掺杂Fe元素对Pd/C催化剂性能的影响

用Fe作为掺杂元素, 以活性炭为载体, 通过浸渍还原方法制备了Pd:Fe原子比分别为1:1、2:1、1:2的Pd-Fe/C催化剂.采用TEM和XRD技术对合金催化剂的物理性质进行了测试. 结果表明, 获得的Pd-Fe/C催化剂合金粒子在载体上分布均匀, 粒径<5nm,Fe的掺杂量对Pd/C催化剂晶体结构有很大影响, 通过电化学性能测试比较, 分析了三个不同比例的Pd-Fe/C催化剂和Pd/C催化剂对氢和甲酸的电催化氧化性能. 结果得出:在相同的峰值电位下, 几种催化剂的电流密度大小顺序为: Pd-Fe/C(1:1)>Pd-Fe/C(2:1)>Pd/C>Pd-Fe/C(1:2). 结果表明, 适量掺杂Fe提高了Pd/C催化剂的催化性能, 且Pd:Fe原子比为1:1时催化性能最好.     

Fatigue crack growth rate properties of SA508 and SA533 pressure vessel steels and submerged arc weldments in room and elevated temperature air environments

The stage II fatigue crack growth rate (FCGR) properties of four pressure vessel steels (SA508 Cl 2a, SA533 Gr A Cl 2, SA508 Cl 3a and SA533 Gr B Cl 2) and two automatic submerged arc weldments (SA508 Cl 2a and SA533 Gr A Cl 2) were developed in an air environment at 24 and 288°C (75 and 550°F). Tests were conducted at load ratios of 0.20 and 0.70. The air environment FCGR properties of these four base materials and two weldments proved independent of both load ratio and temperature and conformed to the ASME Section XI air environment reference curve. Furthermore, the base and weld metal air environment FCGR properties of these six pressure vessel steels were essentially identical.     

Phase formation kinetics in SrO-Al2O3-SiO2-B2O3 glass

Phase formation in Sr-celsian glass, containing 3 wt% B₂O₃ (SA2SB), was investigated by using non-isothermal and isothermal kinetic analyses. While stoichiometric celsian (SA2S) glass showed two-stage crystallization of glass, from glassy state to hexacelsian and from hexacelsian to monocelsian, SA2SB glass showed direct crystallization of glass to monocelsian, resulting in considerable decrease in the temperature of monocelsian formation. The activation energy for monocelsian formation in SA2SB glass was 390 kJ/mol, which is lower than those for hexacelsian and monocelsian formation respectively in SA2S glass. The Avrami exponent of SA2SB glass was 2.0, indicating two-dimensional crystal growth with interface-controlled mechanism at a zero nucleation rate.     

Pdn-Fe纳米合金作为Mg-H2O2半燃料电池阴极研究

通过化学还原方法制备Pd:Fe原子比(n)为2 : 1、4 : 1、8 : 1的Pd_n-Fe/C催化剂。采用TEM、XRD和XPS技术对复合催化剂进行表征。结果显示, Fe加入Pd/C催化剂中, 与Pd形成合金, Pd_n-Fe/C催化剂的粒径发生变化; 获得的Pd₄-Fe纳米合金粒子在C载体表面分布均匀, 平均粒径为2~3 nm, Fe的加入对Pd/C催化剂晶体结构有很大影响。电化学(CV, LSV, CA)测试表明: 加入Fe提高了Pd/C催化剂的催化性能, Pd/Fe原子比为4 : 1时, Pd_n-Fe/C的催化性能最好。当E=0.2 V时, Pd/C电极电流密度为17.71 mA/cm², 而Pd₄-Fe/C电极电流密度可达19.42 mA/cm²。电池测试表明, 以Pd₄-Fe/C和Pd/C催化剂为阴极的Mg-H₂O₂半燃料电池的开路电势均为1.8 V左右, 而当电流密度为180 mA/cm²时, 以Pd₄-Fe/C为阴极的电池最大能量密度比Pd/C为阴极的电池高41 mW/cm²。     

Preparation and characterization of protein-loaded polyanhydride microspheres

Poly(1,3-bis-(p-carboxyphenoxy propane)-co-(sebacic anhydride) (P(CPP-SA)) have the anhydride bonds in copolymer backbone, which are available for degradation on the base of passive hydrolysis. This chemical structure made it degraded within a short time in linear degradation rate. For this property, polyanhydrides are one of the most suitable biodegradable polymers employed as drug carriers. This paper aimed at researching the erosion and degradation of P(CPP-SA) microspheres with CPP/SA monomer ratios of 20:80, 35:65 and 50:50. In vitro protein release from the microspheres was also investigated in this paper. Human serum albumin (HSA) was used as the model protein. In this research, the microspheres degradation and drug release rate from microspheres can be adjusted by altering the CPP/SA ratios of P(CPP-SA). The features of surface erosion were observed in SEM. The structural integrity of HSA extracted from microspheres was detected by gel permeation chromatography, compared with native HSA. The results showed HSA remained its molecule weight after encapsulated.     

Electrical conduction in light rare-earth tungstates

This paper reports the results of electrical conductivity (σ) and thermoelectric power (H) of light rare-earth tungstates in the temperature range 600–1200K. Holes are the dominant charge carriers over the whole studied temperature range for Nd, Sm and Gd tungstates. However, in the case of La, Ce and Pr tungstates, the conduction is dominated by electrons at lower temperatures, but above 950K in La, 800K in Ce and 950K in Pr the dominant charge carriers become holes. A sharp break and change in the log σ vs 1/T slope occurs in La, Ce and Pr tungstates around the same temperature at which the dominant charge carrier changes from electrons to holes. In the case of Nd, the conductivity anomaly occurs around 1020K without any change in the nature of the charge carrier. The data have been analysed using band theory.     

Dynamic fracture toughness of heavy section, narrow gap, gas tungsten arc weldments

Dynamic fracture toughness tests were performed on three, ASME SA533 Gr A Cl 2 narrow gap, gas tungsten arc weldments (minimum yield strength equals 70 ksi, 485 MPa). Linear elastic K_Id results were obtained at low temperatures while J-integral techniques were utilized to evaluate dynamic fracture toughness over the transition and upper shelf temperature ranges. Loading rates in terms of K averaged 4.41 × 10⁴ksi√(in.)/sec (4.88 × 10⁴MPa√(m)/sec). Tensile, Charpy impact and drop weight nil ductility transition (NDT) tests were also performed. The dynamic fracture toughness of both stress relieved (24 hr at 1125°F, 607°C) plus quenched and tempered SA533 Gr A Cl 2 narrow gap, gas tungsten arc weldments: (a) easily transcended the ASME specified minimum reference toughness K_IR curve, and (b) significantly exceeded the fracture toughness demonstrated by lower strength, stress relieved (3/3.5 hr at 1125°F, 607°F) SA533 Gr A Cl 2 automatic submerged arc weldments.     

EFFECT OF DEVELOPER PROPERTIES ON PRINT QUALITY

We investigated the dependence of the toner charge-to-mass ratio (q/m) in a two-component electrophotographic developer on the shaking time, toner concentration (T/C), carrier sizes, and the carrier core and the coating materials, as well as the resulting print qualities in terms of print density, background density, tone reproduction, resolution, and dot gain. Four different sizes of spherical ferrite carriers, four different carrier coating materials, and an irregular iron carrier were used with two types of toner: 14 um red toner (NP-4080) and 8 um cyan toner (CLC-500). The q/m measurement by the blow-off method showed that the red toner charge was positive while the cyan toner charge was negative with these carriers. The toner q/m values, which depended on the shaking time and decreased with the increasing T/C were much more affected by the larger carrier and the smaller toner. The carriers which yielded charges in the proper range produced better print qualities than did the other carriers that yielded a toner q/m     

Development of Diclofenac Sodium Controlled Release Solid Dispersions by Spray Drying Using Optimization Strategy I. Powder Formulation

Diclofenac sodium (DS) controlled release solid dispersions were prepared by spray drying using ethylcellulose (EC), methacrylic acid copolymer (Eudragit), chitosan, hydroxypropyl methylcellulose (HPMC), and carbomer as single carriers and EC-chitosan as combined carriers. Among solid dispersions of 3:1 drugsingle carrier, the system containing chitosan exhibited the slowest dissolution followed by the systems containing Eudragit, EC, HPMC, and carbomer, respectively. Combined carriers of EC-chitosan exhibited more dissolution retarding effect than single carrier of EC or chitosan. An Hadamard matrix H[8] was employed to estimate the main effects of four parameters: spray feeding volume and contents of absolute ethanol, EC, and chitosan. Optimization strategy using multiple linear regression and a feasibility computer program was utilized to obtain the optimum quantities of the four parameters that would result in a required DS controlled release solid dispersion. The validation of the optimum DS solid dispersion was confirmed by statistical analysis. The optimized 10: (2.5+0.02) DS:(EC+chitosan) controlled release solid dispersion exhibited a dissolution profile that was well fitted to Higuchi model.     

Optimizing flurbiprofen-loaded NLC by central composite factorial design for ocular delivery

The purpose of this study was to design and optimize a new topical delivery system for ocular administration of flurbiprofen (FB), based on lipid nanoparticles. These particles, called nanostructured lipid carriers (NLC), were composed of a fatty acid (stearic acid (SA)) as the solid lipid and a mixture of Miglyol(?) 812 and castor oil (CO) as the liquid lipids, prepared by the hot high pressure homogenization method. After selecting the critical variables influencing the physicochemical characteristics of the NLC (the liquid lipid (i.e. oil) concentration with respect to the total lipid (cOil/L (wt%)), the surfactant and the flurbiprofen concentration, on particle size, polydispersity index and encapsulation efficiency), a three-factor five-level central rotatable composite design was employed to plan and perform the experiments. Morphological examination, crystallinity and stability studies were also performed to accomplish the optimization study. The results showed that increasing cOil/L (wt%) was followed by an enhanced tendency to produce smaller particles, but the liquid to solid lipid proportion should not exceed 30 wt% due to destabilization problems. Therefore, a 70:30 ratio of SA to oil (miglyol + CO) was selected to develop an optimal NLC formulation. The smaller particles obtained when increasing surfactant concentration led to the selection of 3.2 wt% of Tween(?) 80 (non-ionic surfactant). The positive effect of the increase in FB concentration on the encapsulation efficiency (EE) and its total solubilization in the lipid matrix led to the selection of 0.25 wt% of FB in the formulation. The optimal NLC showed an appropriate average size for ophthalmic administration (228.3 nm) with a narrow size distribution (0.156), negatively charged surface (-33.3 mV) and high EE (～90%). The in vitro experiments proved that sustained release FB was achieved using NLC as drug carriers. Optimal NLC formulation did not show toxicity on ocular tissues.     

Development of Diclofenac Sodium Controlled Release Solid Dispersions by Spray Drying Using Optimization Strategy I. Powder Formulation

Abstract

Diclofenac sodium (DS) controlled release solid dispersions were prepared by spray drying using ethylcellulose (EC), methacrylic acid copolymer (Eudragit), chitosan, hydroxypropyl methylcellulose (HPMC), and carbomer as single carriers and EC-chitosan as combined carriers. Among solid dispersions of 3:1 drugsingle carrier, the system containing chitosan exhibited the slowest dissolution followed by the systems containing Eudragit, EC, HPMC, and carbomer, respectively. Combined carriers of EC-chitosan exhibited more dissolution retarding effect than single carrier of EC or chitosan. An Hadamard matrix H[8] was employed to estimate the main effects of four parameters: spray feeding volume and contents of absolute ethanol, EC, and chitosan. Optimization strategy using multiple linear regression and a feasibility computer program was utilized to obtain the optimum quantities of the four parameters that would result in a required DS controlled release solid dispersion. The validation of the optimum DS solid dispersion was confirmed by statistical analysis. The optimized 10: (2.5+0.02) DS:(EC+chitosan) controlled release solid dispersion exhibited a dissolution profile that was well fitted to Higuchi model.     

Thermoelectric properties of porous zinc oxide ceramics doped with praseodymium

We evaluated praseodymium (Pr) doping effects on thermoelectric properties of porous zinc oxide (ZnO) ceramics. The low density ceramics composed of ZnO and an additive of Pr (0.5 and 0.1 mol%) oxide were prepared by sintering processes in different atmospheres (air and oxygen), where the additives were Pr₆O₁₁ known for phase transformations and the trioxide Pr₂O₃ with low valence state different from Pr₆O₁₁. Thermoelectric properties of the samples were measured between 313 K and 903 K. At high-temperature around 590 K, some samples showed a maximum of electrical resistivity. We discussed the origin of the maximum on the basis of carrier transport model on gas sensor and varistor. From the results, The maximum appearance was attributable to an interchange of carriers through defects complex closely related with enhanced zinc vacancies acceptor-like in the vicinity of grain boundaries (GB), where the defect complex seemed to be caused by Pr with valence state between 3+ and 3.78+ around GB. The doping Pr into ZnO matrix is expected to be advantageous to improve thermoelectric power.     

反应堆压力容器用SA508Gr.4N钢的热变形行为

利用Gleeble-1500D热模拟试验机,在温度为1050~1250℃、应变速率为0.001~0.1s-1、真应变量0.16的条件下,研究和分析SA508Gr.4N钢高温塑性变形及动态再结晶行为。结果表明:SA508Gr.4N钢的高温真应力-应变曲线主要以动态再结晶为特征,峰值应力随变形温度的降低或应变速率的升高而增加,属于温度和应变速率敏感材料;在真应力-应变曲线的基础上,建立材料热变形本构方程,较好地表征了材料高温流变特征,其热激活能为383.862kJ/mol;其硬化率-应力(θ-σ)曲线均呈现拐点且-dθ/dσ-σ曲线出现极小值;临界应变随应变速率的增大与变形温度的降低而增加,且临界应变(εc)与峰值应变(εp)之间具有一定相关性,即εc/εp=0.517;临界应变与Z参数之间的函数关系为εc=8.57×10-4 Z0.148。     

正癸酸-月桂酸-硬脂酸三元低共熔体系/膨胀石墨复合相变材料的制备与表征

将正癸酸(DA)、月桂酸(LA)和硬脂酸(SA)熔融共混制备了三元体系相变材料(DA-LA-SA),以DA-LA-SA为相变材料,膨胀石墨(EG)为载体材料,用熔融共混法制备不同DA-LA-SA含量的三元低共熔脂肪酸/膨胀石墨复合相变材料(DA-LASA/EG-PCMs)。采用FT-IR、XRD、SEM、TGA和DSC对其组成成分、晶体结构、微观形貌、相变温度和相变焓进行表征。结果表明,当DA、LA和SA的质量配比为1∶8∶1时,DA-LA-SA具有较低的相变温度和较高的相变焓;EG由大量的微孔构成,通过微孔束缚和表面吸附与DA-LA-SA物理结合,具有良好的稳定性;EG质量分数为10%时,所制备的DA-LA-SA/EG-PCMs三元相变体系复合相变材料的相变温度为38.6℃,相变焓为123J/g,导热系数为3.572 1 W·(m·K)-1,分散均匀,颗粒粒径较小,具有优良的热性能和稳定性。     

Extraction and separation of Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid solutions with selected cyanamides as novel extractants

Three structurally related novel extractants namely: N,N-dihexylcyanamide (DHCY), N,N-di(2-ethylhexyl)cyanamide (DEHCY) and N,N-di-octylcyanamide (DOCY) were synthesized in our laboratory and characterized by different techniques. The general method for synthesizing these extractants was based on the reaction of relevant secondary amines with cyanogen bromide in presence of sodium acetate anhydride. Their extracting ability in toluene as a diluent for Pd(II), Pt(IV), Fe(III), Zn(II), Cu(II) and Ag(I) from hydrochloric acid media has been studied. The extraction of hydrochloric acid was studied also. Pd(II) was strongly extracted by these extractants at low hydrochloric acid concentrations and the extraction decreased with increasing hydrochloric acid concentration while the reverse was obtained in the extraction of Pt(IV), Fe(III) and Zn(II). Under similar extraction conditions Cu(II) and Ag(I) were found poorly extracted. Hydrochloric acid was extracted only in its high concentration region. A systematic investigation has been carried out on the extraction of Pd(II) using two of the synthesized extractants. Pd(II) was extracted as a solvated complex with the composition, metal:chloride ion:extractant=1:2:2. The extracted species were studied also using IR spectra.     

In vitro skin permeation of hinokitiol loaded in vesicles composed of behenyltrimethylammonium chloride and stearic acid

Introduction: Behenyltrimethylammonium chloride (BTAC) and stearic acid (SA) could be associated with each other through salt bridges, and the associated BTAC/SA could build bilayer vesicles with the aid of hinokitiol (HKL). Method: The vesicles were prepared by a precipitation method and used to enhance the skin permeation of HKL. Results: In case the molar ratio of BTAC/SA/HKL was 1/1/0, no vesicle was observed on transmission electron microscope photos. When the molar ratio of BTAC/SA/HKL was 1/1/0.4, vesicle was observed together with some agglomerates. When the content of HKL increased to the ratios of 1/1/0.8 and 1/1/1.2, vesicles were exclusively observed. In vitro fluxes for 18 hours through hairless mouse skin of HKL dissolved in alcoholic solutions were less than 1 mg/cm2/h. Whereas the fluxes of HKL encapsulated in the vesicles were about three times higher than that of HKL in the alcoholic solutions. Conclusion: The vesicles could be used for the hair growth promotion.     

Evaluation of hydrophilic matrix tablets based on Carbopol® 971P and low-viscosity sodium alginate for pH-independent controlled drug release

Background: The aim of this study was to evaluate matrix tablets containing different ratios of Carbopol^® 971P (CP) to low-viscosity sodium alginate (SA) and assess their suitability for pH-independent controlled drug release. Methods: Two processing methods (physical mixing, PM and spray-drying, SD) were applied before compaction and the release from corresponding matrices was compared. The release from CP-SA PM matrices was also investigated using three model drugs (paracetamol, salicylic acid, and verapamil HCl) and two dissolution media (0.1 N HCl or phosphate buffer, pH?=?6.8), and the release rate, mechanism, and pH-dependence were characterized by fitting of Higuchi and Peppas models, and evaluation of similarity factor. Furthermore, swelling behavior of CP-SA matrix tablets was studied for evaluating its impact on drug release. Results: The processing method (SD or PM) markedly affected the drug release from CP-SA matrices. ANOVA tests showed significant effects of the CP:SA ratio and drug type on the release rate (expressed by the constant, K_H, from Higuchi model) and of the dissolution medium on the release mechanism (expressed by the exponent, n, from Peppas model). Similarity factor (f₂) indicated that the CP:SA ratios ≥?25:75 and ≥?50:50 were suitable for pH-independent release of paracetamol and salicylic acid, respectively, although for verapamil HCl, the matrix with low CP:SA ratio (0:100) showed remarkably reduced pH-dependence of release. Swelling parameters (water uptake and mass loss) were significantly changed with experimental variables (CP:SA ratio, medium, and time) and were in good correlation with drug release. Conclusion: Matrix tablets based on CP and SA form a potentially useful versatile system for pH-independent controlled drug release.     

Hydrogen Storage in Carbon-Based Nanostructured Materials

Carbon nanostructures represent a revolution in science and hold the potential for a large range of applications because of their interesting electrical, mechanical, and optical properties. Multiwall carbon nanotubes and carbon nanofibers of herringbone formation were grown by chemical vapor deposition on different catalysts from a number of hydrocarbon sources. After the total or particle removal of the catalyst system, the carbon nanostructures were analyzed for hydrogen uptake. Six samples of nanofibers grown on a Pd-based catalyst system (with a surface area of 425–455 m²/g) were controlled oxidized in air, such that they had different ratios of Pd/C varying from 0.05 to 0.9 mole ratio. The hydrogen uptake experiments were performed volumetrically in a Sievert-type installation and showed that the quantity of desorbed hydrogen (for pressure intervals ranging from 1 to 100 bars) by the carbon nanostructures free of any metal catalyst particles was between 0.04 and 0.33% by weight. For the samples of nanofibers that contained Pd in various Pd/C ratios, palladium revealed catalytic properties and supplied atomic hydrogen at the Pd/C interface by dissociating the H₂ molecules. The results show a direct correlation between the Pd/C ratio and the quantity of hydrogen absorbed by these samples. A saturation value of about 1.5 wt.% was reached for a high ratio of about 1:1 of Pd/C. The multiwall carbon nanotubes grown on a Fe:Co:CaCO₃ catalytic system and purified by acid cleaning and air oxidation showed a hydrogen uptake value of 0.1 to 0.2 wt.%.     

Evaluation of salicylic acid fatty ester prodrugs for UV protection

The purpose of this study was to investigate the physicochemical properties and in vitro evaluation of fatty ester prodrugs of salicylic acid for ultraviolet (UV) protection. The physicochemical properties such as lipophilicity, chemical stability and enzymatic hydrolysis were investigated with the following fatty ester prodrugs of salicylic acid: octanoyl (C8SA), nonanoyl (C9SA), decanoyl (C10SA), lauroyl (C12SA), myristoyl (C14SA) and palmitoyl oxysalicylate (C16SA). Furthermore, their skin permeation and accumulation were evaluated using a combination of common permeation enhancing techniques such as the use of a lipophilic receptor solution, removal of stratum corneum and delipidization of skin. Their k' values were proportional to the degree of carbon-carbon saturation in the side chain. All these fatty esters were highly stable in 2-propanol, acetonitrile and glycerin, but unstable in methanol and ethanol. They were relatively unstable in liver and skin homogenates. In particular, C16SA was mostly hydrolyzed to its parent compound in hairless mouse liver and skin homogenates, suggesting that it might be converted to salicylic acid after its topical administration. In the skin permeation and accumulation study, C16SA showed the poorest permeation in all skins, suggesting that it could not be permeated in the skin. Furthermore, C14SA and C16SA were less accumulated in delipidized skin compared with normal skin or stripped skin, suggesting that these esters had relatively strong affinities for lipids compared with the other prodrugs in the skin. C16SA showed significantly higher dermal accumulation in all skins compared with its parent salicylic acid. Thus, the palmitoyl oxysalicylate (C16SA) might be a potential candidate for UV protection due to its absence of skin permeation, smaller uptake in the lipid phase and relatively lower skin accumulation.     

Characterization of ibuproxam binary and ternary dispersions with hydrophilic carriers

This work investigates the possibility of increasing the dissolution properties of ibuproxam (a poorly water-soluble anti-inflammatory drug) using hydrophilic carriers such as polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), or urea, alone or in combination. Phase-solubility studies showed that the carrier solubilizing power was in the order PEG>PVP>urea and evidenced a synergistic effect in drug solubility improvement when using carrier combinations. Binary and ternary systems, at 20/80 or 20/40/40 (w/w) drug/carrier(s) ratios, prepared by coevaporation of their ethanolic solutions or by cogrinding physical mixtures in a high-energy vibrational micromill, were characterized by differential scanning calorimetry (DSC), hot stage microscopy (HSM), and scanning electron microscopy (SEM) analyses. The results of dissolution tests (USP paddle method), in terms of Dissolution Efficiency, indicated that ternary systems were up to 35% more effective than the corresponding binary preparations and coevaporated products were up to 45% more efficacious than the corresponding coground ones. The IBUX-PEG-PVP coevaporated was the best product, allowing a more than three-times increase in Dissolution Efficiency with respect to drug alone; moreover, t50% (> 60 min for pure ibuproxam) was < 10 min, and 90% dissolution was achieved after 30 min, whereas only 40% was obtained after 60 min for pure drug. The best performance of this system was attributed to a joined effect of the strong amorphizing power of PVP (as demonstrated by solid state analyses) with the high solubilizing efficacy of PEG (as emerged from phase-solubility studies). The drug dissolution rate from solid dispersions remained practically unchanged after one-year storage at room temperature in closed containers.