全文获取类型
收费全文 | 6340篇 |
免费 | 241篇 |
国内免费 | 27篇 |
专业分类
化学 | 4459篇 |
晶体学 | 40篇 |
力学 | 176篇 |
数学 | 968篇 |
物理学 | 965篇 |
出版年
2024年 | 6篇 |
2023年 | 57篇 |
2022年 | 187篇 |
2021年 | 203篇 |
2020年 | 162篇 |
2019年 | 159篇 |
2018年 | 114篇 |
2017年 | 118篇 |
2016年 | 256篇 |
2015年 | 213篇 |
2014年 | 224篇 |
2013年 | 335篇 |
2012年 | 401篇 |
2011年 | 493篇 |
2010年 | 286篇 |
2009年 | 263篇 |
2008年 | 391篇 |
2007年 | 367篇 |
2006年 | 365篇 |
2005年 | 336篇 |
2004年 | 308篇 |
2003年 | 245篇 |
2002年 | 210篇 |
2001年 | 80篇 |
2000年 | 72篇 |
1999年 | 76篇 |
1998年 | 49篇 |
1997年 | 54篇 |
1996年 | 78篇 |
1995年 | 49篇 |
1994年 | 47篇 |
1993年 | 40篇 |
1992年 | 50篇 |
1991年 | 39篇 |
1990年 | 24篇 |
1989年 | 22篇 |
1988年 | 13篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 26篇 |
1984年 | 22篇 |
1983年 | 22篇 |
1982年 | 17篇 |
1981年 | 13篇 |
1980年 | 18篇 |
1979年 | 18篇 |
1977年 | 9篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1974年 | 4篇 |
排序方式: 共有6608条查询结果,搜索用时 15 毫秒
971.
Callierotti G Bianco A Castiglioni C Bertarelli C Zerbi G 《The journal of physical chemistry. A》2008,112(32):7473-7480
Molecular polarizabilities of photochromic diarylethenes bearing different chemical groups as substituents have been calculated by density functional theory (DFT) simulations with the aim to obtain an estimate of the refractive index of a glassy matrix containing diarylethenes as active species. Simple models have been introduced in order to take into account the effects that occur in bulk materials. The results obtained show that the choice of suitable substituents enhances the modulation of the refractive index driven by the photochromic reaction; moreover, the trends predicted are consistent with the experimental data. This opens the way to use quantum chemical predictions on model molecules to foresee performances relative to the photoinduced modulation of the refractive index in bulk materials. 相似文献
972.
Gómez-Zavaglia A Kaczor A Almeida R Cristiano Mde L Fausto R 《The journal of physical chemistry. A》2008,112(8):1762-1772
In this work, the conformational space of the pseudosaccharyl ether 3-(allyloxy)-1,2-benzisothiazole 1,1-dioxide (ABID) has been studied by means of infrared spectroscopy and density functional theory (DFT) calculations. Five different low energy conformers (TSk, TC, GSk, GSk' and GC, with relative energies of 0.00, 1.97, 2.00, 3.82 and 6.02 kJ mol(-1), respectively) were found on the DFT(B3LYP)/6-311++G(3df,3pd) potential energy surface of the molecule, all of them differing in the conformation of the allyl substituent. According to the calculations, in the gaseous phase all conformers are significantly populated (TSk:TC:GSk:GSk':GC = 47%:16%:18%:12%:7%, at 350 K). In the cryogenic matrices, however, only the TSk and TC conformers exist due to isomerization from the higher energy gauche forms to the most stable trans isomers during deposition of the matrix (conformational cooling). The observed conformational cooling is in consonance with the low calculated energy barriers for the GSk --> TSk, GSk' --> TSk and GC --> TC isomerization processes. Results from annealing experiments in krypton matrix doubtlessly show that in this matrix the order of stability of the TSk and TC conformers is reversed, with the more planar TC form becoming the most stable conformer. 相似文献
973.
Since secondary structure elements are known to play a key role in stabilizing the 3D-fold of proteins for the design of non-natural proteins composed of beta-amino acid residues, the construction of suitable secondary structural elements is mandatory. Folding analogues of alpha-helices and beta-strands of beta-polypeptides were already described (Chem. Biodiversity 2004, 1, 1111 (1)). Here, we present several collagen-like folds composed exclusively of beta-Ala(s). Unlike their natural counterpart, these tubular nanostructures can be composed of more than three polypeptide chains aligned parallel and/or antiparallel. By using ab initio and DFT calculations we have optimized a large number of versatile collagen-like antiparallel nanostructures. In these tubular systems, oligopeptide strands are interconnected by i --> (i) type H-bonds, except for the "closing" set. This latter is called "the H-bond zipper" and is either (i) --> i, ( i + 1) --> i, or ( i + 2) --> i type. Antiparallel, tubular foldamers composed of l number of strands, each of k number of beta-amino acid residues (e.g., apbeta-T(l) i+l ) k , ap(beta-T(l) i+1 ) k , or ap(beta-T(l) i+2 ) k ), are unexpectedly stable supramolecular complexes. Independent of k and l, the local backbone fold of the amino acid residues is usually spiral, abbreviated as "S(P)" or "S*(P)". Nevertheless, in contrast to parallel, in antiparallel nanotubes the backbone fold can occasionally twist out from S(P) or S*(P) type into an alternative local structure. However, the more the local geometry of the strands resembles to S(P) or S*(P), the higher the stability is. Besides the backbone twisting, the overall stability is determined by the type and the geometrical properties of the constituent H-bonds. Interestingly, higher number of total H-bonds can provide a lower overall stability, when H-bond parameters are inferior. In general, the increase of both the number of strands and their length stabilize the supramolecular complex. Now that, for beta-peptides, collagen-like overall folds with their stability were determined, their POG- or PPG-like sequence specificity has to be revealed. 相似文献
974.
We show that the complementary error function, $\text{erfc} (z)= \frac{2}{\sqrt{\pi}}\int_z^{\infty}{e^{-s^2} \text{d}s}$ , has no zeros in $\text{D}= \left\{ z : \frac{3}{4} \ \pi \le Arg z \le\frac{5}{4} \ \pi \right\}$ . 相似文献
975.
Andrea Bettinelli Alberto Ceselli Giovanni Righini 《4OR: A Quarterly Journal of Operations Research》2008,6(4):361-374
The two-dimensional level strip packing problem (2LSPP) consists in packing rectangular items of given size into a strip of
given width divided into levels. Items packed into the same level cannot be put on top of one another and their overall width
cannot exceed the width of the strip. The objective is to accommodate all the items while minimizing the overall height of
the strip. The problem is -hard and arises from applications in logistics and transportation. We present a set covering formulation of the 2LSPP suitable
for a column generation approach, where each column corresponds to a feasible combination of items inserted into the same
level. For the exact optimization of the 2LSPP we present a branch-and-price algorithm, in which the pricing problem is a
penalized knapsack problem. Computational results are reported for benchmark instances with some hundreds items. 相似文献
976.
Gómez-Ruiz S Wolf R Bauer S Bittig H Schisler A Lönnecke P Hey-Hawkins E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(15):4511-4520
[Na{cyclo-(P(5)tBu(4))}] (1) reacts with [CuCl(PCyp(3))(2)] (Cyp=cyclo-C(5)H(9)) and [CuCl(PPh(3))(3)] (1:1) to give the corresponding copper(I) complexes with a tetra-tert-butylcyclopentaphosphanide ligand, [Cu{cyclo- (P(5)tBu(4))}(PCyp(3))(2)] (2) and [Cu{cyclo-(P(5)tBu(4))}(PPh(3))(2)] (3). The CuCl adduct of 2, [Cu(2)(mu-Cl){cyclo-(P(5)tBu(4))}(PCyp(3))(2)] (4), was obtained from the reaction of 1 with [CuCl(PCyp(3))(2)] (1:2). Compounds 2 and 3 rearrange, even at -27 degrees C, to give [Cu(4){cyclo- (P(4)tBu(3))PtBu}(4)] (5), in which ring contraction of the [cyclo-(P(5)tBu(4))](-) anion has occurred. The reaction of 1 with [AgCl(PCyp(3))](4) or [AgCl(PPh(3))(2)] (1:1) leads to the formation of [Ag(4){cyclo-(P(4)tBu(3))PtBu}(4)] (6). Intermediates, which are most probably mononuclear, "[Ag{cyclo-(P(5)tBu(4))}(PR(3))(2)]" (R=Cyp, Ph) could be detected in the reaction mixtures, but not isolated. Finally, the reaction of 1 with [AuCl(PCyp(3))] (1:1) yielded [Au{cyclo-(P(5)tBu(4))}(PCyp(3))] (7), whereas an inseparable mixture of [Au(3){cyclo-(P(5)tBu(4))}(3)] (8) and [Au(4){cyclo-(P(4)tBu(3))PtBu}(4)] (9) was obtained from the analogous reaction with [AuCl(PPh(3))]. Complexes 3-7 were characterised by (31)P NMR spectroscopy, and X-ray crystal structures were determined for 3-9. 相似文献
977.
Ley SV Abad-Somovilla A Anderson JC Ayats C Bänteli R Beckmann E Boyer A Brasca MG Brice A Broughton HB Burke BJ Cleator E Craig D Denholm AA Denton RM Durand-Reville T Gobbi LB Göbel M Gray BL Grossmann RB Gutteridge CE Hahn N Harding SL Jennens DC Jennens L Lovell PJ Lovell HJ de la Puente ML Kolb HC Koot WJ Maslen SL McCusker CF Mattes A Pape AR Pinto A Santafianos D Scott JS Smith SC Somers AQ Spilling CD Stelzer F Toogood PL Turner RM Veitch GE Wood A Zumbrunn C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(34):10683-10704
We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O-alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5-exo-radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule. 相似文献
978.
Cabrera S Reyes E Alemán J Milelli A Kobbelgaard S Jørgensen KA 《Journal of the American Chemical Society》2008,130(36):12031-12037
It is shown that racemic oxazolones are excellent reagents for the synthesis of chiral quaternary amino acids and its derivatives by the diastereo- and enantioselective nucleophilic addition to alpha,beta-unsaturated aldehydes catalyzed by diarylprolinol silyl ethers. The scope of this new organocatalytic reaction is demonstrated for different oxazolones having aromatic and alkyl groups at the reactive carbon atom and different aromatic and aliphatic substituted alpha,beta-unsaturated aldehydes, for which the stereoselective reaction proceeds with good yield, moderate to good to very high diastereoselectivity, and very high enantioselectivity. The potential of the reaction is shown for the synthesis of optically active alpha,alpha-disubstituted alpha-amino acids, alpha-quaternary proline derivatives, amino alcohols, lactams, and tetrahydropyranes. Furthermore, we have calculated by DFT-methods the transition-state structures that account for both the diastereo- and enantioselectivity observed for the addition of oxazolones to the alpha,beta-unsaturated aldehydes. For one class of compounds, the stereoselectivity is controlled by a hydrogen-bonding interaction of the enolate-form of the oxazolone with an ortho-hydroxy-phenyl substituent of the alpha,beta-unsaturated aldehyde, whereas the benzhydryl-protecting group in the oxazolone determines the diastereo- and enantioselectivity in a more general manner for both aromatic and aliphatic alpha,beta-unsaturated aldehydes. 相似文献
979.
980.
High-resolution electron energy loss spectroscopy (HREELS), temperature-programmed desorption (TPD), and density functional theory (DFT) calculations were used to study the adsorption and reaction of 1-epoxy-3-butene (EpB) on Pt(111). These investigations were conducted to help elucidate mechanisms for improving olefin hydrogenation selectivity in reactions of unsaturated oxygenates. EpB dosed to Pt(111) at 91 K adsorbs molecularly on the surface through the vinyl group with apparent rehybridization to a di-sigma-bound state. By 233 K, however, EpB undergoes epoxide ring opening to form an aldehyde intermediate, which further decomposes upon heating to yield gas phase products CO, H2, and propylene. Comparison of the HREELS and TPD data to experiments performed with 2-butenal (crotonaldehyde) shows that EpB and 2-butenal decompose through related pathways. However, the EpB-derived aldehyde intermediate clearly has a unique structure, features of which have been elucidated by DFT calculations. In conjunction with previous surface science studies of EpB chemistry, these results can help explain selectivity trends for reactions of EpB on Pt catalysts and bimetallic PtAg catalysts, with indications that the enhanced olefin hydrogenation selectivity of PtAg catalysts likely originates from a bifunctional effect. 相似文献