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101.
Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster 下载免费PDF全文
Dr. Salvador Cardona‐Serra Dr. Juan M. Clemente‐Juan Prof. Eugenio Coronado Dr. Alejandro Gaita‐Ariño Dr. Nicolas Suaud Dr. Ondrej Svoboda Dr. Roland Bastardis Prof. Nathalie Guihéry Dr. Juan J. Palacios 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):763-769
Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV14O40]8? (in short V14) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V14 system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure. 相似文献
102.
Micro‐/Nanostructured Multicomponent Molecular Materials: Design,Assembly, and Functionality 下载免费PDF全文
Prof. Dr. Dongpeng Yan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):4880-4896
Molecule‐based micro‐/nanomaterials have attracted considerable attention because their properties can vary greatly from the corresponding macro‐sized bulk systems. Recently, the construction of multicomponent molecular solids based on crystal engineering principles has emerged as a promising alternative way to develop micro‐/nanomaterials. Unlike single‐component materials, the resulting multicomponent systems offer the advantages of tunable composition, and adjustable molecular arrangement, and intermolecular interactions within their solid states. The study of these materials also supplies insight into how the crystal structure, molecular components, and micro‐/nanoscale effects can influence the performance of molecular materials. In this review, we describe recent advances and current directions in the assembly and applications of crystalline multicomponent micro‐/nanostructures. Firstly, the design strategies for multicomponent systems based on molecular recognition and crystal engineering principles are introduced. Attention is then focused on the methods of fabrication of low‐dimensional multicomponent micro‐/nanostructures. Their new applications are also outlined. Finally, we briefly discuss perspectives for the further development of these molecular crystalline micro‐/nanomaterials. 相似文献
103.
Green solvent approach for printable large deformation thermoplastic elastomer based piezoresistive sensors and their suitability for biomedical applications 下载免费PDF全文
Bruna F. Gonçalves Pedro Costa Juliana Oliveira Sylvie Ribeiro Vitor Correia Gabriela Botelho Senentxu Lanceros‐Mendez 《Journal of Polymer Science.Polymer Physics》2016,54(20):2092-2103
Composites based on biocompatible thermoplastic elastomer styrene‐ethylene/butylene‐styrene (SEBS) as matrix and multi‐walled carbon nanotubes (MWCNT) as nanofillers show excellent mechanical and piezoresistive properties from low to large deformations. The MWCNT/SEBS composites have been prepared following a green solvent approach, to extend their range of applicability to biomedical applications. The obtained composites with 2, 4, and 5 wt % MWCNT content provide suitable piezoresistive response up to 80% deformation with a piezoresistive sensibility near 2.7, depending on the applied strain and MWCNT content. Composite sensors were also developed by spray and screen printing and integrated with an electronic data acquisition system with RF communication. The possibility to accurately control the composites properties and performance by varying MWCNT content, viscosity, and mechanical properties of the polymer matrix, shows the large potential of the system for the development of large deformation printable piezoresistive sensors. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2092–2103 相似文献
104.
105.
Specific Design of Titanium(IV) Phenolato Chelates Yields Stable and Accessible,Effective and Selective Anticancer Agents 下载免费PDF全文
Sigalit Meker Dr. Ori Braitbard Dr. Matthew D. Hall Prof. Jacob Hochman Prof. Edit Y. Tshuva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):9986-9995
Octahedral titanium(IV) complexes of phenolato hexadentate ligands were developed and showed very high stability for days in water solutions. In vitro cytotoxicity studies showed that, whereas tetrakis(phenolato) systems are generally of low activity presumably due to inaccessibility, smaller bis(phenolato)bis(alkoxo) complexes feature high anticancer activity and accessibility even without formulations, also toward a cisplatin‐resistant cell line. An all‐aliphatic control complex was unstable and inactive. A leading phenolato complex also revealed: 1) high durability in fully aqueous solutions; accordingly, negligible loss of activity after preincubation for three days in medium or in serum; 2) maximal cellular accumulation and induction of apoptosis following 24–48 h of administration; 3) reduced impact on noncancerous fibroblast cells; 4) in vivo efficacy toward lymphoma cells in murine model; 5) high activity in NCI‐60 panel, with average GI50 of 4.6±2 μm . This newly developed family of TiIV complexes is thus of great potential for anticancer therapy. 相似文献
106.
Prediction of 195Pt NMR chemical shifts of dissolution products of H2[Pt(OH)6] in nitric acid solutions by DFT methods: how important are the counter‐ion effects? 下载免费PDF全文
Athanassios C. Tsipis Ioannis N. Karapetsas 《Magnetic resonance in chemistry : MRC》2016,54(8):656-664
195Pt NMR chemical shifts of octahedral Pt(IV) complexes with general formula [Pt(NO3)n(OH)6 ? n]2?, [Pt(NO3)n(OH2)6 ? n]4 ? n (n = 1–6), and [Pt(NO3)6 ? n ? m(OH)m(OH2)n]?2 + n ? m formed by dissolution of platinic acid, H2[Pt(OH)6], in aqueous nitric acid solutions are calculated employing density functional theory methods. Particularly, the gauge‐including atomic orbitals (GIAO)‐PBE0/segmented all‐electron relativistically contracted–zeroth‐order regular approximation (SARC–ZORA)(Pt) ∪ 6–31G(d,p)(E)/Polarizable Continuum Model computational protocol performs the best. Excellent second‐order polynomial plots of δcalcd(195Pt) versus δexptl(195Pt) chemical shifts and δcalcd(195Pt) versus the natural atomic charge QPt are obtained. Despite of neglecting relativistic and spin orbit effects the good agreement of the calculated δ 195Pt chemical shifts with experimental values is probably because of the fact that the contribution of relativistic and spin orbit effects to computed σiso 195Pt magnetic shielding of Pt(IV) coordination compounds is effectively cancelled in the computed δ 195Pt chemical shifts, because the relativistic corrections are expected to be similar in the complexes and the proper reference standard used. To probe the counter‐ion effects on the 195Pt NMR chemical shifts of the anionic [Pt(NO3)n(OH)6 ? n]2? and cationic [Pt(NO3)n(OH2)6 ? n]4 ? n (n = 0–3) complexes we calculated the 195Pt NMR chemical shifts of the neutral (PyH)2[Pt(NO3)n(OH)6 ? n] (n = 1–6; PyH = pyridinium cation, C5H5NH+) and [Pt(NO3)n(H2O)6 ? n](NO3)4 ? n (n = 0–3) complexes. Counter‐anion effects are very important for the accurate prediction of the 195Pt NMR chemical shifts of the cationic [Pt(NO3)n(OH2)6 ? n]4 ? n complexes, while counter‐cation effects are less important for the anionic [Pt(NO3)n(OH)6 ? n]2? complexes. The simple computational protocol is easily implemented even by synthetic chemists in platinum coordination chemistry that dispose limited software availability, or locally existing routines and knowhow. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
107.
Back Cover: Experimental and Theoretical Study of the Reactivity of Gold Nanoparticles Towards Benzimidazole‐2‐ylidene Ligands (Chem. Eur. J. 30/2016) 下载免费PDF全文
Dr. María Rodríguez‐Castillo Gustavo Lugo‐Preciado Dr. Danielle Laurencin Dr. Frederik Tielens Dr. Arie van der Lee Dr. Sébastien Clément Dr. Yannick Guari Dr. José M. López‐de‐Luzuriaga Dr. Miguel Monge Dr. Françoise Remacle Dr. Sébastien Richeter 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(30):10680-10680
108.
Hierarchical Analysis of Self‐Assembled PEGylated Hexaphenylalanine Photoluminescent Nanostructures 下载免费PDF全文
Dr. Carlo Diaferia Dr. Teresa Sibillano Dr. Nicole Balasco Dr. Cinzia Giannini Dr. Valentina Roviello Dr. Luigi Vitagliano Prof. Giancarlo Morelli Dr. Antonella Accardo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(46):16586-16597
Despite the growing literature about diphenylalanine‐based peptide materials, it still remains a challenge to delineate the theoretical insight into peptide nanostructure formation and the structural features that could permit materials with enhanced properties to be engineered. Herein, we report the synthesis of a novel peptide building block composed of six phenylalanine residues and eight PEG units, PEG8‐F6. This aromatic peptide self‐assembles in water in stable and well‐ordered nanostructures with optoelectronic properties. A variety of techniques, such as fluorescence, FTIR, CD, DLS, SEM, SAXS, and WAXS allowed us to correlate the photoluminescence properties of the self‐assembled nanostructures with the structural organization of the peptide building block at the micro‐ and nanoscale. Finally, a model of hexaphenylalanine in aqueous solution by molecular dynamics simulations is presented to suggest structural and energetic factors controlling the formation of nanostructures. 相似文献
109.
Thomas Wittmann Dr. Renée Siegel Nele Reimer Dr. Wolfgang Milius Prof. Dr. Norbert Stock Prof. Dr. Jürgen Senker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):314-323
The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g?1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D ‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking. 相似文献
110.
Single crystals of a new silicate carbonate, K2Ca[Si2O5](CO3), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6322) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P63/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO4) and the other of the high-temperature soda-like α-Na2CO3, Ca substituting for Na. The electro-neutral layer K2[Si2O5] (denoted K) as well as the layer Ca(CO3) (denoted S) may separately correspond to individual structures. In K2Ca[Si2O5](CO3) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability. 相似文献