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101.
The particle-swarm optimization method has been used to predict the stable high pressure structures up to 300 GPa of hydrogen-rich group 17 chlorine (HnCl, n = 2–7) compounds. In comparison to the group 1 and 2 hydrides, the structural modification associated with increasing pressure and hydrogen concentration is much less dramatic. The polymeric HCl chains already present in the low temperature phase under ambient pressure persist in all the high pressure structures. No transfer of electrons from the chlorine atoms into the interstitial sites is found. This indicates the chemical bonding at high pressure in group 17 elements is fundamentally different from the alkali and alkaline elements. It is found that almost perfectly triangular H3
+ ions can be stabilized in the crystalline structure of H5Cl. 相似文献
102.
Arumugam Thangavel Marika Wieliczko Christopher Scarborough Birger Dittrich John Bacsa 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(11):936-943
In the crystal structure of the title homoleptic CrII complex, [Cr(CH3CN)6](C24H20B)2·CH3CN, the [Cr(CH3CN)6]2+ cation is a high‐spin d4 complex with strong static, rather than dynamic, Jahn–Teller distortion. The electron density of the cation was determined by single‐crystal X‐ray refinements using aspherical structure factors from wavefunction calculations. The detailed picture of the electronic density allowed us to assess the extent and directionality of the Jahn–Teller distortion of the CrII cation away from idealized octahedral symmetry. The topological analysis of the aspherical d‐electron density about the CrII cation showed that there are significant valence charge concentrations along the axial Cr—N axes. Likewise, there were significant valence charge depletions about the CrII cation along the equatorial Cr—N bonds. These charge concentrations are in accordance with a Jahn–Teller‐distorted six‐coordinate complex. 相似文献
103.
Alexander Stephenson-Brown Aaron L. Acton Jon A. Preece John S. Fossey Paula M. Mendes 《Chemical science》2015,6(9):5114-5119
Many glycoproteins are intimately linked to the onset and progression of numerous heritable or acquired diseases of humans, including cancer. Indeed the recognition of specific glycoproteins remains a significant challenge in analytical method and diagnostic development. Herein, a hierarchical bottom-up route exploiting reversible covalent interactions with boronic acids and so-called click chemistry for the fabrication of glycoprotein selective surfaces that surmount current antibody constraints is described. The self-assembled and imprinted surfaces, containing specific glycoprotein molecular recognition nanocavities, confer high binding affinities, nanomolar sensitivity, exceptional glycoprotein specificity and selectivity with as high as 30 fold selectivity for prostate specific antigen (PSA) over other glycoproteins. This synthetic, robust and highly selective recognition platform can be used in complex biological media and be recycled multiple times with no performance decrement. 相似文献
104.
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106.
A far-red emitting probe for unambiguous detection of mobile zinc in acidic vesicles and deep tissue
Pablo Rivera-Fuentes Alexandra T. Wrobel Melissa L. Zastrow Mustafa Khan John Georgiou Thomas T. Luyben John C. Roder Kenichi Okamoto Stephen J. Lippard 《Chemical science》2015,6(3):1944-1948
Imaging mobile zinc in acidic environments remains challenging because most small-molecule optical probes display pH-dependent fluorescence. Here we report a reaction-based sensor that detects mobile zinc unambiguously at low pH. The sensor responds reversibly and with a large dynamic range to exogenously applied Zn2+ in lysosomes of HeLa cells, endogenous Zn2+ in insulin granules of MIN6 cells, and zinc-rich mossy fiber boutons in hippocampal tissue from mice. This long-wavelength probe is compatible with the green-fluorescent protein, enabling multicolor imaging, and facilitates visualization of mossy fiber boutons at depths of >100 μm, as demonstrated by studies in live tissue employing two-photon microscopy. 相似文献
107.
Frank W. Lewis Laurence M. Harwood Michael J. Hudson Andreas Geist Valery N. Kozhevnikov Petr Distler Jan John 《Chemical science》2015,6(8):4812-4821
We report the first examples of hydrophilic 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) ligands, and their applications as actinide(iii) selective aqueous complexing agents. The combination of a hydrophobic diamide ligand in the organic phase and a hydrophilic tetrasulfonated bis-triazine ligand in the aqueous phase is able to separate Am(iii) from Eu(iii) by selective Am(iii) complex formation across a range of nitric acid concentrations with very high selectivities, and without the use of buffers. In contrast, disulfonated bis-triazine ligands are unable to separate Am(iii) from Eu(iii) in this system. The greater ability of the tetrasulfonated ligands to retain Am(iii) selectively in the aqueous phase than the corresponding disulfonated ligands appears to be due to the higher aqueous solubilities of the complexes of the tetrasulfonated ligands with Am(iii). The selectivities for Am(iii) complexation observed with hydrophilic tetrasulfonated bis-triazine ligands are in many cases far higher than those found with the polyaminocarboxylate ligands previously used as actinide-selective complexing agents, and are comparable to those found with the parent hydrophobic bis-triazine ligands. Thus we demonstrate a feasible alternative method to separate actinides from lanthanides than the widely studied approach of selective actinide extraction with hydrophobic bis-1,2,4-triazine ligands such as CyMe4-BTBP and CyMe4-BTPhen. 相似文献
108.
Julie M. Herniman Peter R. Worsley Rachel Greenhill Dan L. Bader G. John Langley 《Journal of separation science》2022,45(2):542-550
Liquid chromatography-mass spectrometry methods were required to afford the rapid separation and detection of purines and small organic acids. These compounds are found in sweat and sebum and are potential biomarkers for the early detection of pressures sores. Two ultra-high-performance supercritical fluid chromatography-mass spectrometry assays have been successfully developed for both classes of compounds. Separation for purines was achieved using a gradient of supercritical carbon dioxide and methanol with a 1-aminoanthracene sub 2 μm particle size column followed by positive ion electrospray ionization. Separation for organic acids was achieved using a gradient of supercritical carbon dioxide and methanol (50 mM ammonium acetate 2% water) with a Diol sub 2 μm particle size column followed by negative ion electrospray ionization. Calibration curves were created in the absence of internal standards and R2 values > 0.96 were achieved using single ion monitoring methods for the protonated purines and the deprotonated acids. The two new assays afford rapid analytical methods for the separation and detection of potential biomarkers in human sweat leading to the early detection and prevention of pressure sores. 相似文献
109.
Green chemistry (GC) metrics provide insight into the relative waste, time and cost implications of pharmaceutical chemical processes and serve to guide scientists in the strategic application of resources to develop more efficient and sustainable processes. Examples of the application of GC metrics in evaluating pharmaceutical process efficiency and the subsequent development toward improvement exist in abundance from journals such as Organic Process Research and Development, Green Chemistry, or as encompassed by the winning examples from the ACS GCI Pharmaceutical Roundtable's [1] Peter J. Dunn award [2] or the US EPA's Green Chemistry Challenge award [3]. By their nature, GC metrics are continuously evolving but justify the necessary, unceasing investment in understanding and application as they offer unique, opportunistic insight serving to guide scientific resource deployment when developing greener pharmaceutical, chemical processes. 相似文献
110.
Lithium‐ion (Li‐ion) cells have gained considerable attention in recent years as a power source for various applications owing to their high voltage, high energy density, low self‐discharge, and excellent cycle life. Polymeric materials play a pivotal role in the processing, performance, and safety of Li‐ion cells. The polymeric materials used in Li‐ion cells include: binder for electrode processing, separator, electrolyte, and electrode active material. Active research is being pursued in all of these areas to improve the energy density, power density, cycle life, and safety of Li‐ion cells. This review article gives an overview of the various polymeric materials used in Li‐ion cells and the recent advances in these materials. Copyright © 2017 John Wiley & Sons, Ltd. 相似文献