Effect of the drawing process on the wet spinning of polyacrylonitrile fibers in a system of dimethyl sulfoxide and water

The effect of the drawing process on the structural characteristics and mechanical properties of polyacrylonitrile (PAN) fibers was comparatively studied. The protofibers extruded from the spinneret were the initial phase of stretching, which involved the deformation of the primitive fiber with the concurrent orientation of the fibrils. Wet‐spun PAN fibers observed by scanning electron microscopy exhibited different cross‐sectional shapes as the draw ratio was varied. X‐ray diffraction results revealed that the crystalline orientation of PAN fibers increased with increasing draw ratio; these differences in the orientation behaviors were attributed to the various drawing mechanisms involved. The crystalline and amorphous orientations of the PAN fibers showed different features; at the same time, the tensile properties were strongly dependent on the draw ratio. However, the stream stretch ratio had most influence on the tensile strength and the orientation of PAN fibers for the selected process parameters. Electron spin resonance proved that the local morphology and segmental dynamics of the protofibers were due to a more heterogeneous environment caused by the sequence structure. Differential scanning calorimetry indicated that the size and shape of the exotherm and exoenergic reaction were strongly dependent on the morphology and physical changes occurring during fiber formation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1026–1037, 2007     

Bicyclic Peptide Inhibitor of Urokinase‐Type Plasminogen Activator: Mode of Action

The development of protease inhibitors for pharmacological intervention has taken a new turn with the use of peptide‐based inhibitors. Here, we report the rational design of bicyclic peptide inhibitors of the serine protease urokinase‐type plasminogen activator (uPA), based on the established monocyclic peptide, upain‐2. It was successfully converted to a bicyclic peptide, without loss of inhibitory properties. The aim was to produce a peptide cyclised by an amide bond with an additional stabilising across‐the‐ring covalent bond. We expected this bicyclic peptide to exhibit a lower entropic burden upon binding. Two bicyclic peptides were synthesised with affinities similar to that of upain‐2, and their binding energetics were evaluated by isothermal titration calorimetry. Indeed, compared to upain‐2, the bicyclic peptides showed reduced loss of entropy upon binding to uPA. We also investigated the solution structures of the bicyclic peptide by NMR spectroscopy to map possible conformations. An X‐ray structure of the bicyclic‐peptide–uPA complex confirmed an interaction similar to that for the previous upain‐1/upain‐2–uPA complexes. These physical studies of the peptide–protease interactions will aid future designs of bicyclic peptide protease inhibitors.     

The Structure of Glycerol Trinitrate Reductase NerA from Agrobacterium radiobacter Reveals the Molecular Reason for Nitro‐ and Ene‐Reductase Activity in OYE Homologues

In recent years, Old Yellow Enzymes (OYEs) and their homologues have found broad application in the efficient asymmetric hydrogenation of activated C?C bonds with high selectivities and yields. Members of this class of enzymes have been found in many different organisms and are rather diverse on the sequence level, with pairwise identities as low as 20 %, but they exhibit significant structural similarities with the adoption of a conserved (αβ)₈‐barrel fold. Some OYEs have been shown not only to reduce C?C double bonds, but also to be capable of reducing nitro groups in both saturated and unsaturated substrates. In order to understand this dual activity we determined and analyzed X‐ray crystal structures of NerA from Agrobacterium radiobacter, both in its apo form and in complex with 4‐hydroxybenzaldehyde and with 1‐nitro‐2‐phenylpropene. These structures, together with spectroscopic studies of substrate binding to several OYEs, indicate that nitro‐containing substrates can bind to OYEs in different binding modes, one of which leads to C?C double bond reduction and the other to nitro group reduction.     

Investigation of the crystalline phase morphology of a β‐nucleated impact polypropylene copolymer

This study covers the preparation and the characterization of β‐nucleated impact polypropylene copolymer (NA‐IPC). Calcium stearate (CaSt), as well as pimelic (Pim) and adipic (Adi) acids, were doped into IPC as mono‐ or bicomponent nucleating agents (NAs) at varying mass ratios. Possible chemical interactions between the NAs and with IPC, as well as the effect of the NAs on the crystallization behavior and nonisothermal crystallization kinetics, were investigated. DSC and XRD results revealed that IPC nucleated with Pim and Pim‐CaSt nucleants induced up to 90% β‐crystals, whereas Adi and Adi‐CaSt formed only about 17% β‐crystals. This was associated with the strong nucleation efficiency of Pim. The nonisothermal crystallization kinetics showed that the crystallization of IPC and NA‐IPC followed a three‐dimensional growth with athermal nucleation mechanism. FTIR showed that none of the NAs chemically reacted with IPC, and the chemical structure of the polymer was thus intact during the treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39923.     

Electropolymerization kinetics of a binary mixture of pyrrole and o‐aminobenzoic acid and characterization of the obtained polymer films

Poly (pyrrol‐co‐o‐aminobenzoic acid) has been synthesized electrochemically from an aqueous acid medium. The initial rate of electrocopolymerization reaction on platinum electrode is small and the rate law is: Rate = K₂ [D]^1.02[HCl] ^1.44[M]^2.00. The apparent activation energy (E_a) is found to be 90.11 kJ mol^?1. The polymer films obtained have been characterized by cyclic voltammetry, X‐ray diffraction, elemental analysis, thermogravimetric analysis, scanning electron microscopy, ¹H NMR, and IR‐spectroscopy. The mechanism of the electrochemical polymerization reaction has been discussed. The monomer reactivity ratios (r₁ and r₂) were calculated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Self‐assembling metal coatings from phosphated and siloxane‐modified polyurethane dispersions: An analysis of the coating–air interface

Polyurethane dispersion coatings containing phosphate and siloxane chains were evaluated for their self‐assembling properties for a single‐coating system. Dynamic contact angles (DCAs) and X‐ray photoelectron spectroscopy (XPS) were used to study the coating–air interface. The siloxane chains were the predominant species on the surfaces of the coatings. The wetting properties of the coating–air interface were reversed when the coated panels were immersed in an ionic solution, and the decrease in hydrophobicity was linear with time. Results from XPS and DCA analyses were similar. The self‐assembling properties of the coatings could be useful in the development of hydrophobic coatings from hydrophilic polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 893–899, 2003     

Crystal Structure Determination and Mutagenesis Analysis of the Ene Reductase NCR

The crystal structure of the “ene” nicotinamide‐dependent cyclohexenone reductase (NCR) from Zymomonas mobilis (PDB ID: 4A3U) has been determined in complex with acetate ion, FMN, and nicotinamide, to a resolution of 1.95 Å. To study the activity and enantioselectivity of this enzyme in the bioreduction of activated α,β‐unsaturated alkenes, the rational design methods site‐ and loop‐directed mutagenesis were applied. Based on a multiple sequence alignment of various members of the Old Yellow Enzyme family, eight single‐residue variants were generated and investigated in asymmetric bioreduction. Furthermore, a structural alignment of various ene reductases predicted four surface loop regions that are located near the entrance of the active site. Four NCR loop variants, derived from loop‐swapping experiments with OYE1 from Saccharomyces pastorianus, were analysed for bioreduction. The three enzyme variants, P245Q, D337Y and F314Y, displayed increased activity compared to wild‐type NCR towards the set of substrates tested. The active‐site mutation Y177A demonstrated a clear influence on the enantioselectivity. The loop‐swapping variants retained reduction efficiency, but demonstrated decreased enzyme activity compared with the wild‐type NCR ene reductase enzyme.     

Self‐welding 1‐butene/ethylene copolymers from metallocene catalysts: Structure,morphology, and mechanical properties

Samples of random copolymers consisting of 1‐butene modified with a low ethylene content (4, 5, 8% by weight) produced with metallocene catalysts were studied to elucidate the polymorphic behavior of this new class of materials and to characterize them from a structural, morphological, and mechanical point of view. The samples cooled down from the melt are in amorphous phase and crystallize in a mixture of form I and I′ or in pure form I′ with aging time, according to the C2 content. Infrared and nuclear magnetic resonance spectroscopy, X‐ray diffraction and microscopic techniques were used to follow the changes of the material with aging time and to correlate the structural and morphological behavior with the peculiar mechanical properties that differentiate the samples with increasing C2 content. The presence, in the aged samples with higher C2 content, of the pure form I′ induces the peculiar ability to self‐welding and these copolymers combine high flexibility with good elasticity and ductility and can be processed directly or used as modifying agents in polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40119.     

Unique Crystal Structure of a Novel Surfactant Protein from the Foam Nest of the Frog Leptodactylus vastus

Breeding by releasing eggs into stable biofoams (“foam nests”) is a peculiar reproduction mode within anurans, fish, and tunicates; not much is known regarding the biochemistry or molecular mechanisms involved. Lv‐ranaspumin (Lv‐RSN‐1) is the predominant protein from the foam nest of the frog Leptodactylus vastus. This protein shows natural surfactant activity, which is assumed to be crucial for stabilizing foam nests. We elucidated the amino acid sequence of Lv‐RSN‐1 by de novo sequencing with mass‐spectrometry and determined the high‐resolution X‐ray structure of the protein. It has a unique fold mainly composed of a bundle of 11 α‐helices and two small antiparallel β‐strands. Lv‐RSN‐1 has a surface rich in hydrophilic residues and a lipophilic cavity in the region of the antiparallel β‐sheet. It possesses intrinsic surface‐active properties, reducing the surface tension of water from 73 to 61 mN m^?1 (15 μg mL^?1). Lv‐RSN‐1 belongs to a new class of surfactants proteins for which little has been reported regarding structure or function.     

Enhanced adsorption and recovery of Pb(II) from aqueous solution by alkali‐treated persimmon fallen leaves

Persimmon fallen leaves were employed to prepare a renewable and low‐cost biosorbent named as NPFL. Effects of initial pH, contact time, initial Pb(II) concentration, coexisting metal ions, and ionic strength on adsorption of Pb(II) from aqueous solution by NPFL were studied in detail. Enhanced removal capacity of NPFL toward Pb(II) was observed, and the maximum adsorption capacity was evaluated as 256 mg g^?1 by Langmuir modeling calculation. The fast adsorption process and the well‐fitted kinetics data with pseudo‐second‐order model indicated that chemisorption is the main rate‐limiting step for the adsorption process. NPFL had superior adsorption selectivity for Pb(II) from aqueous solution with coexisting metal ions. Characterization of NPFL and adsorption mechanism (electrostatic attraction, ion exchange, and chelation) were performed using XRD, SEM‐EDS, FT‐IR, XPS, and TGA. The results suggested that NPFL could be utilized as a potential candidate for the preconcentration of Pb(II) recovery and its removal in practice. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43656.     

Crystal structure of the bacterial ribosomal decoding site complexed with a synthetic doubly functionalized paromomycin derivative: a new specific binding mode to an a-minor motif enhances in vitro antibacterial activity

The crystal structure of the complex between oligonucleotide containing the bacterial ribosomal decoding site (A site) and the synthetic paromomycin analogue 1, which contains the gamma-amino-alpha-hydroxybutyryl (L-haba) group at position N1 of ring II (2-DOS ring), and an ether chain with an O-phenethylaminoethyl group at position C2' of ring III, is reported. Interestingly, next to the paromomycin analogue 1 specifically bound to the A site, a second molecule of 1 with a different conformation is observed at the crystal packing interface which mimics the A-minor interaction between two bulged-out adenines from the A site and the codon-anticodon stem of the mRNA-tRNA complex. Improved antibacterial activity supports the conclusion that analogue 1 might affect protein synthesis on the ribosome in two different ways: 1) specific binding to the A site forces maintenance of the "on" state with two bulged out adenines, and 2) a new binding mode of 1 to an A-minor motif which stabilizes complex formation between the ribosome and the mRNA-tRNA complex regardless of whether the codon-anticodon stem is of the cognate or near-cognate type.     

Adhesion properties of phosphate‐ and siloxane‐containing polyurethane dispersions to steel: An analysis of the metal–coating interface

Polyurethane dispersions containing phosphate and siloxane groups in the main chain were investigated as possible self‐assembling metal coatings. Improved adhesion of the polymer to the metal was observed because of the formation of an insoluble metal phosphate layer at the metal–coating interface. The neutralizing amine of the dispersions affected the formation of this metal phosphate, and the metal phosphate formation was dependent on the curing temperature and boiling point of the amine used for neutralization. A crosscut comparative study of adhesion proved that the phosphate‐containing coatings had better adhesion because of the formation of ionic bonds at the metal–coating interface. A solid‐state adhesion prediction method based on thermodynamic considerations was used. The results of the solid‐state adhesion method correlated well with that obtained from the crosscut adhesion test method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 900–907, 2003     

Kinetics of the Initial Stage of Sintering from Shrinkage Data: Simultaneous Determination of Activation Energy and Kinetic Model from a Single Nonisothermal Experiment

A new method for the kinetic analysis of the initial stage of sintering for constant-heating-rate data has been proposed. Unlike all of the methods previously reported in the literature, this new method proposed here allows the simultaneous determination of the activation energy and the kinetic model from a single dilatometric curve recorded under a linear-heating-rate program. The proposed method has been tested with simulated sintering curves and experimental results have been obtained for the sintering of a rutile sample.     

Crystal Structures of a Bioactive 6′‐Hydroxy Variant of Sisomicin Bound to the Bacterial and Protozoal Ribosomal Decoding Sites

Parasitic infections recognized as neglected tropical diseases are a source of concern for several regions of the world. Aminoglycosides are potent antimicrobial agents that have been extensively studied by biochemical and structural studies in prokaryotes. However, the molecular mechanism of their potential antiprotozoal activity is less well understood. In the present study, we have examined the in vitro inhibitory activities of some aminoglycosides with a 6′‐hydroxy group on ring I and highlight that one of them, 6′‐hydroxysisomicin, exhibits promising activity against a broad range of protozoan parasites. Furthermore, we have conducted X‐ray analyses of 6′‐hydroxysisomicin bound to the target ribosomal RNA A‐sites in order to understand the mechanisms of both its antibacterial and antiprotozoal activities at the molecular level. The unsaturated ring I of 6′‐hydroxysisomicin can directly stack on G1491, which is highly conserved in bacterial and protozoal species, through π–π interaction and fits closer to the guanidine base than the typically saturated and hydroxylated ring I of other structurally related aminoglycosides. Consequently, the compound adopts a lower energy conformation within the bacterial and protozoal A‐sites and makes pseudo pairs to either A or G at position 1408. The A‐site‐selective binding mode strongly suggests that 6′‐hydroxysisomicin is a potential lead for the design of next‐generation aminoglycosides targeting a wide variety of infectious diseases.     

Crystal Structure of the Human Monoacylglycerol Lipase,a Key Actor in Endocannabinoid Signaling

2‐Arachidonoylglycerol plays a major role in endocannabinoid signaling, and is tightly regulated by the monoacylglycerol lipase (MAGL). Here we report the crystal structure of human MAGL. The protein crystallizes as a dimer, and despite structural homologies to haloperoxidases and esterases, it distinguishes itself by a wide and hydrophobic access to the catalytic site. An apolar helix covering the active site also gives structural insight into the amphitropic character of MAGL, and likely explains how MAGL interacts with membranes to recruit its substrate. Docking of 2‐arachidonoylglycerol highlights a hydrophobic and a hydrophilic cavity that accommodate the lipid into the catalytic site. Moreover, we identified Cys201 as the crucial residue in MAGL inhibition by N‐arachidonylmaleimide, a sulfhydryl‐reactive compound. Beside the advance in the knowledge of endocannabinoids degradation routes, the structure of MAGL paves the way for future medicinal chemistry works aimed at the design of new drugs exploiting 2‐arachidonoylglycerol transmission.     

New hyperbranched polymers for membranes of high‐temperature polymer electrolyte membrane fuel cells: Determination of the crystal structure and free‐volume size

The key requirements for a membrane in polymer electrolyte membrane fuel cells are a high ion conductivity, mechanical strength, and barrier properties. We reported earlier on two new promising hyperbranched polymers: poly(benzimidazole‐co‐aniline) (PBIANI), with a uniform rectangular net structure, and poly(benzimidazole‐co‐benzene) (PBIB), with a honeycomb structure. Both polymers exhibit a high ion conductivity and mechanical strength and have proven themselves suitable for the membranes of high‐temperature polymer electrolyte membrane fuel cells. In this article, we deal with the determination of crystal structure and free‐volume cell/microvoid size of these two polymers. Both PBIANI and PBIB had the same d‐spacing (3.5 Å). However, the percentage of crystallinity was higher and the crystallite size was larger for PBIB. The kinetic diameters of hydrogen (2.89 Å), oxygen (3.46 Å), water (2.60 Å), and methanol (～ 4.00 Å) were much larger than the free‐volume cell/microvoid diameters of PBIANI (1.81 Å) and PBIB (1.96 Å) but much smaller than those of Nafion 115 (6.54 Å) and polybenzimidazole (PBI) (～ 6.00 Å). The very small free‐volume sizes of PBIANI and PBIB ensured good barrier properties against hydrogen, oxygen, water, and methanol, unlike those of Nafion‐ and PBI‐type membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011