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101.
GIAO/DFT evaluation of 13C NMR chemical shifts of selected acetals based on DFT optimized geometries
DFT/B3LYP calculations of the ground-state conformation of eight cyclic and acyclic acetals are presented and compared with experimental data. Results of single-point GIAO/DFT calculations at five different levels of theory show that isotropic shieldings need to be empirically scaled to achieve agreement with experimental chemical shifts. Statistical evaluation of data indicates that the most accurate prediction of 13C chemical shifts is achieved at the MPW1PW91/6-311G** level of theory. An empirical equation describing the relationship between delta values and shielding constants is postulated. This equation has been applied to the non-chair ground-state conformation of the six-membered acetonide and to the conformationally flexible benzodioxonine derivative. The agreement observed between the experimental and predicted chemical shifts shows that calculations at the MPW1PW91/6-311G** level of theory are adequate for addressing questions of conformation. 相似文献
102.
For most oxide/electrolyte systems potentiometric titration curves measured for different ionic strengths have a Common Intersection Point (CIP) which corresponds to the Point of Zero Charge (PZC). However, there are systems where a CIP exists but the surface charge at this point does not equal zero (PZC CIP). In this paper theoretical analysis of the systems in which the PZC and CIP do not coincide is presented. It is based on the well-known 2-pK surface charging approach and Triple Layer Model (TLM) as well as the Four Layer Model (FLM) of the electric double layer. The appropriate mathematical criterion for CIP existence was applied with detailed derivations, both for TLM and FLM. Having determined in this manner the parameter values, one can draw proper conclusions about the features of oxide/electrolyte adsorption systems, in which PZC and CIP do not coincide. The values of adsorption parameters are found by fitting simultaneously the obtained theoretical expressions to both of the experimental titration isotherms, and to the individual isotherms of electrolyte cation adsorption measured using radiometric methods. 相似文献
103.
Speed of sound and density of 1-propanol + heavy water were measured in the whole concentration range at temperatures from 293 to 313 K. Isentropic compressibility was calculated from the Laplace formula. The partial molar volume of 1-propanol reaches a minimum at the mole fraction of 1-propanol x
1 0.03. At the same concentration, the compressibility isotherms intersect one another. These features of the investigated system are similar to those of 1-propanol + H2O, that points to essential similarity of the two mixtures. A clathrate-like structure was suggested to explain the experimental results for dilute solutions of the alcohol. Somewhat more pronounced hydrophobic hydration in D2O than in H2O is manifested by an effect similar to that resulting from the elongation of the alcohol molecule. 相似文献
104.
Aleksandra Dubiella-Jackowska Żaneta Polkowska Lech Dariusz Piotr Pasławski Wojciech Staszek Jacek Namieśnik 《Central European Journal of Chemistry》2009,7(1):35-41
A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass
spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma
mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified
with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol
L−1 thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L−1 level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection
limit (MDL) was found to be 1 ng L−1 for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%).
The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.
相似文献
105.
Cahill MA Wozny W Schwall G Schroer K Hölzer K Poznanovic S Hunzinger C Vogt JA Stegmann W Matthies H Schrattenholz A 《Rapid communications in mass spectrometry : RCM》2003,17(12):1283-1290
The new method of analysis of relative isotopologue abundances (ARIA) applied here is based on the evaluation of total isotope patterns of tryptic protein fragments measured by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) to calculate the mixing ratios of composites consisting of stable isotope labelled and isotopically natural (unlabelled) proteins, as described in an accompanying paper in this issue. Recently, Sechi (Rapid Commun. Mass Spectrom. 2002; 16: 1416-1424) and Gehanne et al. (Rapid Commun. Mass Spectrom. 2002; 16: 1692-1698) introduced the use of differential quantitative mass analysis by MALDI-TOFMS using mixtures of standard proteins alkylated prior to two-dimensional polyacrylamide gel electrophoresis (2D-PAGE) with either acrylamide (AA) or deuterium-labelled [2,3,3'-D(3)]-acrylamide (D3AA). In the present study we validate the AA/D3AA system, firstly by measuring the yield of proteins alkylated with AA, and secondly by using differential radioactive labels ((125)I and (131)I) to quantitatively establish that non-comigration in 2D-PAGE is negligible. ARIA is then applied to quantitatively estimate the relative proportions of peptides labelled with AA or D3AA in the validated system, using typical silver-stained 2D-PAGE protein spots from 2D gels loaded with 150 microg of total liver protein. The precision and limitations of ARIA quantification of peptides differentially alkylated with isotopomeric reagents are discussed. 相似文献
106.
Wojciech Marynowski Tomasz Klucznik Katarzyna Baranowska Anna Dołęga Dr. Wiesław Wojnowski 《无机化学与普通化学杂志》2010,636(5):685-687
Tri(mesityloxy)silanethiol (TMST) was isolated as the only product of the reaction between SiS2 and 2,4,6‐trimethylphenol. TMST crystallizes in the triclinic system. Good quality of the crystal allowed the unrestricted refinement of the mercapto group; the resulting S–H distance is 1.29(4) Å and the Si–S–H bond angle is 95.4(17)°. Molecules of TMST show no hydrogen bonds in the crystal – the FT‐IR spectrum of the solid sample exhibits a very sharp, well‐resolved band of isolated –SH group at 2562 cm–1. 相似文献
107.
Karolina Hyz Robert Kawȩcki Elżbieta Bednarek Wojciech Bocian Jerzy Sitkowski Lech Kozerski 《Magnetic resonance in chemistry : MRC》2010,48(8):575-584
Topotecan (TPT) is in clinical use as an antitumor agent, hycamtin?. Because of this, it requires both biologically and chemically useful information to be available. TPT acts by binding to the covalent complex formed by nicked DNA and topoisomerase I. This has a poisonous effect since inserted into the single‐strand nick and TPT inhibits its religation. We used NMR to trace TPT dynamics, tautomerism and solvolysis products in various solvents and conditions. Chemical stability was assessed in methanol and DMSO as compared to water, and the regioselectivity of the N‐ and O‐methylation was studied using various alkylating agents. The reaction products of quaternization of the nitrogen atom and methylation of the oxygen atom were characterized by means of ESI MS, 1H/13C‐HMBC and ‐HSQCAD NMR. We have focused on the NMR characterization of TPT with an anticipation that its aggregation, tumbling properties and the intramolecular dipolar interactions will be a common feature for other compounds described in this article. These features can also be useful in tracing the interactions of this class of topoisomerase I (TopoI) poisons with DNA. Moreover, the results explained shed light on the recently disclosed problem of lack of stability of TPT in the heart tissue homogenate samples using the analytical assays developed for this class of compounds carried out in the presence of methanol. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
108.
JPC – Journal of Planar Chromatography – Modern TLC - 相似文献
109.
110.
Dipl.‐Chem. Lukas Zöphel Dr. Kunal S. Mali Dr. Puniredd Sreenivasa Reddy Dr. Manfred Wagner Prof. Dr. Steven De Feyter Dr. Wojciech Pisula Prof. Dr. Klaus Müllen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(11):3264-3276
Pyrene‐fused tetraazaporphyrins were synthesized from pyrene‐4,5‐dicarbonitrile precursors using a recently reported procedure as the key step for the asymmetric substitution of pyrene. Metal‐free, zinc‐ and lead‐centered pyrenocyanines were obtained and their optical properties as well as their molecular assembly in the solution and bulk phases and at the liquid/solid interface were studied. The characteristic Q‐band appears broadened, most likely owing to distortion of the molecule introduced by the steric demand of the angularly extended aromatic residue. The angular annulation does not bathochromically shift the Q‐band as far as would have been expected for the linear case. Peripheral substitution with linear and branched alkoxy chains affords solubility of the compounds in organic solvents. The influence of the distinct steric demand of the substituents on aggregation was investigated for metal‐centered pyrenocyanines by using temperature‐dependent 1H NMR and UV/Vis spectroscopy. The self‐assembly at the liquid/solid interface was studied using scanning tunneling microscopy. The alkoxy substituents facilitate the anchoring of these slightly non‐planar molecules on the surface of graphite. Pyrenocyanine molecules form well‐ordered 2D arrays in which the molecules are arranged in rows. The angular annulation of the pyrenocyanine residue leads to characteristic adsorption behavior at the liquid/solid interface, in which the molecules adsorb in two different adsorption geometries. The alkoxy side‐chains give rise to a discotic columnar superstructure and induce distinct thermotropic behavior. Dependent on the steric demand of the branched chains and the central metal atom, the molecules are rotated with respect to each other to form helical organization. 相似文献