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991.
Dr. Ross McLellan Maria A. Palacios Dr. Christine M. Beavers Dr. Simon J. Teat Dr. Stergios Piligkos Prof. Euan K. Brechin Dr. Scott J. Dalgarno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(7):2804-2812
Methylene‐bridged calix[4]arenes have emerged as extremely versatile ligand supports in the formation of new polymetallic clusters possessing fascinating magnetic properties. Metal ion binding rules established for this building block allow one to partially rationalise the complex assembly process. The ability to covalently link calix[4]arenes at the methylene bridge provides significantly improved control over the introduction of different metal centres to resulting cluster motifs. Clusters assembled from bis‐calix[4]arenes and transition metal ions or 3d‐4f combinations display characteristic features of the analogous calix[4]arene supported clusters, thereby demonstrating an enhanced and rational approach towards the targeted synthesis of complex and challenging structures. 相似文献
992.
Dr. Graeme J. Stasiuk Dr. Florencia Minuzzi Dr. Myra Sae‐Heng Charlotte Rivas Dr. Hans‐Paul Juretschke Dr. Lorenzo Piemonti Dr. Peter R. Allegrini Dr. Didier Laurent Andrew R. Duckworth Prof. Andrew Beeby Prof. Guy A. Rutter Prof. Nicholas J. Long 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5023-5033
Despite the contribution of changes in pancreatic β‐cell mass to the development of all forms of diabetes mellitus, few robust approaches currently exist to monitor these changes prospectively in vivo. Although magnetic‐resonance imaging (MRI) provides a potentially useful technique, targeting MRI‐active probes to the β cell has proved challenging. Zinc ions are highly concentrated in the secretory granule, but they are relatively less abundant in the exocrine pancreas and in other tissues. We have therefore developed functional dual‐modal probes based on transition‐metal chelates capable of binding zinc. The first of these, Gd ?1 , binds ZnII directly by means of an amidoquinoline moiety (AQA), thus causing a large ratiometric Stokes shift in the fluorescence from λem=410 to 500 nm with an increase in relaxivity from r1=4.2 up to 4.9 mM ?1 s?1. The probe is efficiently accumulated into secretory granules in β‐cell‐derived lines and isolated islets, but more poorly by non‐endocrine cells, and leads to a reduction in T1 in human islets. In vivo murine studies of Gd ?1 have shown accumulation of the probe in the pancreas with increased signal intensity over 140 minutes. 相似文献
993.
Dr. Geraldine Echue Prof. Guy C. Lloyd‐Jones Dr. Charl F. J. Faul 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5118-5128
A chiral perylene diimide building block has been prepared based on an amine derivative of the amino acid L ‐phenylalanine. Detailed studies were carried out into the self‐assembly behaviour of the material in solution and the solid state using UV/Vis, circular dichroism (CD) and fluorescence spectroscopy. For the charged building block BTPPP, the molecular chirality of the side chains is translated into the chiral supramolecular structure in the form of right‐handed helical aggregates in aqueous solution. Temperature‐dependent UV/Vis studies of BTPPP in aqueous solution showed that the self‐assembly behaviour of this dye can be well described by an isodesmic model in which aggregation occurs to generate short stacks in a reversible manner. Wide‐angle X‐ray diffraction studies (WXRD) revealed that this material self‐organises into aggregates with π–π stacking distances typical for π‐conjugated materials. TEM investigations revealed the formation of self‐assembled structures of low order and with no expression of chirality evident. Differential scanning calorimetry (DSC) and polarised optical microscopy (POM) were used to investigate the mesophase properties. Optical textures representative of columnar liquid–crystalline phases were observed for solvent‐annealed samples of BTPPP. The high solubility, tunable self‐assembly and chiral ordering of these materials demonstrate their potential as new molecular building blocks for use in the construction of chiro‐optical structures and devices. 相似文献
994.
Well‐Defined Palladium Nanoparticles Supported on Siliceous Mesocellular Foam as Heterogeneous Catalysts for the Oxidation of Water 下载免费PDF全文
Dr. Oscar Verho Dr. Torbjörn Åkermark Dr. Eric V. Johnston Karl P. J. Gustafson Dr. Cheuk‐W. Tai Henrik Svengren Dr. Markus D. Kärkäs Prof. Jan‐E. Bäckvall Prof. Björn Åkermark 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5909-5915
Herein, we describe the use of Pd nanoparticles immobilized on an amino‐functionalized siliceous mesocellular foam for the catalytic oxidation of H2O. The Pd nanocatalyst proved to be capable of mediating the four‐electron oxidation of H2O to O2, both chemically and photochemically. The Pd nanocatalyst is easy to prepare and shows high chemical stability, low leaching, and recyclability. Together with its promising catalytic activity, these features make the Pd nanocatalyst of potential interest for future sustainable solar‐fuel production. 相似文献
995.
Facile Interchange of 3d and 4f Ions in Single‐Molecule Magnets: Stepwise Assembly of [Mn4], [Mn3Ln] and [Mn2Ln2] Cages within Calix[4]arene Scaffolds 下载免费PDF全文
Dr. Maria A. Palacios Dr. Ross McLellan Dr. Christine M. Beavers Dr. Simon J. Teat Dr. Høgni Weihe Dr. Stergios Piligkos Dr. Scott J. Dalgarno Prof. Euan K. Brechin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11212-11218
The central MnII ions in a series of calix[4]arene‐stabilised butterflies can be sequentially replaced with LnIII ions, maintaining the structural integrity of the molecule but transforming its magnetic properties. The replacement of MnII for GdIII allows for the examination of the transferability of spin‐Hamiltonian parameters within the family as well as permitting their reliable determination. The introduction of the 4f ions results in weaker intramolecular magnetic exchange, an increase in the number of low‐lying excited states, and an increase in magnetisation relaxation, highlighting the importance of exchange over single‐ion anisotropy for the observation of SMM behaviour in this family of complexes. The presence of the [TMII/III(TBC[4])(OH)(solvent)] metalloligand (TM=transition metal, TBC=p‐tBu‐calix[4]arene) suggests that magnetic calix[n]arene building blocks can be employed to encapsulate a range of different “guests” within structurally robust “hosts”. 相似文献
996.
Bioorthogonal SERS Nanoprobes for Mulitplex Spectroscopic Detection,Tumor Cell Targeting,and Tissue Imaging 下载免费PDF全文
Junzhou Wu Duanwei Liang Qingqing Jin Dr. Jie Liu Prof. Dr. Meiling Zheng Prof. Dr. Xuanming Duan Prof. Dr. Xinjing Tang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(37):12914-12918
A surface‐enhanced Raman scattering (SERS) technique shows extraordinary features for a range of biological and biomedical applications. Herein, a series of novel bioorthogonal SERS nanoprobes were constructed with Gold nanoflower (AuNF) and Raman reporters, the signals of which were located in a Raman‐silent region of biological samples. AS1411 aptamer was also co‐conjugated with AuNF through a self‐assembled monolayer coverage strategy. Multiplex SERS imaging using these nanoprobes with three different bioorthogonal small‐molecule Raman reporters is successfully achieved with high multiplexing capacity in a biologically Raman‐silent region. These Raman nanoprobes co‐conjugated with AS1411 showed high affinity for tumor cells with overexpressed nucleolin and can be used for selective tumor cell screening and tissue imaging. 相似文献
997.
Dr. Maria A. Antunes Joana T. Coutinho Dr. Isabel C. Santos Dr. Joaquim Marçalo Prof. Manuel Almeida José J. Baldoví Dr. Laura C. J. Pereira Dr. Alejandro Gaita‐Ariño Prof. Eugenio Coronado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(49):17817-17826
A tetravalent uranium compound with a radical azobenzene ligand, namely, [{(SiMe2NPh)3‐tacn}UIV(η2‐N2Ph2.)] ( 2 ), was obtained by one‐electron reduction of azobenzene by the trivalent uranium compound [UIII{(SiMe2NPh)3‐tacn}] ( 1 ). Compound 2 was characterized by single‐crystal X‐ray diffraction and 1H NMR, IR, and UV/Vis/NIR spectroscopy. The magnetic properties of 2 and precursor 1 were studied by static magnetization and ac susceptibility measurements, which for the former revealed single‐molecule magnet behaviour for the first time in a mononuclear UIV compound, whereas trivalent uranium compound 1 does not exhibit slow relaxation of the magnetization at low temperatures. A first approximation to the magnetic behaviour of these compounds was attempted by combining an effective electrostatic model with a phenomenological approach using the full single‐ion Hamiltonian. 相似文献
998.
Sustainable Synthesis of Chiral Tetrahydrofurans through the Selective Dehydration of Pentoses 下载免费PDF全文
Robert W. Foster Dr. Christopher J. Tame Dr. Dejan‐Krešimir Bučar Prof. Helen C. Hailes Dr. Tom D. Sheppard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(45):15947-15950
L ‐Arabinose is an abundant resource available as a waste product of the sugar beet industry. Through use of a hydrazone‐based strategy, L ‐arabinose was selectively dehydrated to form a chiral tetrahydrofuran on a multi‐gram scale without the need for protecting groups. This approach was extended to other biomass‐derived reducing sugars and the mechanism of the key cyclization investigated. This methodology was applied to the synthesis of a range of functionalized chiral tetrahydrofurans, as well as a formal synthesis of 3R‐3‐hydroxymuscarine. 相似文献
999.
Remote Construction of Chiral Vicinal Tertiary and Quaternary Centers by Catalytic Asymmetric 1,6‐Conjugate Addition of Prochiral Carbon Nucleophiles to Cyclic Dienones 下载免费PDF全文
Yuan Wei Zunwu Liu Xinxin Wu Jie Fei Xiaodong Gu Xiaoqian Yuan Prof. Dr. Jinxing Ye 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(52):18921-18924
An unprecedented remote construction of chiral vicinal tertiary and quaternary centers by a catalytic asymmetric 1,6‐conjugate addition of prochiral carbon nucleophiles to cyclic dienones has been developed. Both 5H‐oxazol‐4‐ones and 2‐oxindoles were found to be very efficient carbon nucleophiles in this reaction at a remote position, giving products with excellent enantio‐ and diastereoselectivities (up to 99 % ee and >19:1 d.r. for 5H‐oxazol‐4‐ones and up to 97 % ee and >19:1 d.r. for 2‐oxindoles). 相似文献
1000.
Back Cover: Switch‐On Fluorescence of a Perylene‐Dye‐Functionalized Metal–Organic Framework through Postsynthetic Modification (Chem. Eur. J. 30/2015) 下载免费PDF全文