Mechanical reinforcement from two-dimensional nanofillers: model, bulk and hybrid polymer nanocomposites.

Thanks to their intrinsic properties, multifunctionality and unique geometrical features, two-dimensional nanomaterials have been used widely as reinforcements in polymer nanocomposites. The effective mechanical reinforcement of polymers is, however, a multifaceted problem as it depends not only on the intrinsic properties of the fillers and the matrix, but also upon a number of other important parameters. These parameters include the processing method, the interfacial properties, the aspect ratio, defects, orientation, agglomeration and volume fraction of the fillers. In this review, we summarize recent advances in the mechanical reinforcement of polymer nanocomposites from two-dimensional nanofillers with an emphasis on the mechanisms of reinforcement. Model, bulk and hybrid polymer nanocomposites are reviewed comprehensively. The use of Raman and photoluminescence spectroscopies is examined in light of the distinctive information they can yield upon stress transfer at interfaces. It is shown that the very diverse family of 2D nanofillers includes a number of materials that can attribute distrinctive features to a polymeric matrix, and we focus on the mechanical properties of both graphene and some of the most important 2D materials beyond graphene, including boron nitride, molybdenum disulphide, other transition metal dichalcogenides, MXenes and black phosphorous. In the first part of the review we evaluate the mechanical properties of 2D nanoplatelets in "model" nanocomposites. Next we examine how the performance of these materials can be optimised in bulk nanocomposites. Finally, combinations of these 2D nanofillers with other 2D nanomaterials or with nanofillers of other dimensions are assessed thoroughly, as such combinations can lead to additive or even synergistic mechanical effects. Existing unsolved problems and future perspectives are discussed.

Quantifying intuition: Bayesian approach to figures of merit in EXAFS analysis of magic size clusters.

Analysis of the extended X-ray absorption fine structure (EXAFS) can yield local structural information in magic size clusters even when other structural methods (such as X-ray diffraction) fail, but typically requires an initial guess - an atomistic model. Model comparison is thus one of the most crucial steps in establishing atomic structure of nanoscale systems and relies critically on the corresponding figures of merit (delivered by the data analysis) to make a decision on the most suitable model of atomic arrangements. However, none of the currently used statistical figures of merit take into account the significant factor of parameter correlations. Here we show that ignoring such correlations may result in a selection of an incorrect structural model. We then report on a new metric based on Bayes theorem that addresses this problem. We show that our new metric is superior to the currently used in EXAFS analysis as it reliably yields correct structural models even in cases when other statistical criteria may fail. We then demonstrate the utility of the new figure of merit in comparison of structural models for CdS magic-size clusters using EXAFS data.

Utilising buckling modes for the determination of the anisotropic mechanical properties of As2S3 nanosheets.

The mechanical properties and interfacial behaviour of two-dimensional (2D) materials are crucial for their use in a number of technological applications. In this paper, two buckling modes, wrinkling and buckling delamination, were used to characterize the mechanics of As2S3 nanosheets. The plane-strain moduli of As2S3 nanosheets along the armchair (AC) and zigzag (ZZ) directions were determined via periodic wrinkles to be 16.7 ± 0.5 GPa and 51.5 ± 1.9 GPa, respectively. This is one of the largest reported anisotropies of in-plane mechanical properties among 2D materials. Using the delaminated buckles, the adhesion energy of few-layer As2S3 nanosheets on silicon and polymer (polymethyl methacrylate and polydimethylsiloxane) substrates was determined to be 0.110 ± 0.006 and 0.022 ± 0.002 J m-2, respectively. A buckling mode map for As2S3 nanosheets on different substrates is presented.

Nanomechanics of graphene oxide-bacteriophage based self-assembled porous composites.

Graphene oxide, integrated with the filamentous bacteriophage M13, forms a 3D large-scale multifunctional porous structure by self-assembly, with considerable potential for applications. We performed Raman spectroscopy under pressure on this porous composite to understand its fundamental mechanics. The results show that at low applied pressure, the [Formula: see text] bonds of graphene oxide stiffen very little with increasing pressure, suggesting a complicated behaviour of water intercalated between the graphene layers. The key message of this paper is that water in a confined space can have a significant impact on the nanostructure that hosts it. We introduced carbon nanotubes during the self-assembly of graphene oxide and M13, and a similar porous macro-structure was observed. However, in the presence of carbon nanotubes, pressure is transmitted to the [Formula: see text] bonds of graphene oxide straightforwardly as in graphite. The electrical conductivity of the composite containing carbon nanotubes is improved by about 30 times at a bias voltage of 10 V. This observation suggests that the porous structure has potential in applications where good electrical conductivity is desired, such as sensors and batteries.

Explanation of the Colour Change in Alexandrites.

Alexandrites are remarkable and rare gemstones. They display an extraordinary colour change according to the ambient lighting, from emerald green in daylight to ruby red in incandescent light from tungsten lamps or candles. While this colour change has been correctly attributed to chromium impurities and their absorption band in the yellow region of the visible light spectrum, no adequate explanation of the mechanism has been given. Here, the alexandrite effect is fully explained by considering the von Kries model of the human colour constancy mechanism. This implies that our colour constancy mechanism is real (objective) and primarily attuned to correct for the colour temperature of black-body illuminants.

Enzyme sequence and its relationship to hyperbaric stability of artificial and natural fish lactate dehydrogenases.

The cDNAs of lactate dehydrogenase b (LDH-b) from both deep-sea and shallow living fish species, Corphaenoides armatus and Gadus morhua respectively, have been isolated, sequenced and their encoded products overproduced as recombinant enzymes in E. coli. The proteins were characterised in terms of their kinetic and physical properties and their ability to withstand high pressures. Although the two proteins are very similar in terms of their primary structure, only 21 differences at the amino acid level exist between them, the enzyme from the deep-sea species has a significantly increased tolerance to pressure and a higher thermostability. It was possible to investigate whether the changes in the N-terminal or C-terminal regions played a greater role in barophilic adaptation by the construction of two chimeric enzymes by use of a common restriction site within the cDNAs. One of these hybrids was found to have even greater pressure stability than the recombinant enzyme from the deep-living fish species. It was possible to conclude that the major adaptive changes to pressure tolerance must be located in the N-terminal region of the protein. The types of changes that are found and their spatial location within the protein structure are discussed. An analysis of the kinetic parameters of the enzymes suggests that there is clearly a trade off between K(m) and k(cat) values, which likely reflects the necessity of the deep-sea enzyme to operate at low temperatures.