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排序方式: 共有282条查询结果,搜索用时 31 毫秒
81.
Two novel supramolecular architectures, [[Ag(2)L(1)(2)][X](2)] with X = CF(3)SO(3)(-) (2a) or X = NO(3)(-) (2b) and [[AgL(1)(2)][X]](n) with X = BF(4)(-) (3), were constructed by self-assembly and obtained in quantitative yields, using AgX as a building block and L(1) as the bridging ligand (L(1) = 1,3-bis(benzimidazol-1-ylmethyl)benzene). The X-ray molecular structures of 2a and 3 are reported. Complex 2a was identified as a metallomacrocycle in which one ligating triflate anion is coordinated to each of the two unsaturated Ag(I) ions. 2a crystallizes in monoclinic unit cell P2(1)/n with a = 9.728(6) A, b = 17.303(4) A, c = 13.268(3) A, beta = 92.52(4) degrees, V = 2231(2) A(3), and Z = 2. Remarkably, the X-ray structure of 2a shows a layered network structure consisting of infinite metallomacrocycles held together through pi-pi interactions between benzimidazole rings. In dramatic contrast, the product 3 prepared from AgBF(4) and L(1) lacks metal-counterion bonding, leading to a supramolecular 3D network with the following three outstanding features: (i) in one dimension, metallomacrocycles containing two Ag centers and two bridging ligands form infinite, double-stranded chains; (ii) neighboring chains are arranged by two distinct pi-pi interactions, one between substituted benzene rings and the other between benzimidazole rings, leading to a 3D structure; (iii) cavities within the 3D network contain BF(4)(-) counteranions. 3 crystallizes in monoclinic unit cell C2/c with a = 25.33(3) A, b = 11.655(6) A, c = 18.466(8) A, beta = 123.00(8) degrees, V = 4572(8) A(3), and Z = 4. Interestingly, electrospray mass spectroscopy suggests in either case that the identified elemental subunit [AgL(1)(2)](+) is the key building block which self-assembles and subsequent anion templation provides either the macrocycles 2a, b or the inorganic polymer 3. Remarkably, in dichloromethane solvent ligand-to-metal stoichiometries of 2:1 in 3 and 1:1 in 2a, b are obtained even with excess ligand, showing the power of metal-anion interactions in determining the overall supramolecular structure. Anion metathesis, showing supramolecular structural rearrangements from 2a to 2b and more spectacularly from 3 to 2b, smoothly occurred. The crucial effect and the nature of coordinating counteranions (BF(4)(-), CF(3)SO(3)(-), NO(3)(-)) on the supermolecule design are presented and discussed. 相似文献
82.
Kuligowski C Bezzenine-Lafollée S Chaume G Mahuteau J Barrière JC Bacqué E Pancrazi A Ardisson J 《The Journal of organic chemistry》2002,67(13):4565-4568
Synthesis of the lactone core 17 of 8-epi-griseoviridin is reported. Thioethynyl derivative 11 was easily prepared via an anionic coupling reaction between acetylenic compound 9 and sulfone 10. After desilylation of 11, saponification of the resulting hydroxy ester 12 followed by a Mitsunobu macrolactonization furnished the unusual triple-bond-containing nine-membered lactone 13 in 50% yield for the last two steps (39% after recrystallization). Stannylation under Magriotis conditions led to the pure regio- and stereocontrolled vinyltin 14 (80% yield). After a Sn/I exchange, palladium-catalyzed carbonylation delivered either the ester lactone 16 in 67% yield or the propargyl amide 17 in 65% yield. Synthesis of propargyl amide 17 of the lactone core of 8-epi-griseoviridin was achieved in 11.9% overall yield from commercial L-cystin dimethyl ester (nine steps). 相似文献
83.
Bustelo E Guérot C Hercouet A Carboni B Toupet L Dixneuf PH 《Journal of the American Chemical Society》2005,127(33):11582-11583
The regioselective head-to-head [2 + 2] cyclodimerization of allenyl boronate catalyzed by the ruthenium catalyst [Cp*RuCl(COD)] leads to a novel diboronated 1,3-dimethylenecyclobutane. Consecutive palladium-catalyzed C-C couplings open a route to novel disubstituted 1,3-dimethylenecyclobutane species. The X-ray crystalline structure of the phenyl-substituted 1,3-dimethylenecyclobutane is provided. 相似文献
84.
Paul M. Forster Andrea R. Burbank Melanie C. O'Sullivan Nathalie Guillou Carine Livage Grard Frey Norbert Stock Anthony K. Cheetham 《Solid State Sciences》2005,7(12):1549
A new form of cobalt succinate has been discovered using high-throughput methods and its structure was solved by single crystal X-ray diffraction. Co7(C4H4O4)4(OH)6(H2O)37H2O crystallizes in the monoclinic space group P21/c with cell parameters: a=7.888(2) Å, b=19.082(6) Å, c=23.630(7) Å, β=91.700(5)°, V=3555(2) Å3, R1=0.0469. This complex structure, containing 55 crystallographically distinct non-hydrogen atoms, is compared to the previously reported nickel phase, characterized using ab initio structure solution from synchrotron powder diffraction data. 相似文献
85.
Berrier E Zoller C Beclin F Turrell S Bouazaoui M Capoen B 《The journal of physical chemistry. B》2005,109(48):22799-22807
Silica xerogels were synthesized and annealed at 1000 degrees C for different durations to yield stable silica materials. The samples were prepared through base-catalyzed hydrolysis and condensation of tetramethyl orthosilicate in methanol. After aging and drying steps, clear and solid xerogels exhibiting a narrow pore size distribution were achieved. The annealing treatment of these xerogels was performed at 1000 degrees C and proved in the present study to lead to a monolithic glass when a progressive heat-treatment procedure was employed to attain 1000 degrees C. In addition to the expected glass, silica foams and ordered phases were observed when the samples were instantaneously heat-treated at 1000 degrees C. Raman spectra of the foamed materials exhibit the classical features of amorphous silica, whereas transmission electronic microscopy pictures reveal the presence of crystallized domains within the vitreous matrix. These crystallites are prone to nucleation and growth processes, which jeopardize the believed stability of the silica foam. The assessment of the hydroxyl content by IR spectroscopy reveals the role played by the latter polycondensation of silanols. The occurrence of foaming process was thus found to result from two competitive phenomena occurring at 1000 degrees C: evacuation of water-related species and viscous sintering. 相似文献
86.
Audrey Cassen Yann Gloaguen Laure Vendier Carine Duhayon Amalia Poblador‐Bahamonde Christophe Raynaud Eric Clot Gilles Alcaraz Sylviane Sabo‐Etienne 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(29):7699-7703
Tuning the nature of the linker in a L∼BHR phosphinoborane compound led to the isolation of a ruthenium complex stabilized by two adjacent, δ‐C H and ε‐Bsp2 H, agostic interactions. Such a unique coordination mode stabilizes a 14‐electron “RuH2P2” fragment through connected σ‐bonds of different polarity, and affords selective B H, C H, and B C bond activation as illustrated by reactivity studies with H2 and boranes. 相似文献
87.
A Remarkable Solvent Effect on the Nuclearity of Neutral Titanium(IV)‐Based Helicate Assemblies 下载免费PDF全文
David Michael Weekes Carine Diebold Dr. Pierre Mobian Dr. Clarisse Huguenard Dr. Lionel Allouche Prof. Marc Henry 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):5092-5101
The spontaneous self‐assembly of a neutral circular trinuclear TiIV‐based helicate is described through the reaction of titanium(IV) isopropoxide with a rationally designed tetraphenolic ligand. The trimeric ring helicate was obtained after diffusion of n‐pentane into a solution with dichloromethane. The circular helicate has been characterized by using single‐crystal X‐ray diffraction study, 13C CP‐MAS NMR and 1H NMR DOSY solution spectroscopic, and positive electrospray ionization mass‐spectrometric analysis. These analytical data were compared with those obtained from a previously reported double‐stranded helicate that crystallizes in toluene. The trimeric ring was unstable in a pure solution with dichloromethane and transformed into the double‐stranded helicate. Thermodynamic analysis by means of the PACHA software revealed that formation of the double‐stranded helicates was characterized by ΔH(toluene)=?30 kJ mol?1 and ΔS(toluene)=+357 J K?1 mol?1, whereas these values were ΔH(CH2Cl2)=?75 kJ mol?1 and ΔS(CH2Cl2)=?37 J K?1 mol?1 for the ring helicate. The transformation of the ring helicate into the double‐stranded helicate was a strongly endothermic process characterized by ΔH(CH2Cl2)=+127 kJ mol?1 and ΔH(n‐pentane)=+644 kJ mol?1 associated with a large positive entropy change ΔS=+1115 J K?1?mol?1. Consequently, the instability of the ring helicate in pure dichloromethane was attributed to the rather high dielectric constant and dipole moment of dichloromethane relative to n‐pentane. Suggestions for increasing the stability of the ring helicate are given. 相似文献
88.
89.
Eric Clement Anke Lindner Carine Douarche Harold Auradou 《The European physical journal. Special topics》2016,225(11-12):2389-2406
Fluids laden with motile bacteria enter in the category of active matter, a new field currently developing at the convergence of biology, hydrodynamics and statistical physics. Such suspensions were shown recently to exhibit singular macroscopic transport properties. In this paper we review some recent results, either theoretical or experimental, on the active fluid rheology. We focus principally on bacteria suspensions and the objective is to provide the basis for understanding the emergence of the singular constitutive relations characterizing the macroscopic transport properties of such an active fluid under flow. 相似文献
90.
Fürstner A Nevado C Waser M Tremblay M Chevrier C Teplý F Aïssa C Moulin E Müller O 《Journal of the American Chemical Society》2007,129(29):9150-9161
A concise and convergent total synthesis of the highly cytotoxic marine natural products iejimalide A-D (1-4) is reported, which relies on an effective ring-closing metathesis (RCM) reaction of a cyclization precursor containing no less than 10 double bonds. Because of the exceptional sensitivity of this polyunsaturated intermediate and its immediate precursors toward acid, base, and even gentle warming, the assembly process hinged upon the judicious choice of protecting groups and the careful optimization of all individual transformations. As a consequence, particularly mild protocols for Stille as well as Suzuki reactions of elaborate coupling partners have been developed that hold considerable promise for applications in other complex settings. Moreover, a series of non-natural "iejimalide-like" compounds has been prepared, differing from the natural lead in the polar head groups linked to the macrolide's N-terminus. With the aid of these compounds it was possible to uncover the hitherto unknown effect of iejimalide and analogues on the actin cytoskeleton. Their capacity to depolymerize this microfilament network rivals that of the latrunculins which constitute the standard in the field. Structural modifications of the peptidic terminus in 2 are thereby well accommodated, without compromising the biological effects. The iejimalides hence constitute an important new class of probe molecules for chemical biology in addition to their role as promising lead structures for the development of novel anticancer agents. 相似文献