Injectable Hydrogel for Sustained Protein Release by Salt‐Induced Association of Hyaluronic Acid Nanogel

A hyaluronic acid‐based anionic nanogel formed by self‐assembly of cholesteryl‐group‐bearing HA is designed for protein delivery. The HA nanogel spontaneously binds various types of proteins without denaturation, such as recombinant human growth hormone, erythropoietin, exendin‐4, and lysozyme. The HA nanogel shows unique colloidal properties, in particular that an injectable hydrogel is formed by salt‐induced association of the HA nanogel. A pharmacokinetic study in rats shows that an in situ gel formulation, prepared by simply mixing rhGH and HA nanogel in phosphate buffer, maintains plasma rhGH levels within a narrow range over one week. Therefore, HA nanogels offer a simple method for easy formulation of therapeutic proteins and are effective for sustained protein release systems.

     

Proton acceleration to 40 MeV using a high intensity, high contrast optical parametric chirped-pulse amplification/Ti:sapphire hybrid laser system

Using a high-contrast (10(10):1) and high-intensity (10(21) W/cm(2)) laser pulse with the duration of 40 fs from an optical parametric chirped-pulse amplification/Ti:sapphire laser, a 40 MeV proton bunch is obtained, which is a record for laser pulse with energy less than 10 J. The efficiency for generation of protons with kinetic energy above 15 MeV is 0.1%.     

Local unitary transformation method for large-scale two-component relativistic calculations: case for a one-electron Dirac Hamiltonian

An accurate and efficient scheme for two-component relativistic calculations at the spin-free infinite-order Douglas-Kroll-Hess (IODKH) level is presented. The present scheme, termed local unitary transformation (LUT), is based on the locality of the relativistic effect. Numerical assessments of the LUT scheme were performed in diatomic molecules such as HX and X(2) (X = F, Cl, Br, I, and At) and hydrogen halide clusters, (HX)(n) (X = F, Cl, Br, and I). Total energies obtained by the LUT method agree well with conventional IODKH results. The computational costs of the LUT method are drastically lower than those of conventional methods since in the former there is linear-scaling with respect to the system size and a small prefactor.     

Is CO2 fixation promoted through the formation of DBU bicarbonate salt?

The bicyclic amidines, 1,8‐diazabicyclo [5.4.0]undec‐7‐ene (DBU) and 1,5‐diazabicyclo[4.3.0] non‐5‐ene (DBN), were used for the chemical fixation of carbon dioxide. The promotion for CO₂ fixation is often reported through the formation of a thermally unstable DBU or DBN bicarbonate salt. To examine the effects of the DBU or DBN bicarbonate salt, reactions of 2‐aminobenzonitrile with the DBU salt or DBN salt in dimethylformamide (DMF) were performed at 20°C for 24 h in argon or carbon dioxide (0.1 MPa). However, in all the cases, 1H‐quinazoline‐2,4‐dione was not obtained completely. In contrast with room temperature reactions, 2‐aminobenzonitriles and DBU bicarbonate salt in DMF reacted for 4 h under high temperature (80°C) and CO₂ atmosphere (0.1 MPa) gave 1H‐quinazoline‐2,4‐diones in good to excellent yields. At high‐temperature conditions, DBU bicarbonate salt is decomposed to DBU and carbon dioxide. Also, the carbonylation of 2‐aminobenzonitrile using DBU and carbon dioxide afforded 1H‐quinazoline‐2,4‐dione in good yields under similar reaction conditions. These results suggest that the combination of DBU or DBN as a strong base and carbon dioxide is much more important than the in situ formation of DBU or DBN bicarbonate salt for the acceleration of CO₂ fixation. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:276–280, 2012; View this article online at wileyonlinelibrary.com . DOI 10.1002/hc.21014     

动态光散射和透射电镜法研究pH和NaCl对 丝胶蛋白微观结构的影响

应用近红外光谱法、动态光散射法及透射电镜扫描法,研究了pH和NaCl浓度对丝胶蛋白聚集微观结构的影响。近红外光谱显示丝胶蛋白在酰氨Ⅰ带1 700～1 600 cm-1附近有较强吸收峰。通过zeta电势法测定丝胶蛋白的表观等电点为pH 3.7。应用动态光散射法测定了在不同pH和NaCl浓度下丝胶蛋白颗粒的分散粒径,pH 4及高NaCl浓度时,丝胶蛋白聚集颗粒粒径大且分散系数大;pH 3或pH 8及低NaCl浓度时丝胶蛋白聚集颗粒粒径和分散系数相对较小。采用透射扫描电镜观察丝胶蛋白在pH 3或pH 8条件下聚集形成松散的松针状微观结构,在pH 4或者高NaCl浓度下会聚集形成相对紧密的微观结构。pH 4时可以观察到丝胶蛋白的椭圆形单聚体大小约为(60±6)nm(n=10)。并探讨了静电斥力、氢键和范德华吸引力对丝胶蛋白微观结构形成的影响,为丝胶蛋白作为生物材料的应用提供了理论依据。     

Dissociative and non-dissociative adsorption of selenophene on Au(1 1 1) depending on the preparation method

Selenophene (C₄H₄Se) monolayers on Au(1 1 1) were prepared by two different methods: ultrahigh vacuum (UHV) and atmospheric vapor adsorption method. Near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) results clearly indicate that the two monolayers are in different chemical forms; selenophene is molecularly adsorbed under UHV condition, while it is dissociatively chemisorbed via the C–Se bond cleavage under atmospheric condition. The dissociative chemisorption under atmospheric condition is interpreted in terms of the trapping mediated adsorption in the presence of a high-pressure ambient gas phase.     

A Fully Conjugated Porphyrin-[36]Octaphyrin-Porphyrin Hybrid Tape Exhibiting Möbius Aromaticity

Directly meso-meso linked porphyrin-tetrabromo[36]octaphyrin-porphyrin hybrid trimer 10 was successfully synthesized via acid-catalyzed condensation reaction and subsequent oxidation. Zn^II-metalation of 10 induced transannular meso-meso bond formation to give Möbius aromatic bis-Zn^II octaphyrin 11 , which was oxidized by DDQ/Sc(OTf)₃ to provide fully conjugated porphyrin-[36]octaphyrin-porphyrin hybrid tape 12 as the first example of porphyrin tape exhibiting Möbius aromaticity. Hybrid tape 12 displays significantly red-shifted absorption and small electrochemical HOMO-LUMO gap, indicating the effective conjugation through the whole chromophores.     

Asymmetric [2,3]Wittig sigmatropic rearrangement involving a chiral azaenolate as the migrating terminus. A simple synthesis of (+)-verrucarinolactone

The diastereo- and/or enantioselection are described in the title rearrangement of the chiral 2-(2-alkenyloxy)methyl 2-oxazolines which eventually provides optically active -hydroxy, γ,δ- unsaturated esters and (+)-verrucarinolactone.     

Antimony-121 mössbauer spectra of antimony (III) compounds with a stereochemically active lone pair

The Sb-121 Mössbauer parameters at 20 K for 23 antimony(III) compounds were obtained and the data are discussed in terms of known crystal structures. The isomer shifts and quadrupole coupling constants depend strongly on the type of configuration around the Sb(III) atoms with stereochemically active lone pair electrons.     

Generation and characterization of electrons from a gas target irradiated by high-peak-power lasers

We present the results of electron generation experiments conducted at the Advanced Photon Research Center, Japan Atomic Energy Research Institute, using 23-fs relativistically intense 20-TW tightly focused laser pulses with underdense plasma. We observed electron energies up to 40 MeV characterized by a two-temperature Maxwell distribution. With the help of particle-in-cell simulations, we found that these are due to different plasma wave-breaking processes. A charge of 5 nC/shot was obtained at a small solid angle, which corresponds to high peak current generation.