Thermal behavior and solid fraction dependent gel strength model of waxy oils

Thermal behavior of waxy oils is investigated using the techniques of thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). Model waxy oils and real waxy crude oils are utilized. Decomposition temperatures of waxy oils are obtained using TG analysis. The effects of thermal history, wax content, and additive on the gelation process of waxy oils are investigated using DSC. The DSC method provides a measure of wax solubility as well as solid fraction. An integration method and a computation method are utilized to predict solid fraction. In addition, wax crystallization onset points are obtained at the cooling rates ranging from 1 to 20 °C min^?1. Similarly, wax dissolution endset points are obtained at heating rates ranging from 1 to 20 °C min^?1. Extrapolated onset and endset points yield wax precipitation temperature and wax dissolution temperature, respectively. Subsequently, wax solubility curves are obtained using thermodynamic computations. A wax precipitation temperature method and a wax dissolution temperature method combine thermodynamic phase behavior with onset/endset points to predict solid fraction. Both the wax precipitation temperature method and the wax dissolution temperature method can predict solid fraction of waxy oil samples. The wax precipitation temperature method and the wax dissolution temperature method are accurate when the temperature is close to the wax appearance temperature. A heat-integration method provides accurate values of the solid fraction at temperatures significantly below the wax appearance temperature. Therefore, integration method and wax precipitation temperature/wax dissolution temperature method are combined to predict solid fraction. The effect of solid fraction on yield stress is also investigated using differential scanning calorimetry and rheometry. Finally, a new solid fraction dependent gel strength model is obtained for shut in and restart of waxy crude oil pipelines.     

Improvement in Solubility of Poorly Water Soluble Drug by Cogrinding with Highly Branched Cyclic Dextrin

We investigated the enhancement of the solubility of glibenclamide (GCM), a poorly water soluble anti-diabetes drug, by cogrinding it with highly branched cyclic dextrin (HBCD) using a ball mill. Highly branched cyclic dextrin (HBCD) is a novel cyclic glucan produced from waxy corn starch by the cyclization reaction of a branching enzyme. When GCM crystals were coground with HBCD for 2 h, the solubility of GCM was improved to 12.4 μg/ml, while the concentration of HBCD was 5.0 mg/ml. Additionally, the GCM solubilized with HBCD was chemically stable in aqueous solution for at least 1 week at room temperature. The peak intensity assigned to crystalline GCM disappeared after cogrinding it by observing its powder X-ray diffraction pattern, which means that the crystalline structure of GCM could be disrupted. In the DSC measurement, the ground mixture showed a single endothermic peak, even though a temperature depression of the endothermic peak due to GCM crystal was observed. After the cogrinding, two sharp peaks assigned to sulfonylurea and benzoyl carbonyl stretching bands varied to broaden the peak to around 1640 cm⁻¹ in the C=O stretching region. These results suggested the formation of solid dispersion between GCM and HBCD.     

Effects of heat–moisture treatment on organic cassava starch

Organic foods and crops are produced throughout the world under strict controls on growing conditions, so that synthetic chemicals, irradiation or genetic modifications are avoided. Organic starch is extracted following the same rules. Heat–moisture treatment (HMT) on starch is a physical method considered to be natural: it consists of heating starch at a temperature above its gelatinisation point with insufficient moisture (<35 %) to cause gelatinisation. Samples of organic cassava starch (with 12.8 % moisture) were dried in an oven with forced air circulation at 50 °C for 48 h and, immediately, distilled water was added to each sample until it reached the ratios of 10, 20, and 30 %, respectively. The samples were transferred into 100 mL pressure flasks, sealed tightly with a cap, and maintained in an autoclave for 60 min at 120 °C. The flasks were opened and the samples were kept in a desiccator containing anhydrous calcium chloride up to constant mass. The effects of HMT were studied using the following techniques: thermogravimetry and derivative thermogravimetry (TG/DTG), differential scanning calorimetry (DSC), rapid viscoamylographic analysis (RVA), reflectance photocolorimetry, atomic force microscopy (NC-AFM) and X-ray diffractometry (XRD). Rheological properties such as the pasting temperature (RVA) and the peak temperature (DSC) increased, while gelatinisation enthalpy ?H (DSC) decreased. The average diameters of the granules showed no significant changes, while the degree of relative crystallinity decreased.     

Retrogradation characteristics of high hydrostatic pressure processed corn and wheat starch

High hydrostatic pressure (HHP) has been investigated as an alternative to thermal processing for food preservation. HHP has been known to affect high molecular weight polymers causing phase change. Starch is gelatinized at a pressure on the order of 600–700 MPa, at 25 °C. Gelatinized starch recrystallizes during storage affecting the texture and shelf life of food products. The effect of HHP processing on the crystallization of starches from different botanical origins during storage at 4 and 23 °C was investigated. Crystallization kinetics of HHP treated wheat and corn starch gels were compared using DSC. The effect of crystallization on structure was evaluated in terms of storage modulus. The rate of retrogradation depended on the storage temperature (23 °C and 4 °C) and the botanical origin of the starch. The least crystallization was observed in HHP treated wheat starch stored at 23 °C. The storage modulus increased with crystallization of starch.     

Development and characterization of amphiphilic hydroxyethyl starch derivatives

Novel amphiphilic hydroxyethyl starch derivatives 2,4-bistertbutylphenoxy-[1,3,5] -triazine-6-yl)-hydroxyethyl starch with different degrees of substitution of hydrophilic triazine group and hydrophobic hydroxyethyl were prepared by reacting corn starch with chlorohydrin and 2,4-Ditertbutyl phenoxyl-6-chloro-[1,3,5]-triazine, successively. Their structure was characterized by FTIR, ¹H NMR, and SEM. It exhibits ideal surfacial abilities and compressive strength. The surface tension of the amphiphilic hydroxyethyl starch derivatives (MS = 1.1, DS = 0.026) reached 33.35 mN · m^?1 at the critical aggregation concentration (CAC) at 25°C. The compressive strength of foam concrete was 0.97 MPa when the amount of added starch derivatives (MS = 1.1, DS = 0.026) reached 0.1 wt% of the total weight.     

Compatibility study between sitagliptin and pharmaceutical excipients used in solid dosage forms

Differential scanning calorimetry (DSC) is a primary technique for measuring the thermal properties of materials, which reflects the physico-chemical properties of drug substances. In the present study, it is used as a screening technique for assessing the compatibility of sitagliptin with some currently employed pharmaceutical excipients. The influence of processing conditions and their effects (simple blending, co-grinding or kneading) on drug stability was evaluated. Sitagliptin showed a sharp endothermic peak at 212.1 °C with an enthalpy change of 131.5 J g^?1 indicating melting of drug. Facile transformation of dehydrated sitagliptin to monohydrate form was observed in some mixtures, disappearance of sharp melting endothermic peak of sitagliptin was observed in some mixtures. On the basis of DSC results, sitagliptin was found to be compatible with micro crystalline cellulose, croscarmellose, and pregelatinized starch. Some excipient interaction was observed with magnesium stearate, ascorbic acid, and citric acid. X-ray diffractometry and FT-IR were used as supportive tools in interpreting the DSC results. Overall, the excipients selected were compatible with the API and the mixtures are stable within the tested conditions. These results would be useful for formulation development of the film coated tablets of sitaglitptin.     

Studies on ionic liquid-based corn starch biopolymer electrolytes coupling with high ionic transport number

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF₆) and ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BmImTf) were prepared by solution casting technique. The ionic conductivity was found to increase with increasing ionic liquid concentration. Upon doping with 80 wt% of BmImTf, the ionic conductivity increased by three orders of magnitude. The highest ionic conductivity of (3.21 ± 0.01) × 10^?4 S cm^?1 was achieved at ambient temperature. The complexation between corn starch, LiPF₆ and BmImTf was further proven in attenuated total reflectance-Fourier transform infrared findings. The highest conducting biopolymer electrolyte was stable up to 230 °C, as proven in thermogravimetric analysis.     

The effect of microwave radiation on some thermal,rheological and structural properties of cassava starch

Three samples of native or untreated cassava starch were exposed to microwave radiation for periods of 5, 10 or 15 min. The temperature of each sample was measured immediately after each exposure time and the temperature of the samples was around 135 °C. The samples were cooled to room temperature and maintained in a desiccator with anhydrous calcium chloride. All the samples were analysed by thermogravimetry-derivative thermogravimetry, differential scanning calorimetry (DSC), rapid viscoamylographic analysis (RVA), X-ray diffraction powder patterns, non-contact atomic force microscopy and colour characteristics by reflectance spectrophotometry. The thermal behaviour, gelatinisation temperatures, enthalpy and pasting properties were determined. Relative to the time of microwave exposure, the peak viscosity and gelatinisation (RVA and DSC) increased slightly after 5 min, and, after 10 and 15 min, it decreased considerably. The degree of relative crystallinity (%) decreased, while the average roughness increased. The reflectance spectrophotometry showed that microwave action occured quickly and progressively, causing colour changes (mainly with trends to yellow) and very small differences to the starch samples that were heated at controlled temperature in a conventional oven.     

Assessment of waxy and non-waxy corn and wheat cultivars as starch substrates for ethanol fermentation

The amylose/amylopectin ratio in cereal substrates is one of the parameters affecting starch hydrolysis and fermentation process. Waxy (less than 1 mass % of amylose) starch seems to be suitable for improving the fuel ethanol production. The main aim of this paper was to characterize the fermentation performance of corn and wheat waxy and non-waxy cultivars in terms of simultaneous saccharification and fermentation (SSF) as well as of the separated hydrolysis and fermentation (SHF) type. Two corn (waxy and non-waxy) and two wheat (waxy and non-waxy) cultivars were used for the comparison applying separate enzymatic hydrolysis and fermentation. In the SHF process, the glucose content was higher after saccharification in the waxy corn and wheat compared to that in non-waxy corn and wheat. In the SSF of waxy varieties, the glucose content after the pre-saccharification was also higher than in the non-waxy ones. Although the starch content did not vary significantly, differences in the glucose content after saccharification were observed. The ethanol yield obtained after the distillation of mash varied from 229.2–262.3 L per ton for the SHF fermentation, while it was in the range of 311.5–347.9 L per ton for the SSF process.     

Electroreduction of Zonisamide at Hanging Mercury Drop Electrode and Its Determination in Pharmaceutical Formulations and Spiked Human Serum Samples

A simple and rapid voltammetric method has been developed for the quantitative determination of zonisamide (ZNS) in pharmaceutical formulations and spiked human serum samples. Studies with differential pulse voltammetry (DPV) were carried out using a hanging mercury drop electrode (HMDE) in 0.1 M HCl solution. A well-defined reduction peak of ZNS was obtained at ?930 mV vs. saturated calomel electrode (SCE). The current-concentration plots are linear over the range from 0.13 to 17.05 μg ml^?1 in 0.1 M HCl. The statistical parameters and the recovery study data clearly indicate good reproducibility and accuracy of the method.     

Thermodynamic characteristics of supramolecular complexes of aroma compounds with ordered structures of polysaccharides of corn starch and its cryotextures

Supramolecular complexes of organic odorants (n-octanol and n-octyl acetate) with polysaccharides of corn starch, its cryotextures, and waxy corn starch cryotextures were studied by differential scanning microcalorimetry. It was shown that complexes are formed with amylose-containing starch and no complexes are formed with amylopectin starch. The melting enthalpies of the complexes were determined. It was shown that complexes of the odorants with native corn starch and its cryotextures have different thermodynamic characteristics.     

DSC study on the thermal properties of soybean protein isolates/corn starch mixture

The use of soybean protein isolates (SPI) and corn starch (CS) for the manufacturing of textured protein by thermo-mechanical means requires a characterization of their thermal properties. SPI and CS mixtures were examined at starch mass fractions from 0 (pure SPI) to 100 (pure CS). The blends were determined by means of differential scanning calorimetry, with water content of 30, 50, and 70 % and heating rate of 5 and 10 °C min^?1 over 20 to 130 °C. The results obtained showed that protein in the blend increased the onset (T _o) and peak (T _p) temperatures of the starch gelatinization, while starch in the blend decreased the ΔH and ΔT_1/2 of the protein. T _o , T _p, and ΔT_1/2 of SPI and CS decreased significantly with the increase of water content. T _p and ΔT_1/2 of SPI and CS had a marked increase with an increase of heating rate from 5 to 10 °C min^?1. These results suggested that there was no chemical reaction between SPI and CS when they were heated from 20 to 130 °C. SPI in the blend restricted the CS gelatinization, while the presence of CS protected the SPI from denaturation. The increasing water content did promote thermal transition of the mixture. Higher heating rate leads to higher transition temperature.     

Fast-scan vs conventional differential scanning calorimetry (DSC) techniques in detection of crystallization events of tolbutamide–polyethylene glycol composite

This study investigated the capacity of fast-scan (400 °C min^?1) against conventional (10 °C min^?1) differential scanning calorimetry (DSC) techniques to track crystallization phenomenon in tolbutamide–polyethylene glycol 3000 composites prepared by hot melt method (mass ratios 1:1, 1:5, and 1:9) and stored at 25 and 75 % relative humidities. Drug crystallization in composites was indicated by X-ray diffractometry (XRD) and scanning electron microscopy characterization over 40 days storage. With reference to XRD as gold measurement standard, fast-scan DSC could not map the crystallization events of composites (Pearson correlation: fast-scan DSC peak temperature and enthalpy versus XRD peak intensity and area, p > 0.05). Conventional DSC was able to indicate marked drug crystallization through an increase in endothermic enthalpy value of peaks at high temperature regimes between 250 and 360 °C due to formation of high melting point crystal form.     

Characterization of crystalline and amorphous content in pharmaceutical solids by dielectric thermal analysis

Morphological and thermodynamic transitions in drugs as well as their amorphous and crystalline content in the solid state have been distinguished by thermal analytical techniques, which include dielectric analysis (DEA), differential scanning calorimetry (DSC), and macro-photomicrography. These techniques were used successfully to establish a structure versus property relationship with the United States Pharmacopeia standard set of active pharmaceutical ingredient (API) drugs. A distinguishing method is the DSC determination of the amorphous and crystalline content which is based on the fusion properties of the specific drug and its recrystallization. The DSC technique to determine the crystalline and amorphous content is based on a series of heat and cool cycles to evaluate the drugs ability to recrystallize. To enhance the amorphous portion, the API is heated above its melting temperature and cooled with liquid nitrogen to ?120 °C (153 K). Alternatively a sample is program heated and cooled by DSC at a rate of 10 °C min^?1. DEA measures the crystalline solid and amorphous liquid API electrical ionic conductivity. The DEA ionic conductivity is repeatable and differentiates the solid crystalline drug with a low conductivity level (10^?2 pS cm^?1) and a high conductivity level associated with the amorphous liquid (10⁶ pS cm^?1). The DSC sets the analytical transition temperature range from melting to recrystallization. However, analysis of the DEA ionic conductivity cycle establishes the quantitative amorphous and crystalline content in the solid state at frequencies of 0.10–1.00 Hz and to greater than 30 °C below the melting transition as the peak melting temperature. This describes the “activation energy method.” An Arrhenius plot, log ionic conductivity versus reciprocal temperature (K^?1), of the pre-melt DEA transition yields frequency dependent activation energy (E _a, J mol^?1) for the complex charging in the solid state. The amorphous content is inversely proportional to the E _a where the E _a for the crystalline form is higher and lower for the amorphous form with a standard deviation of ±2%. There was a good agreement between the DSC crystalline melting, recrystallization, and the solid state DEA conductivity method with relevant microscopic evaluation. An alternate technique to determine amorphous and crystalline content has been established for the drugs of interest based on an obvious amorphous and crystalline state identified by macro-photomicrography and compared to the conductivity variations. This second “empirical method” correlates well with the “activation energy” method.     

TLC Determination of Amitriptyline HCl,Trifluoperazine HCl,Risperidone and Alprazolam in Pharmaceutical Products

A simple, sensitive, and precise thin layer chromatographic (TLC) method for simultaneous analysis of psychopharmacological drugs like amitriptyline HCl, trifluoperazine HCl, risperidone and alprazolam in their single dosage forms has been developed, validated, and used for determination of the compounds in commercial pharmaceutical products. The TLC separation was carried out on Merck TLC aluminium sheets of silica gel 60 F254 using carbon tetrachloride:acetone:triethylamine (8:2:0.3, v/v/v), as mobile phase. Densitometric measurements of their spots were achieved at 250 nm over the concentration range for amitriptyline HCl (50–1,200 ng spot⁻¹), trifluoperazine HCl (50–1,200 ng spot⁻¹), risperidone (100–2,400 ng spot⁻¹) and alprazolam (25–600 ng spot⁻¹). Limit of detection (LOD) for amitriptyline HCl (20 ng spot⁻¹), trifluoperazine HCl (20 ng spot⁻¹), risperidone (40 ng spot⁻¹) and alprazolam (5 ng spot⁻¹) was obtained. The study showed that TLC was sensitive and selective for determination of amitriptyline HCl, trifluoperazine HCl, risperidone and alprazolam using a single mobile phase. This proposed method is able for simultaneous determination of psychopharmacological drugs and also applicable for analysis of pharmaceutical formulations.

     

Synthesis and characterization of microcrystalline cellulose powder from corn husk fibres using bio-chemical route

In the present study low cost microcrystalline cellulose (MCC) powder was prepared from cornhusk fibres, extracted chemically followed by anaerobic consortium treatment. Cornhusk fibres were treated with 10% alkali at 120 °C for 60 min followed by anaerobic consortium treatment for 3 days. It was then bleached with hydrogen peroxide and finally washed. Bleached pulp was hydrolysed using 4 N HCl to get the MCC. In the present investigation, we have characterized the MCC prepared from cornhusk fibres thoroughly for its physico-chemical properties and compared with Avicel^®-PH 101, a commercial grade MCC. Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Powder Diffraction (XRD) and Differential Scanning Calorimetry (DSC) were used for characterization of samples. Similarly the powder and flow properties of the MCC prepared from cornhusk fibres were also investigated and the results were compared with Avicel^®-PH 101. Our results showed that various properties and the purity of MCC prepared from cornhusk fibres are comparable to the commercial grade MCC. Since, cornhusk is an agricultural waste product, MCC obtained from cornhusk fibres will be from cheaper raw materials than current market MCC.     

Electrochemical sensor for estriol hormone detection in biological and environmental samples

A stable conducting film for sensing using reduced graphene oxide (RGO), gold nanoparticles (GNPs), and potato starch (PS) is proposed. The characterization of the nanomaterials was obtained by ultraviolet and visible spectroscopy, dynamic light scattering, zeta potential, Fourier transform infrared spectroscopy, atomic force microscopy, and cyclic voltammetry. The voltammetric behavior of the RGO-GNPs-PS/GCE electrodes was studied in the presence of estriol and the results showed a high anodic peak current at 0.64 V. Under optimal conditions, an analytical curve was obtained, in which the anodic peak estriol was linear in the range from 1.5 to 22 μmol L^?1, with a detection limit of 0.48 μmol L^?1. The modified electrodes were applied for determination of estriol in environmental and biological samples. The proposed electrode was used for estriol determination in water and urine samples, which presented a recovery range from 92.1 to 106%, showing that RGO-GNPs-PS/GCE is a viable alternative for the detection of estriol and can be attractive for several electrochemical applications.     

Effects of common ammonium salt on the thermal behavior of reconstituted tobacco sheet

Understanding the role of chemical burn additives on modifying the toxic gaseous constituents and thermal behavior of reconstituted tobacco sheet (RTS) has recently taken center stage through a number of initiatives. In this current study, the effects of ammonium chloride (AC), ammonium sulfate, diammonium phosphate, and monoammonium phosphate on the formation of evolved gaseous products, specifically carbonyl compounds and thermal behavior were investigated. Results on cigarette smoking tests revealed that ammonium salt was a potential burn additive to reduce carbonyl compounds delivery in the cigarette mainstream smoke of RTS. The yield per puff of carbonyl compounds of pure RTS was decreased from 247.8 µg to 133.30 µg with the incorporation of AC. Thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) were used to investigate the thermal decomposition of RTS. TG results revealed that the incorporation of ammonium salt into RTS could improve the thermal stability of RTS. The DSC results showed that the maximum exothermic peak was drastically decreased with the addition of ammonium salt, for example, from 14.8 mW mg^?1 of pure RTS to 10.27 mW mg^?1 of AC-RTS. Results on Fourier transform infrared spectrometer (FTIR) which was employed to investigate the generation of evolved volatile products showed that these four ammonium salts as burn additives were efficiently high enough to decrease the formation of gaseous products. From our findings, compared with the virgin RTS and other three modified RTS, AC-RTS could significantly decrease the yields of nicotine and phenolic compounds in the cigarette mainstream smoke of RTS.     

Fast detection of sildenafil in adulterated commercial products using differential scanning calorimetry

Adulteration of drugs is a serious issue and can have a great impact on human health. It is mainly done with the intention of boosting the effects of products. For many years, the enforcement officers in Malaysia have had difficulty deciding whether some products should be confiscated as they have not been able to produce fast reliable evidence of adulteration. For that reason, we explored the use of differential scanning calorimetry (DSC) as a potential fast detection method of commercial products marketed in Malaysia that may be adulterated. We confirmed the outcomes qualitatively with high pressure liquid chromatography. DSC was set at a heating rate of 10 °C min^?1 and within a temperature range of 100–250 °C with nitrogen as a purge gas at a flow rate of 20 mL min^?1 to analyse a sildenafil reference standard (RS), sildenafil tablets and sildenafil adulterated commercial products. Four sildenafil adulterated commercial products were analysed. Since the melting point of sildenafil in the mixture tended to shift, the presence of sildenafil in three of these adulterated commercial products was confirmed using the spiking method and was re-analysed using DSC. The re-analysed results indicated that the enthalphy of fusion (?H) and the resolution peak of sildenafil increased accordingly depending upon the amount of spiked sildenafil RS. Apart from these results, the DSC curves also showed different patterns for sildenafil RS and the mixtures. Therefore, we concluded that DSC can potentially be used to detect sildenafil in adulterated commercial products.     

Supercapacitors based on carbide-derived carbons synthesised using HCl and Cl2 as reactants

Micro- and mesoporous carbide-derived carbons (CDCs) were synthesised from TiC powder via a gas-phase reaction using HCl and Cl₂ within the temperature range of 700–1,100 °C. Analysis of X-ray diffraction results show that TiC-CDCs consist mainly of graphitic crystallites. The first-order Raman spectra showed the graphite-like absorption peaks at ~1,577 cm^?1 and the disorder-induced peaks at ~1,338 cm^?1. The low-temperature N₂ sorption experiments were performed, and specific surface areas up to 1,214 and 1,544 m²?g^?1 were obtained for TiC-CDC (HCl) synthesised at T?=?800 °C and TiC-CDC (Cl₂) synthesised at T?=?900 °C, respectively. For the TiC-CDC powders synthesised, a bimodal pore size distribution has been established with the first maximum in the region up to 1.5 nm and the second maximum from 2 to 4 nm. The energy-related properties of supercapacitors based on 1 M (C₂H₅)₃CH₃NBF₄ in acetonitrile and TiC-CDC (Cl₂) and TiC-CDC (HCl) as electrode materials were also investigated by cyclic voltammetry, impedance spectroscopy, galvanostatic charge/discharge and constant power methods. The specific energy, calculated at U?=?3.0 V, are maximal for TiC-CDC (Cl₂ 800 °C) and TiC-CDC (HCl 900 °C), which are 43.1 and 31.1 W?h?kg^?1, respectively. The specific power, calculated at cell potential U?=?3.0 V, are maximal for TiC-CDC (Cl₂ 1,000 °C) and TiC-CDC (HCl 1,000 °C), which are 805.2 and 847.5 kW?kg^?1, respectively. The Ragone plots for CDCs prepared by using Cl₂ or HCl are quite similar, and at high power loads, the TiC-CDC material synthesised using Cl₂ at 900 °C, i.e. the material with optimal pore structure, delivers the highest power at constant energy.