Synthesis of polyurethanes from fluorinated diisocyanates

A number of polyurethanes based on fluorinated aliphatic diisocyanates, perfluorinated aromatic diisocyanates, and chlorinated aromatic diisocyanates have been prepared. The polyurethane prepared from perfluorotrimethylene diisocyanate and hexafluoropentanediol was a rubbery solid which hydrolyzed readily in air to a liquid or sticky solid but was stable if protected from moisture. The products of hydrolysis were isolated and identified. Polyurethanes based on hexafluoropentamethylene diisocyanate were synthesized by reaction of hexafluoropentanediamine with hexafluoropentamethylene bischloroformate and with tetrafluoro-p-phenylene bischloroformate. Polyurethanes were synthesized by reaction of tetrafluoro-p-phenylene diisocyanate with hexafluoropentanediol and pentanediol. Other perfluoroaryl diisocyanate-based polyurethanes were synthesized by reaction of tetrafluoro-m-phenylene diisocyanate with hexafluoropentanediol and with tetrafluoro-p-hydroquinone. Polyurethanes were also synthesized by reaction of tetrachloro-p-phenylene diisocyanate and 2,3,5,6-tetrachloro-p-xylylene-α,α′-diisocyanate with hexafluoropentanediol.     

Biosorption of nickel using filamentous fungi

Nickel (Ni) uptake capability from aqueous solutions was studied in a filamentous fungi strains group ofRhizopus sp.,Penicillium sp.Aspergillus sp.,Trichoderma sp.,Byschoclamyss sp., andMucor sp. The metal uptake of aRhizopus sp. strain, which has the highest uptake capacity, was corroborated by electron microscopy; no Ni deposits were observed on the cell wall, but rather a homogeneous accumulation was seen on the cell surface. The influence on the capacity of metal uptake by environmental parameters such as pH, temperature, time, and the interference of other ions in the solution, was also studied. Nickel accumulation by the selected strains is fast, occurring in less than 30 min, and does not require a microorganism’s active metabolism to take place. Sorption isotherms were established for the selected fungi, in order to determine the maximum metal uptake capacity. The sorption isotherms were fixed to the mathematical models of Freundlich and Langmuir, obtaining better performance on the Langmuir model.     

Anharmonic Effect of the Unimolecular Isomerization/Decomposition of Benzyne

The anharmonic and harmonic rate constants were calculated for the unimolecular decomposition of o‐benzyne, the isomerization of o‐benzyne to m‐benzyne, the isomerization of m‐benzyne to p‐benzyne and unimolecular decomposition of p‐benzyne by using the Rice–Ramsperger–Kassel–Marcus (RRKM) theory respectively, in the canonical and microcanonical systems. The geometry and the vibrational frequencies were calculated by MP2 and B3LYP methods with 6‐311G(d,p) basis set and the barrier energies were corrected using CBS‐QB3 theory. The anharmonic effect on the reactions was also examined. Comparison of results for the decompositions of benzyne indicate that both in microcanonical and canonical cases, the anharmonic effect on the decomposition of the o‐C₆H₄ and p‐C₆H₄ are significant, while the anharmonic effect on the two isomerizations are not pronounced.     

Electron spin resonance studies of several anion radicals of nitro-substituted thioacylpiperidines and morpholines

The radical anions of m- and p- nitro-substituted derivatives of several classes of N-(thioacyl)-piperidines and -morpholines have been studied by ESR spectroscopy. The anion radicals were found to be centred on the nitro group, and the distribution of the unpaired electron was found to be dependent on the extent of conjugation between the thiocarbonyl group and the aromatic moiety of the molecule. The hfs constants were discussed in terms of the spin densities calculated by the McLachlan procedure.     

Functionality and structure of polymers. II. Photodimerization of polymer-bound anthryl groups and thermal dissociation of the photodimers

Anthryl groups bound to various polyesters and polyesterurethanes as side groups were photodimerized in solid state in a nitrogen atmosphere. The rate of photodimerization is strongly affected by polymer structure as observed in the photodimerization of dilute solutions. The results revealed the importance of segment mobility rather than local concentration of anthryl groups. Temperature effects on the rate of photodimerization indicated that the rate jumped above the glass transition temperature (T_g). A definite difference in photodimerization behavior was apparent between polyesters and polyesterurethanes. Anthryl groups in polyesters were to some extent photodimerized at T_g, whereas polyesterurethanes did not react at all. Hydrogen bonding in polyesterurethanes restricted the movement of anthryl groups and consequently additional energy was required to liberate them and allow photodimerization to proceed. The anthryl groups can be recovered from the photodimerized polymers by heating to 80–100°C. The activation energy of thermal dissociation of the photodimer depends to a great extent on polymer structure. These results were interpreted as being due to the strain brought about by photodimer formation exhibited this dependence. The photodimerization–thermal dissociation cycle was reversible (reversibility: 95–100% under nitrogen). A novel principle of reversible photomemory, based on dry unit processes that consisted of image recording above T_g, fixation of image by cooling below T_g, and image erasure at elevated temperature, was proposed.     

Nitrosation of Phenolic Compounds: Effects of Alkyl Substituents and Solvent

Summary.  Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO⁺/NO₂H₂ ⁺ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant. Received July 13, 2001. Accepted (revised) September 18, 2001     

Evaluation of soybean seed protein extraction focusing on metalloprotein analysis

Two methods of protein extraction for soybean seeds were evaluated in terms of preservation of the metal ions bound to proteins after the extraction and separation procedures. The proteins were firstly separated according to their molar masses by polyacrylamide gel electrophoresis. Then, the protein bands were mapped by synchrotron radiation X-ray fluorescence in order to establish which metal ions were present in each one. Finally, some mapped protein bands were decomposed by microwave-assisted combustion and Ca, Cu, K, Mg, Mn, and Zn were quantified by inductively coupled plasma mass spectrometry or inductively coupled plasma optical emission spectrometry. The extraction methods studied were Method A (based on the treatment of ground soybean seeds with hexane and their extraction with Tris–HCl and β-mercaptoethanol) and Method B (based on the treatment of ground soybean seeds with petroleum ether and their extraction with Tris–HCl, dithiothreitol, phenylmethanesulfonyl fluoride, sodium dodecyl sulfate and potassium chloride). The best method was Method B, in which a 78% higher extraction efficiency was obtained when compared to Method A. Additionally, the metal-protein interactions were more appropriately preserved when Method B was applied, where the most affected ions were those that are bound weakly to proteins, such as Ca, K, and Mg.     

Electrical conductivity of polycrystalline films of p-sexiphenyl

In this work the results of DC conductivity measurements of polycrystalline p-sexiphenyl thin films are presented. The investigations concerned the effect of temperature, film thickness and electric field on the DC conductivity mechanism. The thickness of the investigated material varied from 0.2 to 2.5 μm. The measurements were carried out for different electrode polarities of the 0 -100 V voltage and at temperatures ranging from 15 to 325 K. Thin films of p-sexiphenyl were obtained by controlled vacuum sublimation on BK-7 glass substrate with gold and aluminium electrodes. Analyzing the obtained results we conclude that injection of the charge carrier from electrodes into the investigated material proceeds by thermionic emission and field emission and it is dependent on temperature and external electric field. The charge carrier transport is controlled by localized states (traps) in the forbidden energy gap. The activation energy calculated from formula ln I = f(1/kT) varied from kT for low temperature up to 1.0 eV.     

Preparation of Albumin Microspheres Grafted Galactose Residues Through Polyethylene-Glycol Spacers,Release Behavior of 5-Fluorouracil from Them,and Their Lectin-Mediated Aggregation

Small-sized albumin gel microspheres, MSs, containing 5-fluorouracil (5FU) with targeting moieties on their surfaces (average diameter: 1.5 μm) were prepared by the glutaraldehyde crosslinking method and suspension technique. Since galactose is known to interact specifically with the asialoglycoprotein receptor on hepato-cyte, the galactose residues were introduced on the surface of MSs as the targeting moieties for hepatoma through polyethylene glycol (PEG) spacers. PEG spacers were employed to depress the immu-nogenicity of albumin, to keep the mobility of the galactose residues, and to heighten the distributive stability of the MSs in aqueous solution. It was confirmed by ESC A analysis that the PEG chains were introduced onto the surfaces of MSs. The amount of galactose residues introduced to MS were estimated to be 0.013 wt%. The intra-MSs aggregation was observed by the addition of Ricinus Communis Agglutinin I (RCA120) into the MS suspension, and then the aggregation of MSs was dissociated by addition of free lactose. Moreover, by incubation of the MSs with human hepatoma HLE cells, the phenomena of MS's specific binding onto HLE cell surfaces and phagocytosis of MSs by HLE cells were observed. These results suggested that the galactose residues on the surface of MSs were recognized with the galactose receptors on hepatoma cell surfaces. The release rate of 5FU from MSs was investigated in vitro in physiological saline at 37OC. About 90% of encapsulated 5FU were found to be released from MSs through incubation for 8 h.     

微量热法研究蒽醌化合物的抑菌活性和毒理作用

The growth therrnogenic curves of Staphylococcus aureus and Tetrahymena thermophila affected by 1,8-dihydroxyanthraquinone, emodin and rhein were determined quantitatively by microcalorimetry. The inhibitory effects of the three anthraquinones （AQ） on S. aureus revealed that the sequence of antimicrobial activity of those was rhein〉emodin〉 1,8-dihydroxyanthraquinone. The toxicity of the three AQ on T. thermophila indicated that all the tested AQ were toxic to the tested protozoa and the hydroxyl and carboxyl substituted at different position of anthraquinone ring resulted in the enhancement of toxicity.     

Nitrosation of Phenolic Compounds: Effects of Alkyl Substituents and Solvent

 Nitrosation reactions of phenol, o-cresol, 2,6-dimethylphenol, o-tert-butylphenol, 2-hydroxyacetophenone, and 2-allylphenol in water and water/acetonitrile were studied. Kinetic monitoring of the reactions was accomplished by spectrophotometric analysis of the nitrosated products at 345 nm. The dominant reaction was C-nitrosation via a mechanism consisting of an attack on the nitrosatable substrate by NO⁺/NO₂H₂ ⁺ followed by a slow proton transfer. The values of the rate constants of phenolic C-nitrosation were increased by electron donating substituents, and a good Hammett correlation was observed with ρ = −6.1. The results also revealed the strong effect of pH and the permitivity of the reaction medium on the rate constant, whose maximum values were observed for pH ≈ 3, decreasing strongly for higher pH values. The study in water/acetonitrile with up to 25% acetonitrile showed that it is possible to inhibit the reaction strongly by increasing the percentage of the organic component. The conclusions drawn show that (i) it is possible to predict the rate of nitrosation of phenolics as a function of the meta-substituents on the phenol ring and (ii) the nitrosation of phenolics can be strongly inhibited by increasing the pH of the reaction medium as well as by lowering its dielectric constant.     

Effects of ortho-substituents on reactivities,tacticities, and ceiling temperatures of radical polymerizations of phenyl methacrylates

Radical polymerization and copolymerization of some o-alkylphenyl methacrylates were carried out and the effect of the ortho-substituents on the ability to homopolymerize, on the monomer reactivities, and on the ceiling temperatures of the monomers was studied. The effect of the substituent on tacticities and thermal stabilities of the polymers formed was also discussed. The ability to honiopolymerize and the monomer reactivity were considerably decreased by the introduction of the o-substituent. 2,6-Di-tert-butylphenyl methacrylate formed no methanol-insoluble polymer at 60°C. On the basis of the tacticity determined it was noted that the o-substituted phenyl methacrylates preferred syndiotactic addition in the propagation reaction less than did phenyl methacrylate or methyl methacrylate. The polymers formed from the o-substituted monomers were thermally less stable than poly(phenyl methacrylate), and, consistent with this finding, ceiling temperatures of the o-substituted phenyl methacrylates seemed to be lower than that of phenyl methacrylate. The effects observed were characteristic of the o-substituents conformationally close to the carbon-carbon double bond of the monomer or the carbon carrying the unpaired electron of the polymer radical.     

Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. V. Effects of p-benzoquinone and dose rate on methyl methacrylate–silica gel system

In order to elucidate the mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the effects of p-benzoquinone addition and dose rate were studied in detail. Most of the polymerization is inhibited by p-benzoquinone at levels above 10^-2 mole/l. The GPC spectra of both graft polymers and homopolymers show two peaks. The high molecular weight material appears to have been formed by polymerization by a radical mechanism, because these peaks decrease as p-benzoquinone concentration increases; on the other hand, their low molecular weight polymers seem to be products of an ionic polymerization mechanism because those peaks are almost not affected by p-benzoquinone. The four GPC peaks differ in dose rate dependences of their polymerization rate. The dose-rate exponents of polymerization rate were obtained for the four GPC peaks. The behavior of the low molecular weight peaks of graft polymers and homopolymers were quite different, suggesting that the polymers differ considerably in formation mechanism.     

Effects of electron beam preirradiation on the γ radiolysis of polyethylene

The γ radiolysis of polyethylene preirradiated with electron beams to 3 Mrad was carried out at 30–100°C in vacuo with a dose rate of 6.35 × 10⁵ rad/hr. The hydrogen formation in the γ radiolysis was little affected by the preirradiation of electron beams, whereas the formation of trans-vinylene unsaturation and gel was somewhat retarded. The rates of the formation of hydrogen and trans-vinylene unsaturation were described by the zero-order formation kinetics with respect to each concentration combined with the first-order disappearance. The apparent rate constants and activation energies for the formation and disappearance of hydrogen and trans-vinylene unsaturation were almost independent of the preirradiation. The gel fraction was analyzed by using the Charlesby–Pinner equation. The G values of crosslinking and main chain scission were increased by the preirradiation, whereas their activation energies remained unaltered. On the basis of these results the effects of preirradiation on the reactions induced by γ rays in polyethylene were discussed.     

Immobilization of a recombinant cutinase by entrapment and by covalent binding

Fusarium solani pisi recombinant cutinase, immobilized by entrapment in calcium alginate and by covalent binding on porous silica, was used to catalyze the hydrolysis of tricaprylin. The influence of relevant parameters on the catalytic activity such as pH, temperature, and the substrate concentration were studied. Cutinase immobilized by entrapment presented a Michaelis-Menten kinetics for tricaprylin concentrations up to 200 mM. At higher concentrations of substrate, inhibition was observed. For covalent binding immobilization, diffusional limitations were observed at low substrate concentrations and substrate inhibition occurred for concentrations higher than 150 mM. The stability of immobilized cutinase was also evaluated. The enzyme immobilized by entrapment showed a high stability, in contrast to the immobilization on porous silica.     

Determination of the volatile constituents of ChineseCoriandrum sativum L. by gas chromatography—Mass spectrometry with solid-phase microextraction

Summary Fifteen main volatile compounds in ChineseCoriandrum sativum L. were separated and identified by gas chromatography—mass spectrometry (GC-MS) combined with solid-phase microextraction (SPME). Fresh ChineseCoriandrum sativum L. was ground and its volatile compounds were extracted by SPME with a 100 μm polydimethylsiloxane fiber. The fibers were desorbed in a GC injection liner at 250°C for 3 min. More than 15 peaks were separated by headspace SPME-GC-MS analysis. The main compounds in headspace ofCoriandrum sativum L. identified by mass spectrometry included decanal, 2-decenal, 1-decanol,trans-2-decen-1-ol,trans-2-decen-1-al,trans-2-tridecenal etc, which were verified by reference compounds. Their relative contents were calculated on basis of peak areas. SPME extraction conditions and capillary chromatography column used to separate the volatile compounds were investigated.     

Pharmacokinetic study of the major chemical constituents in Xanthoceras sorbifolia wood after oral administration of methanol extract,wood powder,and single constituents

The wood powder and extract of Xanthoceras sorbifolia are used to treat rheumatism, gout, and other diseases in Mongolian medicine. Information on the pharmacokinetic differences between various forms of the herb drug is needed. Eight Xanthoceras constituents were examined simultaneously in rat plasma by ultra liquid chromatography-triple quadrupole mass spectrometry. In vitro experiments were performed to determine the influence of digestive juices on the pharmacokinetic profiles. Epicatechin and dihydromyricetin had higher AUC values in rats that were gavaged with X. sorbifolia extract versus the pure compounds. The AUC value of epicatechin in rats that were gavaged with X. sorbifolia wood powder was higher than that with the methanol extract. The nonextractable epicatechin polymer in the wood powder could be degraded to epicatechin by gastric juice, consequently elevating the epicatechin levels in blood.     

Study of energy transfer to solvent in radiation graft polymerization of styrene onto polyethylene

The radiation-initiated graft polymerization of styrene onto polyethylene was studied to determine whether energy transfer to diluent was responsible for the previously observed high orders of dependence of the grafting rate on monomer concentration. n-Octane was used as the diluent instead of benzene. If energy transfer from excited polyethylene to benzene were present, it should not be with n-octane. The percent swelling of polyethylene by various n-octane–styrene mixtures was determined. The compositions of various n-octane–styrene mixtures absorbed inside polyethylene were determined by ultraviolet and refractive index measurements and found to be richer in styrene than the corresponding mixtures in which the polyethylene had been placed. The graft polymerization rates were determined at 0.000761, 0.0371, and 0.213 Mrad/hr and plotted against the inside styrene concentrations on a log-log scale to yield the kinetic orders of dependence of rate on monomer as 2,3, and 3, respectively. It was concluded that energy transfer to diluent was not responsible for the high-order dependence observed.     

Mechanism of Aniline Methylation on Zeolite Catalysts Investigated by In Situ 13C NMR Spectroscopy

The alkylation reaction of aniline with methanol on zeolites HY and CsOH/CsNaY was studied by in situ ¹³C NMR spectroscopy under flow and batch conditions. Attention was focused on the identification of intermediates and on the determination of the formation mechanisms of N-methylaniline, N,N-dimethylaniline, and toluidines. To refine the main steps of the reaction, the transformations of the following individual compounds and intermediates, which were detected in the course of alkylation, were studied: dimethyl ether, surface methoxy groups, methylanilinium ions, formaldehyde, and N-methyleneaniline. It was found that N-methylaniline and N,N-dimethylaniline were formed as a result of aniline methylation by methanol dehydration products (methoxy groups or dimethyl ether) on acidic zeolites or as a result of alkylation by formaldehyde or methoxy groups on basic zeolites. Toluidines were formed by the isomerization ofN-methylanilinium ions, which were produced only on acidic zeolites, rather than by the direct alkylation of aniline.     

Determination of Antioxidant Activity of Hibiscus Flowers by Flow Injection Analysis with Chemiluminescence Detection

This study reports a simple and rapid method for the determination of the antioxidant activity of the phenolics present in plants of the Hibiscus genus. The protocol is based on the ability of the phenolic compounds to inhibit luminol chemiluminescence through the inactivation of free radicals in a flow injection system. Using the optimized operational conditions, the antioxidant activities of several phenolics were measured. The results were explained on the basis of structure–reactivity relationships. The antioxidant activities of dried flowers of Hibiscus rosa-sinensis and Hibiscus sabdariffa were evaluated. The protocol was validated by the 2,2-diphenyl-1-picrylhydrazyl-hydrate free radical assay. The differences in the antiradical activities were explained based on the concentrations of total polyphenol and flavonoid concentrations determined by spectrophotometric methods. It was concluded that the chemiluminescence method was complementary for the evaluation of hydrophilic antioxidants in plants.