Search results for "TYR"

Preparation of monodisperse polyethylene oxides by gel permeation chromatography of discontinuous polymer-homologous series

1970

Abstract Starting from triethylene glycol, monodisperse polyethylene oxides of a molecular weight (MW) up to 2000 (degree of polymerisation (DP) During the first step the ditosylate of triethylene glycol is reacted with the sodium alkoxide of the same diol at room temperature. The condesation product (polymer homologues of triethylene glycol) was separated by molecular distillation and yielded the pure oligomers nonaethylene glycol (DP = 9, MW 414) and pentadecaethylene glycol (DP = 15, MW = 678), as proved by gel chromatography. During the next step the polymer homologues of nonaethylene glycol were synthesised in a similar way. The pure oligomers hepteicosa (DP = 27, MW = 1207) and pentat…

Effect of polystyrene coating on pore, structural and chromatographic properties of silica packings

1990

Abstract A series of mesoporous and macroporous silicas with a mean pore diameter (PD), between 6 and 200 nm were reacted with a copolymer of styrene and vinyl-methyldiethoxysilane. The mass load of coated silicas corresponded to the monolayer capacity of the polymer calculated on the basis of the molecular cross-sectional area, except for the two mesoporous silcias of PD = 6 and 7.5 nm. Depending on the pore size, changes occurred in the specific surface area, as, between the native and the coated product. A comparison of the specific pore volume, νp, of silicas before and after polymer immobilization indicated a major loss of νp for the two mesoporous silicas whereas this effect was much …

Conformational characteristics of homo-oligopeptides of O-benzyl-L-tyrosine+

1983

Conformational studies of X[-L-Tyr(Bzl)-]n-series bound to polyethyleneglycol (X = H2, Nps; n = 3-8) in the solid state and in solvents of different polarities and capabilities of forming hydrogen bonds are reported. By using i.r. absorption, the occurrence of the beta-structure in the higher oligomers in the solid state was established. By means of i.r. absorption and CD the onset of that ordered conformation in solution was assessed as a function of chain length. The effects induced by the presence of the N-protecting group and added base, and by changing the nature of solvent on the conformational preferences of the [-L-Tyr(Bzl)-]n homo-peptides were also examined. The 2-nitrophenylsulph…

1978

The phenomenon of co-nonsolvency, i.e. the formation of nonsolvents by mixing two solvents, was studied for the system N,N-dimethylformamide/cyclohexane/polystyrene (DMF/CH/PS) which is characterized by the fact that the components of the mixed solvent are only incompletely miscible below 48,6°C. A number of quasibinary sections (stepwise addition of the second solvent to given solutions of the polymer in the first solvent) for a sample (M = 110000) of high molecular uniformity yielded a cloud point surface which gives “island curves” (closed solubility gaps) for constant temperatures between the critical temperature of DMF/CH and the top of the cloud point surface (51,3°C). The attainment …

Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 2. Experiment and Theory

1997

Cloud point temperatures (Tcp) were measured at different constant shear rates for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) (CHO/PS/PBMA) by means of a newly constructed rheo-optical apparatus that can be operated in the temperature range from 0 to 100 °C up to maximum shear rates of 1440 s-1 and maximum stresses of 384 Pa. In all cases one observes an extension of the homogeneous region as the shear rate γ is raised. With the system CHO/PS 196w/PBMA 2050 (the figures denote the molar masses of the polymers in kilograms/mole) the effects become maximum for high concentrations of PBMA, where the demixing temperatures increase by more th…

Shear Effects on the Phase Diagrams of Solutions of Highly Incompatible Polymers in a Common Solvent. 1. Equilibrium Behavior and Rheological Propert…

1997

Phase diagrams (cloud points, tie lines, critical compositions) and viscosities of homogeneous solutions were determined at temperatures ranging from 20 to 100 °C for three representatives of the ternary system cyclohexanone/polystyrene/poly(n-butyl methacrylate) [CHO/PS/PBMA] in preparation of a study on shear influences. An only moderate increase of the two-phase region observed upon heating (LCST behavior) witnesses little heat effects upon mixing. Tie lines which are nearly parallel to the PS/PBMA edge of the Gibbs phase triangle indicate comparable solvent quality of CHO for both polymers. The quantitative mathematical description of the equilibrium behavior-required for a theoretical …

Vitrification of polymer solutions as a function of solvent quality, analyzed via vapor pressures.

2006

Vapor pressures (headspace sampling in combination with gas chromatography) and glass transition temperatures [differential scanning calorimetry (DSC)] have been measured for solutions of polystyrene (PS) in either toluene (TL) (10-70 degrees C) or cyclohexane (CH) (32-60 degrees C) from moderately concentrated solutions up to the pure polymer. As long as the mixtures are liquid, the vapor pressure of TL (good solvent) is considerably lower than that of CH (theta solvent) under other identical conditions. These differences vanish upon the vitrification of the solutions. For TL the isothermal liquid-solid transition induced by an increase of polymer concentration takes place within a finite …

1984

Sedimentation coefficients of S of polystyrene covering a broad range of molecular weights M, are measured in toluene and 2-butanone in the semidilute regime. The results are compared with literature data using a plot of S · NA · η/(1 − νρ) = M · η/f versus concentration c, allowing experiments in different solvents of different density ρ and viscosity η to be compared (ν: partial specific volume of polymer; f: friction coefficient; NA: Avogadro number). According to scaling theory for concentrations higher than a critical concentration c, linear plots are to be expected. This is true for the theta-solvent cyclohexane, but for the theta-solvent cyclopentane as well as for the thermodynamica…

Immobilized Chiral ortho-Metalated Dirhodium(II) Compounds as Catalysts in the Asymmetric Cyclopropanation of Styrene with Ethyl Diazoacetate

2007

Immobilization of ortho-metalated dirhodium(II) compounds has been achieved by a carboxylate interchange reaction between (M)-Rh2(l-protos)2[(p-XC6H3)P(p-XC6H4)2]2 diastereoisomers and carboxyethylpolystyrene polymer (PS-C6H4(CH2)2CO2H). The immobilized chiral catalysts have been tested in the standard reaction of asymmetric cyclopropanation of styrene with ethyl diazoacetate, giving higher yields than homogeneous chiral trifluoroacetate derivatives, but their diastereo- and enantioselectivities were lower. Some of the immobilized catalysts have proved to be very robust. The catalytic behavior of (M)-Rh2(O2C(CH2)2C6H5)2[(p-XC6H3)P(p-XC6H5)2]2 compounds has been studied as a model for the im…

Developmental and biochemical studies on the phenylalanine hydroxylation system in Drosophila melanogaster

1992

Abstract The enzyme phenylalanine hydroxylase, the substrate phenylalanine, the product of the reaction tyrosine, and the probable in vivo cofactors (6R)- l -erytro-5,6,7,8-tetrahydrobiopterin (H4Bip) and 5,6,7,8-tetrahydropterin (H4Ptr), have been measured during development in Drosophila. The developmental profile of phenylalanine hydroxylase activity shows two peaks. The larger occurs at the time of pupation, coiciding with an important accumulation of tyrosine in the insect. The minor peak appears at the time of adult emergence. The developmental profile of H4Bip shows also two peaks, coinciding with those of maximal phenylalanine hydroxylase activity. However, H4Ptr is only detectable …