Effect of compression on interaction between 1,4-dihydropyridine compounds and lactose monohydrate

Manidipine dihydrochloride or benidipine hydrochloride will change to hydrate form in part, when differential scanning calorimetric (DSC) measurement is carried out together with lactose monohydrate. This interaction was accelerated by compressing their mixture. It can be suggested that the interaction may cause by the disruption of crystal structure of lactose monohydrate due to compression to set free of water molecules. A new DSC peak at 170 degrees C, which was not observed in each component, appeared in DSC measurement of a mixture. This will be based on hydrate formed by the interaction, i.e., movement of water molecules. The profile of the plotting of the DSC peak area ratio before and after compression against the compression force changed by the molar ratio of lactose monohydrate in a mixture. In the case of low molar ratio of lactose monohydrate, profiles for manidipine dihydrochloride and benidipine hydrochloride differed from each other. This will be because manidipine dihydrochloride is stickier than benidipine hydrochloride. The profile for manidipine dihydrochloride became more gradual and showed lag compression force region when the amount of addition of the lubricant, magnesium stearate in a mixture increased. The endothermic peak area at 170 degrees C for manidipine dihydrochloride was larger than that for benidipine hydrochloride. It should be suggested that benidipine hydrochloride is easier to be transformed to its hydrate than manidipine dihydrochloride.     

Prolonged release of drug from triacetyl-β-CyD complex for oral and rectal administration

Triacetyl--cyclodextrin (TA--CyD), a hydrophobic cyclodextrin derivative, that is insoluble in water, was used to form a complex with flufenamic acid (FA). FA-TA--CyD complex formation was demonstrated by differential scanning calorimetry and powder X-ray diffractometry. The release rate of FA from the FA-TA--CyD complexes in phosphate buffer pH 6.8 was significantly retarded compared to that of FA from the FA and glucose mixture. When the FA-TA--CyD complexes were administered directly into the intraduodenal lumen, the plasma concentration of FA remained at a plateau level (10-18 g/ml) for 6–8 h. An increased mean residence time of FA following FA-TA--CyD complexes administration was observed. These results indicate that TA--CyD may serve as a hydrophobic carrier in prolonged-release preparations of FA.     

Stratum corneum lipid abnormalities in UVB-irradiated skin

Stratum corneum (SC) lipids are of particular importance in maintaining the permeability barrier function. Although many studies have demonstrated that UVB irradiation of mammalian skin reduces barrier function, the responsible alterations in SC lipid profiles are not known. In this study, we investigated both compositional and morphological alterations in SC lipids with the development of barrier abnormalities caused by daily UVB irradiation in hairless rat skin. The UVB irradiation of suberythemal doses (0.5 minimal erythema dose) significantly increased transepidermal water loss (TEWL) relative to nonirradiated control, indicating a diminished barrier function. Under these conditions, the total amounts of major SC lipid species (ceramides, cholesterol, free fatty acids) in UVB-irradiated SC did not differ from those in nonirradiated SC. However, electron microscopic observations revealed marked abnormalities in the intercellular domains of UVB-irradiated SC, where naturally occurring intercellular multilamellar structures were often absent and leaving the area with the appearance of an empty space. Moreover, in UVB-irradiated SC, individual corneocytes often showed small amounts of intercellular deposition product with abnormal lamellar structure, where lamellar body sphingomyelinase activity was present. These observations demonstrated a partial failure of lamellar body secretion in UVB-irradiated SC and suggested that a defect in the secretion of lamellar body-derived lipids and enzymes to SC intercellular space is, at least in part, responsible for the observed abnormal intercellular structure and barrier disruption.     

Eu-Doped KCl storage phosphor for erasable and rewritable optical memory utilizing photostimulated luminescence phenomenon

Intense photostimulated luminescence (PSL) with a peak at 420 nm is observed in ultraviolet (UV) Iight-irradiated europium-doped potassium chloride (KCl: Eu) crystalline phosphors. The PSL characteristics of UV-irradiated KCl: Eu phosphor for optical memory application were studied. The excitation and emission mechanisms of the 420 nm PSL, which are consistent with the results obtained, are discussed.     

Study of the factors affecting the photoelectrode characteristics of a perylene/phthalocyanine bilayer working in the water phase

Some types of phthalocyanines (MPc (M = H(2), Cu, or Zn), a p-type semiconductor) were used in combination with 3,4,9,10-perylenetetracarboxyl-bisbenzimidazole (PTCBI, an n-type semiconductor), with which those photoelectrode characteristics in the water phase were investigated in terms of kinetics. Each film of the PTCBI/MPc bilayer functioned as a photoanode, where the photoinduced oxidation of thiol occurs at the MPc/water interface along with the hole conduction through the MPc layer. The holes originate on account of the photophysical events in the p/n interior, involving the charge separation of excitons at the p/n interface. The typical photoelectrochemical characteristic in the PTCBI/MPc photoanodes involved a transient photocurrent occurring in the initial stage under illumination (under potentiostatic conditions): thereafter, it attained a steady state. Moreover, both the initial spiky photocurrents and the steady-state photocurrents exhibited saturation at higher concentrations. An analysis with photoelectrode kinetics was performed by assuming an adsorption step prior to a rate-limiting charge transfer step, where equations were applied to photocurrents based on the Langmuir adsorption equilibrium. The kinetic analyses evidently showed that the photoanodic reactions are kinetically dominated by the charge transfer between MPc and thiol, where the overall kinetics for thiol oxidation decreases in the following order: H(2)Pc > ZnPc > CuPc; that is, it appeared that H(2)Pc acts as the more efficient photofunctional interface capable of oxidation in the water phase when PTCBI was concurrently employed as an electron conductor. Considering that the photocurrent generated is proportional to the surface concentration of thiol (Gamma) at the MPc as well as the intrinsic oxidation rate (cf., ZnPc > H(2)Pc approximately CuPc), the higher efficiency in the output at the H(2)Pc surface was attributed to an exceptionally high Gamma (i.e., from the kinetic analyses, the Gamma value at the H(2)Pc surface was also inferred to be 2-3 times higher than that at the other MPcs). Through the present kinetic analysis, it also revealed that the activity for thiol oxidation taking place at Pc ring is comparable to that at the conventional active catalysts (i.e., polycarboxyphthalocyaninato Co(ii) and Fe(iii)) where a central metal is an active site.     

Contraction of supramolecular double-threaded dimer formed by alpha-cyclodextrin with a long alkyl chain

A double-threaded dimer bearing a long substituent part and a large stopper group has been prepared and showed a conformational change with increased solvent polarity. [structure: see text]     

Synthesis of Well‐Defined Polybenzamide‐block‐Polystyrene by Combination of Chain‐Growth Condensation Polymerization and RAFT Polymerization

Well‐defined diblock copolymers composed of poly(N‐octylbenzamide) and polystyrene were synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization of styrene with a polyamide chain transfer agent (CTA) prepared via chain‐growth condensation polymerization. Synthesis of a dithioester‐type macro‐CTA possessing the polyamide segment as an activating group was unsatisfactory due to side reactions and incomplete introduction of the benzyl dithiocarbonyl unit. On the other hand, a dithiobenzoate‐CTA containing poly(N‐octylbenzamide) as a radical leaving group was easily synthesized, and the RAFT polymerization of styrene with this CTA afforded poly(N‐octylbenzamide)‐block‐polystyrene with controlled molecular weight and narrow polydispersity.

     

Highly efficient near-infrared-emitting lanthanide(III) complexes formed by heterogeneous self-assembly of Ag(I), Ln(III), and thiacalix[4]arene-p-tetrasulfonate in aqueous solution (Ln(III) = Nd(III), Yb(III))

Heterogeneous self-assembly of thiacalix[4]arene-p-tetrasulfonate (TCAS), Ag(I), and Ln(III) (= Nd(III), Yb(III)) in aqueous solutions conveniently afforded ternary complexes emitting Ln(III)-centered luminescence in the near-infrared (NIR) region. A solution-state study revealed that the Ag(I)-Nd(III)-TCAS system gave a complex Ag(I)(4)·Nd(III)·TCAS(2) in a wide pH range of 6-12. In contrast, the Ag(I)-Yb(III)-TCAS system gave Ag(I)(2)·Yb(III)(2)·TCAS(2) at a pH of around 6 and Ag(I)(2)·Yb(III)·TCAS(2) at a pH of approximately 9.5. The structures of the Yb(III) complexes were proposed based on comparison with known Ag(I)-Tb(III)-TCAS complexes that show the same self-assembly behavior. In Ag(I)(2)·Yb(III)(2)·TCAS(2), two TCAS ligands sandwiched a cyclic array of a Ag(I)-Ag(I)-Yb(III)-Yb(III) core. In Ag(I)(2)·Yb(III)·TCAS(2), Yb(III) was accommodated in an O(8) cube consisting of eight phenolate O(-) groups from two TCAS ligands linked by two S-Ag-S linkages. Crystallographic analysis of Ag(I)(4)·Nd(III)·TCAS(2) revealed that the structure was similar to Ag(I)(2)·Yb(III)·TCAS(2) but that it had four instead of two S-Ag-S linkages. The number of water molecules coordinating to Ln(III) (q) estimated on the basis of the luminescent lifetimes was as follows: Ag(I)(4)·Nd(III)·TCAS(2), 0; Ag(I)(2)·Yb(III)(2)·TCAS(2), 2.4; and Ag(I)(2)·Yb(III)·TCAS(2), 0. These findings were compatible with the solution-state structures. The luminescent quantum yield (Φ) for Ag(I)(4)·Nd(III)·TCAS(2) was 4.9 × 10(-4), which is the second largest value ever reported in H(2)O. These findings suggest that the O(8) cube is an ideal environment to circumvent deactivation via O-H oscillation of coordinating water. The Φ values for Ag(I)(2)·Yb(III)(2)·TCAS(2) and Ag(I)(2)·Yb(III)·TCAS(2) were found to be 3.8 × 10(-4) and 3.3 × 10(-3), respectively, reflecting the q value. Overall, these results indicate that the ternary systems have the potential for a noncovalent strategy via self-assembly of the multidentate ligand, Ln(III), and an auxiliary metal ion to obtain a highly efficient NIR-emissive Ln(III) complex that usually relies on elaborate covalent linkage of a chromophore and multidentate ligands to expel coordinating water.     

Outcomes of Physiotherapy on Activities of Daily Living and Discharge to the Community in Psychiatric Long-term Care Ward Patients

Objective: The purpose of this study was to investigate the outcomes of physiotherapy on patients in psychiatric long-term care wards in Japan and to identify the characteristics of patients who have been discharged to the community. Methods: The subjects comprised 50 patients who were admitted to the psychiatric long-term care wards at four different hospitals in Japan and prescribed physiotherapy. General physiotherapy for the patients’ diseases was provided. The main outcome was whether a patient was discharged to the community (discharged group) or remained hospitalized (hospitalized group) at the end of physiotherapy. Basic subject characteristics, including age, sex, F-code, classification of the diagnosis that led to physiotherapy, length of hospital stay, and length of physiotherapy, were collected from medical records. The Functional Independence Measure (FIM) tool was administered at the initial and final evaluations. Results: At the end of physiotherapy, there were 14 subjects in the discharged group and 36 subjects in the hospitalized group. There were significant differences in the classification of diagnosis, length of stay (LOS), and classification of LOS between the two groups. Two-way analysis of variance showed interactions between the FIM subitems of self-care, transfer, and locomotion. Conclusion: The discharged group had higher FIM scores at the start of physiotherapy and a greater FIM gain.     

Characterization of Cu species on SiO2 and ZSM-5 by temperature-programmed reduction by ammonia

We studied the temperature-programmed reduction by NH₃ (NH₃-TPR) as a supplement to the temperature-programmed reduction by H₂ (H₂-TPR) for the characterization of supported Cu species. The NH₃-TPR profile of Cu/SiO₂, which contained only bulk CuO, exhibited two peaks for N₂ formation in equal amounts, suggesting stepwise reduction of the bulk CuO. In contrast, the H₂-TPR profile exhibited only one H₂ consumption peak. We also studied Cu-NaZSM-5 samples with various Cu and Na loadings. The Cu ions on ZSM-5 were reduced to Cu⁺ but no further. Kinetic analysis revealed that the NH₃-TPR profile exhibited peaks for separate reductions of isolated and binuclear Cu²⁺ ions. Thus, we found NH₃-TPR to be useful for detailed analysis of the reducibility of Cu²⁺ to Cu⁺ in zeolite pores.