Mapping Understory Vegetation Density in Mediterranean Forests: Insights from Airborne and Terrestrial Laser Scanning Integration.

The understory is an essential ecological and structural component of forest ecosystems. The lack of efficient, accurate, and objective methods for evaluating and quantifying the spatial spread of understory characteristics over large areas is a challenge for forest planning and management, with specific regard to biodiversity and habitat governance. In this study, we used terrestrial and airborne laser scanning (TLS and ALS) data to characterize understory in a European beech and black pine forest in Italy. First, we linked understory structural features derived from traditional field measurements with TLS metrics, then, we related such metrics to the ones derived from ALS. Results indicate that (i) the upper understory density (5-10 m above ground) is significantly associated with two ALS metrics, specifically the mean height of points belonging to the lower third of the ALS point cloud within the voxel (HM1/3) and the corresponding standard deviation (SD1/3), while (ii) for the lower understory layer (2-5 m above ground), the most related metric is HM1/3 alone. As an example application, we have produced a map of forest understory for each layer, extending over the entire study region covered by ALS data, based on the developed spatial prediction models. With this study, we also demonstrated the power of hand-held mobile-TLS as a fast and high-resolution tool for measuring forest structural attributes and obtaining relevant ecological data.

Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles.

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.

Photo- and radio-luminescence of porphyrin functionalized ZnO/SiO2 nanoparticles.

The development of hybrid nanoscintillators is hunted for the implementation of modern detection technologies, like in high energy physics, homeland security, radioactive gas sensing, and medical imaging, as well as of the established therapies in radiation oncology, such as in X-ray activated photodynamic therapy. Engineering of the physico-chemical properties of nanoparticles (NPs) enables the manufacture of hybrids in which the conjugation of inorganic/organic components leads to increased multifunctionality and performance. However, the optimization of the properties of nanoparticles in combination with the use of ionizing radiation is not trivial: a complete knowledge on the structure, composition, physico-chemical features, and scintillation property relationships in hybrid nanomaterials is pivotal for any applications exploiting X-rays. In this paper, the design of hybrid nanoscintillators based on ZnO grown onto porous SiO2 substrates (ZnO/SiO2) has been performed in the view to create nanosystems potentially suitable in X-ray activated photodynamic therapy. Indeed, cytotoxic porphyrin dyes with increasing concentrations have been anchored on ZnO/SiO2 nanoparticles through amino-silane moieties. Chemical and structural analyses correlated with photoluminescence reveal that radiative energy transfer between ZnO and porphyrins is the principal mechanism prompting the excitation of photosensitizers. The use of soft X-ray excitation results in a further sensitization of the porphyrin emission, due to augmented energy deposition promoted by ZnO in the surroundings of the chemically bound porphyrin. This finding unveils the cruciality of the design of hybrid nanoparticles in ruling the efficacy of the interaction between ionizing radiation and inorganic/organic moieties, and thus of the final nanomaterial performances towards the foreseen application.

Silica hairy nanoparticles: a promising material for self-assembling processes.

"Hairy" nanoparticles (HNPs), i.e. inorganic NPs functionalized with polymer chains, are promising building blocks for the synthesis of advanced nanocomposite (NC) materials having several technological applications. Recent evidence shows that HNPs self-organize in a variety of anisotropic structures, resulting in an improvement of the functional properties of the materials, in which are embedded. In this paper, we propose a three-step colloidal synthesis of spherical SiO2-HNPs, with controlled particle morphology and surface chemistry. In detail, the SiO2 core, synthesized by a modified Stöber method, was first functionalized with a short-chain amino-silane, which acts as an anchor, and then covered by maleated polybutadiene (PB), a rubbery polymer having low glass transition temperature, rarely considered until now. An extensive investigation by a multi-technique analysis demonstrates that the synthesis of SiO2-HNPs is simple, scalable, and potentially applicable to different kind of NPs and polymers. Morphological analysis shows the overall distribution of SiO2-HNPs with a certain degree of spatial organization, suggesting that the polymer coating induces a modification of NP-NP interactions. The role of the surface PB brushes in influencing the special arrangement of SiO2-HNPs was observed also in cis-1,4-polybutadiene (cis-PB), since the resulting NC exhibited the particle packing in "string-like" superstructures. This confirms the tendency of SiO2-HNPs to self-assemble and create alternative structures in polymer NCs, which may impart them peculiar functional properties.

Tailoring the Thermal Conductivity of Rubber Nanocomposites by Inorganic Systems: Opportunities and Challenges for Their Application in Tires Formulation.

The development of effective thermally conductive rubber nanocomposites for heat management represents a tricky point for several modern technologies, ranging from electronic devices to the tire industry. Since rubber materials generally exhibit poor thermal transfer, the addition of high loadings of different carbon-based or inorganic thermally conductive fillers is mandatory to achieve satisfactory heat dissipation performance. However, this dramatically alters the mechanical behavior of the final materials, representing a real limitation to their application. Moreover, upon fillers' incorporation into the polymer matrix, interfacial thermal resistance arises due to differences between the phonon spectra and scattering at the hybrid interface between the phases. Thus, a suitable filler functionalization is required to avoid discontinuities in the thermal transfer. In this challenging scenario, the present review aims at summarizing the most recent efforts to improve the thermal conductivity of rubber nanocomposites by exploiting, in particular, inorganic and hybrid filler systems, focusing on those that may guarantee a viable transfer of lab-scale formulations to technological applicable solutions. The intrinsic relationship among the filler's loading, structure, morphology, and interfacial features and the heat transfer in the rubber matrix will be explored in depth, with the ambition of providing some methodological tools for a more profitable design of thermally conductive rubber nanocomposites, especially those for the formulation of tires.

Survival rate and load to failure of premolars restored with inlays: An evaluation of different inlay fabrication methods.

STATEMENT OF PROBLEM: Studies that evaluate the survival rate and load to fracture of premolars restored with inlays produced using different methods are lacking. PURPOSE: The purpose of this in vitro study was to compare the survival rate and fracture load of premolars restored with inlays fabricated using different methods. MATERIAL AND METHODS: Thirty maxillary premolars were selected, embedded, and prepared to receive inlays fabricated using different methods (n=10): LaCom-digital scanning with Lava C.O.S. scanner (3M ESPE), followed by milling of composite resin block (Lava Ultimate; 3M ESPE) in a milling unit; CeCom-digital scanning with Cerec 3D Bluecam scanner (Dentsply Sirona), followed by milling of a Lava Ultimate block in Cerec (Dentsply Sirona); PresDis-impression with polyvinyl siloxane, inlay made using the lost wax technique, and IPS e.max Press (Ivoclar Vivadent AG) pressed ceramic (lithium disilicate). A dual-polymerizing resin cement system was used to lute the inlays. Inlays were mechanically cycled (2 Hz, 106 mechanical pulses, 80 N) after 24 hours, and the specimens were stored in distilled water at 37°C for 11 months. Then, a fatigue test was conducted using a 10-Hz frequency and 400-N load on the inner inclines of the cusps. The test was complete when the specimen fractured or when the specimen reached 1.5×106 cycles. The specimens that survived fatigue testing were submitted to a single-load fracture test in a universal testing machine and analyzed using a stereoscope for failure classification. Survival rates were estimated using the Kaplan-Meier method and log-rank test (Mantel-Cox). Fracture load data were analyzed using 1-way ANOVA (α=.05). RESULTS: No significant differences were detected among the groups for the survival rate (P=.87) or for the load to fracture (P=.78). Most failures were longitudinal, catastrophic fractures. CONCLUSIONS: Premolars restored with inlays fabricated using the tested methods had similar survival rates and loads to fracture.

A fully digital approach to replicate peri-implant soft tissue contours and emergence profile in the esthetic zone.

OBJECTIVE: This short communication reports on a novel digital technique designated - the "Fully Digital Technique (FDT)" - to take the impression of the peri-implant soft tissue and emergence profile with an intraoral scanner, digitally capturing both the three dimensional position of the implant platform and the coronal and gingival parts of the provisional retained restoration. MATERIALS AND METHODS: A first intraoral digital impression, which generated a standard triangulation language file (STL1), was taken using a standardized implant scanbody to detect the position of the implant. A second digital impression (STL2) with the provisional retained restoration in situ was performed in two steps: the first part of the scan captured all details of the vestibular and palatal sides of the provisional retained restoration and the adjacent teeth. The provisional retained restoration was then unscrewed, and the subgingival part of the restoration was scanned directly out of the mouth to determine its subgingival shape. STL1 and STL2 were imported into imaging software and superimposed using the "best fit" algorithm to achieve a new merged file (STL3) with the 3D implant position, the peri-implant mucosa, and emergence profile. The merged file was used to design the CAD/CAM customized abutment and to realize a stereolithographic model by 3D printing. RESULTS: The STL superimposition of digital impressions of the implant position and the provisional retained restoration constitute a novel technique to obtain a single STL file with the implant position and its peri-implant mucosal architecture. CONCLUSIONS: FDT is a rapid digital approach for achieving all information of the peri-implant soft tissue and emergence profile directly from the provisional retained restoration.

Fracture Strength of Endodontically Treated Teeth Restored with Composite Overlays with and without Glass-fiber Reinforcement.

PURPOSE: To evaluate the fracture strength and the failure mode of endodontically treated teeth restored with composite resin overlays with and without glass-fiber reinforcement. MATERIALS AND METHODS: A total of 32 extracted molars were divided into four equal groups. In the NFR-NFRC (no foundation restoration, no fiber-reinforced composite) and NFR-FRC (no foundation restoration, fiber-reinforced composite) groups, only a 5-mm-thick composite resin layer sealed the pulp chamber floors, whereas in the FR-NFRC (foundation restoration, no fiber-reinforced composite) and FR-FRC (foundation restoration, fiber-reinforced composite) groups, a 3.0-mm foundation restoration was used. NFR-NFRC and FR-NFRC groups were restored with composite resin overlays, whereas NFR-FRC and FR-FRC groups were restored with fiber-reinforced composite resin overlays. All specimens were subjected to mechanical loading in a computer-controlled masticator and then the fracture resistance was evaluated. Differences in means were compared using two-way ANOVA and Tukey's test. The level of significance was set at ɑ = 0.05. RESULTS: All specimens successfully completed the fatigue test. The least fracture-resistant group was NFR-FRC, exceeded by FR-NFRC, NFR-NFRC, and FR-FRC, in that order, with FR-FRC being the most fracture-resistant group. Statistically significant differences were detected between the pairs NFR-NFRC/FR-FRC (p = 0.001), NFR-FRC/FR-FRC (p = 0.001), and FR-NFRC/FR-FRC (p = 0.001). Eight vertical root fractures occurred in group FR-NFRC, six in group NFR-NFRC, four in group NFR-FRC, and none occurred in group FR-FRC. CONCLUSIONS: Within the limitations of this in vitro study, the incorporation of glass fibers and the presence of a foundation restoration were found to increase the fracture resistance and can favorably influence the fracture mode.

Updates on the Construction of an Eyeglass-Supported Nasal Prosthesis Using Computer-Aided Design and Rapid Prototyping Technology.

This study was undertaken to design an updated connection system for an eyeglass-supported nasal prosthesis using rapid prototyping techniques. The substructure was developed with two main endpoints in mind: the connection to the silicone and the connection to the eyeglasses. The mold design was also updated; the mold was composed of various parts, each carefully designed to allow for easy release after silicone processing and to facilitate extraction of the prosthesis without any strain. The approach used in this study enabled perfect transfer of the reciprocal position of the prosthesis with respect to the eyeglasses, from the virtual to the clinical environment. Moreover, the reduction in thickness improved the flexibility of the prosthesis and promoted adaptation to the contours of the skin, even during functional movements. The method described here is a simplified and viable alternative to standard construction techniques for nasal prostheses and offers improved esthetic and functional results when no bone is available for implant-supported prostheses.

Marginal Adaptation, Gap Width, and Fracture Strength of Teeth Restored With Different All-Ceramic Vs Metal Ceramic Crown Systems: An in Vitro Study.

This study evaluated marginal adaptation before and after thermomechanical (TCML) loading, gap width and fracture strength of all-ceramic single crowns, as compared to porcelain-fused-to-metal (PFM). Thirty extracted premolars were prepared with a round shoulder of 1.0 mm depth. Specimens were restored with zirconia-ceramic (Group 1), lithium disilicate (Group 2) and metal-ceramic single crowns (Group 3). The replica of each sample was observed with a scanning electron microscope (SEM) to evaluate the crown-cement (c-c) and tooth-cement interface (t-c). After TCML, perfect margins decreased to 91.3% (c-c) and 93.9% (t-c) in Group 1, 94.6% (c-c) and 96.0% (t-c) in Group 2 and 73.5% (c-c) and 53.1% (t-c) in Group 3. The mean fracture strengths were 654.8 ± 98.1 N for Group 1, 551.3 ± 127 N for Group 2 and 501.43 ± 110.1 N for Group 3. All-ceramic systems could substitute for metal-ceramic crowns, but chipping of veneering ceramics, especially in zirconia-based crowns, should be investigated.

Work flow for the prosthetic rehabilitation of atrophic patients with a minimal-intervention CAD/CAM approach.

The implant-supported fixed rehabilitation of patients with an atrophic edentulous crest remains a challenge if bone augmentation is not planned. A minimal intervention approach for bone regeneration is necessary to minimize the flap overextension needed to close the defect over the augmented bone. Prosthetically guided bone regeneration can determine the amount of bone augmentation necessary for definitive prosthetic fixed rehabilitation. The positions of the implants and prosthetic restoration were planned; a 0.3 mm thick titanium mesh was customized for bone augmentation by using computer-aided design and computer-aided manufacturing and rapid prototyped by laser sintering, and the definitive prosthetic rehabilitation was carried out according to the initial treatment plan. This resulted in minimal bone augmentation relative to the functional needs of the definitive prosthetic rehabilitation.

A novel non-aqueous sol-gel route for the in situ synthesis of high loaded silica-rubber nanocomposites.

Silica-natural rubber nanocomposites were obtained through a novel non-aqueous in situ sol-gel synthesis, producing the amount of water necessary to induce the hydrolysis and condensation of a tetraethoxysilane precursor by esterification of formic acid with ethanol. The method allows the synthesis of low hydrophilic silica nanoparticles with ethoxy groups linked to the silica surface which enable the filler to be more dispersible in the hydrophobic rubber. Thus, high loaded silica composites (75 phr, parts per hundred rubber) were obtained without using any coupling agent. Transmission Electron Microscopy (TEM) showed that the silica nanoparticles are surrounded by rubber layers, which lower the direct interparticle contact in the filler-filler interaction. At the lowest silica loading (up to 30 phr) silica particles are isolated in rubber and only at a large amount of filler (>60 phr) the interparticle distances decrease and a continuous percolative network, connected by thin polymer films, forms throughout the matrix. The dynamic-mechanical properties confirm that the strong reinforcement of the rubber composites is related to the network formation at high loading. Both the improvement of the particle dispersion and the enhancement of the silica loading are peculiar to the non-aqueous synthesis approach, making the method potentially interesting for the production of high-loaded silica-polymer nanocomposites.

The Chemistry of Chelation for Built Heritage Cleaning: The Removal of Copper and Iron Stains.

Chelators are widely used in conservation treatments to remove metal stains from marble, travertine, and limestone surfaces. In the current review the chemical aspects underlying the use of chelators for the removal of copper and iron stains from built heritage are described and clear criteria for the selection of the most efficient stain removal treatment are given. The main chelator structural features are outlined and the operating conditions for effective metal stain removal (pH, time of application, etc.) discussed, with a particular emphasis on the ability to form stable metal complexes, the high selectivity towards the metal that should be removed, and the high sustainability for the environment. Dense matrices often host chelators for higher effectiveness, and further research is required to clarify their role in the cleaning process. Then, relevant case studies of copper and iron stain removal are discussed. On these bases, the most effective chelators for copper and stain removal are indicated, providing chemists and conservation scientists with scientific support for conservation operations on stone works of art and opening the way to the synthesis of new chelators.

Morphological and structural design through hard-templating of PGM-free electrocatalysts for AEMFC applications.

This study delves into the critical role of customized materials design and synthesis methods in influencing the performance of electrocatalysts for the oxygen reduction reaction (ORR) in anion exchange membrane fuel cells (AEMFCs). It introduces a novel approach to obtain platinum-free (PGM-free) electrocatalysts based on the controlled integration of iron active sites onto the surface of silica nanoparticles (NPs) by using nitrogen-based surface ligands. These NPs are used as hard templates to form tailored nanostructured electrocatalysts with an improved iron dispersion into the carbon matrix. By utilizing a wide array of analytical techniques including infrared and X-ray photoelectron spectroscopy techniques, X-ray diffraction and surface area measurements, this work provides insight into the physical parameters that are critical for ORR electrocatalysis with PGM-free electrocatalysts. The new catalysts showed a hierarchical structure containing a large portion of graphitic zones which contribute to the catalyst stability. They also had a high electrochemically active site density reaching 1.47 × 1019 sites g-1 for SAFe_M_P1AP2 and 1.14 × 1019 sites g-1 for SEFe_M_P1AP2, explaining the difference in performance in fuel cell measurements. These findings underscore the potential impact of a controlled materials design for advancing green energy applications.

Environmental Impact Prediction of a New Tire Vulcanization Activator.

Zinc oxide (ZnO) is the most common curing activator used to manufacture tires. To minimize environmental impacts by decreasing the zinc content and rolling resistance of tires, ZnO nanoparticles (NPs) anchored on SiO2 NPs (ZnO@SiO2) are currently under development as new activators at the pilot scale. Here, we applied prospective life cycle assessment to predict the impacts on human health, ecosystem quality, and resource scarcity of synthesizing ZnO@SiO2 for the production of passenger car tires at an industrial scale. We found that the life cycle impacts of the synthesis are expected to decrease by 89 to 96% between the pilot and industrial scale. The largest contributors to the synthesis of ZnO@SiO2 were electricity consumption and waste treatment of the solvent. Using the new activator for tire production led to potential reductions of 9 to 12% in life cycle impacts compared to tires that are currently in use. Those reductions were due to the expected decrease in rolling resistance, leading to lower fuel consumption, which outweighed the additional environmental impacts of the synthesis, as well as the potential decrease in lifetime. Our work highlights an opportunity for manufacturers to mitigate their impacts over the full life cycle of the tire.

Efficacy of surface treatments on the bond strength of resin cements to two brands of zirconia ceramic.

PURPOSE: To compare the shear bond strengths (SBS) of two cements to two Y-TZP ceramics subjected to different surface treatments. MATERIALS AND METHODS: Zirconia specimens were made from Lava (n = 36) and IPS e.max ZirCAD (n = 36), and their surfaces were treated as follows: no treatment (control), silica coating with 30-µm silica-modified alumina (Al2O3) particles (CoJet Sand), or coating with liners Lava Ceram for Lava and Intensive ZirLiner for IPS e.max ZirCAD. Composite resin cylinders were bonded to zirconia with Panavia F or RelyX Unicem resin cements. All specimens were thermocycled (6000 cycles at 5°C/55°C) and subjected to SBS testing. Data were analyzed by three-way ANOVA and Tukey's (HSD) post-hoc test (α = 0.05). Failure mode was analyzed by stereomicroscope and SEM. RESULTS: CoJet Sand and liners promoted significantly higher SBS than their control groups, but had similar results to one another. Panavia F provided significantly higher SBS values than RelyX Unicem (p < 0.01) for nontreated zirconia specimens of both brands. When Lava and IPS e.max ZirCAD were abraded with CoJet Sand, RelyX Unicem promoted significantly higher SBS values than Panavia F (p < 0.001). There was no significant difference between the two cements when the zirconia specimens were treated with their respective liners. The nontreated specimens and those treated with CoJet Sand exhibited a high percentage of adhesive and mixed A failures, while the specimens treated with liners presented an increase in mixed A and mixed C failures as well as some cohesive failure in the bulk of Lava Ceram for both cements. CONCLUSION: CoJet Sand and liners provided the best surface treatment for Lava and IPS e.max ZirCAD. The best surface treatment/cement combinations were CoJet Sand/RelyX Unicem and liner/Panavia F. SBS of Panavia F and RelyX Unicem was not influenced by the zirconia brand.

Recent Advances on Porous Siliceous Materials Derived from Waste.

In recent years, significant efforts have been made in view of a transition from a linear to a circular economy, where the value of products, materials, resources, and waste is maintained as long as possible in the economy. The re-utilization of industrial and agricultural waste into value-added products, such as nanostructured siliceous materials, has become a challenging topic as an effective strategy in waste management and a sustainable model aimed to limit the use of landfill, conserve natural resources, and reduce the use of harmful substances. In light of these considerations, nanoporous silica has attracted attention in various applications owing to the tunable pore dimensions, high specific surface areas, tailorable structure, and facile post-functionalization. In this review, recent progress on the synthesis of siliceous materials from different types of waste is presented, analyzing the factors influencing the size and morphology of the final product, alongside different synthetic methods used to impart specific porosity. Applications in the fields of wastewater/gas treatment and catalysis are discussed, focusing on process feasibility in large-scale productions.

Layered Na(0.71)CoO(2): a powerful candidate for viable and high performance Na-batteries.

The present study reports on the synthesis and the electrochemical behavior of Na(0.71)CoO(2), a promising candidate as cathode for Na-based batteries. The material was obtained in two different morphologies by a double-step route, which is cheap and easy to scale up: the hydrothermal synthesis to produce Co(3)O(4) with tailored and nanometric morphology, followed by the solid-state reaction with NaOH, or alternatively with Na(2)CO(3), to promote Na intercalation. Both products are highly crystalline and have the P2-Na(0.71)CoO(2) crystal phase, but differ in the respective morphologies. The material obtained from Na(2)CO(3) have a narrow particle length (edge to edge) distribution and 2D platelet morphology, while those from NaOH exhibit large microcrystals, irregular in shape, with broad particle length distribution and undefined exposed surfaces. Electrochemical analysis shows the good performances of these materials as a positive electrode for Na-ion half cells. In particular, Na(0.71)CoO(2) thin microplatelets exhibit the best behavior with stable discharge specific capacities of 120 and 80 mAh g(-1) at 5 and 40 mA g(-1), respectively, in the range 2.0-3.9 V vs. Na(+)/Na. These outstanding properties make this material a promising candidate to construct viable and high-performance Na-based batteries.

On the In Vitro and In Vivo Hazard Assessment of a Novel Nanomaterial to Reduce the Use of Zinc Oxide in the Rubber Vulcanization Process.

Zinc oxide (ZnO) is the most efficient curing activator employed in the industrial rubber production. However, ZnO and Zn(II) ions are largely recognized as an environmental hazard being toxic to aquatic organisms, especially considering Zn(II) release during tire lifecycle. In this context, aiming at reducing the amount of microcrystalline ZnO, a novel activator was recently synthetized, constituted by ZnO nanoparticles (NPs) anchored to silica NPs (ZnO-NP@SiO2-NP). The objective of this work is to define the possible hazards deriving from the use of ZnO-NP@SiO2-NP compared to ZnO and SiO2 NPs traditionally used in the tire industry. The safety of the novel activators was assessed by in vitro testing, using human lung epithelial (A549) and immune (THP-1) cells, and by the in vivo model zebrafish (Danio rerio). The novel manufactured nanomaterial was characterized morphologically and structurally, and its effects evaluated in vitro by the measurement of the cell viability and the release of inflammatory mediators, while in vivo by the Fish Embryo Acute Toxicity (FET) test. Resulting data demonstrated that ZnO-NP@SiO2-NP, despite presenting some subtoxic events, exhibits the lack of acute effects both in vitro and in vivo, supporting the safe-by-design development of this novel material for the rubber industry.

Photogenerated defects in shape-controlled TiO2 anatase nanocrystals: a probe to evaluate the role of crystal facets in photocatalytic processes.

The promising properties of anatase TiO(2) nanocrystals exposing specific surfaces have been investigated in depth both theoretically and experimentally. However, a clear assessment of the role of the crystal faces in photocatalytic processes is still under debate. In order to clarify this issue, we have comprehensively explored the properties of the photogenerated defects and in particular their dependence on the exposed crystal faces in shape-controlled anatase. Nanocrystals were synthesized by solvothermal reaction of titanium butoxide in the presence of oleic acid and oleylamine as morphology-directing agents, and their photocatalytic performances were evaluated in the phenol mineralization in aqueous media, using O(2) as the oxidizing agent. The charge-trapping centers, Ti(3+), O(-), and O(2)(-), formed by UV irradiation of the catalyst were detected by electron spin resonance, and their abundance and reactivity were related to the exposed crystal faces and to the photoefficiency of the nanocrystals. In vacuum conditions, the concentration of trapped holes (O(-) centers) increases with increasing {001} surface area and photoactivity, while the amount of Ti(3+) centers increases with the specific surface area of {101} facets, and the highest value occurs for the sample with the worst photooxidative efficacy. These results suggest that {001} surfaces can be considered essentially as oxidation sites with a key role in the photoxidation, while {101} surfaces provide reductive sites which do not directly assist the oxidative processes. Photoexcitation experiments in O(2) atmosphere led to the formation of Ti(4+)-O(2)(-) oxidant species mainly located on {101} faces, confirming the indirect contribution of these surfaces to the photooxidative processes. Although this work focuses on the properties of TiO(2), we expect that the presented quantitative investigation may provide a new methodological tool for a more effective evaluation of the role of metal oxide crystal faces in photocatalytic processes.