Modelling of drug diffusion through swellable polymeric systems

A drug diffusion model for the case of diffusion of an initially uniformly distributed drug through a polymeric matrix is presented and solved. Drug diffusion from a single surface is analyzed for the case of countercurrent diffusion of a solvent which is thermodynamically compatible with the polymer. Due to swelling, considerable volume expansion is observed leading to a moving-boundary diffusion problem. Drug concentration profiles within the polymer and drug release rates can be determined. The results are in agreement with experimental data obtained for the system of KCl distributed in hydrophilic hydroxypropyl methyl cellulose matrices, in the form of tablets.     

Determination of sorbic acid with sodium chlorite

A new method for the determination of sorbic acid is proposed, using sodium chlorite in hydrochloric add medium as reagent. In these conditions the hydrochloric acid is oxidized to chlorine which adds on to the double bonds of the sorbic acid. The addition is rapid (30-90 sec) and for this reason the determination is more rapid then others similar to it. Sorbic acid has been determined in foods by this method, after a preliminary solvent extraction or steam-distillation.     

Investigation of water diffusion process in ethyl cellulose-based films by attenuated total reflectance Fourier transform infrared spectroscopy and two-dimensional correlation analysis

Two-dimensional correlation spectroscopy (2Dcos) analysis on the time-resolved attenuated total reflectance Fourier transform infrared spectroscopy has been employed to investigate the diffusion behavior of water in ethyl cellulose/triethyl citrate (EC/TEC) films with varied TEC content. The diffusion coefficients of water in the EC-based films are calculated from the diffusion curves according to the Fickian Diffusion Model. And they are observed to increase with TEC content, possibly caused by the increased free volume in the film matrix. In the 2Dcos analysis, the broad O–H stretching vibration region is split into at least four bands, which can be assigned to four different states of water molecules, that is, bulk water, cluster water, relatively free water and free water. Moreover, it is found that as water molecules disperse into the EC-based films, cluster water with moderate hydrogen bonds diffuses faster than bulk water with strong hydrogen bonds. The relatively free water and free water are formed during the diffusion process due to their interactions with the films matrix, which makes water molecules confined and restricted in limited space.     

Fabrication of superhydrophobic cellulose-based materials through a solution-immersion process

An industrial waterproof reagent [(potassium methyl siliconate) (PMS)] was used for fabricating a superhydrophobic surface on a cellulose-based material (cotton fabric or paper) through a solution-immersion method. This method involves a hydrogen bond assembly and a polycondensation process. The silanol, which was formed by a reaction of PMS aqueous solution with CO 2, was assembled on the cellulose molecule surface via hydrogen bond interactions. The polymethylsilsesquioxane coatings were prepared by a polycondensation reaction of the hydroxyl between cellulose and silanol. The superhydrophobic cellulose materials were characterized by FTIR spectroscopy, thermogravimetry, and surface analysis (XPS, FESEM, AFM, and contact angle measurements). Analytical characterization revealed that nanoscale roughness protuberances uniformly covered the surface, thus transforming the cellulose from superhydrophilic to superhydrophobic with a water contact angle of 157 degrees . The superhydrophobic coatings were satisfactory with regard to both chemical and mechanical durability, and because of the transparency of the coatings the native cotton fabric displayed no changes with regard to either morphology or color. The easy availability of the materials and simplicity of this method render it convenient for mass production.     

Protonation and dip-coating synergistically enhancing dimensional stability of multifunctional cellulose-based films

Cellulose - Cellulose-derived films have received increased attention for replacing petrochemical substrates in various high-tech applications. However, many cellulose composite films are usually...     

Donnan effects in the steady-state diffusion of metal ions through charged thin films

The steady-state diffusion of metals ions through thin films with fixed charged groups was investigated using diffusive gradients in thin films (DGT) measurements. Copolymers of acrylamide and sodium acrylate cross-linked with N,N'-methylenebisacrylamide were used as diffusive gels. The rate of diffusion of cadmium ions through the gels was measured by determining the mass of cadmium bound to a backing chelex resin after a known deployment time. Variation of the ionic strength as well as the fixed charge density and the thickness of the gel layer allowed evaluation of the impact of the Donnan partitioning and the diffusion layer in solution on the observed steady-state flux of ions through the layer. The results underscore that, as the Donnan partitioning increases, the impact of the diffusion layer in solution becomes more significant. At modest Donnan potentials, Donnan partitioning controls the net flux of metal ions, whereas at conditions of increasing Donnan potential, i.e., at decreasing ionic strength, the flux is increasingly limited by diffusion in solution. An analytical expression is developed to describe the influence of Donnan partitioning on the observed steady-state flux of metal ions.     

Catalytic conversion of cellulose-based biomass and glycerol to lactic acid

Catalytic transformation of cellulose into value-added chemicals is of great importance for utilization of renewable and abundant biomass. Due to the high oxygen content, cellulose serves as an ideal candidate for the production of oxygenates, in particular lactic acid which is a versatile building block in chemical industry. The efficient conversion of cellulose to lactic acid generally requires selective activation of specific C–O and C–C bonds, and therefore multifunctional catalysts that combine several key reactions including hydrolysis, isomerization and retro-aldol fragmentation are highly desirable. This review article highlights the recently developed catalytic systems and catalysts for the selective transformation of cellulose and cellulose-derived carbohydrates into lactic acid, lactates and/or its esters. Emphases will be put on the reaction mechanism and key factors that exert effects on the catalytic performances. In addition, the catalytic transformation of glycerol, a C_3 compound over-supplied from biodiesel industry, will also be surveyed. Recent advances in the development of new catalysts or strategies are analyzed and discussed to gain insight into the transformation of C_3 compound to lactic acid.     

Permeability of acetic acid through organic films at the air-aqueous interface

Recent field studies of collected aerosol particles, both marine and continental, show that the outermost layers contain long-chain (C >or= 18) organics. The presence of these long-chain organics could impede the transport of gases and other volatile species across the interface. This could effect the particle's composition, lifetime, and heterogeneous chemistry. In this study, the uptake rate of acetic acid vapor across a clean interface and through films of long-chain organics into an aqueous subphase solution containing an acid-base indicator (bromocresol green) was measured under ambient conditions using visible absorption spectroscopy. Acetic acid is a volatile organic compound (VOC) and is an atmospherically relevant organic acid. The uptake of acetic acid through single-component organic films of 1-octadecanol (C(18)H(38)O), 1-triacontanol (C(30)H(62)O), cis-9-octadecen-1-ol (C(18)H(36)O), and nonacosane (C(29)H(60)) in addition to two mixed films containing equimolar 1-triacontanol/nonacosane and equimolar 1-triacontanol/cis-9-octadecen-1-ol was determined. These species represent long-chain organic compounds that reside at the air-aqueous interface of atmospheric aerosols. The cis-9-octadecen-1-ol film had little effect on the net uptake rate of acetic acid vapor into solution; however, the uptake rate was reduced by almost one-half by an interfacial film of 1-triacontanol. The measured uptake rates were used to calculate the permeability of acetic acid through the various films which ranged from 1.5 x 10(-3) cm s(-1) for 1-triacontanol, the least permeable film, to 2.5 x 10(-2) cm s(-1) for cis-9-octadecen-1-ol, the most permeable film. Both mixed films had permeabilities that were between that of the single-component films comprising the mixture. This shows that the permeability of a mixed film may not be solely determined by the most permeable species in the mixture. The permeabilities of all the films studied here are discussed in relation to their molecular properties, pressure-area isotherms, and atmospheric implications.     

Determination of sorbic acid in urine by gas chromatography-mass spectrometry.

The average daily uptake of the common food preservative sorbic acid is estimated to range from 0.01 to 1.1 mg kg-1. Sorbic acid mainly is metabolised to carbon dioxide. Minor amounts are converted to trans,trans-muconic acid (ttMA) as well as excreted unchanged into the urine. Since urinary ttMA is a biomarker for the occupational and environmental exposure to benzene, there is an additional need for monitoring the uptake of sorbic acid, particularly at low, environmental benzene exposure levels. For this purpose, a simple, robust and rapid method for the determination of sorbic acid in urine at trace levels was developed. After addition of 10 ml of water and 5 ml of 8 M hydrochloric acid to 10 ml of the thawed urine, the sample was water steam distilled using an automated distillation device. A total of 100 ml of the distillate were solid-phase extracted. After washing, the sorbic acid was eluted with 4 ml methanol. The eluate was reduced under a stream of nitrogen to a volume of 300 microliters. After addition of 500 microliters boron trifluoride in methanol and incubation for 1 h at 60 degrees C, the resulting sorbic acid methyl ester was extracted three times with 1 ml heptane. To the combined heptane layers, sorbic acid ethyl ester was added as an internal standard. After reducing to a volume of 100 microliters in a stream of nitrogen, the final analysis was performed by GC-MS using the fragment ions m/z 126 for the analyte and m/z 140 for the internal standard. The limit of detection was 0.7 ng ml-1 urine and the R.S.D. of 69 duplicate determinations was 7.5%. In a controlled, experimental study and in a field study, we were able to show that urinary sorbic acid is a marker for the dietary uptake of sorbic acid and that sorbic acid is converted to ttMA. On average, 0.1% of the dietary sorbic acid is excreted unchanged into the urine. Excretion is complete within 24 h. We found that, on average, 0.23% of the oral dose of sorbic acid is excreted as urinary ttMA. There was a significant correlation between urinary excretions of sorbic acid and ttMA (r = 0.74, n = 69). We conclude that urinary sorbic acid can be used to correct the urinary ttMA level in order to determine the portion related to benzene exposure. This appears to be necessary particularly at low, environmental benzene levels.     

Polarographic determination of sorbic acid in fruit juices and soft drinks

A simple differential-pulse polarographic method using a laboratory-built hanging mercury drop electrode as the working electrode was developed for the determination of sorbic acid in fruit juices and soft drinks. Sorbic acid was extracted from the samples with diethyl ether. After reduction of the ethereal solution to a small volume by direct evaporation, the residual ether was dissolved in the supporting electrolyte (25 ml of acetonitrile + 1 ml of 0.06 M acetic acid + 0.8 g of tetraethylammonium bromide). Peak current was measured at -1.7 V. The working range of the method, without dilution or pre-concentration of the samples, was from 4 to 229 p.p.m. for the original juice and drink samples. The validity of the method was confirmed by parallel determinations using the method of the Association of Official Analytical Chemists and by recovery tests on a large variety of juice samples. Satisfactory recoveries and agreement in results from the two methods were obtained. The recovery and precision (relative standard deviation) of the method were 97 +/- 4 and 100 +/- 3%, respectively, for blackcurrant juice for five determinations.     

Diffusion of acid and alkaline salt solutions through the Nernst diffusion layer

The behavior of diffusion layer under the conditions of salt transfer with excess of acid or alkali, involving the hydrogen and hydroxyl ions, is studied. The transfer is affected by the applying of current. The method of investigation was mathematical simulation based on the solving of boundary problems by using the Nernst-Planck equation with regard to the corresponding conditions of the transfer.     

Fabrication,characterization and evaluation of bacterial cellulose-based capsule shells for oral drug delivery

Bacterial cellulose (BC) was investigated for the first time for the preparation of capsule shells for immediate and sustained release of drugs. The prepared capsule shells were characterized using X-ray diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy. The BC capsule shells were studied for drug release using an USP type-I dissolution apparatus. Irrespective of the drying method and the thickness of the BC sheet, the capsule shells displayed an immediate drug release profile. Moreover, the addition of release-retardant cellulosic polymers sustained the drug release having first-order kinetics for hydroxypropylmethylcellulose and carboxymethyl cellulose sodium with R ² values of 0.9995 and 0.9954, respectively. Furthermore, these capsules shells remained buoyant in 0.1 N HCl (pH 1.2) solution up to 12 h. This study showed that BC is a promising alternative to gelatin capsules with both immediate and sustained drug release properties depending upon the compositions of the encapsulated materials.     

食品中苯甲酸和山梨酸的气相色谱法分离分析

用毛细管气相色谱法对食品中的防腐剂苯甲酸和山梨酸进行了分离分析。样品用乙醚萃取，萃取物蒸发至干，残渣用氯仿溶解后直接进行色谱分析，FFAP石英毛细管柱，柱温220℃，邻苯二甲酸二甲酯为内标物。两种化合物在0.25mg/mL-4.00mg/mL范围内具有良好的线性关系。     

Modelling the formation and growth of anodic passive films on metals in concentrated acid solutions

Two model approaches to the formation of passive films as adsorbed layers during the active anodic dissolution of a metal in acid and their subsequent growth are presented. The first depicts passivation as proceeding in parallel to active dissolution. Adsorption of water on active surface sites leads to passivation, whereas adsorption of acid leads to active dissolution of the metal. The model is consistent with the impedance response during passivation of Fe and an Fe-20%Mo alloy in concentrated H₃PO₄. The second model is an updated version of the so-called surface charge approach to the mechanism of conduction of anodic passive films. It is based on the assumptions that oxygen vacancies are the main ionic charge carriers and the field strength in the barrier layer is constant. A negative surface charge built up at the film/solution interface via accumulation of metal vacancies accelerates oxygen vacancy transport, thus explaining the pseudoinductive behaviour of the metal/film/electrolyte system under small amplitude a.c. perturbation. The model describes the growth of thin anodic films on Fe, Mo and an Fe-20%Mo alloy in concentrated H₃PO₄. Received: 24 January 1997 / Accepted: 18 April 1997     

pH dependence of hydrochloric acid diffusion through gastric mucus: correlation with diffusion through a water layer using a membrane-mounted glass pH electrode

Solute diffusion coefficients (D) can indicate a dependence upon actual solute concentrations. Here a single compartment has been utilized, in which effective HCl diffusion to a membrane-mounted glass pH electrode can be measured across the pH spectrum. The study has investigated HCl diffusion through both mucus and water layers as a function of HCl concentration. The observed dynamic responses of a liquid-film and mucus-coated electrodes over a range of HCl concentrations suggest that the speed at which equilibrium is attained is pH dependent; equilibrium was reached rapidly under more acidic and alkaline conditions. Estimated values of DHCl also indicate a strong pH dependence for both liquid film and mucus. In both instances, a greater than 10-fold reduction in DHCl at pH 7.5 as compared with that at pH 3.5 has been demonstrated. Furthermore, estimated values of DHCl are approximately 4-fold smaller through the mucus gel, as compared with a water layer. The findings indicate that the most powerful influence on diffusional resistance is pH itself, whereby a marked drop in H+ diffusion is likely to occur towards neutral pH irrespective of the composition of the gel barrier. Possible implications of the findings are discussed in relation to mucosal protection from acid.     

Determination of azelaic and sorbic acid in pharmaceduticals by capillary electrophoresis

Summary Capillary electrophoresis with indirect UV detection at 254 nm was applied to simultaneous determination of ∼20% of azelaic acid and ∼0.1% of sorbic acid in AKNOREN cream. The acids were separated in fused silica capillary (45 cm × 50 μm) at 30 kV. Optimised back-ground electrolyte was 30 mM benzoate buffer (pH∼6, adjusted with TRIS) containing 7 mM β-cyclodextrin and 5% of methanol; internal standard was 2-hydroxysobutyric acid (HIBA). Rectilinear calibration ranges were 0.4–4 mg mL⁻¹ for azelaic acid and 2–20 μg mL⁻¹ for sorbic acid and the recoveries were 97.2–100.5%. A single analysis took <15 min.     

Concise and highly selective asymmetric synthesis of acosamine from sorbic acid

Diastereoselective conjugate addition of lithium (R)-N-benzyl-N-(α-methylbenzyl)amide to tert-butyl sorbate and subsequent chemo- and diastereoselective ammonium-directed olefinic oxidation of the resultant conjugate addition product {tert-butyl (3S,αR)-3-[N-benzyl-N-(α-methylbenzyl)amino]hex-4-ene} have been used as the key steps in a concise and highly selective asymmetric synthesis of the 2,3,6-trideoxy-3-aminohexose l-acosamine. This sequence of two chemical operations allows rapid assembly of the molecular architecture and facilitates the de novo asymmetric synthesis of methyl N,O-diacetyl-α-l-acosaminide in only 7 steps from commercially available sorbic acid in 15% overall yield.     

Total internal reflectance fluorescence (TIRF) measurements of tracer diffusion through swollen supported polymer films

This work introduces a new method for tracer diffusion studies which emphasizes interfacial effects. Total internal reflectance fluorescence (TIRF) was employed to monitor rhodamine dye tracer diffusion normal to the interface in PDMS films whose swelling in THF was constrained by adhesion to a rigid support. In these constrained films, the tracer diffusivities were equal to or lower than those in freely swollen samples, with the difference most pronounced in samples of relatively low crosslink density. This indicated that swelling was reduced by adhesion to the substrate. In the supported films, tracer diffusion deviated from Fickian kinetics, suggesting that the region of the film near the substrate contained relatively less solvent at equilibrium than did the bulk film. © 1996 John Wiley & Sons, Inc.     

Solubility and solution thermodynamics of sorbic acid in eight pure organic solvents

By the gravimetric method, the solubility of sorbic acid in eight solvents including ethanol, 2-propanol, methanol, 1-butanol, ethyl acetate, methyl tert-butyl ether, acetone and acetonitrile was determined over a temperature range from 285.15 to K at atmospheric pressure. For the temperature range investigated, the solubility of sorbic acid in the solvents increased with increasing temperature. The experimental values were correlated with the linear solvation energy relationship, modified Apelblat equation, λh equation, non-random two-liquid (NRTL) model, and Wilson model. On the other hand, the enthalpy, entropy and Gibbs free energy of dissolution were obtained from these solubility values by using the van’t Hoff and Gibbs equations. The excess enthalpy of solution was estimated on the basis of λh equation. Furthermore, the a priori predictive model COSMO-RS was employed to predict the solubility of sorbic acid in selected solvents and reasonable agreement with experimental values is achieved.