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1.
Guanidine dichloroacetate was synthesized and separated as crystals. Differential scanning calorimetry (DSC) measurement shows that this compound undergoes a reversible phase transition at about 275 K with a heat hysteresis of 28 K. Step-like dielectric anomaly observed at 274 K further confirms the phase transition. The single-crystal X-ray diffraction data suggested that these was a transition from a room-temperature phase with the space group of P21/n (a = 8.030(5), b = 12.014(9), c = 8.124(6) Å, β = 96.089(1)°, V = 779.3(1) Å3, and Z = 4) to a low-temperature one with the space group of P21/c (a = 7.941(2), b = 11.828(3), c = 10.614(2) Å, β = 130.985(1)°, V = 752.6(3) Å3, and Z = 4). The displacements of hydrogen bonds induce the structure phase transition.  相似文献   

2.
We report a series of thermoresponsive cellulose nanocrystals (CNCs) decorated with poly(poly(ethylene glycol) methylacrylate) copolymers (poly(PEGMA)-g-CNCs) synthesized by surface initiated-atom transfer radical polymerization (SI-ATRP). The chemical structures and surface morphologies were subsequently confirmed by FT-IR, XPS, and AFM measurements. With regard to thermally responsive behavior, poly(PEGMA)-g-CNCs show tunable lower critical solution temperature (LCST) values in the range of 34–66 °C by varying the feeding ratios of comonomers. The reversible morphological transformation from individual nano-rod structures to larger globule aggregates was further verified by AFM during the LCST transition. These functionalized CNCs have potential as smart film filters and biosensors.  相似文献   

3.
The kinetics of the hydrolysis of methyl cellulose (MC, DS 1.27 and 1.95) was studied by a two-step procedure, comprising partial hydrolysis in 1 M TFA in water and water/acetone at 120 °C for various time periods, labeling of generated reducing ends by reductive amination, complete depolymerization by methanolysis followed by trimethylsilylation, and gas chromatographic analysis of the two sets of partially O-methylated glucose derivatives. Rate constants of MCs were all in the order of 10?4 s?1. In aqueous TFA, overall rate of hydrolysis of the MC with lower DS was faster than of the MC with higher DS. When substituting half of the water by acetone, reaction was slowed down while selectivity regarding different O-methyl glucosyl residues increased. Compared to the parent glucosyl unit methylation at O-2 and at O-6 decreased rate of hydrolysis, while 3-O-methyl favored it especially in the early stage of the conversion of the macromolecules. Beside slight differences between the two MCs and reaction conditions, rate constants k i (i = position of methyl) followed the order k 36 ≈ k 3 > k 0 ≈ k 23 > k 6 > k 2 ≥ k 236 > k 26. For the higher substituted MC2 an initial slow phase with more pronounced differences of k i, followed by a faster less selective period was observed. Regioselectivity of hydrolysis with respect to methyl positions was expressed as standard deviation of k i and was between 16 and 46% depending on MC and conditions. Findings are discussed with respect to electronic effects, solvent-effect, H-bonding pattern and solution state.  相似文献   

4.
Sodium carboxymethyl cellulose (SCMC) with different degrees of substitution (DS) possesses structural characteristics and physicochemical properties that are important in broad areas of industrial applications. This reported work investigated the structural characteristics, including the effective length (L ef), the radius of gyration (R g), and the hydrodynamic radius (R H), and the physicochemical properties, including intrinsic viscosity ([η]) and salt tolerance, of SCMC with a DS more than 1.0 in NaCl solution using molecular dynamics (MD) simulations. In the MD simulations, the DS of SCMC varied from 1.2 to 2.8, and the NaCl concentration varied from 0 to 1.4 mol/L. MD simulation results showed that with the increment of NaCl concentration, the L ef (or R g or R H) of SCMC decreased; with the increment of the DS, the L ef of SCMC increased. Also, the variation tendency of [η] in the NaCl solution was consistent with its L ef (or R g or R H). It was noted that the salt tolerance (represented by D) of SCMC increased as the DS increased. In addition, the sharp variation of the D value of SCMC occurred in the range of DS of 1.6 to 2.0, which agreed with the reported experimental results. Radial distribution function analyses showed that the Na+ cations had a stronger interaction with the carboxyl groups in SCMC with lower DS when it was present in a salt solution of higher concentration, which also reasonably explained the variation of L ef, R g, R H, [η], and D of SCMC in NaCl solution.  相似文献   

5.
Potassium hydrogen bis-dichloroacetate (1) was synthesized and separated as crystals. Differential scanning calorimetry (DSC) measurement reveals that this compound undergoes a reversible phase transition at about 259 K with a heat hysteresis of 23.5 K. Dielectric anomaly observed at 260 K in the heating process further confirms the phase transition. The room temperature X-ray single-crystal structure determination indicates that 1 crystallizes in the monoclinic crystal system with a centrosymmetric space group P21/c, and cell parameters are a =?6.240(1), b =?23.177(4), c =?7.335(1) Å, β =?106.938(1)°, V =?1014.8(3) Å3, and Z =?4. In the low temperature phase, 1 also crystallizes in monolinic with space group P21/c, and cell parameters are a =?6.180(1), b =?22.988(2), c =?7.200(1) Å, β =?108.098(1)°, V =?972.4(1) Å3, and Z =?4. The structural phase transition is dominating caused by the torsion of bond angles.  相似文献   

6.
Dihydromyricetin-mediated silver nanoparticles (DMY-AgNPs) were synthesized and their efficacy against fungal pathogens tested in vitro. The shape of DMY-AgNPs appeared to be spherical with size of ~34 nm. Fourier-transform infrared (FT-IR) analysis indicated that –OH and C=O groups were involved in nanoparticle formation. The XRD pattern of DMY-AgNPs showed strong peaks at 38°, 44°, and 64°, corresponding to reflection from (111), (200), and (220) planes. Five opportunistic fungal pathogens, namely Aspergillus fumigatus, Aspergillus niger, Paecilomyces formosus, Candida albicans, and Candida parapsilosis, were isolated from patients suffering from respiratory tract infections. Growth of each fungal strain was inhibited by DMY-AgNPs. The zone of inhibition of DMY-AgNPs against A. fumigatus, A. niger, P. formosus, C. albicans, and C. parapsilosis was 17.6, 19.2, 22.2, 15.8, and 18.5 mm. The minimal inhibitory concentration was found to be 0.83, 0.73, 0.67, 0.95, and 0.89 µg mL?1, respectively. This is the first report on DMY-AgNPs as an effective antifungal agent. DMY-AgNPs are a potential alternative to commercially available antifungal fungicidals.  相似文献   

7.
Nicotinic acid (also known as niacin) was recrystallized from anhydrous ethanol. X-ray crystallography was applied to characterize its crystal structure. The crystal belongs to the monoclinic system, space group P2(1)/c. The crystal cell parameters are a = 0.71401(4) nm, b = 1.16195(7) nm, c = 0.71974(6) nm, α = 90°, β = 113.514(3)°, γ = 90° and Z = 4. Molar enthalpies of dissolution of the compound, at different molalities m/(mol·kg?1) were measured with an isoperibol solution–reaction calorimeter at T = 298.15 K. The molar enthalpy of solution at infinite dilution was calculated, according to Pitzer’s electrolyte solution model and found to be \( \Delta_{\text{sol}} H_{m}^{\infty } = ( 2 7. 3 \pm 0. 2) \) kJ·mol?1 and Pitzer’s parameters (\( \beta_{{\text{MX}}}^{{\text{(0)}L}} \), \( \beta_{{\text{MX}}}^{{\text{(1)}L}} \) and \( C_{{\text{MX}}}^{\phi L} \)) were obtained. The values of apparent relative molar enthalpies (\( {}^{\phi }L \)) and relative partial molar enthalpies (\( \overline{{L_{2} }} \) and \( \overline{{L_{1} }} \)) of the solute and the solvent at different molalities were derived from the experimental enthalpy of dissolution values of the compound. Also, the standard molar enthalpy of formation of the anion \( {\text{C}}_{ 6} {\text{H}}_{ 4} \text{NO}_{2}^{-} \) in aqueous solution was calculated to be \( {\Delta_{\text{f}}^{} H}_{\text{m}}^{\text{o}} ({\text{C}}_{ 6} {\text{H}}_{ 4} {\text{NO}}_{2}^{-} \text{,aq}) = - \left( {603.2 \pm 1.2} \right)\;{\text{kJ}}{\cdot}{\text{mol}}^{-1} \).  相似文献   

8.
As phenylalanine dehydrogenase (PheDH) plays an important role in the synthesis of chiral drug intermediates and detection of phenylketonuria, it is significant to obtain a PheDH with specific and high activity. Here, a PheDH gene, pdh, encoding a novel BhPheDH with 61.0% similarity to the known PheDH from Microbacterium sp., was obtained. The BhPheDH showed optimal activity at 60 °C and pH 7.0, and it showed better stability in hot environment (40–70 °C) than the PheDH from Nocardia sp. And its activity and thermostability could be significantly increased by sodium salt. After incubation for 2 h in 3 M NaCl at 60 °C, the residual activity of the BhPheDH was found to be 1.8-fold higher than that of the control group (without NaCl). The BhPheDH could tolerate high concentration of ammonium chloride and its activity could be also enhanced by the high concentration of ammonium salts. These characteristics indicate that the BhPheDH possesses better thermostability, ammonium chloride tolerance, halophilic mechanism, and high salt activation. The mechanism of thermostability and high salt tolerance of the BhPheDH was analyzed by molecular dynamics simulation. These results provide useful information about the enzyme with high-temperature activity, thermostability, halophilic mechanism, tolerance to high concentration of ammonium chloride, higher salt activation and enantio-selectivity, and the application of molecular dynamics simulation in analyzing the mechanism of these distinctive characteristics.  相似文献   

9.
10.
Densities for aqueous solutions of magnesium tetraborate MgB4O7(aq) at the molalities of (0.00556–0.03341) mol·kg?1 were measured with an Anton Paar Digital vibrating-tube densimeter at temperature intervals of 5 K from 283.15 to 363.15 K and 0.1 MPa. Apparent molar volumes were obtained based on the experimental density data, and the 3D diagrams of the apparent molar volume (V ? ) of MgB4O7(aq) against temperature (T) and molality (m) were plotted. On the basis of the Vogel–Tamman–Fulcher equation, the coefficients of the correlation equation for densities of MgB4O7(aq) against temperature and molality were parameterized. According to the Pitzer ion-interaction model of the apparent molar volume, the temperature correlation equations of Pitzer single-salt parameters F(i,p,T)?=?a0?+?a1?×?T?+?a2?×?T 2?+?a3/T?+?a4?×?ln(T)?+?a5?×?T 3 (where T is temperature in Kelvin, a i are model parameters) for MgB4O7 were obtained for the first time.  相似文献   

11.
In pursuit of improving performance of the methylene blue adsorption process, the potential of a novel 4A-zeolite/polyvinyl alcohol (PVA) membrane adsorbent was investigated. Adding 4A-zeolite particles to the PVA membrane adsorbent provided an effective structure for the adsorptive membrane in dye removal processes. Effect of zeolite content was also studied via synthesis of different mixed matrix membrane adsorbents (MMMAs) with 5, 10, 15, and 20 wt% 4A-zeolite content. Morphology of MMMAs was analyzed by scanning electron microscope and the intermolecular interactions were determined by Fourier transform infrared spectroscopy. X-ray diffraction was performed to determine the crystal structure of MMMAs. For the sake of finding optimum condition, the adsorption capacity was examined at various operating parameters, such as contact time, temperature, pH, and initial concentration. The maximum value of the adsorption capacity (q e) of 41.08 mg g?1 and the highest removal efficiency of 87.41 % were obtained by applying 20 wt% loading of 4A-zeolite. The experimental data were fitted well with the Freundlich adsorption isotherm model (R 2 = 0.9917) compared with the Langmuir (R 2 = 0.9489) and the Tempkin (R 2 = 0.8886) adsorption isotherm models, and the adsorption kinetic data verified the best fitting with the pseudo-second-order model (R 2 = 0.9999). The estimated data for Gibb’s free energy (ΔG°) showed that the adsorption process is spontaneous at lower temperature values and non-spontaneous at higher temperature values. Other evaluated thermodynamic parameters such as changing in enthalpy (ΔH°) and entropy (ΔS°) revealed that the adsorption process is exothermic with an increase in orderliness at the solid/solution interface.  相似文献   

12.
From three cell-associated β-xylosidases produced by Aureobasidium pullulans CBS 135684, the principal enzyme was enriched to apparent homogeneity and found to be active at high temperatures (60–70 °C) over a pH range of 5–9 with a specific activity of 163.3 units (U) mg?1. The enzyme was thermostable, retaining over 80% of its initial activity after a 12-h incubation at 60 °C, with half-lives of 38, 22, and 10 h at 60, 65, and 70 °C, respectively. Moreover, it was tolerant to xylose inhibition with a K i value of 18 mM. The K m and V max values against p-nitrophenyl-β-d-xylopyranoside were 5.57 ± 0.27 mM and 137.0 ± 4.8 μmol min?1 mg?1 protein, respectively. When combining this β-xylosidase with xylanase from the same A. pullulans strain, the rate of black liquor xylan hydrolysis was significantly improved by up to 1.6-fold. The maximum xylose yield (0.812 ± 0.015 g g?1 dry weight) was obtained from a reaction mixture containing 10% (w/v) black liquor xylan, 6 U g?1 β-xylosidase and 16 U g?1 xylanase after incubation for 4 h at 70 °C and pH 6.0.  相似文献   

13.
The application of alkaline phytase as a feed additive is restricted by the poor specific activity. Escherichia coli is a frequently used host for directed evolution of proteins including alkaline phytase towards improved activity. However, it is not suitable for production of food-grade products due to potential pathogenicity. To combine the advantages of different expression systems, mutants of the alkaline phytase originated from Bacillus subtilis 168 (phy168) were first generated via directed evolution in E. coli and then transformed to food-grade hosts B. subtilis and Pichia pastoris for secretory expression. In order to investigate the suitability of different expression systems, the phy168 mutants expressed in different hosts were characterized and compared in terms of specific activity, pH profile, pH stability, temperature profile, and thermostability. The specific activity of B. subtilis-expressed D24G/K70R/K111E/N121S mutant at pH 7.0 and 60 °C was 30.4 U/mg, obviously higher than those in P. pastoris (22.7 U/mg) and E. coli (19.7 U/mg). Moreover, after 10 min incubation at 80 °C, the B. subtilis-expressed D24G/K70R/K111E/N121S retained about 70 % of the activity at pH 7.0 and 37 °C, whereas the values were only about 25 and 50 % when expressed in P. pastoris and E. coli, respectively. These results suggested B. subtilis as an appropriate host for expression of phy168 mutants and that the strategy of creating mutants in one host and expressing them in another might be a new solution to industrial production of proteins with desired properties.  相似文献   

14.
孙培健  王佛松 《高分子科学》2015,33(11):1598-1605
Microspheres with thermo-responsible surface were fabricated by PCL-b-PEO-b-PNIPAM triblock copolymers. Thermo-responsible morphological changes of PCL-b-PEO-b-PNIPAM microspheres immersed in aqueous solution at temperatures above the LCST (e.g. 37 °C) were observed from porous surface structure to compact surface layer. Enzymatic degradation and in vitro drug release results showed that the thermo-responsible surface layer greatly influenced the degradation of microspheres as well as the drug release behavior from microspheres. With the copolymerization of PNIPAM block into PCL-b-PEO copolymers, the drug release could be well regulated by changing temperatures and microspheres composition, which revealed the great potentials of microspheres with thermo-responsible surface for controlled drug release.  相似文献   

15.
In this study, silver nanoparticles (AgNPs) were biosynthesized using Stachys lavandulifolia and Lathyrus sp. The first sign of the reduction of silver ions to AgNPs was the change in color of S. lavandulifolia and Lathyrus sp. extracts changed into dark brown and auburn after treating with silver nitrate, respectively. The UV–Vis spectroscopy of reaction mixture (extract+silver nitrate) produced by S. lavandulifolia and Lathyrus sp. showed the strong adsorption peaks at ?440 and 420 nm, respectively. The transmission electron microscope images showed the synthesis of AgNPs using S. lavandulifolia and Lathyrus sp. with an average size of 7 and 11 nm, respectively. The result of X-ray diffraction pattern showed four diffraction peaks at 38°, 44°, 64°, and 77° for both types of biosynthesized AgNPs. Fourier transform infrared spectroscopy showed the possible role of involved proteins and polyhydroxyl functional groups in the synthesis process of AgNPs. Inductively coupled plasma analysis determined the conversion rate (percentage) of silver ions to silver nanoparticles in reaction mixtures of S. lavandulifolia and Lathyrus sp. 99.73 and 99.67 %, respectively. In addition, antifungal effect of AgNPs, synthesized by both extracts, was studied separately on mycelial growth of Dothiorella sarmentorum, in a completely randomized design on potato dextrose agar (PDA) medium. The inhibition rate of mycelial growth was strongly depended on the density of AgNPs and it strongly increased with increasing the density of AgNPs in the PDA medium. AgNPs more than 90 % of them inhibited from the mycelia growth of the fungus at the concentration of 40 µg/mL and higher.  相似文献   

16.
Bioethanol was produced using polysaccharide from soybean residue as biomass by separate hydrolysis and fermentation (SHF). This study focused on pretreatment, enzyme saccharification, and fermentation. Pretreatment to obtain monosaccharide was carried out with 20% (w/v) soybean residue slurry and 270 mmol/L H2SO4 at 121 °C for 60 min. More monosaccharide was obtained from enzymatic hydrolysis with a 16 U/mL mixture of commercial enzymes C-Tec 2 and Viscozyme L at 45 °C for 48 h. Ethanol fermentation with 20% (w/v) soybean residue hydrolysate was performed using wild-type and Saccharomyces cerevisiae KCCM 1129 adapted to high concentrations of galactose, using a flask and 5-L fermenter. When the wild type of S. cerevisiae was used, an ethanol production of 20.8 g/L with an ethanol yield of 0.31 g/g consumed glucose was obtained. Ethanol productions of 33.9 and 31.6 g/L with ethanol yield of 0.49 g/g consumed glucose and 0.47 g/g consumed glucose were obtained in a flask and a 5-L fermenter, respectively, using S. cerevisiae adapted to a high concentration of galactose. Therefore, adapted S. cerevisiae to galactose could enhance the overall ethanol fermentation yields compared to the wild-type one.  相似文献   

17.
A new high-nitrogen complex [Cu(Hbta)2]·4H2O (H2bta = N,N-bis-(1(2)H-tetrazol-5-yl) amine) was synthesized and characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analyses. X-ray structural analyses revealed that the crystal was monoclinic, space group P2(1)/c with lattice parameters a = 14.695(3) Å, b = 6.975(2) Å, c = 18.807(3) Å, β = 126.603(1)°, Z = 4, D c = 1.888 g cm?3, and F(000) = 892. The complex exhibits a 3D supermolecular structure which is built up from 1D zigzag chains. The enthalpy change of the reaction of formation for the complex was determined by an RD496–III microcalorimeter at 25 °C with the value of ?47.905 ± 0.021 kJ mol?1. In addition, the thermodynamics of the reaction of formation of the complex was investigated and the fundamental parameters k, E, n, \( \Updelta S_{ \ne }^{{{\uptheta}}} \), \( \Updelta H_{ \ne }^{{{\uptheta}}} \), and \( \Updelta G_{ \ne }^{{{\uptheta}}} \) were obtained. The effects of the complex on the thermal decomposition behaviors of the main component of solid propellant (HMX and RDX) indicated that the complex possessed good performance for HMX and RDX.  相似文献   

18.
The thermal analyses and the water state diagrams of agavin and inulin were investigated. The thermogravimetric analysis and differential scanning calorimetry (DSC) were used to know the difference between fructans. Linear inulin (220.0 °C) showed a higher thermal stability than the branched agavins (206.7 °C). The samples displayed different physical states and lightness depending on the water activity of storage (a w). The agavin showed different physical states: powder (a w < 0.33), soft lump (a w ≈ 0.43), sticky (0.55 < a w < 0.77), and liquid (a w > 0.85), while inulin showed two physical states: an amorphous powder at a w < 0.55 and a semicrystalline solid at a w > 0.69. These physical states decreased the lightness of fructans. The GAB equation and the Gordon–Taylor equation showed a good fit to the experimental data (R 2 > 0.95). The K constant of GAB equation predicted a lower water affinity of inulin powder, while the agavin powder presented a higher water affinity. The DSC showed a glass transition temperature of 118.1 and 135.3 °C for agavin and inulin anhydrous powders, respectively. An increase in water content in agavin showed a higher depression in the glass transition temperature than in inulin. Also, the inulin exhibited a melting point while agavin not. The water state diagrams showed the critical water activity at which the agavin (0.50) and inulin (0.59) powders were stable to physical changes. This knowledge is used to understand the physical and structural behaviors of agavin and inulin at the different water activities.  相似文献   

19.
In this article we present a singularly almost P-stable exponentially-fitted four-step method for the approximate solution of the one-dimensional Schrödinger equation. More specifically we present a method that is singularly almost P-stable (a concept later introduced in this article) and also integrates exactly any linear combination of the functions {1, x, exp ( ±I v x) , x exp ( ±I v x) , x 2 exp ( ±I v x)}. The numerical experimentation showed that our method is considerably more efficient compared to well known methods used for the approximate solution of resonance problem of the radial Schrödinger equation.  相似文献   

20.
In this study, we obtained a novel salt of ambazone (AMB) with p-aminobenzoic acid (PABA) that exhibits improved solubility and antibacterial activity. The salt was produced by solvent-drop grinding and characterized by powder X-ray diffraction, thermal analysis and Fourier transform infrared spectroscopy. The salt nature of the new form was confirmed by infrared spectroscopy based on the characteristic vibrational band of the protonated amino group. Based on the X-ray powder diffraction data, the compound crystallizes in the triclinic P-1 space group with the following unit cell parameters: a = 14.294 Å, b = 9.162 Å, c = 8.777 Å, α = 95.90°, β = 100.63°, γ = 91.73°. Thermal analysis reveals the thermal events and different decomposition steps of this solid form as compared to the starting compounds. Powder dissolution measurements showed solubility improvement compared with pure ambazone of 2 and 3.3 times in water and phosphate buffer, respectively. Antibacterial tests showed higher activity of the salt to Gram-negative Escherichia coli and Salmonella bacteria as compared to AMB and PABA. The study demonstrates that the pharmaceutical salt of ambazone with p-aminobenzoic acid (AMB–PABA) can be a possible alternative to ambazone in the treatment of infections with Gram-negative bacteria.  相似文献   

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