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.     

Cellulose nanofibril (CNF) reinforced starch insulating foams

In this study, biodegradable foams were produced using cellulose nanofibrils (CNFs) and starch (S). The availability of high volumes of CNFs at lower costs is rapidly progressing with advances in pilot-scale and commercial facilities. The foams were produced using a freeze-drying process with CNF/S water suspensions ranging from 1 to 7.5 wt% solids content. Microscopic evaluation showed that the foams have a microcellular structure and that the foam walls are covered with CNF’s. The CNF’s had diameters ranging from 30 to 100 nm. Pore sizes within the foam walls ranged from 20 to 100 nm. The materials’ densities ranging from 0.012 to 0.082 g/cm³ with corresponding porosities between 93.46 and 99.10 %. Thermal conductivity ranged from 0.041 to 0.054 W/m-K. The mechanical performance of the foams produced from the starch control was extremely low and the material was very friable. The addition of CNF’s to starch was required to produce foams, which exhibited structural integrity. The mechanical properties of materials were positively correlated with solids content and CNF/S ratios. The mechanical and thermal properties for the foams produced in this study appear promising for applications such as insulation and packaging.     

Glass transition and thermal degradation of rigid polyurethane foams derived from castor oil–molasses polyols

Rigid polyurethane (PU) foams having saccharide and castor oil structures in the molecular chain were prepared by reaction between reactive alcoholic hydroxyl group and isocyanate. The apparent density of PU foams was in a range from 0.05 to 0.15 g cm^?3. Thermal properties of the above polyurethane foams were studied by differential scanning calorimetry, thermogravimetry and thermal conductivity measurement. Glass transitions were observed in two steps. The low-temperature side glass transition was observed at around 220 K, regardless of castor oil content. This transition is attributed to the molecular motion of alkyl chain groups of castor oil. The high-temperature side glass transition observed in the temperature range from 350 to 390 K depends on the amount of molasses polyol content. The high-temperature side glass transition is attributed to the molecular motion of saccharides, such as sucrose, glucose, fructose as well as isocyanate phenyl rings, which act as rigid components. Thermal decomposition was observed in two steps at 570 and 620–670 K. Thermal conductivity was observed at around 0.032 J sec^?1 m^?1 K^?1. Compression strength and modulus of PU foams were obtained by mechanical test. It was confirmed that the thermal and mechanical properties of PU foams could be controlled by changing the mixing ratio of castor oil and molasses for suitable practical applications.     

Flow injection determination of cyromazine in natural water samples using diperiodatoargentate(III)–H2SO4–chemiluminescence system

A simple and sensitive chemiluminescence (CL) procedure is proposed for the determination of cyromazine (CYR) using flow injection technique. CYR has strong enhancing effect on the CL reaction of diperiodatoargentate-(III) complex (DPA) in H₂SO₄ medium. The CL intensity with solid phase extraction (SPE) technique and with and without using online ion exchange resin column (IERC; OH-form) was proportional to the concentration of CYR over the range 0.1–200, 10–1000 and 2–2500 µg L^–1 (R² = 0.9974, 0.9980 and 0.9990, n = 7 each), respectively. Under the conditions, the limits of detection (S/N = 3) 0.029, 2.5 and 0.5 µg L^–1, relative standard deviations (n = 3) 1.9–3.6%, 1.4–2.7% and 1.0–3.0% and sample throughputs were 120, 80 and 120 h^–1. The effect of reagents concentration, flow rate, sample loop volume, photomultiplier voltage and IERC length was optimised. The mean results for natural water samples analysed by the proposed method were not significantly different at 95% confidence limit with the previously reported HPLC method. Interference from chloride ions could be eliminated by using SPE procedure or incorporating an in-line IERC. The CL mechanism of DPA–H₂SO₄–CYR system was also discussed briefly.     

Synthesis and thermal studies of flexible polyurethane nanocomposite foams obtained using nanoclay modified with flame retardant compound

This work presents thermal studies of nanocomposites based on the flexible polyurethane (PU) matrix and filled using montmorillonite organically modified with organophosphorus flame retardant compound. Flexible PU nanocomposite foams were prepared in the reaction carried out between reactive alcoholic hydroxyl and isocyanate groups with the ratio of NCO to OH groups equal to 1.05. The amount of an organoclay ranging from 3 to 9 vol% was added to the polyol component of the resin before mixing with isocyanate. The apparent density of PU foams was ranging from 0.066 to 0.077 g cm^?1. Thermal properties of the flexible PU nanocomposite foams were investigated by thermogravimetry and dynamical mechanical analysis. Glass transition temperatures (T _g) were defined as maximum peak on tanδ curve. Thermal decomposition was observed at 310–320 °C (calculated from the onset of TG curve). Tensile strength of the PU foams was determined using mechanical test. The microstructure of the nanoparticles and the composites was investigated by X-ray diffraction. Finally, it was confirmed that the thermal and mechanical properties of flexible PU nanocomposite depend on the amount of nanoclay.     

Ultra-lightweight cellulose foam material: preparation and properties

Ultra-lightweight cellulose foams were prepared by regeneration of sodium dodecyl sulfate (SDS)/cellulose/NaOH/urea blend solution via mechanical agitation and then freeze-drying. The morphology and properties of the blend solutions and foams were investigated via optical microscope, rheometer, BET and SEM. As a result, it was found that the inclusion complex structure between cellulose macromolecules and the solvent molecules was not destroyed. Moreover, the bubbles were about 20–50 μm in the solutions and larger (>100 μm) in the foams. Not only the micropores (bubbles) but also the nanopores could be observed in the wet and dried foams. The cellulose foams possessed ultra-low density of about 30 mg/cm³ and high specific surface area. The result of X-ray diffraction and Fourier transform infrared spectroscopy indicated that the cellulose foams were transited from cellulose I to cellulose II after dissolution and gelation. Bubbles inside the wet foams weakened the mechanical properties, but inversely increased the mechanical properties in the dried foams. Typical “J”-shaped curves were observed during the mechanical test, which revealed good compressive strength of dried foams. In this work, cellulose foams with ultra-lightweight and good mechanical properties were obtained, which exhibited great potentials for further development and comprehensive utilization of cellulose.     

A simple method for self-attenuation correction in <Superscript>210</Superscript>Pb activity measurement in a well-type HPGe detector

A simple method for ²¹⁰Pb determination in a well-type detector for matrix with apparent densities ranging from ρ = 0.430 g cm^?3 to ρ = 2.037 g cm^?3 is presented. Ten spiked samples of ²¹⁰Pb were prepared to obtain the detector efficiency as a quadratic function of the matrix density. Then this equation was validated and successfully used to measure ²¹⁰Pb concentration activity in other samples. The equation proposed in this work is specific for each germanium detector; however it is proposed an extrapolation of the method to other well-type germanium detector by preparing a spiked sample and determining the efficiency for ²¹⁰Pb.     

A Monoclonal Antibody-Based Indirect Competitive Enzyme-Linked Immunosorbent Assay for the Determination of Olaquindox in Animal Feed

A reliable indirect competitive enzyme-linked immunosorbent assay (ELISA) based on a new specific monoclonal antibody was developed to determine olaquindox in animal feed. The influence of several physicochemical factors (nonfat dried milk solution, organic solvent, incubation time) on the immunoassay was investigated. In the optimized system, the 50% inhibition concentration was 9.66 ± 1.81 µ g L^?1. The limits of detection for porcine, chicken, and fish feed were 0.28, 0.46, and 0.48 µg kg^?1. The limits of quantification were 1.00 µg kg^?1 for the feed samples. The recoveries from porcine, chicken, and fish feed spiked with olaquindox were 90–104%, 77–103%, and 78–107%, respectively, with coefficients of variation (CVs) between 3.8 and 14.1%. The cross-reactivity was less than 2.08% with four structurally related compounds and no recognition of five other restricted or forbidden drugs was observed. Parallel analysis of the three spiked feed samples showed comparable results between the indirect competitive ELISA and the standard high-performance liquid chromatography method in China (R² = 0.9985 for porcine feed, R² = 0.9896 for chicken feed, and R² = 0.9987 for fish feed). These data suggest that the developed indirect competitive ELISA is a specific and convenient method and is suitable for olaquindox determination in animal feed.     

Thermal, rheological, and structural behaviors of natural and modified cassava starch granules, with sodium hypochlorite solutions

The use of chemically modified starches is widely accepted in various industries, with several applications. In this research, natural cassava starch granules were treated with standard sodium hypochlorite solution at 0.8, 2.0, and 5.0 g Cl/100 g starch. The native and modified starch samples were investigated by means of the following techniques: simultaneous thermogravimetry–differential thermal analysis, which allowed us to verify the thermal decomposition associated with endothermic or exothermic phenomena; and differential scanning calorimetry that was used to determine gelatinization enthalpy as well as the rapid viscoamylographic analysis that provided the pasting temperature and viscosity. By means of non-contact-atomic force microscopy method and X-ray powder patterns diffractometry, it was possible to observe the surface morphology, topography of starch granules, and alterations in the granules’ crystallinity.     

A tunable hierarchical porous carbon from starch pretreated by calcium acetate for high performance supercapacitors

Hierarchical porous carbons (HPCs) with abundant mesopores have been prepared by a facile route from the starch that was pretreated by calcium acetate. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and N₂ adsorption–desorption tests show that hierarchical porous carbons with bimodal mesopores have been obtained. Moreover, the pore sizes are tunable by simply adjusting the reactants ratio and carbonization temperature. The as-synthesized hierarchical porous carbon materials (HPCs-2-800) possesses the highest Brunauer-Emmett-Teller (BET)-specific surface area of 464 m² g^?1 and mesoporous volume of 0.663 cm³ g^?1 at the carbonization temperature of 800 °C and starch to calcium acetate mass ratio of 2. Electrochemical measurements also display that the HPCs-2-800 electrodes have a high reversible capacity of 244 F g^?1 at the current density of 0.1 A g^?1 and 182 F g^?1 at the current density of 10 A g^?1. When the current density is elevated from 0.1 to 10 A g^?1, the high capacitance retention of 74.6 % reveals a good rate performance. Long charge–discharge cycling measurements disclose good stabilities over 25,000 cycles at different current densities of 1–10 A g^?1 (5000 cycles at each current density) for HPCs-2-800 electrode. The cycling results indicate a high capacitance retention of 99.6 % over 5000 charge–discharge cycles even at the current density of 10 A g^?1. The excellent supercapacitive performances imply that HPCs-2-800 is a promising candidate for supercapacitors.     

Generic Automated Fluorimetric Assay for the Quality Control of Gamma Aminobutyric Acid-Analogue Anti-Epileptic Drugs Using Sequential Injection

The first sequential injection assay for the generic determination of gabapentin and pregabalin is reported. The analytes react with o-phthalaldehyde in the presence of N-acetylcysteine as a nucleophilic reagent in alkaline medium under flow conditions to form highly fluorescent derivatives. The effect of the main instrumental and chemical variables on the assay was examined. The proposed method was validated for both analytes in terms of linearity, detection, and quantitation limits (c _L  = 160 μg L^?1, c _Q  = 480 μg L^?1 for gabapentin, and c _L  = 70 μg L^?1, c _Q  = 210 μg L^?1 for pregabalin), precision (s _r  < 1.0% in both cases), selectivity, and accuracy. The applicability of the assay was demonstrated by successfully analyzing commercially available formulations. The experimental percent recoveries were in the range of 97.9–102.0% for gabapentin and 98.3–102.3% for pregabalin.     

Preparation and characterization of composites from starch with sugarcane bagasse nanofibres

This paper reports on the results of using unbleached sugar cane bagasse nanofibres (average diameter 26.5 nm; aspect ratio 247 assuming a dry fibre density of 1,500 kg/m³) to improve the physico-chemical properties of starch-based films. The addition of bagasse nanofibres (2.5 to 20 wt%) to modified potato starch (i.e. soluble starch) reduced the moisture uptake by up to 17 % at 58 % relative humidity. The film’s tensile strength and Young’s modulus increased by up to 100 % (3.1 to 6.2 MPa) and 300 % (66.3 to 198.3 MPa) respectively with 10 and 20 wt% fibre addition. However, the strain at yield dropped by 50 % for the film containing 10 wt% fibre. Models for composite materials were used to account for the strong interactions between the nanofibres and the starch matrix. The storage and loss moduli as well as the glass transition temperature (T_g) obtained from dynamic mechanical thermal analysis, were increased with the starch-nanofibre films indicating decreased starch chain mobility due to the interacting effect of the nanofibres. Evidence of the existence of strong interactions between the starch matrix and the nanofibres was revealed from detailed Fourier transform infra-red and scanning electron microscopic evaluation.     

Computational studies on 3,5,7,10,12,14,15,16-octanitro-3,5,7,10,12,14,15,16-octaaza-pentacyclo[7.5.1.12,8.04,13.06,11]hexadecane as potential high-energy-density compound

The B3LYP/6-31G(d) method of density functional theory was used to study molecular geometry, electronic structure, infrared spectrum, and thermodynamic properties. Detonation properties were evaluated using Kamlet–Jacobs equations based on the calculated density and heat of formation. Thermal stability of 3,5,7,10,12,14,15,16-octanitro-3,5,7,10,12,14,15,16-octaaza-pentacyclo[7.5.1.1^2,8.0^4,13.0^6,11]hexadecane (cage-HMX) was investigated by calculating the bond dissociation energy at unrestricted B3LYP/6-31G(d) level. The calculated results show that the first step of pyrolysis is the rupture of the N–NO₂ bond. The crystal structure obtained by molecular mechanics belongs to P2₁ space group, with lattice parameters a = 8.866 Å, b = 11.527 Å, c = 13.011 Å, Z = 4, and ρ = 2.219 g cm^?3. Both the detonation velocity of 9.79 km s^?1 and the detonation pressure of 45.45 GPa are better than those of CL-20. According to the quantitative standard of energetics and stability as a high-energy-density compound, cage-HMX essentially satisfies this requirement. These results provide basic information for molecular design of novel HEDCs.     

Selenium content of Argentinean infant formulae and baby foods by pseudo-cyclic instrumental neutron activation analysis coupled to Compton suppression

The selenium levels of Argentinean infant formulae and baby food were measured using the 162-keV gamma-ray of ^77mSe (t _½ = 17.4 s) by a pseudo-cyclic instrumental neutron activation analysis (PC-INAA) method in conjunction with Compton suppression spectrometry (CSS). For comparison purposes, 5 selected infant formulae were also analyzed for selenium by a radiochemical neutron activation analysis (RNAA) method. The selenium levels for three samples agreed between ±2.8 and 6.5 % while the other two differed by 12 and 17 % which could perhaps be attributed to sample inhomogeneity. The selenium content of cow milk-based infant formulae varied from 42–146 μg kg^?1 compared to 52–63 μg kg^?1 for soy-based milk formulae. In the case of baby foods, the selenium levels varied from 34 to 74 μg kg^?1. The detection limits for selenium by PC-INAA–CSS for all the samples analyzed in this work were between 8.5 and 65 μg kg^?1 depending on the major elements present in the samples, while it was 20 μg kg^?1 for the RNAA method. The expanded uncertainty (κ = 2) of the PC-INAA–CSS method was 7.0 % at the end of cycle #4 for a sample containing 73.7 μg kg^?1 selenium compared to the RNAA value of 24.2 % for a sample of 67.0 μg kg^?1 selenium content.     

A Novel Method for the Determination of Streptomycin Using Sodium Nitroprusside as a Chromogenic Reagent by Spectrophotometry

Abstract

A rapid and simple spectrophotometric method for the determination of streptomycin has been developed and validated. The method was based on the reaction of streptomycin with sodium nitroprusside in the alkaline medium forming a red product measured at the maximum absorption of 495 nm. The stoichiometric ratio of the product is 1:1. Beer's law is obeyed in a range of 1.87 µg mL^?1 ～ 279.8 µg mL^?1 of streptomycin and ?₄₉₅ is 6.0 × 10³ L·mol^?1 cm^?1.Under the optimum condition, the equation of linear regression is A = 0.00742 + 0.05683 C (× 10⁵ mol·L^?1), with a linear correlation coefficient of 0.9990. The detection limit (3σ/k) is 0.96 µg mL^?1, the relative standard deviation (RSD) is 2.40%, and the average recovery rate is 98.3%–102.7%. Every parameter has been optimized, and the reaction mechanism has been studied. The proposed method has been successfully applied to the determination of streptomycin for injections and tablets of pharmaceutical preparation. Analytical results obtained by this new method were very gratifying.     

Determination of reference interval values for inorganic elements in whole blood samples of humans and laboratory animals by X-ray fluorescence spectrometry

Inorganic elements are responsible for essential bodily functions, such as osmotic regulation, cardiac frequency and contractibility, blood clotting and neuromuscular excitability. The determination of inorganic elements in corporeal fluids such as blood, serum, plasma and urine is used as a monitor for a part or the whole organism; their values, then, are compared with reference interval values. In this study, the energy dispersive X-ray fluorescence spectrometry (EDXRF), applying the Fundamental Parameters method, for the determination of inorganic elements in whole blood samples from humans and laboratory animals, was used. Peripheral blood samples were collected and, before coagulation, 100 μL of sample were deposited onto Whatman No. 41 filter paper and dried, using infrared spotlight. The reference interval values for healthy Brazilian population of Na were found to be 1,788–1,826 μg g^?1, of Mg 63–75 μg g^?1, of P 602–676 μg g^?1, of S 1,519–1,718 μg g^?1, of Cl 2,743–2,867 μg g^?1, of K 1,508–1,630 μg g^?1, of Ca 214–228 μg g^?1, of Fe 170–184 μg g^?1, of Cu 4–6 μg g^?1 and of Zn 1–3 μg g^?1. The reference interval values for golden hamster (Mesocricetus auratus) of Na were found to be 1,714–1,819 μg g^?1, Mg 51–79 μg g^?1, P 970–1,080 μg g^?1, S 1,231–1,739 μg g^?1, Cl 2,775–2,865 μg g^?1, of K 1,968–2,248 μg g^?1, of Ca 209–257 μg g^?1, of Fe 145–267 μg g^?1, of Cu 4–6 μg g^?1 and of Zn 3–5 μg g^?1. A comparative study between EDXRF and instrumental neutron activation analysis data was carried out and the results for both techniques are statistically equal (α = 0.05). The results contribute for the establishment of reference interval values for Na, Mg, P, S, Cl, K, Ca, Cu and Zn in the healthy Brazilian population and the referred laboratory animal species.     

A Novel Enhanced Chemiluminescence System with Ag(III) Complex for the Determination of Ofloxacin and Levofloxacin in Pharmaceutical Preparation and Biological Fluid

A novel chemiluminescence (CL) method is developed for determination of ofloxacin and levofloxacin with Ag(III) complex in H₂SO₄ solution medium. The CL intensity is proportional to drug concentration in a wider range with a correlation coefficient of 0.999. The limit of detection (s/n = 3) for ofloxacin and levofloxacin was 5.3 × 10^?9 g ml^?1 and 8.3 × 10^?9 g ml^?1, respectively, and their recoveries from urine and serum samples were in the range of 90.1–112% with the RSDs of 1.0–2.8%. The proposed method was applied for analysis of real samples with satisfactory result. The possible CL mechanism was discussed.     

Determination of Organotin Compounds in Wine by Microwave-Assisted Extraction and High Performance Liquid Chromatography–Inductively Coupled Plasma Mass Spectrometry

A new analytical procedure for the determination of five organotin compounds in several matrix wine samples is reported. The organotin compounds were extracted by microwave-assisted extraction with n-hexane. Extraction conditions, such as volume of n-hexane required, extraction temperature, and extraction time, were investigated and optimized by an orthogonal array experimental design. The determination of organotin compounds in the final extracts was carried out by liquid chromatography–inductively coupled plasma mass spectrometry. The procedure showed limits of detection between 0.029–0.049 µg · L^?1. The linearity was in the range of 0.5 to 100 µg · L^?1. The precision expressed as relative standard deviation (RSD) was below 9.43%. The developed method was successfully employed to analyze different matrix wine samples, and some analytes were detected at the level of 0.053 to 1.14 µg · L^?1.     

Determination of N-methylcarbamate pesticides using flow injection with photoinduced chemiluminescence detection

A sensitive, economic, rapid and simple method for the determination of four N-methylcarbamate pesticides: methomyl (2.0–80 μg L^?1), aldicarb (5.0–50 μg L^?1), butocarboxim (2.0–60 μg L^?1) and oxamyl (2.0–60 μg L^?1); is reported. It relies on the coupling of photoinduced chemiluminescence (PICL) detection with flow injection (FI) methodology. The automation of FI together with the use of light as a reagent decreased the environmental impact of the analysis. The proposed method was based on the oxidation of these pesticides, previously irradiated on-line with UV light, with cerium(IV), using quinine as a sensitiser. Limits of detection below the legal limits (100 ng L^?1) established by the European Union for drinking waters were obtained without the need of preconcentration steps. A good inter-day reproducibility (1.6–6.4%, n = 5), repeatability (rsd = 2.7 %, n = 25) and high throughput (123 h^?1) were achieved. The method was successfully applied to the determination of methomyl in natural waters with mean recoveries ranging from 90% to 98%.     

Analysis of PAHs in Water and Fruit Juice Samples by DLLME Combined with LC-Fluorescence Detection

A simple, rapid and efficient method termed dispersive liquid–liquid microextraction combined with liquid chromatography-fluorescence detection, has been developed for the extraction and determination of polycyclic aromatic hydrocarbons (PAHs) in water and fruit juice samples. Parameters such as the kind and volume of extraction solvent and dispersive solvent, extraction time and salt effect were optimized. Under optimum conditions, the enrichment factors ranged from 296 to 462. The linear range was 0.01–100 μg L^?1 and limits of detection were 0.001–0.01 μg L^?1. The relative standard deviations (RSDs, for 5 μg L^?1 of PAHs) varied from 1.0 to 11.5% (n = 3). The relative recoveries of PAHs from tap, river, well and sea water samples at spiking level of 5 μg L^?1 were 82.6–117.1, 74.9–113.9, 77.0–122.4 and 86.1–119.3%, respectively. The relative recoveries of PAHs from grape and apple juice samples at spiking levels of 2.5 and 5 μg L^?1 were 80.8–114.7 and 88.9–123.0%, respectively. It is concluded that the proposed method can be successfully applied for determination of PAHs in water and fruit juice samples.