共查询到20条相似文献，搜索用时 31 毫秒
1.
de Jong JJ Lucas LN Kellogg RM van Esch JH Feringa BL 《Science (New York, N.Y.)》2004,304(5668):278-281
In nature, key molecular processes such as communication, replication, and enzyme catalysis all rely on a delicate balance between molecular and supramolecular chirality. Here we report the design, synthesis, and operation of a reversible, photoresponsive, self-assembling molecular system in which molecular and supramolecular chirality communicate. It shows exceptional stereoselectivity upon aggregation of the molecules during gel formation with the solvent. This chirality is locked by photochemical switching, a process that is subsequently used to induce an inverted chiral supramolecular assembly as revealed by circular dichroism spectroscopy. The optical switching between different chiral aggregated states and the interplay of molecular and supramolecular chirality offer attractive new prospects for the development of molecular memory systems and smart functional materials. 相似文献
2.
DR Link G Natale R Shao JE Maclennan NA Clark E Korblova DM Walba 《Science (New York, N.Y.)》1997,278(5345):1924-1927
A smectic liquid-crystal phase made from achiral molecules with bent cores was found to have fluid layers that exhibit two spontaneous symmetry-breaking instabilities: polar molecular orientational ordering about the layer normal and molecular tilt. These instabilities combine to form a chiral layer structure with a handedness that depends on the sign of the tilt. The bulk states are either antiferroelectric-racemic, with the layer polar direction and handedness alternating in sign from layer to layer, or antiferroelectric-chiral, which is of uniform layer handedness. Both states exhibit an electric field-induced transition from antiferroelectric to ferroelectric. 相似文献
3.
A disk-shaped molecule with chiral tails is shown to form long fibers of molecular diameter and micrometer length by self-assembly in chloroform. The molecules are derived from crown ethers and contain a phthalocyanine ring. In the fibers, they have a clockwise, staggered orientation that leads to an overall right-handed helical structure. These structures, in turn, self-assemble to form coiled-coil aggregates with left-handed helicity. Addition of potassium ions to the fibers leaves their structure intact but blocks the transfer of the chirality from the tails to the cores, leading to loss of the helicity of the fibers. These tunable chiral materials have potential in optoelectronic applications and as components in sensor devices. 相似文献
4.
手性农药毒性评价进展 总被引：2，自引：0，他引：2
长期以来,手性农药都被当作单一化合物进行环境行为和生态毒性研究,但是由于手性农药对映体与生物大分子相互作用的立体选择性,手性农药对动物及人类的毒性作用可能具有对映体选择性.本文介绍了有机磷、有机氯、拟除虫菊酯、苯基吡唑等手性农药对内分泌、神经、免疫、生殖、发育等毒性作用的对映体选择性,分析了对映体选择性产生的机制,在此基础上提出了未来的研究方向. 相似文献
5.
Enzymes and synthetic chiral catalysts have found widespread application to produce single enantiomers, but in situ switching of the chiral preference of a catalytic system is very difficult to achieve. Here, we report on a light-driven molecular motor with integrated catalytic functions in which the stepwise change in configuration during a 360° unidirectional rotary cycle governs the catalyst performance both with respect to activity and absolute stereocontrol in an asymmetric transformation. During one full rotary cycle, catalysts are formed that provide either racemic (R,S) or preferentially the R or the S enantiomer of the chiral product of a conjugate addition reaction. This catalytic system demonstrates how different molecular tasks can be performed in a sequential manner, with the sequence controlled by the directionality of a rotary cycle. 相似文献
6.
Keren K Krueger M Gilad R Ben-Yoseph G Sivan U Braun E 《Science (New York, N.Y.)》2002,297(5578):72-75
Recent advances in the realization of individual molecular-scale electronic devices emphasize the need for novel tools and concepts capable of assembling such devices into large-scale functional circuits. We demonstrated sequence-specific molecular lithography on substrate DNA molecules by harnessing homologous recombination by RecA protein. In a sequence-specific manner, we patterned the coating of DNA with metal, localized labeled molecular objects and grew metal islands on specific sites along the DNA substrate, and generated molecularly accurate stable DNA junctions for patterning the DNA substrate connectivity. In our molecular lithography, the information encoded in the DNA molecules replaces the masks used in conventional microelectronics, and the RecA protein serves as the resist. The molecular lithography works with high resolution over a broad range of length scales from nanometers to many micrometers. 相似文献
7.
Sodium chlorate (NaClO(3)) crystals are optically active although the molecules of the compound are not chiral. When crystallized from an aqueous solution while the solution is not stirred, statistically equal numbers of levo (L) and dextro (D) NaClO(3) crystals were found. When the solution was stirred, however, almost all of the NaClO(3) crystals (99.7 percent) in a particular sample had the same chirality, either levo or dextro. This result represents an experimental demonstration of chiral symmetry breaking or total spontaneous resolution on a macroscopic level brought about by autocatalysis and competition between L- and D-crystals. 相似文献
8.
The discovery of distinct modes of asymmetric catalysis has the potential to rapidly advance chemists' ability to build enantioenriched molecules. As an example, the use of chiral cation salts as phase-transfer catalysts for anionic reagents has enabled a vast set of enantioselective transformations. Here, we present evidence that a largely overlooked analogous mechanism wherein a chiral anionic catalyst brings a cationic species into solution is itself a powerful method. The concept is applied to the enantioselective fluorocyclization of olefins with a cationic fluorinating agent and a chiral phosphate catalyst. The reactions proceed in high yield and stereoselectivity, especially considering the scarcity of alternative approaches. This technology can in principle be applied to the large portion of reaction space that uses positively charged reagents and reaction intermediates. 相似文献
9.
Electron transmission experiments demonstrate a large asymmetry in the scattering probability of polarized electrons by thin organized films of chiral molecules. This large asymmetry results from the interaction of the electron's wavefunction with many scatterers (molecules) in the organized monolayer structure and represents a manifestation of quantum interference on the scale of supramolecular lengths. 相似文献
10.
Wolf SG Landau EM Lahav M Leiserowitz L Deutsch M Kjaer K Als-Nielsen J 《Science (New York, N.Y.)》1988,242(4883):1286-1290
A measurement and interpretation on a molecular level of a phase transition in an ordered Langmuir monolayer is reported. The diagram of surface pressure (pi) versus molecular area of a monolayer of chiral (S)-[CF(3)-(CF(2))(9)-(CH(2))(2)-OCO-CH(2)-CH (NH(3)(+))CO(2)(-)] over water shows a change in slope at about pi(s)= 25 millinewtons per meter. Grazing-incidence x-ray diffraction and specular reflectivity measurements indicate a solid-solid phase transition at pi(s). The diffraction pattren at low pressures reveals two diffraction peaks of equal intensities, with lattice spacings d of 5.11 and 5.00 angstroms; these coalesce for pi >/=pi(s). Structural models that fit the diffraction data show that at pi> pi(s) the molecules pack in a two-dimensional crystal with the molecules aligned vertically. At pi < pi(s) there is a molecular tilt of 16 degrees +/- 7 degrees . Independent x-ray reflectivity data yield a tilt of 26 degrees +/- 7 degrees . Concomitant with the tilt, the diffraction data indicate a transition from a hexagonal to a distorted-hexagonal lattice. The hexagonal arrangement is favored because the -(CF(2))(9)CF(3) moiety adopts a helical conformation. Compression to 70 millinewtons per meter yields a unit cell with increased crystallinity and a coherence length exceeding 1000 angstroms. 相似文献
11.
J Bailey A Chrysostomou JH Hough TM Gledhill A McCall S Clark F Menard M Tamura 《Science (New York, N.Y.)》1998,281(5377):672-674
Strong infrared circular polarization resulting from dust scattering in reflection nebulae in the Orion OMC-1 star-formation region has been observed. Circular polarization at shorter wavelengths might have been important in inducing chiral asymmetry in interstellar organic molecules that could be subsequently delivered to the early Earth by comets, interplanetary dust particles, or meteors. This could account for the excess of L-amino acids found in the Murchison meteorite and could explain the origin of the homochirality of biological molecules. 相似文献
12.
I Kuzmenko R Buller WG Bouwman K Kjaer J Als-Nielsen M Lahav L Leiserowitz 《Science (New York, N.Y.)》1996,274(5295):2046-2049
Thin interdigitated films composed of a long-chain, water-insoluble chiral acid (p-pentadecylmandelic acid of absolute configuration R) and a water-soluble chiral base (phenylethylamine, R') were constructed at the air-solution interface. The (R, R') structure was characterized to near-atomic resolution by grazing-incidence x-ray diffraction (GIXD). The two diastereomeric systems, (R, R') and (R, S'), demonstrate similar surface pressure-molecular area isotherms, but their structures are completely different on the molecular level, as monitored by GIXD. Complementary data on these two architectures were provided by atomic force microscopy. 相似文献
13.
14.
Devries GA Brunnbauer M Hu Y Jackson AM Long B Neltner BT Uzun O Wunsch BH Stellacci F 《Science (New York, N.Y.)》2007,315(5810):358-361
Nanoparticles can be used as the building blocks for materials such as supracrystals or ionic liquids. However, they lack the ability to bond along specific directions as atoms and molecules do. We report a simple method to place target molecules specifically at two diametrically opposed positions in the molecular coating of metal nanoparticles. The approach is based on the functionalization of the polar singularities that must form when a curved surface is coated with ordered monolayers, such as a phase-separated mixture of ligands. The molecules placed at these polar defects have been used as chemical handles to form nanoparticle chains that in turn can generate self-standing films. 相似文献
15.
Kong J Franklin NR Zhou C Chapline MG Peng S Cho K Dai H 《Science (New York, N.Y.)》2000,287(5453):622-625
Chemical sensors based on individual single-walled carbon nanotubes (SWNTs) are demonstrated. Upon exposure to gaseous molecules such as NO(2) or NH(3), the electrical resistance of a semiconducting SWNT is found to dramatically increase or decrease. This serves as the basis for nanotube molecular sensors. The nanotube sensors exhibit a fast response and a substantially higher sensitivity than that of existing solid-state sensors at room temperature. Sensor reversibility is achieved by slow recovery under ambient conditions or by heating to high temperatures. The interactions between molecular species and SWNTs and the mechanisms of molecular sensing with nanotube molecular wires are investigated. 相似文献
16.
Metals and DNA: molecular left-handed complements 总被引：23，自引：0，他引：23
J K Barton 《Science (New York, N.Y.)》1986,233(4765):727-734
Chiral metal complexes provide unique molecular probes for DNA. Chiral reagents that "recognize" different local structures along the DNA strand have been designed by a process in which the asymmetry in shape and size of the complex is matched to that of the DNA helical groove. As a result, the chiral metal complexes provide very sensitive probes for local helical structure, both left- and right-handed. Direct coordination of chiral complexes to the DNA bases adds an element of sequence selectivity to the probe design. With a suitable reactive metal center, reagents that target chemically specific sites along the strand may be developed. One such chiral reagent, which cleaves left-handed DNA sites with photoactivation, has been useful in mapping this distinct conformation and examining its biological role. The conformation-specific molecular cleaver, much like a DNA-binding enzyme, recognizes and reacts at discrete sites along the DNA strand. These site-specific chiral metal complexes provide exciting new tools for probing the local variations in DNA structure and its role in the regulation of gene expression. 相似文献
17.
We report the cooling of nitric oxide using a single collision between an argon atom and a molecule of NO. We have produced significant numbers (108 to 109 molecules per cubic centimeter per quantum state) of translationally cold NO molecules in a specific quantum state with an upper-limit root mean square laboratory velocity of 15 plus or minus 1 meters per second, corresponding to a 406 plus or minus 23 millikelvin upper limit of temperature, in a crossed molecular beam apparatus. The technique, which relies on a kinematic collapse of the velocity distributions of the molecular beams for the scattering events that produce cold molecules, is general and independent of the energy of the colliding partner. 相似文献
18.
The molecular nutritional requirements exhibited by mammalian cells can vary with the following conditions: whether the cells are plated singly or in massive inoculum; whether a clonal strain or a mixture of different genotypes is employed; whether the macromolecular fraction of serum used as a supplement was previously exposed to prolonged dialysis or other procedures which may release bound micromolecules. In addition, the nature of the medium in which the cells were previously grown, the time permitted for incubation of the cells in the test medium, and the presence of substances or conditions which may specifically introduce the need for certain molecules to preserve balance can strongly influence nutritional requirements. This great versatility may reflect the ability of the mammalian cell to assume different metabolic states characteristic of specific types of differentiation. Under certain conditions, growth of single HeLa cells of the S3 clonal strain requires the presence of cholesterol at a level of 0.5 to 1 microgram per milliliter. 相似文献
19.
There has been a phenomenal growth in the field of biosensor development in recent years with emerging applications in a wide range of disciplines, including medical analysis, food and the environment. The increase in the number of analytes requiring monitoring and others that require control, and the need for high sensitivity, speed, and accuracy of analytical measurements have stimulated considerable interest in developing sensors as diagnostics tools. A range of molecules with biorecognition powers are available naturally such as antibodies, enzymes, cell receptors and nucleic acids and are used as the sensing receptors in biosensors. The combined approaches of computer (molecular) modelling and combinatorial synthesis or molecularly imprinted polymers are undertaken today as a new method to produce synthetic receptors that can be used in sensor development. A wide range of transducers is also feasible to fulfil the rapid monitoring needs of the diagnostic market. Biosensors can also be incorporated into simple-to-use instruments as an on-line monitoring device or a one-shot sensor. This paper deals with recent developments in biosensors and their potential use in the agricultural diagnostic market. 相似文献
20.
Near-atomic resolution images of a two-dimensional heteroepitaxial crystal composed of the relatively "functionally rich" chiral liquid crystal mesogen MDW 74 on graphite have been obtained by scanning tunneling microscopy (STM). This work is aimed at developing an improved understanding of the commercially crucial phenomenon of liquid crystal alignment by studying well-characterized surfaces. Herein is reported molecular-level characterization of the surface underlying a ferroelectric liquid crystal in situ, a requisite starting point for understanding the liquid crystal-solid interface at the molecular level. The results are also important in the context of developing a model for the molecular. origins of the contrast observed in STM images of organic monolayers on conductor surfaces. The data and analysis provide strong evidence that neither frontier orbital alone (highest occupied or lowest unoccupied molecular orbital) is sufficient to describe the observed tunneling efficiency. 相似文献