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991.
992.
Dr. Mónica Arrate Dr. Aritz Durana Dr. Paula Lorenzo Prof. Dr. Ángel R. de Lera Prof. Dr. Rosana Álvarez Dr. José M. Aurrecoechea 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(41):13893-13900
Carbonyl‐tethered propargylic benzoates undergo intramolecular carbonylpropargylation upon treatment with Et2Zn in the presence of a catalytic amount of Pd0 with the formation of 2‐alkynylcyclopentanol products. A ligand/solvent effect on the cis/trans selectivity (referring to the relative positions of alkynyl and OH groups) of ring‐closure has been found. In a non‐coordinating solvent (benzene), increasing the electron‐donating ability of the phosphine ligand (while decreasing its dissociation ability) leads to an increased tendency towards the trans product. On the other hand, the combination of a coordinating solvent (THF) and PPh3, an easily dissociated phosphine, results in the exclusive formation of cis products. Experimental and computational results are compatible with a divergent behavior of an allenylethylpalladium intermediate that partitions between competitive carbonyl‐addition and transmetalation pathways, each leading to a different diastereoisomer. These results also suggest that the dissociating ability of the phosphine regulates that behavior. 相似文献
993.
Dr. Goutam Kumar Kole Dr. Abdul Malik Puthan Peedikakkal Belinda Mei Fang Toh Prof. Dr. Jagadese J. Vittal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(12):3962-3968
An attempt has been made to design double‐stranded ladder‐like coordination polymers (CPs) of hemidirected PbII. Four CPs, [Pb(μ‐bpe)(O2C‐C6H5)2] ? 2H2O ( 1 ), [Pb2(μ‐bpe)2(μ‐O2C‐C6H5)2(O2C‐C6H5)2] ( 2 ), [Pb2(μ‐bpe)2(μ‐O2C‐p‐Tol)2(O2C‐p‐Tol)2] ? 1.5 H2O ( 3 ) and [Pb2(μ‐bpe)2(μ‐O2C‐m‐Tol)2(O2C‐m‐Tol)2] ( 4 ) (bpe=1,2‐bis(4′‐pyridyl)ethylene), have been synthesised and investigated for their solid‐state photoreactivity. CPs 2 – 4 , having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one‐dimensional (1D) CP with guest water molecules aggregating to form a hydrogen‐bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid‐state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2 . In the construction of the double‐stranded ladder‐like structures, the parallel alignment of C?C bonds in 2 – 4 is dictated by the chelating and μ2‐η2:η1 bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double‐stranded ladder‐like structures has also been investigated. A single‐crystal‐to‐single‐crystal transformation occurred when 4 was irradiated under UV light to form [Pb2(rctt‐tpcb)(μ‐O2C‐m‐Tol)2(O2C‐m‐Tol)2] ( 5 ). 相似文献
994.
Shuwen Li Zhengping Dong Honglei Yang Shujing Guo Galian Gou Ren Ren Zhejun Zhu Prof. Jun Jin Jiantai Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(7):2384-2391
A new catalyst consisting of ionic liquid (IL)‐functionalized carbon nanotubes (CNTs) obtained through 1,3‐dipolar cycloaddition support‐enhanced electrocatalytic Pd nanoparticles (Pd@IL(Cl?)‐CNTs) was successfully fabricated and applied in direct ethanol alkaline fuel cells. The morphology, structure, component and stability of Pd@IL(Cl?)‐CNTs were systematic characterized by transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), Raman spectra, thermogravimetric analysis (TGA) and X‐ray diffraction (XRD). The new catalyst exhibited higher electrocatalytic activity, better tolerance and electrochemical stability than the Pd nanoparticles (NPs) immobilized on CNTs (Pd@CNTs), which was ascribed to the effects of the IL, larger electrochemically active surface area (ECSA), and greater processing performance. Cyclic voltammograms (CVs) at various scan rates illustrated that the oxidation behaviors of ethanol at all electrodes were controlled by diffusion processes. The investigation of the different counteranions demonstrated that the performance of the IL‐CNTs hybrid material was profoundly influenced by the subtly varied structures of the IL moiety. All the results indicated that the Pd@IL(Cl?)‐CNTs catalyst is an efficient anode catalyst, which has potential applications in direct ethanol fuel cells and the strategy of IL functionalization of CNTs could be available to prepare other carbonaceous carrier supports to enhance the dispersivity, stability, and catalytic performance of metal NPs as well. 相似文献
995.
Dr. Alessandro Barge Marina Caporaso Prof. Giancarlo Cravotto Dr. Katia Martina Dr. Paolo Tosco Prof. Silvio Aime Dr. Carla Carrera Dr. Eliana Gianolio Dr. Giorgio Pariani Dr. Davide Corpillo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(36):12086-12092
We report the synthesis and characterization of a water‐soluble, star‐shaped macromolecular platform consisting of eight β‐cyclodextrin (β‐CD) units anchored to the narrower rim of a γ‐CD core through bis(triazolyl)alkyl spacers. The efficient synthetic protocol is based on the microwave (MW)‐promoted Cu‐catalyzed 1,3‐dipolar cycloaddition of CD monoazides to CD monoacetylenes. The ligand‐hosting capability of the construct has been assessed by relaxometric titration and nuclear magnetic relaxation dispersion (NMRD) profiling, which showed it to be good, and this was supported by molecular dynamics simulations. To demonstrate the feasibility of obtaining supramolecular structures with high hosting ability, we designed a dimeric platform, formed by joining two nonamers through the γ‐CD cores through a bis(lithocholic acid) linker. With a view to the potential biological applications, cytotoxicity and extent of binding to human serum albumin were assessed. The properties of this dendrimeric multicarrier make it suitable for pharmaceutical and diagnostic purposes, ranging from targeted drug delivery to molecular imaging. 相似文献
996.
Rouzbeh Afrasiabi Prof. Dr. Heinz‐Bernhard Kraatz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1769-1777
An ultra‐short peptide Boc‐L ‐Phe‐L ‐Lys(Z)‐OMe (Z=carbobenzyloxy) was shown to act as a highly efficient and versatile low molecular weight gelator (LMWG) for a variety of aliphatic and aromatic solvents under sonication. Remarkably, this simple dipeptide is not only able to form coiled fibres but also demonstrates self‐healing and thermal chiroptical switching behaviour. The formation of coiled assemblies was found to be influenced by the nature of the solvent and the presence of an additive. By exploiting these properties it was possible to modulate the macroscopic and microscopic properties of the organogels of this ultra‐short peptide, allowing the formation of highly ordered single‐domain networks of helical fibres with dimeric or alternatively fibre‐bundle morphology. The organogels were characterized by using FTIR, SEM, NMR and circular dichroism (CD) spectroscopy. Interestingly, CD experiments showed that the organogels of Boc‐L ‐Phe‐L ‐Lys(Z)‐OMe in aromatic solvents exhibit thermal chiroptical switching. This behaviour was hypothesized to stem from changes in the morphology of the gel accompanied by conformational transformation of the gelling agent. The fact that such a small peptide can demonstrate hierarchical assemblies and the possibility of controlling the self‐association is rather intriguing. The self‐healing ability, chiroptical switching and more importantly the formation of helical assemblies by Boc‐L ‐Phe‐L ‐Lys(Z)‐OMe under sonication, make this dipeptide an interesting example of the self‐assembly ability of ultra‐short peptides. 相似文献
997.
Dr. Chih‐Kai Liang Dr. Galina V. Dubacheva Dr. Thierry Buffeteau Dr. Dominique Cavagnat Dr. Philippe Hapiot Dr. Bruno Fabre Prof. James H. R. Tucker Dr. Dario M. Bassani 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(38):12748-12758
The synthesis of an anthracene‐bearing photoactive barbituric acid receptor and its subsequent grafting onto azide‐terminated alkanethiol/Au self‐assembled monolayers by using an CuI‐catalyzed azide–alkyne reaction is reported. Monolayer characterization using contact‐angle measurements, electrochemistry, and spectroscopic ellipsometry indicate that the monolayer conversion is fast and complete. Irradiation of the receptor leads to photodimerization of the anthracenes, which induces the open‐to‐closed gating of the receptor by blocking access to the binding site. The process is thermally reversible, and polarization‐modulated IR reflection–absorption spectroscopy indicates that photochemical closure and thermal opening of the surface‐bound receptors occur in 70 and 100 % conversion, respectively. Affinity of the open and closed surface‐bound receptor was characterized by using force spectroscopy with a barbituric‐acid‐modified atomic force microscope tip. 相似文献
998.
Dr. Laia Vilà‐Nadal Dr. Scott G. Mitchell Dr. Stanislav Markov Dr. Christoph Busche Dr. Vihar Georgiev Prof. Asen Asenov Prof. Leroy Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16502-16511
We explore the concept that the incorporation of polyoxometalates (POMs) into complementary metal oxide semiconductor (CMOS) technologies could offer a fundamentally better way to design and engineer new types of data storage devices, due to the enhanced electronic complementarity with SiO2, high redox potentials, and multiple redox states accessible to polyoxometalate clusters. To explore this we constructed a custom‐built simulation domain bridge. Connecting DFT, for the quantum mechanical modelling part, and mesoscopic device modelling, confirms the theoretical basis for the proposed advantages of POMs in non‐volatile molecular memories (NVMM) or flash‐RAM. 相似文献
999.
Dr. Nicolas Menard Prof. Dr. Olivia Reinaud Dr. Benoit Colasson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(2):642-653
A biomimetic strategy for the monofunctionalization of a calix[6]arene core is described. It is based on host–guest chemistry (mimicking the Michaelis–Menten adduct in enzymes) and allows the finely tuned pre‐organization of the substrate (an alkyne) with respect to the reactant (three azido groups introduced at the calixarene large rim). It is shown that the thermal Huisgen reaction implemented in this work proceeds under very mild conditions with total regioselectivity of the cycloaddition process. The scope of the reaction was explored and the results suggest that such a supramolecular strategy is quite versatile and could be applied to the selective functionalization of other cavitands bearing different recognition patterns. A detailed structural, thermodynamic, and kinetic study is also reported, highlighting interesting biomimetic features: The importance of the host–guest adduct strength, the high sensitivity of the reaction to the pre‐organization of the reactive partners (alkyne vs. azide), and a significant impact of the embedment on the transition state. The self‐coordination of the monofunctionalized products was also studied and an “endo/exo” switch of the internal side‐chain could be triggered by adding competitive ligands. 相似文献
1000.
Dr. Rubén D. Costa Dr. Juan Aragó Prof. Dr. Enrique Ortí Dr. Ted M. Pappenfus Prof. Dr. Kent R. Mann Dr. Katarzyna Matczyszyn Prof. Dr. Marek Samoc Dr. José L. Zafra Prof. Dr. Juan T. López Navarrete Prof. Dr. Juan Casado 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(4):1476-1488
The linear and non‐linear optical properties of a family of dumbbell‐shaped dinuclear complexes, in which an oligothiophene chain with various numbers of rings (1, 3, and 6) acts as a bridge between two homoleptic tris(2,2′‐bipyridine)ruthenium(II) complexes, have been fully investigated by using a range of spectroscopic techniques (absorption and luminescence, transient absorption, Raman, and non‐linear absorption), together with density functional theory calculations. Our results shed light on the impact of the synergistic collaboration between the electronic structures of the two chemical moieties on the optical properties of these materials. Experiments on the linear optical properties of these compounds indicated that the length of the oligothiophene bridge was critical for luminescent behavior. Indeed, no emission was detected for compounds with long oligothiophene bridges (compounds 3 and 4 , with 3 and 6 thiophene rings, respectively), owing to the presence of the 3π? π* state of the conjugated bridge below the 3MLCT‐emitting states of the end‐capping RuII complexes. In contrast, the compound with the shortest bridge ( 2 , one thiophene ring) shows excellent photophysical features. Non‐linear optical experiments showed that the investigated compounds were strong non‐linear absorbers in wide energy ranges. Indeed, their non‐linear absorption was augmented upon increasing the length of the oligothiophene bridge. In particular, the compound with the longest oligothiophene bridge not only showed strong two‐photon absorption (TPA) but also noteworthy three‐photon‐absorption behavior, with a cross‐section value of 4×10?78 cm6 s2 at 1450 nm. This characteristic was complemented by the strong excited‐state absorption (ESA) that was observed for compounds 3 and 4 . As a matter of fact, the overlap between the non‐linear absorption and ESA establishes compounds 3 and 4 as good candidates for optical‐power‐limiting applications. 相似文献