Bis(PheOH) maleic acid amide-fumaric acid amide photoizomerization induces microsphere-to-gel fiber morphological transition: the photoinduced gelation system

The photoinduced gelation system based on 1 (non-gelling) to 2 (gelling) molecular photoisomerization in water results by microspheres (1) to gel fibers (2) transformation at the supramolecular level.     

Regioselective synthesis of 1- and 4-substituted 7-oxopyrazolo[1,5-a]pyrimidine-3-carboxamides

The synthesis of 7-substituted pyrazolo[1,5-a]pyrimidine-3-carboxamides was studied. First, methyl 7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate (5) was prepared in three steps from methyl 5-amino-1H-pyrazole-4-carboxylate (3). Treatment of 5 with POCl₃ gave the highly reactive 7-chloro derivative 10, which was reacted with amines, benzyl alcohol, and phenylboronic acid in the presence of Pd-catalyst to give the corresponding 7-substituted derivatives 11. Hydrolysis of the esters 5 and 11 followed by amidation gave the corresponding carboxamides 16a–h and 15. Regioselectivity of N-alkylation of 7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylic acid derivatives 5 and 16 was tunable by the carboxy function. Alkylation of the secondary amides 16a–f furnished the 1-alkyl derivatives 17a–f, whereas the ester 5 and the tertiary amides 16g,h gave the 4-alkyl derivatives 14a–d and 16m,n, selectively.     

Gels with exceptional thermal stability formed by bis(amino acid) oxalamide gelators and solvents of low polarity

Some bis (amino acid) oxalamide gelators form common thermo-reversible gels with various organic solvents but also gels of exceptional thermal stability with some solvents of medium and low polarity; the latter gels can be heated up to 50 degrees C higher temperatures than the bp of the solvent without apparent gel-to-sol transition.     

Evaluation of calcium carbonate in eggshells using thermal analysis

The eggshell of the hen is an important structure which provides protection for the developing chick, and also a container for the egg in the food industry. Egg breakage can reach up to 10% of total egg production, causing considerable economic losses. The eggshell consists of membranes, composed mainly of proteins, and the mineral shell composed mainly of the calcite polymorph of CaCO₃. The average CaCO₃ content of a chicken eggshell is between 93 and 97%, depending on animal genotype, age, housing system of laying hens and mineral nutrition. In the present study, eggs of the same breed and approximately same age were collected from four different production systems: organic farming, free-range production, deep litter system and battery cage system. The CaCO₃ content was determined by the standard titration method and by atomic absorption spectroscopy. Thermal properties of dried eggshell powder were measured by thermogravimetric measurements between 30 and 900 °C in air, showing a significant mass loss of?≈?43% between 600 and 850 °C corresponding to the decomposition of CaCO₃ to CaO and CO₂. The relations between the thermal mass loss and CaCO₃ content determined by the titration method/atomic absorption spectroscopy were studied using predictive models fitted by the linear regression method. A good prediction ability with an average prediction error of 0.01% was obtained between CaCO₃ determined by titration and the thermal mass loss, indicating that TG could provide a reliable method for evaluation of CaCO₃ content in eggshells.

     

Design and application of a flow cell for carbon-film based electrochemical enzyme biosensors

A flow cell has been designed for use with an electrochemical enzyme biosensor, based on low-cost carbon-film electrodes. Three types of mediators were used: cobalt and copper hexacyanoferrates and poly(neutral red) (PNR), covered with glucose oxidase (GOx) immobilised by cross-linking with glutaraldehyde in the presence of bovine serum albumin or inside a oxysilane sol–gel network. Mixtures of sol–gel precursors were made from 3-aminopropyl-triethoxysilane (APTOS) together with methyltrimethoxysilane (MTMOS), methyltriethoxysilane (MTEOS), tetraethyloxysilane (TEOS) or 3-glycidoxypropyl-trimethoxysilane (GOPMOS), and the best chosen for encapsulation. Optimisation in batch mode, using amperometric detection at fixed potential, showed the PNR-GOx modified carbon-film electrodes to be best for flow analysis for both glutaraldehyde and sol–gel enzyme immobilisation. Both types of enzyme electrode were tested under flow conditions and the reproducibility and stability of the biosensors were evaluated. The biosensors were used for fermentation monitoring of glucose in grape must and interference studies were also performed.     

Thermal phase transitions of solid chiral N,N′-carbonyl-bis-(l-amino acids) and their methyl and benzyl esters

Compounds derived from different N,N′-carbonyl-bis-(l-amino acids) and their methyl and benzyl esters were synthesized and characterized by elemental analysis, infrared and nuclear magnetic resonance. The amino acids used were valine, leucine, phenylglycine and phenylalanine. All compounds revealed complex thermal behaviour as proved by differential scanning calorimetry, X-ray powder diffractometry and optical birefringence observation by polarizing microscope. Above isotropization temperature N,N′-carbonyl-bis-(l-amino acids) decomposed. The number and kinds of thermal phase transitions of investigated esters vary from a simple phase transition and melting to a complex polymorphism, and strongly depends on molecular structure. One to four phase transitions have been observed upon heating. Phase transition temperatures showed considerable variation with choice of the supstituent on symmetric carbons and therminal carboxylic groups. The results are discussed in terms of the architecture of investigated molecules that hinder mesomorphism.     

Evaluation of measurement uncertainty in the determination of jasmonic acid in <Emphasis Type="Italic">Lemna minor</Emphasis> L. by liquid chromatography with fluorescence detection

The uncertainty was estimated for the determination of jasmonic acid (JA) content in Lemna minor L. plant extracts using a reverse-phase liquid chromatography with fluorescence detection. JA was extracted from plant material, followed by solid-phase extraction procedures, derivatisation and quantification. In the estimation of uncertainty, the sampling, sample processing and chromatographic determination that may significantly influence the uncertainty of analytical data were considered. The results show that the method recovery and sample homogeneity are the two main contributors to uncertainty. The method has a relative expanded uncertainty (coverage factor k = 2) of about 17% at the JA content of approximately 100 ng/g.     

Diversity of TiO<Subscript>2</Subscript> nanopowders’ characteristics relevant to toxicity testing

In this study, the physicochemical properties of several commercial ultrafine TiO₂ powders and their behaviour in the as-received form and colloidal suspensions were analysed. Besides the particle size, the morphology and agglomeration state of the dry powders, dispersibility, ζ-potential and sedimentation in water and in phosphate-buffered saline (PBS) were studied. Also, leaching of ions from the powders during ageing in physiological solution and the ability of the photoactivated powders to decompose organic substances were evaluated. The examined TiO₂ powders revealed diversified characteristics when dispersed in water. In general, while in dry conditions the particle size appeared in the nano-range (down to 32 nm), the particles were agglomerated in aqueous suspensions at pH ~7 and only a minor amount showed dimensions below 200 nm, but none below 100 nm. The inherent pH of the 3 % suspensions varies from 3.7 to 7.5 and the surface charge at these pH values varied from highly positive to highly negative values. In PBS, the surface charge is negative and relatively low for all the samples, which resulted in agglomeration. Five out of six powders exhibited significant photocatalytic activity when exposed to UV irradiation. This also includes one cosmetic-grade powder. Furthermore, during the immersion in aqueous media at physiological temperature, the powders released foreign ions, which might also contribute to the results of cytotoxicity tests. The results revealed the major role of the particle surface charge and its impact on particle dispersion or agglomeration. Due to the high ionic strength in the liquids relevant for cell-surface interaction tests, for all the examined titania powders the nanoparticulate character was lost. However, the presence of impurities and photocatalysis might further contribute to the results of cytotoxicity tests.     

Synthesis of copper-nickel nanoparticles prepared by mechanical milling for use in magnetic hyperthermia

Mechanical alloying of a mixture of copper and nickel powders has been applied for the preparation of copper-nickel alloy particles in the nanometer range. The particles were designed to be used for controlled magnetic hyperthermia applications. The milling conditions were optimized using the desired alloy composition. Utilizing a ball-to-powder mass ratio of 20, we could obtain a nanocrystalline Cu_27.5Ni_72.5 (at%) alloy with a crystallite size of around 10 nm and a Curie temperature of 45 °C.Thermal demagnetization in the vicinity of the Curie temperature of the nanoparticles was determined by thermomagnetic measurements using an adapted TGA-SDTA apparatus. The size and morphology of the particles were determined by XRD measurements and TEM analyses. The magnetic properties were also examined with a VSM. The magnetic heating effects were measured for the powdered material.