全文获取类型
收费全文 | 812篇 |
免费 | 23篇 |
国内免费 | 6篇 |
专业分类
化学 | 512篇 |
晶体学 | 7篇 |
力学 | 39篇 |
数学 | 168篇 |
物理学 | 115篇 |
出版年
2024年 | 3篇 |
2023年 | 9篇 |
2022年 | 23篇 |
2021年 | 33篇 |
2020年 | 28篇 |
2019年 | 25篇 |
2018年 | 24篇 |
2017年 | 15篇 |
2016年 | 49篇 |
2015年 | 24篇 |
2014年 | 37篇 |
2013年 | 68篇 |
2012年 | 49篇 |
2011年 | 49篇 |
2010年 | 29篇 |
2009年 | 32篇 |
2008年 | 32篇 |
2007年 | 27篇 |
2006年 | 39篇 |
2005年 | 35篇 |
2004年 | 20篇 |
2003年 | 26篇 |
2002年 | 8篇 |
2001年 | 8篇 |
2000年 | 7篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 7篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 10篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 12篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1971年 | 2篇 |
1965年 | 1篇 |
排序方式: 共有841条查询结果,搜索用时 31 毫秒
121.
Bouchonnet S Kinani S Sablier M 《European journal of mass spectrometry (Chichester, England)》2007,13(3):223-226
Users of ion trap mass spectrometers frequently develop methods that associate chemical ionization with tandem mass spectrometry detection. With apparatus using internal ionization, the chemical reagent is present in the trap during the collision induced dissociation (CID) step and one may wonder if the reagent influences the fragmentation ratios in MS/MS. We report a comparison of the fragmentation ratios of protonated molecules when using the most common reagents (methane, ammonia, methanol, acetonitrile, isobutane) for performing in situ chemical ionization. Four molecules were chosen in the medical field to serve as models: alprazolam, diazepam, flunitrazepam and acetaminophen. In the non-resonant CID mode, the influence of the reagent mass is clearly seen in spite of its low partial pressure in the ion trap; the reagent acts as a "heavy target": the degree of fragmentation increases with the molecular weight of the reagent. In the resonant CID mode, there is no evident correlation between the fragmentation ratio of MH(+) ions and the nature of the CI reagent; a slight shift of the secular frequency of the precursor ion, which tends to reduce the CID efficiency, could compensate for the "heavy target" effect underscored in the non-resonant mode. 相似文献
122.
Poli MA Rivera VR Neal DD Baden DG Messer SA Plakas SM Dickey RW Said KE Flewelling L Green D White J 《Journal of AOAC International》2007,90(1):173-178
A new competitive electrochemiluminescence-based immunoassay for the type-2 brevetoxins in oyster extracts was developed. The assay was verified by spiking known amounts of PbTx-3 into 80% methanol extracts of Gulf Coast oysters. We also provide preliminary data demonstrating that 100% acetone extracts, aqueous homogenates, and the clinical matrixes urine and serum can also be analyzed without significant matrix interferences. The assay offers the advantages of speed ( 2 h analysis time); simplicity (only 2 additions, one incubation period, and no wash steps before analysis); low limit of quantitation (conservatively, 50 pg/mL = 1 ng/g tissue equivalents); and a stable, nonradioactive label. Due to the variety of brevetoxin metabolites present and the lack of certified reference standards for liquid chromatography-mass spectrometry confirmation, a true validation of brevetoxins in shellfish extracts is not possible at this time. However, our assay correlated well with another brevetoxin immunoassay currently in use in the United States. We believe this assay could be useful as a regulatory screening tool and could support pharmacokinetic studies in animals and clinical evaluation of neurotoxic shellfish poisoning victims. 相似文献
123.
Dubois P Marchand G Gmouh S Vaultier M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(19):5642-5648
Task-specific ionic liquids (TSILs) and more specifically binary task-specific ionic liquids (BTSILs), a unique subclass, have been shown to be excellent supports for solution-phase chemistry. The negligible volatility of ionic liquids enables their use as stable droplet microreactors in atmospheric environments without oil protection or confinement. These droplets can be moved, merged and mixed by electrowetting on a chip. Solution-phase synthesis can be performed on these open digital microfluidic labs-on-a-chip as illustrated by a study of the Grieco three-component reaction in [tmba][NTf(2)]-droplet (tmba=N-trimethyl-N-butylammonium NTf(2)=bis(trifluoromethylsulfonyl)imide) microreactors. A detailed study of matrices and scale effects on conversion and kinetic rates of this three-component condensation is presented in this paper. Reactions have been shown to be slower in droplets than in batches in the absence of additional mixing. Also, a significant influence of the ionic-liquid matrix has been observed. Finally, an increase of droplet's temperature resulted in a kinetics enhancement so as to reach macroscale reaction rates, probably because of a much better mixing of reaction's components involving a Marangoni's effect. 相似文献
124.
Novel monolithic supports (MS/BVPE) were prepared by thermally initiated free radical copolymerisation of p-methylstyrene (MS) and 1,2-bis(p-vinylphenyl)ethane (BVPE). The polymer was synthesised in fused silica capillaries (80 mm x 0.2 mm and 80 mm x 0.53 mm) and in borosilicate glass columns (90 mm x 1.0 mm and 90 mm x 3.0 mm) to yield different HPLC column designs. A comparison of those column dimensions regarding morphology as well as separation efficiency and applicability in bioanalysis is presented. The efficiency towards proteins as well as oligonucleotides was found to be considerably improved with decreasing column I.D. While a 5-protein mixture was baseline separated on all investigated column designs, the separation of small biomolecules like oligonucleotides or peptides on microbore and conventional size glass columns was strongly restricted in terms of resolution due to extensive peak broadening or the occurrence of peak asymmetry. Monolithic MS/BVPE capillary columns up to 0.53 mm I.D., however, proved to be applicable to the fractionation of the whole spectrum of biopolymers, including proteins, peptides, oligonucleotides as well as double-stranded DNA fragments. Due to the fact that reliable chromatography makes great demand on the robustness of the stationary phase, monolithic MS/BVPE capillaries were subjected to a comprehensive reproducibility study including run-to-run as well as batch-to-batch reproducibility. 相似文献
125.
In this paper the synthesis, optimisation and application of a silane based monolithic copolymer for the rapid separation of proteins and oligonucleotides is described. The monolith was prepared by thermal initiated in situ copolymerisation of trimethylsilyl-4-methylstyrene (TMSiMS) and bis(4-vinylbenzyl)dimethylsilane (BVBDMSi) in a silanised 200 microm I.D. fused silica column. Different ratios of monomer and crosslinker, as well as different ratios of micro- (toluene) and macro-porogen (2-propanol) were used for optimising the physical properties of the stationary phase regarding separation efficiency. The prepared monolithic stationary phases were characterised by measurement of permeability with different solvents, determination of pore size distribution by mercury intrusion porosimetry (MIP). Morphology was studied by scanning electron microscopy (SEM). Applying optimised conditions, a mixture comprised of five standard proteins ribunuclease A, cytochrome c, alpha-lactalbumine, myoglobine and ovalbumine was separated within 1 min by ion-pair reversed-phase liquid chromatography (IP-RPLC) obtaining half-height peak widths between 1.8 and 2.4 s. Baseline separation of oligonucleotides d(pT)(12-18) was achieved within 1.8 min obtaining half-height peak widths between 3.6 and 5.4 s. The results demonstrate the high potential of this stationary phase for fast separation of high-molecular weight biomolecules such as oligonucleotides and proteins. 相似文献
126.
Alejandro Madrid Ana Lizeth Morales Valentina Saffirio Mauricio A. Cuellar Enrique Werner Bastin Said Patricio Godoy Nelson Caro Mirna Melo Ivn Montenegro 《Molecules (Basel, Switzerland)》2021,26(21)
In this study, the essential oil (EO) from Laurelia sempervirens was analyzed by GC/MS and safrole (1) was identified as the major metabolite 1, was subjected to direct reactions on the oxygenated groups in the aromatic ring and in the side chain, and eight compounds (4 to 12) were obtained by the process. EO and compounds 4–12 were subjected to biological assays on 24 strains of the genus Saprolegnia, specifically of the species 12 S. parasitica and 12 S. australis. EO showed a significant effect against Saprolegnia strains. Compound 6 presents the highest activity against two resistant strains, with minimum inhibitory concentration (MIC) and minimum oomyceticidal concentration (MOC) values of 25 to 100 and 75 to 125 µg/mL, respectively. The results show that compound 6 exhibited superior activities compared to the commercial controls bronopol and azoxystrobin used to combat these pathogens. 相似文献
127.
H. Othmani R. Ben Said N. Terzi N.-E. Jaidane M. Mogren Al Mogren A. Elmarghany 《Molecular physics》2019,117(13):1589-1603
ABSTRACTIn many cases, 5-fluorouracil (5-FU) is the first-line drug used in combined chemotherapy and radiotherapy treatments due to its radio-sensitization properties. It could participate in a tautomerization process similar to that of uracil, where 5-FU may couple to adenine in DNA. At present, we performed structural and spectroscopic studies using quantum chemical methods of neutral and cationic isolated 5-FU anticarcinogenic drug tautomers, either interacting with a water molecule or embedded into an implicit water solvent. Also, we determined the stationary points (both stable structures and transition states) on their ground potential energy surfaces playing a role during the tautomerization processes. For neutral and ionic species in the gas phase and in solvent, the ordering of the tautomers is found to be the same, where the di-keto form of 5-FU is the most stable structure, followed by the keto–enol and di-enol structural forms. The energy barriers for tautomerization are strongly reduced in solvent (< 0.5?eV) compared to isolated species (~2?eV). The patterns of their lowest electronic states are also computed. Our data may help for the identification of these species in vivo and in the laboratory. 相似文献
128.
We introduce a simple model for free damage propagation based on non-local potentials. The model is developed using a state based peridynamic formulation. The resulting evolution is shown to be well posed. At each instant of the evolution we identify the damage set. On this set the local strain has exceeded critical values either for tensile or hydrostatic strain and damage has occurred. For this model the damage set is nondecreasing with time and associated with damage variables defined at each point in the body. We show that energy balance holds for this evolution. For differentiable displacements away from the damage set we show that the nonlocal model converges to the linear elastic model. 相似文献
129.
B. Amimour M. Slimani C. Sifi R. Khémissi H. Meradji S. Ghemid S. Bin Omran R. Khenata 《Chinese Journal of Physics (Taipei)》2017,55(2):367-377
In this work, the full-potential linearized augmented plane wave (FP-LAPW) method was used to calculate the structural, electronic, thermal and thermodynamic properties of BaS and CaS compounds and their ternary mixtures, Ba1?xCaxS. The local-density approximation (LDA), the Wu-Cohen generalized gradient approximation (WC-GGA) and the Perdew-Burke-Ernzerhof generalized gradient approximation (PBE-GGA) were used as the exchange-correlation potential. Moreover, the modified Becke–Johnson approximation was also used for the band structure calculations. We examined the composition effect on the lattice constants, bulk modulus and band gap. The microscopic origins of the band gap bowing were characterized in detail using the approach of Zunger and colleagues. Pressure and temperature effects on the lattice parameter, heat capacity, Debye temperature, Grüneisen parameter, and thermal expansion coefficient were predicted using the quasi-harmonic Debye model. The thermodynamic stability of these alloys was investigated by calculating the excess enthalpy of mixing, ?Hm, and the phase diagram. It was shown that these alloys are stable at high temperature. 相似文献
130.
Syed Najmul Hejaz Azmi Bashir Iqbal Muna Ahmed Mohad Jaboob Warda Ali Said Al Shahari Nafisur Rahman 《中国化学会会志》2009,56(6):1083-1091
The objective of this work is to develop and validate spectrophotometric method for the determination of piroxicam in commercial dosage forms. The method is based on the chelation of the drug with Fe(III) to form pink coloured metal chelate at room temperature which absorbs maximally at 504 nm. Beer's law is obeyed over the concentration range of 8–160 μg mL?1 (A = 1.07 × 10?3 + 7.75 × 10?3 C). Under the optimized experimental conditions, proposed method is validated as per the International Conference on Harmonisation guidelines. The limits of detection and quantitation for the proposed method are 0.775 and 2.348 μg mL?1, respectively. The proposed method has been successfully applied to the determination of piroxicam in commercial dosage forms. The results are compared with the reference El‐Ries et al. spectrophotometric method. 相似文献