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1.
J Nat Prod ; 84(1): 20-25, 2021 01 22.
Artigo em Inglês | MEDLINE | ID: mdl-33415978

RESUMO

The structural elucidation of chiral molecules with more than one stereocenter is usually a tricky problem. In this paper, efficient 1H NMR spectroscopic approaches for assigning the erythro and threo configurations of 1-oxygenated 1,2-diarylpropan-3-ols were developed. By analysis of the chemical shift differences of diastereotopic methylene H2-3 (Δδ3) in CDCl3 or the chemical shift differences of H-1 and H-2 (Δδ1,2) in methanol-d4, deuterated dimethyl sulfoxide, and acetone-d6, the configurations of 1-oxygenated 1,2-diarylpropan-3-ols can be rapidly and conveniently determined.


Assuntos
1-Propanol/química , Dimetil Sulfóxido/química , Oxigênio/química , Espectroscopia de Ressonância Magnética/métodos , Estereoisomerismo
2.
Chem Senses ; 45(7): 513-521, 2020 10 09.
Artigo em Inglês | MEDLINE | ID: mdl-32609815

RESUMO

Probing the neural mechanisms that underlie each sensory system requires the presentation of perceptually appropriate stimulus concentrations. This is particularly relevant in the olfactory system as additional odorant receptors typically respond with increasing stimulus concentrations. Thus, perceptual measures of olfactory sensitivity provide an important guide for functional experiments. This study focuses on aliphatic alcohols because they are commonly used to survey neural activity in a variety of olfactory regions, probe the behavioral limits of odor discrimination, and assess odor-structure activity relationships in mice. However, despite their frequent use, a systematic study of the relative sensitivity of these odorants in mice is not available. Thus, we assayed the ability of C57BL/6J mice to detect a homologous series of primary aliphatic alcohols (1-propanol to 1-heptanol) using a head-fixed Go/No-Go operant conditioning assay combined with highly reproducible stimulus delivery. To aid in the accessibility of our data, we report the animal's threshold to each odorant according to the 1) ideal gas condition, 2) nonideal gas condition (factoring in the activity of the odorant in the solvent), and 3) the liquid dilution of the odorant in the olfactometer. Of the odorants tested, mice were most sensitive to 1-hexanol and least sensitive to 1-butanol. These updated measures of murine sensitivity will hopefully guide experimenters in choosing appropriate stimulus concentrations for experiments using these odorants.


Assuntos
Álcoois Graxos/química , Limiar Sensorial/fisiologia , Olfato/fisiologia , 1-Butanol/química , 1-Butanol/farmacologia , 1-Propanol/química , 1-Propanol/farmacologia , Animais , Comportamento Animal/efeitos dos fármacos , Álcoois Graxos/farmacologia , Feminino , Gases/química , Heptanol/química , Heptanol/farmacologia , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Limiar Sensorial/efeitos dos fármacos
3.
Molecules ; 25(6)2020 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-32183079

RESUMO

A synthetic strategy for the preparation of two orthogonally protected methyl esters of the non-proteinogenic amino acid 2,3-l-diaminopropanoic acid (l-Dap) was developed. In these structures, the base-labile protecting group 9-fluorenylmethyloxycarbonyl (Fmoc) was paired to the p-toluensulfonyl (tosyl, Ts) or acid-labile tert-butyloxycarbonyl (Boc) moieties. The synthetic approach to protected l-Dap methyl esters uses appropriately masked 2,3-diaminopropanols, which are obtained via reductive amination of an aldehyde prepared from the commercial amino acid Nα-Fmoc-O-tert-butyl-d-serine, used as the starting material. Reductive amination is carried out with primary amines and sulfonamides, and the process is assisted by the Lewis acid Ti(OiPr)4. The required carboxyl group is installed by oxidizing the alcoholic function of 2,3-diaminopropanols bearing the tosyl or benzyl protecting group on the 3-NH2 site. The procedure can easily be applied using the crude product obtained after each step, minimizing the need for chromatographic purifications. Chirality of the carbon atom of the starting d-serine template is preserved throughout all synthetic steps.


Assuntos
1-Propanol/química , Ésteres/síntese química , Serina/química , beta-Alanina/análogos & derivados , Aldeídos/química , Aminação , Cromatografia Líquida de Alta Pressão , Dipeptídeos/síntese química , Dipeptídeos/química , Ésteres/química , Espectrometria de Massas , Metilação , Oxirredução , Estereoisomerismo , Sulfonamidas/química , beta-Alanina/síntese química
4.
Electrophoresis ; 40(18-19): 2256-2262, 2019 09.
Artigo em Inglês | MEDLINE | ID: mdl-30793781

RESUMO

1-propanol is a primary alcohol extensively used in the pharmaceutical, chemical, and food industries. It has been also found as a contaminant in the atmosphere and is considered a model compound to mimic the behavior and fate of aliphatic alcohols exposed to environmental conditions. In order to understand that role of relevant variables, this paper presents results obtained with a simple experimental set-up to investigate the reactivity of 1-propanol under mild oxidizing conditions. Coupling this system with CE-C4 D allowed the quantification of the carboxylic acids formed. For the described experiments, aqueous solutions of 1-propanol were placed inside a photoreactor and oxidized upon the addition of TiO2 and/or H2 O2 . According to the described results, the addition of H2 O2 (0.1% w/w) was the most significant variable, roughly tripled the amount of carboxylic acids generated and led to the conversion of up to 70% of the initially available 1-propanol (1 mmol/L). More importantly, the reaction yielded the formation (within 10 min) of propionate (50 µmol/L), acetate (400 µmol/L), formate (50 µmol/L), and malonate (200 µmol/L). The latter is critically important because it represents the first example of the photochemical oxidation of both terminal carbons of the C3 -chain of 1-propanol under mild conditions, and opens new avenues for the production of this important chemical building block.


Assuntos
1-Propanol , Peróxido de Hidrogênio , Fotólise , 1-Propanol/análise , 1-Propanol/química , 1-Propanol/efeitos da radiação , Condutividade Elétrica , Eletroforese Capilar , Malonatos/análise , Malonatos/química , Oxirredução , Fotólise/efeitos dos fármacos , Fotólise/efeitos da radiação , Raios Ultravioleta
5.
Biomacromolecules ; 20(6): 2167-2173, 2019 06 10.
Artigo em Inglês | MEDLINE | ID: mdl-31117367

RESUMO

Elastin-like polypeptides (ELPs) are one of the most widely-studied classes of protein material because of their lower critical solution temperature (LCST)-like thermoresponsive behavior in aqueous solutions. Here, it is shown that ELPs also exhibit cononsolvency effects, similar to many other water-soluble polymers. The effect of solvent composition on the dilute solution phase behavior of an elastin-like polypeptide is studied here in water/alcohol blends that contain 0-40 vol % methanol, ethanol, isopropanol, or 1-propanol. In all systems studied, the ELP exhibits cononsolvency behavior at low alcohol content, as indicated by a decrease in the transition temperature of the ELP. When the alcohol added is ethanol, isopropanol, or 1-propanol, the decrease in transition temperature is followed by a region of complete ELP insolubility, and, finally, the emergence of upper-critical solution transition (UCST)-like behavior. The ELP is completely soluble at all temperatures measured at alcohol contents above 40 vol %. The effect of sodium chloride on this ELP cononsolvency in water/ethanol blends was also studied. Unlike the previously studied polymer poly( N-isoropylacrylamide) (PNIPAM), ELP exhibits nonmonotonic changes in transition temperature with the addition of sodium chloride at ethanol contents that produce UCST-like transitions of the ELP. This discovery of ELP cononsolvency in water/alcohol systems introduces a new handle with which the solubility of ELPs can be tuned.


Assuntos
Álcoois/química , Elastina/química , Solventes/química , Água/química , 1-Propanol/química , 2-Propanol/química , Etanol/química , Metanol/química , Peptídeos/química , Solubilidade , Temperatura de Transição
6.
Int J Mol Sci ; 20(17)2019 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-31454911

RESUMO

The main aim of this work is to substantiate the mechanism of 1-propanol oxidation by ozone in aqueous solution when the substrate is present in large excess. Further goals are assessment of the products, their formation yields as well as the kinetic parameters of the considered reaction. The reaction of ozone with 1-propanol in aqueous solution occurs via hydride transfer, H-abstraction and insertion. Of these three mechanisms, the largest share is for hydride transfer. This implies the extraction of an hydride ion from the activated C-H group by O3 according to reaction: (C2H5)(H)(HO)C-H + O3 → [(C2H5)(H)(HO)C+ + HO3-]cage → (C2H5)(H)(HO)C+ + HO3-. The experimentally determined products and their overall formation yields with respect to ozone are: propionaldehyde-(60 ± 3)%, propionic acid-(27.4 ± 1.0)%, acetaldehyde-(4.9 ± 0.3)%, acetic acid-(0.3 ± 0.1)%, formaldehyde-(1.0 ± 0.1)%, formic acid-(4.6 ± 0.3)%, hydrogen peroxide-(11.1 ± 0.3)% and hydroxyl radical-(9.8 ± 0.3)%. The reaction of ozone with 1-propanol in aqueous media follows a second order kinetics with a reaction rate constant of (0.64 ± 0.02) M-1·s-1 at pH = 7 and 23 °C. The dependence of the second order rate constant on temperature is described by the equation: l n   k I I = ( 27.17 ± 0.38 ) - ( 8180 ± 120 ) × T - 1 , which gives the activation energy, Ea = (68 ± 1) kJ mol-1 and pre-exponential factor, A = (6.3 ± 2.4) × 1011 M-1 s-1. The nature of products, their yields and the kinetic data can be used in water treatment. The fact that the hydride transfer is the main pathway in the 1-propanol/ozone system can probably be transferred on other systems in which the substrate is characterized by C-H active sites only.


Assuntos
1-Propanol/química , Ozônio/química , Ácidos/química , Aldeídos/metabolismo , Peróxido de Hidrogênio/química , Radical Hidroxila/química , Cinética , Modelos Químicos , Água/química
7.
Biochem Biophys Res Commun ; 498(2): 282-287, 2018 03 29.
Artigo em Inglês | MEDLINE | ID: mdl-28870809

RESUMO

The determination of potentials of mean force for solute insertion in a lipid membrane by means of all-atom molecular dynamics simulations is often hampered by sampling issues. Recently, a multiscale method has been proposed to leverage the conformational ensemble of a lower-resolution model as starting point for higher resolution simulations. In this work, we analyze the efficiency of this method by comparing its predictions for propanol insertion into a lipid membrane against conventional atomistic umbrella sampling simulation results. The multiscale approach is confirmed to provide accurate results with a gain of one order of magnitude in computational time. We then investigate the role of the coarse-grained representation. We find that the accuracy of the results is tightly connected to the presence of a good configurational overlap between the coarse-grained and atomistic models-a general requirement when developing multiscale simulation methods.


Assuntos
Lipídeos de Membrana/química , 1-Propanol/química , Membrana Celular/química , Biologia Computacional/métodos , Dimiristoilfosfatidilcolina/química , Modelos Moleculares , Conformação Molecular , Simulação de Dinâmica Molecular , Fosfatidilcolinas/química
8.
Biochemistry (Mosc) ; 82(1): 13-23, 2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-28320283

RESUMO

Genome search of Bacillus subtilis revealed the presence of an open reading frame annotated as glutathione-dependent formaldehyde dehydrogenase/alcohol dehydrogenase. The open reading frame consists of 1137 nucleotides corresponding to a polypeptide of 378 amino acids. To examine whether the encoded protein is glutathione-dependent formaldehyde dehydrogenase or alcohol dehydrogenase, we cloned and characterized the gene product. Enzyme activity assays revealed that the enzyme exhibits a metal ion-dependent alcohol dehydrogenase activity but no glutathione-dependent formaldehyde dehydrogenase or aldehyde dismutase activity. Although the protein is of mesophilic origin, optimal temperature for the enzyme activity is 60°C. Thermostability analysis by circular dichroism spectroscopy revealed that the protein is stable up to 60°C. Presence or absence of metal ions in the reaction mixture did not affect the enzyme activity. However, metal ions were necessary at the time of protein production and folding. There was a marked difference in the enzyme activity and CD spectra of the proteins produced in the presence and absence of metal ions. The experimental results obtained in this study demonstrate that the enzyme is a bona-fide alcohol dehydrogenase and not a glutathione-dependent formaldehyde dehydrogenase.


Assuntos
1-Propanol/química , Aldeído Oxirredutases/química , Bacillus subtilis/enzimologia , Proteínas de Bactérias/genética , Aldeído Oxirredutases/genética , Bacillus subtilis/genética , Proteínas de Bactérias/química , Estabilidade Enzimática , Especificidade por Substrato
9.
J Labelled Comp Radiopharm ; 60(12): 566-576, 2017 10.
Artigo em Inglês | MEDLINE | ID: mdl-28755455

RESUMO

The multitude of biologically active compounds requires the availability of a broad spectrum of radiolabeled synthons for the development of positron emission tomography (PET) tracers. The aim of this study was to synthesize 1-iodo-2-[11 C]methylpropane and 2-methyl-1-[11 C]propanol and investigate the use of these reagents in further radiosynthesis reactions. 2-Methyl-1-[11 C]propanol was obtained with an average radiochemical yield of 46 ± 6% d.c. and used with fluorobenzene as starting material. High conversion rates of 85 ± 4% d.c. could be observed with HPLC, but large precursor amounts (32 mg, 333 µmol) were needed. 1-Iodo-2-[11 C]methylpropane was synthesized with a radiochemical yield of 25 ± 7% d.c. and with a radiochemical purity of 78 ± 7% d.c. The labelling agent 1-iodo-2-[11 C]methylpropane was coupled to thiophenol, phenol and phenylmagnesium bromide. Average radiochemical conversions of 83% d.c. for thiophenol, 40% d.c. for phenol, and 60% d.c. for phenylmagnesium bromide were obtained. In addition, [11 C]2-methyl-1-propyl phenyl sulphide was isolated with a radiochemical yield of 5 ± 1% d.c. and a molar activity of 346 ± 113 GBq/µmol at the end of synthesis. Altogether, the syntheses of 1-iodo-2-[11 C]methylpropane and 2-methyl-1-[11 C]propanol were achieved and applied as proof of their applicability.


Assuntos
1-Propanol/química , 1-Propanol/síntese química , Radioisótopos do Iodo/química , Propano/química , Propano/síntese química , Alquilação , Marcação por Isótopo , Tomografia por Emissão de Pósitrons , Radioquímica
10.
Sud Med Ekspert ; 60(4): 29-33, 2017.
Artigo em Russo | MEDLINE | ID: mdl-28766526

RESUMO

The objective of the present study was the development and metrological attestation of the method for the determination of concentrations of low-molecular weight (C1-C4) alcohols and acetone in the biological materials, such as urine and blood including partially dehydrated blood. The method is based on the chromatographic analysis of the equilibrium vapour phase with the use of the static headspace autosampler. The calculations were carried out making use of the results obtained with the application of propanol-1 as the internal standard. In order to enhance the reliability of the identification of the analytes in the complex blood matrix, the two-channel configuration was employed that consisted of a single evaporator, passive flow division, two capillary columns of different polarity, and two flame ionization detectors. The proposed technique provided for the first time the unique possibility to perform the quantitative measurement of the internal standard in the starting specimen before the main analysis. The validated procedure for the quantitative determination of the alcohol concentration of blood samples with the reduced water content has been described. The present study made it possible to collect the total amount of relevant statistical data necessary to calculate the metrological characteristics of the method in question. The method was certified based at D.I. Mendeleev All-Russian Research Institute of Metrology under No 754/242-(01.00250)-2016.


Assuntos
Acetona , Concentração Alcoólica no Sangue , Cromatografia Gasosa/métodos , Etanol , Urinálise/métodos , 1-Propanol/análise , 1-Propanol/química , Acetona/análise , Acetona/química , Etanol/análise , Etanol/química , Toxicologia Forense/métodos , Humanos , Peso Molecular , Reprodutibilidade dos Testes
11.
AAPS PharmSciTech ; 17(2): 427-35, 2016 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-26206402

RESUMO

Amodiaquine dihydrochloride monohydrate (AQ-DM) was obtained by recrystallizing amodiaquine dihydrochloride dihydrate (AQ-DD) in methanol, ethanol, and n-propanol. Solid-state characterization of AQ-DD and AQ-DM was performed using X-ray powder diffractometry, Fourier transform infrared spectroscopy, thermogravimetry, and differential scanning calorimetry. All recrystallized samples were identified as AQ-DM. Crystal habits of AQ-DD and AQ-DM were shown to be needle-like and rhombohedral crystals, respectively. When AQ-DD and AQ-DM were exposed to various relative humidity in dynamic vapor sorption apparatus, no solid-state interconversion was observed. However, AQ-DM showed higher solubility than AQ-DD when exposed to bulk water during solubility study, while excess AQ-DM was directly transformed back to a more stable AQ-DD structure. Heating AQ-DM sample to temperatures ≥190°C induced initial change to metastable amorphous form (AQ-DA) which was rapidly recrystallized to AQ-DD upon ≥80%RH moisture exposure. AQ-DD was able to be recrystallized in alcohols (C1-C3) as AQ-DM solid-state structure. In summary, AQ-DM was shown to have different solubility, moisture and temperature stability, and interconversion pathways when compared to AQ-DD. Thus, when AQ-DM was selected for any pharmaceutical applications, these critical transformation and property differences should be observed and closely monitored.


Assuntos
Amodiaquina/química , Etanol/química , 1-Propanol/química , Varredura Diferencial de Calorimetria/métodos , Cristalização , Estabilidade de Medicamentos , Umidade , Metanol/química , Pós/química , Solubilidade , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Temperatura , Água/química , Difração de Raios X/métodos
12.
J Am Chem Soc ; 137(27): 8680-3, 2015 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-26115587

RESUMO

Structure and dynamics regulate protein function, but much less is known about how biomolecule-solvent interactions affect the structure-function relationship. Even less is known about the thermodynamics of biomolecule-solvent interactions and how such interactions influence conformational entropy. When transferred from propanol into 40:60 propanol:water under acidic conditions, a remarkably slow protonation reaction coupled with the conversion of the polyproline-I helix (PPI, having all cis-configured peptide bonds) into polyproline-II (PPII, all trans) helix is observed in this work. Kinetics and equilibrium measurements as a function of temperature allow determination of the thermochemistry and insight into how proton transfer is regulated in this system. For the proton-transfer process, PPI(+)(PrOH) + H3O(+) → PPII(2+)(PrOH/aq) + H2O, we determine ΔG = -20 ± 19 kJ·mol(-1), ΔH = -75 ± 14 kJ·mol(-1), and ΔS= -188 ± 48 J·mol(-1)·K(-1) for the overall reaction, and values of ΔG(⧧) = 91 ± 3 kJ·mol(-1), ΔH(⧧) = 84 ± 9 kJ·mol(-1), and ΔS(⧧) = -23 ± 31 J·mol(-1)·K(-1) for the transition state. For a minor process, PPI(+)(PrOH) → PPII(+)(PrOH/aq) without protonation, we determine ΔG = -9 ± 20 kJ·mol(-1), ΔH = 64 ± 14 kJ·mol(-1), and ΔS= 247 ± 50 J·mol(-1)·K(-1). This thermochemistry yields ΔG = -10 ± 29 kJ·mol(-1), ΔH = -139 ± 20 kJ·mol(-1), and ΔS= -435 ± 70 J·mol(-1)·K(-1) for PPII(+)(PrOH/aq) + H3O(+) → PPII(2+)(PrOH/aq) +H2O. The extraordinarily slow proton transfer appears to be an outcome of configurational coupling through a PPI-like transition state.


Assuntos
Peptídeos/química , 1-Propanol/química , Entropia , Cinética , Modelos Moleculares , Estrutura Secundária de Proteína , Prótons , Solventes/química , Água/química
13.
Faraday Discuss ; 179: 309-28, 2015.
Artigo em Inglês | MEDLINE | ID: mdl-25886651

RESUMO

Over 2100 induction time experiments were carried out for the medium-sized, antipsychotic drug molecule, risperidone in seven different organic solvents. To reach the same induction time the required driving force increases in the order: cumene, toluene, acetone, ethyl acetate, methanol, propanol, and butanol, which reasonably well correlates to the interfacial energies as determined within classical nucleation theory. FTIR spectroscopy has been used to investigate any shifts in the spectra and to estimate the interaction of solute and solvent at the corresponding site. The solution condition has also been investigated by Density Functional Theory (DFT) calculations over (1 : 1) solvent-solute binding interactions at 8 different sites on the risperidone molecule. The DFT computational results agree with the spectroscopic data suggesting that these methods do capture the binding strength of solvent molecules to the risperidone molecule. The difficulty of nucleation correlates reasonably to the DFT computations and the spectroscopic measurements. The results of the different measurements suggest that the stronger the solvent binds to the risperidone molecule in solution, the slower the nucleation becomes.


Assuntos
Risperidona/química , 1-Propanol/química , Acetatos/química , Acetona/química , Derivados de Benzeno/química , Butanóis/química , Cristalização , Metanol/química , Teoria Quântica , Solventes/química , Tolueno/química
14.
Macromol Rapid Commun ; 36(20): 1816-21, 2015 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-26293155

RESUMO

The synthesis and formulation of organic semiconductors for the emerging technology of organic electronics requires the use of preparative methods and solvents being environment friendly. Today most of the active layer materials for the organic photovoltaic devices and modules are using chlorinated solvents, which are toxic and hazardous. In this work, the synthesis of poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2',1',3'-benzothiadiazole] (PCDTBT) in propan-1-ol is presented as the dispersant continuous phase in the presence of poly(vinylpyrrolidone) used as stabilizer. Suzuki-Miyaura polycondensation of 9-(9-heptadecanyl)-9H-carbazole-2,7-diboronic acid bis(pinacol) ester and 4,7-bis(2-bromo-5-thienyl)-2,1,3-benzothiadiazole in alcohol dispersion yields colloidally stable nanoparticles of PCDTBT with particles size of 330-1300 nm, depending on the stabilizer concentration. Other reaction parameters are also discussed such as the amount of base or Pd catalyst.


Assuntos
Nanopartículas/química , Polímeros/síntese química , 1-Propanol/química , Polimerização , Semicondutores , Tiadiazóis/química
15.
J Phys Chem A ; 119(13): 3209-17, 2015 Apr 02.
Artigo em Inglês | MEDLINE | ID: mdl-25774682

RESUMO

The spontaneous polarized Raman spectra of normal and deuterated alcohols (C2-C5) have been recorded in the C-H stretching region. In the isotropic Raman spectra, a doublet of -CαH stretching vibration is found for all alcohols at below 2900 cm(-1) and above 2950 cm(-1). By comparing the experimental and calculated spectra of various deuterated alcohols, the doublets are attributed to the -CαH stretching vibration of different conformers. For ethanol, the band observed at 2970 cm(-1) is assigned as the stretching vibration of -CαH in the Cα-O-H plane of the gauche-conformer, while the band at 2895 cm(-1) is contributed from both the -CαH2 symmetrical stretching vibration of the trans-conformer and the -CαH stretching vibration out of the Cα-O-H plane of the gauche-conformer. The population of gauche-conformer is estimated to be 54% in liquid ethanol. For the larger alcohols, the same assignments for the doublet are obtained, and the populations of gauche-conformers with plane carbon skeleton are found to be slightly larger than that of ethanol, which is consistent with results from molecular dynamics simulations.


Assuntos
1-Propanol/química , Etanol/química , Análise Espectral Raman/métodos , Deutério , Ligação de Hidrogênio , Software
16.
J Opt Soc Am A Opt Image Sci Vis ; 32(6): 1109-17, 2015 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-26367045

RESUMO

The self-assembly of silica microspheres into a close-packed array is a simple method of fabricating three-dimensional photonic crystal structural color films. However, the color is very dull because of the interferences of scattering and background light. In this study, we added a small quantity of surface-modified carbon black (CB) to the system of colloidal silica in n-propanol. The use of n-propanol as a dispersant is beneficial to the rapid development of photonic crystal films during the process of dip-coating. The doping of CB into silica microspheres can absorb background and scattering light, resulting in vivid structural colors.


Assuntos
Materiais Biomiméticos/química , 1-Propanol/química , Cor , Modelos Moleculares , Conformação Molecular , Fótons , Dióxido de Silício/química , Fuligem/química , Propriedades de Superfície
17.
Molecules ; 20(2): 2349-63, 2015 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-25647574

RESUMO

Combinations of TiO2 photocatalysts and various adsorbents have been widely studied for the adsorption and photocatalytic decomposition of gaseous pollutants such as volatile organic compounds (VOCs). Herein, a TiO2-zeolite-porous glass composite was prepared using melt-quenching and partial sintering, hydrothermal treatment, and drop coating for preparation of the porous glass support and X-zeolite and their combination with TiO2, respectively. The obtained composite comprised anatase phase TiO2, X-zeolite, and the porous glass support, which were combined at the micro to nanometer scales. The composite had a relatively high specific surface area of approximately 25 m2/g and exhibited a good adsorption capacity for 2-propanol. These data indicated that utilization of this particular phase-separated glass as the support was appropriate for the formation of the bulk photocatalyst-adsorbent composite. Importantly, the photocatalytic decomposition of adsorbed 2-propanol proceeded under UV light irradiation. The 2-propanol was oxidized to acetone and then trapped by the X-zeolite rather than being released to the atmosphere. Consequently, it was demonstrated that the micrometer-scaled combination of TiO2 and zeolite in the bulk form is very useful for achieving both the removal of gaseous organic pollutants and decreasing the emission of harmful intermediates.


Assuntos
Vidro/química , Titânio/química , Zeolitas/química , 1-Propanol/química , Adsorção , Catálise , Processos Fotoquímicos , Porosidade , Propriedades de Superfície , Difração de Raios X
18.
Molecules ; 20(10): 19002-13, 2015 Oct 19.
Artigo em Inglês | MEDLINE | ID: mdl-26492228

RESUMO

As one of the oldest distillates in the world, flavor compounds of Chinese Baijiu (Chinese liquor) were extremely complex. Propyl lactate was firstly detected by direct injection and gas chromatography-mass spectrometry (GC-MS) in 72 Chinese Baijius. The objectives were to detect the contents of propyl lactate and evaluate its contribution to the aroma of Chinese Baijiu based on odor activity values (OAVs). The levels of propyl lactate in these distillates were determined by internal standard method and selective ion monitoring (SIM), which ranged from 0.050 to 1.900 mg∙L(-1) under investigation. Its detection threshold was determined by Three-Alternative Forced-Choice (3-AFC) and curve fitting (CF), which was 0.740 mg∙L(-1) in 38% ethanol solution. The contribution of propyl lactate on the aroma of these distillate drinks was evaluated by their odor activity values (OAVs), which varied from 0.066 to 4.440. The OAVs of propyl lactate were found to exceed 1 in 13 Chinese Baijius, including 50° Jingzhi Guniang 5 years (4.440), 52° Jingzhi Guniang 10 years (3.024), Jingyanggang (2.568), Xianghe Ronghe Shaofang (2.313), and 1956 Laolang (1.431), which indicated that propyl lactate was one of odor-active components in these Chinese Baijius.


Assuntos
1-Propanol/química , Bebidas Alcoólicas/análise , Cromatografia Gasosa-Espectrometria de Massas/métodos , Ácido Láctico/química , Odorantes/análise , Compostos Orgânicos Voláteis/análise , Compostos Orgânicos Voláteis/química
19.
Biochim Biophys Acta ; 1834(3): 708-16, 2013 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-23270996

RESUMO

Polyproline II (PPII) fold, an unusual structural element was detected in the serine protease from Nocardiopsis sp. NCIM 5124 (NprotI) based on far UV circular dichroism spectrum, structural transitions of the enzyme in presence of GdnHCl and a distinct isodichroic point in chemical and thermal denaturation. The functional activity and conformational transitions of the enzyme were studied under various denaturing conditions. Enzymatic activity of NprotI was stable in the vicinity of GdnHCl upto 6.0M concentration, organic solvents viz. methanol, ethanol, propanol (all 90% v/v), acetonitrile (75% v/v) and proteases such as trypsin, chymotrypsin and proteinase K (NprotI:protease 10:1). NprotI seems to be a kinetically stable protease with a high energy barrier between folded and unfolded states. Also, an enhancement in the activity of the enzyme was observed in 1M GdnHCl upto 8h, in organic solvents (75% v/v) for 72h and in presence of proteolytic enzymes. The polyproline fold remained unaltered or became more prominent under the above mentioned conditions. However, it diminished gradually during thermal denaturation above 60°C. Thermal transition studies by differential scanning calorimetry (DSC) showed scan rate dependence as well as irreversibility of denaturation, the properties characteristic of kinetically stable proteins. This is the first report of PPII helix being the global conformation of a non structural protein, an alkaline serine protease, from a microbial source, imparting kinetic stability to the protein.


Assuntos
Proteínas de Bactérias/química , Endopeptidases/química , Peptídeos/química , Dobramento de Proteína , 1-Propanol/química , 1-Propanol/farmacologia , Acetonitrilas/química , Acetonitrilas/farmacologia , Actinomycetales/enzimologia , Proteínas de Bactérias/metabolismo , Biocatálise/efeitos dos fármacos , Varredura Diferencial de Calorimetria , Dicroísmo Circular , Endopeptidases/metabolismo , Estabilidade Enzimática , Etanol/química , Etanol/farmacologia , Guanidina/química , Guanidina/farmacologia , Cinética , Metanol/química , Metanol/farmacologia , Peptídeos/metabolismo , Ligação Proteica , Desdobramento de Proteína , Temperatura , Tripsina/química , Tripsina/metabolismo
20.
Electrophoresis ; 35(7): 978-85, 2014 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-24132731

RESUMO

Surfactant-coated multiwalled carbon nanotubes (MWNTs) were used as pseudostationary phase (PSP) in CE to investigate the total lipids of high-density lipoproteins and low-density lipoproteins. To optimize the CE conditions, several experimental factors including carbon nanotube concentration, bile salt concentration, sodium phosphate (PB) concentration, organic modifier concentration and buffer pH value have been examined. In addition, the CE capillary temperature and applied voltage have also been examined. The optimal separation buffer selected was a mixture of 3.2 mg/L MWNT, 50 mM bile salt, 10 mM PB, 20% 1-propanol, pH 9.5. The optimal capillary temperature and applied voltage selected were 50°C and 20 kV, respectively. Phosphatidyl choline (PC) has been used as a model analyte and investigated by the optimal CE method. The linear range for PC was 0.1-3 mg/mL with a correlation coefficient of 0.9934, and the concentration LOD was 0.055 mg/mL. The optimal CE method has been used to characterize the total lipids of high-density lipoprotein and low-density lipoprotein. At absorbance 200 nm, one major peak and two or three minor peaks showed for the total lipids of lipoproteins within 13 minutes. Resolutions of the total lipids were enhanced using surfactant-coated MWNTs as PSPs in the CE separation buffer. However, resolutions of the total lipids were not enhanced using surfactant-coated single-walled carbon nanotubes as PSPs in the CE separation buffer.


Assuntos
Eletroforese Capilar/métodos , Lipoproteínas/química , Nanotubos de Carbono/química , Fosfatidilcolinas/sangue , 1-Propanol/química , Ácidos e Sais Biliares/química , Humanos , Concentração de Íons de Hidrogênio , Lipoproteínas/sangue , Fosfatidilcolinas/química , Temperatura
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