Synthesis and X-ray crystal structure of pyrrolo[1,2-a]benzimidazoles

Reaction of nitrilimines 1 with 2-cyanomethylbenzimidazole 2 gave the 3-arylazo-2-methylpyrrolo[1,2-a]benzimidazole 4a rather than the reported 2-arylazo-3-methylpyrrolo[1,2-a]benzimidazole 3a. The correct structure of the product was determined using X-ray crystal structure analysis. The similar reaction of nitrilimines with 2-aminobenzimidazole 5 gave the acyclic nucleophilic addition product 6.     

Heavy metal removal using SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> binary oxide: experimental design approach

Sorption of Ni²⁺ and Cd²⁺ as heavy metals ions at the interface of the binary oxide TiO₂-SiO₂ was investigated. In addition, physical properties of TiO₂-SiO₂ matrices such as BET surface area, X-ray diffraction, and point of zero charge (pH_PZC) were measured. Statistical design of experiments was applied to find the conditions of sorption at which the maximum heavy metal removal was achieved. A second order polynomial function was used to correlate the independent variables (pH, metal ion concentration, and shaking time) and response (heavy metal removal). Values of regression parameters were determined by the computer program, Design expert^® (Stat-Ease Inc.). The quality of fit of the polynomial model equation was expressed by the regression coefficient R ². The sorption results showed that the pH is the most significant factor. In turn, the sorbed percentage reached 100% at high initial concentration and long shaking times due to formation of hydroxyl compounds between the ions and TiO₂-SiO₂ matrices. The results show that there is a Gaussian (normal) distribution of residuals (squared differences between experimentally observed and predicted values from the model), and also that the differences between observed and predicted values are in the range of ±5%. These indicate that experiments were well-conducted and the results have no significant error.     

Equilibrium and hydrolysis ofα-amino acid esters in ternary complexes of copper(II) involving glycyl-L-tyrosine

Summary Binary and ternary complexes of copper(II) with glycyl-L-tyrosine and an amino acid ester were investigated by potentiometric and spectrophotometric techniques. The kinetics of base hydrolysis of the above esters in the presence of copper(II)-glycyl-L-tyrosine complex was studied at 30°C.     

Understanding microscopic binding of human microsomal prostaglandin E synthase-1 with substrates and inhibitors by molecular modeling and dynamics simulation

Microsomal prostaglandin E synthase-1 (mPGES-1) is a promising target for development of next-generation anti-inflammatory drugs. It is crucial for rational design of the next-generation anti-inflammatory drugs to know the three-dimensional (3D) structure of mPGES-1 trimer and to understand how mPGES-1 binds with substrates and inhibitors. In the current work, a 3D structural model of human mPGES-1 trimer has been developed, for the first time, by performing combined homology modeling, molecular docking, and molecular dynamics simulation. The 3D structural model enables us to understand how mPGES-1 binds with its substrates/inhibitors, and the key amino acid residues for the mPGES-1 binding with ligands have been identified. The detailed 3D structures and calculated binding free energies for mPGES-1's binding with substrates and inhibitors are all consistent with available experimental data, suggesting that the 3D model of the mPGES-1 trimer and the enzyme-ligand binding modes are reasonable. The new structural insights obtained from this study should be valuable for rational design of next-generation anti-inflammatory drugs.     

Biocalorimetry as a process analytical technology process analyser; robust in-line monitoring and control of aerobic fed-batch cultures of crabtree-negative yeast cells

Control of bioprocesses requires reliable and robust on- or in-line monitoring tools providing real-time information on process dynamics. Heat generation related to metabolic activity of living systems is currently gaining importance in bioprocess industry due to its non-invasive and essentially instantaneous characteristics. This study deals with monitoring and control of pure aerobic fed-batch cultures of three Crabtree-negative yeast strains, Kluyveromyces marxianus, Candida utilis and Pichia pastoris, based on in-line measured, metabolic heat flow signals. A high resolution biocalorimeter (BioRC1) was developed from a standard bench-scale heat flow calorimeter (RC1). The BioRC1 was equipped with in-line (dielectric spectroscopy, pH probe and dissolved oxygen probe) and at-line (exit gas analyser) sensors to characterise the growth behaviour of the yeast cells. Both metabolic heat flow and biomass profiles exhibited similar behaviour proving the significance of employing heat flow signal as a key-parameter for the system under investigation. A simple estimator for biomass concentration and specific growth rate was formulated based on heat flow values. In order to evaluate the potential of calorimetry as a reliable and powerful process monitoring tool, the robustness, reliability as well as the broad applicability of the developed estimators was assessed through comparison with off-line measurement techniques and showed promising results for general applicability with a wide range of bioprocesses.     

Studies and X‐ray Determinations with 2‐(Acetonylthio)benzothiazole: Synthesis of 2‐(Benzothiazol‐2‐ylthio)‐1‐phenylethanone and 2‐(Acetonylthio)Benzothiazole by C―S Bond Cleavage of 2‐(Acetonylthio)benzothiazole in KOH

New route for the synthesis of 2‐(benzothiazol‐2‐ylthio)‐1‐phenylethanone ( 6 ) and 2‐(acetonylthio)benzothiazole ( 1 ) by using phenacyl bromide and α‐chloroacetone, respectively, through carbon–sulfur bond cleavage reactions in a basic medium has been generated. Treatment of 1 with malononitrile and elemental sulfur afforded the corresponding derivative of 2‐amino‐3‐cyanothiophene ( 12 ), whereas treatment of 1 with cyanoacetohydrazide afforded the corresponding derivative of cyanoacetylhydrazone derivative ( 13 ). The structure of the synthesis compounds has been established on the basis of elemental analyses, ¹H‐NMR, ¹³C‐NMR, correlation spectroscopy, heteronuclear single quantum coherence, MS spectra, and X‐ray crystallographic investigations.     

Synthesis of Some Novel Imidazopyrazole and Pyrazolopyrimidine Derivatives

5‐Amino‐3‐anilino‐1H‐pyrazole‐4‐carbonitrile 1 was alkylated with various halo reagents under phase transfer conditions to give the corresponding imidazopyrazole derivatives 2a , 2b , 2c , 3 , 4 , 5 , 6 . Pyrazolo[1,5‐a] pyrimidine derivatives 11 , 12 , 13 , 14 were prepared by treating compound 1 with different dicarbonyl reagents, namely, diethymalonate, ethyl 3‐oxo‐3‐phenylpropanoate, pentane‐2,4‐dione or ethyl 3‐oxobutanoate.     

HETEROCYCLIZATION OF AMINOTHIAZOLES

Several new 2-arylidinoamino-4-(3-coumaryl)thiazole derivatives were synthesized via the reaction of 2-amino-4-(coumaryl)thiazole with aromatic aldehydes and other reagents. Structural elucidations were based on elementary analysis and spectral data studies.     

Application of New Modified Poly(ethylene Oxide)-Block-Poly(propylene oxide)-Block-Poly(ethylene oxide) Copolymers as Demulsifier for Petroleum Crude Oil Emulsion

Water soluble nonionic amphiphilic block copolymers based on hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(propylene glycol) (PPG) were prepared. Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) copolymers, PEG-PPG-PEG, were prepared in the normal condition. The chemical composition and molecular weights of the prepared copolymers were determined from ¹H NMR and GPC techniques. The surface properties of the prepared surfactants were determined by measuring the surface tension at different temperatures. The prepared nonionic surfactants were evaluated as demulsifiers for water in crude-oil emulsions that were pronounced at different ratios of crude oil: water at 318 K and 333 K. The experimental results showed that the dehydration rate of the prepared demulsifiers reached 100% based on demulsifier chemical compositions and concentrations.