Free Metal Ion Depletion by Good's Buffers. IV. Bicine 1:1 and 2:1 Complexes with Mg(II), Ca(II), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

Abstract

The interaction of “Good's” buffers with a variety of metal ions has been assessed.     

Kinetic analysis of thermogravimetric data

The potassium, ammonium and thirteen amine salts of hexabromoplatinic acid were obtained and characterized by chemical analysis. The thermal decompositions of these complex salts were studied by derivatograph and differential scanning calorimetry. The natures of the pyrolysis processes are discussed and compared with those obtained for the analogous chlorocomplexes. From the TG curves, kinetic parameters were derived for different stages of the thermal decomposition.

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Zusammenfassung Es wurden die Kalium-, Ammonium- und dreizehn verschiedene Aminsalze von Hexabromoplatinsäure hergestellt und mittels Elementaranalyse charakterisiert. Mittels Derivatographie und DSC wurde die thermische Zersetzung dieser Komplexsalze untersucht. Das Wesen der Pyrolysevorgänge wird besprochen und mit dem der analogen Chlorokomplexe verglichen. Anhand der TG-Kurven wurden für verschiedene Schritte der thermischen Zersetzung kinetische Parameter ermittelt.

     

Polymethylmethacrylate derivatives Eudragit E100 and L100: Interactions and complexation with surfactants

Precipitation or coprecipitation of polyelectrolytes has been largely investigated. However, the precipitation of polyelectrolytes via addition of charged and non‐charged surfactants has not been systematically studied and reported. Consequently, the aim of this work is to investigate the effect of different surfactants (anionic, cationic, non‐charged and zwitterionic) on the precipitation of cationic and anionic polymethylmethacrylate polymers (Eudragit). The surfactants effect has been investigated as a function of their concentration. Special attention has been dedicated to the CMC range and to the colloidal characterization of the formed dispersions. Moreover, the effect of salt (NaCl) and pH was also addressed. It is pointed out that non‐ionic and zwitterionic surfactants do not interact with charged Eudragit E100 and L100. For oppositely charged Eudragit E100/SDS and Eudragit L100/CTAB, precipitation occurs, and the obtained dispersions have been characterized in terms of particle size distribution and zeta potential. It was established that the binding of SDS molecules to Eudragit E100 polymer chains is made through the negative charges of the surfactant heads under the CMC value whereas binding of CTAB to Eudragit L100 chains is made at a CTAB concentration 5 times above its CMC. For Eudragit E100/SDS system, a more acidic medium induces aggregation. A same result was observed for the Eudragit L100/CTAB at a more basic pH. Moreover, it was observed that increasing salt concentration (higher than 100 mM) led to aggregation as generally observed for polycations/anionic surfactant systems.     

Thermodynamic Constants of Glycyl Peptides: Solvation and Buffers for the Physiological pH Range

The pK ₂ values for the dissociation of the NH ₃ ⁺ charge center of the glycyl peptides, e.g., glycyl-D-asparagine, glycyl-DL-serine, glycyl-L-leucine, and glycyl-DL-methionine have been determined at 10 temperatures in the range 5–50°C by measurements of the emf of cells without liquid junction, utilizing hydrogen electrodes and silver–silver bromide electrodes. The thermodynamic quantities, H ^o, C _p ^o and S ^o were calculated from the temperature coefficients of the dissociation constants. The pK ₂ values at 25°C are 8.268 (glycyl-D-asparagine), 8.277 (glycyl-DL-serine), 8.323 (glycyl-L-leucine), and 8.408 (gly-cyl-DL-methionine). These values show that changes in the substituents on the -carbon atom have very little effect on the dissociation of the NH ₃ ⁺ , with the possible exception of glycyl-DL-methionine. The suitability of these compounds as buffers in the physiologically important pH range 7–9 is of interest. The thermodynamics of the solute–solvent interaction is interpreted in terms of a mixture model. The peptides chosen for study include both polar and nonpolar substituents.     

Complexation Equilibria of Zn(II), Pb(II) and Cd(II) with Reduced Glutathione (GSH) and Biologically Important Zwitterionic Buffers

The interaction of zinc(II), lead(II), and cadmium(II) with Glutathione (S‐L‐glutamyl‐Lcysteinylglycine) as primary ligand and zwitterionic buffers (N‐[2‐Hydroxyethyl]piperazine‐N′‐[2‐ethanesulfonic acid]) (HEPES) and (N‐Hydroxyethyl]piperazine‐N′‐[2‐hydroxy‐propanesulfonic acid]) (HEPPSO) as secondary ligands were studied by potentiometric‐pH titration in 1:1:1 ratio at 25.0 °C and I = 0.1 mol.dm^?3 (KNO₃). The formation constants of different normal and protonated binary and ternary complex species were calculated. Formation constants for the monohydroxy, and dihydroxy complexes for the binary systems M(II) + HEPES and M(II) + HEPPSO have been evaluated. The distribution curves for the various complex species as a function of pH were constructed.     

Differential Kinetic Determination of Ketone Mixtures

Abstract

A method for the determination of binary ketone mixtures is described which is based on the differential reaction rates of ketones in a large excess of hydroxylamine hydrochloride. The reactions are followed with a pH stat. For mixtures containing ca. 10^?5 moles of ketone, a relative error and precision of 1% was obtained if the rate constants differed by a factor of 5, and 3% if the rate constants differed by 3.     

Kinetic analysis of thermogravimetric data

Four many curves methods, viz. calculation techniques based on Eqs (30), (31), (34) and (36), respectively, for deriving kinetic parameters from several TG curves recorded with different heating rates are tested on two sets of theoretical TG curves. The maximum reaction rate temperature and conversion, as well as the approximate formulae used for their calculation are discussed. Some aspects of the kinetic compensation effect are analysed. The final conclusion is that the use of the many curves methods is not reasonable.     

Kinetic of decomposition of some complexes under non-isothermal conditions

Kinetics of thermal decomposition of three structurally similar complexes Co₂Cu(C₂O₄)₃ (R-diam)₂, where R is ethyl, 1,2-propyl or 1,3-propyl, was studied under non-isothermal conditions and nitrogen dynamic atmosphere at heating rates of 5, 7, 10, 12 and 15 K min⁻¹. For data processing the Flynn-Wall-Ozawa and a modified non-parametric kinetic methods were used. By both methods the activation energy are in the range of 97–102 kJ mol⁻¹. The formal kinetic is r=kα(1−α)². Also a compensation effect between lnA and E was evidenced. The kinetic analysis lead to the conclusion of an identic decomposition mechanism by a single step process.     

Theoretical Photodynamic Study of the Photoprotolytic Cycle of Firefly Oxyluciferin

Firefly oxyluciferin presents a pH‐sensitive fluorescence in aqueous solutions. Its fluorescence spectra are composed of two green peaks at different pH values, despite the enolate anion being the only emitter. A computational approach was used to further elucidate the photoprotolytic cycle of oxyluciferin and investigate its pH sensitivity. It was found that oxyluciferin forms π–π stacking complexes both in the ground and excited states, at basic and acidic/neutral pH. However, at different pH values, these complexes adopt a different conformation, which explains the lower energy of the emission at acidic/neutral pH, in comparison with the emission at basic pH.     

Direct Observation of Kinetic Pathways of Biomolecular Recognition

The pathways of molecular recognition, which is a central event in all biological processes, belong to the most important subjects of contemporary research in biomolecular science. By using fluorescence spectroscopy in a microfluidics channel, it can be determined that molecular recognition of α‐chymotrypsin in hydrous surroundings at two different pH values (3.6 and 6.3) follows two distinctly different pathways. Whereas one corroborates an induced‐fit model (pH 3.6), the other one (pH 6.3) is consistent with the selected‐fit model of biomolecular recognition. The role of massive structural perturbations of differential recognition pathways could be ruled out by earlier XRD studies, rather was consistent with the femtosecond‐resolved observation of dynamic flexibility of the protein at different pH values. At low concentrations of ligands, the selected‐fit model dominates, whereas increasing the ligand concentration leads to the induced‐fit model. From molecular modelling and experimental results, the timescale associated with the conformational flexibility of the protein plays a key role in the selection of a pathway in biomolecular recognition.     

19F VT NMR: Novel Tm3+ and Ce3+ Complexes Provide New Insight into Temperature Measurement Using Molecular Sensors

In the past few decades, magnetic resonance spectroscopy (MRS) and MR imaging (MRI) have developed into a powerful non-invasive tool for medical diagnostic and therapy. Especially ¹⁹F MR shows promising potential because of the properties of the fluorine atom and the negligible background signals in the MR spectra. The detection of temperature in a living organism is quite difficult, and usually external thermometers or fibers are used. Temperature determination via MRS needs temperature-sensitive contrast agents. This article reports first results of solvent and structural influences on the temperature sensitivity of ¹⁹F NMR signals of chosen molecules. By using this chemical shift sensitivity, a local temperature can be determined with a high precision. Based on this preliminary study, we synthesized five metal complexes and compared the results of all variable temperature measurements. It is shown that the highest ¹⁹F MR signal temperature dependence is detectable for a fluorine nucleus in a Tm³⁺-complex.     

Temperature and pH sensitive ionic hydrogels based on new crosslinkers

New crosslinkers were synthesized from reaction of melamine with acryloyl and methacryloyl chloride in the presence of 1‐methyl‐2‐pyrrolidone as a solvent and triethyl amine as acid acceptor. The chemical structures of the prepared crosslinkers were elucidated from FT‐IR, ¹H‐NMR and ¹³C‐NMR analyses. Linear 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid and methacrylic acid (AMPS/MAA) copolymers were prepared and their viscometric properties in aqueous solution were investigated. Different weight percentages of the prepared crosslinkers were used as crosslinking agent (AMPS/MAA) to prepare ionic copolymers using ammonium persulfate as initiator. The percentage of crosslinkers was varied from 0.5 to 4 wt%. The swelling behaviors of crosslinked AMPS/MAA gels in deionized water were measured at different pH and temperatures. All AMPS/MAA copolymers exhibit faster deswelling rate at 50°C except for the copolymer containing 0.9 (mol ratio) AMPS. Copyright © 2005 John Wiley & Sons, Ltd.     

Kinetic analysis of TG data XXXVI: Influence of procedural variables upon the apparent kinetic parameters of the thermal deamination

A number of 7 complexes of the [Co(DH)₂(amine)₂)]I type (DH₂ stands for dimethyloxime) have been studied by means of thermogravimetry and differential scanning calorimetry in nitrogen atmosphere, by using heating rates of 2.5, 5 and 10 K min^–1. In all cases an endothermal deamination reaction occurs leading to the relatively stable [Co(DH)₂I(amine)] intermediate. For this reaction apparent kinetic parameters have been derived. The influence of heating rate is discussed. The validity of a linear and a non-linear kinetic compensation law was verified.This revised version was published online in November 2005 with corrections to the Cover Date.     

Kinetic equations for thermal dissociation processes

Relationships between average degree of transformation and time of dissociation were derived for polydisperse granular materials with account to the type of grain size distribution. It has been checked, under what conditions the kinetic curves obtained by numeric solution of those relationships may be described in terms of equations D1 α²=kt , F2 [1/(1 - α) - 1 =kt] and F3 [1/(1 - α)² - 1=kt]. This revised version was published online in August 2006 with corrections to the Cover Date.     

Doubly hydrophilic multiarm hyperbranched polymers with acylhydrazone linkages as acid-sensitive drug carriers

A novel type of drug carrier capable of controlled drug release is proposed. It consists of an acid-sensitive doubly hydrophilic multiarm hyperbranched copolymer with a hyperbranched polyamidoamine core and many linear poly(ethylene glycol) arms. Using pH-sensitive acylhydrazone linkages, the polymer forms unimolecular micelles that can encapsulate hydrophobic drugs. Due to their amphiphilicity, the drug-loaded unimolecular micelles can self-assemble into multimolecular micelles that show acid-triggered intracellular delivery of the hydrophobic drugs.     

Kinetic aspects associated with the lean reduction of no with C3H6 over well-structured pt nanocrystals

Summary Well-defined platinum nanocrystals (» 52% cubic), with an average diameter of 12 nm, were prepared by colloid method and then supported on alumina. The effect of the exposed Pt surface on lean de-NO_x reaction was investigated. The catalytic data free of transport effects were identified and then used to calculate the kinetic parameters of lean de-NOx reaction.