Development of a method for estimating an accurate equivalence point in nickel titration of cyanide ions

In a nickel titration of cyanide ions using murexide as indicator, an accurate equivalence point was determined by a non-linear least-squares curve-fitting for a titration curve. This method was developed to establish a standard solution for cyanide ions. In a curve-fitting procedure, a theoretical titration curve was calculated, assuming that nickel ion formed only a 1:4 Ni²⁺:CN⁻ complex with cyanide ions and formed only a 1:1 complex with murexide. Results of the curve-fitting were reasonable at any pH and any indicator concentration studied. The combined standard uncertainty for a concentration of a 1000 mg kg⁻¹ cyanide solution by this method was 0.079%.     

Formulation study for lansoprazole fast-disintegrating tablet. II. Effect of triethyl citrate on the quality of the products

The purpose of this study was to develop enteric-coated microgranules for the lansoprazole fast-disintegrating tablet (LFDT), which is a rapidly disintegrating tablet containing enteric-coated microgranules. In our previous study, it was clarified that sufficient flexibility of the enteric layer was achieved by the optimized combined ratio of methacrylic acid copolymer dispersion to ethyl acrylate-methyl methacrylate copolymer dispersion and adding the optimized concentration of triethyl citrate to reduce the damage during the compression process. However, since triethyl citrate has an unpleasant bitter taste and is especially incompatible with lansoprazole, it adversely affects the taste and stability of lansoprazole in the enteric-coated microgranules. The enteric layer containing macrogol 6000 was proven useful to improve the unpleasant bitter taste and stability of lansoprazole, because macrogol 6000 does not have an unpleasant bitter taste and is more compatible than triethyl citerate. By covering the inner (first enteric layer) and outer side (third enteric layer) of the enteric layer containing triethyl citrate (second enteric layer) with the enteric layer containing macrogol 6000, we resolved the stability problem of lansoprazole and the unpleasant bitter taste. Finally, we developed enteric-coated microgranules comprising seven layers: 1) core, 2) active compound layer, 3) intermediate layer, 4) first enteric layer, 5) second enteric layer, 6) third enteric layer, and 7) over coating layer. The enteric-coated microgranules have the multiple functions of reducing the damage to the enteric layer during the compression process, improving the stability of lansoprazole, and masking the unpleasant bitter taste.     

Synthesis of 3-aminopyrazolo[3,4-d]pyrimidine derivatives using N-bis(methylthio)methylene-p-toluenesulfonamide

N-Bis(methylthio)methylene-p-toluenesulfonamide ( 1 ) reacted with active methylene compounds such as malononitrile ( 2a ) and, cyanoacetamide ( 2b ) to give the corresponding 3-methylthio-3-p-toluenesulfonylami-nopropenenitrile derivatives 3a,b which were found to be convenient starting materials for the synthesis of 3,5-diaminopyrazole derivatives. Reaction of 3a and 3b with hydrazines gave the corresponding 3,5-diaminopyrazoles 4a-e , key intermediates for the synthesis of 3-aminopyrazolo[3,4-d]pyrimidine derivatives 5a-d .     

Practical synthesis of a neuropeptide Y antagonist via stereoselective addition to a ketene

[Reaction: see text]. The synthesis of neuropeptide Y antagonist 1, currently under clinical investigation for the treatment of obesity, is described. The convergent synthesis from trans-spirolactone carboxylic acid intermediate 2a and aminopyrazole 3 is predicated on a stereoselective route to the former. The coupling reaction of ethyl 4-oxocyclohexanecarboxylate (10a) with lithiated isonicotinamide 11 was investigated in detail, but even optimized conditions only provided a 45:55 ratio of trans:cis isomers (12a:12b). While selective crystallization schemes were developed to isolate the thermodynamically less stable trans isomer 2a, improved stereocontrol was subsequentially achieved by the application of ketene chemistry. The ketene formation and quench was investigated under a variety of conditions aimed at maximizing the trans:cis ratio. Reacting a mixture of carboxylic acids 2a and 2b with POCl3 in THF, followed by concomitant addition of tert-butyl alcohol in the presence of TMEDA at 35 degrees C provided a 4:1 ratio of trans:cis tert-butyl esters (18a:18b) via in situ ketene formation. Ester hydrolysis, followed by selective crystallization of undesired 2b as the HCl salt, led to isolation of 2a in 47% overall yield. Aminopyrazole intermediate 3 was synthesized via the condensation reaction of 2-fluorophenylhydrazine hydrochloride (4a) with acrylonitrile derivative 5 in 65-70% yield. Coupling of advanced intermediates 2a and 3b via activation with thionyl chloride gave a 92% yield of 1.     

Assembled structures of nanocrystals in polymer/calcium carbonate thin-film composites formed by the cooperation of chitosan and poly(aspartate)

Assembled structures of calcium carbonate (CaCO₃) nanocrystals have been examined for polymer/CaCO₃ thin-film composites synthesized through a self-organization process inspired by biomineralization. For the crystallization of CaCO₃, a thin-film matrix of chitosan has been used as a polymeric substrate. When the matrix is immersed into a supersaturated aqueous solution of CaCO₃ containing 1.4 × 10⁻³ wt % poly(aspartate) (PAsp), thin-film crystals of CaCO₃ are formed spontaneously. Three kinds of disklike films have been observed under a polarizing optical microscope. Electron diffraction analyses of each film have revealed that one is aragonite, displaying radial orientation of the c axes, and the others are vaterite, exhibiting different orientations. Detailed observation by scanning electron microscopy has clarified that these films are assemblies of crystalline particles 10–20 nm in size. The thin-film composites have been obtained over a PAsp concentration range of 4.4 × 10⁻⁴ to 1.0 × 10⁻² wt %. Vaterite formation becomes dominant when the concentration of PAsp is increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5153–5160, 2006     

Synthesis of poly(ethylene glycol)‐based hydrogels and their swelling/shrinking response to molecular recognition

To synthesize the novel molecular‐ and pH‐stimulus‐responsive hydrogel, we prepared poly(ethylene glycol)‐based hydrogel containing ionic groups. We evaluated the fundamental swelling/shrinking properties of the hydrogels synthesized by various conditions. Decreasing the molecular weight of a crosslinker provided the increasing of the equilibrium swelling ratio. Also, the equilibrium swelling ratio was changed by the introduction of functional ionic monomers and its compositions. Furthermore, the swelling/shrinking behaviors of the hydrogels were affected by the environmental condition of aqueous solution, in fact the hydrogels were considerably shrunk (to one‐fifth volume) using a di‐ionic solute in the aqueous solution through the ionic interactions between the hydrogel and the solutes. Additionally, the specific shrinking to diamine compounds was also observed in response to pH change. These results clearly show the swelling/shrinking responsibility of the hydrogels toward the molecular recognitions and its pH conditions. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3153–3158     

Electrical conductivity of SmS polycrystals

The electrical conductivity of SmS polycrystals has been studied in the temperature range 300?C870 K. It has been shown that, at 300 K ?? T ?? 700 K, the concentration of conduction electrons is determined by electron transfer from impurity donor levels, and at T > 700 K, by that from the samarium 4f levels.     

Holographic window for solar power generation

A new photovoltaic generation unit based on the application of holographic technologies called a Holo-Window is proposed in this work. The basic principle and the optical configuration used for the basic experimental unit are described. Suitable fabrication technology for a hologram with the broadband spectrum required to provide the appropriate sunlight capture capability is then discussed. Finally, a laboratory-prototype Holo-Window unit was developed and its performance was evaluated.     

Formation of polyketone particle structure by hexafluoroisopropanol solvent evaporation and effects of plasticizer addition

Few solvents are capable of dissolving polyketones (PKs). 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (hexafluoroisopropanol, HFIP) is a better solvent than trifluoroethanol and m‐cresol. When HFIP was evaporated from a PK/HFIP solution, a porous cast‐film with a microparticle structure was formed because the isotactic PKs adopted a helical conformation, and convection during evaporation of the high polarity and low‐boiling‐point HFIP caused aggregation and rolling of the polymer molecules. The addition of plasticizer suppressed particle formation, improving the surface structure and mechanical properties of the film. In particular, the dielectric properties of the film improved significantly. This will enable PKs, which are rigid insulating materials, to be used as dielectric materials, broadening their range of applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 887–892