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  • Cell & Developmental Biology  (89)
  • Biochemistry and Biotechnology  (49)
  • thermodynamics  (11)
  • 1
    ISSN: 0173-0835
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: A procedure for the isolation of protein markers of epidermal differentiation in vitro is described. Human epidermal keratinocytes were cultured and radiolabelled in vitro. Fractionation was performed according to buoyant density (which reflects the degree of terminal differentiation) using Percoll density gradient centrifugation. Subpopulations of keratinocytes were characterised using light and electron microscopy, and proteins fractionated using high resolution two-dimensional gel electrophoresis. Radio-labelled proteins were detected using autoradiography and fluorography. Integral membrane proteins were characterised using Triton X-114 phase shift extraction. Data from this in vitro study were compared to silver stained gels of samples from intact epidermis (in vivo). We report quantitative differences between 14 specific protein moieties expressed in subpopulations of keratinocytes and identify some of these proteins. The differential expression of these protein markers and their possible use in the interpretation of the keratinocyte maturation pathway in cultured cells from patients with skin diseases are discussed.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0173-0835
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: A procedure is described for the detection of keratinocyte specific proteins. Fibroblasts and keratinocytes were isolated from human skin and radiolabelled in vitro. Samples were separated by two-dimensional polyacrylamide gel electrophoresis to compare the proteins synthesised by the different types of cultured skin cells. Dual label autoradiography of samples radiolabelled with [35S]methionine and [75Se]selenomethionine was used to identify keratinocyte specific proteins. We report 45 keratinocyte-specific components and identify some of these proteins. The differential expression of these proteins and their relevance to epidermal differentiation are discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Electrophoresis 12 (1991), S. 579-584 
    ISSN: 0173-0835
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Using histochemical techniques an abnormal programme of epidermal differentiation has been well documented in psoriasis. In order to characterise further the biochemistry of this process we have cultured dermal fibroblasts and epidermal keratinocytes from involved psoriatic skin. This has facilitated metabolic radiolabelling of skin cells and analysis of protein synthesis by two-dimensional polyacrylamide gel electrophoresis. The expression of keratin and differentiation markers was identical to that of normal keratinocytes, suggesting that psoriatic epidermal differentiation is not truncated in vitro as has been postulated to be the case in vivo. Low molecular mass components (5-8.5 kDa), previously shown to be upregulated in suprabasal keratinocytes, were detected in epidermal fractions from psoriatic skin enriched for basal cells. Of especial interest was a component of 26 kDa, pI 5.9, which was highly upregulated in psoriatic as compared to normal cultured keratinocytes and was not detected in fibroblasts. These findings are in accord with a qualitatively abnormal pattern of differentiation for keratinocytes in the involved psoriatic epidermis.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 22 (1993), S. 125-136 
    ISSN: 1572-8927
    Keywords: Formic acid ; methanoic acid ; dissociation constant ; thermodynamics ; potentiometry ; ionic strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The dissociation quotients of formic acid were measured potentiometrically from 25 to 200°C in NaCl solutions at ionic strengths of 0.1, 0.3 1.0, 3.0, and 5.0 mol-kg−1. The experiments were carried out in a concentration cell with hydrogen electrodes. The resulting molal acid dissociation quotients for formic acid, as well as a set of infinite dilution literature values and a calorimetrically-determined enthalpy of reaction, were fitted by an empirical equation involving an extended Debye Hückel term and seven adjustable parameters involving functions of temperature and ionic strength. This regressional analysis yielded the following thermodynamic quantities for 25°C: logK=−3.755±0.002, ΔHo=−0.09±0.15 kJ-mol−1, ΔSo=−72.2±0.5 J-K−1-mol−1, and ΔC p o =−147±4 J-K−1-mol−1. The isocoulombic form of the equilibrium constant is recommended for extrapolation to higher temperatures.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 19 (1990), S. 159-173 
    ISSN: 1572-8927
    Keywords: Aluminum ; Bis-tris ; dextrose ; solubility ; Raman ; complex ; thermodynamics ; aqueous
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Gibbsite, Al(OH)3, solubility studies in aqueous NaCl solutions at pH 9 demonstrate that the aluminate anion forms a strong complex with the neutral Bis-tris molecule 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol, at low temperatures. The logarithm of the molal concentration quotient for the reaction $$Al(OH)_4^ - + H_2 [Bis - tris] _ \leftarrow ^ \to Al(OH)_2 [Bis - tris]^ - + 2H_2 O$$ in aqueous NaCl solutions at 0.1 molal ionic strength is 2.63±0.03 at 25°C and 2.6±0.1 at 50°C. Raman spectroscopy of NaOH−NaAl(OH)4 solutions at 25°C quantitatively verifies these results and indicates that a complex with symmetrical vibrational frequencies at 498 and 574 cm−1 is stabilized in the presence of excess Bis-tris in these solutions. Gibbsite solubility and Raman spectroscopy also indicate that a similar complexation reaction between the aluminate anion and dextrose occurs, with a molal equilibrium quotient of 100.65 at 25°C, 0.1 molal ionic strength. These complexation reactions are suggested to be equivalent to the wellknown reactions involving the borate anion and polyhydroxyl sugar-like molecules. Experiments with ethylene glycol, glycerol, mannitol and sucrose indicate no significant complexing of these compounds with the aluminate anion.
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  • 6
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 24 (1995), S. 65-87 
    ISSN: 1572-8927
    Keywords: Succinic acid ; butanedioic acid ; dissociation constants ; thermodynamics ; potentiometry ; ionic strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The first and second molal dissociation quotients of succinic acid were measured potentiometrically with a hydrogen-electrode, concentration cell. These measurements were carried out from 0 to 225°C over 25° intervals at five ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The dissociation quotients from this and two other studies were combined and treated with empirical equations to yield the following thermodynamic quantities for the first acid dissociation equilibrium at 25°C: log K1a=−4.210±0.003; ΔH 1a 0 =2.9±0.2 kJ-mol−1; ΔS 1a 0 =−71±1 J-mol−1-K−1; and ΔC p1a 0 =−98±3 J-mol−1-K−1; and for the second acid dissociation equilibrium at 25°C: log K2a=−5.638±0.001; ΔH 2a 0 = −0.5±0.1 kJ-mol−1; ΔS 2a 0 =−109.7±0.4 J-mol−1-K−1; and ΔC p2a 0 = −215±8 J-mol−1-K−1.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 26 (1997), S. 63-84 
    ISSN: 1572-8927
    Keywords: Citric acid ; dissociation constants ; thermodynamics ; potentiometry ; ionic strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The three molal dissociation quotients for citric acid were measured potentiometrically with a hydrogen-electrode concentration cell from 5 to 150°C in NaCl solutions at ionic strengths of 0.1, 0.3, 0.6, and 1 molal. The molal dissociation quotients and available literature data at infinite dilution were fitted by empirical equations in the all-anionic form involving an extended Debye-Hückel term and up to five adjustable parameters involving functions of temperature and ionic strength. This treatment yielded the following thermodynamic quantitites for the first dissociation equilibrium at 25°C: logK 1a=−3.127±0.002, ΔH 1a o =4.1±0.2 kJ-mol−1, ΔS 1a o =−46.3±0.7 J-K−1-mol−1, and ΔCp 1a o =−162±7 J-K−1-mol−1; for the second acid dissociation equilibrium at 25°C: logK 2a =−4.759±0.001, ΔH 2a o =2.2±0.1, ΔS 2a o =−83.8±0.4, and ΔCp 2a o =−192±15, and for the third dissociation equilibrium at 25°C: logK 3a=−6.397±0.002, ΔH 3a o =−3.6±0.2, ΔS 3a o =−134.5±0.7, and ΔCp 3a o =−231±7.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 21 (1992), S. 883-900 
    ISSN: 1572-8927
    Keywords: Malonic acid ; propanedioic acid ; dissociation constants ; thermodynamics ; potentiometry ; ionic strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The first and second molal dissociation quotients of malonic acid were measured potentiometrically in a concentration cell fitted with hydrogen electrodes. The hydrogen ion molality of malonic acid/bimalonate solutions was measured relative to a standard aqueous HCl solution from 0 to 100°C over 25° intervals at five ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The molal dissociation quotients and available literature data were treated in the all anionic form by a seven-term equation. This treatment yielded the following thermodynamic quantities for the first acid dissociation equilibrium at 25°C: logK 1a =-2.852±0.003, ΔH 1a /o =0.1±0.3 kJ-mol−1, ΔS 1a o =−54.4±1.0 J-mol−1-K−1, and ΔC p,1a o =−185±20 J-mol−1-K−1. Measurements of the bimalonate/malonate system were made over the same intervals of temperature and ionic strength. A similar regression of the present and previously published equilibrium quotients using a seven-term equation yielded the following values for the second acid dissociation equilibrium at 25°C: logK2a=−5.697±0.001, ΔH 2a o =−5.13±0.11 kJ-mol−1, ΔS 2a o =−126.3±0.4 J-mol−1-K−1, and ΔC p,2a o =−250+10 J-mol−1-K−1.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 18 (1989), S. 545-559 
    ISSN: 1572-8927
    Keywords: 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol ; equilibrium constant ; thermodynamics ; buffer ; association ; salt effect ; temperature dependence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The ionic strength and temperature dependencies of the molal acid association quotients of 2,2-Bis(hydroxymethyl)-2,2′,2″-nitrilotriethanol (also abbreviated as bis-tris) were determined potentiometrically in a concentration cell fitted with hydrogen electrodes. The emf was recorded for equimolal bis-tris/bis- trisHCl buffer solutions from 5 to 125°C at approximately 25°C intervals, and at nine ionic strengths from 0.05 to 5.0m (NaCl). The molal association quotients, combined with infinite dilution values from the literature, are described precisely by a seven parameter equation which yielded the following thermodynamic quantities at infinite dilution and 25°C: logK=6.481±0.003, ΔH o =−28.5±0.2 kJ-mol −1 , ΔS o =28.5±0.8 J-K −1 -mol −1 , and ΔC P o =−22±5 J-K −1 -mol −1 . The equation incorporates a simple three term expression for logK, but requires four terms to describe the rather complex ionic strength dependence despite the reaction being isocoulombic. The molal association quotients from this study and the literature were also subjected to the Pitzer ion interaction treatment.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 20 (1991), S. 905-927 
    ISSN: 1572-8927
    Keywords: Oxalic acid ; ethanedioic acid ; dissociation constants ; thermodynamics ; potentiometry ; ionic strength
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The first and second molal dissociation quotients of oxalic acid were measured potentiometrically in a concentration cell fitted with hydrogen electrodes. The emf of oxalic acid-bioxalate solutions was measured relative to an HCl standard solution from 25 to 125°C over 25o intervals at nine ionic strengths ranging from 0.1 to 5.0 molal (NaCl). The molal dissociation quotients and available literature data were treated in the all anionic form by a five-term equation that yielded the following thermodynamic quantities at infinite dilution and 25°C: logK1a=−1.277±0.010, ΔH 1a o =−4.1±1.1 kJ-mol−1, ΔS 1a o =38±4 J-K−1-mol−1, and ΔC p,1a o =−168±41 J-K−1-mol−1. Similar measurements of the bioxalate-oxalate system were made at 25o intervals from 0 to 175°C at seven ionic strengths from 0.1 to 5.0m. A similar regression of the experimentally-derived and published equilibrium quotients using a seven-term equation yielded the following values at infinite dilution and 25°C: logK2a=−4.275±0.006, ΔH 2a o =−6.8±0.5 kJ-mol−1, ΔS 2a o =−105±2 J-K−1-mol−1, and ΔC p,2a o =−261±12 J-K−1-mol−1.
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