The kinetic and thermodynamic study of KNiPO4·H2O from DSC and TG data

The DSC and TG data showed the dehydration process occurring over the range of 160?C300?°C. The XRD patterns of the synthesized KNiPO₄·H₂O and the calcined product at 350?°C with exposing in the air over 8?h are indexed as the KNiPO₄·H₂O structure, whereas at 600?°C is indexed as KNiPO₄ structure. Hence, these data confirmed that the water molecule was eliminated from the structure at 300?°C, after that the spontaneously reversible hydration?Crehydration process was observed. The activation energy and pre-exponential factor were calculated by Kissinger, Ozawa, and KAS equations. According to the DSC curves, the enthalpy change (??H) of dehydration process can be calculated and was found to be 100.12?kJ?mol^?1. Besides, we suggested another new method to determine the isokinetic temperature value using spectroscopic data. The surface area of synthesized hydrate and its calcined product at 350?°C with exposing in the air at over 8?h were found to be 21.48 and 134.3?m²?g^?1, respectively. The reversible hydration?Crehydration process was observed, and the surface area of final product at 350?°C (aging time over 8?h) is higher than that of the synthesized compound. This behavior is important to develop alternative desiccant materials or other process based on the rehydration mechanism with increasing the surface area.     

A recombinant cyclodextrin glycosyltransferase cloned from Paenibacillus sp. strain RB01 showed improved catalytic activity in coupling reaction between cyclodextrins and disaccharides

Recombinant cyclodextrin glycosyltransferase (CGTase) was obtained by cloning the PCR gene fragment from thermotolerant Paenibacillus sp. strain RB01 screened from hot spring area in Thailand and cloned into the Escherichia coli expression vector. The nucleotide sequence was analyzed and aligned. Nucleotide sequence of the recombinant CGTase contained an open reading frame of 2139 bp encoding 713 amino acid residues. The recombinant required one-third of culture time and neutral pH to produce CGTase compared to wild type. CGTases from both wild type and transformant were purified in parallel by starch adsorption and DEAE cellulose column. Their biochemical properties such as molecular weight, optimum pH and temperature were quite similar. However, the recombinant enzyme showed improved catalytic activity in the coupling reaction between cyclodextrins (CDs) and some disaccharides. Among several sugars tested with excess βCD, cellobiose was the best substrate followed by leucrose. Very low activity was observed with trehalose, lactose and mellibiose. Sucrose and raffinose showed no activity. The K _m and other kinetic parameters of recombinant enzyme were determined for cellobiose and several cyclodextrin derivatives. Recombinant CGTase showed lower K _m for βCD and its derivatives, with improved activity compared to wild type enzyme.     

Isolation of Cyclodextrin Producing Thermotolerant Paenibacillus sp. from Waste of Starch Factory and Some Properties of the Cyclodextrin Glycosyltransferase

A Cyclodextrin (CDs) producing bacteria was isolated from waste of starch factory in Thailand and identified as Bacillus circulans by biochemical characterization and Paenibacillus sp. by 16S rRNA. The Paenibacillus grew and produced cyclodextrin glycosyltransferase (CGTase) at temperature range 37–45 °C. The optimum culturing conditions for highest CD-forming activity were pH 10.0 and 40 °C for 72 h in Horikoshi broth containing 0.5% soluble starch. The CGTase was partially purified by starch absorption, with 64% recovery and purification fold of 27. The optimum temperatures for dextrinizing and CD-forming activity were 70 and 50–55 °C. At the optimum temperature, the optimum pH for dextrinizing activity was 6.0, while CD-forming activity was 7.0. When the enzyme was incubated for 1 h at different temperatures, CD-forming activity retained its full activity up to 70 °C while dextrinizing activity dropped to 60%. Cyclodextrin products analyzed by HPLC was α:β=1:1, temperature of reaction mixture can affect the yield of CDs.     

Thermal decomposition kinetics and reversible hydration study of the Li2Zn(HPO4)2·H2O

The dilithium zinc hydrogen phosphate monohydrate (Li₂Zn(HPO₄)₂·H₂O) was synthesized at the ambient temperature by using zinc acetyl acetonate monohydrate, phosphoric acid and lithium hydroxide monohydrate. The thermal stability of the Li₂Zn(HPO₄)₂·H₂O was studied by non-isothermal kinetic method (Ozawa and Kissinger) from the differential scanning calorimetric (DSC) data. The studied hydrate undergoes two endothermic thermal transformations, which the first transformation is due to the release of water molecule of crystallization and the second one is due to the release of water of constituent from HPO₄^2? anions and transforms to P₂O₇^4?. The activation energies (E_a) calculated for the dehydration step and decomposition step of the Li₂Zn(HPO₄)₂·H₂O from different methods were found to be consistent. The dehydration and rehydration processes of the synthesized compound were investigated and found that the water of crystallization can be removed and rehydrated without the disrupting the structure of the material, provided it is not heated beyond 200 °C. The dehydration and rehydration processes of the synthesized Li₂Zn(HPO₄)₂·H₂O exhibits similar property to the zeolite.     

Formation of Inclusion Complexes between Cyclodextrins and Carbaryl and Characterization of the Complexes

The solubility of carbaryl increased with increasing concentrations of-CD, G₂--CD, and M--CD. The result suggests theformation of soluble inclusion complex. Solubility increase was highestin M--CD-carbaryl, being 18.4 fold higher than that of carbaryl when 100 mM M--CD was used. The apparent formation constant for the complex calculated from phase solubility diagram was 223.18 M^-1. The preparation of the complex in solid form for characterization was successful by kneading andfreeze-drying. The DSC curves for kneading and freeze-drying mixture didnot show the endothermic peak characteristic of carbaryl, but a small new endothermic peak was observed. FTIR analysis showed a shift of the major peak of carbonyl group in carbaryl molecule from 1717 to 1744 and 1734 cm^-1 in kneading and freeze-dried mixtures, respectively. M--CD-carbaryl complex demonstrated higher dissolution rate, higher thermal and UV stability but lower toxicity than its parent carbaryl compound.