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51.
应用分子模拟方法研究了血管紧张素转换酶(Angiotensin-converting enzyme,ACE)C端结构域(C-domain)与两种抑制肽(RIGLF/AHEPVK)的结合机制,预测了两个体系的结合模式,提出在C-domain-RIGLF中His353,Asp377,Asp453,Phe457,His513,Tyr523和Phe527为RIGLF主要结合残基,而在C-domainAHEPVK中Gln281,His353,Ser355,Glu384,Lys511,His513和Tyr523等残基起关键作用.应用结合自由能计算比较了两个体系的结合能力,结果表明,RIGLF和AHEPVK均与C-domain活性位点残基存在较强作用,且AHEPVK对C-domain的结合能力较强,与实验结果一致. 相似文献
52.
硫代嘧啶碱基是光动力疗法潜在的重要光敏剂,其最低单重激发态的光物理研究已有广泛报道。然而,其较高激发态的跃迁性质和反应动力学研究较为稀少。因此,本文采用共振拉曼光谱和密度泛函理论计算方法研究2,4-二硫代尿嘧啶的紫外光谱和几个较高单重激发态的短时结构动力学。首先,基于共振拉曼光谱强度与电子吸收带振子强度f的关系,将紫外光谱去卷积成四个吸收带,分别为358 nm(f=0.0336)中等强度吸收带(A带),338 nm(f=0.1491)、301 nm(f=0.1795)和278 nm(f=0.3532)强而宽的吸收带(B、C和D带)。这一结果既吻合密度泛函理论计算结果,又符合共振拉曼光谱强度模式对紫外光谱带的预期。据此,去卷积得到的四个吸收带被分别指认为S0→S2跃迁、S0→S6跃迁、S0→S7跃迁和S_0→S_8跃迁。同时,分别对B,C和D带共振拉曼光谱进行了详细的指认,获得了短时动力学信息。结果表明,S_8态短时动力学的显著特征是在Franck-Condon区域或附近发生了S8(ππ~*)/S(nπ~*)势能面交叉引发的、伴随超快结构扭转的非绝热过程。S7和S6态短时动力学的主要特征是反应坐标的多维性,它们分别沿C_5C_6/C_2S_8/C_4S_(10)/N_2C_3+C_4N_3H_9/N_1C_2N_3/C_2N_1C_6/C_6N_1H_7/C_5C_6H_(12)和C_5C_6/N_3C_2/C_4S_(10)/C_2S_8+C_6N_1H_7/C_5C_6H_(12)/C_5C_6N_1/C_5C_6H_(12)/C_2N_1C_6/N_1C_2N_3/C_4N_3H_9/N_1C_2N_3等内坐标演化。 相似文献
53.
Yu-Yu LIU Jie-Wei LI Yi-Fan BO Lei YANG Xiao-Fei ZHANG Ling-Hai XIE Ming-Dong YI Wei HUANG 《物理化学学报》2017,33(9):1803-1810
[4]Cyclo-9, 9-dimethyl-2, 7-fluorenylene ([4]CF) was used as a model compound to explore the steric strain effect on the structures and photoelectrical properties of materials. A series of strained cyclic polyfluorene materials, [n]CFs (n=3-8), was designed. It was found that the strain energy decreased and the energy gap increased as the number of n and ring diameter increased. The ionization potential and electronic affinity tended to increase and decrease as the strain energy decreased at the same number of [n]CFs, respectively. With a balance between hole and electron reorganization energies in the system, these compounds demonstrated great potential as ambipolar materials. It was also found that [n]CFs showed an obvious blue shift in their emission spectra wavelengths (λem2) as the strain energy decreased. Steric strain provides a powerful tool for the design of multifunctional semiconductors in organic optoelectronics. 相似文献
54.
55.
A second‐order ensemble method based on a blended backward differentiation formula timestepping scheme for time‐dependent Navier–Stokes equations 下载免费PDF全文
Nan Jiang 《Numerical Methods for Partial Differential Equations》2017,33(1):34-61
We present a second‐order ensemble method based on a blended three‐step backward differentiation formula (BDF) timestepping scheme to compute an ensemble of Navier–Stokes equations. Compared with the only existing second‐order ensemble method that combines the two‐step BDF timestepping scheme and a special explicit second‐order Adams–Bashforth treatment of the advection term, this method is more accurate with nominal increase in computational cost. We give comprehensive stability and error analysis for the method. Numerical examples are also provided to verify theoretical results and demonstrate the improved accuracy of the method. © 2016 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 33: 34–61, 2017 相似文献
56.
Joseph Senan O'Brien Matthew J. Allen Gerardo Andrés Cisneros 《International journal of quantum chemistry》2017,117(17)
Lanthanide complexes have found extensive use as luminescent probes for biological and medical investigations. Recently, a di‐europium complex that exhibits pH‐dependent luminescence‐decay was reported, and the ligand in that complex includes a large number of ionizable sites. To better understand the pH‐dependence of luminescence‐decay of this complex, the pK a's of all tautomers of the di‐Lu3+ version of this complex were calculated computationally. The calculated Boltzmann‐averaged pK a's of the complex are 5.85, ?0.21, and ?1.47 for the di‐Lu3+ complex in its first, second, and third protonation states, respectively. These pK a values across protonation states indicate that changes in luminescence‐decay rate at physiologically relevant pH may be related to first protonation event of the complex exclusively. 相似文献
57.
Structures,stabilities, and electronic properties of fullerene C36 with endohedral atomic Sc,Y, and La: A dispersion‐corrected DFT study 下载免费PDF全文
The M@C36 compounds form a family of small endohedral metallofullerenes. Recently, these have been detected as the smallest endohedral compounds formed with Sc, Y, and La. For the first time, these compounds are studied theoretically. Calculations obtained at the dispersion‐corrected DFT level PBE‐D3(BJ)/def2‐TZVP agree admirably with experimental results. The zero‐point energy corrected binding energies can explain the lower abundance of La@C36 in comparison with Sc@C36 and Y@C36. Their small HOMO‐LUMO gaps denote high reactivity. The bond between Y and Sc with the cage is mostly covalent. In contrast, La is located at the fullerene's center with an ionic interaction; all metals transferred charge to the cage. Furthermore, La@C36 was found in doublet state and the others preferred the quartet state. To conclude, according to the analysis of aromaticity performed by the NICS(0)iso index, the insertion of none of these metals increase the aromaticity. 相似文献
58.
Hua-Nan Tong Cheng Rong Jing-Min Li Yu-Lin Wang Guo-Cong Guo 《Journal of Coordination Chemistry》2017,70(11):1851-1861
We report the exploration of the stabilization effect of the in situ generated N-alkylated DABCO (DABCO = 1,4-diazabicyclo[2.2.2]octane) cation in the family of bromoplumbates and a 1-D bromoplumbate, (Et2DABCO)2n(Pb3Br10)n (1), has been prepared by solvothermal conditions. Optical diffuse reflectance determination shows the band gap of 1 is 3.69 eV, which manifests that 1 is a wide band gap semiconductor. Compared with the band gap of bulk PbBr2 (3.84 eV), 1 exhibits 0.15 eV red shift of absorption edge. While for the reported iodo analogs of this compound, (MPDA)2n(Pb3I10)n and (Et2DABCO)2n(Pb3I10)n, they exhibit 0.53 and 0.47 eV blue shift of the energy gaps compared with the measured value of 2.30 eV for bulk PbI2, respectively. The photoluminescent study of 1 shows that it exhibits a broad emission band centered at 697 nm upon photoexcitation by 345 nm (amount to 3.59 eV). The calculated density of states manifests the theoretical value of the band gap of 1 is 3.422 eV and the origination of photoluminescence can be ascribed to the transition of bonding electrons of Br– anion to the empty orbits of Pb(II) ion. 相似文献
59.
Yao-Yue Fan Shi-Xin Chen Qun-Fang Liu Li-She Gan Jian-Min Yue 《Tetrahedron letters》2017,58(50):4728-4730
Trigochinins A–C (1–3) are three highly oxygenated daphnane-type diterpenes isolated from Trigonostemon chinensis. Their structures with the absolute configurations were initially assigned by a combination of spectroscopic data, X-ray crystallography (Mo Kα radiation) study and CD analysis. In the current study, the absolute configurations of trigochinins A–C were confirmed by single crystal X-ray diffraction (Cu Kα radiation) study, CD spectral analogy, and theoretical ECD study by using quantum chemical TDDFT calculations. 相似文献
60.
Synthesis and Structures of Gallium‐β‐Diketiminate Complexes: Isolation of a Dinuclear Gallium(II) Complex 下载免费PDF全文
The sterically demanding β‐diketiminate ligand Ldmp [Ldmp = HC{(CMe)N(dmp)}2, dmp = C6H3‐2,6‐Me2] was used to stabilize various gallium complexes in the formal oxidation states +II and +III. The reaction of in situ generated [LdmpLi] with gallium chloride affords [LdmpGaCl2] ( 1 ), which was used as starting complex to synthesize a variety of gallium(III) compounds [LdmpGaX2] [X = F ( 2 ), I ( 3 ), H ( 4 ), and Me ( 5 )]. Synthesis of the dinuclear complex [LdmpGaI]2 ( 6 ), with gallium in the formal oxidation state +II was accomplished by converting “GaI” with in situ generated [LdmpLi] in toluene. All compounds were characterized by elemental analyses, NMR spectroscopy, LIFDI‐TOF‐MS, and single‐crystal X‐ray diffraction. Additionally DFT calculations were performed for analysis of the bonding in 6 . 相似文献