Graphene nanoplatelets and other 2D-materials as protective means against the fading of coloured inks, dyes and paints.

The present work demonstrates the ability of graphene nanoplatelets (GNPs) and other two-dimensional materials (2DMs) like tungsten disulfide (WS2), molybdenum disulfide (MoS2) and hexagonal boron nitride (hBN) to act as protective barriers against the fading of architectural paints and also inks/paints used in art. The results present a new approach for improving the lightfastness of colours of artworks and painted indoor/outdoor wall surfaces taking advantage of the remarkable properties of 2DMs. As shown herein, commercial inks and architectural paints of different colours doped with graphene nanoplatelets (GNPs), graphene oxide (GO), reduced graphene oxide (rGO) and other 2DMs, exhibit a superior resistance to fading under ultraviolet radiation or even under exposure to visible light. A spectroscopic study on these inks and dyes reveals that the peaks which are characteristic of the colour pigments are less affected from aging/fading when the GNPs and the other 2DMs are present. The protection mechanism for the GNPs and the other 2DMs differs. For GNPs, mainly their high surface area which leads to free radicals scavenging (especially hydroxyl radicals), and secondarily their UV absorption, are responsible for their protection effects, while for GO, a transition to rGO structures and consequently to 'smart' paints can be observed after the performed aging routes. In this way, the paint gets improved by time preventing or slowing its own fading and decolorization. For the other 2DMs, the transition-metal dichalcogenides performed better than hBN, even though they all absorb in the UV region. This can be ascribed to the facts that the formers also absorb in the visible, while hBN does not, while most importantly, they can trap reactive oxygen species (ROS) and corrosive gases in their structure as opposed to hBN. By conducting colorimetric measurements, we have discovered that the lifetime of the as-developed 2DM-doped inks and paints can be extended by up to ∼40%.

Preventing colour fading in artworks with graphene veils.

Modern and contemporary art materials are generally prone to irreversible colour changes upon exposure to light and oxidizing agents. Graphene can be produced in thin large sheets, blocks ultraviolet light, and is impermeable to oxygen, moisture and corrosive agents; therefore, it has the potential to be used as a transparent layer for the protection of art objects in museums, during storage and transportation. Here we show that a single-layer or multilayer graphene veil, produced by chemical vapour deposition, can be deposited over artworks to protect them efficiently against colour fading, with a protection factor of up to 70%. We also show that this process is reversible since the graphene protective layer can be removed using a soft rubber eraser without causing any damage to the artwork. We have also explored a complementary contactless graphene-based route for colour protection that is based on the deposition of graphene on picture framing glass for use when the direct application of graphene is not feasible due to surface roughness or artwork fragility. Overall, the present results are a proof of concept of the potential use of graphene as an effective and removable protective advanced material to prevent colour fading in artworks.

Stress transfer at the nanoscale on graphene ribbons of regular geometry.

The knowledge of the mechanism of stress transfer from a polymer matrix to a 2-dimensional nano-inclusion such as a graphene flake is of paramount importance for the design and the production of effective nanocomposites. For efficient reinforcement the shape of the inclusion must be accurately controlled since the axial stress transfer from matrix to the inclusion is affected by the axial-shear coupling observed upon loading of a flake of irregular geometry. Herein, we study true axial phenomena on regular- exfoliated-graphene micro-ribbons which are perfectly aligned to the loading direction. We exploit the strain sensitivity of vibrational wave numbers in order to map point-by-point the strain built up along the length of graphene. By considering the balance of shear-to-axial forces, we identify the shear stress at the interface and develop a universal inverse-length parameter that governs the stress transfer process at the nanoscale. An important parameter that has come out of this approach is the prediction and measurement of the transfer length that is required for efficient stress in these systems.

Wrinkling formation in simply-supported graphenes under tension and compression loadings.

Wrinkles in supported graphenes can be formed either by uniaxial compression or uniaxial tension beyond a certain critical load depending on the mode of loading. In the first case, the wrinkling direction is normal to the compression axis whereas in tension, wrinkles of the same pattern are formed parallel to the loading direction due to Poisson's (lateral) contraction. Herein we show by direct AFM observations that in simply-supported graphenes such instabilities appear as periodic wrinkles over existing stochastic undulations caused by the underlying-substrate-roughness. The critical strain for the generation of these wrinkles in both tension and compression is less than 1% which particularly for the former is far lower than the predicted tensile strain to fracture of suspended graphene estimated at ∼30%. Based on these findings, a constitutive model that provides the critical tensile strain for induced buckling in the lateral direction is proposed that depends only on the graphene-support interaction and not on the nature of the substrate. Understanding the wrinkling failure of graphenes under strain is of paramount importance as it leads to new threshold limits beyond which the physical-mechanical properties of graphene are impaired.

Altered intestinal permeability to mannitol in diabetes mellitus type I.

BACKGROUND: Intestinal permeability has seldom been investigated in diabetes mellitus, even though patients frequently report gastrointestinal symptoms, and it has recently been shown that the prevalence of celiac disease associated with diabetes mellitus is higher than expected. METHODS: Intestinal permeability to cellobiose and mannitol was investigated in 31 patients affected by type I uncomplicated diabetes mellitus. Values were compared with those obtained in 32 normal subjects. RESULTS: The percentage of mannitol recovery was far higher than normal in two thirds of the investigated patients and correlated with the length of disease, even though the probes' ratio (cellobiose/mannitol) was in the normal range. CONCLUSIONS: A not previously reported increase of intestinal permeability to mannitol, clear-cut and not associated with that of the larger probe, is found in type I uncomplicated diabetes mellitus. These results may describe a primary feature of type I diabetes mellitus and the initial steps of evolution to celiac disease.

[Risk factors in calcium urolithiasis]. / Fattori di rischio nell'urolitiasi calcica.

The aim of the study has been to evaluate, retrospectively, if the association of urolithiasis different pathogenetic factors increases stone formation and recurrences. The study included 41 children, 20 males and 21 females, aged 3-15 years, divided into three groups: patients with hypercalciuric or normocalciuric urolithiasis and isolated hypercalciuria. In all of them renal function, blood and urinary pH, serum and urinary electrolytic levels, citraturia (dosed with anenzymatic quantitative method), oxalaturia (enzymatic colorimetric method), urinary glycosaminoglycans (dosed by means of cetylpyridinum chloride precipitation and quantitative analysis) have been considered. Statistical analysis was done using Student's "t"-test, with p < 0.05. In all children with hypercalciuric urolithiasis who during the follow-up presented a decreased citraturia, the number of recurrences increased and was above two. The children who during the follow-up remained hypercalciuric without urolithiasis, in spite of the high familiarity, presented an increased citraturia. In conclusion the association between hypercalciuria and low citraturia increases the risk of stone formation and recurrences in children with calcic urolithiasis.

Promoters and inhibitors of calcium urolithiasis in children.

We have evaluated the urinary excretion of promoting (calcium, phosphorus, uric acid, oxalate) and inhibiting (citrate, magnesium, glycosaminoglycans) factors of crystallization in subjects with idiopathic hypercalciuria and calcium urolithiasis and in a control group. The examined children had a free diet and were drug free for the last 2 weeks. They were not affected by malabsorption, D-RTA, urinary tract infection, or urinary tract malformation (factors interfering with urinary excretion of citrate and oxalate). In the patients with calcium urolithiasis, the daily urinary excretion of oxalate was significantly higher (p less than 0.01), and the urinary excretion of citrate was significantly lower (p less than 0.001) than in the subjects with idiopathic hypercalciuria and in the control group. Among the subjects with idiopathic hypercalciuria, those aged 4-9 years had a significantly reduced, though in the normal range, urinary excretion of citrate as compared with those aged 10-15 years (362 +/- 189 and 503 +/- 198 mg/g creatinine/24 h, respectively; p less than 0.01). Our data show that hypocitruria may play an important role in the pathogenesis of urolithiasis in children with idiopathic hypercalciuria. In these cases, the urinary citrate excretion was not inversely related to age, as has been suggested by other authors.