Synthesis beyond the molecule

Weak, noncovalent interactions between molecules control many biological functions. In chemistry, noncovalent interactions are now exploited for the synthesis in solution of large supramolecular aggregates. The aim of these syntheses is not only the creation of a particular structure, but also the introduction of specific chemical functions in these supramolecules.     

分子激子理论及其在光谱解析中的应用

分子聚集体是通过分子间相互作用形成的,其特殊作用和功能首先在生物体系中得到了人们的认识。分子光谱是聚集态分子研究的有力工具。分子激子理论基于激发态共振相互作用处理分子聚集体,给出了分子聚集体的光谱性质与分子结构之间的关系。本文将对分子激子理论做一简要介绍,并给出分子激子理论在光谱解析中的几个例子。     

Chemically derived, ultrasmooth graphene nanoribbon semiconductors

We developed a chemical route to produce graphene nanoribbons (GNR) with width below 10 nanometers, as well as single ribbons with varying widths along their lengths or containing lattice-defined graphene junctions for potential molecular electronics. The GNRs were solution-phase-derived, stably suspended in solvents with noncovalent polymer functionalization, and exhibited ultrasmooth edges with possibly well-defined zigzag or armchair-edge structures. Electrical transport experiments showed that, unlike single-walled carbon nanotubes, all of the sub-10-nanometer GNRs produced were semiconductors and afforded graphene field effect transistors with on-off ratios of about 10(7) at room temperature.     

Giant supramolecular liquid crystal lattice

Self-organized supramolecular organic nanostructures have potential applications that include molecular electronics, photonics, and precursors for nanoporous catalysts. Accordingly, understanding how self-assembly is controlled by molecular architecture will enable the design of increasingly complex structures. We report a liquid crystal (LC) phase with a tetragonal three-dimensional unit cell containing 30 globular supramolecular dendrimers, each of which is self-assembled from 12 dendron (tree-like) molecules, for the compounds described here. The present structure is one of the most complex LC phases yet discovered. A model explaining how spatial arrangement of self-assembled dendritic aggregates depends on molecular architecture and temperature is proposed.     

Supracolloidal reaction kinetics of Janus spheres

Clusters in the form of aggregates of a small number of elemental units display structural, thermodynamic, and dynamic properties different from those of bulk materials. We studied the kinetic pathways of self-assembly of "Janus spheres" with hemispherical hydrophobic attraction and found key differences from those characteristic of molecular amphiphiles. Experimental visualization combined with theory and molecular dynamics simulation shows that small, kinetically favored isomers fuse, before they equilibrate, into fibrillar triple helices with at most six nearest neighbors per particle. The time scales of colloidal rearrangement combined with the directional interactions resulting from Janus geometry make this a prototypical system to elucidate, on a mechanistic level and with single-particle kinetic resolution, how chemical anisotropy and reaction kinetics coordinate to generate highly ordered structures.     

Probing the solvent-assisted nucleation pathway in chemical self-assembly

Hierarchical self-assembly offers a powerful strategy for producing molecular nanostructures. Although widely used, the mechanistic details of self-assembly processes are poorly understood. We spectroscopically monitored a nucleation process in the self-assembly of p-conjugated molecules into helical supramolecular fibrillar structures. The data support a nucleation-growth pathway that gives rise to a remarkably high degree of cooperativity. Furthermore, we characterize a helical transition in the nucleating species before growth. The self-assembly process depends strongly on solvent structure, suggesting that an organized shell of solvent molecules plays an explicit role in rigidifying the aggregates and guiding them toward further assembly into bundles and/or gels.     

Molecular chaperones: the plant connection

Molecular chaperones are a family of unrelated proteins found in all types of cell. They mediate the correct assembly of other polypeptides, but are not components of the mature assembled structures. Chaperones function by binding specifically to interactive protein surfaces that are exposed transiently during many cellular processes and so prevent them from undergoing incorrect interactions that might produce nonfunctional structures. The concept of molecular chaperones originated largely from studies of the chloroplast enzyme rubisco, which fixes carbon dioxide in plant photosynthesis; the function of chaperones forces a rethinking of the principle of protein self-assembly.     

Self-assembly of disk-shaped molecules to coiled-coil aggregates with tunable helicity

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.     

Diacetylenic lipid tubules: experimental evidence for a chiral molecular architecture

Molecular self-assembly is of key importance for the rational design of advanced materials. To investigate the causal relation between molecular structure and the consequent self-assembled microstructure, self-assembled tubules of diacetylenic lipids were studied. Circular-dichroism studies give experimental evidence that the formation of tubules is driven by chiral molecular packing, in agreement with recent theories of tubules. On the basis of these results, a molecular mechanism for the formation of tubules is proposed.     

Light-directed, spatially addressable parallel chemical synthesis

Solid-phase chemistry, photolabile protecting groups, and photolithography have been combined to achieve light-directed, spatially addressable parallel chemical synthesis to yield a highly diverse set of chemical products. Binary masking, one of many possible combinatorial synthesis strategies, yields 2n compounds in n chemical steps. An array of 1024 peptides was synthesized in ten steps, and its interaction with a monoclonal antibody was assayed by epifluorescence microscopy. High-density arrays formed by light-directed synthesis are potentially rich sources of chemical diversity for discovering new ligands that bind to biological receptors and for elucidating principles governing molecular interactions. The generality of this approach is illustrated by the light-directed synthesis of a dinucleotide. Spatially directed synthesis of complex compounds could also be used for microfabrication of devices.     

Changes in organic C stability within soil aggregates under different fertilization patterns in a greenhouse vegetable field

Knowledge of the stability of soil organic C(SOC) is vital for assessing SOC dynamics and cycling in agroecosystems. Studies have documented the regulatory effect of fertilization on SOC stability in bulk soils. However, how fertilization alters organic C stability at the aggregate scale in agroecosystems remains largely unclear. This study aimed to appraise the changes of organic C stability within soil aggregates after eight years of fertilization(chemical vs. organic fertilization) in a greenhouse vegetable field in Tianjin, China. Changes in the stability of organic C in soil aggregates were evaluated by four methods, i.e., the modified Walkley-Black method(chemical method), ~(13)C NMR spectroscopy(spectroscopic method), extracellular enzyme assay(biological method), and thermogravimetric analysis(thermogravimetric method). The aggregates were isolated and separated by a wet-sieving method into four fractions: large macroaggregates(2 mm), small macroaggregates(0.25–2 mm), microaggregates(0.053–0.25 mm), and silt/clay fractions(0.053 mm). The results showed that organic amendments increased the organic C content and reduced the chemical, spectroscopic, thermogravimetric, and biological stability of organic C within soil aggregates relative to chemical fertilization alone. Within soil aggregates, the content of organic C was the highest in microaggregates and decreased in the order microaggregatesmacroaggregatessilt/clay fractions. Meanwhile, organic C spectroscopic, thermogravimetric, and biological stability were the highest in silt/clay fractions, followed by macroaggregates and microaggregates. Moreover, the modified Walkley-Black method was not suitable for interpreting organic C stability at the aggregate scale due to the weak correlation between organic C chemical properties and other stability characteristics within the soil aggregates. These findings provide scientific insights at the aggregate scale into the changes of organic C properties under fertilization in greenhouse vegetable fields in China.     

Self-assembly of large and small molecules into hierarchically ordered sacs and membranes

We report here the self-assembly of macroscopic sacs and membranes at the interface between two aqueous solutions, one containing a megadalton polymer and the other, small self-assembling molecules bearing opposite charge. The resulting structures have a highly ordered architecture in which nanofiber bundles align and reorient by nearly 90 degrees as the membrane grows. The formation of a diffusion barrier upon contact between the two liquids prevents their chaotic mixing. We hypothesize that growth of the membrane is then driven by a dynamic synergy between osmotic pressure of ions and static self-assembly. These robust, self-sealing macroscopic structures offer opportunities in many areas, including the formation of privileged environments for cells, immune barriers, new biological assays, and self-assembly of ordered thick membranes for diverse applications.     

Posttranslational quality control: folding, refolding, and degrading proteins

Polypeptides emerging from the ribosome must fold into stable three-dimensional structures and maintain that structure throughout their functional lifetimes. Maintaining quality control over protein structure and function depends on molecular chaperones and proteases, both of which can recognize hydrophobic regions exposed on unfolded polypeptides. Molecular chaperones promote proper protein folding and prevent aggregation, and energy-dependent proteases eliminate irreversibly damaged proteins. The kinetics of partitioning between chaperones and proteases determines whether a protein will be destroyed before it folds properly. When both quality control options fail, damaged proteins accumulate as aggregates, a process associated with amyloid diseases.     

Covalently bridging gaps in single-walled carbon nanotubes with conducting molecules

Molecular electronics is often limited by the poorly defined nature of the contact between the molecules and the metal surface. We describe a method to wire molecules into gaps in single-walled carbon nanotubes (SWNTs). Precise oxidative cutting of a SWNT produces carboxylic acid-terminated electrodes separated by gaps of 相似文献   

分子印迹技术及其在痕量分析的应用

分子印迹技术是近年来集高分子合成、分子设计、分子识别、仿生生物工程等众多学科优势发展起来的一门边缘学科分支.分子印迹聚合物由于具有与天然抗体同样的识别性能和与高分子同样的抗腐蚀性能的双重优点,因而广泛应用于生物工程、临床医学、环境监测、食品工业等众多领域.介绍了分子印迹技术的基本原理,对分子印迹聚合物合成研究的最新进展进行了综述,主要介绍了它在痕量分析中的应用.     

Single crystals of single-walled carbon nanotubes formed by self-assembly

We report the self-assembly of single crystals of single-walled carbon nanotubes (SWCNTs) using thermolysis of nano-patterned precursors. The synthesis of these perfectly ordered, single crystals of SWCNTs results in extended structures with dimension on the micrometer scale. Each crystal is composed of an ordered array of tubes with identical diameters and chirality, although these properties vary between crystals. The results show that SWCNTs can be produced as a perfect bulk material on the micrometer scale and point toward the synthesis of bulk macroscopic crystalline material.     

Ouabain resistance conferred by expression of the cDNA for a murine Na+, K+-ATPase alpha subunit

The molecular basis for the marked difference between primate and rodent cells in sensitivity to the cardiac glycoside ouabain has been established by genetic techniques. A complementary DNA encoding the entire alpha 1 subunit of the mouse Na+- and K+-dependent adenosine triphosphatase (ATPase) was inserted into the expression vector pSV2. This engineered DNA molecule confers resistance against 10(-4) M ouabain to monkey CV-1 cells. Deletion of sequences encoding the carboxyl terminus of the alpha 1 subunit abolish the activity of the complementary DNA. The ability to assay the biological activity of this ATPase in a transfection protocol permits the application of molecular genetic techniques to the analysis of structure-function relationships for the enzyme that establishes the internal Na+/K+ environment of most animal cells. The full-length alpha 1 subunit complementary DNA will also be useful as a dominant selectable marker for somatic cell genetic studies utilizing ouabain-sensitive cells.     

Supramolecular chemistry: receptors, catalysts, and carriers

Supramolecular chemistry is the study of the structures and functions of the supermolecules that result from binding substrates to molecular receptors. Macropolycyclic receptors and coreceptors have been designed that form cryptate inclusion complexes and display molecular recognition towards spherical, tetrahedral, and linear substrates of various kinds (metal cations, inorganic anions, and organic or biological cations or anions). Anion binding has led to the development of anion coordination chemistry. Metalloreceptors simultaneously bind organic molecules and metal ions; speleands combine polar and nonpolar binding subunits. Receptors bearing reactive functional groups may act as molecular reagents or catalysts, performing a chemical transformation on the bound substrates (by such reactions as hydrogen transfer, ester cleavage, and protoadenosinetriphosphatase and protokinase activities). Receptors fitted with lipophilic groups can operate as molecular carriers, translocating bound species through a membrane; this transport can be coupled to chemical potentials (proton and redox gradients).     

Self-assembly at all scales

Self-assembly is the autonomous organization of components into patterns or structures without human intervention. Self-assembling processes are common throughout nature and technology. They involve components from the molecular (crystals) to the planetary (weather systems) scale and many different kinds of interactions. The concept of self-assembly is used increasingly in many disciplines, with a different flavor and emphasis in each.     

Recognition and transport of adenine derivatives with synthetic receptors

Several new synthetic agents show high affinity for binding adenine derivatives. The structures feature complementary hydrogen bonds that cause the molecular chelation of the purine nucleus. The high lipophilicity of the new agents permits the transport of adenosine and deoxyadenosine across organic liquid membranes. The use of synthetic receptors for small biological targets may have application in drug delivery.