Novel Poly(ester urethane urea)/Polydioxanone Blends: Electrospun Fibrous Meshes and Films

In this work, we report the electrospinning and mechano-morphological characterizations of scaffolds based on blends of a novel poly(ester urethane urea) (PHH) and poly(dioxanone) (PDO). At the optimized electrospinning conditions, PHH, PDO and blend PHH/PDO in Hexafluroisopropanol (HFIP) solution yielded bead-free non-woven random nanofibers with high porosity and diameter in the range of hundreds of nanometers. The structural, morphological, and biomechanical properties were investigated using Differential Scanning Calorimetry, Scanning Electron Microscopy, Atomic Force Microscopy, and tensile tests. The blended scaffold showed an elastic modulus (~5 MPa) with a combination of the ultimate tensile strength (2 ± 0.5 MPa), and maximum elongation (150% ± 44%) in hydrated conditions, which are comparable to the materials currently being used for soft tissue applications such as skin, native arteries, and cardiac muscles applications. This demonstrates the feasibility of an electrospun PHH/PDO blend for cardiac patches or vascular graft applications that mimic the nanoscale structure and mechanical properties of native tissue.     

Elastic instability of bilayer graphene using atomistic finite element

In-plane elastic instability of bilayer graphene sheets is investigated using atomistic finite element approaches. The equivalent homogenised properties of graphene sheet are expressed in terms of the thickness, equilibrium lengths and force-field models used to represent the C–C bonds of the graphene lattice. The covalent bonds are represented as structural beams with stretching, bending, torsional and shear deformation, and the strain energies associated to affine deformation mechanisms. The overall mechanical properties and geometric configurations of the nano-structures represented as truss assemblies are then calculated minimising the total potential energy associated to the loading, thickness and average equilibrium lengths of the bonds. Different boundary conditions and aspect ratios are considered for both bilayer and single-layer graphene sheets. The bilayer graphene sheets are found to be offering remarkably higher buckling strengths as compared to single-layer sheets.     

Time-delay-induced phase-transition to synchrony in coupled bursting neurons

Signal transmission time delays in a network of nonlinear oscillators are known to be responsible for a variety of interesting dynamic behaviors including phase-flip transitions leading to synchrony or out of synchrony. Here, we uncover that phase-flip transitions are general phenomena and can occur in a network of coupled bursting neurons with a variety of coupling types. The transitions are marked by nonlinear changes in both temporal and phase-space characteristics of the coupled system. We demonstrate these phase-transitions with Hindmarsh-Rose and Leech-Heart interneuron models and discuss the implications of these results in understanding collective dynamics of bursting neurons in the brain.     

SILAC-Pulse Proteolysis: A Mass Spectrometry-Based Method for Discovery and Cross-Validation in Proteome-Wide Studies of Ligand Binding

Reported here is the use of stable isotope labeling with amino acids in cell culture (SILAC) and pulse proteolysis (PP) for detection and quantitation of protein–ligand binding interactions on the proteomic scale. The incorporation of SILAC into PP enables the PP technique to be used for the unbiased detection and quantitation of protein–ligand binding interactions in complex biological mixtures (e.g., cell lysates) without the need for prefractionation. The SILAC-PP technique is demonstrated in two proof-of-principle experiments using proteins in a yeast cell lysate and two test ligands including a well-characterized drug, cyclosporine A (CsA), and a non-hydrolyzable adenosine triphosphate (ATP) analogue, adenylyl imidodiphosphate (AMP-PNP). The well-known tight-binding interaction between CsA and cyclophilin A was successfully detected and quantified in replicate analyses, and a total of 33 proteins from a yeast cell lysate were found to have AMP-PNP-induced stability changes. In control experiments, the method’s false positive rate of protein target discovery was found to be in the range of 2.1% to 3.6%. SILAC-PP and the previously reported stability of protein from rates of oxidation (SPROX) technique both report on the same thermodynamic properties of proteins and protein–ligand complexes. However, they employ different probes and mass spectrometry-based readouts. This creates the opportunity to cross-validate SPROX results with SILAC-PP results, and vice-versa. As part of this work, the SILAC-PP results obtained here were cross-validated with previously reported SPROX results on the same model systems to help differentiate true positives from false positives in the two experiments. Graphical Abstract

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Electrophile‐Induced Nucleophilic Substitution of the nido‐Dicarbaundecaborate Anion nido‐7,8‐C2B9H12− by Conjugated Heterodienes

Substitution of the dicarbaundecaborate anion nido‐7,8‐C₂B₉H₁₂^? ( 1 ) by precise hydride abstraction followed by nucleophilic attack usually leads to symmetric products 10‐R‐nido‐7,8‐C₂B₉H₁₁. However, thioacetamide (MeC(S)NH₂) as nucleophile and acetone/AlCl₃ as hydride abstractor gave asymmetric 9‐[MeC(NHiPr)S]‐nido‐7,8‐C₂B₉H₁₁ ( 2 ), whereas N,N‐dimethylthioacetamide (MeC(S)NMe₂) gave the expected symmetric 10‐[MeC(NMe₂)S]‐nido‐7,8‐C₂B₉H₁₁ ( 4 ). For the formation of 2 , acetone and thioacetamide are assumed to give the intermediate MeC(S)N(CMe₂) ( 3 ), which then attacks 1 with formation of 2 . Similarly, reaction of acetyliminium chloride [MeC(O)NH(CPh₂)]Cl ( 5 ) with 1 in THF gave a mixture of 9‐ and 10‐substituted [MeC(NHCHPh₂)O]‐nido‐7,8‐C₂B₉H₁₁ ( 6 and 7 , respectively). These reactions are the first examples in which compounds (here heterodienes) that unite the functionalities of both hydride acceptor and nucleophilic site react with 1 in a bimolecular fashion. Furthermore, the analogous reaction of 1 and 5 (in an equilibrium mixture with acetyl chloride and benzophenone imine) in MeCN afforded 10‐[MeC(NCPh₂)NH]‐nido‐7,8‐C₂B₉H₁₁ ( 8 ) and MeC(O)NHCHPh₂ ( 9 ).     

Quantification of non-viscous damping in discrete linear systems

The damping forces in a multiple-degree-of-freedom engineering dynamic system may not be accurately described by the familiar ‘viscous damping model’. The purpose of this paper is to develop indices to quantify the extent of any departures from this model, in other words the amount of ‘non-viscosity’ of damping in discrete linear systems. Four indices are proposed. Two of these indices are based on the non-viscous damping matrix of the system. A third index is based on the residue matrices of the system transfer functions and the fourth is based on the (measured) complex modes of the system. The performance of the proposed indices is examined by considering numerical examples.     

Investigation of the micromechanical deformation behavior of styrene–butadiene star block copolymer/polystyrene blends with high‐voltage electron microscopy

The deformation behavior of blends consisting of a styrene–butadiene star block copolymer and a polystyrene homopolymer was studied by high‐voltage electron microscopy with a tensile device. The mechanical properties and micromechanical deformation mechanisms in the star block copolymer/polystyrene blends were directly influenced by their morphology. Although the pure block copolymer deformed in a very unequal manner (because of a thin‐layer‐yielding mechanism) and revealed no local deformation zones, a transition to the formation of crazelike zones was observed in the blends. This transition in the deformation mechanisms was correlated to the abrupt change in the macroscopic strain at break of the injection‐molded specimens. At lower contents of added polystyrene, a craze‐stopping mechanism was observed, whereas the blends with higher polystyrene contents demonstrated crazing like that in pure polystyrene. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1157–1167, 2003     

Sonochemical bromination of acetophenones using p-toluenesulfonic acid-N-bromosuccinimide.

Substituted acetophenones react with N-bromosuccinimide (NBS) and p-toluenesulfonic acid (p-TsOH) in the presence of ultrasound in methanol at 35 +/- 2 degrees C to give alpha-bromoacetophenones in high yield. In the absence of ultrasound the reaction takes place at the boiling point of methanol (65 degrees C) and takes longer time. The reaction does not take place in the absence of p-TsOH thermally or sonically. However the reaction is possible under photochemical conditions in the absence of p-TsOH. The best solvent for the reaction was found to be methanol.     

Structural, spectroscopic, and theoretical elucidation of a redox-active pincer-type ancillary applied in catalysis

Pincer-type ligands are believed to be very robust scaffolds that can support multifarious functionalities as well as highly reactive metal motifs applied in organometallic chemistry, especially in the realm of catalysis. In this paper, we describe the redox and, therefore, noninnocent behavior of a PNP (PNP- = N[2-P(CHMe2)2-4-methylphenyl]2) pincer ancillary bound to nickel. A combination of structural, spectroscopic, and theoretical techniques suggests that this type of framework can house an electron hole when coordinated to Ni(II).     

Cu−NHC Complex for Chan-Evans-Lam Cross-Coupling Reactions of N-Heterocyclic Compounds and Arylboronic Acids

An efficient copper(II) N-heterocyclic carbene (NHC) complex with an NCN coordination mode was optimized to catalyze the Chan–Evans-Lam (CEL) cross-coupling reaction of imidazole and other N-heterocyclic nucleophiles with arylboronic acid. This air-stable copper catalyst shows robust catalytic performance and tolerates a diverse array of functional groups on both the N-nucleophile and arylboronic acid coupling partners in C−N bond forming reactions with up to 95 % yield. Formation of the Cu−NHC complex in situ generated similar catalytic performance for CEL coupling. Alternative metal ions (Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Zn²⁺, Ru²⁺, and Pd²⁺) were also screened in the presence of the NHC precursor as CEL catalysts.