全文获取类型
收费全文 | 6250篇 |
免费 | 134篇 |
国内免费 | 3篇 |
专业分类
化学 | 3449篇 |
晶体学 | 32篇 |
力学 | 138篇 |
数学 | 1442篇 |
物理学 | 1326篇 |
出版年
2021年 | 46篇 |
2020年 | 51篇 |
2019年 | 69篇 |
2018年 | 149篇 |
2017年 | 136篇 |
2016年 | 204篇 |
2015年 | 156篇 |
2014年 | 211篇 |
2013年 | 509篇 |
2012年 | 312篇 |
2011年 | 430篇 |
2010年 | 235篇 |
2009年 | 198篇 |
2008年 | 345篇 |
2007年 | 346篇 |
2006年 | 328篇 |
2005年 | 246篇 |
2004年 | 209篇 |
2003年 | 147篇 |
2002年 | 138篇 |
2001年 | 94篇 |
2000年 | 80篇 |
1999年 | 61篇 |
1998年 | 51篇 |
1997年 | 52篇 |
1996年 | 52篇 |
1995年 | 49篇 |
1994年 | 29篇 |
1993年 | 46篇 |
1992年 | 58篇 |
1991年 | 46篇 |
1990年 | 48篇 |
1989年 | 54篇 |
1988年 | 53篇 |
1987年 | 50篇 |
1986年 | 41篇 |
1985年 | 70篇 |
1984年 | 70篇 |
1983年 | 67篇 |
1982年 | 71篇 |
1981年 | 43篇 |
1980年 | 57篇 |
1979年 | 49篇 |
1978年 | 75篇 |
1977年 | 39篇 |
1976年 | 54篇 |
1975年 | 40篇 |
1974年 | 50篇 |
1973年 | 42篇 |
1972年 | 35篇 |
排序方式: 共有6387条查询结果,搜索用时 15 毫秒
21.
Using controlled radical polymerization to confirm the lower critical solution temperature of an N‐(alkoxyalkyl) acrylamide polymer in aqueous solution 下载免费PDF全文
Xeniya Savelyeva Lucia Li Milan Marić 《Journal of polymer science. Part A, Polymer chemistry》2015,53(1):59-67
N‐(3‐Methoxypropyl) acrylamide (MPAM) was polymerized by controlled radical polymerization (CRP) methods such as nitroxide‐mediated polymerization (NMP) and reversible addition–fragmentation chain‐transfer polymerization (RAFT). CRP was expected to yield well‐defined polymers with sharp lower critical solution temperature (LCST) transitions. NMP with the BlocBuilder (2‐([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino]oxy)‐2‐methylpropanoic acid) and SG1 ([tert‐butyl[1‐(diethoxyphosphoryl)‐2,2‐dimethylpropyl]amino] oxidanyl) initiating system revealed low yields and lack of control (high dispersity, ? ~ 1.5–1.6, and inhibition of chain growth). However, RAFT was far more effective, with linear number average molecular weight, , versus conversion, X, plots, low ? ~ 1.2–1.4 and the ability to form block copolymers using N,N‐diethylacrylamide (DEAAM) as the second monomer. Poly(MPAM) (with = 13.7–25.3 kg mol?1) thermoresponsive behavior in aqueous media revealed cloud point temperatures (CPT)s between 73 and 92 °C depending on solution concentration (ranging from 1 to 3 wt %). The and the molecular weight distribution were the key factors determining the CPT and the sharpness of the response, respectively. Poly(MPAM)‐b‐poly(DEAAM) block copolymer ( = 22.3 kg mol?1, ? = 1.41, molar composition FDEAAM = 0.38) revealed dual LCSTs with both segments revealing distinctive CPTs (at 75 and 37 °C for poly(MPAM) and poly(DEAAM) blocks, respectively) by both UV–Vis and dynamic light scattering. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 59–67 相似文献
22.
Cyclotetrabenzoin: Facile Synthesis of a Shape‐Persistent Molecular Square and Its Assembly into Hydrogen‐Bonded Nanotubes 下载免费PDF全文
Qing Ji Ha T. M. Le Dr. Xiqu Wang Dr. Yu‐Sheng Chen Dr. Tatyana Makarenko Prof. Allan J. Jacobson Prof. Ognjen Š. Miljanić 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17205-17209
Cyanide‐catalyzed benzoin condensation of terephthaldehyde produces a cyclic tetramer, which we propose to name cyclotetrabenzoin. Cyclotetrabenzoin is a square‐shaped macrocycle ornamented with four α‐hydroxyketone functionalities pointing away from the central cavity, the dimensions of which are 6.9×6.9 Å. In the solid state, these functional groups extensively hydrogen bond, resulting in a microporous three‐dimensional organic framework with one‐dimensional nanotube channels. This material exhibits permanent—albeit low‐porosity, with a Langmuir surface area of 52 m2 g?1. Cyclotetrabenzoin’s easy and inexpensive synthesis and purification may inspire the creation of other shape‐persistent macrocycles and porous molecular crystals by benzoin condensation. 相似文献
23.
Dr. Aleksander Rebane Geoffrey Wicks Dr. Mikhail Drobizhev Dr. Thomas Cooper Aleksander Trummal Dr. Merle Uudsemaa 《Angewandte Chemie (International ed. in English)》2015,54(26):7582-7586
We present a new approach for determining the strength of the dipolar solute‐induced reaction field, along with the ground‐ and excited‐state electrostatic dipole moments and polarizability of a solvated chromophore, using exclusively one‐photon and two‐photon absorption measurements. We verify the approach on two benchmark chromophores N,N‐dimethyl‐6‐propionyl‐2‐naphthylamine (prodan) and coumarin 153 (C153) in a series of toluene/dimethyl sulfoxide (DMSO) mixtures and find that the experimental values show good quantitative agreement with literature and our quantum‐chemical calculations. Our results indicate that the reaction field varies in a surprisingly broad range, 0–107 V cm?1, and that at close proximity, on the order of the chromophore radius, the effective dielectric constant of the solute–solvent system displays a unique functional dependence on the bulk dielectric constant, offering new insight into the close‐range molecular interaction. 相似文献
24.
25.
A detailed study of the geometry, aromatic character, electronic and magnetic properties for a series of positively charged N-doped polycyclic aromatic hydrocarbons (PAHs) was performed. Magnetic properties of the examined molecules were analyzed by means of the magnetically induced current density calculated using the diamagnetic-zero version of the continuous transformation of origin of current density (CTOCD-DZ) method. The comparative study of the local aromaticity of the studied molecules was performed using several different indices: energy effect (ef), harmonic oscillator model of aromaticity (HOMA) index, six centre delocalization index (SCI) and nucleus independent chemical shifts (NICS). The presence of N-atoms in the inner rings was found to cause a planarity distortion in the studied N-doped systems. The geometric changes and charged nature of the studied N-doped systems do not significantly influence the current density and the local aromaticity distribution in comparison with the corresponding parent benzenoid hydrocarbons. The present study demonstrates how quantum chemical calculations can be used for rational design of novel PAHs and for fine tuning of their properties. 相似文献
26.
Given a connected surface \({\mathbb {F}}^2\) with Euler characteristic \(\chi \) and three integers \(b>a\ge 1<k\), an \((\{a,b\};k)\)-\({\mathbb {F}}^2\) is a \({\mathbb {F}}^2\)-embedded graph, having vertices of degree only k and only a- and b-gonal faces. The main case are (geometric) fullerenes (5, 6; 3)-\({\mathbb {S}}^2\). By \(p_a\), \(p_b\) we denote the number of a-gonal, b-gonal faces. Call an \((\{a,b\};k)\)-map lego-admissible if either \(\frac{p_b}{p_a}\), or \(\frac{p_a}{p_b}\) is integer. Call it lego-like if it is either \(ab^f\)-lego map, or \(a^fb\)-lego map, i.e., the face-set is partitioned into \(\min (p_a,p_b)\) isomorphic clusters, legos, consisting either one a-gon and \(f=\frac{p_b}{p_a}\,b\)-gons, or, respectively, \(f=\frac{p_a}{p_b}\,a\)-gons and one b-gon; the case \(f=1\) we denote also by ab. Call a \((\{a,b\};k)\)-map elliptic, parabolic or hyperbolic if the curvature \(\kappa _b=1+\frac{b}{k}-\frac{b}{2}\) of b-gons is positive, zero or negative, respectively. There are 14 lego-like elliptic \((\{a,b\};k)\)-\({\mathbb {S}}^2\) with \((a,b)\ne (1,2)\). No \((\{1,3\};6)\)-\({\mathbb {S}}^2\) is lego-admissible. For other 7 families of parabolic \((\{a,b\};k)\)-\({\mathbb {S}}^2\), each lego-admissible sphere with \(p_a\le p_b\) is \(a^fb\) and an infinity (by Goldberg–Coxeter operation) of \(ab^f\)-spheres exist. The number of hyperbolic \(ab^f\,(\{a,b\};k)\)-\({\mathbb {S}}^2\) with \((a,b)\ne (1,3)\) is finite. Such \(a^f b\)-spheres with \(a\ge 3\) have \((a,k)=(3,4),(3,5),(4,3),(5,3)\) or (3, 3); their number is finite for each b, but infinite for each of 5 cases (a, k). Any lego-admissible \((\{a,b\};k)\)-\({\mathbb {S}}^2\) with \(p_b=2\le a\) is \(a^f b\). We list, explicitly or by parameters, lego-admissible \((\{a,b\};k)\)-maps among: hyperbolic spheres, spheres with \(a\in \{1,2\}\), spheres with \(p_b\in \{2,\frac{p_a}{2}\}\), Goldberg–Coxeter’s spheres and \((\{a,b\};k)\)-tori. We present extensive computer search of lego-like spheres: 7 parabolic (\(p_b\)-dependent) families, basic examples of all 5 hyperbolic \(a^fb\) (b-dependent) families with \(a\ge 3\), and lego-like \((\{a,b\};3)\)-tori. 相似文献
27.
ABSTRACTHere we report on the synthesis and mesomorphic properties of a series of imino-linked dimeric molecules. In order to improve our understanding of the structure–NTB phase correlations, we have studied the impact of geometric and electronic factors arising from varying mesogenic units, different spacer lengths and from the ratio (n/m) between the lengths of terminal chains (n) and spacer (m). From the perspective of the molecular geometry, the results show that the stability of the NTB phase results from increasing effective molecular bending and with the broadening of the mesogenic unit, in particular near the spacer, and that the n/m ratio plays a substantial role in conjunction with the specific mesogenic unit. A computational study of the electronic properties shows that a broadening of the mesogenic core in the vicinity of the spacer is associated with an increased anisotropy of the electrostatic potential distribution. Within a given series of materials our study suggests that the incidence of the NTB phase and its thermal stability are governed by the synergy of specific geometrical factors and the anisotropy of the electrostatic potential distribution of the mesogenic core. 相似文献
28.
Tom Alberts Jeremy Clark Saša Kocić 《Stochastic Processes and their Applications》2017,127(10):3291-3330
We study a directed polymer model defined on a hierarchical diamond lattice, where the lattice is constructed recursively through a recipe depending on a branching number and a segment number . When it is known that the model exhibits strong disorder for all positive values of the inverse temperature , and thus weak disorder reigns only for (infinite temperature). Our focus is on the so-called intermediate disorder regime in which the inverse temperature vanishes at an appropriate rate as the size of the system grows. Our analysis requires separate treatment for the cases and . In the case we prove that when the inverse temperature is taken to be of the form for , the normalized partition function of the system converges weakly as to a distribution and does so universally with respect to the initial weight distribution. We prove the convergence using renormalization group type ideas rather than the standard Wiener chaos analysis. In the case we find a critical point in the behavior of the model when the inverse temperature is scaled as ; for an explicitly computable critical value the variance of the normalized partition function converges to zero with large when and grows without bound when . Finally, we prove a central limit theorem for the normalized partition function when . 相似文献
29.
30.
Vladimir Piterbarg Goran Popivoda Siniša Stamatović 《Lithuanian Mathematical Journal》2017,57(1):128-141
Let ξ(t), t ∈ [0, T],T > 0, be a Gaussian stationary process with expectation 0 and variance 1, and let η(t) and μ(t) be other sufficiently smooth random processes independent of ξ(t). In this paper, we obtain an asymptotic exact result for P(sup t∈[0,T](η(t)ξ(t) + μ(t)) > u) as u→∞. 相似文献