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Physicochemical and crystallographic characterization of mefenamic acid complexes with alkanolamines.

The preparation of mefenamic acid (MH)-alkanolamine (propanolamine, diethanolamine, triethanolamine) complexes was attempted to increase the transdermal flux of MH. Differential scanning calorimetry, Fourier transform infrared spectroscopy, and X-ray crystallographic studies demonstrated that MH and each alkanolamine formed an ion pair complex. The series of amine complexes had a lower melting point and higher solubility in water compared with pure MH.

Alkanes↗

Novel micropelletization technique: highly improved dissolution, wettability and micromeritic behavior of domperidone.

The aim of the investigation is to improve the dissolution, wettability, and micromeritic behavior of domperidone, a dopamine antagonist, used in the treatment of nausea and vomiting. Micropelletization technique, a possible approach for ensuring maximum dissolution with enhanced wettability, and uniform pellet size almost spherical so as to achieve the smooth gastric transit of drug have been estimated. Micropellets were prepared utilizing solvent diffusion technique and all the process parameters such as solvent-non-solvent ratio, stirring speed, temperature, and effect of aggregating agent on the micropellets formulation have been optimized. The addition of an aggregating agent (10%v/v of isopropyl alcohol) improved the uniform micropellets formation and the method was reproducible. The micromeritic properties such as size distribution, surface property (using Scalar-USB digital photomicroscope), packability, and flowability of the formulated micropellets were characterized. Fourier transform infrared spectroscopy (FTIR) and Differential scanning calorimetric (DSC) analysis were performed to explain the results. Formulated micropellets showed clear and highly improved in vivo dissolution behavior, probably due to high wettability. The micropelletized drug was stable at room temperature, 25 degrees C/60% relative humidity (RH), and 45 degrees C/70% RH, after 12 weeks.

Calorimetry, Differential Scanning↗

Detecting the chemoselective ligation of peptides to silicon with the use of cobalt-carbonyl labels.

While fluorescent-based methods are generally used to detect the immobilization and the interactions of biomolecules to solid supports, recent studies have shown their limitations in the case of silicon surfaces. As an alternative, we investigated the synthesis of peptides labeled with a metal transition complex and their subsequent immobilization to the silicon surfaces. The feasibility of using such probes has been explored by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). By starting with hydrogen-terminated or oxidized silicon surfaces, we functionalized those surfaces with semicarbazide groups and showed the site-specific linkage of glyoxylyl peptides labeled with a Co2(CO)6 moiety.

Cobalt↗

Near- versus mid-infrared diffuse reflectance spectroscopy for determination of minerals in dried poultry manure.

The objective of this study was to determine if accurate calibrations for mineral content in dried poultry manures could be developed using near- or mid-infrared spectra. Samples (n = 124) were obtained from a commercial testing laboratory along with conventionally determined values for Ca, Cu, K, Mg, Mn, P, S, and Zn. Samples were blended in a food blender, dried at 60 C, ground to 20 mesh, and scanned in the near-infrared (rotating sample cup) on a scanning monochromator. Samples were also scanned in the mid-infrared on a Fourier transform spectrometer using a custom-made sample transport. Results showed that calibrations based on nearor mid-infrared spectra were not satisfactory for the accurate determination of Ca, Cu, K, Mg, Mn, P, S, or Zn in dried poultry manures. At best, most of the calibrations would be suitable for only gross estimates, although the mid-infrared calibration for P might be suitable for some needs in which only a limited degree of accuracy was needed. Either spectral range could be used to separate dried poultry manure samples into those containing less than 3% and greater than 8% Ca but not to accurately differentiate samples within those two groupings. Finally, although the mid-infrared calibrations were the more accurate for five of the eight minerals studied, the differences between the two sets of calibrations were so varied that it would be difficult to say that one region is better for mineral content measurement.

Animals↗

Self-assembling organic nanotubes based on a cyclic peptide architecture.

Hollow tubular structures of molecular dimensions may offer a variety of applications in chemistry, biochemistry and materials science. Concentric carbon nanotubes have attracted a great deal of attention, while the three-dimensional tubular pore structures of molecular sieves have long been exploited industrially. Nanoscale tubes based on organic materials have also been reported previously. Here we report the design, synthesis and characterization of a new class of organic nanotubes based on rationally designed cyclic polypeptides. When protonated, these compounds crystallize into tubular structures hundreds of nanometres long, with internal diameters of 7-8 A. Support for the proposed tubular structures is provided by electron microscopy, electron diffraction, Fourier-transform infrared spectroscopy and molecular modelling. These tubes are open-ended, with uniform shape and internal diameter. We anticipate that they may have possible applications in inclusion chemistry, catalysis, molecular electronics and molecular separation technology.

Amino Acid Sequence↗

[The application of infrared spectra and clustering analysis in the discrimination of geographical origin of Flos Chrysanthemi].

OBJECTIVE: To identify the origin of Flos Chrysanthemi. METHODS: FTIR (Fourier transform infrared spectroscopy) and SIMCA (sofe independent modeling of class analogy). RESULTS: The correctness of every classification was higher than 60%. CONCLUSION: This approach was proved to be a reliable and practicable method for the discrimination of geographical origin of Chrysanthemum.

Chrysanthemum↗

Structural changes of pharaonis phoborhodopsin upon photoisomerization of the retinal chromophore: infrared spectral comparison with bacteriorhodopsin.

Archaeal rhodopsins possess a retinal molecule as their chromophores, and their light energy and light signal conversions are triggered by all-trans to 13-cis isomerization of the retinal chromophore. Relaxation through structural changes of the protein then leads to functional processes, proton pump in bacteriorhodopsin and transducer activation in sensory rhodopsins. In the present paper, low-temperature Fourier transform infrared spectroscopy is applied to phoborhodopsin from Natronobacterium pharaonis (ppR), a photoreceptor for the negative phototaxis of the bacteria, and infrared spectral changes before and after photoisomerization are compared with those of bacteriorhodopsin (BR) at 77 K. Spectral comparison of the C--C stretching vibrations of the retinal chromophore shows that chromophore conformation of the polyene chain is similar between ppR and BR. This fact implies that the unique chromophore-protein interaction in ppR, such as the blue-shifted absorption spectrum with vibrational fine structure, originates from both ends, the beta-ionone ring and the Schiff base regions. In fact, less planer ring structure and stronger hydrogen bond of the Schiff base were suggested for ppR. Similar frequency changes upon photoisomerization are observed for the C==N stretch of the retinal Schiff base and the stretch of the neighboring threonine side chain (Thr79 in ppR and Thr89 in BR), suggesting that photoisomerization in ppR is driven by the motion of the Schiff base like BR. Nevertheless, the structure of the K state after photoisomerization is different between ppR and BR. In BR, chromophore distortion is localized in the Schiff base region, as shown in its hydrogen out-of-plane vibrations. In contrast, more extended structural changes take place in ppR in view of chromophore distortion and protein structural changes. Such structure of the K intermediate of ppR is probably correlated with its high thermal stability. In fact, almost identical infrared spectra are obtained between 77 and 170 K in ppR. Unique chromophore-protein interaction and photoisomerization processes in ppR are discussed on the basis of the present infrared spectral comparison with BR.

Archaeal Proteins↗

Degradation of mechanical properties of UHMWPE acetabular liners following long-term implantation.

We tested the hypothesis that the mechanical and chemical behavior of gamma radiation-sterilized ultrahigh-molecular-weight polyethylene (UHMWPE) changes after implantation. Relationships between the mechanical behavior and oxidation index were explored in a cohort of 16 consecutive traceable Hexloc acetabular components (Biomet, Warsaw, IN) that were machined from extruded, stearate-containing UHMWPE and gamma sterilized in air. Shelf aging time (average, 0.4 years) and implantation time (average, 11.5 years) were determined for all 16 inserts. The retrieved liners exhibited significant mechanical degradation, which was most severe in the unloaded surface regions. Analysis of the Fourier transform infrared spectroscopy data revealed a significant association between the oxidation index and mechanical degradation of the UHMWPE. The results of this study strongly support the hypothesis that the degradation of mechanical properties for the liners occurred during implantation.

Adult↗

Composition and structure of agents responsible for development of water repellency in soils following oil contamination.

Soil from the Ellerslie site of experimental oil contamination in Alberta developed water repellency some years after initial remediation. The water-repellent soils were compared to clean soils and contaminated but wettable soils by solid-state nuclear magnetic resonance (NMR). The effects of extraction with CH2Cl2 (for petroleum hydrocarbons), NaOH (for natural organic matter), and 2-propanol/ammonia (IPA/NH3) on wettability were evaluated by the molarity of the ethanol droplet (MED) test. Soil extracts and whole soils, after extraction, were examined using NMR and Fourier transform infrared spectroscopy (FTIR). On the basis of the structure--MED correlations, a model of a thin-layer natural organic matter--petroleum products complex formed under strong drying conditions is proposed to account for the development of water repellency. Studies of two similar soils from accidental oil spills are supportive.

Environmental Pollution↗

Characterization of the oligomeric states of insulin in self-assembly and amyloid fibril formation by mass spectrometry.

The self-assembly and aggregation of insulin molecules has been investigated by means of nanoflow electrospray mass spectrometry. Hexamers of insulin containing predominantly two, but up to four, Zn(2+) ions were observed in the gas phase when solutions at pH 4.0 were examined. At pH 3.3, in the absence of Zn(2+), dimers and tetramers are observed. Spectra obtained from solutions of insulin at millimolar concentrations at pH 2.0, conditions under which insulin is known to aggregate in solution, showed signals from a range of higher oligomers. Clusters containing up to 12 molecules could be detected in the gas phase. Hydrogen exchange measurements show that in solution these higher oligomers are in rapid equilibrium with monomeric insulin. At elevated temperatures, under conditions where insulin rapidly forms amyloid fibrils, the concentration of soluble higher oligomers was found to decrease with time yielding insoluble high molecular weight aggregates and then fibrils. The fibrils formed were examined by electron microscopy and the results show that the amorphous aggregates formed initially are converted to twisted, unbranched fibrils containing several protofilaments. Fourier transform infrared spectroscopy shows that both the soluble form of insulin and the initial aggregates are predominantly helical, but that formation of beta-sheet structure occurs simultaneously with the appearance of well-defined fibrils.

Amyloid↗

7S globulins from Phaseolus vulgaris L.: Impact of structural aspects on the nutritional quality.

7S globulins were extracted from common bean (Phaseolus vulgaris L.) seeds and characterized. SDS-PAGE showed major bands corresponding to the phaseolin subunits (43-53 kDa). An amino acid analysis indicated that, in spite of the limited amounts of sulphur amino acids and tryptophan, the globulins contained very high levels of essential amino acids. The protein solubility profiles of native and denatured (120 degrees C for 20 min) 7S globulins in water and in 0.5 M NaCl showed that NaCl had a limited effect on increasing the solubility of either the native or denatured proteins. The in vivo small intestinal digestibility of the 7S globulins was 90%, this being decreased to 86% after a thermal treatment. Fourier transform infrared spectroscopy revealed a high content of beta-sheet and beta-turn structures, together with a contribution at 1687 cm(-1) that was assigned to intramolecular beta-sheets. These features are diagnostic of a high propensity to irreversible aggregation that may be related to an adverse effect on the protein quality.

Amides↗

A preliminary investigation of the stages of adipocere formation.

Adipocere is a postmortem decomposition product which forms from a body's adipose tissue. This study aimed to chemically demonstrate the process of conversion from adipose tissue to adipocere. Samples of adipocere were collected from pig cadavers that were allowed to decompose for varying intervals. Samples of soil were collected from beneath the cadavers and analyzed to determine the leaching effect of adipocere. Gas chromatography/mass spectrometry (GC/MS) was used to quantify the fatty acid composition of pig adipocere. Fourier transform infrared spectroscopy (FTIR) was used as a confirmatory test and to identify other components such as triglycerides and calcium salts of fatty acids. The study demonstrates the process of adipocere formation and the stages of formation through which the process passes using chemical techniques.

Adipose Tissue↗

Development of an ophthalmic formulation containing ciprofloxacin-hydroxypropyl-b-cyclodextrin complex.

Ophthalmic formulations of ciprofloxacin were formulated using inclusion complexes of ciprofloxacin HCl (CFLX HCl) and hydroxypropyl-beta-cyclodextrin (HP-beta-CD). The complexes were prepared by the method of freeze drying and evaluated by phase solubility studies, differential scanning calorimetry, powder X-ray diffractiometry, fourier transform infrared spectroscopy and scanning electron microscopy. The ophthalmic solutions formulated using the complexed drug exhibited better stability, biological activity and ocular tolerance in comparison to another ophthalmic solution formulated using uncomplexed drug and also in comparison to a marketed preparation.

2-Hydroxypropyl-beta-cyclodextrin↗

Inhibition of initial adhesion of uropathogenic Enterococcus faecalis by biosurfactants from Lactobacillus isolates.

In this study, 15 Lactobacillus isolates were found to produce biosurfactants in the mid-exponential and stationary growth phases. The stationary-phase biosurfactants from lactobacillus casei subsp. rhamnosus 36 and ATCC 7469, Lactobacillus fermentum B54, and Lactobacillus acidophilus RC14 were investigated further to determine their capacity to inhibit the initial adhesion of uropathogenic Enterococcus faecalis 1131 to glass in a parallel-plate flow chamber. The initial deposition rate of E. faecalis to glass with an adsorbed biosurfactant layer from L. acidophilus RC14 or L. fermentum B54 was significantly decreased by approximately 70%, while the number of adhering enterococci after 4 h of adhesion was reduced by an average of 77%. The surface activity of the biosurfactants and their activity inhibiting the initial adhesion of E. faecalis 1131 were retained after dialysis (molecular weight cutoff, 6,000 to 8,000) and freeze-drying. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that the freeze-dried biosurfactants from L. acidophilus RC14 and L. fermentum B54 were richest in protein, while those from L. casei subsp. rhamnosus 36 and ATCC 7469 had relatively high polysaccharide and phosphate contents.

Bacterial Adhesion↗

Crystallization and preliminary X-ray diffraction data of two different human low-density lipoprotein (LDL) subfractions.

Human LDL subfractions LDL-2 (d = 1.031-1.034 g/ml) and LDL-5 (d = 1.040-1.044 g/ml) were crystallized in two different crystal forms by using polyethylene glycol as a precipitant. Both fractions were from one donor. Crystals of LDL-5 were yellow, hexagonal, and showed no dichroism. Crystals of LDL-2 were of the same color, had a rodlike shape with notches at both ends, and were highly dichroitic. LDL-2 crystals diffracted to a resolution of 29 A by using synchrotron radiation. Indexing in P1 resulted in preliminary parameters for the reduced cell of a = 171 A, b = 438 A, c = 519 A, alpha = 102 degrees, beta = 99 degrees, gamma = 91. These dimensions are consistent with the size of LDL particles. Using Fourier transform infrared spectroscopy (FTIR) and agarose gel electrophoresis, we could further confirm that the crystals consist of LDL. The FTIR spectrum showed bands characteristic for lipids and protein. Dissolved crystals exhibited a mobility similar to native LDL in agarose gels and could be stained with anti-human apolipoprotein B (apoB).

Crystallization↗

Spectral characterization of apatite formation on poly(2-hydroxyethylmethacrylate)-TiO2 nanocomposite film prepared by sol-gel process.

Poly(2-hydroxyethylmethacrylate) films incorporated with titanium dioxide nanoparticles were successfully synthesized by an in situ sol-gel process. The in vitro bioactive properties of the films were assessed after immersion in simulated body fluid for up to 21 days through biomimetic method. Hydroxyapatite formation was observed on the surfaces of nanocomposites. This indicates that prepared composites are bioactive. Fourier transforms infrared spectroscopy, X-ray diffraction patterns, X-ray photoelectron spectroscopy and scanning electron microscope images confirm the hydroxyapatite formation on nanocomposite. The present study provides an analytical method for the assessment of titanium dioxide nanoparticles filled poly(2-hydroxyethylmethacrylate) polymer nanocomposites for biomedical applications.

Apatites↗

Stability of crystalline proteins.

By using two model proteins, glucose oxidase and lipase, we demonstrate that dry crystalline formulations are significantly more stable than their amorphous counterparts. The results of Fourier-transform infrared spectroscopy indicate that crystalline proteins better maintain their native conformation in accelerated stability studies. The lower tendency of crystalline proteins to aggregate is confirmed by size-exclusion chromatography. The data suggest that protein crystallization may significantly improve some aspects of protein handling, and change the way biopharmaceuticals are produced, formulated, and delivered.

Chromatography, Gel↗

Multiunit controlled-release diclofenac sodium capsules using complex of chitosan with sodium alginate or pectin.

This study explored the application of chitosan-alginate (CA) and chitosan-pectin (CP) complex films as drug release regulator for the preparation of multiunit controlled-release diclofenac sodium capsules. Pellets containing drug and microcrystalline cellulose, in a ratio of 3:5, were prepared in a fluidized rotary granulator. The pellets were coated with CA, CP, sodium alginate, pectin, and chitosan solutions. The pellets, equivalent to 75 mg drug, were filled into capsules. After 2 h of dissolution test in acidic medium, the amount of the drug released from any preparation was negligible. The pellets were further subject to pH 6.8 phosphate buffer More than 80% drug release at 12 h was observed with the uncoated pellets and those coated with sodium alginate, pectin or chitosan. Both 1% CA and 3% CP coated pellets exhibited drug release profiles similar to that of Voltaren SR75. It was found that approximately 60% and 85% of the drug were released at 12 and 24 h, respectively. Both Differential thermal analysis (DTA) and Fourier transform infrared spectroscopy (FTIR) analyses revealed complex formation between chitosan and these anionic polymers. It could be concluded that CA and CP complex film could be easily applied to diclofenac sodium pellets to control the release of the drug.

Alginates↗