全文获取类型
收费全文 | 1729篇 |
免费 | 47篇 |
国内免费 | 7篇 |
专业分类
化学 | 1369篇 |
晶体学 | 8篇 |
力学 | 18篇 |
数学 | 154篇 |
物理学 | 234篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 18篇 |
2021年 | 103篇 |
2020年 | 40篇 |
2019年 | 61篇 |
2018年 | 74篇 |
2017年 | 49篇 |
2016年 | 71篇 |
2015年 | 77篇 |
2014年 | 58篇 |
2013年 | 163篇 |
2012年 | 82篇 |
2011年 | 107篇 |
2010年 | 92篇 |
2009年 | 76篇 |
2008年 | 106篇 |
2007年 | 120篇 |
2006年 | 82篇 |
2005年 | 88篇 |
2004年 | 56篇 |
2003年 | 63篇 |
2002年 | 47篇 |
2001年 | 15篇 |
2000年 | 11篇 |
1999年 | 23篇 |
1998年 | 13篇 |
1997年 | 17篇 |
1996年 | 23篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 12篇 |
1991年 | 5篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1980年 | 1篇 |
1979年 | 2篇 |
排序方式: 共有1783条查询结果,搜索用时 15 毫秒
991.
Maksim A. Kolosov Elena H. Shvets Dmitriy A. Manuenkov Sergey A. Vlasenko Irina V. Omelchenko Svetlana V. Shishkina Valeriy D. Orlov 《Tetrahedron letters》2017,58(12):1207-1210
6-Unsubstituted 7-R-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidines (R = H or Me) were synthesized via two pathways: (a) deacylation of the corresponding 5-acetyl Biginelli-like precursors in KOH/H2O and (b) reduction of the corresponding 1,2,4-triazolo[1,5-a]pyrimidines using LiAlH4. The products could be easily formylated at position 6, which is promising for the further synthesis of functionalized 6-substituted derivatives of 4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidines. In contrast, 6-acetyl-7-(4-(N,N-dimethylaminophenyl))-5-methyl-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidine undergoes a cascade process in KOH/H2O, leading to the formation of a 4,5,8,9-tetrahydro[1,2,4]triazolo[5,1-b]quinazoline derivative. 相似文献
992.
Svetlana V. Amosova Irina A. Novokshonova Maxim V. Penzik Andrey S. Filippov Alexander I. Albanov Vladimir A. Potapov 《Tetrahedron letters》2017,58(46):4381-4383
The regioselective reaction of 2-bromomethyl-1,3-thiaselenole 1 with thiourea is accompanied by rearrangement, expanding the ring to afford the corresponding six-membered isothiuronium salt, 2-[amino(imino)methyl]sulfanyl-2,3-dihydro-1,4-thiaselenine hydrobromide 2, a synthon of the 2,3-dihydro-1,4-thiaselenin-2-ylthiolate anion. The latter was used for the synthesis of the first representatives of 2-(organylsulfanyl)-2,3-dihydro-1,4-thiaselenines 3a–g, bis(2,3-dihydro-1,4-thiaselenin-2-yl) disulfide 5 and 1,6-bis(2,3-dihydro-1,4-thiaselenin-2-ylsulfanyl)hexane 6. 相似文献
993.
Vera P. Kashparova Victor A. Klushin Irina Yu. Zhukova Igor S. Kashparov Daria V. Chernysheva Irina B. Ilchibaeva Nina V. Smirnova Efim Sh. Kagan Victor M. Chernyshev 《Tetrahedron letters》2017,58(36):3517-3521
An efficient method for the oxidation of alcohols to aldehydes or ketones in a two-phase CH2Cl2/NaHCO3 (aq.) system, using iodine and catalytic amounts of 4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxyl and 2,4,6-trimethylpyridine, was developed. The performance of the method was demonstrated by the selective oxidation of 37 variously substituted alcohols in ≥90% yield, including the gram-scale synthesis of the important chemical 2,5-diformylfuran from biomass-derived 5-hydroxylmethylfurfural. 相似文献
994.
In this article, dispersive liquid-liquid microextraction (DLLME), based on the use of so-called switchable polarity dispersive solvent (SPDS) for microextraction, is presented for the first time. The new extraction technique makes use of a mixture of extraction solvent (dichloromethane) and the SPDS (acrylic acid). This mixture is injected into the aqueous sample solution, which was previously fortified with the alkaline agent (NaOH). The SPDS is dissolved in aqueous phase and a cloudy solution consisting of fine droplets of extraction solvent fully dispersed in the aqueous phase is observed. Simultaneously, as a consequence of the fast neutralization reaction, the SPDS investigated is converted into water-soluble salt and phase separation is achieved because the SPDS switches its polarity. Conversion of the SPDS excludes the negative influence of the conventional dispersive solvents used in DLLME on the solubility of target analytes in aqueous phase and, as a result, increases the DLLME efficiency. 相似文献
995.
996.
Arkhipova D. M. Ermolaev V. V. Miluykov V. A. Gaynanova G. A. Valeeva F. G. Zakharova L. Ya. Konovalov A. I. Islamov D. R. Kataeva O. N. Sinyashin O. G. 《Russian Chemical Bulletin》2015,64(10):2486-2492
Russian Chemical Bulletin - A crystal structure and aggregation properties of tri-n-butyl(octadecyl)phosphonium tetrafluoroborate were studied. Palladium nanoparticles stabilized by this... 相似文献
997.
Real‐time Monitoring of Discrete Synaptic Release Events and Excitatory Potentials within Self‐reconstructed Neuromuscular Junctions 下载免费PDF全文
Yu‐Tao Li Shu‐Hui Zhang Xue‐Ying Wang Xin‐Wei Zhang Dr. Alexander I. Oleinick Prof. Dr. Irina Svir Prof. Dr. Christian Amatore Prof. Dr. Wei‐Hua Huang 《Angewandte Chemie (International ed. in English)》2015,54(32):9313-9318
Chemical synaptic transmission is central to the brain functions. In this regard, real‐time monitoring of chemical synaptic transmission during neuronal communication remains a great challenge. In this work, in vivo‐like oriented neural networks between superior cervical ganglion (SCG) neurons and their effector smooth muscle cells (SMC) were assembled in a microfluidic device. This allowed amperometric detection of individual neurotransmitter release events inside functional SCG‐SMC synapse with carbon fiber nanoelectrodes as well as recording of postsynaptic potential using glass nanopipette electrodes. The high vesicular release activities essentially involved complex events arising from flickering fusion pores as quantitatively established based on simulations. This work allowed for the first time monitoring in situ chemical synaptic transmission under conditions close to those found in vivo, which may yield important and new insights into the nature of neuronal communications. 相似文献
998.
Ignatieva NY Zakharkina OL Andreeva IV Sobol EN Kamensky VA Myakov AV Averkiev SV Lunin VV 《Photochemistry and photobiology》2007,83(3):675-685
The purpose of this study was to characterize essential changes in the structure of annulus fibrosus (AF) after hydrothermal and infrared (IR) laser treatment and to correlate these results with alterations in tissue state. Polarization-sensitive optical coherence tomography imaging was used to measure collagen birefringence in AF. Differential scanning calorimetry was used as a complementary technique, providing detailed information on thermodynamic processes in the tissue. Birefringence, peak of the denaturation endotherm, and the enthalpy of denaturation (DeltaHm) were determined before and after hydrothermal heat treatment (85 degrees C for 15 min) and non-ablative Er:glass fiber laser exposures on AF in the whole disk (vertebrae-disk-vertebrae complex). Our data have demonstrated quantitative differences between results of laser and hydrothermal heating. Birefringence did not disappear and DeltaHm did not change after treatment in the water bath, but loss of birefringence and a decrease in the enthalpy did occur after laser exposure. These results could be explained by the photomechanical effect of laser irradiation. We suggest that thermo-mechanical stress played a dominant role in the disruption of the collagen network of AF under non-homogeneous laser heating. 相似文献
999.
Angel A. Martí Steffen Jockusch Zengmin Li Bindu Raveendra Irina Morozova Daniel L. Akins Nicholas J. Turro 《Tetrahedron》2007,63(17):3591-3600
We report the design, synthesis, and characterization of binary oligonucleotide probes for mRNA detection. The probes were designed to avoid common problems found in standard binary probes such as direct excitation of the acceptor fluorophore and overlap between the donor and acceptor emission spectra. Two different probes were constructed that contained an array of either two or three dyes and were characterized using steady-state fluorescence spectroscopy, time-resolved fluorescence spectroscopy, and fluorescence depolarization measurements. The three-dye binary probe (BP-3d) consists of a Fam fluorophore which acts as a donor, collecting light and transferring it as energy to Tamra, which subsequently transfers energy to Cy5 when the two probes are hybridized to mRNA. This design allows the use of 488 nm excitation, which avoids the direct excitation of Cy5 and at the same time provides a good fluorescence resonance energy transfer (FRET) efficiency. The two-dye binary probe system (BP-2d) was constructed with Alexa488 and Cy5 fluorophores. Although the overlap between the fluorescence of Alexa488 and the absorption of Cy5 is relatively low, FRET still occurs due to their close physical proximity when the probes are hybridized to mRNA. This framework also decreases the direct excitation of Cy5 and reduces the fluorescence overlap between the donor and the acceptor. Picosecond time-resolved spectroscopy showed a reduction in the fluorescence lifetime of donor fluorophores after the formation of the hybrid between the probes and target mRNA. Interestingly, BP-2d in the presence of mRNA shows a slow rise in the fluorescence decay of Cy5 due to a relatively slow FRET rate, which together with the reduction in the Alexa488 lifetime provides a way to improve the signal to background ratio using time-resolved fluorescence spectra (TRES). In addition, fluorescence depolarization measurements showed complete depolarization of the acceptor dyes (Cy5) for both BP-3d (due to sequential FRET steps) and BP-2d (due to the relatively low FRET rate) in the presence of the mRNA target. 相似文献
1000.