J. Fraser Stoddart

Bio: J. Fraser Stoddart is an academic researcher from Northwestern University. The author has contributed to research in topics: Catenane & Supramolecular chemistry. The author has an hindex of 147, co-authored 1239 publications receiving 96083 citations. Previous affiliations of J. Fraser Stoddart include Zhejiang University & Northwest University (United States).

A reversible light-operated nanovalve on mesoporous silica nanoparticles.

Abstract: Two azobenzene α-cyclodextrin based nanovalves are designed, synthesized and assembled on mesoporous silica nanoparticles. Under aqueous conditions, the cyclodextrin cap is tightly bound to the azobenzene moiety and capable of holding back loaded cargo molecules. Upon irradiation with a near-UV light laser, trans to cis-photoisomerization of azobenzene initiates a dethreading process, which causes the cyclodextrin cap to unbind followed by the release of cargo. The addition of a bulky stopper to the end of the stalk allows this design to be reversible; complete dethreading of cyclodextrin as a result of unbinding with azobenzene is prevented as a consequence of steric interference. As a result, thermal relaxation of cis- to trans-azobenzene allows for the rebinding of cyclodextrin and resealing of the nanopores, a process which entraps the remaining cargo. Two stalks were designed with different lengths and tested with alizarin red S and propidium iodide. No cargo release was observed prior to light irradiation, and the system was capable of multiuse. On/off control was also demonstrated by monitoring the release of cargo when the light stimulus was applied and removed, respectively.

Design and Synthesis of Nonequilibrium Systems

Abstract: The active transport of ions and molecules across cell membranes is essential to creating the concentration gradients that sustain life in all living organisms, be they bacteria, fungi, plants, animals or Homo sapiens. Nature uses active transport everywhere for everything. Molecular biologists have long been attracted to the study of active transport and continue to this day to investigate and elucidate the tertiary structures of the complex motor proteins that sustain it, while physicists, interested in nonequilibrium statistical mechanics, have developed theoretical models to describe the driven ratcheting motions that are crucial to its function. The increasingly detailed understanding that contemporary science has acquired relating to active transport, however, has yet to lead to the design and construction of artificial molecular motors capable of employing ratchet-driven motions that can also perform work against concentration gradients. Mechanically interlocked molecules (MIMs) in the form of pseu...

A molecular meccano kit

Abstract: A range of secondary dialkylammonium (R2NH2+) ions has been shown to thread through the cavities of appropriately-sized crown ether compounds to afford interwoven complexes. X-Ray crystallographic investigations to probe the solid-state properties of these supermolecules have revealed that many subtle factors—e.g., solvent of crystallisation, crown ether conformation and anion interactions—can influence the nature of the overall three-dimensional superstructures. Nonetheless, a family of building blocks—namely R2NH2+ ions and crown ethers—can be generated, which constitute a molecular meccano kit. By mixing and matching these modules in different ways, intricate interwoven supramolecular architectures can be constructed. From relatively simple beginnings—where one R2NH2+ ion is threaded through one monotopic crown ether (dibenzo[24]crown-8)—the designed evolution of the building blocks in the molecular meccano kit has led to more elaborate multiply encircled and/or multiply threaded superstructures. The effects of crown ether constitution, macroring size, and both crown ether as well as R2NH2+ ion substitution, upon the solid-state behaviour of these interwoven complexes have also been examined. A statistical analysis of the hydrogen bonding interactions observed in these systems has been carried out. It reveals that a reasonable correlation exists between N+–H⋯O bond angle and H⋯O bond length. The correlation between C–H⋯O bond angle and H⋯O distance is poor, suggesting that C–H⋯O hydrogen bonding interactions are of secondary importance in determining the co-conformations adopted by these supermolecules.

A Redox-Switchable α-Cyclodextrin-Based [2]Rotaxane

Abstract: A bistable [2]rotaxane comprising an α-cyclodextrin (α-CD) ring and a dumbbell component containing a redox-active tetrathiafulvalene (TTF) ring system within its rod section has been synthesized using the Cu(I)-catalyzed azide−alkyne cycloaddition, and the redox-driven movements of the α-CD ring between the TTF and newly formed triazole ring systems have been elucidated. Microcalorimetric titrations on model complexes suggested that the α-CD ring prefers to reside on the TTF rather than on the triazole ring system by at least an order of magnitude. The fact that this situation does pertain in the bistable [2]rotaxane has not only been established quantitatively by electrochemical experiments and backed up by spectroscopic and chiroptical measurements but also been confirmed semiquantitatively by the recording of numerous cyclic voltammograms which point, along with the use of redox-active chemical reagents, to a mechanism of switching that involves the oxidation of the neutral TTF ring system to either its radical cationic (TTF^(•+)) or dicationic (TTF^(2+)) counterparts, whereupon the α-CD ring, moves along the dumbbell to encircle the triazole ring system. Since redox control by both chemical and electrochemical means is reversible, the switching by the bistable [2]rotaxane can be reversed on reduction of the TTF^(•+) or TTF^(2+) back to being a neutral TTF.

Fast parallel algorithms for short-range molecular dynamics

Abstract: Three parallel algorithms for classical molecular dynamics are presented. The first assigns each processor a fixed subset of atoms; the second assigns each a fixed subset of inter-atomic forces to compute; the third assigns each a fixed spatial region. The algorithms are suitable for molecular dynamics models which can be difficult to parallelize efficiently—those with short-range forces where the neighbors of each atom change rapidly. They can be implemented on any distributed-memory parallel machine which allows for message-passing of data between independently executing processors. The algorithms are tested on a standard Lennard-Jones benchmark problem for system sizes ranging from 500 to 100,000,000 atoms on several parallel supercomputers--the nCUBE 2, Intel iPSC/860 and Paragon, and Cray T3D. Comparing the results to the fastest reported vectorized Cray Y-MP and C90 algorithm shows that the current generation of parallel machines is competitive with conventional vector supercomputers even for small problems. For large problems, the spatial algorithm achieves parallel efficiencies of 90% and a 1840-node Intel Paragon performs up to 165 faster than a single Cray C9O processor. Trade-offs between the three algorithms and guidelines for adapting them to more complex molecular dynamics simulations are also discussed.

疟原虫var基因转换速率变化导致抗原变异[英]／Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A

Abstract: 抗原变异可使得多种致病微生物易于逃避宿主免疫应答。表达在感染红细胞表面的恶性疟原虫红细胞表面蛋白1（PfPMP1）与感染红细胞、内皮细胞、树突状细胞以及胎盘的单个或多个受体作用，在黏附及免疫逃避中起关键的作用。每个单倍体基因组var基因家族编码约60种成员，通过启动转录不同的var基因变异体为抗原变异提供了分子基础。

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

Abstract: Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

The Chemistry and Applications of Metal-Organic Frameworks

Abstract: Crystalline metal-organic frameworks (MOFs) are formed by reticular synthesis, which creates strong bonds between inorganic and organic units. Careful selection of MOF constituents can yield crystals of ultrahigh porosity and high thermal and chemical stability. These characteristics allow the interior of MOFs to be chemically altered for use in gas separation, gas storage, and catalysis, among other applications. The precision commonly exercised in their chemical modification and the ability to expand their metrics without changing the underlying topology have not been achieved with other solids. MOFs whose chemical composition and shape of building units can be multiply varied within a particular structure already exist and may lead to materials that offer a synergistic combination of properties.