Surface characterization of nanomaterials and nanoparticles: Important needs and challenging opportunities.

This review examines characterization challenges inherently associated with understanding nanomaterials and the roles surface and interface characterization methods can play in meeting some of the challenges. In parts of the research community, there is growing recognition that studies and published reports on the properties and behaviors of nanomaterials often have reported inadequate or incomplete characterization. As a consequence, the true value of the data in these reports is, at best, uncertain. With the increasing importance of nanomaterials in fundamental research and technological applications, it is desirable that researchers from the wide variety of disciplines involved recognize the nature of these often unexpected challenges associated with reproducible synthesis and characterization of nanomaterials, including the difficulties of maintaining desired materials properties during handling and processing due to their dynamic nature. It is equally valuable for researchers to understand how characterization approaches (surface and otherwise) can help to minimize synthesis surprises and to determine how (and how quickly) materials and properties change in different environments. Appropriate application of traditional surface sensitive analysis methods (including x-ray photoelectron and Auger electron spectroscopies, scanning probe microscopy, and secondary ion mass spectroscopy) can provide information that helps address several of the analysis needs. In many circumstances, extensions of traditional data analysis can provide considerably more information than normally obtained from the data collected. Less common or evolving methods with surface selectivity (e.g., some variations of nuclear magnetic resonance, sum frequency generation, and low and medium energy ion scattering) can provide information about surfaces or interfaces in working environments (operando or in situ) or information not provided by more traditional methods. Although these methods may require instrumentation or expertise not generally available, they can be particularly useful in addressing specific questions, and examples of their use in nanomaterial research are presented.

X-ray and NMR crystallography in an enzyme active site: the indoline quinonoid intermediate in tryptophan synthase.

Chemical-level details such as protonation and hybridization state are critical for understanding enzyme mechanism and function. Even at high resolution, these details are difficult to determine by X-ray crystallography alone. The chemical shift in NMR spectroscopy, however, is an extremely sensitive probe of the chemical environment, making solid-state NMR spectroscopy and X-ray crystallography a powerful combination for defining chemically detailed three-dimensional structures. Here we adopted this combined approach to determine the chemically rich crystal structure of the indoline quinonoid intermediate in the pyridoxal-5'-phosphate-dependent enzyme tryptophan synthase under conditions of active catalysis. Models of the active site were developed using a synergistic approach in which the structure of this reactive substrate analogue was optimized using ab initio computational chemistry in the presence of side-chain residues fixed at their crystallographically determined coordinates. Various models of charge and protonation state for the substrate and nearby catalytic residues could be uniquely distinguished by their calculated effects on the chemical shifts measured at specifically (13)C- and (15)N-labeled positions on the substrate. Our model suggests the importance of an equilibrium between tautomeric forms of the substrate, with the protonation state of the major isomer directing the next catalytic step.

Cytokines in Febrile Diseases.

The human body has a perfect thermoregulatory system to meet the needs of normal life activities. The central regulation of body temperature is mainly explained by the theory of "setting point (setpoint, SP)". Fever is a positive but nonspecific response of the body to infections and other pyrogens, which causes immune cells to release cytokines, leading to a brain protein-mediated rise in body temperature. Cytokines can be roughly divided into 2 categories: proinflammatory cytokines and anti-inflammatory cytokines. IL-1, TNF-α, and IL-6 are proinflammatory cytokines, whereas IL-4 and IL-10 are anti-inflammatory cytokines. IL-2 is a cytokine that can both activate and inhibit immunity. IL-8 is a neutrophil chemotactic factor, and IFN is a cytokine that plays a key role in the proper induction and maintenance of innate and acquired immunity. This article reviews the pathophysiological characteristics of fever and the cytokines related to fever (IL-2, 4, 6, 8, 10, IFN, TNF, etc.).

Graphene-Based Composite Membrane Prepared from Solid Carbon Source Catalyzed by Ni Nanoparticles.

Emerging as a light, flexible and highly thermally conductive material, graphene-based membranes have attracted extensive attention in thermal management field. However, the preparation of high-quality graphene-based membranes usually involves complex processes and thermal annealing at ultra-high temperature, which limits their large-scale application in thermal management field. In our study, reduced graphene oxide-Ni-hydroxypropyl methyl cellulose (RGO-Ni-HPMC) composite membrane was prepared from catalytic pyrolysis of hydroxypropyl methyl cellulose (HPMC) with Ni nanoparticles to generate multilayer graphene and form phonon transport channels between adjacent graphene layers. Further, our study shows that the RGO-Ni-HPMC composite membrane has a good heat dissipation effect at the hot spots at high temperature. The average temperature of hot spots is reduced by 11.5 °C. It is expected to solve the heat dissipation problem of high-power electronic equipment.

Carbonized Dehydroascorbic Acid: Aim for Targeted Repair of Graphene Defects and Bridge Connection of Graphene Sheets with Small Size.

The thermal dissipation issue of electronics devices becomes increasingly prominent as they evolve to smaller sizes and more complicated structures. Therefore, the development of materials with excellent heat conduction properties and light weight turns out to be an urgent demand to solve the heat transfer problem of electronics devices with high performance. For this purpose, we put forward an innovative strategy that carbonized dehydroascorbic acid (CDA) be applied to graphene layers for the targeted repair of defects among them and bridge connection of the layers to produce graphene heat conduction materials with excellent properties. Firstly, hydrogen bonds formed from dehydroascorbic acid (DHAA, products of the oxidation of vitamin C) and each of ketone, carboxyl, and oxhydryl groups on graphene layers were absorbed at targeted locations where oxidation graphene produces defects, then targeted repair was conducted for those defects to be filled and for the graphene layers of a small size to grow into large sheet materials with improved continuity by CDA generated in thermally pressing reduction reaction at 800 °C. In our investigation, the planar thermal conductivity of rGO/VC membrane reached 1031.9 ± 10.2 Wm-1K-1, while the added mass content of vitamin C (VC) was 15%. Being a reference, the planar thermal conductivity of primitive graphene membrane was only 610.7 ± 11.7 Wm-1K-1.

Influence of peripheral groups on the physical and chemical behavior of cinchona alkaloids.

While cinchona alkaloids play a key role in many applications, from medicine to catalysis, there is not yet a complete understanding of the reasons for their unique chemical behavior. Past studies have identified the chiral pocket formed by the two main constituting moieties of the cinchona, the quinoline and quinuclidine rings, as the main factor determining their physiological and enatioselective reactivity. That explanation, however, does not account for the differences observed among similar cinchona alkaloids. Here we show that subtle changes in the position of the substituent groups outside the central chiral pocket explain the disparities observed in basic physicochemical properties between pairs of near-enantiomers (quinine vs quinidine, cinchonidine vs cinchonine) such as crystal structure, solubility, and adsorption equilibrium. Both energetic and entropic factors need to be considered to fully account for the trends observed.

Improved Performance of Graphene in Heat Dissipation when Combined with an Orientated Magnetic Carbon Fiber Skeleton under Low-Temperature Thermal Annealing.

The high thermal conductivity and stability, outstanding mechanical properties, and low weight make graphene suitable for many applications in the realm of thermal management, especially in high integration systems. Herein, we report a high-performance, low-temperature reduced graphene oxide/magnetic carbon fiber composite film. Magnetic carbon fibers were prepared using a co-precipitation method, and the graphene oxide solution was prepared using an improved Hummers' method. The magnetic carbon fibers were orientated by magnetite and immersed in the graphene oxide solution during filtration, followed by annealing at 800 °C. The composite film exhibited improved thermal conductivity (over 600 W/m·K) and mechanical properties (tensile strength of 37.1 MPa and bending cycle of up to 8000). The experimental results illustrate that the graphene in the composite membrane provides heat transfer channels to promote in-plane thermal conductivity, while the magnetic carbon fiber acts as a scaffold to reinforce the mechanical properties and improve the quality of the graphene. Due to the synergistic effect of the graphene and magnetic carbon, this composite has wide potential applications in heat dissipation.

J-based 2D homonuclear and heteronuclear correlation in solid-state proteins.

Scalar-based two-dimensional heteronuclear experiments are reported for NCO and NCA chemical shift correlation in the solid state. In conjunction with homonuclear CACO correlation, these experiments form a useful set for tracing connectivities and assigning backbone resonances in solid-state proteins. The applicability of this approach is demonstrated on two proteins, the ß 1 immunoglobulin binding domain of protein G at 9.4 T and reassembled thioredoxin at 14.1 T, using different decoupling conditions and MAS frequencies. These constant-time J-based correlation experiments exhibit increased resolution in the indirect dimension owing to homonuclear and heteronuclear decoupling, and because the indirect evolution and transfer periods are combined into a single constant time interval, this increased resolution is not obtained at the cost of sensitivity. These experiments are also shown to be compatible with in-phase anti-phase (IPAP) selection, giving increased resolution in the directly detected dimension.

J-Based 3D sidechain correlation in solid-state proteins.

Scalar-based three-dimensional homonuclear correlation experiments are reported for (13)C sidechain correlation in solid-state proteins. These experiments are based on a sensitive constant-time format, in which homonuclear scalar couplings are utilized for polarization transfer, but decoupled during chemical shift evolution, to yield highly resolved indirect dimensions and band selectivity as desired. The methods therefore yield spectra of high quality that give unique sets of sidechain correlations for small proteins even at 9.4 Tesla (400 MHz (1)H frequency). We demonstrate versions of the pulse sequence that enable correlation from the sidechain to the backbone carbonyl as well as purely sidechain correlation sets; together these two data sets provide the majority of (13)C-(13)C correlations for assignment. The polarization transfer efficiency is approximately 30% over two bonds. In the protein GB1 (56 residues), we find essentially all cross peaks uniquely resolved. We find similar efficiency of transfer (approximately 30%) in the 140 kDa tryptophan synthase (TS), since the relaxation rates of immobilized solid proteins are not sensitive to global molecular tumbling, as long as the correlation time is much longer than the magic-angle spinning rotor period. In 3D data sets of TS at 400 MHz, some peaks are resolved and, in combination with higher field data sets, we anticipate that assignments will be possible; in this vein, we demonstrate 2D (13)C-(13)C spectra of TS at 900 MHz that are well resolved. These results together provide optimism about the prospects for assigning the spectra of such large enzymes in the solid state.