Simultaneous determination of C1-C4 carboxylic acids and aldehydes using 2,4-dinitrophenylhydrazine-impregnated silica gel and high-performance liquid chromatography

A new method for the simultaneous determination of aliphatic carboxylic acids and aldehydes in air is described. In this work, carboxylic acids were allowed to react with 2,4-dinitrophenylhydrazine (DNPH) to form the corresponding carboxylic 2,4-dinitrophenylhydrazides. These derivatives have excellent thermal stability, with melting points higher than those of the corresponding hydrazones by 32-50 degrees C. C1-C4 carboxylic acid 2,4-dinitrophenylhydrazides exhibited maximum absorption wavelengths of 331-334 nm and molar absorption coefficients of 1.4 x 10(4) L/mol/cm. They were completely separated by high-performance liquid chromatography (HPLC) with an RP-Amide C16 column. Cartridges packed with DNPH-coated silica particles (DNPH cartridge) were used for sampling formic acid and aldehydes. Formic acid was physically adsorbed on the silica particles as the first step of the sampling mechanism. Gradual reaction with DNPH followed. Formic acid reacted very slowly with DNPH at room temperature (20 degrees C), but reacted completely at 80 degrees C over 4 h. In field measurements, the sample air was drawn through a DNPH cartridge. After sampling, the cartridges were heated at 80 degrees C for 5 h and extracted with acetonitrile for HPLC analysis. Under these optimized conditions, the LOD is 0.4 ug/m(3) for an air sample collected for 24 h at 100 mL/min (144 L).     

Immobilization of crown ether carboxylic acids on silica gel and their use in column concentration of alkali metal cations from dilute aqueous solutions

Eight crown ethers with pendent carboxylic acid groups are immobilized on silica gel and utilized for column concentration of alkali metal cations from dilute aqueous solutions. The column concentration selectivity and efficiency are found to be strongly influenced by (1) the cavity size of the crown ether unit, (2) conformational positioning of the proton-ionizable side arm with respect to the crown ether cavity, and (3) capping of residual silanol surface groups with trimethylsilyl functions. By use of a chromatographic stripping technique, selective column concentration of Na(+), K(+), (Rb(+) and Cs(+)), and Cs(+) by different functionalized silica gels has been achieved.     

Protonic polymer gel electrolytes based on carboxylic acids: ortho and inductive effects

The conductivity of polymer gel electrolytes containing three aromatic and three aliphatic carboxylic acids has been studied, viz. (i) ortho-, meta- and para-hydroxybenzoic acids and (ii) oxalic, malonic and succinic acids. Polymeric gels were prepared by adding different wt% of polymer poly(methylmethacrylate) (PMMA) in solutions of respective acids in high dielectric constant organic solvent mixtures of propylene carbonate, ethylene carbonate and dimethylformamide. The highest conductivity in the first of the above group of acids is for o-hydroxy benzoic acid and oxalic acid in the second group of acids. Results have been explained on the basis of ortho and/or inductive effects which depend upon the relative positions of the substituted hydroxyl (–OH) and carboxyl (–COOH) group or that of the two carboxylic groups.     

Growth and characterization of calcium pyrophosphate dihydrate grown in silica gel

Calcium pyrophosphate dihydrate crystals, which are responsible for various arthritic diseases, were grown in sodium metasilicate gel. Variations in gel density, pH value and concentration of the reactants were found to have profound effect on the growth of the crystals. The grown crystals were characterized using IR, XRD, TGA and optical microscopy.     

Effect of crystallization parameters and presence of aqueous extract of Nigella Sativa on growth inhibition of calcium oxalate monohydrate particles

For the first time, nucleation kinetics, crystal growth and agglomeration of calcium oxalate monohydrate (COM) are studied as a crystal growth inhibitor with and without Nigella Sativa(NS) extract. The induction period was determined under different supersaturation ratios ranging from 1.63 to 4.51 at 37°C using the conductivity method. Based on the classical homogeneous nucleation theory; the critical nucleation parameters were evaluated at higher supersaturation ratio. The calculated surface energy was increased from 7.97?mJ/m² without additive to 10.31?mJ/m² with NS extract. However, the nucleation rate at a supersaturation ratio of 3.26 corresponding to 5.44 with the NS extract was decreased from 3.9?×?10²⁹ nuclei/cm³.s (without additive) to 1.3?×?10²⁹ nuclei/cm³.s with NS extract addition. The number of molecules required for the formation of a stable nucleus was calculated with and without NS extract at different supersaturation ratios. The crystallite sizes of the formed crystals without and with the additive are 93 and 51?nm, respectively. Scanning electron microscopy (SEM) photomicrographs show the formation of small crystals and less aggregated with the NS inhibitor compared with the baseline (without the inhibitor). This study can help us with a clear understanding of the inhibition mechanism of an aqueous NS extract on COM crystals.     

Simultaneous crystallization of calcium phosphate and calcium oxalate in the presence of ascorbic acid under physiological conditions

Ascorbic acid (AA—Vitamin C) plays a vital role in human body to preserve optimal health. However, high intake may cause the formation of pathological calcium oxalate stones. Calcium oxalate and calcium phosphates are the major crystalline constituents of the urinary calculi and commonly found together. The effect of AA on the crystallization of calcium phosphate was studied in gel matrix under physiological conditions. Calcium phosphates such as hydroxyapatite (HAp), brushite (DCPD) and calcium oxalate dihydrate (COD—Weddellite) were found to crystallize simultaneously in the gel matrix. The formation of HAp is accelerated by AA. A possible reaction scheme for the formation of COD by the metal induced conversion of AA is proposed.     

Inhibiting Au nanoparticle aggregation in freeze-thawing by presence of various additives

After freezing aqueous suspensions of gold nanoparticles (AuNPs) in the presence of various substances, the resulting aggregation of the nanoparticles was evaluated and the anti-aggregation effects of the different additives were compared. Many of the additives exhibited an anti-aggregation effects during freeze-thawing, the extent of which was greater at higher additive concentrations and the effects were 5 ~ 35% less than during the actual freeze-drying. Dextran and polyvinylpyrrolidone highly inhibited the aggregation even at markedly low additive concentrations (2 µg/mL). The use of a combination of a disaccharide (2 mg/mL of sucrose) and a sugar ester (20 µg/mL of sucrose palmitate) successfully preserved the redispersibility of the product after freeze-thawing while using each separately did not. Regarding the influence freezing and thawing conditions, a higher thawing temperature (from 4˚C to 60˚C) resulted in 10 ~ 20% better redispersibility of the AuNPs whereas the freezing temperature had no significant affect. The effect of freezing/thawing cycles of suspensions of AuNPs was also examined. The concentration of additive molecules on the surfaces of the frozen particles was monitored by In-situ Fourier transform IR spectroscopy. The collective findings of this study indicate that the additives essentially exert an anti-aggregation effect by slowing down the movement of the AuNPs.     

SiO2对Al2O3凝胶纤维相变的影响

以尿素催化硅酸乙酯水解制得SiO2溶胶。采用29Si NMR、27 Al NMR、FT-IR、TEM、DTA、XRD和SEM等对SiO2溶胶、Al2O3凝胶纤维化学结构和微观结构研究结果表明,该SiO2溶胶稳定性好,含有大量的单硅酸Si(OH)4,能和Al2O3表面的Al—OH反应生成Al—O—Si键而有效地将其包裹,从而阻止了过渡态Al2O3微晶的相互接触,抑制了α-Al2O3的成核和生长。     

Microtopographical and Raman spectral studies on calcium sulphate dihydrate (gypsum) crystals grown in silica gel in the presence and absence of barium chloride as additive

A procedure for the growth of calcium sulphate dihydrate (gypsum) crystals, CaSO₄ · 2H₂O, by a gel technique in the presence of barium chloride as an additive as well as without the additive, is described. Optimum conditions for the growth of good quality crystals are worked out. Needle-shaped crystals with well-defined prism faces are obtained. Microtopographical studies of the crystals are carried out. The observed surface structures on the prism faces of the crystals include vertical striations and parallelogram-shaped, oriented growth hillocks. Etch patterns on these faces are described and discussed. Reciprocity of the growth and etch mechanisms is established. Laser Raman spectral studies of these crystals are also made. Splitting of the non-degenerate fundamental is observed in the spectrum of the crystals grown in the presence of the additive. The present studies indicate that the additive used enhances the quality of the crystals.     

Effect of electric field on the growth of barium molybdate crystals in silica gel

The growth of BaMoO₄ crystals in silica gel under the influence of an externally applied uniform electric field is studied. The habit changes resulting from different growth parameters are reported. Crystals up to 4.0 mm×1.2 mm×0.9 mm were obtained under field. The morphology of some crystals is examined by optical and scanning electron microscopy.     

Sorption of phenolics and carboxylic acids on polybenzimidazole

The sorption of phenolics and carboxylic acids on the new ion-exchange resin polybenzimidazole (PBI) has been measured using aqueous solutions of the sorbates and compared with the sorption on another weak-base resin, poly(4-vinyl pyridine) (PVP). The phenolics used include phenol, p-cresol, p-chlorophenol and m-aminophenol, while the carboxylic acids chosen are formic, acetic, propionic and butyric acids. For aminophenol and phenol, the equilibrium sorption capacities of PBI and PVP are comparable, while for more acidic p-cresol and p-chlorophenol, PVP has significantly higher equilibrium sorption than PBI. On the other hand, for carboxylic acids at low concentrations, PBI exhibits considerably higher sorption capacity than PVP, the difference being more pronounced for acids with smaller acidity. At low concentrations, formic acid has several-fold higher sorption than phenol on PBI, which thus offers a simple method for separation of formic acid from phenol in dilute solutions. PBI has fast sorption kinetics for both phenols and carboxylic acids and a fast rate of stripping and regeneration with dilute NaOH, being much superior to PVP in both these respects.     

In situ synthesis of calcium phosphates on chitosan macromolecules in the presence of glutamic and aspartic acids

Calcium hydrogen phosphate dihydrate and amorphous calcium phosphate have been synthesized in an aqueous suspension of medium molecular weight chitosan in the presence of glutamic or aspartic acid. X-ray diffraction and transmission and scanning electron microscopy characterization showed that the morphology of the phases present depended on the nature of the amino acid. The amino acids participate in the protonation of the amino groups of the chitosan and, probably, in the formation of chelate intermediate compounds with calcium ions, which act as calcium phosphate nucleation centers.     

Mediation of calcium oxalate crystal growth on human kidney epithelial cells with different degrees of injury

The current study examined the role of injured human kidney tubular epithelial cell (HKC) in the mediation of formation of calcium oxalate (CaOxa) crystals by means of scanning electronic microscopy and X-ray diffraction. HKC was injured using different concentrations of H₂O₂. Cell injury resulted in a significant decrease in cell viability and superoxide dismutase (SOD) concentration and an increase in the level of malondialdehyde (MDA) and expression of osteopontin (OPN). Injured cells not only promote nucleation and aggregation of CaOxa crystals, but also induce the formation of calcium oxalate monohydrate (COM) crystals that strongly adhere to cells. These results imply that injured HKCs promote stone formation by providing more nucleating sites for crystals, promoting the aggregation of crystals, and inducing the formation of COM crystals.     

Preparation of a silica gel–carbon black composite by the sol–gel process in the presence of polymer-grafted carbon black

This paper is concerned with the preparation of a silica gel–carbon black composite by the sol–gel process, which consists of tetraethoxysilane and polymer-grafted carbon black. Polymer-grafted carbon black was synthesized by three methods: (1) cationic polymerization of N-vinyl-2-pyrrolidone, (2) cationic ring-opening polymerization of 2-methyl-2-oxazoline, and (3) radical polymerization of glycidyl methacrylate followed by reaction of glycidyl groups in the grafted polymer chains with 3-aminopropyltriethoxysilane. The polycondensation of tetraethoxysilane proceeded under acidic conditions in the presence of polymer-grafted carbon black to give a deep black silica gel–carbon black composite. The more the content of untreated carbon black was increased, the more the gelation time was shortened. On the contrary, gelation was retarded by grafted polymer chains on the carbon black surface in the case of polymer-grafted carbon black. The scratch hardness of the resulting silica gel–carbon black composite was almost equal regardless of the carbon black content in the presence of untreated carbon black, whereas it was liable to decrease as the content of polymer-grafted carbon black increased. The solvent adsorption properties of the silica gel–polymer-grafted carbon black composite varied with the solubility of grafted polymer chains on the carbon black surface towards the immersion solvent. © 1998 Chapman & Hall