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Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV–visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch–sepiolite composite materials.

Ladder-like polysilsesquioxanes (LPSQs) are characterized by a double-stranded siloxane backbone, whose chemical and structural properties depend on both the synthesis parameters and the nature of the organic side-chains. In the case of ladder-like (methacryloxypropyl) polysilsesquioxanes (LPMASQ), polymer matrices can be produced by exploiting the presence of photocurable methacrylate groups. Consequently, they can be used to prepare functional nanocomposites (NCs), either by blending with organic polymers such as polybutadiene or exploiting the inorganic fillers’ dispersion. Since the properties of LPMASQ-based NCs are strongly related to their structure, the structural changes of polymerized LPMASQ were investigated upon addition of low loadings of TiO2 nanoparticles (up to 3 wt%) by solid state nuclear magnetic resonance and X-ray diffraction. The filler addition leads to the reduction of the polymerization capacity of the LPMASQ organic side-chains. Moreover, a different organization of ladder chains has been highlighted, ascribable to the increase in fully condensed linear ladder units at the expenses of folded chains and defective structures. The methodological approach here adopted can be extended to other composite systems and may help to describe the properties at the filler-matrix interface, offering valuable hints for a better design of these materials.

Photocatalytic chemical transformations in the presence of irradiated TiO2 are generally considered in terms of interfacial electron transfer. However, more elusive energy-transfer-driven reactions have been also hypothesized to occur, mainly on the basis of the indirect evidence of detected reaction products whose existence could not be justified simply by electron transfer. Unlike in homogeneous and colloidal systems, where energy transfer mechanisms have been investigated deeply for several organic syntheses, understanding of similar processes in heterogeneous systems is at only a nascent level. However, this gap of knowledge can be filled by considering the important achievements of synthetic heterogeneous photocatalysis, which bring the field closer to industrial exploitation. The present manuscript summarizes the main findings of previous literature reports and, also on the basis of some novel experimental evidences, tentatively proposes that the energy transfer in TiO2 photocatalysis could possess a Förster-like nature.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.

Background: Bladder cancer (BCa) emits specific volatile organic compounds (VOCs) in the urine headspace that can be detected by an electronic nose. The diagnostic performance of an electronic nose in detecting BCa was investigated in a pilot study. Methods: A prospective, single-center, controlled, non-randomized, phase 2 study was carried out on 198 consecutive subjects (102 with proven BCa, 96 controls). Urine samples were evaluated with an electronic nose provided with 32 volatile gas analyzer sensors. The tests were repeated at least two times per sample. Accuracy, sensitivity, specificity, and variability were evaluated using mainly the non-parametric combination method, permutation tests, and discriminant analysis classification. Results: Statistically significant differences between BCa patients and controls were reported by 28 (87.5%) of the 32 sensors. The overall discriminatory power, sensitivity, and specificity were 78.8%, 74.1%, and 76%, respectively; 13/96 (13.5%) controls and 29/102 (28.4%) BCa patients were misclassified as false positive and false negative, respectively. Where the most efficient sensors were selected, the sensitivity and specificity increased up to 91.1% (72.5–100) and 89.1% (81–95.8), respectively. None of the tumor characteristics represented independent predictors of device responsiveness. Conclusions: The electronic nose might represent a potentially reliable, quick, accurate, and cost-effective tool for non-invasive BCa diagnosis.

The construction is described of the third intake tunnel at Lake Mead, Nevada, USA. The reservoir was formed by the Hoover Dam, which extends across the Colorado River between Nevada and Arizona. A hybrid shielded tunnel boring machine was employed with the capability of excavating in either closed or open mode depending on the hydrogeological conditions of the rock mass. The machine is designed to withstand a maximum hydraulic head pressure of 17 bar and is equipped with drill rigs to perform geological investigations or pre-excavation ground treatment. After about 280 m of excavation along the first curve of the alignment the tunnel boring machine penetration values became lower and lower and the machine stopped advancing. The decision was made to lower the face pressure to zero bar to inspect the cutterhead. It was important to estimate in advance the quantity of water inflow, and a procedure was developed in which the tunnel boring machine was used as a large-scale constant-head permeameter. Three permeability tests were conducted but all were aborted at 10 bar, and it was decided to drill and grout the ground ahead of the tunnel boring machine to reduce the permeability, increase the overall stability and allow personnel to enter the cutterhead. An inspection of the cutterhead was found to be possible using a camera installed on a steel pipe and indicated insignificant wear of the cutter. Subsequent camera inspections showed wear of the cutter and a series of pre-excavation grouting campaigns were carried out to allow for maintenance., The construction is described of the third intake tunnel at Lake Mead, Nevada, USA. The reservoir was formed by the Hoover Dam, which extends across the Colorado River between Nevada and Arizona. A hybrid shielded tunnel boring machine was employed with the capability of excavating in either closed or open mode depending on the hydrogeological conditions of the rock mass. The machine is designed to withstand a maximum hydraulic head pressure of 17 bar and is equipped with drill rigs to perform geological investigations or pre-excavation ground treatment. After about 280 m of excavation along the first curve of the alignment the tunnel boring machine penetration values became lower and lower and the machine stopped advancing. The decision was made to lower the face pressure to zero bar to inspect the cutterhead. It was important to estimate in advance the quantity of water inflow, and a procedure was developed in which the tunnel boring machine was used as a large-scale constant-head permeameter. Three permeability tests were conducted but all were aborted at 10 bar, and it was decided to drill and grout the ground ahead of the tunnel boring machine to reduce the permeability, increase the overall stability and allow personnel to enter the cutterhead. An inspection of the cutterhead was found to be possible using a camera installed on a steel pipe and indicated insignificant wear of the cutter. Subsequent camera inspections showed wear of the cutter and a series of pre-excavation grouting campaigns were carried out to allow for maintenance.