of Eu(Ⅱ) and Ce(Ⅲ) are lower because of the energy migration in Eu(Ⅱ)-Eu(Ⅱ) and Ce(Ⅲ)-Ce(Ⅲ). The quenching mechanism is acquired by the relation between their emission intensities and their concentrations, which is dipole-dipole interaction. The energy transfer from Ce (Ⅲ) to Eu(Ⅱ) was found in the system BaYF5. A mechanism of radiationless energy transfer is proposed based on the electric multipole-multipole interaction in the system.There also exist a radiative transfer. A possible way for energy transfer is given.
In present paper luminescent characteristics of Eu (Ⅱ) and Ce(Ⅲ) and their concentration quenching in BaYF5 are studied. Both ions show d-f excitation and emission. By comparison with the values reported before,the quenching concentrations of Eu(Ⅱ) and Ce(Ⅲ) are lower because of the energy migration in Eu(Ⅱ)-Eu(Ⅱ) and Ce(Ⅲ)-Ce(Ⅲ). The quenching mechanism is acquired by the relation between their emission intensities and their concentrations, which is dipole-dipole interaction. The energy transfer from Ce (Ⅲ) to Eu(Ⅱ) was found in the system BaYF5. A mechanism of radiationless energy transfer is proposed based on the electric multipole-multipole interaction in the system.There also exist a radiative transfer. A possible way for energy transfer is given.
1989, 6(5): 31-34
Abstract:
Five solid complexes of gold (Ⅲ) or platinum (Ⅳ) with crown ethers have been prepared firstly. These complexes have been characterized by elemental analysis, IR and UV spectra,molar conductances and 1H NMR measurements. The complexes were found to have following constitution: [K(B15C5)2]AuCl4, [Na(B15C5)2]PtCl6, (K18C6)]AuCl4, [K(DB15C5)]AuCl4 and [NH4(DB24C8)]AuCl4, where B=benzo, DB=dibenzo.
Five solid complexes of gold (Ⅲ) or platinum (Ⅳ) with crown ethers have been prepared firstly. These complexes have been characterized by elemental analysis, IR and UV spectra,molar conductances and 1H NMR measurements. The complexes were found to have following constitution: [K(B15C5)2]AuCl4, [Na(B15C5)2]PtCl6, (K18C6)]AuCl4, [K(DB15C5)]AuCl4 and [NH4(DB24C8)]AuCl4, where B=benzo, DB=dibenzo.
1989, 6(5): 35-38
Abstract:
The China made hydroxylterminated polybutadiene (HTPB) has been characterized using VPO, IR, GPC and TLC techniques. The polymer was found to have Mn=3220,Mw/Mn=1.69,fn=2.16 and fw=2.27 with its number average functionlity being inereased with molecular weight. The reliability of TLC to determine the functionality distribution of HTPB has been discussed.
The China made hydroxylterminated polybutadiene (HTPB) has been characterized using VPO, IR, GPC and TLC techniques. The polymer was found to have Mn=3220,Mw/Mn=1.69,fn=2.16 and fw=2.27 with its number average functionlity being inereased with molecular weight. The reliability of TLC to determine the functionality distribution of HTPB has been discussed.
1989, 6(5): 39-43
Abstract:
A new sensitive colour system of Ethyl Rhodamin B-molybdophosphoric acid-PVAhas been studied. The optimum conditions for pbosphorus determination are [HNO3]=0.56mol/dm3,[MoO42-]=2.4×10-2mol/dm3, [ERB+]=8.0×10-5smol/dm3 and 0.12% PVA. The ion-associate exhibits maximum absorptivity at 584nm. At the working wavelength of 586 nm its apparent molar absorptivity was found to be 3.2×105 L·mol-1·cm-1.Beer's law is obeyed in the range of 0 to 1.5μg of P(V) per 25mL. The colour of the aqueous solution was stable for at least lh. The molar ratio of P(V) to FRB+ in ion-associate was established to be 1:4. Infrared spectra studies show that an ionic bond occurs between ERB and phosphomolybdate and that the structure of the dye molccule is not of effected by the formation of the ion-assosiate.The effect of inteifering ions, such as As(Ⅴ), Si(Ⅳ) can be decreased by increasing the acidity and adding mixed reductants. Phosphorus in steel and some chemical reagents were determined directly at 1×10-5% level by the proposed methodwith satisfactory results.
A new sensitive colour system of Ethyl Rhodamin B-molybdophosphoric acid-PVAhas been studied. The optimum conditions for pbosphorus determination are [HNO3]=0.56mol/dm3,[MoO42-]=2.4×10-2mol/dm3, [ERB+]=8.0×10-5smol/dm3 and 0.12% PVA. The ion-associate exhibits maximum absorptivity at 584nm. At the working wavelength of 586 nm its apparent molar absorptivity was found to be 3.2×105 L·mol-1·cm-1.Beer's law is obeyed in the range of 0 to 1.5μg of P(V) per 25mL. The colour of the aqueous solution was stable for at least lh. The molar ratio of P(V) to FRB+ in ion-associate was established to be 1:4. Infrared spectra studies show that an ionic bond occurs between ERB and phosphomolybdate and that the structure of the dye molccule is not of effected by the formation of the ion-assosiate.The effect of inteifering ions, such as As(Ⅴ), Si(Ⅳ) can be decreased by increasing the acidity and adding mixed reductants. Phosphorus in steel and some chemical reagents were determined directly at 1×10-5% level by the proposed methodwith satisfactory results.
1989, 6(5): 44-46
Abstract:
Some novel p-bromophenacyl-2,3-oxirane carboxylic esters were synthesized by Darzen's condensation and esterification. The compounds were characterized by IR, 1H NMR spectroscopy and clemental analysis. The antifungal activity of the compounds in vitro has been determined. It is found that, in general, the antifungal activity against Pellicularia Sasakii was higher than that against Macyodhane Kawatasukai and Gibberella Zeae. p-Bromophenacyl-3, 3-pentamethy1ene-2, 3-oxiranepropanoic ester(2), p-bromophenacyl-3-(β-naphthyl)-2,3-oxiranepropanoicester(11) were the most effective which can completely inhibite the mycelial growth of P. Sasakil, M. Kawatsukai in amount of 100 ppm. p-Bromophenacyl-5-methyl-2,3-oxiranehexanoic ester (1) and p-bromophenacyl-3-(p-chlorophenyl)-2, 3-oxiranebutanoic ester(7) were highly active against P.Sasakii.
Some novel p-bromophenacyl-2,3-oxirane carboxylic esters were synthesized by Darzen's condensation and esterification. The compounds were characterized by IR, 1H NMR spectroscopy and clemental analysis. The antifungal activity of the compounds in vitro has been determined. It is found that, in general, the antifungal activity against Pellicularia Sasakii was higher than that against Macyodhane Kawatasukai and Gibberella Zeae. p-Bromophenacyl-3, 3-pentamethy1ene-2, 3-oxiranepropanoic ester(2), p-bromophenacyl-3-(β-naphthyl)-2,3-oxiranepropanoicester(11) were the most effective which can completely inhibite the mycelial growth of P. Sasakil, M. Kawatsukai in amount of 100 ppm. p-Bromophenacyl-5-methyl-2,3-oxiranehexanoic ester (1) and p-bromophenacyl-3-(p-chlorophenyl)-2, 3-oxiranebutanoic ester(7) were highly active against P.Sasakii.
1989, 6(5): 47-50
Abstract:
The degree of phase separation of thermoplastic polyurethane elastomers (TPUE) has been studied by means of DMA and DSC measurements. The influence of hard segment content, molecular peight of soft segment on the degree of phase separetion of TPUE and the dependence of |△E'/△T|,△αs,1/2 in the αs,1/2 transition range on Wh have also been investigeted.Tt is found that there exist a lincar relation between |△E'/△T|,△αs,1/2,1/tanδ,(△Cp2)/(△Cp1) and Wh.
The degree of phase separation of thermoplastic polyurethane elastomers (TPUE) has been studied by means of DMA and DSC measurements. The influence of hard segment content, molecular peight of soft segment on the degree of phase separetion of TPUE and the dependence of |△E'/△T|,△αs,1/2 in the αs,1/2 transition range on Wh have also been investigeted.Tt is found that there exist a lincar relation between |△E'/△T|,△αs,1/2,1/tanδ,(△Cp2)/(△Cp1) and Wh.
1989, 6(5): 51-55
Abstract:
A series of aryloxyacetanilidts have been synthesized by means of liquid-phuid phase transfer catalysis. The structures of the compounds have been characterized by elemental analysis, UV, IR and 1~H-NMR spectroscopy measurement. Promoting effects of the compounds on plant growth were observed preliminary.
A series of aryloxyacetanilidts have been synthesized by means of liquid-phuid phase transfer catalysis. The structures of the compounds have been characterized by elemental analysis, UV, IR and 1~H-NMR spectroscopy measurement. Promoting effects of the compounds on plant growth were observed preliminary.
1989, 6(5): 56-58
Abstract:
In this work using ligands exchange reaction between η3-allylirontricarbonyl iodide and α,α'-dipyridyl or phenanthrolire, two new and catalytically active nitrogenous complexes of η3-allyliron halide, η3-C3H5 FeI(CO) dipy and η3-C3H5 FeI(CO)phen,were synthesized successfully.Their chemical structures were characterized by elemental analysis, GC and IR.
In this work using ligands exchange reaction between η3-allylirontricarbonyl iodide and α,α'-dipyridyl or phenanthrolire, two new and catalytically active nitrogenous complexes of η3-allyliron halide, η3-C3H5 FeI(CO) dipy and η3-C3H5 FeI(CO)phen,were synthesized successfully.Their chemical structures were characterized by elemental analysis, GC and IR.
1989, 6(5): 59-62
Abstract:
Eight compounds of (GcCH2CH2COOAr)2O3 type were synthesized. Their constitutes and structures were determined by elemental analysis and IR specrophotometry. Three of them were tested for antitumour activities against Hela cells in vitro, showing some tumour inhibitory activity. Their effects on diploid cell were not obvious in mitosis and shape.
Eight compounds of (GcCH2CH2COOAr)2O3 type were synthesized. Their constitutes and structures were determined by elemental analysis and IR specrophotometry. Three of them were tested for antitumour activities against Hela cells in vitro, showing some tumour inhibitory activity. Their effects on diploid cell were not obvious in mitosis and shape.
1989, 6(5): 63-66
Abstract:
The isothermal solubilities of MgSO4-C2H5OH-H2O ternary system at-5, 0,25,30. 35 and 50℃ have been determined, the liquid-solid phase diagram has been drawn out and the equilibrium vapor pressures have been determined by static pressure method at 25℃ and 30℃ respectively. According to Jaque's pseudobinary model,the Wilson equation and NRTL equation have been tested to calculate the vapor-Jiquid equilibrium data of the system. It is shown that NRTL equilibrium equation is more agreeable with the experimental values.
The isothermal solubilities of MgSO4-C2H5OH-H2O ternary system at-5, 0,25,30. 35 and 50℃ have been determined, the liquid-solid phase diagram has been drawn out and the equilibrium vapor pressures have been determined by static pressure method at 25℃ and 30℃ respectively. According to Jaque's pseudobinary model,the Wilson equation and NRTL equation have been tested to calculate the vapor-Jiquid equilibrium data of the system. It is shown that NRTL equilibrium equation is more agreeable with the experimental values.
MEASUREMENT OF SPECIFIC ELECTRICAL CONDUCTIVITY OF Na3AlF6-Al2O3-RE2O3 MELT BY FOUR ELECTRODE METHOD
1989, 6(5): 67-69
Abstract:
Four electrode method has beenused in measuring the specific electrical conductivity k of Na3AlF6-Al2O3-RE2O3 melt. It is found.that k is decreased with increasing the contents of Al2,O3 and RE2O3 in the melt and is increased with temperature. The apparent activiation energy calculated is 18.84kJ/mol.The effect of the Al2O3 content on k is greater than that of the RE2O3 content.A mathematical model of the specific electrical conductivity of the melt is deduced with an accuracy of 95%.
Four electrode method has beenused in measuring the specific electrical conductivity k of Na3AlF6-Al2O3-RE2O3 melt. It is found.that k is decreased with increasing the contents of Al2,O3 and RE2O3 in the melt and is increased with temperature. The apparent activiation energy calculated is 18.84kJ/mol.The effect of the Al2O3 content on k is greater than that of the RE2O3 content.A mathematical model of the specific electrical conductivity of the melt is deduced with an accuracy of 95%.
1989, 6(5): 70-72
Abstract:
The basic princip'e and the techinque of measuring tbe long chain branching degree of polymers by gel permeation chromatography combined with low angle laser light scattering (GPC-LALLS) ale described. The branching degrees of a number of Ni catalysed cis-1,4-polybutadiene samples were measured. Using this technique the average branching factor(g),weight average numbor of branching points per mclecule(nw) and average branching degree(λ) and their distribution as well as molecular weight distribution can be obtained simultaneously.
The basic princip'e and the techinque of measuring tbe long chain branching degree of polymers by gel permeation chromatography combined with low angle laser light scattering (GPC-LALLS) ale described. The branching degrees of a number of Ni catalysed cis-1,4-polybutadiene samples were measured. Using this technique the average branching factor(g),weight average numbor of branching points per mclecule(nw) and average branching degree(λ) and their distribution as well as molecular weight distribution can be obtained simultaneously.
1989, 6(5): 73-76
Abstract:
The kinetics and mechanism of the extraction of Co(Ⅰ) from sulphate solution with quatornary ammonium thiocyanate (QSCN, Q-CH3 N [CH2(CH2)6-10CH3]3) in kerosene were studied by means ot single drop method at 298K. The experimental results indicate that the extraction process is controlled by the following interface reactions:CoSO4+2QSCN(i)
CoSO4·2QSCN(i), slow CoSO4·2QSCN(i)+2QSCN(o)
Q2Co(SCN)Q4(o)+Q2SO4, slow lgK1'=lgK1[QSCN]2(i)=-4.49;lgK-1/K2=2.56.where(o) and (i) represent organic phase and interface, respectively.
The kinetics and mechanism of the extraction of Co(Ⅰ) from sulphate solution with quatornary ammonium thiocyanate (QSCN, Q-CH3 N [CH2(CH2)6-10CH3]3) in kerosene were studied by means ot single drop method at 298K. The experimental results indicate that the extraction process is controlled by the following interface reactions:CoSO4+2QSCN(i)
CoSO4·2QSCN(i), slow CoSO4·2QSCN(i)+2QSCN(o)Q2Co(SCN)Q4(o)+Q2SO4, slow lgK1'=lgK1[QSCN]2(i)=-4.49;lgK-1/K2=2.56.where(o) and (i) represent organic phase and interface, respectively.
1989, 6(5): 77-80
Abstract:
Hexapeptide Ile-Thr-(Val)Thz-lle-Thr-(Val)Thz, the product of cycle opening of ascidiacyclamide, was synthesized by DCC-HOBT coopling method. The(Val) Thiazole amino acid was prepared by Hantzsch method
Hexapeptide Ile-Thr-(Val)Thz-lle-Thr-(Val)Thz, the product of cycle opening of ascidiacyclamide, was synthesized by DCC-HOBT coopling method. The(Val) Thiazole amino acid was prepared by Hantzsch method
1989, 6(5): 81-82
Abstract:
Three methylferrocene derivatives have been synthesized: bis(methyldicyclopentadienyl iron) methane, 2, 2-bis (methyldicyclopentadienyl iron)propane, and 2,2-bis(methyldicyclopentadienyl iron)butane. Their compositions and structures were characterized by elemental analysis, mass spectra and NMR determination.
Three methylferrocene derivatives have been synthesized: bis(methyldicyclopentadienyl iron) methane, 2, 2-bis (methyldicyclopentadienyl iron)propane, and 2,2-bis(methyldicyclopentadienyl iron)butane. Their compositions and structures were characterized by elemental analysis, mass spectra and NMR determination.
1989, 6(5): 83-85
Abstract:
The graft copolymer,of acrylonitrile onto corn starch was prepared by using [Mn(H2P2O7)3]3- as initiator and its morphology, structure and thermal stability have been studied,using scanning electron microscopy, x-ray diffraction and thermogravimetric analysis. The result showed that compared with the raw starch the grafted starch granules became large in size, rough in surface and its shape was changed. The crystallinity of the grafted starch granules decreased with thermal stability being increased.
The graft copolymer,of acrylonitrile onto corn starch was prepared by using [Mn(H2P2O7)3]3- as initiator and its morphology, structure and thermal stability have been studied,using scanning electron microscopy, x-ray diffraction and thermogravimetric analysis. The result showed that compared with the raw starch the grafted starch granules became large in size, rough in surface and its shape was changed. The crystallinity of the grafted starch granules decreased with thermal stability being increased.
1989, 6(5): 86-88
Abstract:
In this paper,four fractions of xanthan gum with different molecular weight determined by SALS technique were prepared by ultrasonication. Taking these fractions as standards, the various average molecular weight of natural xanthan, Mn=1.41×106,Mw=3.08×106,Mv=2.80×10, Mz=6.65×106, were obtained by GPC in 0.80M NaCl aqueous solution. The molecular weight distribution index D and intrinsic viscosity of native xanthan werecalculated as 2.18 and 2049.5mL/g respectively.
In this paper,four fractions of xanthan gum with different molecular weight determined by SALS technique were prepared by ultrasonication. Taking these fractions as standards, the various average molecular weight of natural xanthan, Mn=1.41×106,Mw=3.08×106,Mv=2.80×10, Mz=6.65×106, were obtained by GPC in 0.80M NaCl aqueous solution. The molecular weight distribution index D and intrinsic viscosity of native xanthan werecalculated as 2.18 and 2049.5mL/g respectively.
1989, 6(5): 89-92
Abstract:
The free radical concentration of plasma polymerized hexafluoropropene (PPHFP) was found to be 9.97×1019 spins/gram using CuSO4·5H2O single-crystal as a standard. The half-life of the radical in Ar gas was near half a year at room temperature.There was one radical in every two PPHFP chains. The activation energy and rate constants of the radical deterioration at different temperature have been calculated. Twenty hyperfine lines in ESR spectra were recorded for gascous products during plasma polymerization. The radicals of gascous products have similar stability.
The free radical concentration of plasma polymerized hexafluoropropene (PPHFP) was found to be 9.97×1019 spins/gram using CuSO4·5H2O single-crystal as a standard. The half-life of the radical in Ar gas was near half a year at room temperature.There was one radical in every two PPHFP chains. The activation energy and rate constants of the radical deterioration at different temperature have been calculated. Twenty hyperfine lines in ESR spectra were recorded for gascous products during plasma polymerization. The radicals of gascous products have similar stability.
1989, 6(5): 93-96
Abstract:
The three-exit extraction separation process(TESP) has been widely used in the separation of rare earths. For the simultaneous separation of A/B/C, there are four kinds of TESP. Based on the static equilibrium of A, B and C. in extraction, formulae of the extreme values were derived for determing the separation parameters of the TESP. With computer simulation, parameters for the separation of Gd/Tb/Dy were determined.It is shown that Tb component has been richened from 4.5% to 53.5% with 98% recovery in the experimental test.
The three-exit extraction separation process(TESP) has been widely used in the separation of rare earths. For the simultaneous separation of A/B/C, there are four kinds of TESP. Based on the static equilibrium of A, B and C. in extraction, formulae of the extreme values were derived for determing the separation parameters of the TESP. With computer simulation, parameters for the separation of Gd/Tb/Dy were determined.It is shown that Tb component has been richened from 4.5% to 53.5% with 98% recovery in the experimental test.
1989, 6(5): 97-99
Abstract:
Coated wire electrodes were prepared by coating PVC membrane on a platinum wire which had been modified with polyaniline or polyvinyl alcohol (containing a redox pair of K4Fe(CN)6/K3Fe(CN)6 and Lidocaine)respectively. The electrodes prepared not only have merits of Pt wire coated. with PVC membrame, but also an improved stability.
Coated wire electrodes were prepared by coating PVC membrane on a platinum wire which had been modified with polyaniline or polyvinyl alcohol (containing a redox pair of K4Fe(CN)6/K3Fe(CN)6 and Lidocaine)respectively. The electrodes prepared not only have merits of Pt wire coated. with PVC membrame, but also an improved stability.
1989, 6(5): 100-101
Abstract:
In this paper the complexes of rare earth ions RE(Ⅲ) with Rutin were prepared. The composition and stability constants of the complexes are reported.
In this paper the complexes of rare earth ions RE(Ⅲ) with Rutin were prepared. The composition and stability constants of the complexes are reported.
