A preferential attachment model with Poisson growth for scale-free networks

We propose a scale-free network model with a tunable power-law exponent. The Poisson growth model, as we call it, is an offshoot of the celebrated model of Barabási and Albert where a network is generated iteratively from a small seed network; at each step a node is added together with a number of incident edges preferentially attached to nodes already in the network. A key feature of our model is that the number of edges added at each step is a random variable with Poisson distribution, and, unlike the Barabási–Albert model where this quantity is fixed, it can generate any network. Our model is motivated by an application in Bayesian inference implemented as Markov chain Monte Carlo to estimate a network; for this purpose, we also give a formula for the probability of a network under our model.     

Irreversible temperature‐responsive formation of high‐strength hydrogel from an enantiomeric mixture of starburst triblock copolymers consisting of 8‐arm PEG and PLLA or PDLA

Starburst triblock copolymers consisting of 8‐arm poly(ethylene glycol) (8‐arm PEG) and biodegradable poly(L ‐lactide) (PLLA) or its enantiomer poly(D ‐lactide) (PDLA), 8‐arm PEG‐b‐PLLA‐b‐PEG ( Stri‐L ), and 8‐arm PEG‐b‐PDLA‐b‐PEG ( Stri‐D ) were synthesized. An aqueous solution of a 1:1 mixture ( Stri‐Mix ) of Stri‐L and Stri‐D assumed a sol state at room temperature, but instantaneously formed a physically crosslinked hydrogel in response to increasing temperature. The resulting hydrogel exhibited a high‐storage modulus (9.8 kPa) at 37 °C. Interestingly, once formed at the transition temperature, the hydrogel was stable even after cooling below the transition temperature. The hydrogel formation process was irreversible because of the formation of stable stereocomplexes. In aqueous solution, gradual hydrolytic erosion was observed because of degradation of the hydrogel. The combination of rapid temperature‐triggered irreversible hydrogel formation, high‐mechanical strength, and degradation behavior render this polymer mixture system suitable for use in injectable biomedical materials, for example, as a drug delivery system for bioactive reagents or a biodegradable scaffold for tissue engineering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6317–6332, 2008     

Tripodal imidazole containing ligands for copper catalyzed ATRP

Tripodal imidazole containing ligands, bis((2‐pyridyl)methyl)(1‐methylimidazole‐2‐yl)methyl)amine (BPIA) and bis(1‐methylimidazole‐2‐yl)methyl)((2‐pyridyl)methyl)amine (BIPA), were synthesized and used for copper catalyzed atom transfer radical polymerization (ATRP) of n‐butyl acrylate (nBA). The molecular weights of poly(n‐butyl acrylate) (PnBA) catalyzed by CuBr/BPIA and CuBr/BIPA complexes increased linearly with nBA conversions and they were close to theoretical values with low polydispersities. ATRP equilibrium rate constant (K_ATRP) measurements showed that bothCuBr/BPIA and CuBr/BIPA complexes had high K_ATRP values, similar to that of CuBr/tri(2‐pyridylmethyl)amine (TPMA), which is one of the ATRP most active ligands. Activators regenerated by electron transfer (ARGET) ATRP of nBA with CuBr₂/BPIA and CuBr₂/BIPA complexes were also conducted and polymerization reached high nBA conversions, resulting in PnBA with low polydispersities. This suggests that the copper complexes with BPIA and BIPA were sufficiently stable and active to conduct ATRP when catalyst concentration was low. ARGET ATRP to form high molecular weight PnBA with CuBr₂/BPIA and CuBr₂/BIPA complexes was also successful. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2015–2024, 2008     

p42MAPK-mediated phosphorylation of xEIAP/XLX in <Emphasis Type="Italic">Xenopus</Emphasis> cytostatic factor-arrested egg extracts

Background  

BIR family proteins are evolutionarily conserved anti-apoptotic molecules. One member of Xenopus BIR family proteins, xEIAP/XLX, is a weak apoptosis inhibitor and rapidly degraded in a cell-free apoptotic execution system derived from interphase egg extracts. However, unfertilized eggs are naturally arrested at the metaphase of meiosis II by the concerted activities of Mos-MEK-p42MAPK-p90Rsk kinase cascade (cytostatic factor pathway) and many mitotic kinases. Previous studies suggest that cytostatic factor-arrested egg extracts are more resistant to spontaneous apoptosis than interphase egg extracts in a p42MAPK-dependent manner. We tested whether xEIAP/XLX might be phosphorylated in cytostatic factor-arrested egg extracts, and also examined whether xEIAP/XLX could be functionally regulated by phosphorylation.     

Asymmetric cross-benzoin condensation promoted by a chiral triazolium precatalyst bearing a pyridine moiety

Cross-benzoin condensation catalyzed by NHC, prepared from chiral triazolium salts bearing a pyridine ring, afforded α-hydroxy ketones with reasonable chemical yields and enantioselectivities. A wide range of aliphatic and aromatic aldehydes were successfully used in the reaction.     

Platinum Nanoflowers on Scratched Silicon by Galvanic Displacement for an Effective SALDI Substrate

We report a new and facile method for synthesizing 3D platinum nanoflowers (Pt Nfs) on a scratched silicon substrate by electroless galvanic displacement and discuss the applications of the Pt Nfs in surface‐assisted laser desorption/ionization‐mass spectrometry (SALDI‐MS). Surface scratching of n‐type silicon is essential to induce Pt Nf growth on a silicon substrate (to obtain a Pt Nf silicon hybrid plate) by the galvanic displacement reaction. The Pt Nf silicon hybrid plate showed excellent SALDI activity in terms of the efficient generation of protonated molecular ions in the absence of a citrate buffer. We propose that the acidity of the Si? OH moieties on silicon increases because of the electron‐withdrawing nature of the Pt Nfs; hence, proton transfer from the Si? OH groups to the analyte molecules is enhanced, and finally, thermal desorption of the analyte ions from the surface occurs. Signal enhancement was observed for protonated molecular ions produced from a titania nanotube array (TNA) substrate on which Pt nanoparticles had been photochemically deposited. Moreover, surface modification of the Pt Nf silicon hybrid plate by perfluorodecyltrichlorosilane (FDTS) (to obtain an FDTS‐Pt Nf silicon hybrid plate) was found to facilitate soft SALDI of labile compounds. More interestingly, the FDTS‐Pt Nf silicon hybrid plate acts 1) as a high‐affinity substrate for phosphopeptides and 2) as a SALDI substrate. The feasibility of using the FDTS‐Pt Nf silicon hybrid plate for SALDI‐MS has been demonstrated by using a β‐casein digest and various analytes, including small molecules, peptides, phosphopeptides, phospholipids, carbohydrates, and synthetic polymers. The hybridization of Pt Nfs with a scratched silicon substrate has been found to be important for achieving excellent SALDI activity.     

Origins of hole doping and relevant optoelectronic properties of wide gap p-type semiconductor, LaCuOSe

LaCuOSe is a wide band gap (～2.8 eV) semiconductor with unique optoelectronic properties, including room-temperature stable excitons, high hole mobility ～8 cm(2)/(Vs), and the capability of high-density hole doping (up to 1.7 × 10(21) cm(-3) using Mg). Moreover, its carrier transport and doping behaviors exhibit nonconventional results, e.g., the hole concentration increases with decreasing temperature and the high hole doping does not correlate with other properties such as optical absorption. Herein, secondary ion mass spectroscopy and photoemission spectroscopy reveal that aliovalent ion substitution of Mg at the La site is not the main source of hole doping and the Fermi level does not shift even in heavily doped LaCuOSe:Mg. As the hole concentration increases, the subgap optical absorption becomes more intense, but the increase in intensity does not correlate quantitatively. Transmission electron microscopy indicates that planar defects composed of Cu and Se deficiencies are easily created in LaCuOSe. These observations can be explained via the existence of a degenerate low-mobility layer and formation of complex Cu and Se vacancy defects with the assistance of generalized gradient approximation band calculations.     

Enantioselective desymmetrization of meso-N-(heteroarenesulfonyl)aziridines with TMSN3 catalyzed by chiral Lewis acids

A catalytic enantioselective desymmetrization of meso-N-(heteroarenesulfonyl)aziridines with TMSN₃ using chiral Lewis acids afforded products with high enantioselectivity. As proof of the utility of this procedure, the precursor of selective κ-opioid agonist (1S,2S)-(−)-U-50,488 was synthesized.     

Dynamical properties of ethylene glycol and glucose studied by temperature-modulated differential scanning calorimetry and Brillouin scattering

The fragility of ethylene glycol and glucose aqueous solution systems has been investigated by temperature-modulated differential scanning calorimetry (TMDSC). The frequency and temperature dependences of complex specific heat have been observed in the vicinity of a glass-transition temperature T _g . It is shown that the value of the fragility index m can be determined from the temperature dependence of the α-relaxation times observed by TMDSC. We have also studied the elastic properties of these aqueous solutions by micro-Brillouin scattering, and determined these relaxation times of elastic properties in the gigahertz range.