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941.
Silvia?Faranda Giorgia?Foca Andrea?Marchetti Lorenzo?TassiEmail author Alessandro?Ulrici Claudia?Zucchi 《Journal of solution chemistry》2004,33(10):1181-1197
Kinematic viscosities were measured for 2-butanone + 2-butanol binary liquid mixtures with a capillary Ubbelohde routine viscometer in the temperature range from 273.15 to 353.15 K at atmospheric pressure, and covering the whole miscibility field (0xi1). Experimental data have been correlated by means of different empirical or semiempirical relationships, such as =(T), =(xi), and =(T, xi). Viscosity deviations, , from ideal behavior are negative at all experimental conditions, confirming that structure breaking effects prevail in the liquids. Furthermore, the thermodynamics of viscous flow and excess Gibbs energy of activation of viscous flow, G*E, have been calculated. As an alternative and complementary approach to such investigations, the fluidity () of this binary system has been analyzed by the modified—Batschinski theory. The results are discussed in terms of the specific molecular interactions between the mixture components. 相似文献
942.
The influence of simulation methods, cutoff based and particle mesh Ewald (PME) on the accuracy by which experimentally derived nuclear Overhauser effect (NOE) data are reproduced, has been investigated using 500-ns-long molecular dynamics simulations on a model -sheet peptide in explicit solvent. The structural and conformational features under the different conditions were evaluated in terms of flexibility, secondary structure content, hydrogen-bonding pattern and percent of native contacts as a function of time. It was found that the different simulation methods strongly influence the dynamics of the peptide, confirming previous observations based on ideal peptide models simulated for much shorter times. Moreover, the results of our simulations prove once more that it is necessary to reach extremely long time scales to obtain enough statistics to accurately reproduce experimental NOE restraints even in the case of the PME method, despite its tendency to the stabilization of conformations which are structurally closely related to the ones derived through experiment. Possible implications regarding the stabilization and folding mechanisms, together with their relationship to the experimental study of peptide models, are discussed. 相似文献
943.
A new shipboard analytical method for determining picomolar levels of manganese in seawater has been developed. The method is based on a combination of chelating resin column extraction and improved chemiluminescence (CL) detection in a closed flow system. In this method, manganese in sample solution is selectively collected on newly-developed iminodiacetate-immobilized chelating resin, and then eluted with acidic solution containing hydrogen peroxide. The resulting eluent is mixed with luminol solution and aqueous ammonia after removal of iron ions by a chelating resin column, and then the mixture is introduced into the CL cell. The manganese concentration is obtained from the CL intensity. The detection limit (3SD) of manganese is 5 pmol L–1 from 9 mL of seawater sample. The method was applied to seawater samples collected at the Okinawa Trough. 相似文献
944.
Hsu FF Turk J Shi Y Groisman EA 《Journal of the American Society for Mass Spectrometry》2004,15(1):1-11
Acylphosphatidylglycerol (Acyl-PG), a polar lipid class containing three fatty acyl groups, was isolated from Salmonella bacteria and characterized by tandem quadrupole and quadrupole ion-trap mass spectrometric methods with electrospray ionization. The structural characterization of the acyl-PG with various acyl groups (A-B/C-PG, where A not equal B not equal C) is based on the findings that the carboxylate anions (R(x)CO(2)(-)) arising from sn-2 (R(2)CO(2)(-)) is more abundant than that arising from sn-3' (R(3')CO(2)(-)), which is much more abundant than that arising from sn-1 (R(1)CO(2)(-)). This information provides a simple method for determination of the fatty acyl moieties and their positions in the molecule. The structural identification of the molecule can also be achieved by the findings that the fragment ion reflecting the ketene loss at sn-2 is more prominent than that reflecting the acid loss (i.e., [M - H - R'(2)CH=CO](-) > [M - H - R(2)CO(2)H](-)), while the ion arising from acid loss at sn-1 or sn-3' is, respectively, more abundant than the corresponding ketene loss (i.e., [M - H - R(1)CO(2)H](-) > [M - H - R'(1)CH=CO](-); [M - H - R(3')CO(2)H](-) > [M - H -R'(3')CH=CO](-)). The identity of the acyl moiety at sn-3' can be confirmed by an acyl-glycerophosphate anion observed in the product-ion spectrum obtained with a triple-stage quadrupole (TSQ) instrument, but not in that obtained with an ion-trap mass spectrometer (ITMS). However, the MS(2)-spectrum obtained with an ITMS is featured by the ion series that abundances of [M - H - R'(2)CH=CO - R(3)CO(2)H - 74](-) > [M - H - R'(2)CH=CO - R(1)CO(2)H - 74](-) z.Gt; [M - H - R'(1(or 3'))CH=CO - R(3'(or 1))CO(2)H - 74](-). This information also facilitates structural elucidation of the acyl-PG subclass that contains various acyl substituents. Structural identifications of molecular species having two identical fatty acyl substituents at sn-1, sn-2, or sn-3' or consisting of more than one isomeric structures are also demonstrated. The identities of the minor isomeric species in the molecules can be revealed by the aforementioned structural information arising from the various ion series combined. 相似文献
945.
Karlsson NG Schulz BL Packer NH 《Journal of the American Society for Mass Spectrometry》2004,15(5):659-672
Neutral O-linked oligosaccharides released from the salivary mucin MUC5B were separated and detected by negative ion LC-MS and LC-MS(2). The resolution of the chromatography and the information obtained from collision induced dissociation of detected [M - H](-) ions were usually sufficient to identify the sequence of individual oligosaccharides, illustrated by the fact that 50 different oligosaccharides ranging from disaccharides to nonasaccharides could be assigned from the sample. Fragmentation was shown to yield mostly reducing end sequence fragments (Z(i) and Y(i)), enabling primary sequence assignment. Specific fragmentation pathways or patterns were also detected giving specific linkage information. The reducing end core (Gal/GlcNAcbeta1-3GalNAcol or Gal/GlcNAcbeta1-3(GlcNAcbeta1-6)GalNAcol) could be deduced from the pronounced glycosidic C-3 cleavage and A(i) type cleavages of the reducing end GalNAcol, together with the non reducing end fragment from the loss of a single substituted GalNAcol. Substitution patterns on GlcNAc residues were also found, indicative for C-4 substitution ((0,2)A(i) - H(2)O cleavage) and disubstitution of C-3 and C-4 (Z(i)/Z(i) cleavages). This kind of fragmentation can be used for assigning the mode of chain elongation (Galbeta1-3/4GlcNAcbeta1-) and identification of Lewis type antigens like Lewis a/x and Lewis b/y on O-linked oligosaccharides. In essence, negative ion LC-MS(2) was able to generate extensive data for understanding the overall glycosylation pattern of a sample, especially when only a limited amount of material is available. 相似文献
946.
Investigation of sulfur release in ETV-ICP-AES and its application for the determination of sulfates 总被引:3,自引:0,他引:3
Antje Mroczek Gerhard Werner R. Wennrich Werner Schr?n 《Fresenius' Journal of Analytical Chemistry》1998,361(1):34-42
Electrothermal vaporization inductively coupled plasma atomic emission spectrometry was applied to the determination of sulfur
species in aqueous solutions. The sensitivity for sulfur as sulfate was found to be depending on the cations in the sample.
For understanding this phenomenon the thermal behavior of sulfuric acid, ammonium sulfate and the sulfates of sodium, zinc,
magnesium and silver was studied. There were significant differences in the thermal release of sulfur from these sulfates.
To explain these phenomena different reaction mechanisms were calculated using thermodynamic data. Pd(NO3)2 and Ge in KOH were successfully applied as modifiers for the stabilization of the sulfates during the thermal pre-treatment
step and to establish a uniform thermal behavior of different sulfates. The stabilization of sulfur using Ge and Pd as modifiers
is based on the reduction of the sulfates in presence of carbon, resulting in the formation of GeS and PdS, respectively.
This explanation has been supported by comparing the experimental results with thermodynamic calculations considering different
reactions for the thermal decomposition of the sulfates. Applying Ge (in KOH) as modifier the absolute detection limit was
300 pg sulfur (e.g. LOD 30 ng mL–1). The significant influence of phosphates on the determination of sulfur could be essentially reduced by Pd as modifier.
Received: 11 November 1997 / Revised: 14 January 1998 / Accepted: 18 January 1998 相似文献
947.
Yu. I. Aristov G. Di Marco M. M. Tokarev V. N. Parmon 《Reaction Kinetics and Catalysis Letters》1997,61(1):147-154
In this communication we present a low-temperature “solidification-melting” phase diagram for CaCl2/H2O solutions confined in KSK and KSM silica gels. At salt concentrations of 0–48 wt. %, the diagram has been found to lie below
the diagram reported for the bulk system by 15–30°C. It shows a depression of the solution melting point due to its confinment
to the pores. Several other peculiarities of melting and solidification in this system are also reported and discussed. Beside
fundamental interest, the data obtained could be of importance in many commercial areas such as refrigeration, accumulation
of low temperature heat, frost prevention in building materials,etc. 相似文献
948.
A case study is presented for the establishment of traceability for ammonium nitrogen determination in wastewater in a routine laboratory in order to fulfil the requirements of ISO/IEC standard 17025. The necessary relevant information was obtained from the method validation data, the quality control data and equipment calibration certificates. The method of measurement is described together with the measurement equation, selected traceable reference standards and the associated measurement uncertainty. The major sources of uncertainty of the result of measurement were identified and the combined uncertainty was calculated. Identification of the main uncertainty sources represents the basis for target operations for reducing the measurement uncertainty of this determination. 相似文献
949.
?zdemir ümmühan Karacan Nurcan ?entürk Ozan Sanlι Sert Sema U?ur Fadime 《Transition Metal Chemistry》2003,28(4):443-446
Five new complexes, [M(CO)5(apmsh)] [M = Cr; (1), Mo; (2), W; (3)], [Re(CO)4Br(apmsh)] (4) and [Mn(CO)3(apmsh)] (5) have been synthesized by the photochemical reaction of metal carbonyls [M(CO)6] (M = Cr, Mo and W), [Re(CO)5Br], and [Mn(CO)3Cp] with 2-hydroxyacetophenone methanesulfonylhydrazone (apmsh). The complexes have been characterized by elemental analysis, mass spectrometry, f.t.-i.r. and 1H spectroscopy. Spectroscopic studies show that apmsh behaves as a monodentate ligand coordinating via the imine N donor atom in [M(CO)5(apmsh)] (1–4) and as a tridentate ligand in (5). 相似文献
950.
Liu JM Hu SR He XM Li XL Zhan FP Zeng LQ Li LD Zhu GH Huang XM 《Analytical and bioanalytical chemistry》2005,382(7):1507-1512
Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin–SiO2) have been synthesized by the sol–gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin–SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (Ip) is directly proportional to the concentration of bismuth in the working range 0.16–14.4 ag spot–1 (sample volume 0.40 L spot–1, corresponding to the concentration range 0.40–36.0 fg mL–1). The regression equation of the working curve is Ip=14.86+5.279×[Bi3+] (ag spot–1) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot–1 (corresponding to a concentration of 6.5×10–17 g mL–1).This sensitive, reproducible and accurate method has been used for successful analysis of real samples. 相似文献