Revealing the stability of CuWO4/g-C3N4 nanocomposite for photocatalytic tetracycline degradation from the aqueous environment and DFT analysis.

Graphitic carbon nitride (g-C3N4) is an emerging metal-free photocatalyst, however, engineering the photocatalytic efficiency for the effective degradation of hazardous molecules is still challenging. An unstable and low bandgap CuWO4 was composited with g-C3N4 to achieve synergistic benefits of tuning the visible light responsiveness and stability of CuWO4. CuWO4/g-C3N4 nanocomposite exhibited a relatively high visible light absorption region and the bandgap was modified from 2.77 to 2.53 eV evidenced via UV-DRS. Moreover, the fast electron transfer rate was observed with CuWO4/g-C3N4 nanocomposite as confirmed using PL and photocurrent studies. XRD, FT-IR, and HR-TEM analyses signified the formation of CuWO4/g-C3N4 nanocomposite. CuWO4/g-C3N4 nanocomposite showed enhanced photocatalytic degradation of Tetracycline (TC) about ∼7.4 fold greater than pristine g-C3N4 in 120 min. Notably, the OH• and •O2- radicals played a most significant role in photocatalytic TC degradation. Furthermore, the energy band structure, density of state, and Bader charge analyses of these molecules were performed.

An ultrasound-assisted photocatalytic treatment to remove an herbicidal pollutant from wastewaters.

Pollutants of emerging concern contaminate surface and ground water. Advanced oxidation processes treat these molecules and degrade them into smaller compounds or mineralization products. However, little information on coupled advanced oxidation techniques and on the degradation pathways of these pollutants is available to identify possible ecotoxic subproducts. In the present work, we investigate the ultrasound assisted photocatalytic degradation pathway of the herbicide Isoproturon. We worked in batch mode in a thermostatic glass reactor. We compared the activity of nanometric TiO2 P25 with that of Kronos 1077, a micrometric TiO2. We discuss the individual, additive and synergistic degradation action of photolysis, sonolysis, sonophotolysis, and sonophotocatalysis by varying catalyst loading and/or ultrasound power for the last three techniques. With 0.1 g L-1 catalyst, photocatalysis and sonophotopcatalysis completely degrade Isoproturon within 240 min and 60 min, respectively (>99% conversion). Sonophotocatalysis breaks Isoproturon down into smaller molecules than photocatalysis alone.

Ultrasound to improve both synthesis and pollutants degradation based on metal nanoparticles supported on TiO2.

Sonochemistry is based on acoustic cavitation, which consist in the formation, growth, and implosive collapse of bubbles within a liquid. Collapsing bubbles generate localized hot spots, characterized by temperatures up to 5000 K and pressures up to 1800 atm. These extreme conditions allow producing a variety of nanostructured and amorphous materials, as well as they are advantageous for chemical processes. Ultrasound requires inexpensive equipment and fewer steps than conventional methods. Combining ultrasound and photocatalysis enhances the performance of the processes, reduces reaction time, avoids the use of extreme physical conditions and improves the photocatalytic materials properties increasing their activity. Here, we reported the positive effect of US in synthesizing Me-modified TiO2 (Me = Ag, Cu, Mn) for pollutants degradation in gas-phase; also, we proved the advantageous application of ultrasound for the photocatalytic removal of organic compounds in water. Ultrasound produced more efficient Me-doped TiO2, which showed higher activity in visible light. When combined with photocatalytic water treatment, the organic compounds degradation and mineralization increases.

Micro-TiO2 coated glass surfaces safely abate drugs in surface water.

The ingredients of Pharmaceuticals and Personal Care Products (PPCPs) persist in water and conventional treatment plants are not able to remove them efficiently. Sonochemical treatment is insufficient to mineralize organics such as ibuprofen into CO2 and H2O. TiO2 degrades ibuprofen (IBP) under UV light; however, it does not reach a high grade of conversion. Here, we investigated the mineralization of ibuprofen to CO2 by TiO2 UV-C photocatalysis. We replaced nano-sized P25 (the standard catalyst) with a micro-sized commercial sample of TiO2 to preclude the use of nanoparticles which are dangerous for human health and because typical filtration systems are expensive and inefficient. We deposited micro-TiO2 on glass Raschig rings to ensure an easy recovery and reuse of the photocatalyst and we studied its performance both with a batch and a continuous reactor. Micro-TiO2 mineralized 100% of IBP in 24 h. TiO2-coated glass Raschig rings degraded 87% of IBP in 6 h of UV-C irradiation in a continuous reactor, with a mineralization of 25%. Electronspray ionization mass spectrometer (ESI-MS, positive mode) analyses identified 13 different byproducts and we hypothised a degradration pathway for IBP degradation.

Production and application of O2 enriched air produced by fresh and salt water desorption in chemical plants.

Oxygen enriched air intensifies oxidation processes since smaller reactors reach the same conversion of typical unit operations that employ simple air as reactant. However, the cost to produce pure oxygen or oxygen enriched air with traditional methods, i.e. cryogenic separation or membrane technologies, may be unaffordable. Here, we propose a new continuous technology for gas mixture separation, focusing on the production of oxygen enriched air as a case study. This operation is an absorption-desorption process that takes advantage of the higher oxygen solubility in water compared to nitrogen. In a pressurized solubilisation tank, water absorbs air. Subsequently, reducing pressure desorbs oxygen enriched air. PRO/II 9.3 (Simsci-Scheider Electrics) simulated, optimized, and calculated the capital and operative expenses of this technology. Moreover, we tested for the first time salt water instead of distilled water as appealing possibility for chemical plant near sea and ocean. We varied the inlet water flowrate between 5 and 15 m3/h. The optimum operative absortion unit pressure is 15-35 barg. After degassing, water may be recycled. With salt water, the extracted quantity of enriched air decreases compared with the desorption from fresh water (20% less), while the concentration of oxygen is independent from the salt concentration. The cost of enriched air at the optimum condition is 2-3.35 EUR/Nm3.

Ultrasound assisted synthesis of Ag-decorated TiO2 active in visible light.

Titanium dioxide is the most popular photocatalyst to degrade organic pollutants in air, as well as in water. The principal drawback preventing its commercial application lies in its limited absorption of the visible light (400-700nm), while it is active under UV irradiation (≤387nm). Supporting noble metals in the form of nanoparticles on TiO2 increases its activity in the visible range. However, both the synthesis of noble metal nanoparticles and their deposition on TiO2 are multi-step processes that often require organic solvents. Here, we deposit Ag nanoparticles from AgNO3 on the surface of micrometric TiO2 with H2O as a solvent and under ultrasound irradiation at 30Wcm-2. Ultrasound increases the surface amount of Ag on TiO2 with heterogeneous size distribution of Ag nanoparticles, which are bigger and overlaid (1-20nm vs. 0.5-3nm) compared to the sample obtained in traditional conditions (TEM images). While this change in morphology had no effect on acetone photodegradation under UV light, the 5%, 10%, and 20% Ag-TiO2 degraded 17%, 20% and 24% acetone under visible light, respectively. The 10% by weight Ag-TiO2 sample obtained in absence of ultrasound only degraded 14% acetone in 6h, while the bare TiO2 was not active.

Efficient photocatalytic degradation of organics present in gas and liquid phases using Pt-TiO2/Zeolite (H-ZSM).

TiO2-encapsulated H-ZSM photocatalysts were prepared by physical mixing of TiO2 and zeolites. Pt was immobilized on the surface of the TiO2-encapsulated zeolite (H-ZSM) catalysts by a simple photochemical reduction method. Different weight ratios of both TiO2 and Pt were hybridized with H-ZSM and the catalytic performance of the prepared catalysts was investigated for 2-propanol oxidation in liquid phase and acetaldehyde in gas phase reaction. Around 5-10 wt% TiO2-encapsulated H-ZSM catalysts was found to be optimal amount for the effective oxidation of the organics. Prior to light irradiation, Pt-TiO2-H-ZSM showed considerable amount of catalytic degradation of 2-propanol in the dark, forming acetone as an intermediate. In this study, Pt has played a major and important role on the total oxidation of 2-propanol as well as acetaldehyde. As a result, no residual organics were present in the pores of the zeolites. The catalysts could be reused more than three times without losing their catalytic activity in both phases. The Pt-TiO2-H-ZSM photocatalysts could overcome the problem of strong adsorption of organics in the zeolite pores (after the reaction). Thus, Pt-TiO2-H-ZSM can be used as a potential catalyst for both liquid and gas phase oxidation of organic pollutants.

Solitary thyroid metastasis from colon cancer: fine-needle aspiration cytology and molecular biology approach.

Thyroid gland is one of the most vascularized organs of the body, nevertheless clinical and surgical series report an incidence of secondary malignancies in this gland of only 3%. Colorectal carcinoma metastatic to the thyroid gland is not as uncommon as previously believed, infact the number of cases seems to be increased in recent years due to the more frequent use of fine-needle aspiration cytology (FNAC) guided by ultrasonography. Although kidney, breast and lung metastases to the thyroid are frequent, metastasis from colon cancer is clinically rare with 52 cases reported in the literature in the last 5 decades and three cases described as solitary thyroid metastasis from the colon cancer without any other visceral metastases. To the best of our knowledge, we report the fourth case of solitary, asymptomatic thyroid metastasis from colon cancer without involvement of other organs. We discuss the importance of FNAC to detect metastatazing process as a compulsory step of the diagnostic and therapeutic management algorithm, combined with a molecular biology approach. A review of the last 5 decades literature, to update the number of cases described to date, is also included.

Ultrasonic free fatty acids esterification in tobacco and canola oil.

Ultrasound accelerates the free fatty acids esterification rate by reducing the mass transfer resistance between methanol in the liquid phase and absorbed organic species on Amberlyst®46 catalyst. The reaction rates of canola oil is three times greater than for tobacco seed oil but half the reaction rate of pure oleic acid as measured in a batch reactor. The beneficial effects of ultrasound vs. the conventional approach are more pronounced at lower temperatures (20°C and 40°C vs. 63°C): at 20°C, the free fatty acids conversion reaches 68% vs. 23% with conventional mechanical stirring. The increased conversion is attributed to acoustic cavitation that increases mass transfer in the vicinity of the active sites. The Eley-Rideal kinetic model in which the concentration of the reacting species is expressed taking into account the mass transfer between the phases is in excellent agreement with the experimental data. Ultrasound increases the mass transfer coefficient in the tobacco oil 6 and 4.1 fold at 20°C and 40°C, respectively.

Surface modification of Ti-6Al-4 V alloy for biomineralization and specific biological response: part II, alkaline phosphatase grafting.

Titanium and its alloys are the most widespread materials for the realization of orthopaedic and dental implants due to their good mechanical properties and biocompatibility. Surface functionalization of biomaterials aimed to improve and quicken implant integration and tissue regeneration is an active research field. The opportunity to confer biological activity (ability to directly stimulate cells with proper biological signals) to the Ti6Al4 V alloy, previously modified to be bioactive from the inorganic point of view (apatite precipitation), was explored in this research work. The alkaline phosphatase (ALP) enzyme was grafted to metal surface via tresyl chloride activation, maintaining its activity. A synergistic effect between biological functionalization and inorganic bioactivity was observed.

Surface modification of Ti-6Al-4V alloy for biomineralization and specific biological response: Part I, inorganic modification.

Titanium and its alloys represent the gold standard for orthopaedic and dental prosthetic devices, because of their good mechanical properties and biocompatibility. Recent research has been focused on surface treatments designed to promote their rapid osteointegration also in case of poor bone quality. A new surface treatment has been investigated in this research work, in order to improve tissue integration of titanium based implants. The surface treatment is able to induce a bioactive behaviour, without the introduction of a coating, and preserving mechanical properties of Ti6Al4V substrates (fatigue resistance). The application of the proposed technique results in a complex surface topography, characterized by the combination of a micro-roughness and a nanotexture, which can be coupled with the conventional macro-roughness induced by blasting. Modified metallic surfaces are rich in hydroxyls groups: this feature is extremely important for inorganic bioactivity (in vitro and in vivo apatite precipitation) and also for further functionalization procedures (grafting of biomolecules). Modified Ti6Al4V induced hydroxyapatite precipitation after 15 days soaking in simulated body fluid (SBF). The process was optimised in order to not induce cracks or damages on the surface. The surface oxide layer presents high scratch resistance.

Ultrasound and microwave assisted synthesis of high loading Fe-supported Fischer-Tropsch catalysts.

Supported iron-based Fischer-Tropsch (FT) catalysts with high loading of active metal have been prepared using both traditional and innovative methods. In these latter the impregnation of silica support has been performed by adding a step involving an ultrasound (US) or a microwave (MW) treatment to improve the metal deposition and to increase the catalyst activity. FT results have indicated the catalysts prepared by US as the most efficient, particularly when sonication is performed in argon atmosphere. MW prepared samples have given results very similar to those obtained with the traditional method. In order to explain the different catalytic activity, all the samples have been characterized by BET, TPR, SEM, TEM, XRD and micro-Raman analyses.

Surface functionalization of bioactive glasses.

Different cleaning and silanization methods have been applied to bioactive glasses with the aim of covalently bonding bone morphogenetic proteins (BMP-2) to the surface. Several glasses, with different bioactivity index, were cleaned with acidic, basic, or neutral aqueous media to investigate the role of pH in the formation of silanols on glass surfaces of different reactivity. The cleaned glasses were then functionalized using 3-aminopropyl-triethoxysilane (APTS). After the optimization of the silanization procedure, proteins of different complexity were immobilized on the functionalized glasses. To optimize the protein immobilization, a model protein (carnosine) was first used, and the procedure was then used to bind human BMP-2. The glass surfaces were characterized during each step of the treatment by water contact angles and X-ray photoelectron analyses. The APTS functionalization was then used to immobilize bone morphogenetic protein on the bioactive glasses. This result suggested that such a treatment could be successfully used as an efficient alternative to systemic administration of transforming growth factors for the development of local delivery vehicle implants.

Early stage reactivity and in vitro behavior of silica-based bioactive glasses and glass-ceramics.

The surface reactivity of different sets of glasses and glass-ceramics belonging to the SiO(2)-P(2)O(5)-CaO-MgO-K(2)O-Na(2)O system have been investigated. The attention was focused on the role of their composition on the bioactivity kinetics, in terms of pH modifications, silica-gel formation and its evolution toward hydroxycarbonatoapatite, after different times of soaking in simulated body fluid. Glasses and glass ceramics have been characterized by thermal analysis, SEM-EDS observations and phase analysis (XRD). XPS measurements have been carried out on the most representative set of sample in order to evaluate the evolution of the surface species during the growth of silica-gel and hydroxycarbonatoapatite. The response of murine fibroblast 3T3 to the material before and after a conditioning pre-treatment (immersion in SBF) has been investigated on the same set of samples in order to point out the role of the bioactivity mechanism on cell viability. The main differences among the various glasses have been related to the modifier oxides ratio and to the MgO content, which seems to have an influence on the glass stability, both in terms of thermal properties and surface reactivity. The surface characterization and in vitro tests revealed few variations in the reactivity of the different glasses and glass-ceramics in their pristine form. On the contrary, the different surface properties before and after the pre-treatment in SBF seem to play a role on the biocompatibility of both glass and glass-ceramics, due to the different ion release and hydrophilicity of the surfaces, affecting both cell viability and protein adsorption.

Photocatalytic degradation of toluene in the gas phase: relationship between surface species and catalyst features.

Photocatalytic activity of both commercial and homemade samples was tested for the degradation of toluene in the gas phase by using two different irradiation sources, UV and solar. The role played by humidity in affecting the final toluene degradation was discussed. Catalyst deactivation (due to the high toluene level, 1000 ppm) and subsequent regeneration, by washing with water, were analyzed. Highest degradations and corresponding kinetic constants were achieved in the case of the anatase/brookite composite samples, while the commercial ones (including P25 Degussa) showed lower efficiency. Various adsorbed aromatic species (benzoic acid, the major surface product hydroquinone, benzylic alcohol, benzaldehyde, and cresols) obtained by washing the exhaust catalysts were analyzed by HPLC. Parallel results were achieved by Fourier transform infrared attenuated total reflectance (FTIR-ATR) spectroscopy. The presence of different photodegradation surface species for the various photocatalysts suggests the occurrence of different reaction pathways, depending on the fine physicochemical features of the specific TiO2 adopted in the reaction.

Sono-photocatalytic degradation of 2-chlorophenol in water: kinetic and energetic comparison with other techniques.

The degradation of 2-chlorophenol in water was kinetically investigated using the following different techniques, employed either separately or simultaneously, always with the same experimental set-up: light irradiation (315-400 nm), sonication, photocatalysis with different types of TiO2, photocatalysis with sonication. The influence of the reaction volume and of different gas mixtures, containing Ar and O2, as well as O2/O3, was also investigated. Finally, an energetic comparison among these different techniques was performed, focused on an industrial application of some of them.

New ultrasonically prepared Co-based catalysts for Fischer-Tropsch synthesis.

An extensive study of different preparation methods for Co/SiO2 catalysts is reported in this paper. In addition to the conventional impregnation, other more innovative methods are used including ultrasound. The prepared samples are fully characterized and tested in the CO hydrogenation (Fischer-Tropsch synthesis). The best catalytic performance, both as CO conversion and hydrocarbons selectivity, is shown by one of the sample prepared using ultrasound.

Preparation of Pd/C catalysts via ultrasound: a study of the metal distribution.

Palladium supported on active carbon catalysts was prepared using ultrasound during one of the preparation steps. An investigation of the metal distribution into the pores of the support was performed both by a deep characterization of the prepared samples and by a catalytic reaction involving some organic reactants to be reduced.