A biocompatible composite based on poly(ε‐caprolactone fumarate) and hydroxyapatite

Fabrication of biodegradable composites applicable as hard tissue substitutes consisting of poly(ε‐caprolactone fumarate) (PCLF), methacrylic acid (MAA), and hydroxyapatite (HA) was investigated. PCLF macromers were synthesized by reaction of PCL diol with fumaryl chloride in the presence of propylene oxide and characterized by gel permeation chromatography, FTIR, and ¹H NMR spectroscopy. Composites were fabricated by incorporating HA as inorganic filler in PCLF matrix which followed by thermal curing of the composition using benzoyl peroxide and MAA as a free radical initiator and reactive diluent, respectively. Uniform distribution of the fine ceramic phase in the polymer matrix was elucidated by scanning electron microscopy. The effects of the initial macromer molecular weight and the filler volume fraction on mechanical properties and cytotoxicity of the composites were also examined. Significant enhancement in the mechanical properties was observed upon increasing HA content and/or initial PCLF molecular weight. The biocompatibility of the specimens was also improved with increasing ceramic phase. Copyright © 2010 John Wiley & Sons, Ltd.     

Design of thermal hybrid composites based on liquid crystal polymer and hexagonal boron nitride fiber network in polylactide matrix

Development of high thermally conductive and electrically insulative composites is of interest for electronic packaging industry. Advancements in smaller and more compact electronic devices required improvements in packing materials, including their weight, thermal conductivity, and electrical resistivity. In addition, with the increasing environmental awareness, the usage of green (bio‐based) alternatives was equally important. In the present study a hybrid based on fibers of highly concentrated hexagonal boron nitride (hBN) in liquid crystal polymer (LCP) matrix were fabricated. These hybrids were formed by arranging hBN platelets into LCP fiber form to reach high filler concentration and then randomly mix it in polylactide (PLA) matrix. With appropriate filler interaction within the hybrid, thermal conductivity similar to that of pure fiber could be achieved. Filler interaction may be tailored by optimizing the fibers aspect ratio. This study demonstrated the effect of random fillers in fibers shape in increasing the overall thermal conductivity of PLA polymeric hybrid using hBN and LCP fibers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 457–464     

Demonstration of a thick holographic Stokesmeter

A holographic Stokesmeter has the potential to be useful in high-speed polarization imaging applications. Highly polarization-sensitive gratings are an important component for this device. Using two sets of multiplexed gratings, we measured the Stokes parameters for three different polarization states of an input beam. These measured values compared well to values measured using the quarter-wave plate/linear polarizer method. This establishes the feasibility of such a Stokesmeter in its original configuration. We demonstrate further the basic mechanism behind a compact architecture for this device, requiring only a single substrate and a single imaging system, and describe a spectrally scanned polarimetric imaging system.     

Lytic transglycosylase MltB of Escherichia coli and its role in recycling of peptidoglycan strands of bacterial cell wall

The cell wall is an indispensable structure for the survival of bacteria and a target for antibiotics. Peptidoglycan is the major constituent of the cell wall, which is comprised of backbone repeats of N-acetylglucosamine (NAG) and N-acetylmuramic acid (NAM). A peptide stem is appended to the NAM unit, which in turn experiences cross-linking with a peptide from another peptidoglycan in the final steps of cell wall assembly. In the normal course of bacterial growth, as much as 60% of the parental cell wall is recycled, a process that is not fully understood. A polymeric cell wall is fragmented by the family of lytic transglycosylases, and certain key fragments are transported to the cytoplasm for recycling. The genes for the six known lytic transglycosylases of Escherichia coli were cloned, and the enzymes were purified in this study. It is shown that MltB is the only lytic transglycosylase to turn over a synthetic peptidoglycan fragment of two NAG-NAM repeats; hence this enzyme is likely to be the lytic transglycosylase responsible for processing of shorter peptidoglycan strands. Lytic transglycosylases have been proposed to go through an oxocarbenium species that would trap the 6-hydroxyl moiety of the glucosamine residue of muramic acid to generate the so-called 1,6-anhydromuramyl moiety. It is documented herein by characterization of the products of turnover that this process takes place to the total exclusion of the entrapment of a water molecule by the reactive intermediary oxocarbenium species. Furthermore, turnover of the E. coli sacculus (whole cell wall) by MltB was characterized. It is documented that each MltB molecule is able to process the cell wall 14000 times in the course of a single doubling time for E. coli.     

Investigation of the mechanism of the cell wall DD-carboxypeptidase reaction of penicillin-binding protein 5 of Escherichia coli by quantum mechanics/molecular mechanics calculations

Penicillin-binding protein 5 (PBP 5) of Escherichia coli hydrolyzes the terminal D-Ala-D-Ala peptide bond of the stem peptides of the cell wall peptidoglycan. The mechanism of PBP 5 catalysis of amide bond hydrolysis is initial acylation of an active site serine by the peptide substrate, followed by hydrolytic deacylation of this acyl-enzyme intermediate to complete the turnover. The microscopic events of both the acylation and deacylation half-reactions have not been studied. This absence is addressed here by the use of explicit-solvent molecular dynamics simulations and ONIOM quantum mechanics/molecular mechanics (QM/MM) calculations. The potential-energy surface for the acylation reaction, based on MP2/6-31+G(d) calculations, reveals that Lys47 acts as the general base for proton abstraction from Ser44 in the serine acylation step. A discrete potential-energy minimum for the tetrahedral species is not found. The absence of such a minimum implies a conformational change in the transition state, concomitant with serine addition to the amide carbonyl, so as to enable the nitrogen atom of the scissile bond to accept the proton that is necessary for progression to the acyl-enzyme intermediate. Molecular dynamics simulations indicate that transiently protonated Lys47 is the proton donor in tetrahedral intermediate collapse to the acyl-enzyme species. Two pathways for this proton transfer are observed. One is the direct migration of a proton from Lys47. The second pathway is proton transfer via an intermediary water molecule. Although the energy barriers for the two pathways are similar, more conformers sample the latter pathway. The same water molecule that mediates the Lys47 proton transfer to the nitrogen of the departing D-Ala is well positioned, with respect to the Lys47 amine, to act as the hydrolytic water in the deacylation step. Deacylation occurs with the formation of a tetrahedral intermediate over a 24 kcal x mol(-1) barrier. This barrier is approximately 2 kcal x mol(-1) greater than the barrier (22 kcal x mol(-1)) for the formation of the tetrahedral species in acylation. The potential-energy surface for the collapse of the deacylation tetrahedral species gives a 24 kcal x mol(-1) higher energy species for the product, signifying that the complex would readily reorganize and pave the way for the expulsion of the product of the reaction from the active site and the regeneration of the catalyst. These computational data dovetail with the knowledge on the reaction from experimental approaches.     

Demonstration of a tunable-bandwidth white-light interferometer using anomalous dispersion in atomic vapor

Recently, the design of a white-light cavity has been proposed using negative dispersion in an intracavity medium to make the cavity resonate over a large range of frequencies and still maintain a high cavity buildup. This Letter presents the first demonstration of this effect in a free-space cavity. The negative dispersion of the intracavity medium is caused by bifrequency Raman gain in an atomic vapor cell. A significantly broad cavity response over a bandwidth greater than 20 MHz has been observed. A key application of this device would be in enhancing the sensitivity-bandwidth product of the next generation gravitational wave detectors that make use of the so-called signal-recycling mirror.     

Large Ultrathin Shelled Drops Produced via Non‐Confined Microfluidics

We present a facile approach for producing large and monodisperse core–shell drops with ultrathin shells using a single‐step process. A biphasic compound jet is introduced into a quiescent third (outer) phase that ruptures to form core–shell drops. Ultrathin shelled drops could only be produced within a certain range of surfactant concentrations and flow rates, highlighting the effect of interfacial tension in engulfing the core in a thin shell. An increase in surfactant concentrations initially resulted in drops with thinner shells. However, the drops with thinnest shells were obtained at an optimum surfactant concentration, and a further increase in the surfactant concentrations increased the shell thickness. Highly monodisperse (coefficient of variation smaller than 3 %) core–shell drops with diameter of ～200 μm–2 mm with shell thickness as small as ～2 μm were produced. The resulting drops were stable enough to undergo polymerisation and produce ultrathin shelled capsules.     

On Nested Chain Decompositions of Normalized Matching Posets of Rank 3

In 1975, J. Griggs conjectured that a normalized matching rank-unimodal poset possesses a nested chain decomposition. This elegant conjecture remains open even for posets of rank 3. Recently, Hsu, Logan, and Shahriari have made progress by developing techniques that produce nested chain decompositions for posets with certain rank numbers. As a demonstration of their methods, they prove that the conjecture is true for all rank 3 posets of width at most 7. In this paper, we present new general techniques for creating nested chain decompositions, and, as a corollary, we demonstrate the validity of the conjecture for all rank 3 posets of width at most 11.     

Aminoglycosides modified by resistance enzymes display diminished binding to the bacterial ribosomal aminoacyl-tRNA site

Understanding the basic principles that govern RNA binding by aminoglycosides is important for the design of new generations of antibiotics that do not suffer from the known mechanisms of drug resistance. With this goal in mind, we examined the binding of kanamycin A and four derivatives (the products of enzymic turnovers of kanamycin A by aminoglycoside-modifying enzymes) to a 27 nucleotide RNA representing the bacterial ribosomal A site. Modification of kanamycin A functional groups that have been directly implicated in the maintenance of specific interactions with RNA led to a decrease in affinity for the target RNA. Overall, the products of reactions catalyzed by aminoglycoside resistance enzymes exhibit diminished binding to the A site of bacterial 16S rRNA, which correlates well with a loss of antibacterial ability in resistant organisms that harbor these enzymes.