Mononuclear Ca(II)-bulky aryl-phosphate monoanion and dianion complexes with ortho-amide groups

Two new mononuclear Ca(II) complexes with aryl dihydrogen phosphate ligands having two strategically oriented bulky amide groups, 2,6-(Ph3CCONH)2C6H3OPO3H2 (1), including one with a phosphate monoanion, (NMe4)[CaII[O2P(OH)OC6H3-2,6-(NHCOCPh3)2]3(NCMe)3] (3), and one with a phosphate dianion, [CaII[O3POC6H3-2,6-(NHCOCPh3)2](H2O)3(MeOH)2] (4). Both are analogues for the NH...O hydrogen bonds in the active site of Ca(II)-containing phosphotransferase. Crystallographic studies of these Ca(II) complexes revealed that the amide NHs are directed to uncoordinated O atoms of the phosphates, and the IR and 1H NMR spectra indicate that strong NH...O hydrogen bonds are formed only in the phosphate dianion state. The ligand exchange reaction of 3 with a non-hydrogen-bonded phosphate ligand shows that the NH...O hydrogen bonds prevent the Ca-O bond from dissociation. A scatter plot analysis comparing the distance of a Ca-O bond with the Ca-O-P angle, the Fourier density analysis, and DFT calculations reveal that a partial degree of covalency in the Ca-O(phosphate) bonds is present.     

Low-voltage electroosmosis pump for stand-alone microfluidics devices

Two types of low-voltage electroosmosis pumps were developed using microfabrication technology for usage in handy or stand-alone applications of the micrototal analysis systems (micro-TAS) and the lab-on-a-chip. This was done by making a thin (< 1 microm) region in the flow path and by only applying voltages near this thin region using electrodes inserted into the flow path. The inserted electrodes must be free from bubble formation and be gas-tight in order to avoid pressure leakage. For these electrodes, Ag/AgCl or a gel salt bridge was used. For patterning the gel on the chip, a hydrophilic photopolymerization gel and a photolithographic technique were optimized for producing a gel with higher electric conductivity and higher mechanical strength. For high flow rate application, wide (33.2 mm) and thin (400 nm) pumping channels were compacted into a 1 mm x 6 mm area by folding. This pump achieves an 800 Pa static pressure and a flow of 415 nL/min at 10 V. For high-pressure application, a pump was designed with the thin and thick regions in series and positive and negative electrodes were inserted between them alternatively. This pump could increase the pumping pressure without increasing the supply voltage. A pump with 10-stage connections generated a pressure of 25 kPa at 10 V.     

Oxygen‐binding Protein Fiber and Microgel: Supramolecular Myoglobin–Poly(acrylate) Conjugates

A supramolecular conjugate of myoglobin (Mb) and water‐soluble poly(acrylate), (PA_5k and PA_25k, where 5k and 25k represent the molecular weight of the polymers, respectively), is constructed on the basis of a noncovalent heme‐heme pocket interaction. The modified heme with an amino group linked to the terminus of one of the heme‐propionates is coupled to the side‐chain carboxyl groups of poly(acrylate) activated by N‐hydroxysuccinimide. The ratios of the heme‐modified monomer unit and the unmodified monomer unit (m:n) in the polymer chains of Heme‐PA_5k and Heme‐PA_25k were determined to be 4.5:95.5 and 3.1:96.9, respectively. Subsequent addition of apoMb to the conjugated polymers provides Mb‐connected fibrous nanostructures confirmed by atomic force microscopy. A mixture of the heme‐modified polymer and dimeric apomyoglobin as a cross‐linker forms a microgel in which the reconstituted myoglobin retains its native exogenous ligand binding activity.     

Effects of trimethylsilylation of copper(II)-phthalocyanine sulfonyl-aminopropyl silica gels on the separation of pi-electron-rich compounds by high-performance liquid chromatography.

As an attempt to elucidate the factor(s) responsible for the poor performance of a copper(II)-phthalocyanine aminopropylsilica gels (CU-PCSD) column for HPLC, the silanol and/or amino groups remaining on Cu-PCSD were endcapped with trimethylchlorosilane (TMCS) or N-trimethylsilylimidazole (TMSI). The trimethylsilylated Cu-PCS(D)S (Cu-PCSD-TMCS and -TMSI) were investigated concerning their performance as an HPLC-stationary phase in the separation of pi-electron-rich polyaromatic hydrocarbons (PAHs), such as mutagenic anthracene and pyrene. As a result, trimethylsilylation with TMSI, which reacts only with silanol-groups, was not effective to improve the column efficiency. In contrast, trimethylsilylation by TMCS, which reacts with both the silanol- and amino-groups, improved the theoretical plate numbers (N) for PAHs separation with the Cu-PCS(D) column, indicating that the low N values on the Cu-PCSD column were caused by electrostatic interactions between PAHs and the remaining amino-groups on Cu-PCS(D). Furthermore, the retention data of mutagenic heterocyclic amines (HCAs) indicated that the remaining amino groups interact with the polar groups of HCAs.     

Chemically programmed supramolecular assembly of hemoprotein and streptavidin with alternating alignment

Alternating: a cofactor dyad consisting of a heme group (red in picture) and a bis(biotin) unit (blue) was synthesized and shown to specifically bind to both apomyoglobin and streptavidin. In the presence of the dyad, the 1:1 association of a disulfide-bridged myoglobin dimer (green) with streptavidin (gray) afforded a submicrometer-sized fibrous alternating copolymer.     

Photoinduced switching of intramolecular hydrogen bond between amide NH and carboxyl oxygen

In this study, we synthesized two novel carboxylic acid and carboxylate compounds, both of which had an amide group linked with an azomethine moiety to introduce photoinduced switching of the intramolecular NH...O hydrogen bond. We suggest that the cis-carboxylate compound forms a stronger intramolecular NH...O hydrogen bond than the cis-carboxylic acid compound.     

Synthesis of polycarbosilanes having a five‐membered cyclic carbonate structure and their application to prepare gel polymer electrolytes for lithium ion batteries

A silacyclobutane having a five‐membered cyclic carbonate structure (SBMC) was prepared, and its transition metal‐catalyzed ring‐opening polymerization at the four‐membered carbosilane unit was investigated as well as formation of carbosilane networked polymers and polymer gel electrolytes. The SBMC was synthesized by epoxidation of 1‐(4‐butenyl)‐1‐methylsilacyclobutane followed by insertion of CO₂ to the epoxide. Ring‐opening polymerization of the silacyclobutane moiety in the SBMC readily proceeded by a transition metal catalyst such as platinum divinyltetramethyldisiloxane complex. A flexible networked polymer film was obtained by copolymerization of the SBMC with a small amount of crosslinker, hexamethylene‐1,6‐bis(1‐methylsilacyclobutane) (HMBS). The copolymerization of SBMC and HMBS in 1 M LiPF₆ solution in ethylene carbonate and diethyl carbonate (3/7 v/v) gave a gel polymer electrolyte, which showed good ionic conductivity and could be applied to lithium ion batteries. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Disorder-enhanced dielectric response of nanoscale and mesoscopic insulators

Enhancement of the dielectric response of insulators by disorder is theoretically proposed, where the quantum interference of electronic waves through the nanoscale or mesoscopic system and its change due to external perturbations control the polarization. In the disordered case with all the states being localized, the resonant tunneling, which is topologically protected, plays a crucial role, and enhances the dielectric response by a factor 30-40 compared with the pure case. The realization of this idea with accessible materials or structures is also discussed.     

Quantum theory of multiferroic helimagnets: collinear and helical phases

We study the quantum fluctuation in the cycloidal helical magnet in terms of the Schwinger boson approach. In sharp contrast to the classical fluctuation, the quantum fluctuation is collinear in nature which gives rise to the collinear spin density wave state slightly above the helical cycloidal state as the temperature is lowered. Physical properties such as the reduced elliptic ratio of the spiral, the neutron scattering and infrared absorption spectra are discussed from this viewpoint with the possible relevance to the quasi-one dimensional LiCu2O2 and LiCuVO4.