Polypeptide-synthetic polymer hybrids, 1. Miscibility of poly(vinyl alcohol) with poly(sodium α,β-D,L-aspartate)

The present paper describes materials of polypeptide-commodity polymer hybrids from poly(vinyl alcohol) (PVA) and poly(sodium α,β-D ,L -aspartate) ( 1 ). Miscible blend films of polypeptide 1 and PVA were prepared by the solvent-cast method from a homogeneous aqueous solution. Differential scanning calorimetry. Fourier transform infrared, and scanning electron microscopy combined with energy dispersive X-ray spectroscopy (EDX) were used to investigate the blends. It was revealed that 1 and PVA are miscible in a wide range of compositions.     

Optical Characteristics of Hybrid Macrocycles with Dithienogermole and Tricoordinate Boron Units

The introduction of unconventional elements into π-conjugated systems has been studied to manipulate the electronic states and properties of compounds. Herein, boron- and germanium-containing hybrid macrocycles, as a new class of element-hybrid conjugated systems, have been synthesized. The palladium-catalyzed Stille cross coupling of bis(bromothienyl)borane and bis(trimethylstannylthienyl)- or bis(trimethylstannylphenyl)-substituted dithienogermoles as the boron- and germanium-containing building blocks, respectively, produced a mixture of several macrocyclic compounds. Single-crystal X-ray analysis of the 2:2 coupling product revealed a planar structure with a cavity inside the macrocycle. The optical properties of the macrocyclic products indicated rather small electronic interactions between the building units. However, intramolecular photoenergy transfer from the dithienogermole unit to the boron unit was clearly observed with respect to the fluorescence spectra.     

In situ Raman imaging of osteoblastic mineralization

Hydroxyapatite (HA) is synthesized at early stages of bone formation by osteoblasts. Nondestructive observation of early stages of osteoblastic mineralization provides crucial information for biological mechanism of bone formation. Raman microscopy serves as an ideal tool to observe the osteoblastic mineralization process because it shows the chemical information of the sample at a minimally invasive level. In addition, HA is a marker for osteoblastic mineralization, and HA Raman signal is strong enough to identify mineralized spots in osteoblasts. In this research, we visualized the distribution of HA in cultured mouse osteoblasts by Raman imaging and observed the location of the mineralized spots in the culture. We monitored HA Raman signal from osteoblast culture for 3 days after administrating the osteogenic differentiation medium and observed Raman signal associated with HA. We identified mineralized spots of KUSA‐A1 by Raman imaging constructed from the distribution of HA Raman signal. We successfully visualized the distribution of the mineralized spots in the culture of KUSA‐A1. We compared our Raman images with Alizarin red S staining assay, which was a conventional method to evaluate the mineralization process. Raman imaging of the KUSA‐A1 culture visualized the mineralized spots more accurately than Alizarin red S staining assay. Raman imaging of HA serves as a powerful tool to identify the mineralized spots in an in vitro culture of osteogenic lineage cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Efficient generation of Xe K-shell x rays by high-contrast interaction with submicrometer clusters

The interaction between a 25 TW laser and Xe clusters at a peak intensity of 1 × 101? W/cm2 has been investigated. Xe K-shell x rays, whose energies are approximately 30 keV, were clearly observed with a hard x-ray CCD at 3.4 MPa. Moreover, we studied the yield of the Xe K-shell x rays by changing the pulse duration of the laser at a constant laser energy and found that the pulse duration of 40 fs is better than that of 300 fs for generating Xe K-shell x rays.     

Tetraspanin CD9 modulates ADAM17-mediated shedding of LR11 in leukocytes

LR11, also known as SorLA or SORL1, is a type-I membrane protein from which a large extracellular part, soluble LR11 (sLR11), is released by proteolytic shedding on cleavage with a disintegrin and metalloproteinase 17 (ADAM17). A shedding mechanism is presumed to have a key role in the functions of LR11, but the evidence for this has not yet been demonstrated. Tetraspanin CD9 has been recently shown to regulate the ADAM17-mediated shedding of tumor necrosis factor-α and intercellular adhesion molecule-1 on the cell surface. Here, we investigated the role of CD9 on the shedding of LR11 in leukocytes. LR11 was not expressed in THP-1 monocytes, but it was expressed and released in phorbol 12-myristate 13-acetate (PMA)-induced THP-1 macrophages (PMA/THP-1). Confocal microscopy showed colocalization of LR11 and CD9 proteins on the cell surface of PMA/THP-1. Ectopic neo-expression of CD9 in CCRF-SB cells, which are LR11-positive and CD9-negative, reduced the amount of sLR11 released from the cells. In contrast, incubation of LR11-transfected THP-1 cells with neutralizing anti-CD9 monoclonal antibodies increased the amount of sLR11 released from the cells. Likewise, the PMA-stimulated release of sLR11 increased in THP-1 cells transfected with CD9-targeted shRNAs, which was negated by treatment with the metalloproteinase inhibitor GM6001. These results suggest that the tetraspanin CD9 modulates the ADAM17-mediated shedding of LR11 in various leukemia cell lines and that the association between LR11 and CD9 on the cell surface has an important role in the ADAM17-mediated shedding mechanism.     

A Basic Germanodecatungstate with a −7 Charge: Efficient Chemoselective Acylation of Primary Alcohols

The synthesis of highly negatively charged polyoxometalates with electrically and structurally controlled uniform basic sites can lead to the unique base catalysis. In this work, a γ‐Keggin germanodecatungstate, [γ‐HGeW₁₀O₃₆]^7? ( A ), having a ?7 charge was, for the first time, successfully synthesized by the reaction of [γ‐H₂GeW₁₀O₃₆]^6? with one equivalent of [(n‐C₄H₉)₄N]OH under non‐aqueous conditions. The activities of germanodecatungstates for base‐catalyzed reactions dramatically increased with increase in the number negative charges from ?6 to ?7. In the presence of A , various combinations of acylating agents and primary alcohols including those with acid‐sensitive functional groups chemoselectively gave the desired acylated products in high yields even under the stoichiometric conditions.     

Biodegradable polymers based on renewable resources. IX. Synthesis and degradation behavior of polycarbonates based on 1,4:3,6‐dianhydrohexitols and tartaric acid derivatives with pendant functional groups

Novel polycarbonates, with pendant functional groups, based on 1,4:3,6‐dianhydrohexitols and L ‐tartaric acid derivatives were synthesized. Solution polycondensations of 1,4:3,6‐dianhydro‐bis‐O‐(p‐nitrophenoxycarbonyl)hexitols and 2,3‐di‐O‐methyl‐L ‐threitol or 2,3‐O‐isopropylidene‐L ‐threitol afforded polycarbonates having pendant methoxy or isopropylidene groups, respectively, with number average molecular weight (M_n) values up to 3.6₁ × 10⁴. Subsequent acid‐catalyzed deprotection of isopropylidene groups gave well‐defined polycarbonates having pendant hydroxyl groups regularly distributed along the polymer chain. Differential scanning calorimetry (DSC) demonstrated that all the polycarbonates were amorphous with glass transition temperatures ranging from 57 to 98 °C. Degradability of the polycarbonates was assessed by hydrolysis test in phosphate buffer solution at 37 °C and by biochemical oxygen demand (BOD) measurements in an activated sludge at 25 °C. In both tests, the polycarbonates with pendant hydroxyl groups were degraded much faster than the polycarbonates with pendant methoxy and isopropylidene groups. It is noteworthy that degradation of the polycarbonates with pendant hydroxyl groups was remarkably fast. They were completely degraded within only 150 min in a phosphate buffer solution and their BOD‐biodegradability reached nearly 70% in an activated sludge after 28 days. The degradation behavior of the polycarbonates is discussed in terms of their chemical and physical properties. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3909–3919, 2005     

Rhodium/chiral diene-catalyzed asymmetric 1,4-addition of arylboronic acids to arylmethylene cyanoacetates

Asymmetric 1,4-addition of arylboronic acids to (E)-methyl 2-cyano-3-arylpropenoates proceeded in the presence of a rhodium catalyst (3 mol %) coordinated with a chiral diene ligand, (R,R)-Ph-bod*, to give high yields of the corresponding methyl 3,3-diaryl-2-cyanopropanoates with high enantioselectivity (up to 99% ee). This catalytic asymmetric transformation was applied to the asymmetric synthesis of (R)-tolterodine.     

Mu-eta1:eta1-peroxo-bridged dinuclear peroxotungstate catalytically active for epoxidation of olefins

The reaction of the dinuclear peroxotungstate, [(n-C4H9)4N]2[{WO(O2)2}2(mu-O)] (II), with H2O2 gives the novel mu-eta1:eta1-peroxo-bridging dinuclear tungsten species, [(n-C4H9)4N]2[{WO(O2)2}2(mu-O2)] (I), which has been characterized by X-ray crystallography, elemental analysis, IR, Raman, UV-vis, and 183W NMR. Only I is active for the epoxidation of cyclic, internal, and terminal olefins, whereas II is inactive for each. The low XSO (XSO=(nucleophilic oxidation)/(total oxidation)) value of I (0.18+/-0.02) in comparison with that of II (0.39+/-0.01) for the stoichiometric oxidation of thianthrene 5-oxide, which is a mechanistic probe for determining the electronic character of an oxidant, reveals that I is more electrophilic than II. On the basis of the kinetic and spectroscopic results, the catalytic epoxidation proceeds by the reaction of I with an olefin to form II and the corresponding epoxide followed by the regeneration of I by the reaction of II with H2O2.