Complexes of stannic chloride and alkyl phenols and the influence of these complexes and of free phenol on the cationic polymerization of isobutene

1970 ◽  
Vol 48 (8) ◽  
pp. 1251-1262 ◽  
Author(s):  
R. F. Bauer ◽  
R. T. LaFlair ◽  
K. E. Russell
Keyword(s):  
Equilibrium Constants ◽  
Monomer Concentration ◽  
Stannic Chloride ◽  
Substituted Phenols ◽  
Experimental Conditions ◽  
Free Phenol ◽  
Rate Of Polymerization ◽  
Alkyl Phenols ◽  
A Chain ◽  
Active Initiator

The polymerization of isobutene in ethyl chloride solution at −78.5 °C has been studied using stannic chloride as catalyst and alkyl substituted phenols as cocatalysts. In preliminary experiments, the nature and extent of the complexing between phenols and stannic chloride was examined and it was shown that σ-complexing occurs between the oxygen of the phenol and the stannic chloride. Equilibrium constants were determined over the temperature range 30 to −50 °C and were used, together with hydrogen bonding data, to estimate the concentrations of complex and free phenol in the polymerization mixtures at −78.5 °C. The active initiator in the polymerization is probably the σ-complex but the free phenol acts as a chain terminating agent. This explains the ability of the cocatalyst to decrease the rate of polymerization under some experimental conditions. For isobutene concentrations up to 3 M and at constant dielectric constant the rate of polymerization and the molecular weight are proportional to the monomer concentration. A mechanism is proposed to account for the main features of the experimental results.

Free-base corroles: determination of deprotonation constants in non-aqueous media

2007 ◽  
Vol 11 (04) ◽  
pp. 269-276 ◽  
Author(s):  
Jing Shen ◽  
Zhongping Ou ◽  
Jianguo Shao ◽  
Michał Gałęzowski ◽  
Daniel T. Gryko ◽  
...  
Keyword(s):  
Equilibrium Constants ◽  
Aqueous Media ◽  
Free Base ◽  
Organic Base ◽  
Experimental Conditions ◽  
Spectral Changes ◽  
Base Analysis ◽  
Uv Visible ◽  
The Given

A series of free-base corroles with different electron-donating or electron-withdrawing substituents were reacted with piperidine, 4-aminopyridine, 2-methylimidazole, 2-aminopyridine or pyridine in PhCN and the UV-visible spectral changes monitored during conversion of ( Cor ) H 3 to [( Cor ) H 2]- as a function of the concentration and strength of the added organic base. Analysis of the UV-visible spectral changes as a function of the added base concentration enabled calculation of equilibrium constants ( logK ) for deprotonation of each corrole under the given experimental conditions. Relationships are examined between the experimentally measured logK values and previously published spectroscopic and structural properties of the compounds.

scholarly journals Iodination of insulin in aqueous and organic solvents

1969 ◽  
Vol 115 (1) ◽  
pp. 11-18 ◽  
Author(s):  
A. Massaglia ◽  
U. Rosa ◽  
G. Rialdi ◽  
C. A. Rossi
Keyword(s):  
Ethylene Glycol ◽  
Organic Solvents ◽  
Molecular Conformation ◽  
Aqueous Media ◽  
Native Structure ◽  
Experimental Conditions ◽  
Polar Environment ◽  
Polar Area ◽  
The Difference ◽  
A Chain

1. The iodination of insulin was studied under various experimental conditions in aqueous media and in some organic solvents, by measuring separately the uptake of iodine by the four tyrosyl groups and the relative amounts of monoiodotyrosine and di-iodotyrosine that are formed. In aqueous media from pH1 to pH9 the iodination occurs predominantly on the tyrosyl groups of the A chain. Some organic solvents increase the iodine uptake of the B-chain tyrosyl groups. Their efficacy in promoting iodination of Tyr-B-16 and Tyr-B-26 is in the order: ethylene glycol and propylene glycol≃methanol and ethanol>dioxan>8m-urea. 2. It is suggested that each of the four tyrosyl groups in insulin has a different environment: Tyr-A-14 is fully exposed to the solvent; Tyr-A-19 is sterically influenced by the environmental structure, possibly by the vicinity of a disulphide interchain bond; Tyr-B-16 is embedded into a non-polar area whose stability is virtually independent of the molecular conformation; Tyr-B-26 is probably in a situation similar to Tyr-B-16 with the difference that its non-polar environment depends on the preservation of the native structure.

scholarly journals Probing the Kinetic and Thermodynamic Fingerprints of Anti-EGF Nanobodies by Surface Plasmon Resonance

2020 ◽  
Vol 13 (6) ◽  
pp. 134
Author(s):  
Salvador Guardiola ◽  
Monica Varese ◽  
Marta Taulés ◽  
Mireia Díaz-Lobo ◽  
Jesús García ◽  
...  
Keyword(s):  
Surface Plasmon Resonance ◽  
Surface Plasmon ◽  
Plasmon Resonance ◽  
Molecular Mechanisms ◽  
Tumour Progression ◽  
Equilibrium Constants ◽  
Target Antigen ◽  
Biological Drugs ◽  
Experimental Conditions ◽  
Technical Features

Despite the widespread use of antibodies in clinical applications, the precise molecular mechanisms underlying antibody–antigen (Ab–Ag) interactions are often poorly understood. In this study, we exploit the technical features of a typical surface plasmon resonance (SPR) biosensor to dissect the kinetic and thermodynamic components that govern the binding of single-domain Ab or nanobodies to their target antigen, epidermal growth factor (EGF), a key oncogenic protein that is involved in tumour progression. By carefully tuning the experimental conditions and transforming the kinetic data into equilibrium constants, we reveal the complete picture of binding thermodynamics, including the energetics of the complex-formation transition state. This approach, performed using an experimentally simple and high-throughput setup, is expected to facilitate mechanistic studies of Ab-based therapies and, importantly, promote the rational development of new biological drugs with suitable properties.

THE HYDROGEN–CHLORINE SYSTEM IN THE MM PRESSURE RANGE: I. ENERGY DISTRIBUTION AMONG VIBRATIONALLY EXCITED STATES

1964 ◽  
Vol 42 (10) ◽  
pp. 2176-2192 ◽  
Author(s):  
F. D. Findlay ◽  
J. C. Polanyi
Keyword(s):  
Excited States ◽  
Rotational Temperature ◽  
Relative Rate ◽  
Infrared Emission ◽  
Vibrational States ◽  
Vibrationally Excited ◽  
Experimental Conditions ◽  
Reduced Pressure ◽  
A Chain ◽  
First Time

When atomic plus molecular hydrogen coming from a Wood's discharge tube are mixed with molecular chlorine, infrared emission is observed (1). At low reagent pressures, ~10−2 mm Hg, this emission can be related to the relative rate of the reaction H + Cl2 → HCl†ν + Cl proceeding to form HCl in vibrationally excited states ν = 1–6, of the ground electronic state. In the present work this system has been investigated for the first time at ~100 × the reagent pressure (~1 mm Hg). The reaction was shown to proceed by a chain mechanism. The translational–rotational temperature was 1300 ± 100 °K under the experimental conditions normally used. The vibrational distribution was notable for the presence of vibrators in levels ν = 7 and 8, which are respectively 4 and 10 kcal higher in energy than the exothermicity of the H + Cl2 reaction. The population in these levels appeared to be related to that in the levels with [Formula: see text]; it was proposed that vibrational–vibrational exchange among these lower levels was responsible for populating the higher ones. A simple model yielded a collision efficiency for HCl†ν=1 + HCl†ν=6 → HCl†ν=7 + HCl†ν=0, of Z1,6t = 6 × 103 collisions per transfer. Addition of HCl to the reaction mixture brought about a redistribution among vibrationally excited states indicative of a fast vibrational transfer, HClν=0 + HCl†ν=2 → 2 HCl†ν=1.At reduced pressure of HCl† the stationary-state distribution among higher vibrational states approximated closely to that observed at 10−2 mm Hg total pressure (where collisional deactivation is insignificant), suggesting that collisional deactivation was not of major importance even at the pressure used in the present work. In order to account for the high translational–rotational temperature, in the absence of substantial vibrational deactivation, it was necessary to suppose that the greater part of the energy liberated by the reaction H + Cl2 went directly into translational and rotational motion of the products.

scholarly journals Purification, properties and cellular localization of the stereospecific CS2 secondary alkylsulphohydrolase of Comamonas terrigena

1977 ◽  
Vol 167 (3) ◽  
pp. 723-729 ◽  
Author(s):  
G W J Matcham ◽  
K S Dodgson ◽  
J W Fitzgerald
Keyword(s):  
Chain Length ◽  
Cellular Localization ◽  
Indirect Evidence ◽  
Initial Study ◽  
Potassium Salts ◽  
Experimental Conditions ◽  
Alkyl Sulphate ◽  
A Subunit ◽  
A Chain ◽  
Comamonas Terrigena

The availability of homogeneous samples of the potassium salts of L- and D-octan-2-yl sulphate has enabled the separation of the optically stereospecific CS1 and CS2 secondary alkysulphohydrolases from extracts of cells of Comamonas terrigena. The CS2 enzyme was purified to homogeneity, and an initial study was made of its general properties, specificity, cellular localization and relationship to the CS1 enzyme. The CS2 enzyme has a molecular weight of approx. 250000 and a subunit size of approx. 58000, indicating that the molecule is a tetramer. Under the experimental conditions used the enzyme appears to be specific for (+)-secondary alkyl sulphate esters with the sulphate group at C-2 and with a chain length of at least six carbons. Enzyme activity towards racemic C-2 sulphates increases with increasing chain length up to C10, and there is some indirect evidence to suggest that activity declines when that chain length is exceeded. Other indirect evidence confirms that the CS1 enzyme exhibits similar specificity, except that only (-)-isomers can serve as substrates. Both enzymes are present in broth-grown stationary-phase cells of C. terrigena in approximately equal amounts.

Solvent and acidity effects on the UV-visible spectra and protonation-deprotonation of free-base octaethylcorrole

2008 ◽  
Vol 12 (01) ◽  
pp. 1-10 ◽  
Author(s):  
Zhongping Ou ◽  
Hongxia Sun ◽  
Weihua Zhu ◽  
Zulin Da ◽  
Karl M. Kadish
Keyword(s):  
Equilibrium Constants ◽  
Visible Spectrum ◽  
Soret Band ◽  
Free Base ◽  
Tetrabutylammonium Hydroxide ◽  
Experimental Conditions ◽  
Visible Spectra ◽  
Meso Position ◽  
Uv Visible ◽  
Strong Acids

The UV-visible spectrum of free-base octaethylcorrole, (OECor) H 3, was recorded in thirteen different nonaqueous solvents as well as in a mixed acetonitrile/acid solvent containing one of seven different acids. Spectra were also measured in seven different solutions of neat concentrated acid and in CH 3 CN containing piperidine or tetrabutylammonium hydroxide as an added base. The overall data was analyzed as a function of solvent acidity or basicity parameters and the number of protons on the central nitrogens of the macrocycle, the predominant form of the corrole in these solutions being respresented as (OECor)H 3, [ (OECor)H 4]+, [ (OECor)H 2]− or [ (OECor)H ]2− where OECor = trianion of octaethylcorrole. The mono-protonated corrole, [ (OECor)H 4]+, is formed in concentrated acetic acid or in CH 3 CN containing 0.10 M trifluoroacetic acid, H 2 SO 4, HCl , H 3 PO 4 or HClO 4. The mono-deprotonated corrole, [ (OECor)H 2]−, is generated in piperidine while doubly deprotonated [ (OECor)H ]2− exists in solutions of tetrabutylammonium hydroxide. An addition of protons to the macrocycle of [ (OECor)H 4]+ also occurs in the presence of concentrated strong acids and this results in a loss of the characteristic Soret band of the corrole leading presumably to [ (OECor)H 5]2+ where the second proton has been added to a meso-position of the macrocycle. The UV-visible spectral changes upon formation of [ (OECor)H 4]+, [ (OECor)H 2]− or [ (OECor)H ]2− in CH 3 CN were monitored during a titration with the relevent acid or base and equilibrium constants for protonation or deprotonation of (OECor)H 3 were determined using standard equations. The measured logK values are compared to protonation and deprotonation constants obtained for two related corroles and two related porphyrins under the same experimental conditions.

Application en série benzofurannique d'un nouveau procédé de nitration par l'acide nitrique en présence de chlorure stannique

1983 ◽  
Vol 61 (10) ◽  
pp. 2287-2290 ◽  
Author(s):  
Jacques Einhorn ◽  
Pierre Demerseman ◽  
René Royer
Keyword(s):  
Nitric Acid ◽  
Stannic Chloride ◽  
Experimental Conditions

A new nitration technique, using nitric acid in the presence of stannic chloride in dichloromethane, has been extended to a series of benzofurans. The ease of performing the reaction as well as the diversity of products that can be obtained under various experimental conditions make it a worthwhile technique. [Journal translation]

scholarly journals The effect of the polar solvents on the synthesis of poly(urethane-urea-siloxane)s

2012 ◽  
Vol 77 (10) ◽  
pp. 1457-1481 ◽  
Author(s):  
Milica Balaban ◽  
Vesna Antic ◽  
Marija Pergal ◽  
Iolanda Francolini ◽  
Andrea Martinelli ◽  
...  
Keyword(s):  
Monomer Concentration ◽  
Gel Permeation Chromatography ◽  
Molar Ratio ◽  
Solvent Ratio ◽  
Solvent Mixtures ◽  
Scanning Calorimetry ◽  
Experimental Conditions ◽  
Water Contact ◽  
Soft Segments ◽  
Hard Segments

Segmented poly(urethane-urea-siloxanes) (PUUS) based on 4,4?- methylene diphenyl diisocyanate-ethylene diamine (MDI-ED) hard segments and hidroxypropyl-terminated poly(dimethylsiloxane) (PDMS, M n =1000 g mol-1) soft segments were prepared under various experimental conditions. The copolymers with constant molar ratio of hard and soft segments (PDMS:MDI:ED = 1:2:1; 20 wt. % of the hard segments) were synthesized in two different solvent mixtures, by two-step polyaddition procedure. The first one was THF/DMAc with different co-solvent ratio (1/1, 1/2 and 1/9, v/v), whereas the second one was THF/NMP (1/9, v/v). The reaction conditions were optimized by varying the co-solvents ratio, the concentration of the catalyst, the initial monomer concentration, as well as the time of the first and the second step of reaction. The effect of the experimental conditions on the size of PUUS was investigated by gel permeation chromatography (GPC) and viscometry of the dilute solutions [?]. The copolymers with the highest molecular weights were obtained in the THF/NMP mixture (1/9, v/v). The structure and composition of the copolymers were determined by 1H NMR and FTIR spectroscopy. The morphology of the synthesized copolymers was investigated by atomic force microscopy (AFM), while the thermal properties were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The surface properties were evaluated by measuring the water contact angle (WCA). The copolymers showed phase separated microstructure and were stable up to 200?C in nitrogen.

scholarly journals Thermodynamics of metal-ligand bond formation. VIII. Pyridine adducts of zinc(II) β-diketonates

1973 ◽  
Vol 26 (11) ◽  
pp. 2537 ◽  
Author(s):  
DR Dakternieks ◽  
DP Graddon
Keyword(s):  
Benzene Solution ◽  
Equilibrium Constants ◽  
Bond Formation ◽  
Formation Constants ◽  
Adduct Formation ◽  
Enthalpies Of Formation ◽  
Calorimetric Titration ◽  
Experimental Conditions ◽  
Metal Ligand ◽  
Ligand Bond

Equilibrium constants and enthalpies in benzene solution are reported for the formation of 1 : 1-adducts of pyridine with four zinc(II) complexes of β-diketones, determined by calorimetric titration. Adduct formation constants at 30�C fall in the range 300-2000 and enthalpies of formation lie between -15 and - 34 kJ mol-1. Though the enthalpies of formation differ little from those of corresponding copper(II) complexes, the adducts are about a hundred times more stable. The pyridine adduct of bis(2,2,6,6-tetramethylheptane-3,5-dionato)zinc(II) is entropy-stabilized relative to those of other complexes. No evidence was obtained for the addition of a second molecule of pyridine under the experimental conditions used.

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