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1990 Volume 7 Issue 4
1990, 7(4): 1-5
Abstract:
Six monohexadecyl hydrocarbylphosphonate extractants with highly steric hindrance,R1 (R2O) P(O) OH, where R2 represents-CH (C6H13) C2H4CH(C2H5) C4H9 or -CHC6H13)CH2CH (CH3)C6H13), as well as R1 represents CH3, C2H5, i-C3H7, cyclo-C6H11 and C6H5, respe-ctively, were synthesized and their extraction behaviours on Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Fe(Ⅲ) and Ca were investigated. The structural variation of the hydrocarbyl groups in the extrac-tant molecules has the different influences on the extractability of various metal ions.The compounds with isopropyl and cyclohexyl, having higher steric hindrance, possess higher separation ability of Co and Ni, and they are a new class of extractants superior to mono-2-ethylhexyl 2-ethylhexyl phosphonate (P-507), which has already been employed in industry.
Six monohexadecyl hydrocarbylphosphonate extractants with highly steric hindrance,R1 (R2O) P(O) OH, where R2 represents-CH (C6H13) C2H4CH(C2H5) C4H9 or -CHC6H13)CH2CH (CH3)C6H13), as well as R1 represents CH3, C2H5, i-C3H7, cyclo-C6H11 and C6H5, respe-ctively, were synthesized and their extraction behaviours on Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), Fe(Ⅲ) and Ca were investigated. The structural variation of the hydrocarbyl groups in the extrac-tant molecules has the different influences on the extractability of various metal ions.The compounds with isopropyl and cyclohexyl, having higher steric hindrance, possess higher separation ability of Co and Ni, and they are a new class of extractants superior to mono-2-ethylhexyl 2-ethylhexyl phosphonate (P-507), which has already been employed in industry.
1990, 7(4): 6-16
Abstract:
Using the second rank algebraic formulas, the structure seminvariants of six different types of known crystal structure have been estimated. These phases have also been esti-mated with other approaches:the Σ1, Σ4 relationships of probabilistic method and the first rank algebraic formulas. The results show that compared with the probabilistic method, the algebraic method not only gives results as satisfactory as the probabilistic method does,but also increases the computing rate significantly. From the comparison between the second and first rank formula, we get a quite unexpected case-the resultss of all the six structure show unanimously that the first rank formula almost has the same application value as the second one. The first rank formula has a great advantage over the second one in reducing the computing time.
Using the second rank algebraic formulas, the structure seminvariants of six different types of known crystal structure have been estimated. These phases have also been esti-mated with other approaches:the Σ1, Σ4 relationships of probabilistic method and the first rank algebraic formulas. The results show that compared with the probabilistic method, the algebraic method not only gives results as satisfactory as the probabilistic method does,but also increases the computing rate significantly. From the comparison between the second and first rank formula, we get a quite unexpected case-the resultss of all the six structure show unanimously that the first rank formula almost has the same application value as the second one. The first rank formula has a great advantage over the second one in reducing the computing time.
1990, 7(4): 17-21
Abstract:
The yield and the composition of the comb-polyether prepared by plasma-initiated poly-merization methoxypolyglycol methactylates were found in dependence on the power of plasma generator, the discharge time, the temperature and the time of postpolymerization, the kind of solvent, and the monomer concentration.The structure of the comb-polyether is identical with that prepared by radicalinitiated polymerization, but the former has a greater molecular weight and is little crosslinked. The plasma initiated comb-polyether can be plasticized to increase the ionic conductivity of its lithium salt complexes.
The yield and the composition of the comb-polyether prepared by plasma-initiated poly-merization methoxypolyglycol methactylates were found in dependence on the power of plasma generator, the discharge time, the temperature and the time of postpolymerization, the kind of solvent, and the monomer concentration.The structure of the comb-polyether is identical with that prepared by radicalinitiated polymerization, but the former has a greater molecular weight and is little crosslinked. The plasma initiated comb-polyether can be plasticized to increase the ionic conductivity of its lithium salt complexes.
1990, 7(4): 22-26
Abstract:
Six solid ternary complexes of Ln(Ⅲ) (Tb, Eu, La) with o-aminobenzoic acid (o-AA) or N-phenylanthranilic acid (N-PAA) and 1, 10-phenanthroline (Phen) were prepared. The complexes have the compositions Ln (Phen) (o-AA)3 or Ln (Phen) (N-PAA)3 and were characte-rized by elemental analysis, IR, UV, molar conductance, 1H NMR, XPS spectra measure-ments and thermal analysis.Detailed discussion on the luminescence of the complexes is given.
Six solid ternary complexes of Ln(Ⅲ) (Tb, Eu, La) with o-aminobenzoic acid (o-AA) or N-phenylanthranilic acid (N-PAA) and 1, 10-phenanthroline (Phen) were prepared. The complexes have the compositions Ln (Phen) (o-AA)3 or Ln (Phen) (N-PAA)3 and were characte-rized by elemental analysis, IR, UV, molar conductance, 1H NMR, XPS spectra measure-ments and thermal analysis.Detailed discussion on the luminescence of the complexes is given.
1990, 7(4): 27-31
Abstract:
Koumine, C20H22N2O, is the principal alkaloid of Kou-Wen alkaloids, Crystals of koumine belong to the monoclinic system with the space group P21, and the crystallographic data are:a=8.422(0), b=13.209(1), c=7.881(1)A,β=108.201(9), V=834.9953Å, Z=2;Dc=1.29g/cm3. The result shows that the koumine here determined is a stereo-isomer of that reported by Khuong-huu F et al in 1981. They are two non-enantiotopic optical isomers of koumine.
Koumine, C20H22N2O, is the principal alkaloid of Kou-Wen alkaloids, Crystals of koumine belong to the monoclinic system with the space group P21, and the crystallographic data are:a=8.422(0), b=13.209(1), c=7.881(1)A,β=108.201(9), V=834.9953Å, Z=2;Dc=1.29g/cm3. The result shows that the koumine here determined is a stereo-isomer of that reported by Khuong-huu F et al in 1981. They are two non-enantiotopic optical isomers of koumine.
1990, 7(4): 32-36
Abstract:
The synthesis of LnZn (OH)2 (GSH)3·3H2O (Ln=La, Pr and Nd) ternary complexes and the characters of their IR,XPS spectra and TG-DTA graphs are reported. The structures and coordination bond natures of the complexes have been discussed.
The synthesis of LnZn (OH)2 (GSH)3·3H2O (Ln=La, Pr and Nd) ternary complexes and the characters of their IR,XPS spectra and TG-DTA graphs are reported. The structures and coordination bond natures of the complexes have been discussed.
1990, 7(4): 37-41
Abstract:
The adsorption properties of P507 extraction resin for Mo have been investigated. The saturated adsorption capacity of the resin for Mo and the separation conditions of Mo from the solutions of H2SO4-EDTA system in the presence of large amounts of W were deter-mined.
The adsorption properties of P507 extraction resin for Mo have been investigated. The saturated adsorption capacity of the resin for Mo and the separation conditions of Mo from the solutions of H2SO4-EDTA system in the presence of large amounts of W were deter-mined.
1990, 7(4): 42-46
Abstract:
PTHF-MMA block copolymer was synthesized by using azo-containning polytetrahydro-furan (AZO-PTHF) as macro-initiator in the radical polymerization of methyl methacrylate(MMA).The copolymer has been characterized by GPC, IR, H-NMR and thermal mechanical analyses. The physical property indicated that the block copolymer possesses higher crease resistance and toughness than PMMA without obvious loss of transparence and tensile strength.
PTHF-MMA block copolymer was synthesized by using azo-containning polytetrahydro-furan (AZO-PTHF) as macro-initiator in the radical polymerization of methyl methacrylate(MMA).The copolymer has been characterized by GPC, IR, H-NMR and thermal mechanical analyses. The physical property indicated that the block copolymer possesses higher crease resistance and toughness than PMMA without obvious loss of transparence and tensile strength.
1990, 7(4): 47-51
Abstract:
In the solution of (0.4 mol KOH+0.6mol NH4Cl)/L PH=9.5 TPPS produces three po-larographic waves. The first step of reduction which involves 2H+ is a 2e reversible electrode process. Being coordinated with Zn(Ⅱ), the complex of ZnTPPS gave two reduction waves and one oxidation wave. The first reduction wave of ZnTPPS is reversible and involves one H+. Redunction of Zn2+ during or after the first reduction wave may result from the disso-ciation of ZnTPPS. The nearly equal strong adsorption of TPPS and ZnTPPS on Hg electrode was observed and Γ50,β0, K0 and G0 were cal culated.
In the solution of (0.4 mol KOH+0.6mol NH4Cl)/L PH=9.5 TPPS produces three po-larographic waves. The first step of reduction which involves 2H+ is a 2e reversible electrode process. Being coordinated with Zn(Ⅱ), the complex of ZnTPPS gave two reduction waves and one oxidation wave. The first reduction wave of ZnTPPS is reversible and involves one H+. Redunction of Zn2+ during or after the first reduction wave may result from the disso-ciation of ZnTPPS. The nearly equal strong adsorption of TPPS and ZnTPPS on Hg electrode was observed and Γ50,β0, K0 and G0 were cal culated.
1990, 7(4): 52-56
Abstract:
By means of linear potential sweep voltammetry and rotating disk electrode, togather with coulometric electrolysis, the anodic dissolution of gold in acidic thiourea solutions were studied. From the experimental results, it is proposed that the anodic dissolution of gold proceeds according to the following mechanism:Au+TU⇌Au(TU)ads (1) Au(TU)ads⇌Au(TU)ads++c (2) Au(TU)ads++TU→Au(TU)2+ (3) in which (3) is the rate-determining step. The existence of a maximum dissolution rate in the used potential range can be explained by this mechanism.
By means of linear potential sweep voltammetry and rotating disk electrode, togather with coulometric electrolysis, the anodic dissolution of gold in acidic thiourea solutions were studied. From the experimental results, it is proposed that the anodic dissolution of gold proceeds according to the following mechanism:Au+TU⇌Au(TU)ads (1) Au(TU)ads⇌Au(TU)ads++c (2) Au(TU)ads++TU→Au(TU)2+ (3) in which (3) is the rate-determining step. The existence of a maximum dissolution rate in the used potential range can be explained by this mechanism.
1990, 7(4): 57-61
Abstract:
Poly(2,6-dimethylphenylene oxide) (PFO) has been brominated and crosslinked with ammonia, ethylenediamine, m-phenylenediamine and hexamethylenetetramine. It was found that the oxygen permeability of the polymer membrane increased with the aryl-bromine con-tent in BrPPO and decreased with the benzyl-bromine content in BrPPO. NH3-crosslinking of BrPPO increased the oxygen permeability. Ethylenediamine-crosslinking of BrPPO increased the selectivity of oxygen over nitrogen significantly. Through crosslinking of benzyl-bromi-nated PPO a solvent resistant membrane with high selectivity of oxygen over nitrogen was obtained.
Poly(2,6-dimethylphenylene oxide) (PFO) has been brominated and crosslinked with ammonia, ethylenediamine, m-phenylenediamine and hexamethylenetetramine. It was found that the oxygen permeability of the polymer membrane increased with the aryl-bromine con-tent in BrPPO and decreased with the benzyl-bromine content in BrPPO. NH3-crosslinking of BrPPO increased the oxygen permeability. Ethylenediamine-crosslinking of BrPPO increased the selectivity of oxygen over nitrogen significantly. Through crosslinking of benzyl-bromi-nated PPO a solvent resistant membrane with high selectivity of oxygen over nitrogen was obtained.
1990, 7(4): 62-64
Abstract:
Several Schiff base supported silicas have been prepared and their adsorption capacities for metal ions were measured. compared to the Schiff-base-free silica the adsorption capacity of the functionalized ones were greatly improved in the order:Cu2+ > Co2+ > Cd2+ > Pb2+.The Nls photoelectron spectrum of Cu2+ complex with surface Schiff base was quite different from that of Cu2+ ion-free surface Schiff base. Owing to the more extensive back-bonding in the metal-coordinated-N=C-group, the Nls binding energy is far lower for the coordinated group than for the free one.
Several Schiff base supported silicas have been prepared and their adsorption capacities for metal ions were measured. compared to the Schiff-base-free silica the adsorption capacity of the functionalized ones were greatly improved in the order:Cu2+ > Co2+ > Cd2+ > Pb2+.The Nls photoelectron spectrum of Cu2+ complex with surface Schiff base was quite different from that of Cu2+ ion-free surface Schiff base. Owing to the more extensive back-bonding in the metal-coordinated-N=C-group, the Nls binding energy is far lower for the coordinated group than for the free one.
1990, 7(4): 65-68
Abstract:
4-Oxa-6,7-dichloroheptyltrimethoxysilane was synthesized from 4-oxa-6,7-dichlorohept-1-ene via hydrosilylation with trimethoxysilane in the presence of tetrakis (triphenylphos-phine) platinum complex as catalyst. The chlorine-containing silicon monomer was subjected to phosphatization with potassium diphenylphosphide, immobilized on the fumed silica and reacted with potassium chloroplatinite in acetone, giving the title complex. The bidentate phosphine platinum complex was found to exhibit high catalytic activity for the hydrosilylation of decene, dodecene, ω-chloroundecene, phenyl allyl ether,allyl ben-zene and glycidyl allyl ether with triethoxysilane. The yields of the adducts were 72 to 94%.The title complex could be recovered and reused several runs without loss of activity.
4-Oxa-6,7-dichloroheptyltrimethoxysilane was synthesized from 4-oxa-6,7-dichlorohept-1-ene via hydrosilylation with trimethoxysilane in the presence of tetrakis (triphenylphos-phine) platinum complex as catalyst. The chlorine-containing silicon monomer was subjected to phosphatization with potassium diphenylphosphide, immobilized on the fumed silica and reacted with potassium chloroplatinite in acetone, giving the title complex. The bidentate phosphine platinum complex was found to exhibit high catalytic activity for the hydrosilylation of decene, dodecene, ω-chloroundecene, phenyl allyl ether,allyl ben-zene and glycidyl allyl ether with triethoxysilane. The yields of the adducts were 72 to 94%.The title complex could be recovered and reused several runs without loss of activity.
1990, 7(4): 69-71
Abstract:
The poly(ethylene glycol) polyurethaneureas (PEUU) and the complexes composed of the PEUU and LiClO4 were examined by means of XPS and DSC. The DSC studies indicate that the soft segment's Tg of the complexes increases with increasing LiClO4 concentration;it shows that LiClO4 dissolves selectively in the poly (ethylene glycol) (PEG) phase. The XPS data show that the soft segment of PEG is significantly richer on the surface. Being added to PEUU, LiClO4 is advantageous to the further enrichment of PEG on the surface.It is also an evidence of selective dissolvation of LiClO4 in the PEG phase.
The poly(ethylene glycol) polyurethaneureas (PEUU) and the complexes composed of the PEUU and LiClO4 were examined by means of XPS and DSC. The DSC studies indicate that the soft segment's Tg of the complexes increases with increasing LiClO4 concentration;it shows that LiClO4 dissolves selectively in the poly (ethylene glycol) (PEG) phase. The XPS data show that the soft segment of PEG is significantly richer on the surface. Being added to PEUU, LiClO4 is advantageous to the further enrichment of PEG on the surface.It is also an evidence of selective dissolvation of LiClO4 in the PEG phase.
1990, 7(4): 72-74
Abstract:
The new 4-(-N-substituted) aminomethyl phenylalanines are presented. Dialkylamine rea-cted with N-acetyl-4-chloromethyl phenylalanine ethyl ester to give phenylalanine derivatives with basic side groups.After hydrolysis in hydrochloric acid and protection with Boc group the amino acids have been successfully used in solid phase peptide synthesis. This series amino acids combine basicity, aromaticity and hydrophilicity in the same molecule and have different N-dialkyl groups in length, they can be used in systematic research on structure-bioactivity relationships of peptides.
The new 4-(-N-substituted) aminomethyl phenylalanines are presented. Dialkylamine rea-cted with N-acetyl-4-chloromethyl phenylalanine ethyl ester to give phenylalanine derivatives with basic side groups.After hydrolysis in hydrochloric acid and protection with Boc group the amino acids have been successfully used in solid phase peptide synthesis. This series amino acids combine basicity, aromaticity and hydrophilicity in the same molecule and have different N-dialkyl groups in length, they can be used in systematic research on structure-bioactivity relationships of peptides.
1990, 7(4): 75-77
Abstract:
Rare earth oxides have been used as catalysts for the oxidative coupling of methane,La2O3 and Sm2O3 showed higher C2 selectivity. The mixture of La2O3 and alkaline earth oxide was found to be effective for oxidative coupling, among them binary oxide of La-Ba(1:1) gave the highest C2 yield, up to 20%. It is suggested that there could be a combina-tion effect of this binary system due to the structural influences, such as the specific sur-face area. Based on the temperature dependence of the products distribution, a mechanism ofthe reaction was proposed.
Rare earth oxides have been used as catalysts for the oxidative coupling of methane,La2O3 and Sm2O3 showed higher C2 selectivity. The mixture of La2O3 and alkaline earth oxide was found to be effective for oxidative coupling, among them binary oxide of La-Ba(1:1) gave the highest C2 yield, up to 20%. It is suggested that there could be a combina-tion effect of this binary system due to the structural influences, such as the specific sur-face area. Based on the temperature dependence of the products distribution, a mechanism ofthe reaction was proposed.
1990, 7(4): 78-81
Abstract:
The crystal structure of the title compound was determined by X-ray diffractometry. The compound crystallizes in monoclinic space group P21, Z=4, with lattice parameters a=4.429Å,b=18,726Å, c=9.588Å,β=102.63Å, V=776.0Å3 and Dc=1.439g/cm3. Final R=0.0459.
The crystal structure of the title compound was determined by X-ray diffractometry. The compound crystallizes in monoclinic space group P21, Z=4, with lattice parameters a=4.429Å,b=18,726Å, c=9.588Å,β=102.63Å, V=776.0Å3 and Dc=1.439g/cm3. Final R=0.0459.
1990, 7(4): 82-85
Abstract:
The crystal and melecular structure of p-ferrocenylacetophenone has been determined by the single crystal X-ray diffractometry. The crystal is orthorhombic and space group Pbca with the cell constants a=7.7342, b=10.5485, c=34.0332Å and Z=8. The analytic results show that both the CP rings are almost parallel. The plane of each ring is tilt 18 from that of Phenyl ring.The carbon atom of the acetyl group is normal sp2 hybridization, the angles around this carbon is close to 120. One significant result obtained in this structure is that the carbon to carbon bond length in the CP ring linkedto the phenyl group is longer than C-C length in the other CP ring.
The crystal and melecular structure of p-ferrocenylacetophenone has been determined by the single crystal X-ray diffractometry. The crystal is orthorhombic and space group Pbca with the cell constants a=7.7342, b=10.5485, c=34.0332Å and Z=8. The analytic results show that both the CP rings are almost parallel. The plane of each ring is tilt 18 from that of Phenyl ring.The carbon atom of the acetyl group is normal sp2 hybridization, the angles around this carbon is close to 120. One significant result obtained in this structure is that the carbon to carbon bond length in the CP ring linkedto the phenyl group is longer than C-C length in the other CP ring.
1990, 7(4): 86-89
Abstract:
The compounds with the compositions of Sr3Cu5O8+x and CaSrCu3O5+x have been syn-thesized by solid phase reaction method. The crystal structures of both compounds are or-thorhombic with a=3.950Å, b=11.479Å and c=13.420Å for Sr3Cu5O8+x and a=6.489Å,b=11.280Å and c=12.240Å for CaSrCu3O5+x, respectively. The oxygen content and oxida-ation state of copper ion were analysized by the iodometric titration. The electric property measurement indicates that both compounds are p-type semiconductor and have lower resis-tivity. They decomposes at around 936℃.
The compounds with the compositions of Sr3Cu5O8+x and CaSrCu3O5+x have been syn-thesized by solid phase reaction method. The crystal structures of both compounds are or-thorhombic with a=3.950Å, b=11.479Å and c=13.420Å for Sr3Cu5O8+x and a=6.489Å,b=11.280Å and c=12.240Å for CaSrCu3O5+x, respectively. The oxygen content and oxida-ation state of copper ion were analysized by the iodometric titration. The electric property measurement indicates that both compounds are p-type semiconductor and have lower resis-tivity. They decomposes at around 936℃.
1990, 7(4): 90-92
Abstract:
The integral heats of solution of Nd(NCS)3·5DMSO in DMSO-H2O at 298.15K have been measured using a modified RD-1 heat conducting automatic calorimeter.The results can be expressed in following equation:ΔH=-17.95+63.42x2-320.09x22+820.65x23-523.00x24 where x2 is the mole fraction of H2O in DMSO-H2O.
The integral heats of solution of Nd(NCS)3·5DMSO in DMSO-H2O at 298.15K have been measured using a modified RD-1 heat conducting automatic calorimeter.The results can be expressed in following equation:ΔH=-17.95+63.42x2-320.09x22+820.65x23-523.00x24 where x2 is the mole fraction of H2O in DMSO-H2O.
1990, 7(4): 93-95
Abstract:
A glucose electrode was constructed using a cobalt tetraphenyl porphyrin modified elec-trode with response time of less than 4s. A linearship was obtained between the current decrease and the glucose concentration in the range of 0.05-0.8mmol/L. The activity of the glucose oxidase kepr unchanged for 3 months in icebax condition. The selectivity was sati-sfactory.
A glucose electrode was constructed using a cobalt tetraphenyl porphyrin modified elec-trode with response time of less than 4s. A linearship was obtained between the current decrease and the glucose concentration in the range of 0.05-0.8mmol/L. The activity of the glucose oxidase kepr unchanged for 3 months in icebax condition. The selectivity was sati-sfactory.
1990, 7(4): 96-98
Abstract:
The luminescence mechanism, the energy transfer processes, the effects of ligand con-centration and laser energy on the fluorescent intensities of the dysprosium-trifluoroacetylace-tone-tri-n-octylphosphine oxide (Dy-TFA-TOPO) system were studied using Nd:YAG pumped dye laser and SIT vidicon optical multichannel analyzer. The phosphorescence emission of TFA was determined first time on room temperature.The Dy-TFA-TOPO-Tween-20 was adopted in the trace determination of dysprosium.
The luminescence mechanism, the energy transfer processes, the effects of ligand con-centration and laser energy on the fluorescent intensities of the dysprosium-trifluoroacetylace-tone-tri-n-octylphosphine oxide (Dy-TFA-TOPO) system were studied using Nd:YAG pumped dye laser and SIT vidicon optical multichannel analyzer. The phosphorescence emission of TFA was determined first time on room temperature.The Dy-TFA-TOPO-Tween-20 was adopted in the trace determination of dysprosium.
1990, 7(4): 99-101
Abstract:
A set of metal ion-exchanged montmorillonites are prepared, thier activities for catalytic oxidative desulfuration in liquid phase are examined. The results show that as the sulfonated Co2+ -phthalocyanine Ni2+, Co2+ and Mn2+ montmorillonites are an useful desufurizingagent.
A set of metal ion-exchanged montmorillonites are prepared, thier activities for catalytic oxidative desulfuration in liquid phase are examined. The results show that as the sulfonated Co2+ -phthalocyanine Ni2+, Co2+ and Mn2+ montmorillonites are an useful desufurizingagent.
