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71.
Hua-Hua Wang Yi-Yu Jiang Mian HR Mahmood Hai-Yang Liu Herman H.Y. Sung Ian D. Williams Chi K. Chang 《中国化学快报》2015,26(5):529-533
Tetrakis(alloxycarbonyl)porphyrin and its β-octafluoro-substituted derivatives were synthesized via Lindsey method and transformed to their zinc complexes.Single crystal X-ray structures of corresponding Zn(Ⅱ) porphyrins revealed that β-octafluorination will give more compactness of porphyrin moieties in the crystal structure owing to the hydrogen bonding interactions involving β-fluorine atoms.An unusual six-coordinated Zn(Ⅱ) was found via intramolecular coordination of oxygen atom of meso-substituents with central Zn(Ⅱ). 相似文献
72.
Yupeng Wu Yangchun Tao Kuan Cai Siwei Liu Yi Zhang Zhenguo Chi Jiarui Xu Yen Wei 《中国化学》2015,33(12):1338-1346
Two triblock polymers, tetraaniline‐block‐poly(N‐isopropyl acrylamide)‐block‐poly(hydroxyethyl acrylate) (TA‐b‐PNIPAM‐b‐PHEA) and TA‐b‐PHEA‐b‐PNIPAM, were synthesized with unambiguous structure by a two step method. The difference of these two diblock polymers is the connection order of carboxyl group to block, e.g., carboxyl group to PNIPAM block for PNIPAM‐b‐PHEA and to PHEA block for PHEA‐b‐PNIPAM. Secondly, block tetraaniline was linked to the diblock polymer through amidation to yield the corresponding triblock copolymer. Both of them have almost the identical chemical compositions. The only difference is the connection order of each block in the triblock polymers. When they were self‐assembled at 45°C in a suitable solution, both of their aggregates have spherical shape with slight defects on their surface with the average diameter of about 400 nm. However, when their aggregate dispersion was cooled down to 20°C, only TA‐b‐PHEA‐b‐PNIPAM's morphology changed, forming worm‐like aggregates with the diameter of about 100–200 nm transformed from spherical aggregates. Both amphiphilic property and position of each block in this triblock copolymer are very essential for this morphology transformation. Since the worm‐like aggregates presented here by our group have hollow structure inside, its controlled release properties for doxorubicin were evaluated. Drug release experiment indicated that along with the temperature changes, the rearrangement of the intermediate layer structure caused morphology change in aggregate, thus accelerating the speed of drug release. 相似文献
73.
Excellent Stability of a Lithium‐Ion‐Conducting Solid Electrolyte upon Reversible Li+/H+ Exchange in Aqueous Solutions 下载免费PDF全文
Dr. Cheng Ma Dr. Ezhiylmurugan Rangasamy Dr. Chengdu Liang Prof. Jeffrey Sakamoto Dr. Karren L. More Dr. Miaofang Chi 《Angewandte Chemie (International ed. in English)》2015,54(1):129-133
Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long‐term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li7La3Zr2O12 garnet as a Li‐stable solid electrolyte. The material underwent a Li+/H+ exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6 %. When treated with a 2 M LiOH solution, the Li+/H+ exchange was reversed without any structural change. These observations suggest that cubic Li7La3Zr2O12 is a promising candidate for the separator in aqueous lithium batteries. 相似文献
74.
Ortho‐Quinone Methides as Reactive Intermediates in Asymmetric Brønsted Acid Catalyzed Cycloadditions with Unactivated Alkenes by Exclusive Activation of the Electrophile 下载免费PDF全文
MSc. Chien‐Chi Hsiao Dr. Sadiya Raja MSc. Hsuan‐Hung Liao Prof. Dr. Magnus Rueping 《Angewandte Chemie (International ed. in English)》2015,54(19):5762-5765
An efficient method for the highly enantioselective synthesis of chiral chromanes bearing multiple stereogenic centers was developed. A chiral BINOL‐based N‐triflylphosphoramide proved to be an effective catalyst for the in situ generation of ortho‐quinone methides (o‐QMs) and their subsequent cycloaddition reaction with unactivated alkenes provided chromanes with excellent diastereo‐ and enantioselectivity. 相似文献
75.
Revealing the Preferred Interlayer Orientations and Stackings of Two‐Dimensional Bilayer Gallium Selenide Crystals 下载免费PDF全文
Dr. Xufan Li Dr. Leonardo Basile Dr. Mina Yoon Dr. Cheng Ma Dr. Alexander A. Puretzky Dr. Jaekwang Lee Dr. Juan C. Idrobo Dr. Miaofang Chi Dr. Christopher M. Rouleau Dr. David B. Geohegan Dr. Kai Xiao 《Angewandte Chemie (International ed. in English)》2015,54(9):2712-2717
Characterizing and controlling the interlayer orientations and stacking orders of two‐dimensional (2D) bilayer crystals and van der Waals (vdW) heterostructures is crucial to optimize their electrical and optoelectronic properties. The four polymorphs of layered gallium selenide (GaSe) crystals that result from different layer stackings provide an ideal platform to study the stacking configurations in 2D bilayer crystals. Through a controllable vapor‐phase deposition method, bilayer GaSe crystals were selectively grown and their two preferred 0° or 60° interlayer rotations were investigated. The commensurate stacking configurations (AA′ and AB stacking) in as‐grown bilayer GaSe crystals are clearly observed at the atomic scale, and the Ga‐terminated edge structure was identified using scanning transmission electron microscopy. Theoretical analysis reveals that the energies of the interlayer coupling are responsible for the preferred orientations among the bilayer GaSe crystals. 相似文献
76.
White‐Light Emission Strategy of a Single Organic Compound with Aggregation‐Induced Emission and Delayed Fluorescence Properties 下载免费PDF全文
Dr. Zongliang Xie Dr. Chengjian Chen Shidang Xu Jun Li Prof. Yi Zhang Prof. Siwei Liu Prof. Jiarui Xu Prof. Zhenguo Chi 《Angewandte Chemie (International ed. in English)》2015,54(24):7181-7184
A novel white‐light‐emitting organic molecule, which consists of carbazolyl‐ and phenothiazinyl‐substituted benzophenone (OPC) and exhibits aggregation‐induced emission‐delayed fluorescence (AIE‐DF) and mechanofluorochromic properties was synthesized. The CIE color coordinates of OPC were directly measured with a non‐doped powder, which presented white‐emission coordinates (0.33, 0.33) at 244 K to 252 K and (0.35, 0.35) at 298 K. The asymmetric donor–acceptor–donor′ (D‐A‐D′) type of OPC exhibits an accurate inherited relationship from dicarbazolyl‐substituted benzophenone (O2C, D‐A‐D) and diphenothiazinyl‐substituted benzophenone (O2P, D′‐A‐D′). By purposefully selecting the two parent molecules, that is, O2C (blue) and O2P (yellow), the white‐light emission of OPC can be achieved in a single molecule. This finding provides a feasible molecular strategy to design new AIE‐DF white‐light‐emitting organic molecules. 相似文献
77.
Dr. George N. Khairallah Dr. Alan T. Maccarone Dr. Huong T. Pham Timothy M. Benton Dr. Tony Ly Dr. Gabriel da Silva Prof. Stephen J. Blanksby Prof. Richard A. J. O'Hair 《Angewandte Chemie (International ed. in English)》2015,54(44):12947-12951
Although the deleterious effects of ozone on the human respiratory system are well‐known, many of the precise chemical mechanisms that both cause damage and afford protection in the pulmonary epithelial lining fluid are poorly understood. As a key first step to elucidating the intrinsic reactivity of ozone with proteins, its reactions with deprotonated cysteine [Cys?H]? are examined in the gas phase. Reaction proceeds at near the collision limit to give a rich set of products including 1) sequential oxygen atom abstraction reactions to yield cysteine sulfenate, sulfinate and sulfonate anions, and significantly 2) sulfenate radical anions formed by ejection of a hydroperoxy radical. The free‐radical pathway occurs only when both thiol and carboxylate moieties are available, implicating electron‐transfer as a key step in this reaction. This novel and facile reaction is also observed in small cys‐containing peptides indicating a possible role for this chemistry in protein ozonolysis. 相似文献
78.
Chih‐Hsien Wang Chia‐Chi Huang Long‐Liu Lin Wenlung Chen 《Journal of Raman spectroscopy : JRS》2016,47(8):940-947
Disulfide bond is relevant to many protein folding/unfolding functions and conformational diseases. To elucidate the effects of disulfide bonds on protein folding, unfolding, and misfolding, we performed Fourier transform–Raman measurements on serial chemical‐induced denaturations of bovine serum albumin (BSA). By directly monitoring Raman stretching at S–S (~507 cm−1), S–H (~2566 cm−1), amide I (1655 cm−1 for α‐helix; 1667 cm−1 for β‐sheet structure), and amide III (>1300 cm−1 for α‐helix; 1246 cm−1 for β‐sheet structure), the status of disulfide bonds and secondary structure of BSA at different states were elucidated. Both disulfide bonds and secondary structure (mostly in α‐helix) of BSA appeared relatively stable even when the protein was unfolded by urea solution. However, disulfide bonds were completely reduced and protein secondary structure changed from α‐helix to a relatively β‐sheet dominant when the protein was modified by the mixed solution of urea and dithiothreitol (urea/DTT). Adhering to these structural changes, the protein proceeded to different degrees of polymerization. BSA would aggregate into a high molecular mass (over 700 kDa) of protein ensemble when it was exposed to the mixed urea/DTT solution. An irreversible change in S–S/S–H conversion and secondary structure was responsible for protein misfolding. We demonstrate here that Fourier transform–Raman directly probe S–S/S–H conversion and secondary structural change of BSA at different states, and these results clearly indicate that disulfide bonds and secondary structure of BSA serve as concrete frameworks to stabilize protein structure. As the frameworks collapse, the protein undergoes an irreversible structural change and results in protein misfolding. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
79.
Explicit bounds on the elastic moduli of completely random planar polycrystals, the shape and crystalline orientations of the constituent grains of which are uncorrelated, are derived and calculated for a number of crystals of general two-dimensional anisotropy. The bounds on the elastic two-dimensional bulk modulus happen to coincide with the simple third order (in anisotropy contrast) bounds for the subclass of idealistic circular cell polycrystals. The bounds on the shear modulus are close to the much simpler bounds for circular cell polycrystals, which approximate aggregates of equiaxed grains. 相似文献
80.
Chi Tien 《Applied Scientific Research》1967,17(3):233-248
Summary Approximate solutions for laminar natural convection heat transfer between a vertical plate and a power-law fluid with high Prandtl number were obtained using an integral method for cases with various types of boundary conditions. The results were found in good agreement with available experimental evidence.Nomenclature
a
exponent defined by equations (28) and (29)
-
A, B, C, D, E
constants defined by equations (15) to (19)
-
C
1, C
2, M
1, M
2
coefficients for Nusselt number expression defined by (32b), (33b)
-
f
temperature difference, equal to T
s–T
-
f
+
dimensionless temperature difference
-
g
gravitational acceleration
-
Gr
Grashof number defined by (25), (50) and (66), respectively
-
H
heat flux at plate surface
-
h
x
local heat transfer coefficient
-
K
consistency index for Power-law fluid
-
k
thermal conductivity of fluid
-
K
1, K
2
constants defined by (50) and (51)
-
L
height of plate
-
n
flow behavior index for Power-law fluid
-
P
a quantity defined by (54a)
-
T
temperature
-
T
s
plate temperature
-
T
temperature of the bulk of fluid
-
s
constant given by (35)
-
u
velocity component along x-direction
-
u
x
maximum velocity induced by natural convection current, (10)
-
v
velocity component along y-direction
-
x
distance measured along direction parallel to that of gravitational force
-
x
+
dimensionless quantity, defined as x/L
-
y
distance measured away from plate
-
Nu
x
local Nusselt number
-
Nu
av
average Nusselt number
-
Pr
Prandtl number defined by (24)
-
T
temperature difference according to boundary conditions
-
thermal diffusivity of fluid
-
coefficient of thermal expression of fluid
-
boundary layer thickness
-
+
dimensionless boundary layer thickness
-
dimensionless velocity profile
-
dimensionless variable, defined as y/
-
dimensionless temperature difference 相似文献