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91.
Cameron Jones 《Coordination chemistry reviews》2010,254(11-12):1273-1289
This article summarizes the development of a new class of very bulky guanidinate ligands. These have been used to prepare unprecedented examples of heterocycles containing groups 2, 13, 14 or 15 elements in the +1 oxidation state. The ligands have also been harnessed in the preparation of the only examples of guanidinato, and/or closely related amidinato, complexes of iron(I), cobalt(I) and planar four-coordinate lanthanide(II) metals. Preliminary studies of the further chemistry of these very reactive complexes are also reviewed. Throughout, the tendency of the bulky guanidinate ligands to exhibit ligating and stabilizing properties more akin to those of bulky β-diketiminate ligands than less bulky amidinates or guanidinates, will be discussed. 相似文献
92.
Jarrod J. M. Amoore Dr. Suzanne M. Neville Dr. Boujemaa Moubaraki Dr. Simon S. Iremonger Dr. Keith S. Murray Prof. Jean‐François Létard Dr. Cameron J. Kepert Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(6):1973-1982
We previously reported the dinuclear material [FeII2(ddpp)2(NCS)4] ? 4 CH2Cl2 ( 1? 4 CH2Cl2; ddpp=2,5‐di(2′,2′′‐dipyridylamino)pyridine) and its partially desolvated analogue ( 1? CH2Cl2), which undergo two‐ and one‐step spin‐crossover (SCO) transitions, respectively. Here, we manipulate the type and degree of solvation in this system and find that either a one‐ or two‐step spin transition can be specifically targeted. The chloroform clathrate 1? 4 CHCl3 undergoes a relatively abrupt one‐step SCO, in which the two equivalent FeII sites within the dinuclear molecule crossover simultaneously. Partial desolvation of 1? 4 CHCl3 to form 1? 3 CHCl3 and 1? CHCl3 occurs through single‐crystal‐to‐single‐crystal processes (monoclinic C2/c to P21/n to P21/n) in which the two equivalent FeII sites become inequivalent sites within the dinuclear molecule of each phase. Both 1? 3 CHCl3 and 1? CHCl3 undergo one‐step spin transitions, with the former having a significantly higher SCO temperature than 1? 4 CHCl3 and the latter, and each has a broader SCO transition than 1? 4 CHCl3, attributable to the overlap of two SCO steps in each case. Further magnetic manipulation can be carried out on these materials through reversibly resolvating the partially desolvated material with chloroform to produce the original one‐step SCO, or with dichloromethane to produce a two‐step SCO reminiscent of that seen for 1? 4 CH2Cl2. Furthermore, we investigate the light‐induced excited spin state trapping (LIESST) effect on 1? 4 CH2Cl2 and 1? CH2Cl2 and observe partial LIESST activity for the former and no activity for the latter. 相似文献
93.
94.
Biuret is an intermediate in the bacterial metabolism of s-triazine ring compounds and is occasionally used as a ruminant feed supplement. We used bioinformatics to identify a biuret hydrolase, an enzyme that has previously resisted efforts to stabilize, purify and characterize. This newly discovered enzyme is a member of the cysteine hydrolase superfamily, a family of enzymes previously not found to be involved in s-triazine metabolism. The gene from Rhizobium leguminosarum bv. viciae strain 3841 encoding biuret hydrolase was synthesized, transformed into Escherichia coli, and expressed. The enzyme was purified and found to be stable. Biuret hydrolase catalyzed the hydrolysis of biuret to allophanate and ammonia. The k(cat)/K(M) of 1.7 × 10(5) M(-1)s(-1) and the relatively low K(M) of 23 ± 4 μM together suggested that this enzyme acts uniquely on biuret physiologically. This is supported by the fact that of the 34 substrate analogs of biuret tested, only two demonstrated reactivity, both at less than 5% of the rate determined for biuret. Biuret hydrolase does not react with carboxybiuret, the product of the enzyme immediately preceding biuret hydrolase in the metabolic pathway for cyanuric acid. This suggests an unusual metabolic strategy of an enzymatically-produced intermediate undergoing non-enzymatic decarboxylation to produce the substrate for the next enzyme in the pathway. 相似文献
95.
Peter C. Junk Cameron J. Kepert Lioubov I. Semenova Brian W. Skelton Allan H. White 《无机化学与普通化学杂志》2006,632(7):1293-1302
A number of salts of 2,2′:6′,2″ ‐terpyridyl (‘tpy’) with univalent anions (halides : X = Cl, Br, I; oxyanions of increasing basicity: ClO4, NO3, ‘tfa’ = trifluoroacetate, ‘tca’ = trichloroacetate), variously solvated, have been structurally characterized by single crystal X‐ray studies. In all cases the tpy moieties are found to be doubly protonated [tpyH2]2+, the hydrogen atoms being associated with the nitrogen atoms of the peripheral rings, these together with the central nitrogen atom being directed towards a common focus, in most cases ‘chelating’ one of the counter‐ion components in diverse ways. Thus the chloride and bromide compounds are isomorphous [(tpyH2)X]+X−·H2O arrays; a second dihydrate phase is also described for the chloride, the two forms having the unchelated anion and water molecules engaged in hydrogen‐bonded networks essentially independent of [(tpyH2)X]+. The iodide is anhydrous, and of a different structural type, the anions, presumably too large for chelation, lying out of plane to either side, and linking different cations into a one‐dimensional polymer; in the perchlorate, the unsolvated aggregate is now discrete [(tpyH2)X2], a pair of perchlorate ions disposed to either side of the tpy plane, lying each with one oxygen atom interacting with both of the two protonating hydrogen atoms. In the anhydrous X = NO3, tfa, tca arrays, the lattices are solvated by the parent acids; one oxygen atom of each anion is chelated by the [tpyH2]2+ as in the chlorides, the other anion, with the acid, forming an independent ‘acid salt’ counterion [XHX]− in each case, retaining the additional protonic hydrogen rather than further protonating the central ring, all being of the form [(tpyH2)X]X·HX = [(tpyH2)X][X(HX)]. 相似文献
96.
Dr. Lucy Clark Dr. Farida H. Aidoudi Dr. Cameron Black Dr. Kasun S. A. Arachchige Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Russell E. Morris Prof. Dr. Philip Lightfoot 《Angewandte Chemie (International ed. in English)》2015,54(51):15457-15461
The ionothermal synthesis, structure, and magnetic susceptibility of a novel inorganic–organic hybrid material, imidazolium vanadium(III,IV) oxyfluoride [C3H5N2][V9O6F24(H2O)2] (ImVOF) are presented. The structure consists of inorganic vanadium oxyfluoride slabs with kagome layers of V4+ S=${{ 1/2 }}$ ions separated by a mixed valence layer. These inorganic slabs are intercalated with imidazolium cations. Quinuclidinium (Q) and pyrazinium (Pyz) cations can also be incorporated into the hybrid structure type to give QVOF and PyzVOF analogues, respectively. The highly frustrated topology of the inorganic slabs, along with the quantum nature of the magnetism associated with V4+, means that these materials are excellent candidates to host exotic magnetic ground states, such as the highly sought quantum spin liquid. Magnetic susceptibility measurements of all samples suggest an absence of conventional long‐range magnetic order down to 2 K despite considerable antiferromagnetic exchange. 相似文献
97.
Inversion twinning in a second polymorph of the hydrochloride salt of the recreational drug ethylone
T. Stanley Cameron J. Stuart Grossert Chad R. Maheux Idralyn Q. Alarcon Catherine R. Copeland Anthony Linden 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(4):266-270
A second polymorph of the hydrochloride salt of the recreational drug ethylone, C12H16NO3+·Cl−, is reported [systematic name: (±)‐2‐ethylammonio‐1‐(3,4‐methylenedioxyphenyl)propane‐1‐one chloride]. This polymorph, denoted form (A), appears in crystallizations performed above 308 K. The originally reported form (B) [Wood et al. (2015). Acta Cryst. C 71 , 32–38] crystallizes preferentially at room temperature. The conformations of the cations in the two forms differ by a 180° rotation about the C—C bond linking the side chain to the aromatic ring. Hydrogen bonding links the cations and anions in both forms into similar extended chains in which any one chain contains only a single enantiomer of the chiral cation, but the packing of the ions is different. In form (A), the aromatic rings of adjacent chains interleave, but pack equally well if neighbouring chains contain the same or opposite enantiomorph of the cation. The consequence of this is then near perfect inversion twinning in the structure. In form (B), neighbouring chains are always inverted, leading to a centrosymmetric space group. The question as to why the polymorphs crystallize at slightly different temperatures has been examined by density functional theory (DFT) and lattice energy calculations and a consideration of packing compactness. The free energy (ΔG) of the crystal lattice for polymorph (A) lies some 52 kJ mol−1 above that of polymorph (B). 相似文献
98.
Nathanael Ackerman Cameron Freer Aleksandra Kwiatkowska Rehana Patel 《Annals of Pure and Applied Logic》2017,168(1):19-36
We consider the space of countable structures with fixed underlying set in a given countable language. We show that the number of ergodic probability measures on this space that are -invariant and concentrated on a single isomorphism class must be zero, or one, or continuum. Further, such an isomorphism class admits a unique -invariant probability measure precisely when the structure is highly homogeneous; by a result of Peter J. Cameron, these are the structures that are interdefinable with one of the five reducts of the rational linear order . 相似文献
99.
Carter CL McLeod CW Bunch J 《Journal of the American Society for Mass Spectrometry》2011,22(11):1991-1998
Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is a valuable tool for the analysis of molecules
directly from tissue. Imaging of phospholipids is gaining widespread interest, particularly as these lipids have been implicated
in a variety of pathologic processes. Formalin fixation (FF) is the standard protocol used in histology laboratories worldwide
to preserve tissue for analysis, in order to aid in the diagnosis and prognosis of diseases. This study assesses MALDI imaging
of phospholipids directly in formalin fixed tissue, with a view to future analysis of archival tissue. This investigation
proves the viability of MALDI-MSI for studying the distribution of lipids directly in formalin fixed tissue, without any pretreatment
protocols. High quality molecular images for several phosphatidylcholine (PC) and sphingomyelin (SM) species are presented.
Images correspond well with previously published data for the analysis of lipids directly from freshly prepared tissue. Different
ionization pathways are observed when analyzing fixed tissue compared with fresh, and this change was found to be associated
with formalin buffers employed in fixation protocols. The ability to analyze lipids directly from formalin fixed tissue opens
up new doors in the investigation of disease profiles. Pathologic specimens taken for histologic investigation can be analyzed
by MALDI-MS to provide greater information on the involvement of lipids in diseased tissue. 相似文献
100.
Two-dimensional paper networks: programmable fluidic disconnects for multi-step processes in shaped paper 总被引:1,自引:0,他引:1
Most laboratory assays take advantage of multi-step protocols to achieve high performance, but conventional paper-based tests (e.g., lateral flow tests) are generally limited to assays that can be carried out in a single fluidic step. We have developed two-dimensional paper networks (2DPNs) that use materials from lateral flow tests but reconfigure them to enable programming of multi-step reagent delivery sequences. The 2DPN uses multiple converging fluid inlets to control the arrival time of each fluid to a detection zone or reaction zone, and it requires a method to disconnect each fluid source in a corresponding timed sequence. Here, we present a method that allows programmed disconnection of fluid sources required for multi-step delivery. A 2DPN with legs of different lengths is inserted into a shared buffer well, and the dropping fluid surface disconnects each leg at in a programmable sequence. This approach could enable multi-step laboratory assays to be converted into simple point-of-care devices that have high performance yet remain easy to use. 相似文献