The combination of heterogeneous photocatalysis with chemical and physical operations: a tool for improving the photoprocess performance

Heterogeneous photocatalysis is a process of great potential for pollutant abatement and waste treatment. In order to improve the overall performance of the photoprocess, heterogeneous photocatalysis is being combined with physical or chemical operations, which affect the chemical kinetics and/or the overall ef\ufb01ciency. This review addresses the various possibilities to couple heterogeneous photocatalysis with other technologies to photodegrade organic and inorganic pollutants dissolved in actual or synthetic aqueous ef\ufb02uents. These combinations increase the photoprocess ef\ufb01ciency by decreasing the reaction time in respect to the separated operations or they decrease the cost in respect of heterogeneous photocatalysis alone, generally in terms of light energy. Depending on the operation coupled with heterogeneous photocatalysis, two categories of combinations exist. When the coupling is with ultrasonic irradiation, photo-Fenton reaction, ozonation, or electrochemical treatment, the combination affects the photocatalytic mechanisms thus improving the ef\ufb01ciency of the photocatalytic process. When the coupling is with biological treatment, membrane reactor, membrane photoreactor, or physical adsorption, the combination does not affect the photocatalytic mechanisms but it improves the ef\ufb01ciency of the overall process. The choice of the coupling is related to the type of wastewater to be treated. A synergistic effect, giving rise to an improvement of the ef\ufb01ciency of the photocatalytic process, has been reported in the literature for many cases

Model selection for factorial Gaussian graphical models with an application to dynamic regulatory networks

Factorial Gaussian graphical Models (fGGMs) have recently been proposed for inferring dynamic gene regulatory networks from genomic high-throughput data. In the search for true regulatory relationships amongst the vast space of possible networks, these models allow the imposition of certain restrictions on the dynamic nature of these relationships, such as Markov dependencies of low order-some entries of the precision matrix are a priori zeros-or equal dependency strengths across time lags-some entries of the precision matrix are assumed to be equal. The precision matrix is then estimated by l1-penalized maximum likelihood, imposing a further constraint on the absolute value of its entries, which results in sparse networks. Selecting the optimal sparsity level is a major challenge for this type of approaches. In this paper, we evaluate the performance of a number of model selection criteria for fGGMs by means of two simulated regulatory networks from realistic biological processes. The analysis reveals a good performance of fGGMs in comparison with other methods for inferring dynamic networks and of the KLCV criterion in particular for model selection. Finally, we present an application on a high-resolution time-course microarray data from the Neisseria meningitidis bacterium, a causative agent of life-threatening infections such as meningitis. The methodology described in this paper is implemented in the R package sglasso, freely available at CRAN, http://CRAN.R-project.org/package=sglasso

Overview on oxidation mechanisms of organic compounds by TiO2 in heterogeneous photocatalysis

This review provides the reader with a general overview on heterogeneous photocatalytic oxidation mechanisms in the presence of TiO2, with a special address to conversion of aliphatic and aromatic organic species. The aim was to clarify the steps of the photo-oxidation of the various classes of compounds and to relate them with the properties of the catalysts and the experimental conditions used. Reactions carried out to perform complete degradation and photocatalytic partial oxidations have been deeply discussed. Recent isotopic studies highlighted new reaction pathways concerning partial oxidation of alcohols to aldehyde and oxidation of benzene while EPR investigations confirmed that not only the photogenerated hole but also the OH radicals are involved in the oxidation of the substrates

Selective photooxidation of ortho-substituted benzyl alcohols and the catalytic role of ortho-methoxybenzaldehyde

It has been recently reported by Palmisano et al. (2015) [1] that the oxidation of 2-methoxybenzyl alcohol (2-MBA) to 2-methoxybenzaldehyde (2-MBAD) proceeds in water under near-UV light with an unexpected catalytic effect of 2-MBAD. In order to investigate the catalytic role of aldehyde in photolytic oxidation of ortho-substituted benzyl alcohols (OSBAs), reactivity runs were carried out with 2-methylbenzyl alcohol (2-MeBA), 2-nitrobenzyl alcohol (2-NBA), 2-hydroxybenzyl alcohol (2-HBA) and 2-chlorobenzyl alcohol (2-ClBA) in the absence and in the presence of their corresponding aldehyde. None of those alcohols showed a measurable oxidation rate even in the presence of their aldehydes but 2-NBA was oxidised very fast, although no corresponding carbonyl product was obtained. The possible catalytic role of 2-MBAD was investigated for the photolytic oxidation of 4-methoxybenzyl alcohol (4-MBA), 4-nitrobenzyl alcohol (4-NBA), 2-ClBA, 2-HBA, 2-MeBA and ferulic acid (FA). The results showed that 2-MBAD acts as a catalyst only for 4-MBA, 2-HBA and FA. The photocatalytic oxidation of OSBAs in the presence of powdered TiO2 has been also carried out in order to investigate the mutual influences, if any, between homogeneous and heterogeneous processes. The reactivity runs were carried out with TiO2 photocatalyst in water and under near-UV irradiation; a home-prepared (HP) TiO2 sample was used along with Degussa P25. HP catalyst showed the best performance: the 2-MBA half-life time was 5 times smaller and the selectivity to aldehyde 13 times higher than in the presence of Degussa P25

Visible Light Induced Oxidation of Trans-ferulic Acid by TiO2 Photocatalysis

The oxidation of trans-ferulic acid (C 10H 10O 4) in aqueous TiO 2 dispersion occurs via the formation of a charge-transfer complex on the TiO 2 surface that is able to absorb visible light (\u3bb 65 400 nm). The main product is CO 2, whereas secondary oxidation products are organic species such as vanillin, caffeic acid, homovanillic acid, and vanillylmandelic acid. Oxidation through the formation of a charge-transfer complex occurs only in the presence of specific TiO 2 samples. Experiments in the absence of oxygen, in the presence of bromate ions and by using a phosphate-modified TiO 2, have been carried out for investigating the reaction mechanism. In order to study the interaction between trans-ferulic acid and TiO 2 surface and to characterize the charge-transfer complex, UV-Vis diffuse reflectance and FT-IR spectroscopies have been used. FT-IR characterization of TiO 2 samples in contact with the aqueous trans-ferulic acid solution indicates that the charge-transfer complex formation occurs via adsorption of bidentate ferulate species

Validation of lung densitometry threshold at CT for the distinction between senile lung and emphysema in elderly subjects

Background and Aims. An ageing lung is characterised by distal airspace enlargement without alveolar wall destruction: therefore the anatomical distinction between senile lung and emphysema is clear-cut. In clinical settings the definition of precise boundaries between normalcy and pathology is more difficult with the risk of overdiagnosis. CT is an important diagnostic advancement in the field of COPD. Most methods for the evaluation of emphysema are based on the detection and measurement of areas characterised by a density level below a threshold assumed to characterize parenchymal destruction. Methods. Our retrospective study included 47 healthy subjects (65-91 years), 36 never smokers and 11 former smokers. As a reference sample we recruited 9 patients with emphysema (69-81 years). Thoracic scan was performed by single slice spiral CT and acquired without contrast enhancement. For each scan and on both lungs we sampled eighteen regions of interest in the upper, middle and lower field. Mean lung density (MLD) and lower limit of normal (LLN) of density distribution were calculated. Results. MLD for the whole study sample was -846±41 HU. -901 HU was the LLN of density distribution in the study sample. No significant correlation was noted between age and MLD. In the emphysematous sample the average lung density was -946±18 HU. The mean coefficient of variation was 3% in the healthy sample and 2% in the emphysematous one. The difference between groups was significant (p<0.0001). In one healthy subject only we measured a value slightly below the threshold reported in literature for conventional CT; no emphysematous value fell above the LLN. Conclusions. This study highlights the fact that in the elderly the threshold level of lung density commonly adopted in diagnostic algorithms of emphysema is fully applicable. When applying this method to older subjects the risk of misinterpreting areas of physiologic non-destructive reduction of density as emphysema is low

Unassisted solar lignin valorisation using a compartmented photo-electro-biochemical cell

Lignin is a major component of lignocellulosic biomass. Although it is highly recalcitrant to break down, it is a very abundant natural source of valuable aromatic carbons. Thus, the effective valorisation of lignin is crucial for realising a sustainable biorefinery chain. Here, we report a compartmented photo-electro-biochemical system for unassisted, selective, and stable lignin valorisation, in which a TiO2 photocatalyst, an atomically dispersed Co-based electrocatalyst, and a biocatalyst (lignin peroxidase isozyme H8, horseradish peroxidase) are integrated, such that each system is separated using Nafion and cellulose membranes. This cell design enables lignin valorisation upon irradiation with sunlight without the need for any additional bias or sacrificial agent and allows the protection of the biocatalyst from enzymedamaging elements, such as reactive radicals, gas bubbles, and light. The photo-electrobiochemical system is able to catalyse lignin depolymerisation with a 98.7% selectivity and polymerisation with a 73.3% yield using coniferyl alcohol, a lignin monomer