Characterization of N-vinyl carbazole/vinyl 4-tert-butyl-benzoate copolymers of several molar compositions: SEC, DSC and intramolecular excimers in dilute solutions

Several N-vinylcarbazole/vinyl p-tert-butyl-benzoate copolymers of different molar monomer compositions and their respective homopolymers have been synthesized by free-radical polymerization. Their solution properties were characterized by size-exclusion chromatography (SEC) coupled with a differential refractive index (RI) and multiangle light scattering (MALS). Differential scanning calorimetry (DSC) was also used to investigate the glass transition temperatures, T_g. In addition, steady-state fluorescence emission spectra in a dilute solution of several fluid and non-fluid solvents were obtained to study the influence of monomer composition on the intramolecular carbazole excimer formation. The amount of excimers strongly depends on the solvent nature and copolymer composition. Molecular Dynamics (MD) simulations on iso- and syndiotactic homopolymer and copolymer fragments were used to obtain the probability of the conformations that satisfy excimer requirements. The analysis of the MD trajectories allows us to evaluate the amount and types of intramolecular excimers for the different systems.     

Heterogeneity parameters by light scattering for statistical copolymers incorporating long side-chain comonomers

Heterogeneity parameters were obtained by light scattering for a series of statistical copolymers incorporating long side-chain comonomers, by employing the method of Bushuk and Benoit. These copolymers were selected to exhibit varied compositional drift as required by copolymerization theory. The magnitude of the parameters found agreed qualitatively with the heterogeneity expected from the drift in composition with conversion. This was calculated using the treatment of Skeist, as modified by Kruse. However, values greater than the limit of unity were found in two instances for the heterogeneity index, Q/Q_max, which relates the compositional drift constant Q to the maximum value obtained for mixtures of homopolymers. These anomalies were attributed to the insensitivity of the method for heterogeneous copolymers having small differences in the refractive increaments of their respective homopolymers. The magnitude and sign of P, which reflects molecular weight effects on composition, was questionable because of experimental error. Both effects appear to be general deficiencies of the method, which limit its practical use. For solvents with high values of dn/dc (≈0.1), the observed weight-average molecular weight approached the true value.     

Synthesis of homologously pure bacteriochlorophyll-e and f analogues from BChls-c/d via transformation of the 7-methyl to formyl group and self-aggregation of synthetic zinc methyl bacteriopheophorbides-c/d/e/f in non-polar organic solvent

Homologously pure methyl bacteriopheophorbides-e and f (BPhes-e/f_M) were prepared from modification of naturally occurring bacteriochlorophylls-c and d (BChls-c/d), respectively, by transformation of the methyl to formyl group at the 7-position. The absolute configuration of the 1-hydroxyethyl group at the 3-position of (Zn-)BPhes-e/f_M was determined from comparison with structurally known BChl-c/d epimers. Visible spectra of synthetic (Zn-)BPhe-c/d/e/f_M showed that the 7¹-oxidation and the 8²/12¹/20-methylation affected Soret, Q_x and Q_y bands of both the monomeric (in a polar organic solvent) and oligomeric species (in a non-polar solvent).     

Solvent dependence of the spin-allowed transitions in free base tetra-t-butylphthalocyanine

The electronic absorption spectrum of tetra-t-butylphthalocyanine (TTBPc) was studied in various solvents. All bands were slightly red-shifted on increasing polarity of the solvents, indicating π—π* transitions. The oscillator strength of the Q_x band varied between 0.11 (t-butanol) and 0.27 (n-octane) and that of the Q_y band between 0.17 (t-butanol) and 0.28 (pyridine). The influence of the refractive index was masked by other solvent effects. Good agreement of the measured oscillator strength with modern theoretical values was obtained, when the random orientation of the solute molecules was taken into account.     

Biosynthesis and characterization of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer from wild-type Comamonas sp. EB172

Poly(3-hydroxybutyrate) [P(3HB)] homopolymer and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] copolymer was produced by Comamonas sp. EB172 using single and mixture of carbon sources. Poly(3-hydroxyvalerate) P(3HV) incorporation in the copolymer was obtained when propionic and valeric acid was used as precursors. Incorporation of 3HV fractions in the copolymer varied from 45 to 86 mol% when initial pH of the medium was regulated. In fed-batch cultivation, organic acids derived from anaerobically treated palm oil mill effluent (POME) were shown to be suitable carbon sources for polyhydroxyalkanoate (PHA) production by Comamonas sp. EB172. Number average molecular weight (M_n) produced by the strain was in the range of 153-412 kDa with polydispersity index (M_w/M_n) in the range of 2.2-2.6, respectively. Incorporation of higher 3HV units improved the thermal stability of P(3HB-co-3HV) copolymer. Thus the newly isolated bacterium Comamonas sp. EB172 is a suitable candidate for PHA production using POME as renewable and alternative cheap raw materials.     

Determination de l'increment d'indice de refraction dn/dc de polymeres en solution dans des melanges de solvants. Relation entre dn/dc et le volume specifique partiel du polymere

The dependence on various parameters (temperature, volume fraction of one solvent in the mixture) of optical properties of polymer (refractive index and refractive index increment) in mixed solvents has been investigated.The change of refractive index increment with molecular weight in single and mixed solvents has also been shown. From the experimental and also literature values of (dn/dc), partial specific volumes ($\text{v}{}_3$) of polymers in solutions have been calculated according to different relations of specific refractivity (Lorentz-Lorenz and Gladstone-Dale equations). The calculated ($\text{v}{}_3$) values have been compared with experimental values and the accuracy of former relations has been discussed.     

Effects of Nonpolar and Polar Solvents on the Qx and QY Energies of Bacteriochlorophyll a and Bacteriopheophytin a

The effects of nonpolar and polar solvents on the Q_x and Q_y energies of bacteriochlorophyll (BChl) a and bacteriopheophytin (BPhe) a were examined by electronic absorption spectroscopy. All of the four different energies exhibited a linear dependence on R(n) = (n² - l)/(n²+ 2), where n is the refractive index of the solvent, in both nonpolar and polar solvents. The energy of each state of both pigments could be expressed as v = -dR(n) + e (in cm^-1) where coefficient d was related to the dispersive interaction between the solute and the solvent molecules. A theory developed by Nagae showed that coefficient d originates from the quantum-mechanical fluctuation of the multipole moments of the solute, in terms of which the following characteristics of the observed d values were explained: (1) In all of the four cases of the Q_x, and Q_y energies of both BChl a and BPhe a, the d values for the polar solvents were smaller than those for the non-polar solvents. (2) In both nonpolar and polar solvents, the d value of BChl a was larger than that of BPhe a in the Q_y energy, whereas the d value of BPhe a was larger than that of BChl a in the Q_x energy. (3) The d value of the Q_x energy was larger than that of the Q_y, energy for either case of BChl a or BPhe a.     

Autoprotolysis constants and standardization of the glass electrode in acetonitrile-water mixtures. Effect of solvent composition

Standard e.m.f.s for the cell GE/HCl/AgCl/Ag/Pt (GE=glass electrode) in acetonitrile-water mixtures containing 0–70% (w/w) of acetonitrile were obtained. Values of the autoprotolysis constant, K_ap, of these mixed solvents were also determined from e.m.f. measurements of the cell GE/KCl + KS/AgCl/Ag/Pt. The influence of variations in the solvent composition on pK_ap values was evaluated. Over the whole of the composition range studied the pK_ap values were linearly correlated with the mole fraction of acetonitrile and with the reciprocal of the relative permittivity of solvent mixtures. Linear relationships were also obtained for pK_ap values vs. the Kamlet-Taft π^★ polarizability/dipolarity parameter in the range 0–50% (w/w).     

Synthesis of the complex fluoride LiBaF3 and optical spectroscopy properties of LiBaF3:M(M=Eu,Ce) through a solvothermal process

The complex fluoride LiBaF₃ and LiBaF₃:M(M=Eu, Ce) is solvothermally synthesized at 180°C and characterized by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy. In the solvothermal process, the solvents, molar ratios of initial mixtures and reaction temperature play important roles in the formation of products. The excitation and emission spectra of the LiBaF₃:M(M=Eu,Ce) have been measured by fluorescence spectrophotometer. In the LiBaF₃:Eu emission spectra, there is one sharp line emission located at 360 nm arising from f→f transition of Eu²⁺ in the host lattice, and typical doublet 5d-4f emission of Ce³⁺ in LiBaF₃ powder is shown.     

Investigation of the degradation behaviour of poly(ethylene glycol-co-d,l-lactide) copolymer

The aim was to investigate the degradation behaviour of poly(ethylene glycol-co-d,l-lactide) (PEG-d,l-PLA) multiblock copolymer, in bulk and as microspheres, in aqueous medium. The degradation behaviour of PLA homopolymers in bulk and microspheres was evaluated as comparison.Microsphere preparation was performed by the double emulsion solvent evaporation method. Physical-chemical characterization of the raw polymers and the microspheres was performed by nuclear magnetic resonance (NMR) and modulated differential scanning calorimetry (MDSC). Polymer molecular weight, before and after incubation in aqueous environment, was evaluated by GPC; water uptake and mass loss were determined gravimetrically.The presence of PEG segments inside PLA chains gave a characteristic spongy structure to the microspheres. A significant increase in polymer T_g values was found for the microsphere formulations compared to polymer in bulk. After 63 days of incubation in the aqueous environment, the PEG-d,l-PLA microspheres achieved an average M_w reduction of 47% compared to 20% for PLA microspheres. The corresponding M_w decrease of the polymers in bulk was significantly higher: 72% and 41% for PEG-d,l-PLA and PLA, respectively.The data show how the degradation behaviour of polymer in bulk in an aqueous environment is significantly different from the behaviour of the corresponding microspheres. These results highlight the importance of performing a thorough physical-chemical characterization on microsphere formulations.     

Synthesis of arborescent styrene homopolymers and copolymers from epoxidized substrates

The synthesis of arborescent styrenic homopolymers and copolymers was achieved by anionic polymerization and grafting. Styrene and p‐(3‐butenyl)styrene were first copolymerized using sec‐butyllithium in toluene, to generate a linear copolymer with a weight‐average molecular weight M_w = 4000 and M_w/M_n = 1.05. The pendant double bonds of the copolymer were then epoxidized with m‐chloroperbenzoic acid. A comb‐branched (or arborescent generation G0) copolymer was obtained by coupling the epoxidized substrate with living styrene‐p‐(3‐butenyl)styrene copolymer chains with M_w ≈ 5000 in a toluene/tetrahydrofuran mixture. Further cycles of epoxidation and coupling reactions while maintaining M_w ≈ 5000 for the side chains yielded arborescent copolymers of generations G1–G3. A series of arborescent styrene homopolymers was also obtained by grafting M_w ≈ 5000 polystyrene side chains onto the linear and G0–G2 copolymer substrates. Size exclusion chromatography measurements showed that the graft polymers have low polydispersity indices (M_w/M_n = 1.02–1.15) and molecular weights increasing geometrically over successive generations. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Calorimetric study of the metabolic activity of Escherichia coli B infected by T4 phage in restricted medium

The effects of T4 phage on the metabolic rate of resting cells of Escherichia coli B in a restricted medium during the early phase of phage infection were measured calorimetrically. Heat output rate (P) and total quantity of heat (Q) of culture, heat output rate (P₀) and quantity of heat (Q₀) of single cell were determined. P and Q of E. coli-T4 phage system, or P₀ and Q₀ of infected cell, are all higher than that of control. The metabolic activity of infected cell is enhanced by 45-62%. P has a linear correlation with cell concentration (C), P (μW) = 1.68 × 10⁻⁶C (cfu/mL) + 1.86, for E. coli B cells, and for E. coli B-T4 phage system, P (μW) = 2.24 × 10⁻⁶C (cfu/mL) + 3.60. Q does not change significantly with the change of cell concentration. But Q₀ decreases with C increasing, indicating that Q₀ is restrained by cell density.     

A simple method for the fluorodensitometric determination of aflatoxin M1 in milk powder

A simple and accurate method for the fluorodensitometric determination of aflatoxin M₁ is described. Aflatoxin M₁ is extracted into chloroform and spotted on a silica gel thin-layer chromatography plate. A solvent system of ethyl ether-methanol-water (96:3:1) is used. The spots of aflatoxin M₁ are evaluated by direct densitometric light emission measurements.     

α-Trifluoromethyl vinyl acetate. II

Low conversion, low molecular weight homopolymers of α-trifluoromethyl vinyl acetate have been obtained by pyridine initiation and also by employing very large amounts of benzoyl peroxide. Since allylic hydrogens are not present, it appears that the limiting factor in the polymerization of isopropenyl esters is a slow rate of chain growth rather than degradative chain transfer. Copolymerization of the fluoromonomer (M₂) with vinyl acetate (M₁) yields values of r₁ = 0.25 and r₂ = 0.20, and for the fluoromonomer values of 0.069 and 1.51, respectively, for Q and e. Whereas ultraviolet initiation of equimolar mixtures of α-trifluoromethyl vinyl acetate and vinyl acetate yields low molecular weight copolymers, diisopropyl percarbonate-initiated room temperature bulk copolymerizations and emulsion copolymerizations yield polymers of high DP . Differential thermal analysis of an equimolar copolymer of vinyl acetate and the fluoromonomer surprisingly yields a sharp endotherm reminiscent of crystalline polymers. The unhydrolyzed copolymers in acetone and the alcoholyzed copolymers in 0.1N alkali exhibit Huggins k′ values of 0.3–0.4. Like ordinary poly(vinyl alcohol), the polyfluoroalcohols lose viscosity in dilute alkali due to retrograde aldol condensations. The solubilities of the polyfluoroalcohols, together with their thermal behavior, NMR spectrum, polarized infrared spectrum, refractive index, abilities to form visible polarizers, and other properties are also described.     

Block copolymer compatibilizers for polystyrene/poly(dimethylsiloxane) blends

Symmetric polystyrene (PS)–poly(dimethylsiloxane) (PDMS) diblock copolymers were mixed into a 20% dispersion of PDMS in PS. The effect of adding the block copolymer on the blend morphology was examined as a function of the block copolymer molecular weight (M_n,bcp), concentration, and viscosity ratio (η_r). When blended together with the PS and PDMS homopolymers, most of the block copolymer appeared as micelles in the PS matrix. Even when the copolymer was preblended into the PDMS dispersed phase, block copolymer micelles in the PS matrix phase were observed with transmission electron microscopy after mixing. Adding 16 kg/mol PS–PDMS block copolymer dramatically reduced the PDMS particle size, but the morphology, as examined by scanning electron microscopy, was unstable upon thermal annealing. Adding 156 kg/mol block copolymer yielded particle sizes similar to those of blends with 40 or 83 kg/mol block copolymers, but only blends with 83 kg/mol block copolymer were stable after annealing. For a given value of M_n,bcp, a minimum PDMS particle size was observed when η_r ～ 1. When η_r = 2.6, thermally stable, submicrometer particles as small as 0.6 μm were observed after the addition of only 3% PS–PDMS diblock (number‐average molecular weight = 83 kg/mol) to the blend. As little as 1% 83 kg/mol block copolymer was sufficient to stabilize a 20% dispersion of 1.1‐μm PDMS particles in PS. Droplet size reduction was attributed to the prevention of coalescence caused by small amounts of block copolymer at the interface. The conditions under which block copolymer interfacial adsorption and interpenetration were facilitated were explained with Leibler's brush theory. © 2002 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 346–357, 2002; DOI 10.1002/polb.10098     

Thermal and optical properties of highly fluorinated copolymers of methacrylates

Copolymers of pentafluorophenylhexafluoroisopropyl methacrylate (FPPMA) with trifluoroethyl methacrylate (TFEMA) were prepared in THF solution and in bulk using azobisisobutyronitrile as a free radical initiator. The monomer reactivity ratios of TFEMA (M₁) and FPPMA (M₂) were calculated as r₁ = 0.55 and r₂ = 0.07. The refractive indices of poly(TFEMA) and poly(FPPMA) are very similar as 1.435 and 1.430, respectively, at 532 nm, and the copolymer films were transparent. The glass transition temperatures (T_g) of the copolymers were in the range of 80–90°C and showed a negative deviation from the Gordon–Taylor equation. The thermal decomposition temperature (T_d) was increased with the content of FPPMA in copolymers. Low water absorption for 1:1 FPPMA/TFEMA copolymer was detected. Copolymers of FPPMA with hexafluoroisopropyl methacrylate (HFPMA) were also prepared. The monomer reactivity ratios of HFPMA (M₁) and FPPMA (M₂) were calculated as r₁ = 0.43 and r₂ = 0.10. The T_gs of the copolymers were in the range of 88–95°C and showed also a negative deviation from the Gordon–Taylor equation. T_g and T_d of the copolymers were increased with the content of FPPMA. The refractive index of poly(HFPMA) (1.384 at 532 nm) is much lower than that of FPPMA homopolymer, but copolymer films obtained were clear and transparent. Copyright © 2013 John Wiley & Sons, Ltd.     

Regularities in the distribution of TTA and its scandium chelate into a series of ester solvents

The distribution ratios of TTA and its scandium chelate between aqueous perchlorate solutions (μ=0.1) and 15 ester solvents including ethyl acetate were determined at 25°. A good correlation was found between the distribution coefficients of TTA and the “solubility parameter” of the ester solvents. The relationship between the distribution coefficients of the scandium chelate (P_M) and those of TTA (P_HA) was shown to be, log P_M=n log P_HA+ const. The distribution of this chelate into another ester can thus be predicted.     

Immobilization of Invertase in DAD Type Polymers: Combination of Benzothiadiazole Acceptor Unit and 3,4-Ethylenedioxythiophene and Thiophene Donor Units

Conductive polymers with donor-acceptor-donor (DAD) type units; benzothiadiazole acceptor unit and 3,4-ethylenedioxythiophene (EDOT) and thiophene (Th) donor units, were investigated for immobilization of invertase. The polymers were prepared potentiodynamically from their monomers, M₁ (Th-benzothiadiazole-Th), M₂ (EDOT-benzothiadiazole-EDOT), M₃ (Th-benzothiadiazole-EDOT) and a copolymer, which is a homolog to homopolymer of M₃, was prepared from M₁ and M₂. Invertase was trapped between a two layer-composite; DAD polymer and polypyrrole. The characterization of immobilized invertase was performed using a spectrophotometric method at 540 nm. Kinetic parameters, V _max, maximum reaction rate and K_m , Michaelis-Menten constant values of immobilized invertase in DAD type homopolymer (P₃), 0.95 μmol min^?1 and 22.7 mM, respectively, are found between those of homopolymers P₁ and P₂ and are better than the copolymer. Polymers and copolymers exhibited a broad optimal temperature profile between 30 and 50°C compared to the free enzyme. Optimum pH (5.0) is the same as for free invertase. The electrodes were found to be stable with 100% activity during one day for 40 consecutive measurements. As to the self-life, 25% of the initial activity was lost in the first ten days, then the electrodes were stable with 75% activity for a 40 day storage at 4°C.     

Seven new rare-earth transition-metal oxychalcogenides: Syntheses and characterization of Ln4MnOSe6 (Ln=La, Ce, Nd), Ln4FeOSe6 (Ln=La, Ce, Sm), and La4MnOS6

The quaternary oxychalcogenides Ln₄MnOSe₆ (Ln=La, Ce, Nd), Ln₄FeOSe₆ (Ln=La, Ce, Sm), and La₄MnOS₆ have been synthesized by the reactions of Ln (Ln=La, Ce, Nd, Sm), M (M=Mn, Fe), Se, and SeO₂ at 1173 K for the selenides or by the reaction of La₂S₃ and MnO at 1173 K for the sulfide. Warning: These reactions frequently end in explosions. These isostructural compounds crystallize with two formula units in space group of the hexagonal system. The cell constants (a, c in Å) at 153 K are: La₄MnOSe₆, 9.7596(3), 7.0722(4); La₄FeOSe₆, 9.7388(4), 7.0512(5); Ce₄MnOSe₆, 9.6795(4), 7.0235(5); Ce₄FeOSe₆, 9.6405(6), 6.9888(4); Nd₄MnOSe₆, 9.5553(5), 6.9516(5); Sm₄FeOSe₆, 9.4489(5), 6.8784(5); and La₄MnOS₆, 9.4766(6), 6.8246(6). The structure of these Ln₄MOQ₆ compounds comprises a three-dimensional framework of interconnected LnOQ₇ bicapped trigonal prisms, MQ₆ octahedra, and the unusual LnOQ₆ tricapped tetrahedra.