Organic–inorganic bonding in chitosan–silica hybrid networks: Physical properties

Novel biomaterials are needed for bone tissue repair with improved mechanical performance compared to classical bioceramics. The objective of this work was to characterize a hybrid filler material, which is capable to coat as a thin film porous scaffolds improving their mechanical properties for bone tissue engineering. The hybrid filler material is a blend of chitosan and silica network formed through in situ sol–gel using tetraethylortosilicate and 3‐glycidoxypropyltrimethoxysilane (GPTMS) as silica precursors. The hypothesis was that the epoxy ring of GPTMS could react with the amino groups of chitosan in acidic media while it is also reacting the siloxane groups of hydrolyzed silica precursors. The formation of the hybrid organic–inorganic network was assessed by different physical techniques revealing changes in molecular mobility and hydrophilicity upon chemical reaction. Finally, the cytotoxicity of the samples was also evaluated by MTT assay. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1391–1400     

Insights into the Cascade Reaction of CO and Heteroallenes Mediated by Dinitrogen Hafnocene Complexes: The Indirect Effect of Nitride's Nucleophilicity

A DFT mechanistic exploration of the reactivity of the dinitrogen hafnocene complex, [{(η⁵‐C₅H₂‐1,2,4‐Me₃)₂Hf}₂(μ₂‐N₂)], towards mixtures of CO/CO₂ and CO/OCNtBu is reported. The crucial role of the nitride intermediate is highlighted, as well as the importance of the bridging mode of the cyanate ligand between the two Hf metal atoms throughout the process. Interestingly, the CO₂ addition to the nitride intermediate occurs through an outer‐sphere transition state, whereas the addition of the heteroallene is governed by the steric congestion imposed by cyclopentadienyl ligands.     

On the Effect of Secondary Nucleation on Deracemization through Temperature Cycles

Herein, the pivotal role of secondary nucleation in a crystallization-enhanced deracemization process is reported. During this process, complete and rapid deracemization of chiral conglomerate crystals of an isoindolinone is attained through fast microwave-assisted temperature cycling. A parametric study of the main factors that affect the occurrence of secondary nucleation in this process, namely agitation rate, suspension density, and solute supersaturation, confirms that an enhanced stereoselective secondary nucleation rate maximizes the deracemization rate. Analysis of the system during a single temperature cycle showed that, although stereoselective particle production during the crystallization stage leads to enantiomeric enrichment, undesired kinetic dissolution of smaller particles of the preferred enantiomer occurs during the dissolution step. Therefore, secondary nucleation is crucial for the enhancement of deracemization through temperature cycles and as such should be considered in further design and optimization of this process, as well as in other temperature cycling processes commonly applied in particle engineering.     

Darobactin B Stabilises a Lateral-Closed Conformation of the BAM Complex in E. coli Cells

The β-barrel assembly machinery (BAM complex) is essential for outer membrane protein (OMP) folding in Gram-negative bacteria, and represents a promising antimicrobial target. Several conformational states of BAM have been reported, but all have been obtained under conditions which lack the unique features and complexity of the outer membrane (OM). Here, we use Pulsed Electron-Electron Double Resonance (PELDOR, or DEER) spectroscopy distance measurements to interrogate the conformational ensemble of the BAM complex in E. coli cells. We show that BAM adopts a broad ensemble of conformations in the OM, while in the presence of the antibiotic darobactin B (DAR-B), BAM′s conformational equilibrium shifts to a restricted ensemble consistent with the lateral closed state. Our in-cell PELDOR findings are supported by new cryoEM structures of BAM in the presence and absence of DAR-B. This work demonstrates the utility of PELDOR to map conformational changes in BAM within its native cellular environment.     

PET Diagnostic Molecules Utilizing Multimeric Cyclic RGD Peptide Analogs for Imaging Integrin αvβ3 Receptors

Multimeric ligands consisting of multiple pharmacophores connected to a single backbone have been widely investigated for diagnostic and therapeutic applications. In this review, we summarize recent developments regarding multimeric radioligands targeting integrin α_vβ₃ receptors on cancer cells for molecular imaging and diagnostic applications using positron emission tomography (PET). Integrin α_vβ₃ receptors are glycoproteins expressed on the cell surface, which have a significant role in tumor angiogenesis. They act as receptors for several extracellular matrix proteins exposing the tripeptide sequence arginine-glycine-aspartic (RGD). Cyclic RDG peptidic ligands c(RGD) have been developed for integrin α_vβ₃ tumor-targeting positron emission tomography (PET) diagnosis. Several c(RGD) pharmacophores, connected with the linker and conjugated to a chelator or precursor for radiolabeling with different PET radionuclides (¹⁸F, ⁶⁴Cu, and ⁶⁸Ga), have resulted in multimeric ligands superior to c(RGD) monomers. The binding avidity, pharmacodynamic, and PET imaging properties of these multimeric c(RGD) radioligands, in relation to their structural characteristics are analyzed and discussed. Furthermore, specific examples from preclinical studies and clinical investigations are included.     

Lateral post-buckling analysis of beams

Summary The nonlinear lateral buckling response of perfect stocky beams in the vicinity of the critical bifurcational state is discussed. Attention is focused on the initial post-buckling response. This depends on the nature of the critical branching point which is explored by using a nonlinear (lateral) bending-curvature relationship. It is found that the plane of loading (associated with the major moment of inertia) looses its stability through a stable symmetric bifurcation point. Hence, the above beams are not sensitive to imperfections, exhibiting post-buckling strength. However, the post-buckling equilibrium path is quite shallow, so that the load-carrying capacity of such beams above the critical state is rather limited. The analysis is supplemented by illustrative examples forI-beams for which the effect of various parameters on the initial postbuckling path is also discussed.

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Analyse des lateralen nachkritischen Knickverhaltens von Balken

Übersicht Das nichtlineare Knickverhalten von perfekten gedrungenen Balken in der Nachbarschaft des kritischen Verzweigungspunktes wird untersucht, wobei sich die Aufmerksamkeit insbesondere auf den Beginn der nachkritischen Phase richtet. Diese hängt vom Charakter des kritischen Verzweigungspunktes ab, der seinerseits mit Hilfe einer nichtlinearen (lateralen) Biegemoment-und Krümmungs-Beziehung analysiert wird. Es zeigt sich, daß die Stabilität in der Belastungsebene-verbunden mit dem maximalen Flächenmoment zweiter Ordnung-über einen stabilen symmetrischen Verzweigungspunkt verlorengeht. Daher sind solche Balken unempfindlch gegenüber Imperfektionen, sie zeigen nachkritische Belastbarkeit. Der nachkritische Gleichgewichtspfad ist jedoch sehr flach, so daß die Tragfähigkeit dieser Balken oberhalb des kritischen Zustandes recht begrenzt ist. Die Untersuchung ist durch illustrative Beispiele für I-Balken untermauert, für welche der Einfluß der verschiedenen Parameter auf den anfänglichen nachkritischen Pfad herausgearbeitet wird.

     

Numerical exploration of Kaldorian interregional macrodynamics: stability and the trade threshold for business cycles under fixed exchange rates

The stability of equilibrium and the possibility of generation of business cycles in a discrete interregional Kaldorian macrodynamic model with fixed exchange rates are explored using numerical methods. One of the aims is to illustrate the feasibility and effectiveness of the numerical approach for dynamical systems of moderately high dimensionality and several parameters. The model considered is five-dimensional with four parameters, the speeds of adjustment of the goods markets and the degrees of economic interactions between the regions through trade and capital movement. Using a grid search method for the determination of the region of stability of equilibrium in two-dimensional parameter subspaces, and coefficient criteria for the flip bifurcation - and Hopf bifurcation - curve, we determine the stability region in several parameter ranges and identify Hopf bifurcation curves when they exist. It is found that interregional cycles emerge only for sufficient interregional trade. The relevant threshold is predicted by the model at 14 - 16 % of trade transactions. By contrast, no minimum level of capital mobility exists in a global sense as a requirement for the emergence of interregional cycles; the main conclusion being, therefore, that cycles may occur for very low levels of capital mobility if trade is sufficient. Examples of bifurcation and Lyapunov exponent diagrams illustrating the occurrence of cycles or period doubling, and examples of the development of the occurring cycles, are given. Both supercritical and subcritical bifurcations are found to occur, the latter type indicating coexistence of a point and a cyclical attractor.     

Rheological behavior of concentrated suspensions as affected by the dynamics of the mixing process

The rheological characterizations of concentrated suspensions are generally carried out assuming “well-mixed” suspensions. However, the variation of the concentration distributions of the ingredients of the formulation, i.e., the “goodness of mixing”, the size and shape distributions of the particle clusters and the rheological behavior of the suspension all depend on the thermo-mechanical history that the suspension is exposed to during the mixing process. Here, various experimental tools are used for the characterization of the degree of mixedness (concentration distributions) of various ingredients along with the characterization of rheological material functions, wall slip behavior and the maximum packing fraction of a graphite/elastomer suspension. The degree of mixedness values of the ingredients of the suspensions processed using batch and continuous processes and under differing operating conditions were characterized quantitatively using wide-angle X-ray diffraction and thermo gravimetric analysis and were elucidated under the light of the electrical properties of the suspension as affected by the mixing process. Upon achieving better homogeneity of the graphite particles and the binder and decreases in the size and breadth of the size distributions of particle clusters (as inferred from electrical measurements and maximum packing fraction values), the elasticity (storage modulus) and the shear viscosity (magnitude of the complex viscosity from small-amplitude oscillatory shear and shear viscosity from steady torsional and capillary rheometry) of the suspension decreased significantly and the wall slip velocity values increased. These findings demonstrate the intimate relationships that exist between the rheological behavior of concentrated suspensions and the thermo-mechanical history that they are exposed to during the processing stage and suggest that the preparation conditions for suspensions should be carefully selected and well documented to achieve reproducible characterization of rheological material functions.     

Convective mass transfer across fluid interfaces in straight angular pores

Steady convective mass transfer to or from fluid interfaces in pores of angular cross-section is theoretically investigated. This situation is relevant to a variety of mass transport process in porous media, including the fate of residual non-aqueous phase liquid ganglia and gas bubbles. The model incorporates the essential physics of capillarity and solute mass transfer by convection and diffusion in corner fluid filaments. The geometry of the corner filaments, characterized by the fluid–fluid contact angle, the corner half-angle and the interface meniscus curvature, is accounted for. Boundary conditions of zero surface shear (‘perfect-slip’) and infinite surface shear (‘no-slip’) at the fluid–fluid interface are considered. The governing equations for laminar flow within the corner filament and convective diffusion to or from the fluid–fluid interface are solved using finite-element methods. Flow computations are verified by comparing the dimensionless resistance factor and hydraulic conductance of corner filaments against recent numerical solutions by Patzek and Kristensen (J. Colloid Interface Sci 236, 305–317 2001). Novel results are obtained for the average effluent concentration as a function of flow geometry and pore-scale Peclet number. These results are correlated to a characteristic corner length and local pore-scale Peclet number using empirical equations appropriate for implementation in pore network models. Finally, a previously published “2D-slit” approximation to the problem at hand is checked and found to be in considerable error.