High-resolution 2D NMR spectroscopy of bicelles to measure the membrane interaction of ligands

Magnetically aligned bicelles are increasingly being used as model membranes in solution- and solid-state NMR studies of the structure, dynamics, topology, and interaction of membrane-associated peptides and proteins. These studies commonly utilize the PISEMA pulse sequence to measure dipolar coupling and chemical shift, the two key parameters used in subsequent structural analysis. In the present study, we demonstrate that the PISEMA and other rotating-frame pulse sequences are not suitable for the measurement of long-range heteronuclear dipolar couplings, and that they provide inaccurate values when multiple protons are coupled to a 13C nucleus. Furthermore, we demonstrate that a laboratory-frame separated-local-field experiment is capable of overcoming these difficulties in magnetically aligned bicelles. An extension of this approach to accurately measure 13C-31P and 1H-31P couplings from phospholipids, which are useful to understand the interaction of molecules with the membrane, is also described. In these 2D experiments, natural abundance 13C was observed from bicelles containing DMPC and DHPC lipid molecules. As a first application, these solid-state NMR approaches were utilized to probe the membrane interaction of an antidepressant molecule, desipramine, and its location in the membrane.     

Ligand-free Pd/C-catalyzed Suzuki-Miyaura coupling reaction for the synthesis of heterobiaryl derivatives

We have developed a mild and efficient protocol for the ligand-free and heterogeneous Pd/C-catalyzed hetero Suzuki-Miyaura coupling reaction that allows for the synthesis of both heteroaryl-aryl and heteroaryl-heteroaryl derivatives in good to excellent yields.     

Mechanistic study of a Pd/C-catalyzed reduction of aryl sulfonates using the Mg-MeOH-NH(4)OAc system

A method for the deoxygenation of phenolic hydroxy groups via aryl triflates or mesylates has been established by using a combination of Pd/C-Mg-MeOH. The addition of NH(4)OAc to the system markedly accelerated the reaction rate and expanded the scope of the reaction. Mechanistic studies suggested that a single-electron transfer process from the Pd(0) center to the benzene ring is involved in the reduction of aryl sulfonates and that NH(4)OAc works as a solubilization reagent of the Mg salt and as an accelerator of the electron transfer, thus enhancing the reaction process. Our method was also applicable to the regioselective deuteration of benzene derivatives with CH(3)OD as the solvent and deuterium source: the original hydroxy group could be efficiently replaced with a deuterium atom.     

Surface and dynamic structures of bacteriorhodopsin in a 2D crystal, a distorted or disrupted lattice, as revealed by site-directed solid-state 13C NMR

The 3D structure of bacteriorhodopsin (bR) obtained by X-ray diffraction or cryo-electron microscope studies is not always sufficient for a picture at ambient temperature where dynamic behavior is exhibited. For this reason, a site-directed solid-state 13C NMR study of fully hydrated bR from purple membrane (PM), or a distorted or disrupted lattice, is very valuable in order to gain insight into the dynamic picture. This includes the surface structure, at the physiologically important ambient temperature. Almost all of the 13C NMR signals are available from [3-13C]Ala or [1-13C]Val-labeled bR from PM, although the 13C NMR signals from the surface areas, including loops and transmembrane alpha-helices near the surface (8.7 angstroms depth), are suppressed for preparations labeled with [1-13C]Gly, Ala, Leu, Phe, Tyr, etc. due to a failure of the attempted peak-narrowing by making use of the interfered frequency of the frequency of fluctuation motions with the frequency of magic angle spinning. In particular, the C-terminal residues, 226-235, are present as the C-terminal alpha-helix which is held together with the nearby loops to form a surface complex, although the remaining C-terminal residues undergo isotropic motion even in a 2D crystalline lattice (PM) under physiological conditions. Surprisingly, the 13C NMR signals could be further suppressed even from [3-13C]Ala- or [1-13C]Val-bR, due to the acquired fluctuation motions with correlation times in the order of 10(-4) to 10(-5) s, when the 2D lattice structure is instantaneously distorted or completely disrupted, either in photo-intermediate, removed retinal or when embedded in the lipid bilayers.     

Numerical study on reduction of the elevated structure noise by surface absorption on plate girders

With the aim to propose a reasonable and effective countermeasure for the elevated structure noise, the sound field radiated by a steel plate girder, which is the main source of the elevated structure noise, have been theoretically analysed. In the present study, steel plate girders are modelled as infinitely long elastic plate strips placed in parallel and numerical examples on the sound field radiated by the steel plate girders are shown. In the analysis of the radiated sound field, the equivalent source method is employed. Effect of the surface absorption on the sound field radiated by the girders is discussed through numerical examples. The results show that the surface absorption is effective for reduction of the radiated sound field, especially in the area that increase of sound pressure due to reflection by adjacent plate girders is observed. Furthermore, to design for reasonable countermeasure, variation of the noise reduction effect due to changing the pattern of surface absorption area on plate girders is classified.     

The effect of water content on the ultimate properties of rubbery nanocomposite gels

An investigation was conducted into the effects of water content (R) on the ultimate tensile properties of nanocomposite hydrogels (NC gels) based on poly(N‐isopropylacrylamide)/clay networks. Rubbery NC gels with low clay contents (<NC10) exhibited unique changes in their stress–strain curves, depending on the R. At high R, where PNIPA chains are fully hydrated, NC gels retained their rubbery tensile properties, whereas they changed to exhibit plastic‐like deformations with decreasing R. Consequently, for a series of NC gels with different R, a failure envelope was obtained by connecting the rupture points in the stress–strain curves. Here, the counterclockwise movement was observed as either the R decreased or the strain rate increased. This seemed to be analogous to that of a conventional elastomer (e.g., SBR), although the mechanisms are different in the two cases. From the R and C_clay dependences of the ultimate properties, three critical values of R were defined, where R showed a maximum strain at break, a steep increase in initial modulus, and onset of brittle fracture. Compared with NC gels, OR gels (chemically crosslinked hydrogels) showed similar but very small changes in their stress–strain curves on altering R, whereas LR (viscous PNIPA solution) showed a monotonic decrease (increase) in ε_b (E_i) with decreasing R. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2328–2340, 2009     

Recent development of Faith conjecture

Is a semiprimary right self-injective ring a quasi-Frobenius ring? Almost half century has passed since Faith raised this problem. He first conjectured “No” in his book Algebra II. Ring Theory in 1976, but changing his mind, he conjectured “Yes” in his article “When self-injective rings are QF: a report on a problem” in 1990. In this paper, we describe recent studies of this problem based on authors works and raise related problems.     

Unoccupied band dispersion of Si(1 1 1):√3 × √3-Ag surface studied by time- and angle-resolved two-photon photoemission spectroscopy

Band dispersion and transient population of unoccupied electronic states on Si(1 1 1):√3 × √3-Ag surface have been studied by time-resolved (TR) and angle-resolved (AR) two-photon photoemission (2PPE) spectroscopy. The band dispersions originating from unoccupied electronic states have been identified from the comparison between AR-2PPE spectra and angle-resolved one-photon photoemission spectra with synchrotron radiation. A lifetime of unoccupied surface state has been determined from the TR-2PPE spectra.     

Nanocomposite Gels: New Advanced Functional Soft Materials

Summary: Nanocomposite gels (NC gels) consisting of poly(N-alkylacrylamides) and exfoliated inorganic clay were prepared by in-situ, free-radical polymerization at high yield under mild conditions (near ambient temperature, without stirring). Various shapes and different surface forms of NC gels were readily obtained using corresponding vessels and templates, since NC gels were always mechanically tough. The view that polymer/clay networks are formed in NC gels was supported by dynamic viscoelastic and swelling measurements. The entirely different mechanical properties of NC gels, compared with conventional, chemically-crosslinked hydrogels (OR gels), are discussed on the basis of their network structure. In addition to functions previously reported, NC gels exhibit further interesting characteristics, such as inherent incombustibility, good thermal conductivity, large heat capacity, they can be readily colored and fabricated as foams. NC gels can be utilized as environmentally-friendly, soft materials from the viewpoints of resources and waste, as their primary component is water.