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971.
Sciuto SV Liu J Konermann L 《Journal of the American Society for Mass Spectrometry》2011,22(10):1679-1689
Electrosprayed multi-protein complexes can be dissociated by collisional activation in the gas phase. Typically, these processes
follow a mechanism whereby a single subunit gets ejected with a disproportionately high amount of charge relative to its mass.
This asymmetric behavior suggests that the departing subunit undergoes some degree of unfolding prior to being separated from
the residual complex. These structural changes occur concomitantly with charge (proton) transfer towards the subunit that
is being unraveled. Charge accumulation takes place up to the point where the subunit loses physical contact with the residual
complex. This work develops a simple electrostatic model for studying the relationship between conformational changes and
charge enrichment during collisional activation. Folded subunits are described as spheres that carry continuum surface charge.
The unfolded chain is envisioned as random coil bead string. Simulations are guided by the principle that the system will
adopt the charge configuration with the lowest potential energy for any backbone conformation. A finite-difference gradient
algorithm is used to determine the charge on each subunit throughout the dissociation process. Both dimeric and tetrameric
protein complexes are investigated. The model reproduces the occurrence of asymmetric charge partitioning for dissociation
events that are preceded by subunit unfolding. Quantitative comparisons of experimental MS/MS data with model predictions
yield estimates of the structural changes that occur during collisional activation. Our findings suggest that subunit separation
can occur over a wide range of scission point structures that correspond to different degrees of unfolding. 相似文献
972.
Syed SU Sreekumar J Gibson JR Taylor S 《Journal of the American Society for Mass Spectrometry》2011,22(8):1381-1387
We report here a study using a quadrupole mass spectrometer (QMS) in which a static magnetic field is applied transversely
to the body of the mass filter operating in stability zone 3. Significant improvement in QMS performance was obtained under
certain magnetic field conditions, and these have been explained in terms of our theoretical model. The theoretical approach
assumed in the model is that the QMS contains hyperbolic rods as electrodes and that the magnetic field acts over the full
length of the mass filter assembly. Our latest analysis also predicts for what values of operating parameters an enhancement
of the quadrupole resolution is achieved when a transverse magnetic field is applied. The model predicts instrument resolution
R > 5000 for Ar with a 100 mm long mass filter and R > 3500 for a HT and D2 mixture with a 200 mm long mass filter via application of a transverse magnetic field. 相似文献
973.
Castro-Perez J Roddy TP Nibbering NM Shah V McLaren DG Previs S Attygalle AB Herath K Chen Z Wang SP Mitnaul L Hubbard BK Vreeken RJ Johns DG Hankemeier T 《Journal of the American Society for Mass Spectrometry》2011,22(9):1552-1567
A high content molecular fragmentation for the analysis of phosphatidylcholines (PC) was achieved utilizing a two-stage [trap (first generation fragmentation) and transfer (second generation fragmentation)] collision-induced dissociation (CID) in combination with travelling-wave ion mobility spectrometry (TWIMS). The novel aspects of this work reside in the fact that a TWIMS arrangement was used to obtain a high level structural information including location of fatty acyl substituents and double bonds for PCs in plasma, and the presence of alkali metal adduct ions such as [M?+?Li]+ was not required to obtain double bond positions. Elemental compositions for fragment ions were confirmed by accurate mass measurements. A very specific first generation fragment ion m/z 577 (M-phosphoryl choline) from the PC [16:0/18:1 (9Z)] was produced, which by further CID generated acylium ions containing either the fatty acyl 16:0 (C15H31CO+, m/z 239) or 18:1 (9Z) (C17H33CO+, m/z 265) substituent. Subsequent water loss from these acylium ions was key in producing hydrocarbon fragment ions mainly from the α-proximal position of the carbonyl group such as the hydrocarbon ion m/z 67 (+H2C-HC?=?CH-CH?=?CH2). Formation of these ions was of important significance for determining double bonds in the fatty acyl chains. In addition to this, and with the aid of 13C labeled lyso-phosphatidylcholine (LPC) 18:1 (9Z) in the ω-position (methyl) TAP fragmentation produced the ion at m/z 57. And was proven to be derived from the α-proximal (carboxylate) or distant ω-position (methyl) in the LPC. 相似文献
974.
Two analytical procedures used to determine total, soluble, and insoluble solids in tomato paste were evaluated. The microwave oven (MO) method was compared to the vacuum oven (VO) method. The VO method is tedious and measured the three solids fractions in the paste directly, while the MO method measured the total solids directly but used an equation to calculate the water-soluble and -insoluble solids. The MO method was faster and less labor-intensive, and yielded small but statistically significant higher values for total and insoluble solids and lower statistically significant values for soluble solids. 相似文献
975.
Firefly luciferase-catalyzed light emission from D-luciferin is widely used as a reporter of gene expression and enzymatic activity both in vitro and in vivo. Despite the power of bioluminescence for imaging and drug discovery, light emission from firefly luciferase is fundamentally limited by the physical properties of the D-luciferin substrate. We and others have synthesized aminoluciferin analogs that exhibit light emission at longer wavelengths than D-luciferin and have increased affinity for luciferase. However, although these substrates can emit an intense initial burst of light that approaches that of D-luciferin, this is followed by much lower levels of sustained light output. Here we describe the creation of mutant luciferases that yield improved sustained light emission with aminoluciferins in both lysed and live mammalian cells, allowing the use of aminoluciferins for cell-based bioluminescence experiments. 相似文献
976.
Kuai L Ong SE Madison JM Wang X Duvall JR Lewis TA Luce CJ Conner SD Pearlman DA Wood JL Schreiber SL Carr SA Scolnick EM Haggarty SJ 《Chemistry & biology》2011,18(7):891-906
Target identification remains challenging for the field of chemical biology. We describe an integrative chemical genomic and proteomic approach combining the use of differentially active analogs of small molecule probes with stable isotope labeling by amino acids in cell culture-mediated affinity enrichment, followed by subsequent testing of candidate targets using RNA interference-mediated gene silencing. We applied this approach to characterizing the natural product K252a and its ability to potentiate neuregulin-1 (Nrg1)/ErbB4 (v-erb-a erythroblastic leukemia viral oncogene homolog 4)-dependent neurotrophic factor signaling and neuritogenesis. We show that AAK1 (adaptor-associated kinase 1) is a relevant target of K252a, and that the loss of?AAK1?alters ErbB4 trafficking and expression levels,?providing evidence for a previously unrecognized role for AAK1 in Nrg1-mediated neurotrophic?factor signaling. Similar strategies should lead to the discovery of novel targets for therapeutic development. 相似文献
977.
Albrecht C Bode M Pérez JM Daniels J Schnakenburg G Streubel R 《Dalton transactions (Cambridge, England : 2003)》2011,40(11):2654-2665
Synthesis of the first oxaphosphirane chromium(0) and molybdenum(0) complexes of the type [{(R(1)PCH(R(2))-O}M(CO)(5)] (R(1) = C(5)Me(5)) (8a-e, 15a-e) and (R(1) = CH(SiMe(3))(2)) (9a-e, 16a-e) via reaction of dichloro(organo)- (1, 2, 10, 11) and chloro(organo)phosphane complexes (3,4,12) with lithium bases and aldehydes 7a-e is reported. Furthermore, bicyclic 1,3-oxaphospholane complexes 17 and 18 have been obtained via O-protonation of oxaphosphirane complexes 8a and 15a with HCl. All complexes were characterized by NMR, IR spectroscopic, mass spectrometric investigations and, in addition, single-crystal X-ray structures of complexes 8a-e, 9a,c, 15a,b,e, 16a-c, 17, 18 are presented and discussed. 相似文献
978.
Barnes SS Vogels CM Decken A Westcott SA 《Dalton transactions (Cambridge, England : 2003)》2011,40(17):4707-4714
Addition of boranes to N-aryl-salicylaldimines takes place initially at the reactive phenolic O-H bond to give an activated boron-containing imine and dihydrogen. In some cases a subsequent intramolecular hydrogenation step is observed and the C=N imine bond is reduced to the corresponding amine. Reactions with dimesitylborane in THF are unique in that the reduced amine product is the major product observed in solution. 相似文献
979.
980.
Feltham HL Klöwer F Cameron SA Larsen DS Lan Y Tropiano M Faulkner S Powell AK Brooker S 《Dalton transactions (Cambridge, England : 2003)》2011,40(43):11425-11432
A family of thirteen tetranuclear heterometallic zinc(II)-lanthanide(III) complexes of the hexa-imine macrocycle (L(Pr))(6-), with general formula Zn(II)(3)Ln(III)(L(Pr))(NO(3))(3)·xsolvents (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm or Yb), were prepared in a one-pot synthesis using a 3:1:3:3 reaction of zinc(II) acetate, the appropriate lanthanide(III) nitrate, the dialdehyde 1,4-diformyl-2,3-dihydroxybenzene (H(2)L(1)) and 1,3-diaminopropane. A hexanuclear homometallic zinc(II) macrocyclic complex [Zn(6)(L(Pr))(OAc)(5)(OH)(H(2)O)]·3H(2)O was obtained using a 2:0:1:1 ratio of the same reagents. A control experiment using a 1:0:1:1 ratio failed to generate the lanthanide-free [Zn(3)(L(Pr))] macrocyclic complex. The reaction of H(2)L(1) and zinc(II) acetate in a 1:1 ratio yielded the pentanuclear homometallic complex of the dialdehyde H(2)L(1), [Zn(5)(L(1))(5)(H(2)O)(6)]·3H(2)O. An X-ray crystal structure determination revealed [Zn(3)(II)Pr(III)(L(Pr))(NO(3))(2)(DMF)(3)](NO(3))·0.9DMF has the large ten-coordinate lanthanide(III) ion bound in the central O(6) site with two bidentate nitrate anions completing the O(10) coordination sphere. The three square pyramidal zinc(II) ions are in the outer N(2)O(2) sites with a fifth donor from DMF. Measurement of the magnetic properties of [Zn(II)(3)Dy(III)(L(Pr))(NO(3))(3)(MeOH)(3)]·4H(2)O with a weak external dc field showed that it has a frequency-dependent out-of-phase component of ac susceptibility, indicative of slow relaxation of the magnetization (SMM behaviour). Likewise, the Er and Yb analogues are field-induced SMMs; the latter is only the second example of a Yb-based SMM. The neodymium, ytterbium and erbium complexes are luminescent in the solid phase, but only the ytterbium and neodymium complexes show strong lanthanide-centred luminescence in DMF solution. 相似文献