全文获取类型
收费全文 | 3421篇 |
免费 | 258篇 |
国内免费 | 850篇 |
专业分类
化学 | 2294篇 |
晶体学 | 40篇 |
力学 | 191篇 |
综合类 | 46篇 |
数学 | 1493篇 |
物理学 | 465篇 |
出版年
2024年 | 8篇 |
2023年 | 52篇 |
2022年 | 77篇 |
2021年 | 92篇 |
2020年 | 155篇 |
2019年 | 141篇 |
2018年 | 101篇 |
2017年 | 165篇 |
2016年 | 161篇 |
2015年 | 120篇 |
2014年 | 204篇 |
2013年 | 283篇 |
2012年 | 284篇 |
2011年 | 217篇 |
2010年 | 165篇 |
2009年 | 237篇 |
2008年 | 233篇 |
2007年 | 220篇 |
2006年 | 180篇 |
2005年 | 173篇 |
2004年 | 188篇 |
2003年 | 140篇 |
2002年 | 109篇 |
2001年 | 86篇 |
2000年 | 88篇 |
1999年 | 95篇 |
1998年 | 64篇 |
1997年 | 82篇 |
1996年 | 79篇 |
1995年 | 64篇 |
1994年 | 42篇 |
1993年 | 36篇 |
1992年 | 43篇 |
1991年 | 29篇 |
1990年 | 23篇 |
1989年 | 14篇 |
1988年 | 11篇 |
1987年 | 8篇 |
1986年 | 6篇 |
1985年 | 9篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1980年 | 8篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1959年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有4529条查询结果,搜索用时 15 毫秒
91.
研究了1-和2-苯基萘, 1, 1'-和2, 2'-联萘, 2, 2-二羟基-, 2, 2'-二甲氧基和-2, 2'-甲基磺酰氧基-1, 1'-联萘等七种萘衍生物和三氧化硫的磺化反应。1-苯基萘和1, 1'-联萘的磺化先发生在4位上, 第二取代位置为6和7位。2-苯基萘和2, 2'-联萘均首先得到8位磺酸取代物, 进一步磺化得到8, 4'-和8, 8'-二磺酸取代物。2, 2'-二甲氧基-1, 1'-联萘以13:87的比例得到3位和6位磺酸取代物。2, 2'-二甲磺酰氧基-1, 1'-联萘以58:42的比例得到5位和6位磺酸取代物。2, 2'-二羟基-1, 1'-联萘的等摩尔磺化得到比例为35:65的5位和6位磺酸取代物, 和大于6摩尔的SO~3反应则以62:38的比例得到5位和6位磺酸取代物。 相似文献
92.
Photocycloadditionof(4-methyl-7-coumarinyl)OxyaceticAcidPropanediolDiesterandX-rayCrystalStructureofProductDuDa-Ming;WangYong... 相似文献
93.
脲衍生物对环氧树脂/双氰双胺固化体系潜伏性促进作用研究 总被引:5,自引:1,他引:5
本文用DSC、TBA、旋转粘度计等手段对一系列不同结构及不同取代基取代的脲衍生物对环氧树脂/双氰双胺固化体系的潜伏性促进作用作了考察。结果表明,其促进效果随脲的α位取代烷基碳原子数增加而减弱,而其β、γ位上的取代基团变换时对促进作用无明显影响。由此得出4,4-二(N,N-二甲基)脲二苯甲烷(简称M-二甲)和2,4-二(N,N-二甲基)脲甲苯(简称T-二甲)二种脲衍生物在本丈所考察的28种化合物中具有最显著的促进效果,其中T-二甲的促进活性略高于M-二甲,它们均可使上述固化体系的固化温度降至130℃左右,含有此促进剂的固化体系即使在30℃下贮存,其粘度保持基本不变的时间仍可达三个月以上。 相似文献
94.
Eisaku Nomura Yoshio Otsuji Hisaji Taniguchi 《Journal of inclusion phenomena and macrocyclic chemistry》1995,23(1):53-63
This paper deals with the ability ofp-tert-butylcalix[6]arene derivative1, which has six 3,6,9-trioxadecyl substituents at the phenolic oxygens, to encapsulate CT complexes of alkadienes with iodine. By adding I2 to alkadienes in CH2Cl2 in the presence of1, the absorbance at 363 nm, which was ascribed to I
3
–
ion, increased in the order: 1,5-hexadiene<1,9-decadiene 1,7-octadiene. The reactivity features of the CT complexes in the presence of1 are discussed. 相似文献
95.
Wen Weng Qing Le Zeng Bi Xia Yao Wen Shi Lin Qing Hua Wang Xiu Li You 《Chromatographia》2006,64(7-8):463-467
Five structurally related amino acid derivatives were enantioseparated by HPLC with a commercially available chiral stationary phase, Chiralcel OD-H. The chromatographic experiments were performed in the normal phase mode. n-Hexane/polar alcohol was used as mobile phase. Excellent baseline enantioseparations could be obtained for all these solutes. The effects of the concentration of polar alcohol and the column temperature on the retentions and enantioseparations were studied in detail. From the van't Hoff plots the corresponding apparent thermodynamic parameters were derived. Mechanism aspects of chiral recognition were discussed based on the relationship between the thermodynamic parameters and the structures of the solutes. It was found that the substituent of the phenyl group on the residual group of the amino acid derivatives was close relevant to thermodynamic origin of enantioseparation. Much better enthalpy–entropy compensation effect was obtained by plotting the differential, rather than the original, thermodynamic parameters. 相似文献
96.
A solid ion-pair material produced from ammonium tetraphenylborate (ATPB) and naphthalene has been used for the preconcentration of uranium from the large volume of its aqueous complex samples. Uranium reacts with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) to form a water insoluble, coloured complex. This complex is quantitatively retained on the ATPB-naphthalene adsorbent filled in a column in the pH range 7.0–9.5 and at a flow rate of 2 ml/min. The solid mass from the column is dissolved with 5 ml of dimethylformamide (DMF) and uranium is determined by fourth-derivative spectrophotometry. The calibration curve is linear over the concentration range of 0.13–15.0 g of uranium in 5 ml of the final DMF solution. Seven replicate determinations of 6 g of uranium gave a mean peak height (peak-to-peak signal between 592 nm and 582 nm) of 1.02 with a relative standard deviation of 0.95%. The sensitivity is 0.8419 (d4A/d4)/(g ml–1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the estimation of uranium has been studied and the method applied for the determination of uranium in coal fly ash, Zr-base alloy and some synthetic samples corresponding to standard alloys. 相似文献
97.
The Wittig reaction of methyl pyropheophorbide-d 2,obtained from methyl pyropheophorbide-a 1,with ben-zyltriphenylphosphonium bromide was performed to yield isomers 3a and 3b.The Vilsmeier reaction of nickelcomplex 4 or 7 with 3-dimethylaminoacrolein in the presence of phosphoryl chloride was carried out to form20-meso-2'-formylvinylpyropheophorbide-a 5 or 8,which was reacted with Wittig reagent to afford nickel complexisomers 6a and 6b or 9a and 9b,10a and 10b. 相似文献
98.
Markku J. Oila 《Tetrahedron》2005,61(45):10748-10756
A novel supported amino alcohol linker was synthesized and utilized for attachment of picolinic acid derivatives onto different supports. When the resin bound molecule was further activated, the PyOX-moiety could be constructed reliably in enantiopure form. Furthermore, an efficient Pd-catalyzed modification of a picolinic acid derivative is presented. 相似文献
99.
This paper describes a copper selective optical chemical sensor based on static quenching of the fluorescence of 2-(2′-hydroxyphenyl)benzoxazole entrapped in a poly(vinyl chloride) (PVC) membrane. The effect of the composition of the sensing membrane was studied, and experimental conditions were optimized. The sensors exhibit stable response over the concentration range from 4.0 × 10−8 M to 5.0 × 10−5 M Cu2+ at pH 4.0-6.5, and a high selectivity. The response time for Cu2+ with concentration ≤5 × 10−6 M is less than 7 min. The optode can be regenerated using 0.1 M HCl and acetate buffer solution. The sensor has been used for direct measurement of copper content in river water samples with a relative error less than 4% with reference to that obtained by atomic absorption spectrometry. 相似文献
100.
Summary An ,-appended eighteen carbon chains hypercin derivative (2) was synthesized starting from emodin. The overall yield of the seven step synthesis was 12%. The1H and13C NMR, absorption, and emission spectroscopic properties were measured;2 can be dissolved even in apolar solvents and polyethylene.
Synthese und Eigenschaften eines mit C18-Ketten ,-substituierten Hypericinderivats
Zusammenfassung Ein in den Positionen , mit zwei C18-Ketten substituiertes Derivat des Hypericins (2) wurde ausgehend von Emodin synthetisiert. Die Gesamtausbeute der siebenstufigen Synthese betrug 12%. Die1H- und13C-NMR, absorptions- und emissionsspektroskopischen Eigenschaften wurden gemessen;2 kann sogar in apolaren Lösungsmitteln und Polyethylen gelöst werden.相似文献