Solution calorimetry to monitor swelling and dissolution of polymers and polymer blends

The observed rate of drug release from a polymeric drug delivery system is governed by a combination of diffusion, swelling and erosion. It is thus not a simple task to determine the effects of the polymer on the observed drug release rate, because the swelling characteristics of the polymer are inferred from the drug release profile. Here we propose to use solution calorimetry to monitor swelling. Powdered polymer samples (HPMC E4M, K4M, K15M and NaCMC, both alone and in a blend) were dispersed into water or buffer (pH 2.2 and 6.8 McIlvaine citrate buffers) in a calorimeter and the heat associated with the swelling phenomena (hydration, swelling, gelation and dissolution) was recorded. Plots of normalised cumulative heat (i.e. q_t/Q, where q_t is the heat released up to time t and Q the total amount of heat released) versus time were analysed by the power law model, in which a fitting parameter, n, imparts information on the mechanism of swelling.

For all systems the values of n were greater than 1, which indicated that dissolution occurred immediately following hydration of the polymer. However, while not suitable for determining reaction mechanism, the values of n for each polymer were significantly different and, moreover, were observed to vary both as a function of particle size and dissolution medium pH. Thus, the values of n may serve as comparative parameters. Properties of the polymer blends were observed to be different from those of either constituent and correlated with the behaviour seen for polymer tablets during dissolution experiments. The data imply that solution calorimetry could be used to construct quantitative structure–activity relationships (QSARs) and hence to optimise selection of polymer blends for specific applications.     

Isothermal and solution calorimetry to assess the effect of superplasticizers and mineral admixtures on cement hydration

The heat of hydration evolution of eight paste mixtures of various water to binder ratio and containing various pozzolanic (silica fume, fly ash) and latent hydraulic (granulated blast furnace slag) admixtures have been studied by means of isothermal calorimetry during the first 7 days of the hydration process and by means of solution calorimetry for up to 120 days. The results of early heat of hydration values obtained by both methods are comparable in case of the samples without mineral admixtures; the values obtained for samples containing fly ash and granulated blast furnace slag differ though. The results from isothermal calorimetry show an acceleration of the hydration process by the presence of the fine particles of silica fume and retarding action of other mineral admixtures and superplasticizer. The influence of the presence of mineral admixtures on higher heat development (expressed as joules per gram of cement in mixture) becomes apparent after 20 h in case of fly ash without superplasticizer and after 48 h for sample containing fly ash and superplasticizer. In case of samples containing slag and superplasticizer the delay observed was 40 h. The results obtained by solution calorimetry provide a good complement to the ones of isothermal calorimetry, as the solution calorimetry enables to study the contribution of the mineral admixtures to the hydration heat development at later ages of the hydration process, which is otherwise hard to obtain by different methods.     

Isothermal titration calorimetry of Ni(II) binding to histidine and to N-2-aminoethylglycine

Isothermal titration calorimetry (ITC) is used to study the complexation thermodynamics of Ni(II) with histidine (His) and with N-2-aminoethylglycine (EDMA). The titrations were performed in HEPES and Tris buffers at various ionic strengths and pH values around 8. The results show the influence of the experimental conditions on the shape and fitting parameters of the calorimetric curves. For the studied systems, the main reaction is concomitant with a number of side reactions which contribute to the global energy measured. From the calorimetric data measured, the formation constants for the species NiHEPES⁺, Tris⁺His⁻, TrisNiHis⁺ and [Ni(EDMA)₂OH]⁻ have been evaluated for the first time and the values obtained properly validated.     

Analysis of drugs by microcalorimetry Isothermal power-conduction calorimetry and thermometric titrimetry

Microcalorimetric analysis has been the subject of a few review's in recent years, but these reviews have mainly dealt with the wide-ranging capabilities of calorimetric assay. This review, however, discusses the experimental basis and practical exploitation of the method in the particularly important area of pharmaceuticals. This field of analysis embraces both conventional chemical assays and bioassays which involve living microbial species. The review highlights the design of calorimetric instruments appropriate for study of microbial metabolism and interaction with drug substances. For comprehensiveness, both microcalorimetric and thermometric assay systems are discussed and critically assessed.     

Isothermal titration calorimetry studies on the binding of DNA bases and PNA base monomers to gold nanoparticles

An isothermal titration calorimetric (ITC) investigation of the interaction of DNA bases and PNA base monomers with gold nanoparticles is described revealing a binding sequence in the order C > G > A > T. Direct measurement of the strength of interaction of ligands with nanogold by ITC has important implications in surface modification strategies for biomedical, catalysis, and nanoarchitecture applications.     

Capillary headspace - gas chromatography for the characterization of the flavour of fresh vegetables

Summary Static headspace sampling combined with gas chromatography using open-tubular (capillary) columns for the characterization of the flavour of raw vegetables and some vegetable products is described. In order to avoid alteration of the composition of the volatiles, the sample was thermostated for a short time only. Although equilibrium between vapour and sample was not established the reproducibility of such conditions is demonstrated. Typical chromatograms are given; the most characteristic compounds present were identified by mass spectrometry. Enlarged text of a poster presented at the Twelfth International symposium on Capillary Chromatography, September 11–14, 1990, Kobe, Japan     

Ionizing radiation treatment to improve postharvest life and maintain quality of fresh guava fruit

We investigated the potential of ionizing radiation for improving physiological responses, quality, and storage time of fresh guava fruit. Ionizing radiation treatment suppressed the respiration and ethylene production rates and thus retarded the process of fruit ripening during storage. Irradiation treatment also retarded the physical and biochemical changes associated with ripening such as firmness, titratable acidity, soluble solids content, and vitamin C during storage, but for doses higher than 0.25 kGy the vitamin C content decreased. The positive effects of ionizing radiation treatment on delayed fruit ripening and other quality attributes diminished during 22 days of storage at 10 °C. Thus, a combination of ionizing radiation with low-temperature storage (10 °C) did not have much synergistic effect on storage life and quality of guava fruit. In conclusion, ionizing radiation treatment of guava fruit with 0.25 kGy dose increased the postharvest life by 3–4 days, maintained fruit quality, and reduced the decay incidence. The optimal dose (0.25 kGy) for postharvest life extension of guava fruit may be exploited to provide phytosanitary security against many insect pests including fruit flies.     

Isothermal calorimetry as a tool for estimating resistance of wild oat (Avena fatua L.) to aryloxyphenoxypropionate herbicides

The application of isothermal calorimetry for the early detection of the resistance of wild oat to fenoxaprop¹ and diclofop² was investigated. In the first test, three leaf tillers were sprayed with field doses of fenoxaprop or diclofop. For resistant biotypes, the rate of heat flow after 48 h was similar to that in control plants. In susceptible biotypes, fenoxaprop significantly reduced and diclofop significantly increased the rate of heat flow. In the second test, 3-day-old seedlings were put into calorimetric ampoules on filter paper moistured with herbicide solution (152% and 40% of the field dose for fenoxaprop and diclofop, respectively). Rate of heat flow was measured for 72 h, however, differences were already visible in the first hours of germination on each herbicide. Rate of heat flow for seedlings resistant to both herbicides was higher than for susceptible ones. The most evident differences between susceptible and resistant biotypes were noticed after 10-20 h and 25-40 h (of the seedlings’ growth) on fenoxaprop and diclofop, respectively, when a sharp increase of rate of heat flow was observed. In conclusion, calorimetry may be used as a rapid test for the detection of the resistance of wild oat biotypes to fenoxaprop and diclofop.     

Isothermal titration calorimetry and molecular dynamics study of ion-selectivity in mixtures of hydrophobic polyelectrolytes with sodium halides in water

Aliphatic x,y-ionenes are polyelectrolytes in which x and y denote the numbers of methylene groups separating quaternary ammonium ions. They represent useful model substances for studying hydrophobic and charge effects in aqueous solutions. We used isothermal titration calorimetry to measure the enthalpies of mixing, ΔH(mix), of 3,3- and 6,6-ionene fluorides and bromides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) at 298 K in water. The signs and magnitudes of the measured enthalpies depend on the hydrophobicity of the ionene and on the nature of the added salt. For example, addition of sodium fluoride to solutions of 3,3- and 6,6-ionene fluorides produced endothermic effects, while addition of sodium bromide to 3,3-ionene bromide resulted in a strong exothermic effect. Interestingly, mixing of 6,6-ionene bromide and NaBr solutions in water gave a small exothermic heat effect. Polyelectrolyte theories, based on continuum-solvent models, predict enthalpies of mixing to be positive (endothermic) for all the solutions examined in this work. The ion-specific effect is more strongly expressed in ionene solutions with higher charge density (3,3-ionene). The most important result of this work is the finding that the enthalpy of mixing of 3,3- (and of 6,6-ionene) fluorides with sodium halides can be expressed as a linear function of the enthalpy of hydration of the halide counterions. The experimental results were complemented with an explicit water molecular dynamics simulation of solutions of oligoions modelling 3,3- and 6,6-ionenes. The computer simulation results for various nitrogen-counterion pair distribution functions were in most cases consistent with the enthalpy measurements.     

Pesticide residues in fresh fruit and vegetables on the Swedish market, January 1985–December 1989

Conclusion Compared with the previous investigation in 1981–1984, the frequency of samples of fruit and vegetables with excessive amounts of pesticides has decreased from 3.9% to 3.4%.     

Isothermal titration calorimetry and dynamic light scattering studies of interactions between gemini surfactants of different structure and Pluronic block copolymers

The interactions between triblock copolymers of poly(ethylene oxide) and poly(propylene oxide), P103 and F108, EO(n)PO(m)EO(n), m=56 and n=17 and 132, respectively, and m-s-m type gemini surfactants, m=8, 10, 12, and 18, and s = 3, 6, 12, and 16, have been studied in aqueous solution using isothermal titration calorimetry and dynamic light scattering techniques. The enthalpograms of F108 as a function of surfactant concentration show one broad peak at polymer concentrations C(p) < or = 0.50 wt%, below the cmc of the copolymer at 25 degrees C. It is attributed to interactions between the surfactant and the triblock copolymer monomer. DLS results show hydrodynamic radii (R(h)) initially consistent with copolymer monomers that change to values consistent with gemini surfactant micelles as the surfactant concentration is increased. In P103 solutions at C(p) > or = 0.05 wt%, two peaks appear in the enthalpograms, and they are attributed to the interactions between the gemini surfactant and the micelle or monomer forms of the copolymer. An origin-based nonlinear fitting program was employed to deconvolute the two peaks and to obtain estimates of peak properties. An estimate of the fraction of copolymer in aggregated form was also obtained. The enthalpy change due to interactions between the surfactants and P103 aggregates is very large compared to values obtained for traditional surfactants. This suggests that extensive reorganization of copolymer aggregates and surrounding solvent occurs during the interaction. DLS results for the P103 systems containing C(p) > or = 0.05% show evidence of very large aggregates in solution, likely P103 micelle clusters. The transitions observed in the hydrodynamic radii are consistent with a breakdown of micelle clusters with addition of gemini surfactant, followed by mixed micelle formation and/or deaggregation into monomer P103. This is followed by interactions similar to those typically observed in surfactant-nonionic polymer systems. Mechanisms for the interaction and the observed structural changes are discussed.     

Rapid impedance method for predicting the potential shelf life of packaged pasteurized milk

The potential shelf life of packaged pasteurized milk was studied using a rapid impedance method. The results showed a high correlation between the shelf life of Fengxing and Xiang Man-lou pasteurized milks and between the detection time and the logarithm of colony-forming units per milliliter. The impedance detection time was measured after preliminary incubation at 30 degrees C for 6 h for 100 and 200 microL milk samples, or at 37 degrees C for 6 h for 100-400 microL milk samples for Fengxing pasteurized milk, and after 6 h preliminary incubation at 30 degrees C for 300 and 400 microL milk samples or 6 h at 37 degrees C for 100-400 microL milk samples for Xiang Man-lou pasteurized milk. Regressive equations were then constructed to predict the potential shelf life. Compared with the traditional method, the impedance method plus pre-incubation of milk at elevated temperatures (30 and 37 degrees C) was rapid, accurate, and convenient. The entire estimation process was completed within 11-14 and 14-20 h for Fengxing and Xiang Man-lou pasteurized milks, respectively.     

Determination of alkylphenolic residues in fresh fruits and vegetables by extractive steam distillation and gas chromatography-mass spectrometry

This study describes a simple and sensitive method for determining the alkylphenolic compounds, 4-tert-octylphenol (4-t-OP), 4-nonylphenol isomers (4-NPs), and their monoethoxylates (4-t-OP1EO and 4-NP1EOs), in fresh fruits and vegetables. The method involves extracting a sample by a modified Nielson-Kryger steam distillation extraction using n-hexane for 1 h. The alkylphenolic compounds were identified and quantitated by gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. Various pH values and amounts of NaCl added to the sample solution were evaluated as extraction conditions. The quantitation limit of this method was less than 0.2 ng/g in 10 g (fresh weight) of sample. Recovery of alkylphenolic compounds in spiked samples exceeded 64% while R.S.D. ranged from 1.0 to 9.8%. Alkylphenolic residues were detected in fresh fruits and vegetables at concentrations of 4-NPs and 4-t-OP from n.d. to 16 ng/g and from n.d. to 4.8 ng/g (fresh weight), respectively. NP1EO and OP1EO were always below the quantitation limit.     

Application to routine analysis of a method to determine multiclass pesticide residues in fresh vegetables by gas chromatography/tandem mass spectrometry

The use of gas chromatography/tandem mass spectrometry (GC/MS/MS) applied to determine multiple pesticide residues in fresh vegetables has been thoroughly studied. A single injection method to detect, confirm and quantify 54 multiclass pesticides has been developed and applied in a routine analysis laboratory. The proposed method consists of a rapid extraction of 15 g of vegetable sample with dichloromethane. An additional clean-up step is not necessary even when injecting 10 microL of extract. Instead the gas chromatograph was fitted with a carbofrit inserted into the glass liner and a guard column. In addition, the detection mode chosen (MS/MS) provides additional selectivity. The method has been validated and applied to 1300 samples in a routine laboratory following specified quality criteria. The recovery efficiencies obtained for all the pesticides ranged between 70.2 and 110.8% at two different fortification levels. The relative standard deviation for quantification (RSD) was lower than 16.7% for all the compounds. Important experimental parameters, such as the conditioning of carbofrit, overload of the analytical column, and cleanliness of the ion trap, were evaluated for their influence on the performance of the method.     

Application of calorimetry and DTA to metal systems

The calorimetric methods employed for the study of metal systems (solution, combustion, direct reaction calorimetry) are considered and briefly discussed with respect to each other.The development of apparatus for the calorimetry of metals and alloys is examined as a whole, with particular reference to the progressive increase of the maximum limit of the working temperature.The employment of calorimetric methods for the determination of equilibrium phase diagrams is described according to two different approaches: (1) corresponding to classical DTA, based on the identification of phase boundaries by the exploration of the system as a function of temperature, at constant composition; (2) corresponding to the measurement of partial and integral enthalpies of alloy formation as a function of the composition, at constant temperature.A brief report is given of the utilization of calorimetric data for the computation of equilibrium phase diagrams and equations are also given that allow the equilibrium temperature to be calculated between a liquid solution (binary or multicomponent) and a pure component (or an intermetallic compound) as a function of the thermodynamic parameters obtained by calorimetric methods.     

Multiresidue analysis of pesticides in fresh fruits and vegetables using procedures developed by the Florida Department of Agriculture and Consumer Services

Improved quality and efficiency of pesticide residue analysis were achieved by examining all aspects of the laboratory process. In an effort to eliminate methylene chloride hazardous waste, an acetonitrile extraction method, originally developed by the California Department of Agriculture, was modified and adopted. Sample size and solvent consumption were reduced with the new method. Custom glassware racks and disposable supplies reduced overall analysis time. Gravity-fed, solid-phase extraction simplified sample preparation and provided cleaner extracts for gas chromatographic analyses. Modifications to the method were made to achieve the ruggedness needed to maintain quality objectives during routine analysis. Instrumental improvements, including new selective detectors, retention time locking, and mass spectrometry screening for all samples, provided the laboratory with efficient, reliable, and confirmed analytical results.     

The effect of irradiation temperature on the quality improvement of Kimchi,Korean fermented vegetables,for its shelf stability

The present study was conducted to evaluate the effect of irradiation temperature on the shelf stability and quality of Kimchi during storage at 35 °C for 30 days. Kimchi samples were N₂-packaged and heated at 60 °C and then gamma irradiated at 20 kGy under various temperatures (room temperature, ice, dry ice, and liquid nitrogen). In the results of microbial, pH, and acidity analysis, combination treatment of heating and irradiation was able to sterilize microbes in Kimchi regardless of irradiation temperature. When Kimchi was irradiated under frozen temperatures, especially dry ice, the softening of texture and the deterioration of sensory quality of Kimchi were reduced. Also, ESR signal intensities were weakened due to the decrease of irradiation dose and temperature.     

Effects of gamma irradiation on chemical,microbial quality and shelf life of shrimp

In the present study the combined effect of gamma irradiation (1, 3 and 5 kGy) and storage at two temperatures: refrigeration (+4 °C) and frozen (?18 °C), on the shelf-life extension of fresh shrimp meat was investigated. The study was based on microbiological and physicochemical changes occuring in the shrimp samples. Total volatile base nitrogen values and trimethylamine values for irradiated shrimp samples were significantly lower than non-irradiated samples at both storage temperatures, and the rate of decrease was more pronounced in samples irradiated at the higher dose (p<0.05). Thiobarbituric acid values for irradiated shrimp samples were significantly higher than non-irradiated samples at both storage temperatures (p<0.05). pH values of shrimp samples were affected significantly by both irradiating dose and storage temperatures (p<0.05). Microbial counts for non-irradiated shrimp samples were higher than the respective irradiated samples at both storage temperatures (p<0.05). The results revealed that irradiation at high dose (5 kGy) might enhance lipid oxidation, although the growth of microorganisms and protein oxidation was inhibited.