Search PubMed⌕ Search

Biomedical subjects

W Kiefer

Publications and source records attributed to W Kiefer.

At least 37 records · Page 2Linked to original sources

P-N bond length alterations monitored by infrared absorption and Fourier transform Raman spectroscopy in combination with density functional theory calculations.

Fourier transform (FT) Raman and infrared spectroscopy in combination with density functional theory calculations have been applied to the vibrational characterization of the dimeric zinc diphenylphosphanyl(trimethylsilyl)amide complex [(Me3Si)2NZnPh2PNSiMe3]2 and the ortho-metallated species [Li(o-C6H4PPh2NSiMe3)]2 x Et2O in relation to their parent starting materials diphenylphosphanyl (trimethylsilyl)amine Ph2P-N(H)SiMe3 and iminophosphorane Ph3P=NSiMe3. The spectroscopic changes evidenced in the spectra were correlated with the structural parameters in order to provide insight as to what extent the P-N bond is affected by the coordination to the metal center. The employment of density functional theory (DFT) calculations in addition to these spectroscopic methods offers the possibility of predicting whether the Lewis-basic imido nitrogen atom is involved in coordination not only in the solid state, but also in the gas phase.

Chemical Phenomena↗

Crystal-smectic G transformation investigated by temperature-dependent Raman study.

We report on a temperature-dependent Raman study of terephthalidine-bis-butylaniline (TBBA) and terephthalidine-bis-heptylaniline (TB7A) in the temperature range 10-406 K and in the wavenumber regions 1120-1240 cm-1 and 1500-1700 cm-1. The variations of peak positions and linewidths of several Raman marker bands with temperature, which clearly show crystal-SmG transition at approximately 334 K, have been used to discuss the dynamics of this phase transition. The temperature-dependent Raman study revealed that the increased vibration of the long alkyl tail and the rotation around the long molecular axis are the two primary phenomena responsible for the crystal-SmG transition. Density functional theory (DFT) at the B3LPY/6-31G(d) level was employed to obtain the optimized geometry and the harmonic vibrational wavenumbers of TBBA. The eigenvectors of the modes corresponding to these marker bands were also calculated.

Aniline Compounds↗

Raman spectroscopy investigation of biological materials by use of etched and silver coated glass fiber tips.

The results for surface enhanced Raman scattering (SERS) studies on biological samples are reported. Etched and silver coated glass fiber tips were used as a SERS substrate. This method enabled the recording of spectra of biological samples, such as plant tissue or microbiological cells, with a high spatial resolution. Because of the low laser power used with the fiber tips, it was even possible to investigate tissues that are very sensitive toward laser power as it is used in a common micro-Raman setup.

Glass↗

Femtosecond coherent Raman spectroscopy and its application to porphyrins.

The results on femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) experiments for the analysis and control of ground state vibrational dynamics of porphyrin systems are briefly reviewed. By detecting the spectrum of the transient CARS signal, a detailed mapping of the dynamics initiated by the stimulated Raman pump process is achieved. The method yields the dephasing behavior and spectral information of the investigated system at the same time. The different contributions to the ground state vibrational dynamics are selected by changing the direction of the CARS signal analyzer in the polarization arrangement used.

Binding Sites↗

Chemotaxonomy of mints of genus Mentha by applying Raman spectroscopy.

The characterization of mints is often problematic because Mentha is a taxonomically complex genus. In order to provide a fast and easy characterization method, we use a combination of micro-Raman spectroscopy and hierarchical cluster analysis. A classification trial of different mint taxa is possible for one collection time. For spectra measured at different points during the growing season, a more sophisticated pretreatment of the data is necessary to receive good discrimination between the species, as well as between the subspecies and varieties of the mints.

Algorithms↗

Laser scanning microscopy study on adsorption of biologically relevant proteins on implant materials.

The adsorption of proteins at implant surfaces plays a key role in osseointegration and is therefore of great importance in biomaterial science. Laser scanning microscopy (LSM) is described, a method that is used here for the first study of the adsorption of proteins on implant surfaces. These LSM measurements provide information on the surface morphology, and the spatial distribution of adsorbed proteins can be deduced.

Adsorption↗

Simultaneous determination of olanzapine, clozapine and demethylated metabolites in serum by on-line column-switching high-performance liquid chromatography.

An automated method for simultaneous routine quantification of the antipsychotic drugs clozapine, olanzapine and their demethylated metabolites is described. The method included adsorption on a cyanopropyl (CPS) coated clean-up column (10 microm; 10 x 2.0 mm I.D.), washing off interfering serum constituents to waste, and separation on C18 ODS Hypersil reversed phase material (5 microm; 250 x 4.6 mm I.D.) using acetonitrile-water-tetramethylethylenediamine (37:62.6:0.4, v/v/v) adjusted to pH 6.5 with concentrated acetic acid. UV-detection was performed at 254 nm. The limit of quantification was 10-20 ng/ml. Relative day to day standard variations ranged between 4.5 and 13.5%. The method is suitable for routine monitoring of olanzapine and clozapine including their demethylated metabolites.

Antipsychotic Agents↗

Detection of pesticide model compounds in ethanolic and aqueous microdroplets by nonlinear Raman spectroscopy.

Pesticide model compounds are detected in microdroplets by means of in situ nonlinear Raman spectroscopy. The chloro- and nitro-substituted aromatics are dissolved in ethanol as well as in water. Their vibrational spectroscopic fingerprint, that is, Raman bands characteristic of the functional groups attached to the aromatic system, is determined in bulk medium by linear Raman spectroscopy. As a result of the concept of group vibrations, the chosen compounds can be regarded as representatives for a whole class of pesticides containing these residues. External seeding of stimulated Raman scattering (SRS) is applied for the detection of these group vibrations of the pesticide model compounds. This technique can be utilized for in situ diagnostics and a noninvasive vibrational spectroscopic analysis of the chemical composition of microdroplets with natural or anthropogenic origin.

Journal Article↗

Raman and surface enhanced Raman spectroscopy of 2,2,5,5-tetramethyl-3-pyrrolin-1-yloxy-3-carboxamide labeled proteins: bovine serum albumin and cytochrome c.

2,2,5,5-Tetramethyl-3-pyrrolin-1-yloxy-3-carboxamide (tempyo) labeled bovine serum albumin and cytochrome c at different pH values were prepared and investigated using Raman-resonance Raman (RR) spectroscopy and surface enhanced Raman scattering (SERS) spectroscopy. The Raman spectra of tempyo labeled proteins in the pH 6.7-11 range were compared to those of the corresponding free species. The SERS spectra were interpreted in terms of the structural changes of the tempyo labeled proteins adsorbed on the silver colloidal surface. The tempyo spin label was found to be inactive in the Raman-RR and SERS spectra of the proteins. The alpha-helix conformation was concluded to be more favorable as the SERS binding site of bovine serum albumin. In the cytochrome c the enhancement of the bands assigned to the porphyrin macrocycle stretching mode allowed the supposition of the N-adsorption onto the colloidal surface.

Animals↗

Cyclooxygenase inhibitors--current status and future prospects.

Prostaglandins are formed from arachidonic acid by the action of cyclooxygenase and subsequent downstream synthetases. Two closely related forms of the cyclooxygenase have been identified which are now known as COX-1 and COX-2. Both isoenzymes transform arachidonic acid to prostaglandins, but differ in their distribution and their physiological roles. Meanwhile, the responsible genes and their regulation have been clarified. COX-1, the pre-dominantly constitutive form of the enzyme, is expressed throughout the body and performs a number of homeostatic functions such as maintaining normal gastric mucosa and influencing renal blood flow and platelet aggregation. In contrast, the inducible form is expressed in response to inflammatory and other physiological stimuli and growth factors, and is involved in the production of the prostaglandins that mediate pain and support the inflammatory process. All the classic NSAIDs inhibit both COX-1 and COX-2 at standard anti-inflammatory doses. The beneficial anti-inflammatory and analgesic effects are based on the inhibition of COX-2, but the gastrointestinal toxicity and the mild bleeding diathesis are a result of the concurrent inhibition of COX-1. Agents that inhibit COX-2 while sparing COX-1 represent a new attractive therapeutic development and could represent a major advance in the treatment of rheumatoid arthritis and osteoarthritis. Apart from its involvement in inflammatory processes, COX-2 seems to play a role in angiogenesis, colon cancer and Alzheimer's disease, based on the fact that it is expressed during these diseases. The benefits of specific and selective COX-2 inhibitors are currently under discussion and offer a new perspective for a further use of COX-2 inhibitors.

Animals↗

Fourier-transform Raman and infrared spectroscopic analysis of dipyrrinones and mesobilirubins.

The Fourier-transform Raman (FT-Raman), infrared (FT-IR), and UV-visible absorption spectra of four dipyrrinones and two mesobilirubins have been investigated in the solid state and in CH2Cl2 solutions. A detailed spectral analysis, assignment and discussion of these spectra are presented. The bands at 1735-1738, 1691-1707 and 1359-1377 cm(-1) which were assigned to the stretching vibrations of the C-O-C and C-O-H and symmetric deformation of C-H bonds, respectively, can act as a marker to distinguish the compounds of this class. The striking differences between the spectra of the compounds suggest that mesobilirubin XIIIalpha is tending to adopt as ridge-tile conformation, rather than linear conformation.

Bilirubin↗

Fourier-transform Raman and infrared spectroscopic analysis of novel biliverdin compounds.

The vibrational spectroscopy of novel biliverdin compounds were studied by Fourier-transform Raman (FT-Raman) and infrared (FT-IR) spectroscopy. The effects of type, length and position of substituents at C(8) and C(12) or C(1) and C(19) of tetrapyrroles on FT-Raman and FT-IR spectra of these compounds, are discussed. The marker bands are developed in order to distinguish between etiobiliverdin and mesobiliverdin.

Biliverdine↗

Effect of flavonol derivatives on the carrageenin-induced paw edema in the rat and inhibition of cyclooxygenase-1 and 5-lipoxygenase in vitro.

Alkoxyflavonols were synthesized by the Algar-Flynn-Oyamada (AFO) cyclization of chalcones. Hydroxyflavonols were prepared by dealkylation of methoxyflavonols by refluxing in hydroiodic acid. The alkoxyflavonols 3-hydroxy-2-(2,3,4-trimethoxyphenyl)-4H-chromen-4-one (6), 2-(4-ethoxyphenyl)-3-hydroxy-4H-chromen-4-one (7), 2-(4-butoxyphenyl)-3-hydroxy-4H-chromen-4-one (10), and 2-(3-n-butoxyphenyl)-3-hydroxy-4H-chromen-4-one (11) as well as the trihydroxy derivative 3-hydroxy-2-(3,4,5-trihydroxyphenyl)-4H-chromen-4-one (18) displayed high anti-inflammatory activity in carrageenin-induced rat paw edema. Additionally, the inhibition of enzymes of the arachidonic acid cascade by the derivatives was investigated in vitro. In contrast to the natural compound quercetin, the compounds were more potent inhibiting cyclooxygenase-1 than 5-lipoxygenase except for 3-hydroxy-7-methoxy-2-(4-methoxyphenyl)-4H-chromen-4-one (5). No correlation between the anti-inflammatory activity in the rat paw edema test and the inhibition of 5-lipoxygenase or cyclooxygenase-1 could be observed. In conclusion, the present results suggest that other effects than inhibition of these enzymes of the arachidonic acid cascade are important for the anti-inflammatory activity of the investigated alkoxyflavonols.

Animals↗

The pyrrole moiety as a template for COX-1/COX-2 inhibitors.

Aroyl- and thiophene-substituted pyrrole derivatives have been synthesized as a new class of COX-1/COX-2 inhibitors. The inhibition of COX-1 was evaluated in a biological system using bovine PMNLs as the enzyme source, whereas LPS-stimulated human monocytes served as the enzyme source for inducible COX-2. The determination of the concentration of arachidonic acid metabolites was performed by HPLC for COX-1 and RIA for COX-2. Variation of the substitution pattern led to a series of active compounds which showed inhibition for COX-1 and COX-2. Structural requirements for the development of COX-1/COX-2 inhibitors are discussed.

Animals↗

Elastic light scattering from single microparticles on a femtosecond time scale.

Experimentally measured and theoretically calculated elastic light-scattering spectra from single microparticles illuminated by 100-fs pulses are presented. Although in the theoretical calculation only a single incoming femtosecond laser pulse was used, the spectral behavior of scattered light shows all the features seen in the experimental spectrum from many femtosecond pulses, including morphology-dependent resonances (MDR's). The good agreement between experimental and theoretical elastic light-scattering data has stimulated a theoretical investigation of the time-dependent behavior of the elastically scattered light from a single microparticle on a femtosecond time scale. Since the spatial pulse length of the incoming laser pulse is smaller than the particle circumference, the temporal behavior of reflection, diffraction, refraction, and coupling into MDR's can be distinguished. Since the time-dependent scattering is strongly dependent on particle size, refractive index, and pulse chirp, it may be possible to encode several bits of information into a single laser pulse and therefore to increase optical data communication rates.

Elasticity↗

Vibrational spectroscopic study of tetracalcium phosphate in pure polycrystalline form and as a constituent of a self-setting bone cement.

Polycrystalline tetracalcium phosphate (TTCP), a material of considerable interest for human implantation due to its similarity to hydroxyapatite, was studied by means of Raman and FT-IR spectroscopy. The spectra were interpreted on the basis of group theoretical considerations. In addition, the setting reaction of a calcium phosphate cement (CPC) consisting of an equimolar mixture of TTCP and dicalcium phosphate (DCPA) was investigated by Raman spectroscopy. The band of the totally symmetric phosphate mode v1 of TTCP showed marked factor group splittings. The splitting components arose at coincident wave numbers in the IR and Raman spectra. This observation was in accordance with space group P2(1) (factor group C2(2), Z = 4). The characteristic splitting of v1 allowed the setting reaction of CPC to hydroxyapatite to be followed. According to the Raman spectroscopic results, considerable amounts of TTCP must be present at the sample surface after 24 h of setting in an aqueous environment.

Biocompatible Materials↗

FT-Raman investigation of alkaloids in the liana Ancistrocladus heyneanus.

The applicability of the micro-FT-Raman technique for studying alkaloids in vitro and for observing alkaloids in plant cells is demonstrated. This technique is examined using fresh plant material of Ancistrocladus heyneanus, a tropical liana known to produce pharmacologically interesting naphthylisoquinoline alkaloids as secondary metabolites. It will be shown that it is possible to localize and identify some of these alkaloids in different parts of the plant by means of Raman microspectroscopic studies. Data on the in situ structure and the spatial distribution can be obtained, which could provide information about the biosynthesis of the alkaloids in the plant.

Alkaloids↗