RESUMEN
Polysilyne with repeating disilyne units, a silicon analogue of polyacetylene, has a high potential for application to various novel silicon-based electronic devices because of the unique properties of Si=Si units with a smaller HOMO-LUMO energy gap than that of C=C units. However, one-dimensional (1D) polysilyne has not been synthesized yet. Here we propose a planar and air-stable two-dimensional (2D) silicon-based material with one-atom thickness consisting of beryllium-bridged 1D all-trans polysilyne, based on the first-principles calculations. The flat structure of 1D polysilyne, which is essential for the air stability of silicon π-electron conjugated systems, is realized by embedding polysilyne in a planar sheet. It was found that the 2D crystal optimized at the rhombus unit cell with the D2h group symmetry is a silicon-based Dirac semimetal with linear dispersion at the Fermi energy and hosts anisotropic Dirac fermions.
RESUMEN
Van der Waals (VDW) interactions provide fantastic properties for biological systems that function at room temperature. The VDW interaction, which primarily contributes to weak hydrogen bonding, is expected to play a key role in regulating hydrophobic hydration to express the biologically inert biocompatible function of polymerized MPCs (2-methacryloyloxyethyl phosphorylcholine). This report explores at the molecular level the biologically inert function of polymerized MPCs through an array of vibrational spectroscopic and computational characterization of MPC monomers, as temperature-dependent change of intramolecular weak hydrogen bonding. Synchrotron Fourier transform infrared microspectroscopy and terahertz time-domain spectroscopy were used to investigate temperature-dependent spectral changes in the low frequency vibrations of the MPC over the temperature range from cryogenic to room temperature, and the results were analysed by highly reliable well-established density functional theory (DFT) calculations. Complicated spectral features in the low frequency energy region and the uncertain conformations of the MPC in the amorphous powder state are clearly resolved under a polarizable continuum model and dispersion correction to pure DFT calculations.
Asunto(s)
Polímeros , Enlace de Hidrógeno , Conformación Molecular , Interacciones Hidrofóbicas e HidrofílicasRESUMEN
The emergence of flat one- and two-dimensional materials, such as graphene and its nanoribbons, has promoted the rapid advance of the current nanotechnology. Silicene, a silicon analogue of graphene, has the great advantage of its compatibility with the present industrial processes based on silicon nanotechnology. The most significant issue for silicene is instability in the air due to the nonplanar puckered (buckled) structure. Another critical problem is that silicene is usually synthesized by epitaxial growth on a substrate, which strongly affects the π conjugated system of silicene. The fabrication of free-standing silicene with a planar configuration has long been pursued. Here, we report the strategy and design to realize the flat zigzag silicene nanoribbon. We theoretically investigated the stability of various silicene nanoribbons with substituents at the zigzag edges and found that zigzag silicene nanoribbons with beryllium (Be) bridges are very stable in a planar configuration. The obtained zigzag silicene nanoribbon has an indirect negative band gap and is nonmagnetic unlike the magnetic buckled silicene nanoribbons with zigzag edges. The linearly dispersive behavior of the π and π* bands associated with the out-of-plane 3psi and 2pBe orbitals is clearly observed, showing the existence of a Dirac point slightly above the Fermi level. We also observed that spin-orbit coupling induces a gap opening at the Dirac point.
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Low-frequency vibrations of crystalline molecules are very sensitive to the local environment in which the molecules, for example, hydrated ions captured in crystals, find themselves. We present low-temperature X-ray crystallographic measurements on the harvested thiamine crystal containing hydrated ions and its temperature-dependent terahertz spectra and synchrotron infrared microspectra. It is found from the X-ray structure that the hydrated ions and hydration water are in a similar environment to liquid, although those are captured in crystals. The vibrationally resolved THz spectra of two states in the present organic crystals containing hydrated ions are well explained by the difference in the hydrogen-bonded pattern. Peak assignments were performed based on highly accurate first-principles calculations incorporating relativistic effects and dispersion corrections. The temperature dependences are observed for the vibrations around the chloride ions and hydration water due to the loose binding of chloride ions, the bond elongation with increasing temperature, and the cleavage of weak hydrogen bonds.
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Assessment of van der Waals (VDW) interactions is fundamental to all of the central quest of structure that regulates the biological function. VDW interactions contributing to intramolecular weak hydrogen bonding are regarded as an important force to regulate the thermal stimuli-sensitive function of sulfobetaine methacrylate, DMAPS. We present here the conversion from the thermal-motion form at room temperature to the weak-hydrogen-bonded form against thermal motion as a terahertz spectral change with a definite isosbestic point from an absorption peak of one form to the other. Vibrational absorptions are used as a probe for assessing VDW interactions in conjunction with highly reliable and well-established density functional theory (DFT) calculations for analysis. Complicated spectral features and uncertain conformations of DMAPS in the amorphous state are clearly resolved under the polarizable continuum model and the dispersion correction for the pure DFT calculations.
RESUMEN
Silicene is the silicon equivalent of graphene, which is composed of a honeycomb carbon structure with one atom thickness and has attractive characteristics of a perfect two-dimensional π-conjugated sheet. However, unlike flat and highly stable graphene, silicene is relatively sticky and thus unstable due to its puckered or crinkled structure. Flatness is important for stability, and to obtain perfect π-conjugation, electron-donating atoms and molecules should not interact with the π electrons. The structural differences between silicene and graphene result from the differences in their building blocks, flat benzene and chair-form hexasilabenzene. It is crucial to design flat building blocks for silicene with no interactions between the electron donor and π-orbitals. Here, we report the successful design of such building blocks with the aid of density functional theory calculations. Our fundamental concept is to attach substituents that have sp-hybrid orbitals and act as electron donors in a manner that it does not interact with the π orbitals. The honeycomb silicon molecule with BeH at the edge designed according to our concept, clearly shows the same structural, charge distribution and molecular orbital characteristics as the corresponding carbon-based molecule.
RESUMEN
We have investigated the terahertz-spectral property of nicotinamide focusing on the temperature dependence in the range of 14-300 K. We observed that almost all peaks in the terahertz spectrum of the nicotinamide crystal showed a remarkable shift with temperature, whereas the lowest-frequency peak at 34.8 cm-1 showed a negligible shift with temperature. By analyzing the terahertz spectrum with the dispersion-corrected density functional theory calculations, we found that the difference in the temperature dependence of the peak shift is well understood in terms of the presence/absence of stretching vibration of the intermolecular hydrogen bond in the mode and the change of cell parameters. The anharmonicity in the dissociation potential energy of very weak intermolecular hydrogen bonding causes the remarkable peak shift with temperature in the terahertz spectrum of nicotinamide. This finding suggests that the assignment and identification of peaks in the terahertz spectrum are systematically enabled by temperature-dependent measurements.
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BACKGROUND: Previous studies reported that the incidence of intestinal spirochetosis was high in homosexual men, especially those with Human Immunodeficiency Virus infection. The aim of the present study was to clarify the clinicopathological features of intestinal spirochetosis in Japan with special reference to Human Immunodeficiency Virus infection status and species types. METHODS: A pathology database search for intestinal spirochetosis was performed at Tokyo Metropolitan Cancer and Infectious Disease Center Komagome Hospital between January 2008 and October 2011, and included 5265 consecutive colorectal biopsies from 4254 patients. After patient identification, a retrospective review of endoscopic records and clinical information was performed. All pathology slides were reviewed by two pathologists. The length of the spirochetes was measured using a digital microscope. Causative species were identified by polymerase chain reaction. RESULTS: Intestinal spirochetosis was diagnosed in 3 out of 55 Human Immunodeficiency Virus-positive patients (5.5%). The mean length of intestinal spirochetes was 8.5 µm (range 7-11). Brachyspira pilosicoli was detected by polymerase chain reaction in all 3 patients. Intestinal spirochetosis was also diagnosed in 73 out of 4199 Human Immunodeficiency Virus-negative patients (1.7%). The mean length of intestinal spirochetes was 3.5 µm (range 2-8). The species of intestinal spirochetosis was identified by polymerase chain reaction in 31 Human Immunodeficiency Virus-negative patients. Brachyspira aalborgi was detected in 24 cases (78%) and Brachyspira pilosicoli in 6 cases (19%). Both Brachyspira aalborgi and Brachyspira pilosicoli were detected in only one Human Immunodeficiency Virus-negative patient (3%). The mean length of Brachyspira aalborgi was 3.8 µm, while that of Brachyspira pilosicoli was 5.5 µm. The length of Brachyspira pilosicoli was significantly longer than that of Brachyspira aalborgi (p < 0.01). The lengths of intestinal spirochetes were significantly longer in Human Immunodeficiency Virus-positive patients than in Human Immunodeficiency Virus-negative patients (p < 0.05). CONCLUSIONS: The incidence of intestinal spirochetosis was slightly higher in Human Immunodeficiency Virus-positive patients than in Human Immunodeficiency Virus-negative patients. However, no relationship was found between the Human Immunodeficiency Virus status and intestinal spirochetosis in Japan. Brachyspira pilosicoli infection may be more common in Human Immunodeficiency Virus-positive patients with intestinal spirochetosis than in Human Immunodeficiency Virus-negative patients with intestinal spirochetosis.
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Brachyspira/aislamiento & purificación , Infecciones por VIH , Enfermedades Intestinales/epidemiología , Infecciones por Spirochaetales/epidemiología , Adulto , Anciano , Anciano de 80 o más Años , Biopsia , Brachyspira/genética , Colonoscopía , Femenino , Humanos , Incidencia , Enfermedades Intestinales/microbiología , Enfermedades Intestinales/patología , Japón/epidemiología , Masculino , Persona de Mediana Edad , Reacción en Cadena de la Polimerasa , ARN Ribosómico 16S/análisis , Estudios Retrospectivos , Infecciones por Spirochaetales/microbiología , Infecciones por Spirochaetales/patologíaRESUMEN
Hematoxylin-stainability of keratohyalin granules (KHG) using biochemical and immunohistochemical techniques is due to the presence of a fibrinogen γ-chain protein. A protein with a molecular weight of 100 kDa was stained with anti-Ted-H-1 monoclonal antibody and hematoxylin solution (hematoxylin-stainable protein). Since the amino acid sequence of the hematoxylin-stainable protein was to that of fibrinogen γ-chain protein, a peptide was synthesized and an antibody against the peptide was produced. This antibody reacted with the hematoxylin-stainable protein and fibrinogen γ-chain protein on immunoblot analysis and with KHG on immunohistochemical examination. Furthermore, a commercial anti-fibrinogen γ-chain protein antibody (Ab) also reacted with the hematoxylin-stainable protein as well as fibrinogen. In contrast, anti-fibrinogen ß-chain protein Ab did not react with the hematoxylin-stainable protein. The fibrinogen γ-chain protein also stained with hematoxylin. These findings suggested that fibrinogen γ-chain protein may be a novel component protein of KHG and may induce the hematoxylin-stainability of KHG.
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Gránulos Citoplasmáticos/metabolismo , Dermatitis Atópica/metabolismo , Fibrinógeno/metabolismo , Fragmentos de Péptidos/metabolismo , Piel/metabolismo , Anticuerpos Monoclonales , Biomarcadores/metabolismo , Gránulos Citoplasmáticos/patología , Dermatitis Atópica/diagnóstico , Dermatitis Atópica/patología , Dimerización , Fibrinógeno/química , Fibrinógeno/inmunología , Técnica del Anticuerpo Fluorescente Indirecta , Hematoxilina/metabolismo , Humanos , Queratinas/metabolismo , Fragmentos de Péptidos/síntesis química , Fragmentos de Péptidos/inmunología , Unión Proteica , Análisis de Secuencia de Proteína , Piel/patologíaRESUMEN
It is well known that the collagenolytic cathepsins play an important role in the degradation of bone matrix. Therefore, the purpose of this study was to clarify the prevention effect of bone resorption by milk components. Using double-layer reverse zymography, we found a 20 kDa protein in milk which inhibited cysteine proteases. This inhibitory protein was identified as beta-lactoglobulin B. The inhibitory activity of beta-lactoglobulin B against cathepsin K was stronger than that of beta-lactoglobulin A. Beta-lactoglobulin B specifically inhibited papain type cysteine proteases such as cathepsins K and L, but not serine proteases, aspartic proteases or metallo proteases. Beta-lactoglobulin B inhibited cathepsin K non-competitively and the Ki value was 10(-5) M. The formation of osteoclastic pits in the culture system was effectively inhibited by 10(-4)-10(-5) M beta-lactoglobulin B in vitro. Furthermore, we demonstrated that beta-lactoglobulin B inhibited degradation of type I-collagen by collagenolytic cathepsins. Using the everted-sac method in rat small intestines, it was found that beta-lactoglobulin was more easily absorbed from the intestines of young rats (5 wk-old) than from those of older rats (more than 20 wk-old). The digested products of beta-lactoglobulin B with lysyl-endopeptidase showed a similar inhibitory activity against cathepsin K to the intact beta-lactoglobulin B did. Therefore, peroral intake of beta-lactoglobulin in milk and its digested peptides are expected to help protect osteoclastic bone resorption via inhibition of collagenolytic cathepsins K and L.
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Resorción Ósea/prevención & control , Catepsinas/antagonistas & inhibidores , Colágeno/metabolismo , Inhibidores de Cisteína Proteinasa/farmacología , Lactoglobulinas/farmacología , Leche/química , Envejecimiento/fisiología , Secuencia de Aminoácidos , Animales , Catepsina K , Catepsina L , Catepsinas/metabolismo , Bovinos , Colágeno Tipo I/metabolismo , Cisteína Endopeptidasas , Inhibidores de Cisteína Proteinasa/química , Inhibidores de Cisteína Proteinasa/aislamiento & purificación , Absorción Intestinal/fisiología , Lactoglobulinas/química , Lactoglobulinas/farmacocinética , Masculino , Datos de Secuencia Molecular , Fragmentos de Péptidos/metabolismo , Fragmentos de Péptidos/farmacología , Ratas , Ratas Sprague-DawleyRESUMEN
Silicon subiodide clusters (Si(n)I(m), n = 1-20) produced by laser ablation of bulk powder silicone tetraiodide have been investigated by time-of-flight mass spectroscopy and ab initio calculations. Both experimental results and theoretical calculations revealed a tendency to form different structures of the clusters depending on n: chain, ring, and cage structures for n < or = 6, 6 < n < 16, and n > or = 16, respectively. The results showed that iodine, like hydrogen, can be used for stable silicon cluster termination.
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Cristalización/métodos , Yodo/química , Modelos Químicos , Nanoestructuras/química , Nanoestructuras/ultraestructura , Nanotecnología/métodos , Silicio/química , Simulación por Computador , Sustancias Macromoleculares/química , Ensayo de Materiales , Modelos Moleculares , Conformación Molecular , Tamaño de la Partícula , Propiedades de SuperficieRESUMEN
We obtained an antibody, anti-inner root sheath cells antibody (anti-IRSC Ab), that reacted with the inner root sheath (IRS) cells especially trichohyalin granules (THG). In order to compare the properties of anti-IRSC Ab and AE15, which is a specific monoclonal antibody against THG, histochemical and biochemical examinations were performed. In vivo localization with anti-IRSC Ab and AE15 indicated that both antibodies reacted with THG, but anti-IRSC Ab reacted with THG in the suprabulbar region of the Huxley layer, whereas AE15 reacted with THG in the suprabulbar region and upper bulbar portion of the Huxley layer, as shown by immunohistochemical and immunoelectron microscopic analyses. The results of immunoblot analysis showed that anti-IRSC Ab reacted with a protein spot at 45 kDa, pI 6.5, but AE15 reacted with high molecular weight proteins at pI 5.5. Furthermore, anti-IRSC Ab reacted with specimens of squamous cell carcinoma (SCC) but did not react with those of basal cell carcinoma (BCC). In contrast, AE15 reacted with neither SCC nor BCC. These findings suggest that anti-IRSC Ab and AE 15 recognized different component proteins in THG, and therefore indicated that THG, like as keratohyalin granules, might consist of several proteins. It is the novel finding that the anti-IRSC Ab positive substance in THG in the normal hair and SCC cells.
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Anticuerpos Monoclonales/inmunología , Folículo Piloso/metabolismo , Precursores de Proteínas/inmunología , Vesículas Secretoras/metabolismo , Secuencia de Aminoácidos , Anticuerpos Monoclonales/análisis , Carcinoma de Células Escamosas/metabolismo , Carcinoma de Células Escamosas/patología , Folículo Piloso/citología , Folículo Piloso/patología , Humanos , Inmunohistoquímica/métodos , Proteínas de Filamentos Intermediarios , Datos de Secuencia Molecular , Precursores de Proteínas/metabolismo , Vesículas Secretoras/ultraestructura , Neoplasias Cutáneas/metabolismo , Neoplasias Cutáneas/patologíaRESUMEN
Human mast cells are well known to produce a serine protease, tryptase, which appears to play a pathogenic role in various skin inflammations. It was previously reported that a rat homologue of bikunin may inhibit tryptase activity. Various type of cells (i.e. keratinocytes) are able to produce this protein inhibitor, it still remains unclear if bikunin is present in dermal inflammatory milieu, in which mast cells, through secretion of tryptase, play an inflammatory role. Therefore, the purpose of the present study was to exploit expression and production of bikunin in dermis and dermal constituents. We first compared the dermal mast cells in psoriatic lesions with those in lesional skin of atopic dermatitis or of chronic eczema by use of immunoelectron microscopy and immunohistochemical analyses using antibodies to bikunin and tryptase. Then, we tested what kinds of cytokines may regulate the de novo synthesis of bikunin. To do so, RNA was extracted from a human mastocytic cell line, HMC-1, reverse-transcribed, and semiquantitative RT-PCR was performed using primers specific for bikunin. With immunoelectron microscopy, bikunin was found to localize on the cell membrane, while tryptase was in the secretary granules of the mast cells. In psoriatic lesions, around 70% of dermal mast cells were positive for both tryptase and bikunin, and the remaining was mostly positive for tryptase, but the expression of bikunin was under the detection limit of the experimental setting. This observation was seen in only psoriatic lesions, even in almost cured lesions, while in atopic dermatitis or chronic eczema only mast cells doubly positive for bikunin and tryptase were seen. In HMC-1, bikunin was constitutively expressed at an mRNA level, which was upregulated by stimulation with interleukine-4, but was suppressed by interferon-gamma. Bearing in mind the concept that in psoriasis local cytokine milieu is shifted toward a Th1 pattern (predominant secretion of interferon-gamma), tryptase-positive, bikunin-negative mast cells may be induced.
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alfa-Globulinas/metabolismo , Mastocitos/metabolismo , Psoriasis/metabolismo , Triptasas/metabolismo , Biopsia , Línea Celular , Línea Celular Tumoral , Membrana Celular/metabolismo , Membrana Celular/ultraestructura , Regulación de la Expresión Génica/efectos de los fármacos , Regulación Enzimológica de la Expresión Génica/efectos de los fármacos , Humanos , Interferón gamma/farmacología , Interleucina-4/farmacología , Mastocitos/patología , Psoriasis/patología , ARN Mensajero/metabolismo , Piel/metabolismo , Piel/patologíaRESUMEN
As it has been found experimentally [K. Clays and B. Coe, Chem. Mater. 15, 642 (2003); B. J. Coe et al., 126, 10418 (2004)], elongation of the conjugation path length and N-arylation in stilbazolium chromophores both lead to substantial enhancement of the molecular optical nonlinearities. In the present contribution the authors perform a quantum chemical analysis of the excited state properties and quadratic nonlinear optical responses of a series of this type of dyes. Nonlinear optical responses are estimated by both finite-field and two-state model approaches that demonstrate an excellent qualitative mutual agreement. Time-dependent density functional theory calculations on the isolated cations predict redshift in the energy of the intramolecular charge transfer transition that is overestimated for cations with the longer conjugation path length. At the same time, in comparison with the Stark spectroscopy measurements the differences between the excited and ground state dipole moments are grossly underestimated for all compounds. The inclusion of solvent effect by polarizable continuum model affords a better agreement with experiment for these quantities. The authors' calculations demonstrate the crucial dependence of the electronic excitation properties on the way of the investigated compound geometry optimization. The origin of such dependence is discussed.
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Skin samples from patients with extra-mammary Paget disease, Bowen's disease, atopic dermatitis, psoriasis and non-lesional skin of nevus pigmentosus were immunohistochemically examined with an anti-soluble erythropoietin receptor antibody (anti-sEPOR antibody), and only the dermal mast cells positively stained in all skin samples were examined. These positively stained dermal cells were proved to be mast cells by double staining with anti-sEPOR antibody and either with anti-bikunin antibody or anti-tryptase antibody. Immunoelectron microscopically these EPOR were found in the secretory granules of the dermal mast cells. Further, EPOR in the mast cells may be consisting of only the extracellular domain of erythropoietin receptor molecule as the mast cells were immunohistochemically not reacted with an antibody to the C-terminal peptide of EPOR. Human mast cell line, HMC-1 cells has immunohistochemically the erythropoietin receptor, which was consisting of a 43 kDa major protein and a 20 kDa minor protein in the immunoelectrophoresis. These data may indicate that EPOR in the mast cells may not be the whole molecule, but probably the soluble one of EPOR.
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Mastocitos/química , Receptores de Eritropoyetina/análisis , Piel/química , Biopsia , Enfermedad de Bowen/patología , Línea Celular , Humanos , Immunoblotting , Inmunohistoquímica , Mastocitos/patología , Microscopía Inmunoelectrónica , Enfermedad de Paget Extramamaria/patología , Receptores de Eritropoyetina/química , Vesículas Secretoras/química , Vesículas Secretoras/ultraestructura , Piel/patologíaRESUMEN
First principles calculations were used to study the electronic excitation energies (E), transition dipole moments (µ), and difference of dipole moments between ground and excited states (Δµ) for low-lying singlets of the series of ruthenium(II) ammine complexes. Both cases of the gas phase and the acetonitrile solution were investigated in order to explain the discrepancy between the recent experimental and theoretical results and to develop the optimal way of estimation for the first static hyperpolarizability in the framework of a two-state model introduced by Oudar and Chemla. The present calculations reveal that the effect of solvent on the electronic properties of investigated compounds is not only the change of the excitation energy but also the increasing of ground-state molecular polarization and intensification of metal-to-ligand intramolecular charge transfer for electronic excitations. These effects lead to increasing of the values of Δµ and ground-state dipole moment µg in solution as compared with the gas-phase ones. The proposed theoretical approach gives good agreement with experiment and allows one to apply it for designing a new perspective nonlinear optical active organometallics.
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The photochemical reaction mechanisms of model compounds for 4-tert-butyl-1-(4-phenylphenyl)-1-(1,1-dimethylallyl)silacyclohexane are investigated using a complete active space comprised of six electrons in six orbitals with the standard 6-31G(d) basis set. It is concluded that the stereochemistry in the photochemical 1,3-silyl migrations of allylsilanes has a retention preference, in accord with the Woodward-Hoffmann rules. The calculated conical intersection (CI) structure suggests a dissociation path to radicals in addition to a 1,3-shift path. The bulkiness and rigidness of a silacyclohexane moiety does not affect the stereochemistry, but a slightly elongated Si-C bond length in the CI structure would promote the dissociation path.
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To examine the presence of bactericidal/permeability-increasing protein (BPI) in skin, which is an antibacterial protein, has cytotoxicity toward Gram-negative bacteria, and may have an important role against bacterial infection in the skin, immunohistochemical and biochemical analyses were performed. Anti-BPI/KLH Ab reacted with the cytoplasm of the inner root sheath cells of both human and rat hair follicles by immunohistochemical examination. A protein band in 10-M alkaline urea extracts of human scalp skin or 7-day-old rat skin reacted with an antibody against BPI conjugated with KLH (anti-BPI/KLH Ab). Purified skin BPI (sBPI) from rat was a single protein spot and reacted with both anti-BPI/KLH Ab and a commercially available monoclonal antibody against BPI (anti-BPI MoAb). Moreover, sBPI possessed inhibitory activity against LPS. Bactericidal/permeability-increasing protein mRNA was expressed not only in leukocytes but also in human scalp skin and cultured keratinocytes. These findings suggest that sBPI could exist in the inner root sheath cells of human and rat hair follicles, and might play a role as a barrier against anaerobic bacteria in the isthmus of hair follicles.
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Proteínas Sanguíneas/metabolismo , Proteínas de la Membrana , Piel/metabolismo , Secuencia de Aminoácidos , Animales , Péptidos Catiónicos Antimicrobianos , Sitios de Unión , Actividad Bactericida de la Sangre , Proteínas Sanguíneas/genética , Proteínas Sanguíneas/aislamiento & purificación , Folículo Piloso/metabolismo , Humanos , Lipopolisacáridos/química , Datos de Secuencia Molecular , ARN Mensajero/genética , Ratas , Reacción en Cadena de la Polimerasa de Transcriptasa Inversa , Cuero Cabelludo , Piel/químicaRESUMEN
Xerosis is one of the characteristics of aged skin. Xerosis may be caused by a decrease in the stratum corneum free amino acids which are natural moisturizing factors derived from filaggrin. In aged skin, filaggrin is immunohistochemically decreased compared with the levels in young skin. However, the differences in stratum corneum amino acids between aged and young skin have not been analyzed quantitatively. Therefore, in this study we determined the stratum corneum amino acids per 1000 stratum corneum cells in aged and young skin by high-performance liquid chromatography. The amount of filaggrin mRNA in the epidermis was also compared between aged and young skin using RT-PCR. The total amount of amino acids in the stratum corneum was larger in aged senile xerosis skin than in young skin. Only a few amino acids were found in the stratum corneum of ichthyosis vulgaris patients (control skin). The expression of filaggrin mRNA in aged skin was, however, similar to that in young skin. These findings suggest that the immunohistochemical decrease in filaggrin in aged skin may be caused by promotion of filaggrin proteolysis in the upper layers of the stratum spinulosum.
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Aminoácidos/metabolismo , Epidermis/metabolismo , Envejecimiento de la Piel , Enfermedades de la Piel/etiología , Enfermedades de la Piel/metabolismo , Adulto , Anciano , Anciano de 80 o más Años , Estudios de Casos y Controles , Cromatografía Líquida de Alta Presión , Proteínas Filagrina , Humanos , Ictiosis Vulgar/metabolismo , Inmunohistoquímica , Proteínas de Filamentos Intermediarios/genética , Persona de Mediana Edad , ARN Mensajero/metabolismo , Reacción en Cadena de la Polimerasa de Transcriptasa Inversa , Enfermedades de la Piel/patologíaRESUMEN
The mechanism of 1,2-addition reactions of HF and HCl to Si=Si, Si=C, and C=C bonds has been investigated by ab initio quantum chemical methods. Geometries and relative energies of the stationary points and all the transition states were determined by using the MP2/6-311++G(d,p), B3LYP/6-311++G(d,p), and CBS-Q levels of theory. The investigated reactions can be characterized by two main thermodynamic profiles. The type in which the reagent molecule attacks a carbon atom is moderately exothermic with a high activation barrier. The second type in which a hydrogen halide attacks a silicon is strongly exothermic with a low activation energy. At the early stage of all the reactions a weakly bonded initial complex is found which indicates that the initial step of all the reactions is an electrophilic attack of hydrogen halide. The geometry and charge distribution of the transition state of the reactions indicate two main types of mechanism. If silicon is attacked, the halogen-silicon bond formation precedes the H-Y bond breaking. If, however, carbon is attacked, the first step is always an ionic dissociation of the hydrogen halide and a carbenium ion formation, which is stabilized by the C-Y bond formation in the final step of the reaction. The reaction diagrams and proposed mechanisms explain the experimentally found regioselectivity well.