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991.
Adam M. Hawkridge Rebecca B. Wysocky James N. Petitte Kenneth E. Anderson Paul E. Mozdziak Oscar J. Fletcher Jonathan M. Horowitz David C. Muddiman 《Analytical and bioanalytical chemistry》2010,398(2):737-749
The domestic chicken (Gallus domesticus) has emerged as a powerful experimental model for studying the onset and progression of spontaneous epithelial ovarian cancer
(EOC) with a disease prevalence that can exceed 35% between 2 and 7 years of age. An experimental strategy for biomarker discovery
is reported herein that combines the chicken model of EOC, longitudinal plasma sample collection with matched tissues, advanced
mass spectrometry-based proteomics, and concepts derived from the index of individuality (Harris, Clin Chem 20: 1535–1542,
1974). Blood was drawn from 148 age-matched chickens starting at 2.5 years of age every 3 months for 1 year. At the conclusion
of the 1 year sample collection period, the 73 birds that remained alive were euthanized, necropsied, and tissues were collected.
Pathological assessment of resected tissues from these 73 birds confirmed that five birds (6.8%) developed EOC. A proteomics
workflow including in-gel digestion, nanoLC coupled to high-performance mass spectrometry, and label-free (spectral counting)
quantification was used to measure the biological intra-individual variability (CVW) of the chicken plasma proteome. Longitudinal plasma sample sets from two birds within the 73-bird biorepository were selected
for this study; one bird was considered “healthy” and the second bird developed late-stage EOC. A total of 116 proteins from
un-depleted plasma were identified with 80 proteins shared among all sample sets. Analytical variability (CVA) of the label-free proteomics workflow was measured using a single plasma sample analyzed five times and was found to be
≥CVW in both birds for 16 proteins (20%) and in either bird for 25 proteins (31%). Ovomacroglobulin (ovostatin) was found to increase
(p < 0.001) over a 6 month period in the late-stage EOC bird providing an initial candidate protein for further investigation. 相似文献
992.
Testosterone metabolism revisited: discovery of new metabolites 总被引:1,自引:0,他引:1
Oscar J. Pozo Josep Marcos Rosa Ventura Andreu Fabregat Jordi Segura 《Analytical and bioanalytical chemistry》2010,398(4):1759-1770
The metabolism of testosterone is revisited. Four previously unreported metabolites were detected in urine after hydrolysis
with KOH using a liquid chromatography–tandem mass spectrometry method and precursor ion scan mode. The metabolites were characterized
by a product ion scan obtained with accurate mass measurements. Androsta-4,6-dien-3,17-dione, androsta-1,4-dien-3,17-dione,
17-hydroxy-androsta-4,6-dien-3-one and 15-androsten-3,17-dione were proposed as feasible structures for these metabolites
on the basis of the mass spectrometry data. The proposed structures were confirmed by analysis of synthetic reference compounds.
Only 15-androsten-3,17-dione could not be confirmed, owing to the lack of a commercially available standard. That all four
compounds are testosterone metabolites was confirmed by the qualitative analysis of several urine samples collected before
and after administration of testosterone undecanoate. The metabolite androsta-1,4-dien-3,17-dione has a structure analogous
to that of the exogenous anabolic steroid boldenone. Specific transitions for boldenone and its metabolite 17β-hydroxy-5β-androst-1-en-3-one
were also monitored. Both compounds were also detected after KOH treatment, suggesting that this metabolic pathway is involved
in the endogenous detection of boldenone previously reported by several authors. 相似文献
993.
Simultaneous determination of seven alkaloids in Phellodendron chinense Schneid by high-performance liquid chromatography 总被引:1,自引:0,他引:1
By optimizing the extraction, separation, and analytical conditions, a reliable and accurate HPLC method coupled with a photodiode array detector was developed for simultaneous detection and quantification of seven alkaloids, i.e., (-)-(R)-platydesmin, noroxyhydrastinine, berberine, skimmianine, canthin-6-one, chilenine, and pteleine in "huangbo" (the bark of Phellodendron chinense), a commonly used herb in Traditional Chinese Medicine. The optimal condition for separation was achieved on a reversed-phase Cis column with a stepwise mobile phase gradient prepared from 0.1% phosphoric acid and acetonitrile. For all the alkaloids, a good linear regression relationship (r > 0.9997) was obtained between the peak area and concentration at the range of 0.5-700 microg/mL. The LODs and LOQs for the analytes ranged from 0.07 to 0.28 microg/mL and from 0.28 to 1.12 microg/mL, respectively. The optimized method was applied to the determination of alkaloids in several P. chinense samples, and found to be feasible and reliable. This method and quantitative results can provide scientific and technical bases for setting up QC standards to assure the safety and quality of P. chinense bark raw material, as well as for proprietary Chinese medicine products containing P. chinense bark. 相似文献
994.
Juan Peng Lily Zu Weihai Fang Lingyun Huang Yaru Wang Dacheng He 《Journal of mass spectrometry : JMS》2010,45(6):627-634
An understanding of the dissociation of penetratin is important for improving its metabolic stability and cargo‐delivery efficiency. In this study, we describe the selective cleavage of the K15–K16 amide bond of penetratin under the low‐energy collision‐induced dissociation condition in mass spectrometry. A variety of penetratin substitutes have been studied in which key basic amino acids have been substituted within the sequence. The calculated structure indicates that an α‐helix structure prevents the fragmentation of the central peptide domain and the side chain of lysine is involved in the proton translocation process. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
995.
Mata S Cortijo V Caminati W Alonso JL Sanz ME López JC Blanco S 《The journal of physical chemistry. A》2010,114(43):11393-11398
The Fourier transform microwave spectra of the hydrated forms of the tautomeric pair 2-pyridinone/2-hydroxypyridine (2PO/2HP) have been investigated in a supersonic expansion. Three hydrated species, 2PO-H?O, 2HP-H?O, and 2PO-(H?O)?, have been observed in the rotational spectrum. Each molecular complex was confidently identified by the features of the 1?N quadrupole hyperfine structure of the rotational transitions. The presence of water affects the tautomeric equilibrium -N═C(OH)- ? -NH-C(═O)-, which is shifted to the enol form for the bare molecules 2PO/2HP but to the keto tautomer for the hydrated forms. 相似文献
996.
Increase of pH induced by Cu(2+)-catalyzed Fenton reaction promoted ring-opening of triazole-linked fluorescein lactone, which enabled selective "turn-on" fluorescent detection of Cu(2+), along with ultralow naked-eye detection limit down to 200 nM. 相似文献
997.
Yan Lu Gongke Wang Xiumin Lu Juan Lv Meihua Xu Weiwei Zhang 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2010,75(1):261-266
The molecular mechanism of the binding of norfloxacin (NRF) to trypsin was investigated by fluorescence, synchronous fluorescence and UV–vis absorbance spectroscopy and molecular modeling at physiological conditions. The quenching mechanism and the binding mode were investigated in terms of the association constants and basic thermodynamic parameters. The results of spectroscopic measurements suggested that NRF have a strong ability to quench the intrinsic fluorescence of trypsin through static quenching procedure. Moreover, fluorescence experiments were also performed at different values of pH to elucidate the effect of pH on the binding. The NRF–trypsin complex was stabilized by hydrophobic forces and hydrogen bonding, via tryptophan residue as indicated from the thermodynamic parameters, which was consistent with the results of molecular docking and accessible surface area calculations. 相似文献
998.
Quasi-classical trajectory (QCT) calculations are employed for the reaction F + HO(0,0)→HF + O based on the adiabatic potential energy surface (PES) of the ground 3A″triplet state. The average rotational alignment factor P2(j′·k) as a function of collision energy and the four polarization dependent generalized differential cross sections have been calculated in the center-of-mass (CM) frame, separately. The distribution P(θr) of the angle between k and j′, the distribution P(θr) of dihedral angle denoting k-k′-j′ correlation, and the angular distribution P(θr, Φr) of product rotational vectors in the form of polar plots are calculated as well. The effect of Heavy-Light-Heavy (HLH) mass combination and atom F's relatively strong absorbability to charges on the alignment and the orientation of product molecule HF rotational angular momentum vectors j′ is revealed. 相似文献
999.
离子交换树脂催化酯化生物油的试验研究 总被引:1,自引:0,他引:1
生物油黏稠、稳定性差、热值低、腐蚀性强,需要进行改质与品位提升,将生物油中的有机酸通过酯化的方法转化为中性的酯类可以改善生物油的性能。实验利用模型反应,筛选出了适合于生物油体系的732型和NKC-9型两种树脂作为酯化改质的催化剂。生物油和甲醇在间歇釜内以732和NKC-9为催化剂进行改质以后,酸值分别降低了88.54%和85.95%,表明生物油中的有机酸极大地转化为中性酯类。此外,热值分别提高了32.26%和31.64%,水分分别降低了27.74%和30.87%,密度均降低了21.77%,黏度降低均接近97%。732树脂固定床催化酯化生物油后,酸值降低了92.61%。加速陈化实验和铝片腐蚀性实验结果分别表明,改质生物油的稳定性和腐蚀性能得到了改善。 相似文献
1000.