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.

Fast parallel algorithms for short-range molecular dynamics

Luminogenic materials with aggregation-induced emission (AIE) attributes have attracted much interest since the debut of the AIE concept in 2001. In this critical review, recent progress in the area of AIE research is summarized. Typical examples of AIE systems are discussed, from which their structure–property relationships are derived. Through mechanistic decipherment of the photophysical processes, structural design strategies for generating new AIE luminogens are developed. Technological, especially optoelectronic and biological, applications of the AIE systems are exemplified to illustrate how the novel AIE effect can be utilized for high-tech innovations (183 references).

Aggregation-induced emission

This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them. It summarizes cellulose nanoparticles in terms of particle morphology, crystal structure, and properties. Also described are the self-assembly and rheological properties of cellulose nanoparticle suspensions. The methodology of composite processing and resulting properties are fully covered, with an emphasis on neat and high fraction cellulose composites. Additionally, advances in predictive modeling from molecular dynamic simulations of crystalline cellulose to the continuum modeling of composites made with such particles are reviewed (392 references).

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Cellulose nanomaterials review: structure, properties and nanocomposites

Cellulose constitutes the most abundant renewable polymer resource available today. As a chemical raw material, it is generally well-known that it has been used in the form of fibers or derivatives for nearly 150 years for a wide spectrum of products and materials in daily life. What has not been known until relatively recently is that when cellulose fibers are subjected to acid hydrolysis, the fibers yield defect-free, rod-like crystalline residues. Cellulose nanocrystals (CNs) have garnered in the materials community a tremendous level of attention that does not appear to be relenting. These biopolymeric assemblies warrant such attention not only because of their unsurpassed quintessential physical and chemical properties (as will become evident in the review) but also because of their inherent renewability and sustainability in addition to their abundance. They have been the subject of a wide array of research efforts as reinforcing agents in nanocomposites due to their low cost, availability, renewability, light weight, nanoscale dimension, and unique morphology. Indeed, CNs are the fundamental constitutive polymeric motifs of macroscopic cellulosic-based fibers whose sheer volume dwarfs any known natural or synthetic biomaterial. Biopolymers such as cellulose and lignin and † North Carolina State University. ‡ Helsinki University of Technology. Dr. Youssef Habibi is a research assistant professor at the Department of Forest Biomaterials at North Carolina State University. He received his Ph.D. in 2004 in organic chemistry from Joseph Fourier University (Grenoble, France) jointly with CERMAV (Centre de Recherche sur les Macromolecules Vegetales) and Cadi Ayyad University (Marrakesh, Morocco). During his Ph.D., he worked on the structural characterization of cell wall polysaccharides and also performed surface chemical modification, mainly TEMPO-mediated oxidation, of crystalline polysaccharides, as well as their nanocrystals. Prior to joining NCSU, he worked as assistant professor at the French Engineering School of Paper, Printing and Biomaterials (PAGORA, Grenoble Institute of Technology, France) on the development of biodegradable nanocomposites based on nanocrystalline polysaccharides. He also spent two years as postdoctoral fellow at the French Institute for Agricultural Research, INRA, where he developed new nanostructured thin films based on cellulose nanowiskers. Dr. Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research. Chem. Rev. 2010, 110, 3479–3500 3479

Cellulose nanocrystals: chemistry, self-assembly, and applications.

Detection of chemical and biological agents plays a fundamental role in biomedical, forensic and environmental sciences1–4 as well as in anti bioterrorism applications.5–7 The development of highly sensitive, cost effective, miniature sensors is therefore in high demand which requires advanced technology coupled with fundamental knowledge in chemistry, biology and material sciences.8–13

In general, sensors feature two functional components: a recognition element to provide selective/specific binding with the target analytes and a transducer component for signaling the binding event. An efficient sensor relies heavily on these two essential components for the recognition process in terms of response time, signal to noise (S/N) ratio, selectivity and limits of detection (LOD).14,15 Therefore, designing sensors with higher efficacy depends on the development of novel materials to improve both the recognition and transduction processes. Nanomaterials feature unique physicochemical properties that can be of great utility in creating new recognition and transduction processes for chemical and biological sensors15–27 as well as improving the S/N ratio by miniaturization of the sensor elements.28

Gold nanoparticles (AuNPs) possess distinct physical and chemical attributes that make them excellent scaffolds for the fabrication of novel chemical and biological sensors (Figure 1).29–36 First, AuNPs can be synthesized in a straightforward manner and can be made highly stable. Second, they possess unique optoelectronic properties. Third, they provide high surface-to-volume ratio with excellent biocompatibility using appropriate ligands.30 Fourth, these properties of AuNPs can be readily tuned varying their size, shape and the surrounding chemical environment. For example, the binding event between recognition element and the analyte can alter physicochemical properties of transducer AuNPs, such as plasmon resonance absorption, conductivity, redox behavior, etc. that in turn can generate a detectable response signal. Finally, AuNPs offer a suitable platform for multi-functionalization with a wide range of organic or biological ligands for the selective binding and detection of small molecules and biological targets.30–32,36 Each of these attributes of AuNPs has allowed researchers to develop novel sensing strategies with improved sensitivity, stability and selectivity. In the last decade of research, the advent of AuNP as a sensory element provided us a broad spectrum of innovative approaches for the detection of metal ions, small molecules, proteins, nucleic acids, malignant cells, etc. in a rapid and efficient manner.37



Figure 1

Physical properties of AuNPs and schematic illustration of an AuNP-based detection system.



In this current review, we have highlighted the several synthetic routes and properties of AuNPs that make them excellent probes for different sensing strategies. Furthermore, we will discuss various sensing strategies and major advances in the last two decades of research utilizing AuNPs in the detection of variety of target analytes including metal ions, organic molecules, proteins, nucleic acids, and microorganisms.

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Gold nanoparticles in chemical and biological sensing.

Attempts to create hierarchically structured, uniaxially oriented nanocomposites comprising cellulose nanowhiskers (CNWs), which promise anisotropic mechanical properties, are exceedingly rare. We report here the fabrication of uniaxially-oriented arrays of microfibers based on poly(ethylene oxide) (PEO) and CNWs by electrospinning. Compared with the neat PEO fibers, the incorporation of CNWs within the fibers increased the storage modulus (E') of arrays along the fiber axis of the PEO/CNW nanocomposite fibers. Successful incorporation of the CNWs within each of the as-spun PEO/CNW nanocomposite fibers in the direction parallel to the fiber axis was verified by both scanning and transmission electron microscopy.

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Biologically inspired hierarchical design of nanocomposites based on poly(ethylene oxide) and cellulose nanofibers.

Thermoplastic segmented polyurethanes (PUs) can exhibit shape memory behavior, if they feature multiple kinds of physical cross-links that can be dissociated at different temperatures. This is the case if the hydrogen-bonded hard phase is joined with soft segments that can partially crystallize, so that the melting transition acts as the memory switch. For applications in the biomedical field, it is important that the fixation and recovery temperatures can be minutely controlled. We show here that this tailoring can be easily achieved by formulating a commercial PU featuring poly(1,4-butylene adipate) (PBA) as a crystallizable segment (PBA-PU) with either PBA or poly(e-caprolactone) (PCL) of moderate molecular weight. We show that the nature of the end groups and the processing conditions dictate if there is any reaction between the components or if the product is merely a blend. Interestingly, in either case, the addition of PBA or PCL causes nucleation and thereby a noteworthy increase of the crystallization temperature of the switching element from below to above ambient temperature, so that excellent shape fixity (∼98%) can be achieved at 37 °C. The melting temperature is maintained above 50 °C and significant increases in strength and modulus are achieved. The new materials platform is well suited for applications in which a shape is to be fixed at physiological temperature.

Tailoring the Shape Memory Properties of Segmented Poly(ester urethanes) via Blending.

Molecules comprising aliphatic azo moieties are widely used as radical polymerization initiators, but only a few studies have explored their usefulness as stimuli-responsive motifs in macromolecular constructs. The controlled degradation of azo-containing polymers has indeed remained largely unexplored. Here we present the syntheses of linear azo-containing polyamides and polyurethanes and report on their thermally and optically induced responses in solution and the solid state. We show that the stimuli-induced degradation behavior depends strongly on the nature of the polymer backbone, the state of matter, and in solution, on the nature of the solvent. The stimuli-responsive solid-state properties of the azo-containing materials may be particularly useful. In the case of the polyurethanes studied here, temperature- or light-induced cleavage of the azo motifs led to a controllable decrease in the molecular weight, which, in turn, caused a reduction of the elongation at break, modulus, and strength. The co...

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Azo-Containing Polymers with Degradation On-Demand Feature

Cellulose nanocrystals (CNCs) are bio-based rod-like nanoparticles with a quickly expanding market. Despite the fact that a variety of production routes and starting cellulose sources are employed, all industrially produced CNCs consist of cellulose I (CNC-I), the native crystalline allomorph of cellulose. Here a comparative study of the physico-chemical properties and liquid crystalline behavior of CNCs produced from cellulose II (CNC-II) and typical CNC-I is reported. CNC-I and CNC-II are isolated by sulfuric acid hydrolysis of cotton and mercerized cotton, respectively. The two allomorphs display similar surface charge densities and ζ-potentials and both have a right-handed twist, but CNC-II have a slightly smaller average length and aspect ratio, and are less hygroscopic. Interestingly, the self-assembly behavior of CNC-I and CNC-II in water is different. Whilst CNC-I forms a chiral nematic phase, CNC-II initially phase separates into an upper isotropic and a lower nematic liquid crystalline phase, before a slow reorganization into a large-pitch chiral nematic texture occurs. This is potentially caused by a combination of factors, including the inferred faster rotational diffusion of CNC-II and the different crystal structures of CNC-I and CNC-II, which are responsible for the presence and absence of a giant dipole moment, respectively.

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Patience is a virtue: self-assembly and physico-chemical properties of cellulose nanocrystal allomorphs.

/pdf/glassy-poly-methacrylate-terpolymers-with-covalently-5f6xux42mz.pdf

Christoph Weder

Papers

Biologically inspired hierarchical design of nanocomposites based on poly(ethylene oxide) and cellulose nanofibers.

Tailoring the Shape Memory Properties of Segmented Poly(ester urethanes) via Blending.

Azo-Containing Polymers with Degradation On-Demand Feature

Patience is a virtue: self-assembly and physico-chemical properties of cellulose nanocrystal allomorphs.

Glassy poly(methacrylate) terpolymers with covalently attached emitters and sensitizers for low‐power light upconversion