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Feng Jiang, Chen Qian, Alan R Esker, Maren Roman
Residual lignin in pretreated biomass impedes enzymatic hydrolysis. Non-ionic surfactants are known to enhance the enzymatic hydrolysis of lignocellulosic biomass but their mechanisms of action are incompletely understood. This study investigates the effect of a non-ionic surfactant, Tween 80, on the adsorption of cellulases onto model lignin substrates. Lignin substrates were prepared by spin coating of flat substrates with three different types of lignin: organosolv lignin, kraft lignin, and milled wood lignin...
September 19, 2017: Journal of Physical Chemistry. B
Nhi Tran, Justin J Kurian, Avni Bhatt, Robert McKenna, Joanna R Long
The N-terminal 25 amino-acid residues of pulmonary surfactant protein B (SP-B1-25) induces unusual lipid polymorphisms in a model lipid system, 4:1 DPPC/POPG, mirroring the lipid composition of native pulmonary surfactant. It is widely suggested that SP-B1-25 induced lipid polymorphisms within the alveolar aqueous subphase provide a structural platform for rapid lipid adsorption to the air-water interface. Here, we characterize in detail the phase behavior of DPPC and POPG in hydrated lipid assemblies containing therapeutic levels of SP-B1-25 using (2)H and (31)P solid state NMR spectroscopy...
September 5, 2017: Journal of Physical Chemistry. B
Mateusz Gosecki, Slawomir Kazmierski, Monika Gosecka
We present biocompatible hydrogel systems suitable for biomineralization processes based on hyperbranched polyglycidol cross-linked with acrylamide copolymer bearing carbonyl-coordinated boronic acid. At neutral pH, diol functional groups of HbPGL react with boronic acid of polyacrylamide to generate 3D network in water by the formation of boronic ester cross-links. The dynamic associative/dissociative characteristics of the cross-links makes the network reversible. The presented hydrogels display self-healing properties and are injectable, facilitating gap filing of bone tissue...
September 13, 2017: Biomacromolecules
Ben F M Wijnen, Iris Mosweu, Marian H J M Majoie, Leone Ridsdale, Reina J A de Kinderen, Silvia M A A Evers, Paul McCrone
OBJECTIVE: To investigate the responsiveness of and correlation between the EQ-5D-5L and the QOLIE-31P in patients with epilepsy, and develop a mapping function to predict EQ-5D-5L values based on the QOLIE-31P for use in economic evaluations. METHODS: The dataset was derived from two clinical trials, the ZMILE study in the Netherlands and the SMILE study in the UK. In both studies, patients' quality of life using the EQ-5D-5L and QOLIE-31P was measured at baseline and 12 months follow-up...
September 4, 2017: European Journal of Health Economics: HEPAC: Health Economics in Prevention and Care
Riccardo Salvio, Alessandro Casnati
The catalytic activity of the guanidinium units towards the cleavage of phosphoric diesters is deeply investigated both with kinetic experiment and DFT calculations. The first part of the investigation aims to determine how the structure of the substrate (phenyl or alkyl esters) is able to influence the guanidinium-catalyzed hydrolysis changing the mechanism from ANDN to AN+DN. In the cleavage of the DNA model bis(4-nitrophenyl)phospate (BNPP), experimental kinetic data highlight the operation of a guanidine-guanidinium catalytic dyad that can act both intermolecularly and intramolecularly on different molecular scaffolds exhibiting notable values of Effective Molarity...
September 1, 2017: Journal of Organic Chemistry
Ruchi Khajuria, Sandeep Kumar, Mandeep Kour, Atiya Syed, Geeta Hundal, K Sushil Pandey
This work presents four complexes with general formula [(ArO)2PS23Bi] (1-4), where Ar = 2,4-(CH3)2C6H3, 2,5-(CH3)2C6H3, 3,4-(CH3)2C6H3 and 3,5-(CH3)2C6H3, respectively. Reaction of [(ArO)2PS2Na] with Bi(NO3)3 · 5H2O in toluene in 3:1 molar stoichiometry afforded the complexes [(ArO)2PS23Bi]. These newly synthesized complexes have been characterized by elemental analysis, FT-IR and multinuclear NMR (1H, 13C and 31P) NMR. The crystal structure of [(3,5-CH3)2C6H3O2PS2]3Bi (4) has been determined by X-ray crystallography...
September 2017: Acta Chimica Slovenica
Janet Bluemel, Shin Hye Ahn, Nattamai Bhuvanesh
The di(hydroperoxy)alkane adducts of phosphine oxides Ph3PO*(HOO)2CMe2 (1), Cy3PO*(HOO)2CMe2 (2), Ph3PO*(HOO)2CMeEt (3), Cy3PO*(HOO)2CMeEt (4), Cy3PO*(HOO)2CEt2 (5), Cy3PO*(HOO)2C(CH2)5 (6), and Cy3PO*(HOO)2CMePh (7), (Ph2P(O)CH2CH2P(O)Ph2)*((HOO)2CEt2)2 (8), and Ph2P(O)CH2P(O)Ph2*(HOO)2CMe2 (9), are synthesized and fully characterized by 1H, 13C, and 31P NMR and IR spectroscopy. Single crystal X-ray structures are reported for 3-9. Different one-pot synthetic pathways, starting from R3P, R3PO, R3PO*H2O, and R3PO*H2O2 are explored and discussed and a mechanism for the formation of the di(hydroperoxy)alkane adducts of phosphine oxides is suggested...
August 29, 2017: Chemistry: a European Journal
Mei Qu, Huan Li, Lin-Hua Xie, Shuai-Ting Yan, Jian-Rong Li, Jun-Hao Wang, Cai-Yun Wei, Yu-Wei Wu, Xian-Ming Zhang
Determining the total structure of metal nanoparticles is vital to understand their properties. In this work, the first all-alkynyl-protected Ag nanocluster, Ag74(C≡CPh)44, was synthesized and structurally characterized by single crystal diffraction. Ag atoms are arranged in a Ag4@Ag22@Ag48 three shell structure and all 44 phenylethynyl ligands coordinated with Ag in a μ3 mode. In spite of being absent in nanocluster, (31)P NMR study reveals that bidentate phosphine first reacts with Ag(I) to form a dinuclear complex, from which Ag atoms are then released to phenylethynyl ligands...
August 28, 2017: Journal of the American Chemical Society
Ashutosh Singh, Andrew MacKenzie, Geoffrey Girnun, Maurizio Del Poeta
Cryptococcus species cause invasive infections in humans. Lipids play an important role in the progression of these infections. Independent studies done by our group and others provide some detail about the functions of these lipids in Cryptococcus infections. However, pathways of biosynthesis and metabolism of these lipids are not completely understood. To thoroughly understand the physiological role of these Cryptococcus lipids, a proper structure and composition analyses of Cryptococcus lipids is demanded...
August 15, 2017: Journal of Lipid Research
Alexander V Zabula, Yusen Qiao, Alex J Kosanovich, Thibault Cheisson, Brian C Manor, Patrick J Carroll, Oleg V Ozerov, Eric J Schelter
Synthetic methods for the coordination of the monoanionic bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) ligand framework to the cerium(III) cation have been developed and applied for the isolation of a series of {(PNP)Ce} and {(PNP)2Ce} type complexes. The structures of the complexes were studied by X-ray diffraction and multinuclear NMR spectroscopy. We found that the cerium(III) ion can induce the elimination of one of the iPr groups at phosphorus to yield a new dianionic PNP tridentate framework (PNP-iPr) featuring a phosphido-donor functionality, which is bound to the cerium ion with the shortest known Ce-P bond of 2...
August 10, 2017: Chemistry: a European Journal
Ariana B Jones, Guy C Lloyd-Jones, Dušan Uhrín
We report a new pure-shift method, termed SHARPER (Sensitive, Homogeneous, And Resolved PEaks in Real time) designed for the analysis of reactions and equilibria by NMR. By focusing on a single selected signal, SHARPER removes all heteronuclear couplings of a selected nucleus without the need to pulse on X channels, thus overcoming hardware limitations of conventional spectrometers. A more versatile decoupling scheme, termed sel-SHARPER, removes all heteronuclear and homonuclear couplings of the selected signal...
September 19, 2017: Analytical Chemistry
M T Hooijmans, N Doorenweerd, C Baligand, J J G M Verschuuren, I Ronen, E H Niks, A G Webb, H E Kan
OBJECTIVES: To assess the changes in phosphodiester (PDE)-levels, detected by 31P magnetic resonance spectroscopy (MRS), over 24-months to determine the potential of PDE as marker for muscle tissue changes in Duchenne Muscular Dystrophy (DMD) patients. METHODS: Spatially resolved phosphorous datasets were acquired in the right lower leg of 18 DMD patients (range: 5-15.4 years) and 12 age-matched healthy controls (range: 5-14 years) at three time-points (baseline, 12-months, and 24-months) using a 7T MR-System (Philips Achieva)...
2017: PloS One
Tim A D Smith, Su M Phyu, Kholoud S Alzyoud, Chih-Chung Tseng
Androgen receptor (AR) activation is the primary driving factor in prostate cancer which is initially responsive to castration but then becomes resistant (castration-resistant prostate cancer (CRPC)). CRPC cells still retain the functioning AR which can be targeted by other therapies. A recent promising development is the use of inhibitors (Epi-1) of protein-protein interaction to inhibit AR-activated signalling. Translating novel therapies into the clinic requires sensitive early response indicators. Here potential response markers are explored...
2017: BioMed Research International
Alexandra G Pershina, Vladimir V Ivanov, Lina V Efimova, Oleg B Shevelev, Sergey V Vtorushin, Tatjana V Perevozchikova, Alexey E Sazonov, Ludmila M Ogorodova
BACKGROUND: European liver fluke Opisthorchis felineus, causing opisthorchiasis disease, is widespread in Russia, Ukraine, Kazakhstan and sporadically detected in the EU countries. O. felineus infection leads to hepatobiliary pathological changes, cholangitis, fibrosis and, in severe cases, malignant transformation of bile ducts. Due to absence of specific symptoms, the infection is frequently neglected for a long period. The association of opisthorchiasis with almost incurable bile duct cancer and rising international migration of people that increases the risk of the parasitic etiology of liver fibrosis in non-endemic regions determine high demand for development of approaches to opisthorchiasis detection...
July 2017: PLoS Neglected Tropical Diseases
Nicole Harmouche, Christopher Aisenbrey, Fernando Porcelli, Youlin Xia, Sarah E D Nelson, Xi Chen, Jesus Raya, Louic Vermeer, Conrado Aparicio, Gianluigi Veglia, Sven-Ulrik Gorr, Burkhard Bechinger
The antimicrobial peptide GL13K encompasses 13 amino acid residues and has been designed and optimized from the salivary protein BPIFA2 to exhibit potent bacteriocidal and anti-biofilm activity against Gram-negative and Gram-positive bacteria as well as anti-lipopolysaccharide activity in vitro and in vivo. Here, the peptide was analyzed in a variety of membrane environments by circular dichroism spectroscopy and by high-resolution multidimensional solution nuclear magnetic resonance (NMR) spectroscopy. Whereas in the absence of membranes a random coil conformation predominates, the peptide adopts a helical structure from residue 5 to 11 in the presence of dodecylphosphocholine micelles...
August 15, 2017: Biochemistry
Hong Giang T Ly, Tatjana N Parac-Vogt
A recent study [Angew. Chem. Int. Ed. 2015, 54, 7391-7394] has shown that horse heart myoglobin (HHM) is selectively hydrolyzed by a range of zirconium(IV)-substituted polyoxometalates (POMs) under mild conditions. In this study, the molecular interactions between the Zr-POM catalysts and HHM are investigated by using a range of complementary techniques, including circular dichroism (CD), UV/Vis spectroscopy, tryptophan fluorescence spectroscopy, and (1) H and (31) P NMR spectroscopy. A tryptophan fluorescence quenching study reveals that, among all examined Zr-POMs, the most reactive POM, 2:2 Zr(IV) -Keggin, exhibits the strongest interaction with HHM...
July 4, 2017: Chemphyschem: a European Journal of Chemical Physics and Physical Chemistry
Sudipta Roy, Kartik Chandra Mondal, Subrata Kundu, Bin Li, Christian J Schürmann, Sayan Dutta, Debasis Koley, Regine Herbst-Irmer, Dietmar Stalke, Herbert W Roesky
The cyclic alkyl(amino) carbene (cAAC) bonded chlorophosphinidene (cAAC)P-Cl (2/2') was isolated from the direct reaction between cAAC and phosphorus trichloride (PCl3 ). Compound 2/2' has been characterized by NMR spectroscopy and mass spectrometry. (31) P NMR investigations [δ≈160 ppm (major) and δ≈130 ppm (minor)] reveal that there are two different P environments of the P-Cl unit. X-ray single-crystal determination suggests a co-crystallization of two conformational isomers of (cAAC)P-Cl (2/2'); the major compound possessing a cAAC-PCl unit with CcAAC -P 1...
June 26, 2017: Chemistry: a European Journal
Zhenqin Zhang, Xiaoyong Wang, Cheng Luo, Chengcheng Zhu, Kun Wang, Changli Zhang, Zijian Guo
Osteosarcoma is the most common malignant bone tumor primarily affecting adolescents. Targeted platinum(II) complexes are promising candidates for overcoming the general toxicity of conventional platinum anticancer drugs. In this study four dinuclear platinum(II) complexes, {[cis-Pt(NH3 )2 Cl]2 (PD)} (NO3 )2 (1), {[cis-Pt(NH3 )2 Cl]2 (PDBP)} (NO3 )2 (2), {[cis-Pt(DACH)Cl]2 (PD)} (NO3 )2 (3), and {[cis-Pt(DACH)Cl]2 (PDBP)} (NO3 )2 (4) [PD=5,5'-carbonylbis(2-(2-(pyridin-2-yl)ethyl)isoindoline-1,3-dione), PDBP=tetraethyl (((bis(1,3-dioxo-2-(2-(pyridin-2-yl)ethyl)isoindolin-5-yl)methylene)amino) methylene)bis(phosphonate), DACH=1,2-diaminocyclohexane)], were designed and synthesized...
May 29, 2017: Chemistry, An Asian Journal
Eva-Maria Bertschler, Robin Niklaus, Wolfgang Schnick
Li12 P3 N9 was synthesized by solid-state reaction of Li3 N and P3 N5 at 790 °C. It is made up of non-condensed [P3 N9 ](12-) dreier-rings of PN4 -tetrahedra. The corresponding high-pressure polymorph, Li4 PN3 , was synthesized under high-pressure/high-temperature conditions from Li12 P3 N9 or LiPN2 and Li7 PN4 at 6 or 7 GPa, respectively, using the multianvil technique. Li4 PN3 is the first lithium catena-nitridophosphate and contains PN3 zweier-chains of corner sharing PN4 -tetrahedra. To confirm the structure elucidated from single-crystal X-ray data, Rietveld refinement, (6) Li, (7) Li, and (31) P solid-state NMR spectroscopy, FTIR spectroscopy and EDX measurements were carried out...
May 23, 2017: Chemistry: a European Journal
Andrea Němcová, Michal Dubský, Alexandra Jirkovská, Petr Šedivý, Miloslav Drobný, Milan Hájek, Monika Dezortová, Robert Bém, Vladimíra Fejfarová, Anna Pyšná
AIM: The standard method for assessment of effect of revascularization in patients with diabetic foot (DF) and critical limb ischemia (CLI) is transcutaneous oxygen pressure (TcPO2). Phosphorus magnetic resonance spectroscopy (31P MRS) enables to evaluate oxidative muscle metabolism that could be impaired in patients with diabetes and its complications. The aim of our study was to compare MRS of calf muscle between patients with DF and CLI and healthy controls and to evaluate the contribution of MRS in the assessment of the effect of revascularization...
December 0: Vnitr̆ní Lékar̆ství
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