全文获取类型
收费全文 | 319篇 |
免费 | 8篇 |
国内免费 | 1篇 |
专业分类
化学 | 221篇 |
晶体学 | 2篇 |
力学 | 3篇 |
数学 | 39篇 |
物理学 | 63篇 |
出版年
2023年 | 5篇 |
2022年 | 9篇 |
2021年 | 14篇 |
2020年 | 4篇 |
2019年 | 11篇 |
2018年 | 7篇 |
2017年 | 13篇 |
2016年 | 13篇 |
2015年 | 11篇 |
2014年 | 8篇 |
2013年 | 12篇 |
2012年 | 26篇 |
2011年 | 19篇 |
2010年 | 23篇 |
2009年 | 7篇 |
2008年 | 13篇 |
2007年 | 21篇 |
2006年 | 7篇 |
2005年 | 8篇 |
2004年 | 9篇 |
2003年 | 7篇 |
2002年 | 12篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1995年 | 1篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 9篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1975年 | 1篇 |
排序方式: 共有328条查询结果,搜索用时 62 毫秒
1.
One influential parameter which mediates interactions between many types of molecules and biological membranes stems from
the lumped contributions of the transmembrane potential, dipole potential and the difference in the surface potentials on
both sides of a membrane. With relevance to cell physiology, such electrical features of a biomembrane are prone to undergoing
changes as a result of interactions with the aqueous surrounding. Among the most useful tools devoted to exploring changes
of electrical parameters of a lipid membrane induced by certain extracellular ions, lipid composition, and embedded membrane
peptides and proteins, are spectroscopic imaging and the inner field compensation (IFC) method. In this work we layout the
principles of a fully computerized version of the IFC method, which makes it more readily available to users. As a direct
application, we deployed this improved version of the IFC method to time-resolve changes induced by alamethicin monomers upon
membrane dipole potential, following their aggregation within an artificial lipid membrane. Intriguingly, even prior crossing
the membrane core, the membrane-bound alamethicin monomers are shown to significantly increase the dipole potential of the
monolayer they reside in. Such data further emphasize the yet less-explored interplay between membrane-based protein and peptides,
and the membrane dipole potential. 相似文献
2.
3.
4.
Loredana Protesescu Joaquín Calbo Kristopher Williams William Tisdale Aron Walsh Mircea Dinc 《Chemical science》2021,12(17):6129
The development of synthetic routes to access stable, ultra-small (i.e. <5 nm) lead halide perovskite (LHP) quantum dots (QDs) is of fundamental and technological interest. The considerable challenges include the high solubility of the ionic LHPs in polar solvents and aggregation to form larger particles. Here, we demonstrate a simple and effective host–guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. Cr3O(OH)(H2O)2(terephthalate)3 (Cr-MIL-101), made of large mesopore-sized pseudo-spherical cages, allows fast and efficient diffusion of perovskite precursors within its pores, and promotes the formation of stable, ∼3 nm-wide lead bromide perovskite QDs. CsPbBr3, MAPbBr3 (MA+ = methylammonium), and (FA)PbBr3 (FA+ = formamidinium) QDs exhibit significantly blue-shifted emission maxima at 440 nm, 446 nm, and 450 nm, respectively, as expected for strongly confined perovskite QDs. Optical characterization and composite modelling confirm that the APbBr3 (A = Cs, MA, FA) QDs owe their stability within the MIL-101 nanocrystals to both short- and long-range interfacial interactions with the MOF pore walls.We demonstrate a simple and effective host–guest strategy for preparing ultra-small lead bromide perovskite QDs through the use of nano-sized MOFs that function as nucleating and host sites. 相似文献
5.
Correa NM Zorzan DH D'Anteo L Lasta E Chiarini M Cerichelli G 《The Journal of organic chemistry》2004,69(24):8231-8238
Kinetics of the reduction of 3-chloroacetophenone (CAF) with sodium borohydride (NaBH(4)) were followed by UV-vis spectroscopy at 27.0 degrees C in different reverse micellar media, toluene/BHDC/water and toluene/AOT/water, and compared with results in an isooctane/AOT/water reverse micellar system. AOT is sodium 1,4-bis-2-ethylhexylsulfosuccinate, and BHDC is benzyl-n-hexadecyl dimethylammonium chloride. The kinetic profiles were investigated as a function of variables such as surfactant and NaBH(4) concentration and the amount of water dispersed in the reverse micelles, W(0) = [H(2)O]/[surfactant]. In all cases, the first-order rate constant, k(obs), increases with the concentration of surfactant as a consequence of incorporating the substrate into the interface of the reverse micelles where the reaction takes place. The reaction is faster at the cationic interface than at the anionic one probably because the negative ion BH(4)(-) is part of the cationic interface. The effect of the external solvent on the reaction shows that reduction is favored in the isooctane/AOT/water reverse micellar system than that with an aromatic solvent. This is probably due to BH(4)(-) being more in the water pool of the toluene/AOT/water reverse micellar system. The kinetic profile upon water addition depends largely on the type of interface. In the BHDC system, k(obs) increases with W(0) in the whole range studied while in AOT the kinetic profile has a maximum at W(0) approximately 5, probably reflecting the fact that BH(4)(-) is part of the cationic interface while, in the anionic one, there is a strong interaction between water and the polar headgroup of AOT below W(0) = 5 and, above that, BH(4)(-) is repelled from the interface once the water pool has formed. Application of a kinetic model based on the pseudophase formalism, which considers the distribution of the ketone between the continuous medium and the interface and assumes that reaction takes place only at the interface, has enabled us to estimate rate constants at the interface of the reverse micellar systems. At W(0) < 10, it was considered that NaBH(4) is wholly at the interface and, at W(0) >/= 10, where there are free water molecules, also the partitioning between the interface and the water pool was taken into account. The results were used to evaluate CAF and NaBH(4) distribution constants between the different pseudophases as well as the second-order reaction rate constant of the reduction reaction in the micellar interface. 相似文献
6.
Cordaro M Di Donna L Grassi G Maiuolo L Mazzotti F Perri E Sindona G Tagarelli A 《European journal of mass spectrometry (Chichester, England)》2004,10(5):691-697
An evaluation of the gas-phase ion chemistry of rotenone (1) by electrospray ionisation (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS2) is presented, aiming at providing tools for its determination in natural and biological matrices. The behaviour of its cycloadducts with benzonitrile-N-oxide (2) and 2,4,6-trimethylbenzonitrile-N-oxide (3) was also evaluated and the MS data thus obtained have provided evidence into the mechanism of formation of the key product ion at m/z 192 which can be considered a marker in the MS and MS2 spectra of rotenone and its derivatives. 相似文献
7.
Armstrong TA Bettoni D Bharadwaj V Biino C Borreani G Broemmelsiek D Buzzo A Calabrese R Ceccucci A Cester R Church M Dalpiaz P Dalpiaz PF Dimitroyannis D Fabbri M Fast J Gianoli A Ginsburg CM Gollwitzer K Govi G Hahn A Hasan M Hsueh S Lewis R Luppi E Macrí M Majewska AM Mandelkern M Marchetto F Marinelli M Marques J Marsh W Martini M Masuzawa M Menichetti E Migliori A Mussa R Palestini S Pallavicini M Passaggio S Pastrone N Patrignani C Peoples J Petrucci F Pia MG Pordes S Rapidis P Ray R 《Physical review D: Particles and fields》1996,54(11):7067-7070
8.
A new method was developed for the determination of 2-furfural (2-F) and 5-methylfurfural (5-MF), two products of Maillard reaction in vinegar, with head-space solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry (GC-MS). A divinylbenzene (DVB)/carboxen (CAR)/polydimethylsiloxane (PDMS) fibre was used and SPME conditions were optimised, studying ionic strength effect, temperature effect and adsorption time. Both analytes were determined by calibration established on 2-furfural-d4 (2-F-d4). The method showed good linearity in the range studied (from 16 to 0.12 mg/l), with a regression coefficient r2 of 0.9999. Inter-batch precision and accuracy were found between 14.9 and 6.0% and between -11.7 and 0.2%, respectively. Detection limit was 15 microg/l. The method is simple and accurate and it has been applied to a series of balsamic and non-balsamic vinegars. 相似文献
9.
The syntheses and structures of two new compounds are reported. The first compound, [Cr(CO)4]2[C4F2(PPh2)4], obtained from Cr(CO)4(PPh2H)2 and CF3CCF3 in the presence of one equivalent of BuLi has a structure with the ligand 1,2,3,4-tetrakis(diphenylphosphino)-1,4-difluorobutadiene chelating to two Cr(CO)4 groups via the 1,4 and 2,3 phosphine groups. A mechanism for the formation of this compound is suggested which involves sequential deprotonation of a phosphine, nucleophilic attack on the fluorocarbon, and fluoride ion elimination. The second compound, CrC36H28P2O7, arises from a similar base promoted reaction of Cr(CO)4-(PPhH2)2 and PhCCCOOEt. Here the expected initial product from cyclization of these reactants acts as a nucleophile to attack a second equivalent of the acetylene. The intermediate carbanion from this reaction can undergo a ring closure by displacement of OEt-, giving the observed product. 相似文献
10.
Dalpozzo R De Nino A Maiuolo L Procopio A Tagarelli A Sindona G Bartoli G 《The Journal of organic chemistry》2002,67(25):9093-9095
A new and chemoselective method for the cleavage of alkyl and cyclic acetals and ketals at room temperature in wet nitromethane by using catalytic cerium(III) trifluoromethane sulfonate is presented. The high yields, the observed selectivity, the very gentle reaction conditions, and the almost neutral pH make this procedure particularly attractive for multistep synthesis. 相似文献