Copolymers containing functional groups intrinsic to the active centers of serine hydrolases: Synthesis and evaluation of catalytic capability

N-Acryloyl derivatives of histamine, monoethanolamine, and β-alanine, which contain imidazole, hydroxyl, and carboxyl functional groups, respectively, are synthesized and characterized. Copolymers, which are further divided into thermally precipitable and thermally nonprecipitable (soluble) fractions, are obtained via the free-radical copolymerization of N-vinylcaprolactam and the specified comonomers that is initiated by a persulfate–tertiary amine redox system in a medium of 10% aqueous dimethyl sulfoxide (DMSO) at 65°C. It is shown that the soluble fractions of the synthesized copolymers exhibit catalytic activity in the reaction of hydrolysis of 4-nitrophenyl propionate (NPP) at a temperature above the coil-to-globule transition.     

Energetics of the binding of Cu(II) ions by thermosensitive copolymers of N-vinylcaprolactam and N-vinylimidazole in different conformational states of macromolecules

Random and protein-like copolymers based on N-vinylcaprolactam and N-vinylimidazole are synthesized by free radical polymerization in an aqueous solution. The above copolymers show a different thermal behavior in aqueous media at pH 7.2. At 45°C, the solution of a random copolymer experiences phase separation, whereas a protein-like copolymer undergoes a transition from the unfolded conformation to the compact conformation without any phase separation. The method of isothermal titration calorimetry is used to study the binding of Cu(II) ions by protein-like and random copolymers of N-vinylcaprolactam and N-vinylimidazole at 25 and 45°C, which correspond to different conformational states of macromolecules. The standard enthalpy and constant of binding are estimated. For both copolymers, the enthalpies of binding are negative and similar. When temperature is increased from 25 to 45°C, the constant of binding of copper ions by a protein-like copolymer increases by more than three orders of magnitude, whereas the corresponding constant of a random copolymer remains almost unchanged. Therefore, the transition of protein-like copolymer from the coiled conformation to the compact conformation noticeably facilitates the formation of an imidazole quasi-receptor, which is characterized by a certain spatial configuration and by a high affinity for the functional ligand. This effect is provided by an entropy gain no less than 50 J/(mol K).     

Limiting stability temperatures for copper sols stabilized by poly(<Emphasis Type="Italic">N</Emphasis>-vinyllactams)

It has been shown that stable copper sols cannot be prepared through the reduction of copper ions in aqueous solutions of poly(N-vinyllactams) in the presence of poly(N-vinylpyrrolidone) in the temperature range 50–70°C, while in the presence of poly(N-vinylcaprolactam), the said sols cannot be prepared at temperatures below ～12°C. This tendency is related to the thermodynamic instability of complexes formed via noncovalent interactions of copper nanoparticles with polymer macromolecules in corresponding temperature ranges. Stable sols synthesized in the presence of the above polymers at other temperatures rapidly lose stability in the said temperature ranges, and this effect is accompanied by the aggregation of metal particles. The experimental results provide evidence that there is a relationship between the stability of complexes macromolecules-metal nanoparticles and the thermodynamic quality of the solvent.     

Structure of water-glycine solutions in saturated and near-saturated regions according to compressibility data

Ultrasonic velocity and density values are measured for aqueous solutions containing 2.00 mol.%, 4.00 mol.%, and 5.00 mol.% glycine in a temperature range of 15–65°C, 5.50 mol.% glycine (20–65°C), and 6.00 mol.% glycine (25–65°C). Adiabatic compressibilities (κ_S) and molar adiabatic compressibilities (K_S) are calculated. The values of κ_S and K_S decrease monotonically with an increase in glycine concentrations up to saturation at all the temperatures. The temperature dependences of κ_S and κ_S have minima that are typical of water and aqueous solutions; the positions of the minima depend on the glycine concentration. The temperature coefficients of the molar compressibility, ∂K_S/∂T, change their signs from negative to positive at lower temperatures (by approximately 10 deg) than ∂κ_S/∂T.     

Fragments of the phase diagrams of ethylene glycol systems in the region of low second component concentrations

Fragments of the phase diagrams of the ethylene glycol (EG)-tert-butanol (t-BuOH) and EG-tet-ramethylurea (TMU) binary systems were studied by differential scanning calorimetry in the region rich in EG up to a ～40 mol % concentration of the second component. Liquid-phase stratification occurred at ～10–37 mol % t-BuOH and ～8–25 mol % TMU at ?37°C in the EG-t-BuOH system and at ?22°C in the EG-TMU system. The occurrence of liquid stratification was substantiated by visual observations of the solutions of the concentrations specified at a constant temperature of ?20°C. A comparison of the results obtained with the data on light scattering in the systems under study over the temperature range 25–50°C lends support to the hypothesis of the subcritical state of solutions of nonelectrolytes in solvents with a 3D network of hydrogen bonds at low solute concentrations.     

Aktivitätskoeffizient wäßriger Barium-Azidlösungen

The mean activity coefficient of aqueous solutions of barium azide has been measured by the emf between an Ag/Ag(N₃)-electrode and a two-phase Ba-amalgam electrode. For the saturated solution of Ba(N₃)₂, the value at 25°C isf _±=0.260±0.015.     

Aggregation and disaggregation of Aeromonas gum in an aqueous solution under different conditions

The aggregation and disaggregation of Aeromonas (A) gum, an acidic heteropolysaccharide, were investigated by viscometry, a fluorescent probe, and gel permeation chromatography combined with laser light scattering techniques in aqueous solutions containing desired NaCl at different temperatures. The A gum had a strong tendency of aggregation and high viscosity in the aqueous solutions. The weight‐average molecular weight, z‐average radius of gyration, weight‐average molar number (w_ag), and apparent aggregation number (N_ap) of the aggregates were investigated and discussed. The results indicated that there were three regions that corresponded to three kinds of aggregates and two transition temperatures at about 35 and 75 °C in the disaggregation course. When the temperature was higher than 75 °C, the w_ag hardly changed, and there was still a certain amount of aggregates even at 100 °C, indicating that the aggregates were difficult to disrupt completely. Moreover, the aggregation was thermally irreversible. Decreasing polysaccharide concentration reduced the content of the aggregate. However, N_ap remained constant around 20, independent of the polysaccharide concentration in a 0.5 M NaCl aqueous solution at 25 °C. At a salt concentration greater than or equal to 0.05 M, the aggregation was almost independent of the salt concentration used here. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2644–2651, 2000     

Sizes and conformations of hydrophilic and hydrophobic polyelectrolytes in solutions of various ionic strengths

The hydrodynamic characteristics of macromolecules of a random copolymer of N-methyl-N-vinylacetamide and N-methyl-N-vinylamine hydrochloride containing 43.6% charged units in the molecular-mass range of 27 × 10³ to 355 × 10³ are studied. For solutions in 0.2 M NaCl, sedimentation and translational-diffusion coefficients are determined. For salt-free solutions and for solutions in 0.2 and 5.0 M NaCl, the intrinsic viscosities of the fractions are found. The lengths of the statistical segments of the chains are estimated in terms of the Gray-Bloomfield-Hearst theory. The behavior of the polycation, whose uncharged counterpart is a hydrophilic polymer, is compared to the behavior of poly(sodium 4-styrenesulfonate), whose uncharged counterpart is a hydrophobic polymer. The comparison is based on normalized scaling relations. It is shown that the level of compaction of macromolecules of strong polyelectrolytes at a high ionic strength is determined by the degree of hydrophobicity of their polymer chains. Polyelectrolytes based on hydrophilic polymers cannot be compacted into a preglobular state; their chains preserve a swollen coil conformation up to maximally high values of ionic strength.     

Synthesis and Luminescence Characteristics of LaF<Subscript>3</Subscript>:Yb:Er Powders Produced by Coprecipitation from Aqueous Solutions

Hydrated lanthanum fluoride powders, both undoped, and doped with erbium and ytterbium fluorides (to a total content of 6–28 mol %), of the general formula RF₃ · nH₂O (n = 0.30 ± 0.01), crystallizing in the hexagonal system, were obtained by coprecipitation from aqueous solutions of the corresponding nitrates by the interaction with hydrofluoric acid. The dehydration is completed at 380°C. At 600°C, the concentrated solid solution decomposes to precipitate a phase with the structure of orthorhombic YF₃. The efficiency of the upconversion luminescence of the powders, excited at a wavelength of 974 nm, is low.     

Water Activities, Osmotic and Activity Coefficients and Some Correlation of Aqueous Mixtures of Alkaline-Earth and Ammonium Nitrates, NH4NO3-Y(NO3)2-H2O with Y ≡ Ba2+, Mg2+ and Ca2+ at T = 25 °C

The thermodynamic properties of the mixed aqueous electrolyte of ammonium and alkaline earth metal nitrates have been studied using the hygrometric method at 25?°C. The water activities of these {yNH₄NO₃+(1?y)Y(NO₃)₂}(aq) systems with Y ≡ Ba²⁺, Mg²⁺ and Ca²⁺ were measured at total molalities ranging from 0.10 mol?kg^?1 to saturation for different NH₄NO₃ ionic-strength fractions of y=0.20, 0.50 and 0.80. These data allow the calculation of osmotic coefficients. From these measurements, the ionic mixing parameters are determined and used to calculate the solute activity coefficients in the mixtures at different ionic-strength fractions. The results of these ternary solution measurements are compared with those for binary solutions of the alkaline earth nitrates of magnesium, calcium and barium with ammonium nitrates. The behavior of the aqueous electrolyte solutions containing mixtures of barium or calcium or magnesium with ammonium nitrates are correlated and show that ionic interactions are more important for the system containing Mg²⁺ than for Ca²⁺ or Ba²⁺. The trends are mainly due to the effects of the ionic size, polarizability and the hydration of the ions in these solutions.     

Thermally responsive graft copolymer of soy protein isolate and N-isopropylacrylamide: synthesis and self-assembly behavior in aqueous solution

In recent years, soy protein isolate (SPI) has attracted great attention due to its biodegradability, biocompatibility, and wide availability. It has been used in food and pharmaceutical industry such as edible films and drug delivery systems. In this study, we report the synthesis and self-assembly behavior in aqueous solution of thermally responsive graft copolymer (SPI-g-poly(N-isopropylacrylamide) (PNIPA)) of soy protein isolate and N-isopropylacrylamide in aqueous solution. SPI-g-PNIPA was synthesized in the 8 mol/l urea cushioning solution, by using ammonium persulfate as the initiator and mercaptoacetic acid as the protein unfolding agent. Laser light scattering, transmission electron microscopy, and fluorescence spectroscopy have been used to study the self-assembly behavior of SPI-g-PNIPA in aqueous solution. Above the critical micelle concentration (cmc), SPI-g-PNIPA aggregates could assemble into different structures including the simple spherical structure, spherical core–shell structure, and random coil structure, depending on the graft copolymer concentration. The graft copolymer concentration, temperature, pH value, and ionic strength were found to influence the aggregate size and morphology of SPI-g-PNIPA in aqueous solution. With increasing ionic strength, the aggregate size increases. However, pH value, SPI-g-PNIPA concentration, and temperature have complicated influences on the aggregate size. The lower critical solution temperature of the SPI-g-PNIPA at pH 8.5 is 36 °C. The method of intrinsic fluorescence spectroscopy was used for the first time to determine the cmc value of SPI-g-PNIPA in aqueous solution.     

Kinetics of 1,3‐dipolar cycloaddition reaction between C,N‐diphenylnitrone and dimethyl fumarate in various solvents and aqueous solutions

Second‐order rate constants and activation parameters of 1,3‐dipolar cycloaddition reaction between C,N‐diphenylnitrone and dimethyl fumarate were obtained in various solvents and aqueous solutions at 65°C. Second‐order rate constants of the reaction in water and ethylene glycol are approximately 33 and 8 times faster than those expected from solvent polarity, respectively. Increase of the reaction rate in aqueous solutions of ethanol is higher than that of propan‐1‐ol. A multiparameter correlation of log k₂ vs Sp and E_T^N in various solvents and aqueous solutions of ethanol shows that solvophobicity and solvent polarity parameter are important factors in occurrence of the reaction. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 431–434, 2000     

Dilute solutions of polyelectrolytes—III. Unperturbed dimensions of poly(methylene) N,N-dimethylpiperidinium chloride) in aqueous and methanolic solutions in presence of tetraethylammonium bromide

The behaviour of poly(methylene N,N-dimethylpiperidinium chloride) in aqueous and methanolic solutions in the presence of tetraethylammonium bromide has been investigated by light scattering; the parameters characterizing the macromolecular chain have been calculated. Peculiar behaviour of the macromolecules in aqueous solutions was attributed to the influence of the simple electrolyte co-ion due to hydrophobic interactions.     

Synthesis and properties of aromatic polyureas from N,N′-bis(trimethylsilyl)-substituted aromatic diamines and aromatic diisocyanates

Silylated aromatic polyureas were synthesized by the polyaddition of N,N′-bis(trimethylsilyl)-substituted aromatic diamines to aromatic diisocyanates in various organic solvents at a temperature ranging from 30 to 100°C. Colorless and transparent films of the silylated polyureas were obtained by casting directly from these solutions in a dry nitrogen atmosphere. The silylated polyureas thermally decomposed at around 200°C and were easily desilylated with alcohol to convert to almost amorphous aromatic polyureas having inherent viscosities of 0.4–1.0 dL/g. The polyureas exhibited better solubility in organic solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide and had somewhat lower thermal decomposition temperatures (around 300°C) than the polyureas prepared by a conventional method from the parent aromatic diamines and diisocyanates.     

Structural properties of aqueous metoprolol succinate solutions. Density, viscosity, and refractive index at 311 K

Density, viscosity and refractive index of aqueous solutions of metoprolol succinate of different concentrations (0.005–0.05 mol dm^?3) were measured at 38°C. Apparent molar volume of resultant solutions were calculated and fitted to the Masson’s equation and apparent molar volume at infinite dilution was determined graphically. Viscosity data of solutions has been fitted to the Jone-Dole equation and viscosity A- and B-coefficients were determined graphically. Physicochemical data obtained were discussed in terms of molecular interactions.     

Copolymer microgels by precipitation polymerisation of N-vinylcaprolactam and N-isopropylacrylamides in aqueous medium

In this work, we designed copolymer microgels by the copolymerisation of N-vinylcaprolactam (VCL) and two acrylamides (N-isopropylacrylamide (NIPAAm) and N-isopropylmethacrylamide (NIPMAAm)) under precipitation conditions in aqueous phase. In synthesis protocols, the ratio between monomers was varied from 1:5 to 5:1 mol/mol. By NMR and Raman spectroscopy, we determined the chemical composition of PVCL/NIPAAm and PVCL/NIPMAAm copolymer microgels reflecting the initial monomer ratio in the reaction mixture. The hydrodynamic radii of PVCL/NIPAAm microgels are around 375 nm (at 25 °C) and do not vary with the copolymer composition. On the contrary, for PVCL/NIPMAAm microgels, the size decreases from 450 to 250 nm with an increase of the VCL amount in copolymer structure. The heterogeneity of the microgel structure in terms of the distribution of the monomer units was probed by ¹H transverse magnetization relaxation NMR, showing that the VCL, NIPAAm and NIPMAAm units are unorderly distributed in the colloidal networks. The investigation of volume phase transition temperature (VPTT) for copolymer microgels was performed using dynamic light scattering, NMR and differential scanning calorimetry. It has been found that PVCL/NIPAAm microgels show VPTT around 35 °C independently from the copolymer composition; however, PVCL/NIPMAAm particles exhibit a nonlinear increase of VPTT from 34 to 45 °C as the NIPMAAm fraction in copolymer structure increases.     

Thermosensitive Chitosans as Novel Injectable Biomaterials

Two kinds of water soluble thermosensitive chitosan copolymers were prepared by graft polymerization of N-isopropylacrylamide (NIPAAm) onto chitosan using cerium ammonium nitrate (CAN) as an initiator (chitosan-g-NIPAAm) and by coupling monocarboxy Pluronic^® with chitosan using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccin-imide (NHS) as coupling agents (chitosan-Pluronic^®). The physicochemical properties of the resulting copolymers were characterized and they formed thermally reversible hydrogel, which exhibits a lower critical solution temperature (LCST) at 34°C in aqueous solutions. The human mesenchymal stem cells (hMSCs) were cultured in the chiotsan-g-NIPAAm in vitro. Chondrogenic differentiation was induced in the chitosan-g-NIPAAm gel. Therefore, chondrogenic differentiated cells from MSCs with a thermo-sensitive chitosan-g-NIPAAm could be used as an injectable cell-polymer complex. In summary, chitosan-g-NIPAAm and chitosan-Pluronic^® attest to their usefulness as injectable materials because of their thermally reversible property and relatively good biocompatibility.     

NOTE: Synthesis and Characterization of a Poly(acrylamide) with Pendant 1,4-piperazine-2,5-dione Moieties via Post-polymerization Cyclization

A poly(acrylamide) was synthesized from N ^α -Boc-N ^? -acrolyl-l-lysylglycine methyl ester via radical polymerization. This polymer typically had Mn ～ 100,000 g/mol, Mw ～ 300,000 g/mol, and a T_g of 93°C. Removal of Boc with TFA and cyclization with DABCO? in DMSO at 65°C afforded a soluble piperazinedione-containing polymer that had a T_g of 157°C and thermal stability up to 300°C. These results demonstrate a viable and efficient synthetic route to piperazinedione-containing polyacrylamides of high molecular weight. Related polymers that incorporate substituted indane moieties could be useful high T_g materials for fabrication of LC and NLO devices.     

Features of light scattering in aqueous solutions of dimethyl sulfoxide

The water-dimethyl sulfoxide (DMSO) system was studied by means of static light scattering in the concentration range of 0 to 60 mol % DMSO at 20 and 50°C. In the concentration range of 10 mol % DMSO, an abnormal maximum of scattered light was detected, the intensity of which decreases with an increase of temperature. The formation of this maximum is related to hydrophobic effects in the system under study and the existence of an unattainable critical point of delayering. Temperature inversion of light scattering intensity was detected at ∼14 mol % DMSO; at higher concentrations of DMSO, the intensity at 50°C is notably higher than at 20°C (due to the increase in the concentration’s degree of fluctuation upon an increase in temperature); at 60 mol % DMSO, intensities of scattered light at 20 and 50°C almost coincide. The apparent molar volumes of DMSO in solutions were calculated from the published data on density in the temperature range of 5 to 50°C. The minima of these values from 10 to 15 mol % DMSO (i.e., in the range of the abnormal maximum of scattered light) were obtained. The manifestation of hydrophobic effects in aqueous solutions of amphiphilic molecules is explained using the example of the DMSO-H₂O system.     

Reductive carbonylation of nitrobenzene to phenylurethane catalyzed by Ru(III)-schiff base complexes

Ruthenium complexes containing Schiff bases with N₂O₂, N₄ and N₅ donor groups with the general formula [Ru^III(X)Cl_{1 or 2}], where X = Schiff base such as bis(salicylaldehyde)-o-phenylenediimine (saloph), bis(salicylaldehyde)ethylenediimine (salen), bis(picolaldehyde)ethylenediimine (picen), bis(picolaldehyde)-o-phenylenediimine (pic-opd), bis(picolaldehyde)diethylenetriimine (pic-dien), were tested for their catalytic activity towards the reductive carbonylation of nitrobenzene in ethanol to give phenylurethane. The five Ru(III) complexes tested towards reductive carbonylation showed different catalytic activities in the range 160 – 200 °C and CO partial pressure of 15 atm.Among the complexes tested, [Ru(saloph)Cl₂] showed the highest catalytic activity with a turnover rate greater than 80 mol product per mol catalyst per hour at 160 °C and 15 atm CO. [Ru(pic-en)Cl₂]Cl and [Ru(picopd)Cl₂]Cl complexes with N₄ donor systems were found to be less active towards carbonylation of nitrobenzene, as indicated by their turnover rates of 20 and 15 mol product per mol catalyst per hour, respectively, at 200 °C and 15 atm CO. The complex [Ru(pic-dien)Cl]Cl₂N₅ donor system was completely inactive even at 200 °C and 15 atm CO, and no conversion of nitrobenzene was seen even after 12 h contact time.