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131.
An Investigation of Photo‐ and Pressure‐Induced Effects in a Pair of Isostructural Two‐Dimensional Spin‐Crossover Framework Materials 下载免费PDF全文
Dr. Natasha F. Sciortino Dr. Suzanne M. Neville Dr. Cédric Desplanches Dr. Jean‐François Létard Dr. Victor Martinez Prof. José Antonio Real Dr. Boujemaa Moubaraki Prof. Keith S. Murray Prof. Cameron J. Kepert 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7448-7457
Two new isostructural iron(II) spin‐crossover (SCO) framework (SCOF) materials of the type [Fe(dpms)2(NCX)2] (dpms=4,4′‐dipyridylmethyl sulfide; X=S ( SCOF‐6(S) ), X=Se ( SCOF‐6(Se) )) have been synthesized. The 2D framework materials consist of undulating and interpenetrated rhomboid (4,4) nets. SCOF‐6(S) displays an incomplete SCO transition with only approximately 30 % conversion of high‐spin (HS) to low‐spin iron(II) sites over the temperature range 300–4 K (T1/2=75 K). In contrast, the NCSe? analogue, SCOF‐6(Se) , displays a complete SCO transition (T1/2=135 K). Photomagnetic characterizations reveal quantitative light‐ induced excited spin‐state trapping (LIESST) of metastable HS iron(II) sites at 10 K. The temperature at which the photoinduced stored information is erased is 58 and 50 K for SCOF‐6(S) and SCOF‐6(Se) , respectively. Variable‐pressure magnetic measurements were performed on SCOF‐6(S) , revealing that with increasing pressure both the T1/2 value and the extent of spin conversion are increased; with pressures exceeding 5.2 kbar a complete thermal transition is achieved. This study confirms that kinetic trapping effects are responsible for hindering a complete thermally induced spin transition in SCOF‐6(S) at ambient pressure due to an interplay between close T1/2 and T(LIESST) values. 相似文献
132.
133.
T. Terlier R. Tiron A. Gharbi X. Chevalier M. Veillerot E. Martinez J.‐P. Barnes 《Surface and interface analysis : SIA》2014,46(2):83-91
Directed self‐assembly of block copolymers (BCPs) is a promising candidate for next generation nanolithography. In order to validate a given pattern, the lateral and in‐depth distributions of the blocks should be well characterized; for the latter, time‐of‐flight (ToF) SIMS is a particularly well‐adapted technique. Here, we use an ION‐TOF ToF‐SIMS V in negative mode to provide qualitative information on the in‐depth organization of polystyrene‐b‐polymethylmethacrylate (PS‐b‐PMMA) BCP thin films. Using low‐energy Cs+ sputtering and Bi3+ as the analysis ions, PS and PMMA homopolymer films are first analyzed in order to identify the characteristic secondary ions for each block. PS‐b‐PMMA BCPs are then characterized showing that self‐assembled nanodomains are clearly observed after annealing. We also demonstrate that the ToF‐SIMS technique is able to distinguish between the different morphologies of BCP investigated in this work (lamellae, spheres or cylinders). ToF‐SIMS characterization on BCP is in good agreement with XPS analysis performed on the same samples. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
134.
135.
A. Madani S. Zeinoddini S. Varahmi H. Turnbull A. B. Phillion J. A. Olson D. M. Martinez 《Cellulose (London, England)》2014,21(3):2023-2031
A methodology for producing a low density cellulose-based foam has been developed by combining a surfactant with pulp, mixing at high velocity to entrain air, and then drying in a non-restrained fashion. The structure of the foam, characterized through optical microscopy and X-ray computed tomographic microscopy, consists of pulp fibres in random orientations surrounding air bubbles along with large void spaces. Through careful design of experiments, the effect of fibre type, length distribution, surfactant, and air content on the mechanical behavior and permeability of the foam material was investigated. The results indicate that foamed cellulose materials can be produced at a strength of one-half the tensile strength of a standard handsheet, but having a relative density of only one percent. No chemical additives were used to enhance the strength of these samples as the properties of the foam material are enhanced simply through variation of the process parameters. Thus, a strong cellulose-based foam, with a density as low as 10 mg/cm3, can be fabricated using standard papermaking infrastructure and hence at low cost. 相似文献
136.
Single‐Site Zeolite‐Anchored Organoiridium Carbonyl Complexes: Characterization of Structure and Reactivity by Spectroscopy and Computational Chemistry 下载免费PDF全文
Claudia Martinez‐Macias Dr. Mingyang Chen Prof. David A. Dixon Prof. Bruce C. Gates 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11825-11835
A family of HY zeolite‐supported cationic organoiridium carbonyl complexes was formed by reaction of Ir(CO)2(acac) (acac=acetylacetonate) to form supported Ir(CO)2 complexes, which were treated at 298 K and 1 atm with flowing gas‐phase reactants, including C2H4, H2, 12CO, 13CO, and D2O. Mass spectrometry was used to identify effluent gases, and infrared and X‐ray absorption spectroscopies were used to characterize the supported species, with the results bolstered by DFT calculations. Because the support is crystalline and presents a nearly uniform array of bonding sites for the iridium species, these were characterized by a high degree of uniformity, which allowed a precise determination of the species involved in the replacement, for example, of one CO ligand of each Ir(CO)2 complex with ethylene. The supported species include the following: Ir(CO)2, Ir(CO)(C2H4)2, Ir(CO)(C2H4), Ir(CO)(C2H5), and (tentatively) Ir(CO)(H). The data determine a reaction network involving all of these species. 相似文献
137.
Insights into the Complexity of Weak Intermolecular Interactions Interfering in Host–Guest Systems 下载免费PDF全文
Dawei Zhang Dr. Bastien Chatelet Eloisa Serrano Dr. Olivier Perraud Dr. Jean‐Pierre Dutasta Prof. Dr. Vincent Robert Prof. Dr. Alexandre Martinez 《Chemphyschem》2015,16(14):2931-2935
The recognition properties of heteroditopic hemicryptophane hosts towards anions, cations, and neutral pairs, combining both cation–π and anion–π interaction sites, were investigated to probe the complexity of interfering weak intermolecular interactions. It is suggested from NMR experiments, and supported by CASSCF/CASPT2 calculations, that the binding constants of anions can be modulated by a factor of up to 100 by varying the fluorination sites on the electron‐poor aromatic rings. Interestingly, this subtle chemical modification can also reverse the sign of cooperativity in ion‐pair recognition. Wavefunction calculations highlight how short‐ and long‐range interactions interfere in this recognition process, suggesting that a disruption of anion–π interactions can occur in the presence of a co‐bound cation. Such molecules can be viewed as prototypes for examining complex processes controlled by the competition of weak interactions. 相似文献
138.
Multitarget Drug Discovery for Alzheimer's Disease: Triazinones as BACE‐1 and GSK‐3β Inhibitors 下载免费PDF全文
Federica Prati Dr. Angela De Simone Dr. Paola Bisignano Dr. Andrea Armirotti Dr. Maria Summa Dr. Daniela Pizzirani Dr. Rita Scarpelli Dr. Daniel I. Perez Prof. Dr. Vincenza Andrisano Dr. Ana Perez‐Castillo Prof. Dr. Barbara Monti Francesca Massenzio Dr. Letizia Polito Prof. Dr. Marco Racchi Dr. Angelo D. Favia Dr. Giovanni Bottegoni Prof. Dr. Ana Martinez Prof. Dr. Maria Laura Bolognesi Prof. Dr. Andrea Cavalli 《Angewandte Chemie (International ed. in English)》2015,54(5):1578-1582
Cumulative evidence strongly supports that the amyloid and tau hypotheses are not mutually exclusive, but concomitantly contribute to neurodegeneration in Alzheimer′s disease (AD). Thus, the development of multitarget drugs which are involved in both pathways might represent a promising therapeutic strategy. Accordingly, reported here in is the discovery of 6‐amino‐4‐phenyl‐3,4‐dihydro‐1,3,5‐triazin‐2(1H)‐ones as the first class of molecules able to simultaneously modulate BACE‐1 and GSK‐3β. Notably, one triazinone showed well‐balanced in vitro potencies against the two enzymes (IC50 of (18.03±0.01) μM and (14.67±0.78) μM for BACE‐1 and GSK‐3β, respectively). In cell‐based assays, it displayed effective neuroprotective and neurogenic activities and no neurotoxicity. It also showed good brain permeability in a preliminary pharmacokinetic assessment in mice. Overall, triazinones might represent a promising starting point towards high quality lead compounds with an AD‐modifying potential. 相似文献
139.
Monitoring gene expression in vivo is essential to the advancement of biological studies, medical diagnostics, and drug discovery.
Adding to major efforts in developing molecular probes for mRNA monitoring, we have recently developed an alternative tool,
the hybrid molecular probe (HMP). To optimize the probe, a series of experiments were performed to study the properties of
HMP hybridization kinetics and stability. The results demonstrated the potential of the HMP as a prospective tool for use
in both hybridization studies and in vitro and in vivo analyses. The HMP has shown no tendency to produce false positive signals,
which is a major concern for living cell studies. Moreover, HMP has shown the ability to detect the mRNA expression of different
genes inside single cells from both basal and stimulated genes. As an effective alternative to conventional molecular probes,
the proven sensitivity, simplicity, and stability of HMPs show promise for their use in monitoring mRNA expression in living
cells.
Figure Hybrid molecular probe (HMP). HMPs consist of two single strands of DNA (green) and a polyethylene glycol (PEG, purple) linker that is used to tether these two sequences together. When a target (orange strand) containing the complementary sequences to both probes at adjacent positions is added, each strand binds to its corresponding
target sequence, thus bringing the two fluorophores into close proximity, which allows energy transfer to occur 相似文献
140.
This Letter generalizes the Kuczera’s theory of the vibrational canonical force field in order to obtain an unambiguous and uniquely defined expression for the anharmonic force field in terms of curvilinear internal coordinates. By using this generalization it has been shown mathematically that the canonical force constants could be transferred between molecules with the same geometrical structure. As illustration, the theory is used to obtain the expressions for the quadratic and cubic canonical force constants of the methane molecule. 相似文献