全文获取类型
收费全文 | 15161篇 |
免费 | 1346篇 |
国内免费 | 653篇 |
专业分类
化学 | 15073篇 |
晶体学 | 328篇 |
力学 | 22篇 |
综合类 | 9篇 |
数学 | 4篇 |
物理学 | 1724篇 |
出版年
2024年 | 9篇 |
2023年 | 145篇 |
2022年 | 197篇 |
2021年 | 476篇 |
2020年 | 485篇 |
2019年 | 362篇 |
2018年 | 298篇 |
2017年 | 272篇 |
2016年 | 546篇 |
2015年 | 556篇 |
2014年 | 596篇 |
2013年 | 1161篇 |
2012年 | 727篇 |
2011年 | 668篇 |
2010年 | 752篇 |
2009年 | 752篇 |
2008年 | 775篇 |
2007年 | 796篇 |
2006年 | 764篇 |
2005年 | 705篇 |
2004年 | 758篇 |
2003年 | 671篇 |
2002年 | 1402篇 |
2001年 | 371篇 |
2000年 | 313篇 |
1999年 | 316篇 |
1998年 | 290篇 |
1997年 | 217篇 |
1996年 | 419篇 |
1995年 | 397篇 |
1994年 | 143篇 |
1993年 | 114篇 |
1992年 | 128篇 |
1991年 | 78篇 |
1990年 | 51篇 |
1989年 | 67篇 |
1988年 | 66篇 |
1987年 | 36篇 |
1986年 | 41篇 |
1985年 | 55篇 |
1984年 | 39篇 |
1983年 | 24篇 |
1982年 | 21篇 |
1981年 | 20篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 13篇 |
1975年 | 6篇 |
1972年 | 5篇 |
1969年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 312 毫秒
991.
Chao Liang Shu‐ying Han Jun‐qin Qiao Hong‐zhen Lian Xin Ge 《Journal of separation science》2014,37(22):3226-3234
A strategy to utilize neutral model compounds for lipophilicity measurement of ionizable basic compounds by reversed‐phase high‐performance liquid chromatography is proposed in this paper. The applicability of the novel protocol was justified by theoretical derivation. Meanwhile, the linear relationships between logarithm of apparent n‐octanol/water partition coefficients (logKow′′) and logarithm of retention factors corresponding to the 100% aqueous fraction of mobile phase (logkw) were established for a basic training set, a neutral training set and a mixed training set of these two. As proved in theory, the good linearity and external validation results indicated that the logKow′′–logkw relationships obtained from a neutral model training set were always reliable regardless of mobile phase pH. Afterwards, the above relationships were adopted to determine the logKow of harmaline, a weakly dissociable alkaloid. As far as we know, this is the first report on experimental logKow data for harmaline (logKow = 2.28 ± 0.08). Introducing neutral compounds into a basic model training set or using neutral model compounds alone is recommended to measure the lipophilicity of weakly ionizable basic compounds especially those with high hydrophobicity for the advantages of more suitable model compound choices and convenient mobile phase pH control. 相似文献
992.
《Comptes Rendus Chimie》2014,17(4):305-309
Various electron-rich aromatics could be smoothly converted into the corresponding bis(indolyl)methanes in good to moderate yields by treatment of electron-rich aromatics with POCl3 and DMF, followed by treatment with indole at room temperature. The present article is the first report on a novel metal-free one-pot method for the preparation of bis(indolyl)methanes from electron-rich aromatics. 相似文献
993.
Excellent Performance of Few‐Layer Borocarbonitrides as Anode Materials in Lithium‐Ion Batteries 下载免费PDF全文
Borocarbonitrides (BxCyNz) with a graphene‐like structure exhibit a remarkable high lithium cyclability and current rate capability. The electrochemical performance of the BxCyNz materials, synthesized by using a simple solid‐state synthesis route based on urea, was strongly dependent on the composition and surface area. Among the three compositions studied, the carbon‐rich compound B0.15C0.73N0.12 with the highest surface area showed an exceptional stability (over 100 cycles) and rate capability over widely varying current density values (0.05–1 A g?1). B0.15C0.73N0.12 has a very high specific capacity of 710 mA h g?1 at 0.05 A g?1. With the inclusion of a suitable additive in the electrolyte, the specific capacity improved drastically, recording an impressive value of nearly 900 mA h g?1 at 0.05 A g?1. It is believed that the solid–electrolyte interphase (SEI) layer at the interface of BxCyNz and electrolyte also plays a crucial role in the performance of the BxCyNz . 相似文献
994.
Copper‐Catalyzed NH Insertion and Oxidative Aromatization Cascade: Facile Synthesis of 2‐Arylaminophenols 下载免费PDF全文
Dong Ding Xiaobing Lv Dr. Jian Li Guangyang Xu Dr. Bing Ma Prof. Dr. Jiangtao Sun 《化学:亚洲杂志》2014,9(6):1539-1542
A copper‐catalyzed cascade reaction of N‐H insertion and oxidative aromatization has been developed. 2‐Arylaminophenols have been prepared in moderate to high yields from the diazo substrates. Moreover, this newly established methodology allows efficient access to natural 1‐oxygenated carbazole alkaloids, such as glycozolicine and murrayafoline A. 相似文献
995.
996.
Nitro‐Substituted Bishomocubanes: Synthesis,Characterization, and Application as Energetic Materials 下载免费PDF全文
Sohan Lal Dr. Sundaram Rajkumar Amit Tare Dr. Sasidharakurup Reshmi Prof. Dr. Arindrajit Chowdhury Prof. Dr. Irishi N. N. Namboothiri 《化学:亚洲杂志》2014,9(12):3533-3541
Several high‐energy‐density strained polycyclic compounds nitromethyl‐l,3‐bishomocubane (NMBHC), nitromethylene‐1,3‐bishomocubane (NMyBHC), and bis(nitromethyl)‐1,3‐bishomocubane (DNTMBHC), which were synthesized for the first time from bishomocubanone, hold potential for application as standalone fuels in liquid bipropellant systems or as additives in liquid and solid propellant formulations. DFT analysis at the B3LYP/6‐31G(d) level of theory was employed to optimize the geometries of the compounds and to determine their densities, heats of formation, and various thermodynamic properties. The density specific impulse, determined by using equilibrium thermodynamics, demonstrated an improvement of 75 s for NMBHC and NMyBHC over standard hydrocarbons. The specific impulse with ammonium perchlorate showed an improvement of 25–30 s over hydroxy‐terminated polybutadiene. Thermogravimetric analysis revealed that NMBHC, NMyBHC, and DNTMBHC evaporated readily with activation energies of 58.8, 69.2, and 74.5 kJ mol?1, respectively. 相似文献
997.
Henry Insuasty Braulio Insuasty Edison Castro Justo Cobo Christopher Glidewell 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(9):908-911
In the title compound, C15H12N4OS2, the bond distances in the fused heterocyclic system show evidence for aromatic‐type delocalization in the pyrazole ring with some bond fixation in the triazine ring. The thiophenyl substituent is slightly disordered over two sets of atomic sites having occupancies of 0.934 (4) and 0.066 (4). The non‐H atoms in the entire molecule are nearly coplanar, with the planes of the furanyl substituent and the major orientation of the thiophenyl substituent making dihedral angles of 5.72 (17) and 1.8 (3)°, respectively, with that of the fused ring system. Molecules are linked into centrosymmetric R22(10) dimers by C—H...O hydrogen bonds and these dimers are further linked into chains by a single π–π stacking interaction. Comparisons are made with some related 4,7‐diaryl‐2‐(ethylsulfanyl)pyrazolo[1,5‐a][1,3,5]triazines which contain variously substituted aryl groups in place of the furanyl and thiophenyl substituents in the title compound. 相似文献
998.
Naiem Ahmad Wani Vivek Kumar Gupta Rajni Kant Subrayashastry Aravinda Rajkishor Rai 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(8):776-779
The crystal structure of N‐[(1‐{2‐oxo‐2‐[2‐(pyrazin‐2‐ylcarbonyl)hydrazin‐1‐yl]ethyl}cyclohexyl)methyl]pyrazine‐2‐carboxamide monohydrate (Pyr‐Gpn‐NN‐NH‐Pyr·H2O), C19H23N7O3·H2O, reveals an unusual trans–gauche (tg−) conformation for the gabapentin (Gpn) residue around the Cγ—Cβ (θ1) and Cβ—Cα (θ2) bonds. The molecular conformation is stabilized by intramolecular N—H...N hydrogen bonds and weak C—H...O interactions. The packing of the molecules in the crystal lattice shows a network of strong N—H...O and O—H...O hydrogen bonds together with weak C—H...O and π–π inteactions. 相似文献
999.
Viktor Vrbel Július Sivý Peter af tefan Marchalín 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(8):817-822
Molecules of (S)‐6‐oxo‐1‐(thiophen‐2‐ylmethyl)piperidine‐2‐carboxylic acid, C11H13NO3S, crystallize as single enantiomers in the space group P21 and the thiophene ring is disordered over two positions, while (S)‐6‐oxo‐1‐(thiophen‐3‐ylmethyl)piperidine‐2‐carboxylic acid, C11H13NO3S, crystallizes as a single enantiomer in the space group P212121. Their absolute configurations were confirmed by anomalous dispersion effects in diffraction measurements on the crystals. The molecules of each compound are linked by a combination of strong O—H...O hydrogen bonds and weak C—H...O interactions, resulting in two‐ and three‐dimensional networks, respectively, in the crystal structures. 相似文献
1000.
Rim Benali‐Cherif Radhwane Takouachet El‐Eulmi Bendeif Nourredine Benali‐Cherif 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(7):689-692
Two polymorphs of L‐aspartic acid hydrochloride, C4H8NO4+·Cl−, were obtained from the same aqueous solution. Their crystal structures have been determined from single‐crystal data collected at 100 K. The crystal structures revealed three‐ and two‐dimensional hydrogen‐bonding networks for the triclinic and orthorhombic polymorphs, respectively. The cations and anions are connected to one another via N—H...Cl and O—H...Cl interactions and form alternating cation–anion layer‐like structures. The two polymorphs share common structural features; however, the conformations of the L‐aspartate cations and the crystal packings are different. Furthermore, the molecular packing of the orthorhombic polymorph contains more interesting interactions which seems to be a favourable factor for more efficient charge transfer within the crystal. 相似文献