Ring-opening polymerization of epsilon-caprolactone and L-lactide using organic amino calcium catalyst

Poly (6-caprolactone) (PCL) and poly (L-lactide) (PLA) were prepared by ring-opening Polymerization catalyzed by organic amino calcium catalysts (Ca/PO and Ca/EO) which were prepared by reacting calcium ammoniate Ca(NH3)(6) with propylene oxide and ethylene oxide, respectively. The catalysts exhibited high activity and the ring-opening polymerization behaved a quasi-living characteristic. Based on the Fr-IR spectra and the calcium contents of the catalysts, and based on the H-1 NMR end-group analysis of the low molecular weight PCL prepared using catalysts Ca/PO and Ca/EO, it was proposed that the catalysts have the structure of NH2-Ca-O-CH(CH3)(2) and NH2-CaO-CH2CH3 for Ca/PO and Ca/EO, respectively. The ring-opening polymerization of CL and LA follows a coordination-insertion mechanism and the active site is the Ca-O bond.

Synthesis and characterization of PCL/PEG/PCL triblock copolymers by using calcium catalyst

Triblock copolymer PCL-PEG-PCL was prepared by ring-opening polymerization of epsilon-caprolactone (CL) in the presence of poly(ethylene glycol) catalyzed by calcium ammoniate at 60 degreesC in xylene solution. The copolymer composition and triblock structure were confirmed by H-1 NMR and C-13 WR measurements. The differential scanning calorimetry and wide-angle X-ray diffraction analyses revealed the micro-domain structure in the copolymer. The melting temperature T-c and crystallization temperature T-c of the PEG domain were influenced by the relative length of the PCL blocks. This was caused by the strong covalent interconnection between the two domains. Aqueous micelles were prepared from the triblock copolymer. The critical micelle concentration was determined to be 0.4-1.2 mg/l by fluorescence technique using pyrene as probe, depending on the length of PCL blocks, and lower than that of corresponding PCL-PEG diblock copolymers. The H-1 NMR spectrum of the micelles in D2O demonstrated only the -CH2CH2O- signal and thus confirmed. the PCL-core/PEG-shell structure of the micelles.

Synthesis of poly(epsilon-caprolactone)-b-poly(gamma-benzyl-L-glutamic acid) block copolymer using amino organic calcium catalyst

A biodegradable two block copolymer, poly(epsilon-caprolactone)-b- poly(gamma-benzyl-L-glutamic acid) (PCL-PBLG) was synthesized successfully by ring-opening polymerization of N-carboxyanhydride of gamma-benzyl-L-glutamate (BLG-NCA) with aminophenyl-terminated PCL as a macroinitiator. The aminophenethoxyl-terminated PCL was prepared via hydrogenation of a 4-nitrophenethoxyl-teminated PCL, which was novelly obtained from the polymerization of c-caprolactone (CL) initiated by amino calcium 4-nitrobenzoxide. The structures of the block copolymer and its precursors from the initial step of PCL were confirmed and investigated by H-1 NMR, FT-IR, GPC, and FT-ICRMS analyses and DSC measurements.

Liquid crystal alignment generated by linearly polarized UV light on photoactive low molecular mass compounds

Alignment films prepared from low molar mass photo-crosslinkable materials containing the cinnamate group can be used for aligning LCs after irradiating the films with linearly polarized UV light. The high contrast observed in the polarizing optical microscope between dark and bright images indicates that the alignment is quite uniform. As the photoreaction progresses. the average roughness of the films is increased. All the aggregate structures, 'lamellar crystals'. produced by the photo-crosslinking reaction are of a square shape.

VUV-UV excited luminescent properties of calcium borophosphate doped with rare earth ions

The VUV-UV spectra of rare earth ions activated calcium borophosphate, CaBPO5:RE (RE = Ce3+, sm(3+), Eu2+, Eu3+, Tb3+ and Dy3+) were determined. The bands at about 155 nm in the VUV excitation spectra are attributed to the host lattice absorptions. The bands at 166 and 190 nm for the sample CaBPO5:Sm have been considered as related to the f-d transition and the charge transfer band (CTB) of Sm3+ ions, and the band at 169 nm for the sample CaBPO5:Dy is assumed to be connected with the f-d transition of the Dy3+ ions in CaBPO5. The partial reduction of Eu3+ CaBPO5:Eu prepared by high temperature solid state reaction in air is confirmed by the VUV-UV spectra.

Hybrid organic-inorganic compounds doped with terbium carboxyl complexes produced in situ via a sol-gel approach

In situ synthesis of terbium carboxyl complexes in an organic-inorganic hybrid matrix by a sol-gel process has been proposed. The formation of terbium carboxyl complexes in the hybrid matrix is confirmed by the luminescence spectra and IR spectra. It is observed that the location at the amino group in aminobenzoic acid has a large effect on the luminescence properties and lifetimes. Furthermore, the emission intensity decreases with increasing temperature.

Expert system for elucidation of structures of organic compounds (ESESOC) - Algorithm on stereoisomer generation

An algorithm for enumeration of stereoisomers due to asymmetric carbon, C=C double bond and so on has been developed. It consists of three steps. The output of stereoisomers can be represented by 2.5-dimensional connection table.

Investigation of covalency and spectrum shifts in 3d transition-metal compounds

By using a correction factor of d electron effects on bond, PV theory is applied to the calculation of chemical bond;parameters of d transition-metal compounds. Racah parameters and Mossbauer isomer shifts are calculated, and the results are agreement with the experimental values.

Species of rare earth (III), calcium (II) and zinc (II) in the presence of L-histidine and L-typtophane

Rare earth(III)-histidine (His)- tryptophane (Trp). Ca(II)-His-Trp and Zn(II)-His-Trp systems were studied by potentiometric titration and computer simulation under physiological conditions. The species of the systems and their stability constants were determined. The distributions of species of rare earth(III), Ca(II) and Zn(II) were discussed.

Fullerenes-extracted soot: a new adsorbent for collecting volatile organic compounds in ambient air

Fullerenes-extracted soot (FES) is the by-product of fullerenes production. Retention characteristics at different temperatures for 17 volatile organic compounds (VOCs) on FES are measured. The adsorption and desorption efficiencies for VOCs on FES adsorbent tubes range from 40.8 to 117%, most of them being 100+/-20%. The values are compared with Tenax GR, an adsorbent commonly used in environmental analysis. FES can be used as an adsorbent of low cost to collect VOCs in environmental samples. (C) 2000 Elsevier Science B.V. All rights reserved.

Spectroscopy of several beta-diketone compounds and their tautomers

Six beta-diketone compounds, 1,3-bis(4-nitrophenyl)-1,3-propanedione (1), 1-(4-nitrophenyl)-3-(3-nitrophenyl)-1,3-propanedione(2), 1,3-bis(3-nitrophenyl)-1,3-propanedione(3) 1,3-bis(4-amimophenyl)-1,3-propanedione(4), 1-(4-amimophenyl)-3-( 3-amimophenyl)-1,3-propanedione(5) and 1,3-bis (3-amimophenyl)-1,3-propanedione(6) were synthesized, Their structures were characterized by IR, UV-Vis, fluorescence and NMR spectroscopy, The percentage of keto tautomer, enol-keto equilibrium constant and enol tautomer ratio of them were also determined, The percentage of keto tautomer is increased in the order from compound 1 to 3 and decreased in the order from compound 4 to 6, which show the effect of substituent on the tautomer. The results of enol tautomer ratio of compounds 2 and 5 indicated that b-form of enol is slightly more favorable than its a-form.

Theoretical studies of nonlinear optical properties of compounds K(4)Ln(2)(CO3)(3)F-4 (Ln=Pr, Nd, Sm, Eu, Gd)

K(4)Ln(2)(CO3)(3)F-4 (Ln=Pr, Nd, Sm, Eu, Gd) is a special type of frequency doubling compound, whose crystal structure exhibits a scarcity of fluorine ions. This leads to two different coordination polyhedrons in the general position of K(2) atoms: [K(2)O6F(1)(2)F(2)] and [K(21)O6F(1)(2)] in a 2/1 ratio. The chemical bonding structures of all constituent atoms of the compound K4Gd2(CO3)(3)F-4 (KGCOF) are comprehensively studied; moreover, the relationship between the chemical bonding structure and the nonlinear optical (NLO) properties is investigated from the chemical bond viewpoint. The theoretical prediction of the NLO tensor coefficient d(11) of KGCOF is in agreement with experimental observation. Theoretical analyses show that the nonlinearity of this crystal type mainly originates from K-O bonds. In addition, the correlation between the NLO tensor d(11) and the refractive index n(0) of KGCOF is discussed. (C) 2000 American Institute of Physics. [S0021-8979(00)07506-X].

Quantitative structure-property relationship research to the analysis of photoionization sensitivity of organic compounds in gas chromatography

The A(m) index and molecular connectivity index were used for studying the photoionization sensitivity of some organic compounds in gas chromatography. The analysis of structure-property relationship between the photoionization sensitivity of the compounds and the A(m) indices or molecular connectivity indices has been carried out. The genetic algorighm was used to build the correlation model in this field. The results demonstrate that the property of compounds can be described by both A(m) indices and molecular connectivity indices, and the mathematical model obtained by the genetic algorithm was better than that by multivariate regression analysis.

Sol-gel deposition of calcium silicate red-emitting luminescent films doped with Eu3+

Eu3+-activated calcium silicate (CaO-SiO2:Eu3+) luminescent films were prepared by the sol-gel method. The structural evolution of the film was studied by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), and the luminescence properties of the phosphor films were investigated as a function of heat treatment temperature. The XRD study indicates that a kilchoanite phase forms in the film sintered at 800 degreesC, which is different from that in gel powder treated under the same conditions. The SEM results show that the film thickness decreases and the particles in the film become smaller with increasing heat treatment temperature. The CaO-SiO2:Eu film shows the characteristic emission of Eu3+ under UV excitation, with the Eu3+ D-5(0)-->F-7(2) band (616 nm) being the most prominent. A large difference in the Eu3+ lifetime is observed between the film samples treated at 500 and 700 degreesC (or above). Concentration quenching occurs when the Eu3+ doping concentration is above 6 mol% of Ca2+ in the film.

The development in oxidation of olefins to ketones catalyzed by palladium compounds

The development in the oxidation of olefins to ketones catalyzed by palladium compounds was reviewed. Some improved methods for the oxidation of olefins catalyzed by Wacker-type catalyst systems are also summarized. For this reaction, some new catalyst systems and the reaction mechanism are described. Emphasis has been given to the applications of Pd(I)/HPA(heteropoly acid), Pd(I)/FePc (iron phthalocyanine), Pd (I)/HQ (hydroquinone)/FePc, Pd (I)/HQ/HPA, Pd (I)/CuSO4/HPA catalyst systems in the oxidation of olefins to ketones; the application of Pd(I)/LCoNO2, PdCl2 (MeCN)(2)/CuCl, Pd(OAc)(2)/ pyridine, fluorous biphasic catalyst systems in the oxidation of olefins to ketones is also surveyed.