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41.
Stephan Schaumüller Doris Cristurean Stephan Haudum George S. Pappas Markus Himmelsbach Matthias Bechmann Oliver Brüggemann Ian Teasdale 《Journal of polymer science. Part A, Polymer chemistry》2021,59(24):3161-3166
We report a facile post-polymerization modification route to functionalized aromatic polyimides via Diels-Alder cycloaddition. Aromatic polyimides are important, versatile high-performance polymers; however, their structural diversity is restricted by the requirements of the step-growth polymerization. We prepared polyimides with alkynes in their main-chain as macromolecular dienophiles and quantitatively grafted tetraphenylcyclopentadienone based dienes. The resulting solution-processable, wholly aromatic polyimides show a considerable increase in surface area due to the induced conformational changes and bulky, rigid, and contorted molecular structures. The orthogonality of the reaction is exploited to insert functional groups, namely bromine and sulfonates, along the polymer backbone. In a further extension, the phenylene segments undergo cyclodehydrogenation to form nanographene segments within the polymer chains. The Diels-Alder cycloaddition onto polyimides is therefore demonstrated to be an effective, widely applicable route to tunable high-performance polymers with value-added functionality and thus considerable potential in a wide range of advanced materials. 相似文献
42.
Naresh Kumar Rajendran Blassan P. George Nicolette N. Houreld Heidi Abrahamse 《Molecules (Basel, Switzerland)》2021,26(10)
Recently, the biosynthesis of zinc oxide nanoparticles (ZnO NPs) from crude extracts and phytochemicals has attracted much attention. Green synthesis of NPs is cost-effective, eco-friendly, and is a promising alternative for chemical synthesis. This study involves ZnO NPs synthesis using Rubus fairholmianus root extract (RE) as an efficient reducing agent. The UV spectrum of RE-ZnO NPs exhibited a peak at 357 nm due to intrinsic bandgap absorption and an XRD pattern that matches the ZnO crystal structure (JCPDS card no: 36-1451). The average particle size calculated from the Debye–Scherrer equation is 11.34 nm. SEM analysis showed that the RE-ZnO NPs spherical in shape with clusters (1–100 nm). The antibacterial activity of the NPs was tested against Staphylococcus aureus using agar well diffusion, minimum inhibitory concentration, and bacterial growth assay. The R. fairholmianus phytochemicals facilitate the synthesis of stable ZnO NPs and showed antibacterial activity. 相似文献
43.
Numerous single‐site mutants of photoactive yellow protein (PYP) from Halorhodospira halophila and as well as PYP homologs from other species exhibit a shoulder on the short wavelength side of the absorbance maximum in their dark‐adapted states. The structural basis for the occurrence of this shoulder, called the “intermediate spectral form,” has only been investigated in detail for the Y42F mutation. Here we explore the structural basis for occurrence of the intermediate spectral form in a M121E derivative of a circularly permuted H. halophila PYP (M121E‐cPYP). The M121 site in M121E‐cPYP corresponds to the M100 site in wild‐type H. halophila PYP. High‐resolution NMR measurements with a salt‐tolerant cryoprobe enabled identification of those residues directly affected by increasing concentrations of ammonium chloride, a salt that greatly enhances the fraction of the intermediate spectra form. Residues in the surface loop containing the M121E (M100E) mutation were found to be affected by ammonium chloride as well as a discrete set of residues that link this surface loop to the buried hydroxyl group of the chromophore via a hydrogen bond network. Localized changes in the conformational dynamics of a surface loop can thereby produce structural rearrangements near the buried hydroxyl group chromophore while leaving the large majority of residues in the protein unaffected. 相似文献
44.
Ting‐Zheng Xie Kai Guo Zaihong Guo Wen‐Yang Gao Lukasz Wojtas Guo‐Hong Ning Mingjun Huang Xiaocun Lu Jing‐Yi Li Sheng‐Yun Liao Yu‐Sheng Chen Charles N. Moorefield Mary Jane Saunders Stephen Z. D. Cheng Chrys Wesdemiotis George R. Newkome 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(32):9259-9259
45.
Comparison of structural,thermodynamic, kinetic and mass transport properties of Mg2+ ion models commonly used in biomolecular simulations 下载免费PDF全文
Maria T. Panteva George M. Giambaşu Darrin M. York 《Journal of computational chemistry》2015,36(13):970-982
The prevalence of Mg2+ ions in biology and their essential role in nucleic acid structure and function has motivated the development of various Mg2+ ion models for use in molecular simulations. Currently, the most widely used models in biomolecular simulations represent a nonbonded metal ion as an ion‐centered point charge surrounded by a nonelectrostatic pairwise potential that takes into account dispersion interactions and exchange effects that give rise to the ion's excluded volume. One strategy toward developing improved models for biomolecular simulations is to first identify a Mg2+ model that is consistent with the simulation force fields that closely reproduces a range of properties in aqueous solution, and then, in a second step, balance the ion–water and ion–solute interactions by tuning parameters in a pairwise fashion where necessary. The present work addresses the first step in which we compare 17 different nonbonded single‐site Mg2+ ion models with respect to their ability to simultaneously reproduce structural, thermodynamic, kinetic and mass transport properties in aqueous solution. None of the models based on a 12‐6 nonelectrostatic nonbonded potential was able to reproduce the experimental radial distribution function, solvation free energy, exchange barrier and diffusion constant. The models based on a 12‐6‐4 potential offered improvement, and one model in particular, in conjunction with the SPC/E water model, performed exceptionally well for all properties. The results reported here establish useful benchmark calculations for Mg2+ ion models that provide insight into the origin of the behavior in aqueous solution, and may aid in the development of next‐generation models that target specific binding sites in biomolecules. © 2015 Wiley Periodicals, Inc. 相似文献
46.
Radiofluorination of a Pre‐formed Gallium(III) Aza‐macrocyclic Complex: Towards Next‐Generation Positron Emission Tomography (PET) Imaging Agents 下载免费PDF全文
Dr. Rajiv Bhalla Prof. William Levason Dr. Sajinder K. Luthra Dr. Graeme McRobbie George Sanderson Prof. Gillian Reid 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4688-4694
As part of a study to investigate the factors influencing the development of new, more effective metal‐complex‐based positron emission tomography (PET) imaging agents, the distorted octahedral complex, [GaCl(L)]?2 H2O has been prepared by reaction of 1‐benzyl‐1,4,7‐triazacyclononane‐4,7‐dicarboxylic acid hydrochloride (H2L?HCl) with Ga(NO3)3?9 H2O, which is a convenient source of GaIII for reactions in water. Spectroscopic and crystallographic data for [GaCl(L)]?2 H2O are described, together with the crystal structure of [GaCl(L)]?MeCN. Fluorination of this complex by Cl?/F? exchange was achieved in high yield by treatment with KF in water at room temperature over 90 minutes, although the reaction was complete in approximately 30 minutes if heated to 80 °C, giving [GaF(L)]?2 H2O in good yield. The same complex was obtained by hydrothermal synthesis from GaF3?3 H2O and Li2L, and has been characterised by single‐crystal X‐ray analysis, IR, 1H and 19F{1H} NMR spectroscopy and ESI+ MS. Radiofluorination of the pre‐formed [GaCl(L)]?2 H2O has been demonstrated on a 210 nanomolar scale in aqueous NaOAc at pH 4 by using carrier‐free 18F?, leading to 60–70 % 18F‐incorporation after heating to 80 °C for 30 minutes. The resulting radioproduct was purified easily by using a solid‐phase extraction (SPE) cartridge, leading to 98–99 % radiochemical purity. The [Ga18F(L)] is stable for at least 90 minutes in 10 % EtOH/NaOAc solution at pH 6, but defluorinates over this time scale at pH of approximately 7.5 in phosphate buffered saline (PBS) or human serum albumin (HSA). The subtle role of the Group 13 metal ion and co‐ligand donor set in influencing the pH dependence of this system is discussed in the context of developing potential new imaging agents for PET. 相似文献
47.
Laser Machined Plastic Laminates: Towards Portable Diagnostic Devices for Use in Low Resource Environments 下载免费PDF全文
Jason C. Harper Bryan D. Carson George D. Bachand William D. Arndt Melissa R. Finley C. Jeffrey Brinker Thayne L. Edwards 《Electroanalysis》2015,27(11):2503-2512
Despite significant progress in development of bioanalytical devices cost, complexity, access to reagents and lack of infrastructure have prevented use of these technologies in resource‐limited regions. To provide a sustainable tool in the global effort to combat infectious diseases the diagnostic device must be low cost, simple to operate and read, robust, and have sensitivity and specificity comparable to laboratory analysis. In this mini‐review we describe recent work using laser machined plastic laminates to produce diagnostic devices that are capable of a wide variety of bioanalytical measurements and show great promise towards future use in low‐resource environments. 相似文献
48.
In Vivo Endoscopic Tissue Identification by Rapid Evaporative Ionization Mass Spectrometry (REIMS) 下载免费PDF全文
Dr. Julia Balog Dr. Sacheen Kumar James Alexander Ottmar Golf Dr. Juzheng Huang Tom Wiggins Nima Abbassi‐Ghadi Dr. Attila Enyedi Dr. Sandor Kacska James Kinross Prof. George B. Hanna Prof. Jeremy K. Nicholson Prof. Zoltan Takats 《Angewandte Chemie (International ed. in English)》2015,54(38):11059-11062
Gastrointestinal cancers are a leading cause of mortality, accounting for 23 % of cancer‐related deaths worldwide. In order to improve outcomes from these cancers, novel tissue characterization methods are needed to facilitate accurate diagnosis. Rapid evaporative ionization mass spectrometry (REIMS) is a technique developed for the in vivo classification of human tissue through mass spectrometric analysis of aerosols released during electrosurgical dissection. This ionization technique was further developed by utilizing surface induced dissociation and was integrated with an endoscopic polypectomy snare to allow in vivo analysis of the gastrointestinal tract. We tested the classification performance of this novel endoscopic REIMS method in vivo. It was shown to be capable of differentiating between healthy layers of the intestinal wall, cancer, and adenomatous polyps based on the REIMS fingerprint of each tissue type in vivo. 相似文献
49.
Dr. George N. Khairallah Dr. Alan T. Maccarone Dr. Huong T. Pham Timothy M. Benton Dr. Tony Ly Dr. Gabriel da Silva Prof. Stephen J. Blanksby Prof. Richard A. J. O'Hair 《Angewandte Chemie (International ed. in English)》2015,54(44):12947-12951
Although the deleterious effects of ozone on the human respiratory system are well‐known, many of the precise chemical mechanisms that both cause damage and afford protection in the pulmonary epithelial lining fluid are poorly understood. As a key first step to elucidating the intrinsic reactivity of ozone with proteins, its reactions with deprotonated cysteine [Cys?H]? are examined in the gas phase. Reaction proceeds at near the collision limit to give a rich set of products including 1) sequential oxygen atom abstraction reactions to yield cysteine sulfenate, sulfinate and sulfonate anions, and significantly 2) sulfenate radical anions formed by ejection of a hydroperoxy radical. The free‐radical pathway occurs only when both thiol and carboxylate moieties are available, implicating electron‐transfer as a key step in this reaction. This novel and facile reaction is also observed in small cys‐containing peptides indicating a possible role for this chemistry in protein ozonolysis. 相似文献
50.
Synthesis,Structure, and Properties of SrC(NH)3, a Nitrogen‐Based Carbonate Analogue with the Trinacria Motif 下载免费PDF全文
M. Sc. Ronja Missong M. Sc. Janine George Dr. Andreas Houben Dr. Markus Hoelzel Prof. Dr. Richard Dronskowski 《Angewandte Chemie (International ed. in English)》2015,54(41):12171-12175
Strontium guanidinate, SrC(NH)3, the first compound with a doubly deprotonated guanidine unit, was synthesized from strontium and guanidine in liquid ammonia and characterized by X‐ray and neutron diffraction, IR spectroscopy, and density‐functional theory including harmonic phonon calculations. The compound crystallizes in the hexagonal space group P63/m, constitutes the nitrogen analogue of strontium carbonate, SrCO3, and its structure follows a layered motif between Sr2+ ions and complex anions of the type C(NH)32?; the anions adopt the peculiar trinacria shape. A comparison of theoretical phonons with experimental IR bands as well as quantum‐chemical bonding analyses yield a first insight into bonding and packing of the formerly unknown anion in the crystal. 相似文献