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Secondary structures of proteins adsorbed onto aluminum hydroxide: infrared spectroscopic analysis of proteins from low solution concentrations.

Comparative studies of the secondary structures of six model proteins, adsorbed onto aluminum hydroxide gel (Alhydrogel) or in aqueous solution, were carried out by Fourier transform infrared (FTIR) spectroscopy. The analysis of high-quality spectra of all six model proteins, with a broad range of secondary structure compositions, obtained at 15 mg/ml by the conventional method and at 0.5 and 1.0 mg/ml adsorbed to Alhydrogel revealed that adsorption onto hydrophilic surfaces of aluminum hydroxide particles did not alter the secondary structures of the proteins. The results of this study suggest that adsorbing proteins to Alhydrogel provides a means of obtaining FTIR spectra to study secondary structure and conformational changes of proteins in aqueous solution at very low concentrations. The new procedure effectively lowers the concentration requirement for FTIR studies of proteins in aqueous solutions by at least 40-fold, as compared with the conventional FTIR method. It permits FTIR study of proteins to be carried out in the same concentration range as is used for circular dichroism and fluorescence, thereby making it possible to compare structural information obtained by three commonly used techniques in protein biophysical characterization.

Adsorption↗

Inhibition of bacterial adhesion on PVC endotracheal tubes by RF-oxygen glow discharge, sodium hydroxide and silver nitrate treatments.

Medical-grade poly(vinyl chloride) (PVC) was chemically modified to study how the incorporation of monovalent silver influences Pseudomonas aeruginosa adhesion and colonization. The modification investigated consisted of a radio frequency-oxygen (RF-O(2)) glow discharge pre-functionalization, followed by a two-step wet-treatment in sodium hydroxide and silver nitrate solutions. X-ray photoelectron spectroscopy (XPS) analysis and contact angle measurements were used to investigate the chemical nature and surface wettability of the films following each step of the modification. XPS analysis proved that the RF-O(2) plasma pre-functionalization of native PVC reproducibly increased the amount of functional groups representative of PVC additives, including ether/alcohol, esters and carboxyl groups. More specifically, we demonstrated that the O-C=O groups representative of the phthalic ester and zinc carboxylate additives identified for native PVC increased by two-fold following the RF-O(2) plasma pre-functionalization step. Although RF-O(2) pre-functionalization did not have an effect on the silver content of the NaOH/AgNO(3) treated substrates, such a modification was necessary for biomaterial products that did not have reproducible surfaces amongst production lots. XPS analysis also demonstrated that saponification with sodium hydroxide (NaOH) of esters, like those of the phthalic ester additives of PVC is a simple, irreversible method of hydrolysis, which produced sodium carboxylate and sodium phthalate salts. Exposure of native PVC to NaOH resulted in an increased surface hydrophilicity (from ca 90 degrees to ca 60 degrees ) due to dechlorination. XPS analysis following further incubation in silver nitrate demonstrated that silver ions can be trapped when the sodium of sodium carboxylate is replaced by silver after performing a second treatment with a monovalent silver-containing solution. The creation of silver salt on native PVC resulted in an ultra-hydrophobic (>120 degrees ) surface. The chemical modifications using NaOH and AgNO(3) wet treatments completely inhibited bacterial adhesion of four strains of P. aeruginosa to both native and oxygen-pre-functionalized PVC, and efficiently prevented colonization over longer periods (72 h). Our results suggest that surface modifications that incorporate silver ions would be extremely effective at reducing bacterial colonization to medical devices.

Bacterial Adhesion↗

Layered double hydroxide as an efficient drug reservoir for folate derivatives.

Folic acid derivatives such as folinic acid and methotrexate (MTX) have been successfully hybridized with layered double hydroxide (LDH) by ion-exchange reaction. The X-ray diffraction patterns and spectroscopic analyses indicate that these molecules intercalated into the hydroxide interlayer space are stabilized in the tilted longitudinal monolayer mode by electrostatic interaction. No significant changes in their structural and functional properties are found in the hybrids. The cellular uptake test of MTX-LDH hybrid is carried out in the fibroblast (human tendon) and SaOS-2 cell line (Osteosarcoma, human) by in vitro MTT (3-(4,5-dimethylthiazol-2-yl) 2,5-diphenyl tetrazolium bromide) assay. The initial proliferation of SaOS-2 cell is more strongly suppressed by treatment with MTX-LDH hybrid than with MTX alone. This study clearly shows that LDH not only plays a role as a biocompatible-delivery matrix for drugs but also facilitates a significant increase in the delivery efficiency.

Absorption↗

Analysis of hydroxide, inorganic sulphur species and organic anions in kraft pulping liquors by capillary electrophoresis.

A new method has been developed for the determination of hydroxide, sulphide, thiosulphate, sulphate, sulphite, chloride, oxalate and formate in kraft green, white and black liquors by capillary electrophoresis. The method provides baseline resolution of all analytes of interest using an electrolyte composed of 10 mM sodium chromate and 2 mM tetradecyltrimethylammonium hydroxide. Separations are conducted under constant current conditions at 25 degrees C and analytes are quantified by indirect UV-detection at 275 nm. A brief, post run wash of the capillary with 0.5 M NaOH and water gave improved inter- and intra-run repeatability of both migration times and peak areas. Sulphide and other oxysulphur species were relatively stable in white and green liquors diluted in helium-sparged water. However, sulphide present in black liquor samples diluted in the same solvent underwent rapid oxidation to form sulphite and thiosulphate. thereby precluding the measurement of all three anions. We discovered that quinone-type compounds present in black liquor catalyze the oxidation of sulphide and that the addition of reduced glutathione at a concentration of I mg/mL during black liquor dilution completely stabilized sulphide, sulphite and thiosulphate for at least one hour, thus allowing for quantitative analysis of the analytes. A mechanism is proposed to explain the action of both quinones and that of glutathione. Results obtained by the new method compared well with those obtained by ion chromatography, titrimetry, and from spike-recovery experiments.

Anions↗

Determination of total ribonucleotide pool in plant materials by high-pH anion-exchange high-performance liquid chromatography following extraction with potassium hydroxide.

A new, improved method that only requires a potassium hydroxide extraction procedure is presented for the analysis of a full nucleotide pool in plant materials. Quantification was performed by high-pH anion-exchange chromatography (HPAEC) with UV detection after a potassium hydroxide extraction, and allowed the quantification of 13 linear ribonucleotides in a single run. The method has been validated by comparison of six extraction methods and also by measurement of the intracellular nucleotide levels of three plant species (cell cultures and leaves). The evolution of the nucleotide pool of Nicotiana tabacum cell culture during growth has also been measured, and showed an increase in the pool until the fifth day, where the growth rate reaches a maximum, after which a decrease was observed.

Anion Exchange Resins↗

Trace anion determination in concentrated hydrofluoric acid solutions by two-dimensional ion chromatography II. Method performance study with a hydroxide eluent and a low noise suppressor.

The two-dimensional ion exclusion chromatography/ion chromatography (ICE-IC) approach is considered to be the method of choice for the determination of trace anions in concentrated hydrofluoric acid (48-50%, w/w). In order to achieve lower detection limits, this method was for the first time used with electrolytically generated and purified hydroxide eluents in combination with a low noise electrochemical suppressor. Compared to carbonate based eluents, the achieved gain in peak height sensitivity for chloride, sulfate, nitrate and phosphate is a factor of 6, 7, 16 and 13, respectively. The instrumental detection limits, based on the background noise, are 2, 0.2, 0.4 and 1.4 microg/kg HF 50% (w/w) for the same anions. Their method detection limits, calculated according to SEMI, are all within the 6-10microg/kg HF 50% (w/w) range and thus at least 10 times lower than the current Tier C grade requirements. The chromatographic run time could be shortened with some 10 min by the use of a relatively fast high-capacity hydroxide selective anion exchange column.

Anions↗

Selective adsorption of phosphate from seawater and wastewater by amorphous zirconium hydroxide.

Phosphate adsorption from single electrolyte (NaH2PO4), phosphate-enriched seawater, and model wastewater was studied using amorphous zirconium hydroxide, ZrO(OH)2(Na2O)0.05 1.5H2O, as an adsorbent. Batch experiments were carried out to investigate the adsorption of phosphate. The effect of pH on phosphate adsorption from seawater showed that the uptake of phosphate increased with an increase in pH up to 6, and then decreased sharply with a further increase in pH of the solution. The equilibrium data of phosphate adsorption were followed with a Freundlich isotherm. The uptake of phosphate at the adsorbent/solution ratio 0.05 g/2 L was 10 and 17 mg-P/g for the phosphate-enriched seawater and the model wastewater, respectively. A much higher adsorptivity toward phosphate ions in seawater was observed on ZrO(OH)2(Na2O)0.05 1.5H(2)O than on other representative adsorbents based on layered double hydroxides of Mg(II)-Al(III), Mg(II)-Fe(III), and Ni(II)-Fe(III). The effective desorption of phosphate ions on ZrO(OH)2(Na2O)0.05 1.5H2O could be achieved using a 0.1 M NaOH solution. The usefulness of experimental data for practical applications in removing phosphate in seawater and wastewater is discussed.

Adsorption↗

In vitro effects of calcium hydroxide and polymyxin B on endotoxins in root canals.

OBJECTIVES: To evaluate the effects of intracanal medicaments on endotoxins in root canals. METHODS: Seventy-five freshly extracted maxillary incisors were used in this study. The crowns of teeth were sectioned near the CEJ in order to standardize the root length to 14 mm. The root canals were instrumented to an apical size #50 file and irrigated with 1% sodium hypochlorite solution and sterilized with 60Co gamma irradiation. Standardized suspension containing Escherichia coli endotoxin was inoculated into the 60 root canals. The specimens were randomly assigned to 5 groups (n=15), according to the intracanal medicament used: (G1) calcium hydroxide; (G2) polymyxin B; (G3) combination neomycin-polymyxin B-hydrocortisone; (G4) positive control (no intracanal medicament); (G5) negative control (no endotoxin and no intracanal medicament). After 7 days, the detoxification of endotoxin was evaluated by Limulus lysate assay and antibody production in B-lymphocytes culture. RESULTS: Groups 1, 2 and 5 presented the best results by Limulus lysate and were significantly different to groups 3 and 4 (p<0.05). Stimulation of antibodies production in cell culture by groups 1 and 6 was smaller and statistically different than groups 2, 3, 4 and 5 (p<0.05). Groups 2 and 5 induced a small increase in the antibodies production in relation to the groups 1 and 6. Groups 3 and 4 induced a significant increase of antibodies production (p<0.05). CONCLUSIONS: The calcium hydroxide and polymyxin B intracanal medicaments detoxified endotoxin in root canals and altered the properties of LPS to stimulate the antibody production by B-lymphocytes. The combination neomycin-polymyxin B-hydrocortisone did not detoxified endotoxin.

Anti-Bacterial Agents↗

Study on adsorption of glyphosate (N-phosphonomethyl glycine) pesticide on MgAl-layered double hydroxides in aqueous solution.

MgAl-layered double hydroxides with different interlayer anions (nitrate, carbonate and chloride) were evaluated for their abilities to adsorb the organic pesticide glyphosate (N-phosphonomethyl glycine, Gly). The adsorption isotherms of Gly on layered double hydroxides (LDHs) nitrate were described by the Langmuir equation at lower equilibrium concentration of Gly (C(e)<1.0 mmol/L), and the Gly adsorption capacity on LDHs increased with the layer charge density, i.e. the structural Al3+/Mg2+ ratio. Gly adsorption on LDHs nitrate generally occurred through two processes, external surface adsorption and interlayer anion exchange. The adsorption amount on LDHs at C(e)=1.0 mmol/L decreased in the order of interlayer anions: Cl(-)>NO3(-)>CO3(2-).

Aluminum Compounds↗

Comment on "Factors influencing the removal of fluoride from aqueous solution by calcined Mg-Al-CO3 layered double hydroxides".

Lv et al. [L. Lv, J. He, M. Wei, D.G. Evans, X. Duan, Factors influencing the removal of fluoride from aqueous solution by calcined Mg-Al-CO3 layered double hydroxides, J. Hazard. Mater. B 133 (2006) 119-128] previously investigated the fluoride removal using calcined Mg-Al-CO3 layered double hydroxides (CLDH) as the sorbents. The present comment further discusses the mechanism of fluoride adsorption onto CLDH.

Adsorption↗

Hydroxide instead of bicarbonate in the structure of the oxygen evolving complex.

The energy diagram for the catalytic cycle of dioxygen evolution in photosystem II has been recomputed using a slightly different model than the one used previously, since the results showed an erroneous trend in the critical region from S(2) to S(3). By replacing the bicarbonate ligand, which was bridging between calcium and the outer manganese, by a hydroxide a significant improvement of the energy diagram is obtained. Most notably, the S(2) to S(3) transition is now exergonic as it should be. However, for the S(2)(0) state an artificial constraint is needed on the hydrogen bonding, indicating that there is still some problem with the model used. This hydroxide model was used to study the effects of replacing calcium with strontium, magnesium and cadmium. The computed results reproduce the results observed experimentally that magnesium and cadmium suppress water oxidation and that strontium slows it down. For both magnesium and cadmium the process stops already at S(2).

Bicarbonates↗

Aluminum hydroxide adjuvant induces macrophage differentiation towards a specialized antigen-presenting cell type.

Aluminum hydroxide (AlOOH) has been used for many years as a vaccine adjuvant, but little is known about its mechanism of action. We investigated in this study the in vitro effect of aluminum hydroxide adjuvant on isolated macrophages. We showed that AlOOH-stimulated macrophages contain large and persistent intracellular crystalline inclusions, a characteristic property of muscle infiltrated macrophages described in animal models of vaccine injection, as well as in the recently described macrophagic myofasciitis (MMF) histological reaction in humans. AlOOH-loaded macrophages exhibited phenotypical and functional modifications, as they expressed the classical markers of myeloid dendritic cells (HLA-DR(high)/CD86(high)/CD83(+)/CD1a(-)/CD14(-)) and displayed potent ability to induce MHC-II-restricted antigen specific memory responses, but kept a macrophage morphology. This suggests a key role of macrophages, in the reaction to AlOOH-adjuvanted vaccines and these mature antigen-presenting macrophages may therefore be of particular importance in the establishment of memory responses and in vaccination mechanisms leading to long-lasting protection.

Adjuvants, Immunologic↗

Evaluation of metal hydroxide sludge for reactive dye adsorption in a fixed-bed column system.

The capacity and performance of small-scale column, containing coarse particles of metal hydroxide sludge, were evaluated using 30mgl(-1) dye solutions of C.I. Reactive Red 141. The studied bed depths were 2.5-20cm and the studied flow rates were 1.1, 2.2 and 3.3mlmin(-1)cm(-2). At the breakthrough point of 0.1C(t)/C(0), the breakthrough volume was increased with increasing bed depth or decreasing flow rate, due to an increase in empty bed contact time (EBCT). The data followed the bed depth service time model, and the adsorption capacity was 24-26mgcm(-3) or 27-29mgdyesg(-1) adsorbent. The minimum bed depths should be higher 1.02, 2.04 and 2.59cm with flow rates of 1.1, 2.2 and 3.3mlmin(-1)cm(-2), respectively, while the ratio of bed depth to diameter should not be higher than 6. With EBCT above 5min, the usage rate of metal hydroxide sludge was 1.3gl(-1). Using the bed depth of 5cm and the flow rate of 0.55mlmin(-1)cm(-2), 87% of dominant colour, 78% of COD, and 99% of SS could be removed from the textile wastewater, and the leachate of toxic heavy metals was under the standard limitations.

Adsorption↗

Gas chromatographic quantitation of underivatized amines in the determination of their octanol-0.1 M sodium hydroxide partition coefficients by the shake-flask method.

The use of gas chromatography (GC) for the determination of 0.1 M sodium hydroxide-octanol partition coefficients (log P) for a wide variety of ethylamines is demonstrated. The conventional shake-flask procedure (SFP) is utilized, with the addition of an internal reference, which is cleanly separated from the desired solute and solvents on a 10% Apiezon L, 2% potassium hydroxide on 80-100 mesh Chromosorb W AW column. The partitioned solute is extracted from the aqueous phase with chloroform and analyzed by GC. The method provides an accurate and highly reproducible means of determining log P values, as demonstrated by the low relative standard errors. The technique is both rapid and extremely versatile. The use of the internal standard method of analysis introduces consistency, since variables like the exact weight of solute are not necessary (unlike the traditional SFP) and the volume of sample injected is not critical. The technique is readily accessible to microgram quantities of solutes, making it ideal for a wide range of volatile, amine-bearing compounds.

Chromatography, Gas↗

Determination of etoposide phosphate intermediates by gradient liquid chromatography using postcolumn derivatization with cuprammonium hydroxide.

Allyl 4,6-O-ethylidene-beta-D-glucopyranoside is an intermediate used in the synthesis of etoposide phosphate, a water-soluble derivative of the antineoplastic drug etoposide. In this paper, a method for the determination of allyl 4,6-O-ethylidene-beta-D-glucopyranoside and related glucopyranosides is described. Samples are analyzed by gradient high-performance liquid chromatography using postcolumn derivatization with cuprammonium hydroxide. The method is used to monitor the ethylidenation reaction of allyl beta-D-glucopyranoside with acetal to form allyl 4,6-O-ethylidene-beta-D-glucopyranoside. Samples are chromatographed on an octadecyl-bonded phase column with aqueous acetonitrile. Triethylamine is added to the mobile phase to accelerate mutarotation and suppress anomeric separations. The column effluent is mixed via a postcolumn tee with cuprammonium hydroxide and monitored with ultraviolet detection at 310 nm.

Antineoplastic Agents↗

Analysis of condensed phosphates in food products by ion chromatography with an on-line hydroxide eluent generator.

An ion chromatographic method with gradient elution using an automated eluent generator was developed for the simultaneous determination of condensed phosphates (CPs) such as orthophosphate (P1), pyrophosphate (P2), polyphosphate, trimetaphosphate and phytate in food products. The linear calibration curves for P1, P2, tripolyphosphate, and tetrapolyphosphate in the range 0.5-500 microM had a correlation factor of 0.999 or better. The precision of the method for the CP peak areas obtained with the hydroxide eluent generator was better than that obtained with potassium hydroxide eluents prepared off-line. This method was applied to the determination of CPs in food products such as ham, fish paste, and cheese extracted by trichloroacetic acid.

Chromatography, Liquid↗

Biochemical and clinical effects of the prophylactic treatment of renal calcium stones with magnesium hydroxide.

Prophylactic treatment with magnesium hydroxide ws instituted in 56 consecutive cases with renal calcium stones. The patients had been investigated previously with regard to the magnesium metabolism. The urinary magnesium excretion increased promptly and remained on a higher level during treatment. No changes were observed in the serum or urinary calcium concentrations. Most patients have undergone treatment for at least 2 years and 45 have been free of recurrences of formations of new stones. The mean stone episode rate during treatment was 0.03 stones per year compared to 0.8 stones per year before treatment was instituted. The natural history of stone disease also was followed in 34 patients with stones who had received no prophylactic therapy and 15 have experienced recurrences after 2 years. Therefore, in comparison, treatment with magnesium hydroxide appeared to reduce the recurrence rate. Apart from minor gastrointestinal discomfort no adverse effects were observed during treatment.

Adult↗

The hydroxide-assisted hydrolysis of cyanogen chloride in aqueous solution.

The hydrolysis of cyanogen chloride (ClCN) was studied as a function of temperature and pH. Results were used to resolve discrepancies among previously reported kinetic constants. The pH dependence was studied over a range of 9.54-10.93 at a temperature of 21.0 degrees C. The effect of temperature was investigated over the range of 10-30 degrees C at a pH of approximately 10. Changes in the concentrations of ClCN and the reaction products cyanic acid and chloride ion were monitored with time. For the conditions corresponding to these experiments, the hydroxide-assisted hydrolysis pathway predominated. Collision frequency factor and activation energies recommended to represent the hydrolysis of ClCN in aqueous solution are A = 2.06 x 10(11) M-1 s-1 and Ea = 60,980 J mol-1 for the hydroxide-ion-assisted reaction, and A = 9.97 x 10(8) s-1 and Ea = 87,180 J mol-1 for the water-assisted reaction.

Cyanides↗