全文获取类型
收费全文 | 5901篇 |
免费 | 639篇 |
国内免费 | 1387篇 |
专业分类
化学 | 3950篇 |
晶体学 | 22篇 |
力学 | 205篇 |
综合类 | 9篇 |
数学 | 1964篇 |
物理学 | 1777篇 |
出版年
2024年 | 3篇 |
2023年 | 132篇 |
2022年 | 130篇 |
2021年 | 139篇 |
2020年 | 190篇 |
2019年 | 114篇 |
2018年 | 92篇 |
2017年 | 121篇 |
2016年 | 131篇 |
2015年 | 208篇 |
2014年 | 333篇 |
2013年 | 410篇 |
2012年 | 483篇 |
2011年 | 566篇 |
2010年 | 458篇 |
2009年 | 558篇 |
2008年 | 525篇 |
2007年 | 592篇 |
2006年 | 554篇 |
2005年 | 356篇 |
2004年 | 235篇 |
2003年 | 191篇 |
2002年 | 216篇 |
2001年 | 191篇 |
2000年 | 183篇 |
1999年 | 171篇 |
1998年 | 131篇 |
1997年 | 105篇 |
1996年 | 74篇 |
1995年 | 70篇 |
1994年 | 66篇 |
1993年 | 52篇 |
1992年 | 68篇 |
1991年 | 49篇 |
1990年 | 22篇 |
1986年 | 5篇 |
1959年 | 1篇 |
1957年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有7927条查询结果,搜索用时 46 毫秒
991.
Mesoporous Fe2O3 microspheres: rapid and effective enrichment of phosphopeptides for MALDI-TOF MS analysis 总被引:1,自引:0,他引:1
Han L Shan Z Chen D Yu X Yang P Tu B Zhao D 《Journal of colloid and interface science》2008,318(2):315-321
Mesoporous Fe(2)O(3) microspheres have been successfully synthesized by the polymerization (urea and formaldehyde)-induced ferric hydroxide colloid aggregation. The urea-formaldehyde resin was removed by calcination in air. The obtained mesoporous Fe(2)O(3) materials have spherical morphology with uniform particle size of approximately 3.0 microm and porous surface with large inter-particle pores of approximately 48.0 nm. The surface area is as large as approximately 33.3 m(2)/g and the pore volume is 0.31 cm(3)/g. The mesoporous Fe(2)O(3) microspheres were used for the enrichment of phosphopeptides for the first time, in which high sensitivity, selectivity and capacity of specifically enriched phosphopeptides were achieved under a mild condition in a relative short time. After enriched from tryptic digest products of beta-casein by the novel mesoporous Fe(2)O(3) microspheres, phosphopeptides can be selectively detected with high intensity in MALDI-TOF mass spectrometry. Elimination of "shadow effect" was observed by using mesoporous Fe(2)O(3) microspheres, and the detectable limitation is 5x10(-10) M. This material is also effective for enrichment of phosphopeptides from the complex tryptic digests of commercial phosphoprotein casein, with much more phosphorylated sites (26 in 27 of total) and higher signal/noise ratio in the MALDI-TOF mass spectrometry, compared to commercial Fe(2)O(3) nanoparticles. It shows a great potential application in the field of rapid and effective isolation of phosphopeptides. 相似文献
992.
Wang H Zhou X Yu M Wang Y Han L Zhang J Yuan P Auchterlonie G Zou J Yu C 《Journal of the American Chemical Society》2006,128(50):15992-15993
We report a new approach to produce macroporous ( approximately 110 nm in diameter) ordered siliceous foams (MOSF) by using block copolymers as templates in the absence of any organic cosolvent. The fine three-dimensional honeycomb structure of MOSF was determined by electron tomography. A formation mechanism of MOSF that spans from the atomic to macroscopic scale is proposed, which involves the cooperative self-assembly of unilamellar vesicles followed by the supra-assembly of vesicles. The fusion of soft vesicles finally leads to MOSF with well-ordered and defined honeycomb structures. 相似文献
993.
利用激光闪光光解-瞬态吸收光谱技术研究了355 nm 光作用下六氟苯(C6F6)-HNO2水溶液的反应机理, 探讨了中间产物及其动力学行为, 并对终产物进行了分析. 实验表明, C6F6可与HNO2光解产生的OH自由基反应生成加合物C6F6…OH, 二级反应速率常数为1.8×109 L·mol -1·s-1, 加合物吸收峰位置在250、270和400 nm处; C6F6…OH 加合物通过消除反应生成C6F5O·, 其表观生成常数为6.1×105 s-1. C6F6…OH与O2复合转化为C6F6OHO2, 二级反应速率常数为2.8×106 L·mol-1·s-1, C6F6OHO2峰位置与C6F6…OH 加合物相似. 终产物分析表明, OH自由基与六氟苯发生消除HF的反应而生成C6F5OH, 有O2时, 还产生四氟醌C6F4O2, 但无论有氧还是无氧体系, 均不发生硝基化反应. 相似文献
994.
Organoboron-based diarylethene was successfully synthesized and exhibited photochromic property. Furthermore, its photochromic property can be modulated by a fluoride ion. The absorption maximum of the photostationary state shifted from 655 to 490 nm upon addition of a fluoride ion. The modulation mechanism is attributed to the special Lewis acid-base interaction between a trivalent boron atom and a fluoride ion. 相似文献
995.
以廉价国产化试剂合成大孔径高度有序介孔氧化硅分子筛 总被引:4,自引:0,他引:4
新一代大孔径(1~30nm)介孔分子筛在大分子转化、吸附、生物大分子分离以及电磁、传感器、光电子等领域均具有广泛的应用前景犤1~4犦。由昂贵的长链有机季铵盐阳离子表面活性剂为模板合成的MCM-41介孔分子筛,由于其孔径小,水热稳定性差,受到了较大的限制。与其相比,以嵌段高分子共聚物为模板剂合成的介孔分子筛SBA-15具有孔径均一,有序度高,并且其孔径大以及水热性能良好等优点,近年来得到了广泛的研究犤5~9犦。其骨架上修饰有机硅烷,可用于重金属的分离、回收,以及蛋白质的控释与分离。利用主-客体方法在SB… 相似文献
996.
Wu H Yang T Zhao Q Zhou J Li C Li F 《Dalton transactions (Cambridge, England : 2003)》2011,40(9):1969-1976
Iridium(III) complexes with intense phosphorescence in solution have been widely applied in organic light-emitting diodes, chemosensors and bioimaging. However, little attention has been paid to iridium(III) complexes showing weak phosphorescence in solution and enhanced phosphorescence emission in the solid state (EPESS). In the present study, two β-diketonate ligands with different degrees of conjugation, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HL1) and 1-phenyl-3-methyl-4-phenylacetyl-5-pyrazolone (HL2), have been synthesized to be used as ancillary ligands for two iridium(III) complexes, Ir(ppy)(2)(L1) and Ir(ppy)(2)(L2) (Hppy = 2-phenylpyridine). The two complexes have been characterized by single-crystal X-ray crystallography, (1)H NMR and elemental analysis. Interestingly, Ir(ppy)(2)(L1) is EPESS-active whereas Ir(ppy)(2)(L2) exhibits moderately intense emission both in solution and as a neat film, indicating that the degree of conjugation of the β-diketone ligands determines the EPESS-activity. The single-crystal X-ray analysis has indicated that there are π-π interactions between the adjacent ppy ligands in Ir(ppy)(2)(L1) but not in Ir(ppy)(2)(L2). Finally, EPESS-active Ir(ppy)(2)(L1) has been successfully embedded in polymer nanoparticles and used as a luminescent label in bioimaging. 相似文献
997.
A beta-iron oxyhydroxide (FeOOH) was synthesized via a hydrolyzing route and investigated as a lithium intercalation host.
It delivers a capacity of about 170 mAh/g and exhibits good cycling performance when charged/discharged in the voltage range
from 1.6 V to 3.3 V. For the first time we have confirmed that FeOOH is suitable for using it as a negative electrode for
hybrid electrochemical supercapacitor assembled with an activated carbon positive electrode in 1.0 M LiPF6 ethylene carbonate/dimethyl carbonate (EC/DMC, 1:2 in volume) solution. The cell reveals a slightly sloping voltage profile
from 0 V to 2.8 V and gives an estimated specific energy of 45 Wh/kg based on the total weight of two electrode materials,
approximately two times of carbon/carbon electrochemical double layer capacitors. The hybrid supercapacitor shows a good cycling
performance, it remains approximately 96% of initial capacity after 800 cycles at a charge/discharge rate of 4 C. The capacitor
also shows a desirable rate capability, even at 10 C discharge rate, it holds 80% of capacity compared with that at 1 C discharge
rate. 相似文献
998.
将取代色满酮(1)与芳肼反应生成的腙与HNCO发生[3+2]环加成反应,加成产物(2)经氧化得到偕偶氮异氰酸酯(3).化合物3在HBF4的催化下发生环化-重排反应,得到新颖的三环系2-氧代-1,2,4-三唑并[3,2-d][1,5]苯并氧氮杂化合物5a~5g. 相似文献
999.
Yan?Zhang Changchun?Wang Wuli?Yang Bin?Shi Shoukuan?FuEmail author 《Colloid and polymer science》2005,283(11):1246-1252
Biodegradable tri-component diblock copolymer was synthesized by bulk copolymerization of ε-caprolactone (CL) and D, L-lactide (LA) in the presence of methoxy poly(ethylene glycol) (MePEG), using stannous octoate as catalyst. Their chemical
structure and physical properties were investigated by GPC, NMR, DSC, TGAand XRD. The increase of CL/LA ratio in the diblock
copolymer leads to lower T
g, higher decomposition temperature and crystallinity. Nanoparticles formulated from MePEG–poly(CL-co-LA) (PCAE) possess spherical structure, which was characterized by dynamic light scattering (DLS) and transmission electron
microscopy (TEM). The DLS results indicate that the particle size increased with the increase of CL/LA ratio and the hydrophobic
fragment length in the copolymer. The drug encapsulation efficiency and the drug release behavior in vitro conditions of camptothecin
were measured by high performance liquid chromatography (HPLC). The encapsulation efficiency can be achieved as high as 84.4%
and the release behavior can be made well-controlled. MePEG–poly(CL-co-LA) nanoparticles might have a great potential as carriers for hydrophobic drugs. 相似文献
1000.
Investigation of Tomato Plant Defence Response to Tobacco Mosaic Virus by Determination of Methyl Salicylate with SPME-Capillary GC-MS 总被引:2,自引:0,他引:2
Headspace SPME was applied to investigation of tomato plant defence response to tobacco mosaic virus (TMV) by determination of compounds emitted from tomato plants at the extraction conditions of 25 °C and 15 min. It was found that TMV-inoculated tomato plant released large amount of methyl salicylate (MeSA) as response to TMV and MeSA concentration changed dramatically with time after inoculation. Gaseous MeSA as a signaling compound could induce in surrounding tomato plants to produce salicylic acid (SA) and synthesize and release MeSA. These results show that MeSA might be an airborne plant-signalling molecule in tomato plant response to TMV. The present method provided low detection limit of 2.0 ng L–1 and needed little sample preparation time (15 min), so the method makes it easy to find the critical times of tomato plant response to TMV by fast determination of MeSA released from tomato plant. 相似文献