全文获取类型
收费全文 | 750篇 |
免费 | 48篇 |
国内免费 | 42篇 |
专业分类
化学 | 754篇 |
力学 | 19篇 |
数学 | 44篇 |
物理学 | 23篇 |
出版年
2023年 | 16篇 |
2022年 | 8篇 |
2021年 | 14篇 |
2020年 | 17篇 |
2019年 | 28篇 |
2018年 | 28篇 |
2017年 | 23篇 |
2016年 | 43篇 |
2015年 | 36篇 |
2014年 | 77篇 |
2013年 | 45篇 |
2012年 | 33篇 |
2011年 | 78篇 |
2010年 | 38篇 |
2009年 | 50篇 |
2008年 | 53篇 |
2007年 | 52篇 |
2006年 | 43篇 |
2005年 | 55篇 |
2004年 | 34篇 |
2003年 | 7篇 |
2002年 | 5篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 3篇 |
1998年 | 6篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1995年 | 6篇 |
1994年 | 8篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1982年 | 1篇 |
排序方式: 共有840条查询结果,搜索用时 15 毫秒
1.
2.
以B 3 PyMPM∶Cs/Al/HAT-CN作为电荷生成单元制备高效叠层绿色磷光有机电致发光器件,叠层器件的最大电流效率和最大流明效率分别为172.2 cd/A和111.0 lm/W,在5 mA/cm^2电流密度下,叠层器件的电压和亮度分别为传统器件的2.04倍和2.84倍.为了探究叠层器件性能优于传统器件的原因,研究了电荷生成单元内的电荷产生和注入过程,以及薄层铝对电子注入特性和电荷生成单元稳定性的影响.实验结果表明,电荷能够有效地在电荷生成单元内产生并顺利注入电子传输层中,B3PyMPM∶Cs和HAT-CN间Al薄层的插入能够进一步提高电子注入效率及器件结构的稳定性. 相似文献
3.
Ning Ling Jiguang Zhang Meng Wang Zhen Wang Ziyu Mi Surani Bin Dolmanan Mingsheng Zhang Bingqing Wang Wan Ru Leow Jia Zhang Yanwei Lum 《Angewandte Chemie (International ed. in English)》2023,62(36):e202308782
Electrochemical CO2 reduction (CO2R) in acidic media with Cu-based catalysts tends to suffer from lowered selectivity towards multicarbon products. This could in principle be mitigated using tandem catalysis, whereby the *CO coverage on Cu is increased by introducing a CO generating catalyst (e.g. Ag) in close proximity. Although this has seen significant success in neutral/alkaline media, here we report that such a strategy becomes impeded in acidic electrolyte. This was investigated through the co-reduction of 13CO2/12CO mixtures using a series of Cu and CuAg catalysts. These experiments provide strong evidence for the occurrence of tandem catalysis in neutral media and its curtailment under acidic conditions. Density functional theory simulations suggest that the presence of H3O+ weakens the *CO binding energy of Cu, preventing effective utilization of tandem-supplied CO. Our findings also provide other unanticipated insights into the tandem catalysis reaction pathway and important design considerations for effective CO2R in acidic media. 相似文献
4.
Yao Qian Dr. Xiangyu Guo Prof. Yunfang Wang Prof. Zheng Ouyang Prof. Xiaoxiao Ma 《Angewandte Chemie (International ed. in English)》2023,62(52):e202312275
Spatial lipidomics based on mass spectrometry imaging (MSI) is a powerful tool for fundamental biology studies and biomarker discovery. But the structure-resolving capability of MSI is limited because of the lack of multiplexed tandem mass spectrometry (MS/MS) method, primarily due to the small sample amount available from each pixel and the poor ion usage in MS/MS analysis. Here, we report a mobility-modulated sequential dissociation (MMSD) strategy for multiplex MS/MS imaging of distinct lipids from biological tissues. With ion mobility-enabled data-independent acquisition and automated spectrum deconvolution, MS/MS spectra of a large number of lipid species from each tissue pixel are acquired, at no expense of imaging speed. MMSD imaging is highlighted by MS/MS imaging of 24 structurally distinct lipids in the mouse brain and the revealing of the correlation of a structurally distinct phosphatidylethanolamine isomer (PE 18 : 1_18 : 1) from a human hepatocellular carcinoma (HCC) tissue. Mapping of structurally distinct lipid isomers is now enabled and spatial lipidomics becomes feasible for MSI. 相似文献
5.
A novel Pd-catalyzed tandem reaction involving hydroalkynylation,isomerization.Diels-Alder cycloaddition and aromatization reaction to produce phthalan derivatives in moderate yields is reported.The reaction is atom economical and occurs in a highly ordered fashion.The reaction mechanism is discussed. 相似文献
6.
采用液相色谱串联质谱法(LC/MS/MS)测定含藻水氯消毒产生7种亚硝胺类(NAms)消毒副产物(NDMA,NMEA,NDEA,NDPA,NDBA,NPyr,NPip).方法检出限分别为5.0,14,8.6,3.6,2.9,6.3和4.9 ng/L,相关系数r>0.999.除NDBA回收率(60%)较低外,其余6种亚硝胺回收率均在80%~120%之间,相对标准偏差为1.4%~12.6%.分别以藻原液和消毒后藻液配制基质标准曲线,采用其与纯水标准曲线斜率之比评估基质效应.藻原液的基质效应为0.79 ~0.94,藻液消毒后NDMA基质效应为0.36,其他亚硝胺为0.63~0.96.应用此方法检测了自来水、富营养江河水、景观水及藻类悬浮液氯消毒后的亚硝胺含量. 相似文献
7.
Fourteen common drugs of abuse were identified in spiked oral fluid (ng mL−1 levels), analyzed directly from medical swabs using touch spray mass spectrometry (TS-MS), exemplifying a rapid test for drug detection. Multiple stages of mass analysis (MS2 and MS3) provided identification and detection limits sought by international forensic and toxicological societies, Δ9-THC and buprenorphine excluded. The measurements were made using a medical swab as both the sampling probe and means of ionization. The adaptation of medical swabs for TS-MS analysis allows non-invasive and direct sampling of neat oral fluid. Data acquisition was rapid, seconds per drug, and MS3 ensured reliable identification of illicit drugs. The reported data were acquired to investigate (i) ionization of common drugs from commercial swabs, (ii) ion intensity over spray duration, and (iii) dynamic range, all as initial steps in development of a quantitative method. The approach outlined is intended for point-of-care drug testing using oral fluid in clinical applications as well as in situ settings, viz. in forensic applications. The proof-of-concept results presented will require extension to other controlled substances and refinement in analytical procedures to meet clinical/legal requirements. 相似文献
8.
Takahiro Takayama Toshiki Mochizuki Kenichiro Todoroki Jun Zhe Min Hajime Mizuno Koichi Inoue Hiroyasu Akatsu Ichiro Noge Toshimasa Toyo'oka 《Analytica chimica acta》2015
Chiral metabolites are found in a wide variety of living organisms and some of them are understood to be physiologically active compounds and biomarkers. However, the overall analysis of chiral metabolomics is quite difficult due to the high number of metabolites, the significant diversity in their physicochemical properties, and concentration range from metabolite-to-metabolite. To solve this difficulty, we developed a novel approach for chiral metabolomics fingerprinting and chiral metabolomics extraction, which is based on the labeling of a pair of enantiomers of chiral derivatization reagents (i.e., DMT-(S,R)-Pro-OSu and DMT-3(S,R)-Apy) and precursor ion scan chromatography of the derivatives. The multivariate statistics is also required for this strategy. The proposed procedures were evaluated by the detection of a diagnostic marker (i.e., d-lactic acid) using the saliva of diabetic patients. This method was used for the determination of biomarker candidates of chiral amines and carboxyls in Alzheimer's disease (AD) brain homogenates. As the results, l-phenylalanine (L-Phe) and l-lactic acid (L-LA) were identified as the decreased and increased biomarker candidates in the AD brain, respectively. Therefore, the proposed approach seems to be helpful for the determination of non-target chiral metabolomics possessing amines and carboxyls. 相似文献
9.
In this work we demonstrated a facile method for the fabrication of C18 coordination polymer gel in a capillary, called stage-frit, which was efficiently applied to pack sub-2 μm C18 beads into the capillary by a high pressure bomb for the online separation of proteolytic peptides. The back pressure of the column with 10 cm × 75 μm i.d. is regularly lower than 170 bar at a flow rate of 300 nl/min, which could be operated on a common nanoLC system instead of nanoUPLC system due to the good permeability, low back pressure and high mechanical stress of the frit that will totally reduce the cost for the purchase of instrument. The stage-frit allows long-term continuous flow of the solvent and no significant beads loss or pressure instability was observed during the period. The repeatability of retention time for fifteen BSA tryptic peaks was found to be less than 1.08% (RSD) in six time nanoLC-ESI-MS/MS experiments. The average full width at half maximum (FWHM) of peptide peaks is 5.87 s. The sub-2 μm stage-frit nanoLC column showed better sensitivity than the commercial available for large scale proteomic analysis of total tissue proteins from human spleen. The number of identified peptides is approximately 0.4-fold and 0.2-fold higher than that obtained by utilizing commercial columns packed with 3 μm and 1.8 μm C18 materials, respectively. In the field of analytical chemistry, particularly the use of nanoLC systems, stage-frit nanoLC column offers a great potential for the separation of complex mixtures. 相似文献
10.
Glycans are known to be involved in a variety of biological processes throughout human physiology. Mass spectrometry has demonstrated itself as powerful analytical tool for quantitative and structural characterization of glycans. Studying these molecules at the glycopeptide level however, offers distinct advantages, namely the ability to characterize both the glycan and peptide fragments simultaneously, and moreover the ability to assign site specific heterogeneity. In light of this, peptides often dominate the spectrum and hinder the ionization efficiency of glycopeptides. For this reason, enrichment protocols prior to downstream MS analysis need to be developed. Here, we discuss the synthesis and use of carboxymethyl chitosan (CMCH) to enrich glycopeptides from a 12 protein mixture for MS analysis. This protocol was compared to a commercially available glycopeptide enrichment kit offered by EMD Millipore through the use of tandem mass tags (TMT) for relative quantification. Using this approach, we identified 98 unique N-linked glycopeptides and observed, that CMCH was able to enrich more sialylation than the commercial kit. In addition, we observed a trend based on TMT reporter ratios with respect to increasing sialylation. This corroborated that this stationary phase was exhibiting a mixed-mode enrichment through both hydrophilic interaction liquid chromatography (HILIC) and weak anion exchange (WAX) principles. 相似文献