Moduli of model elastomeric networks prepared from polymer chains having a high plateau modulus,and their interpretation in terms of the constrained-chain model

High-molecular weight polybutadiene chains having approximately 47% cis-1,4 units and 45% trans-1,4 units were crosslinked through their carbon-carbon double bonds using p-bis(dimethylsilyl) benzene as crosslinking agent and chloroplatinic acid as catalyst. This particular polymer was chosen because the high plateau modulus it exhibits in the un-crosslinked state is taken to indicate large numbers of chain entanglements, and stress–strain measurements on such networks have frequently been interpreted with the assumption that the trapping of such entanglements during crosslinking should contribute significantly to their modull. It is shown in the present investigation that such results are equally well interpreted in terms of the new constrained-chain theory of rubbery elasticity. © 1993 John Wiley & Sons, Inc.     

Biogels of cytochrome c : Cytochrome c peroxidase complex studied by electron paramagnetic resonance spectroscopy

Cytochrome c: cytochrome c peroxidase (Cc: CcP in 1: 1 ratio) complex was successfully encapsulated in sol-gel derived glass. The electron paramagnetic resonance (e.p.r.) and optical absorption techniques were used to characterize the coordination number, spin state, charge-transfer activity and structural orientation of Cc: CcP complex and its constituents. The sol-gel encapsulation of metalloproteins allows, for the first time, the detection of e.p.r. signals of biological systems at room temperature. CcP exhibits an e.p.r. spectrum representing the high spin and purely axial symmetry with parameters at g 6 and g 2 and an electronic absorption spectrum with a descent in spectral intensity of shoulder band at 380 nm and a blue-shifted charge-transfer band at 620 nm. Cc shows an e.p.r. spectrum characterizing a mixture of high spin (g 6 and g 2) and low spin (g _x=2.7, g _y=2.2 and g _z=1.8) components. Upon complexation, Cc:CcP pair displays a single and broad e.p.r. spectrum at g 2 and a light absorption spectrum with a red-shifted Soret band at 423 nm, a blue-shifted charge-transfer band at 620 nm and an intensified charge-transfer band at 507 nm. These results suggest that the sol-gel encapsulated Cc:CcP complex has the following chemical and physical characteristics: (a) a hexa-coordination, (b) a high-spin state, (c) an active charge-transfer (or redox) pair, and (d) the direction of the g paramagnetic center of Cc : CcP complex lies nearly parallel to that of the heme normal. The structural coordinations of the sol-gel encapsulated Cc, CcP and Cc : CcP are examined. Moreover, the possible use of biogels at the sol, gelation, and xerogel stages during gel processing to control the structural rigidity and spatial separation/orientation of the encapsulated heme proteins and to study their possible routes of long-range electron transfer reactions are also discussed.     

Palladium-catalyzed synthesis of β-hydroxy compounds via a strained 6,4-palladacycle from directed C–H activation of anilines and C–O insertion of epoxides

A palladium-catalyzed C–H activation of acetylated anilines (acetanilides, 1,1-dimethyl-3-phenylurea, 1-phenylpyrrolidin-2-one, and 1-(indolin-1-yl)ethan-1-one) with epoxides using O-coordinating directing groups was accomplished. This C–H alkylation reaction proceeds via formation of a previously unknown 6,4-palladacycle intermediate and provides rapid access to regioselectively functionalized β-hydroxy products. Notably, this catalytic system is applicable for the gram scale mono-functionalization of acetanilide in good yields. The palladium-catalyzed coupling reaction of the ortho-C(sp²) atom of O-coordinating directing groups with a C(sp³) carbon of chiral epoxides offers diverse substrate scope in good to excellent yields. In addition, further transformations of the synthesized compound led to biologically important heterocycles. Density functional theory reveals that the 6,4-palladacycle leveraged in this work is significantly more strained (>10 kcal mol⁻¹) than the literature known 5,4 palladacycles.

The combined experimental and computational study on palladium-catalyzed regioselective C–H functionalization of O-coordinating directing groups with epoxides is described.     

An open-source surface barrier discharge plasma pretreatment for reduced cracking of outdoor wood coatings

The development of a simple surface barrier discharge plasma device is presented to enable more widespread access to and utilization of plasma technology. The application of the plasma device was demonstrated for pretreatment of wood prior to application of protective coatings for outdoor usage. The coatings' overall performance was increased, showing a reduction or absence of cracking due to weathering on plasma-pretreated specimens. Moreover, after ten months of outdoor weathering, the plasma-pretreated specimens showed fewer infections with biotic factors and improved adhesion performance in cross-cut tests, while the surface gloss performed independently from plasma pretreatment. In contrast to that, plasma-pretreated specimens were slightly more prone to discoloration due to outdoor weathering, whereas the plasma pretreatment did not impact the initial color after coating application.

Graphic abstract

     

Covalent Self‐Assembly and One‐Step Photocrosslinking of Tyrosine‐Rich Oligopeptides to Form Diverse Nanostructures

We present covalently self‐assembled peptide hollow nanocapsule and peptide lamella. These biomimetic dityrosine peptide nanostructures are synthesized by one‐step photopolymerization of a tyrosine‐rich short peptide without the aid of a template. This simple approach offers direct synthesis of fluorescent peptide nanocages and free‐standing thin films. The simple crosslinked peptide lamella films provide robust mechanical properties with an elastic modulus of approximately 30 GPa and a hardness of 740 MPa. These nanostructures also allow for the design of peptidosomes. The approach taken here represents a rare example of covalent self‐assembly of short peptides into nano‐objects, which may be useful as microcompartments and separation membranes.     

Four algorithms to solve symmetric multi-type non-negative matrix tri-factorization problem

Journal of Global Optimization - In this paper, we consider the symmetric multi-type non-negative matrix tri-factorization problem (SNMTF), which attempts to factorize several symmetric...     

Superabsorbent polymer with improved permeability and absorption rate using hollow glass microspheres

Itaconic acid-vinyl sulfonic acid based super absorbent polymer (SAP) was synthesized by aqueous solution polymerization using ammonium persulfate as the initiator, tetra (ethylene glycol) diacrylate as the internal crosslinking agent, and sodium hydroxide as the neutralizing agent. Surface-crosslinking was introduced to improve the low absorbency under load of the itaconic acid-based SAP. Hollow glass microspheres were added during surface-crosslinking to improve the absorption properties and permeability of the SAP. Hollow glass microspheres increased the specific surface area of SAP and acted as an incompressible filler resulting in the improvement of gel strength and the relief of gel blocking by preventing adhesion between SAP particles. The surface-crosslinked SAP with 2 wt% hollow glass microspheres showed the highest permeability and absorbency under load. The absorption rate of the synthesized material was also increased.     

Microfluidic channels fabricated on mesoporous electrospun fiber mats: A facile route to microfluidic chips

We report a facile way of preparing microfluidic channels filled with electrospun functional fibers. Patterned elastic molds were in tight contact with electrospun fiber mats without any leak of the analyte solution. As an example of the simple devices, we demonstrated a microfluidic protein chip selectively purifying histidine‐tagged proteins. Highly mesoporous nitrilotriacetic acid‐functionalized polystyrene (PS‐NTA) fibers were produced by taking advantage of interpenetrating phase separation between PS and PEO during electrospinning. The specific interaction of Ni‐complexed PS‐NTA fibers with histidine enabled us to immobilize only target proteins from highly heterogeneous protein mixtures. The easy process to fabricate functionalized microchannels combined with the high production throughput from electrospinning may greatly contribute to chip‐based chromatographic and bioanalytical devices. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Support-Free Pd3Co NCs as an Efficient Heterogeneous Nanocatalyst for New Organic Transformations of C−C Coupling Reactions

A support-free heterogeneous Pd₃Co nanostructured composite (NC), synthesized through a hydrothermal route, acted as an effective catalytic system in multivariate Heck-, Sonogashira-, and Suzuki-type coupling reactions of iodonium ylides. The XPS analysis of the bimetallic Pd₃Co NCs confirmed the elemental composition as 75 % palladium and 25 % cobalt. Furthermore, high-resolution (HR) TEM analysis confirmed the spherical morphology of the Pd₃Co bimetallic nanoparticles. The average diameter of the NCs is 14.8 nm. The coupling reaction proceeded through the generation of α-iodoenones with simultaneous migration of the phenyl group, thereby giving a scaffold with higher atom economy. The heterogeneous Pd₃Co NCs were recycled and reused without any significant change in catalytic ability for up to five reaction cycles. The high concentration of Pd and association of cobalt into the lattice of palladium appears to enhance its catalytic ability for the diverse coupling reactions in comparison with its monometallic counterparts as well as with bimetallic NCs with a comparatively lesser amount of Pd.