Carboxymethyl ß-Cyclodextrin Assistance for the 4-Nitrophenol Reduction Using Cobalt-Based Layered Double Hydroxides.

Cobalt-aluminum-layered double hydroxides containing carboxymethyl ß-cyclodextrin (CMßCD) were synthesized by coprecipitation and evaluated as a cobalt source for the 4-nitrophenol reduction in an aqueous medium. Several physicochemical techniques (XRD, FTIR, TGA) indicated the intercalation of the anionic cyclodextrin without damages to the hydrotalcite-type structure. These lamellar cobalt-aluminum hybrid materials (CoAl_CMßCD) were evaluated in the 4-nitrophenol reduction and showed higher activities in comparison with the CMßCD-free standard material (CoAl_CO3). To rationalize these results, a set of experimental controls going from physical mixtures of CoAl_CO3 with different cyclodextrins to other cobalt-based materials were investigated, highlighting the beneficial effects of both the layered double hydroxide and CMßCD-based hybrid structures. CMßCD also showed a beneficial effect as an additive during the 4-nitrophenol reduction. CoAl_CO3, dispersed in a fresh CMßCD solution could be re-used for five successive cycles without the loss of activity.

Full Selectivity Control over the Catalytic Hydrogenation of Nitroaromatics into Six Products.

A full selectivity control over the catalytic hydrogenation of nitroaromatics leads to the production of six possible products, i.e., nitroso, hydroxylamine, azoxy, azo, hydrazo or aniline compounds, which has however not been achieved in the field of heterogeneous catalysis. Currently, there is no sufficient evidence to support that the catalytic hydrogenation of nitroaromatics with the use of heterogeneous metal catalysts would follow the Haber's mechanistic scheme based on electrochemical reduction. We now demonstrate in this work that it is possible to fully control the catalytic hydrogenation of nitroaromatics into their all six products using a single catalytic system under various conditions. Employing SnO2-supported Pt nanoparticles facilitated by the surface coordination of ethylenediamine and vanadium species enabled this unprecedented selectivity control. Through systematic investigation into the controlled production of all products and their chemical reactivities, we have constructed a detailed reaction network for the catalytic hydrogenation of nitroaromatics. Crucially, the application of oxygen-isolated characterization techniques proved indispensable in identifying unstable compounds such as nitroso, hydroxylamine, hydrazo compounds. The insights gained from this research offer invaluable guidance for selectively transforming nitroaromatics into a wide array of functional N-containing compounds, both advancing fundamental understanding and fostering practical applications in various fields.

Redox Properties of Bacillus subtilis Ferredoxin:NADP+ Oxidoreductase: Potentiometric Characteristics and Reactions with Pro-Oxidant Xenobiotics.

Bacillus subtilis ferredoxin:NADP+ oxidoreductase (BsFNR) is a thioredoxin reductase-type FNR whose redox properties and reactivity with nonphysiological electron acceptors have been scarcely characterized. On the basis of redox reactions with 3-acetylpyridine adenine dinucleotide phosphate, the two-electron reduction midpoint potential of the flavin adenine dinucleotide (FAD) cofactor was estimated to be -0.240 V. Photoreduction using 5-deazaflavin mononucleotide (5-deazaFMN) as a photosensitizer revealed that the difference in the redox potentials between the first and second single-electron transfer steps was 0.024 V. We examined the mechanisms of the reduction of several different groups of non-physiological electron acceptors catalyzed by BsFNR. The reactivity of quinones and aromatic N-oxides toward BsFNR increased when increasing their single-electron reduction midpoint redox potentials. The reactivity of nitroaromatic compounds was lower due to their lower electron self-exchange rate, but it exhibited the same trend. A mixed single- and two-electron reduction reaction was characteristic of quinones, whereas reactions involving nitroaromatics proceeded exclusively via the one-electron reduction reaction. The oxidation of FADH• to FAD is the rate-limiting step during the oxidation of fully reduced FAD. The calculated electron transfer distances in the reaction with nitroaromatics were close to those of other FNRs including the plant-type enzymes, thus demonstrating their similar active site accessibility to low-molecular-weight oxidants despite the fundamental differences in their structures.

Paper and nylon based optical tongues with poly(p-phenyleneethynylene)-fluorophores efficiently discriminate nitroarene-based explosives and pollutants.

Discrimination of nitroarenes with hydrophobic dyes in a polar (H2O) environment is difficult but possible via a lab-on-chip, with polymeric dyes immobilized on paper or nylon membranes. Here arrays of 12 hydrophobic poly(p-phenyleneethynylene)s (PPEs), are assembled into a chemical tongue to detect/discriminate nitroarenes in water. The changes in fluorescence image of the PPEs when interacting with solutions of the nitroarenes were recorded and converted into color difference maps, followed by cluster analysis methods. The variable selection method for both paper and nylon devices selects a handful of PPEs at different pH-values that discriminate nitroaromatics reliably. The paper-based chemical tongue could accurately discriminate all studied nitroarenes whereas the nylon-based devices represented distinguishable optical signature for picric acid and 2,4,6-trinitrotoluene (TNT) with high accuracy.

Chemo-and regioselective aqueous phase, co-acid free nitration of aromatics using traditional and nontraditional activation methods.

Electrophilic aromatic nitrations are used for the preparation of a variety of synthetic products including dyes, agrochemicals, high energy materials, fine chemicals and pharmaceuticals. Traditional nitration methods use highly acidic and corrosive mixed acid systems which present a number of drawbacks. Aside from being hazardous and waste-producing, these methods also often result in poor yields, mostly due to low regioselectivity, and limited functional group tolerance. As a consequence, there is a need for effective and environmentally benign methods for electrophilic aromatic nitrations. In this work, the major aim was to develop reaction protocols that are more environmentally benign while also considering safety issues. The reactions were carried out in dilute aqueous nitric acid, and a broad range of experimental variables, such as acid concentration, temperature, time, and activation method, were investigated. Mesitylene and m-xylene were used as test substrates for the optimization. While the optimized reactions generally occurred at room temperature without any activation under additional solvent-free conditions, slight adjustments in acid concentration, stoichiometric equivalents, and volume were necessary for certain substrates, in addition to the activation. The substrate scope of the process was also investigated using both activated and deactivated aromatics. The concentration of the acid was lowered when possible to improve upon the safety of the process and avoid over-nitration. With some substrates we compared traditional and nontraditional activation methods such as ultrasonic irradiation, microwave and high pressure, respectively, to achieve satisfactory yields and improve upon the greenness of the reaction while maintaining short reaction times.

Photocatalytic Transformation of Organics to Valuable Chemicals - Quo Vadis?

Recent development in photocatalysis is increasingly focused on transforming organic compounds toward producing fine chemicals. Simple, non-selective oxidation reactions (degradation of pollutants) and very demanding solar-to-chemical energy conversion processes (production of solar fuels) face severe economic limitations influenced by still low efficiency and insufficient stability of the systems. Synthesis of fine chemicals, including reductive and oxidative selective transformations, as well as C-C and C-N coupling reactions, can utilise the power of photocatalysis. Herein, we present the recent progress in photocatalytic systems designed to synthesise fine chemicals. In particular, we discuss the factors influencing the efficiency and selectivity of the organic transformations, dividing them into intrinsic (related to individual properties of photocatalysts) and extrinsic (originating from the reaction environment). A rational design of the photocatalytic systems, based on a deep understanding of these factors, opens new perspectives for applied photocatalysis.

Coupling Fe-Co atomic pair to promote the selective reduction of nitroaromatics under mild conditions.

Selectively reducing nitroaromatics into aromatic amines will not only remove nitroaromatic pollutants in waste effluents to reduce environmental risks, but also yield important feedstocks for chemical industrial manufactures. In this study, a FeCo-co-embedded N-doped Carbon (FeCo-N-C) catalyst with Fe-Co atomic pair has been identified with favorable activity, superior selectivity, excellent reusability, as well as outstanding performance in the treatment of real water. The combined results from theoretical study and experimental tests indicate that the improved catalytic performance of FeCo-N-C is owing to the narrowed band gap and electron delocalization caused by the Fe-Co atomic pair which can improve electron transport in its catalytic reaction. The results of isotope experiments and H* quenching experiments confirm that H2O is the source of hydrogen in catalytic reduction of PNP. FeCo-N-C is identified as a superior catalyst to replace multitudinous currently used noble-metal catalysts for the selective catalytic reduction of nitroaromatics in wastewater treatment.

Secondary Formation of Atmospheric Brown Carbon in China Haze: Implication for an Enhancing Role of Ammonia.

Optical characteristics and molecular compositions of brown carbon (BrC) were investigated during winter 2019 at a rural site of China with a focus on nitro-aromatic compounds (NACs) and imidazoles (IMs). The abundance of gaseous nitrophenols relative to CO during the campaign maximized at noontime, being similar to O3, while the particulate NACs during the haze periods strongly correlated with toluene and NO2, suggesting that NACs in the region are largely formed from the gas-phase photooxidation. Strong correlations of particulate IMs in the dry haze periods with the mass ratio of EC/PM2.5 and the concentration of levoglucosan were observed, indicating that IMs during the dry events are largely derived from biomass burning emissions. However, an increase in IMs with the increasing aerosol liquid water content and pH was observed in the humid haze events, along with much lower abundances of levoglucosan and K+ relative to PM2.5, suggesting that IMs were mostly formed from aqueous reactions in the humid haze periods. These IMs exponentially increased with an increasing NH3 owing to an aqueous reaction of carbonyls with free ammonia. Our findings for the first time revealed an enhancing effect of ammonia on BrC formation in China, especially in humid haze periods.

Cloning of two gene clusters involved in the catabolism of 2,4-dinitrophenol by Paraburkholderia sp. strain KU-46 and characterization of the initial DnpAB enzymes and a two-component monooxygenases DnpC1C2.

Little is currently known about the metabolism of the industrial pollutant 2,4-dinitrophenol (DNP), particularly among gram-negative bacteria. In this study, we identified two non-contiguous genetic loci spanning 22 kb of Paraburkholderia (formerly Burkholderia) sp. strain KU-46. Additionally, we characterized four key initial genes (dnpA, dnpB, and dnpC1C2) responsible for DNP degradation, providing molecular and biochemical evidence for the degradation of DNP via the formation of 4-nitrophenol (NP), a pathway that is unique among DNP utilizing bacteria. Reverse transcription polymerase chain reaction (PCR) analysis indicated that dnpA, which encodes the initial hydride transferase, and dnpB which encodes a nitrite-eliminating enzyme, were induced by DNP and organized in an operon. Moreover, we purified DnpA and DnpB from recombinant Escherichia coli to demonstrate their effect on the transformation of DNP to NP through the formation of a hydride-Meisenheimer complex of DNP, designated as H--DNP. The function of DnpB appears new since all homologs of the DnpB sequences in the protein database are annotated as putative nitrate ABC transporter substrate-binding proteins. The gene cluster responsible for the degradation of DNP after NP formation was designated dnpC1C2DXFER, and DnpC1 and DnpC2 were functionally characterized as the FAD reductase and oxygenase components of the two-component DNP monooxygenase, respectively. By elucidating the hqdA1A2BCD gene cluster, we are now able to delineate the final degradation pathway of hydroquinone to ß-ketoadipate before it enters the tricarboxylic acid cycle.

Advance Progress on Luminescent Sensing of Nitroaromatics by Crystalline Lanthanide-Organic Complexes.

Water environment pollution is becoming an increasingly serious issue due to industrial pollutants with the rapid development of modern industry. Among many pollutants, the toxic and explosive nitroaromatics are used extensively in the chemical industry, resulting in environmental pollution of soil and groundwater. Therefore, the detection of nitroaromatics is of great significance to environmental monitoring, citizen life and homeland security. Lanthanide-organic complexes with controllable structural features and excellent optical performance have been rationally designed and successfully prepared and used as lanthanide-based sensors for the detection of nitroaromatics. This review will focus on crystalline luminescent lanthanide-organic sensing materials with different dimensional structures, including the 0D discrete structure, 1D and 2D coordination polymers and the 3D framework. Large numbers of studies have shown that several nitroaromatics could be detected by crystalline lanthanide-organic-complex-based sensors, for instance, nitrobenzene (NB), nitrophenol (4-NP or 2-NP), trinitrophenol (TNP) and so on. The various fluorescence detection mechanisms were summarized and sorted out in the review, which might help researchers or readers to comprehensively understand the mechanism of the fluorescence detection of nitroaromatics and provide a theoretical basis for the rational design of new crystalline lanthanide-organic complex-based sensors.

Detection of Nitroaromatic and Peroxide-Based Explosives with Amine- and Phosphine-Functionalized Diketopyrrolopyrroles.

Effective strategies for the detection and identification of explosives are highly desirable. Herein, we illustrate the efficient optoelectronic detection of nitroaromatic and peroxide-based explosives using amine- and phosphine-substituted diketopyrrolopyrroles. Selective quenching and an unprecedented enhancement of thin-film emission in the presence of nitroaromatic vapors are demonstrated via the judicious choice of amine substituents. The modulation of fluorescence emission in each case is shown to be dominated by electronic and thermodynamic effects, the vapor pressure of explosives, and the thin-film morphology. For peroxide detection, we describe an approach exploiting redox-mediated functional group transformation. The rapid oxidation of triphenylphosphine to phosphine oxide with hydrogen peroxide affords a significant increase in fluorescence emission, facilitating the sensitive turn-on detection of an important class of explosives at ppb concentrations.

Chitosan-supported metal nanocatalysts for the reduction of nitroaromatics.

The second most abundant natural polymer in the earth's crust is chitosan (CS). The unique physical, chemical, structural, and mechanical features of this natural polymer have led to its increased application in a variety of fields such as medicine, catalysis, removal of pollutants, etc. To eliminate various pollutants, it is preferable to employ natural compounds as their use aids the removal of contaminants from the environment. Consequently, employing CS to eliminate contaminants is a viable choice. For this aim, CS can be applied as a template and support for metal nanoparticles (MNPs) and prevent the accumulation of MNPs as well as a reducing and stabilizing agent for the synthesis of MNPs. Among the pollutants present in nature, nitro compounds are an important and wide category of biological pollutants. 4-Nitrophenol (4-NP) is one of the nitro pollutants. There are different ways for the removal of 4-NP, but the best and most effective method for this purpose is the application of a metallic catalyst and a reducing agent. In this review, we report the recent developments regarding CS-supported metallic (nano)catalysts for the reduction of nitroaromatics such as nitrophenols, nitroaniline compounds, nitrobenzene, etc. in the presence of reducing agents. The metals investigated in this study include Ag, Au, Ni, Cu, Ru, Pt, Pd, etc.

Sustainable magnetically recoverable Iridium-coated Fe3O4 nanoparticles for enhanced catalytic reduction of organic pollutants in water.

The reduction of nitroarenes to aromatic amines is one of the potential pathways to remediate the hazardous impact of toxic nitroarenes on the aquatic environment. Aromatic amines obtained from the reduction of nitroaromatics are not only less toxic than nitroaromatics but also act as important intermediates in the synthesis of dyes, drugs, pigments, herbicides, and polymers. There is a huge demand for the development of cost-effective, and eco-friendly catalysts for the efficient reduction of nitroarenes. In the present study, Fe3O4@trp@Ir nanoparticles were explored as efficient catalysts for the reduction of nitroarenes. Fe3O4@trp@Ir magnetic nanoparticles were fabricated by surface coating of Fe3O4 with tryptophan and iridium by co-precipitation method. As-prepared Fe3O4@trp@Ir nanoparticles are environmentally benign efficient catalysts for reducing organic pollutants such as 4-nitrophenol (4-NP), 4-nitroaniline (4-NA), and 1-bromo-4-nitrobenzene (1-B-4-NB). The key parameters that affect the catalytic activity like temperature, catalyst loading, and the concentration of reducing agent NaBH4 were optimized. The obtained results proved that Fe3O4@trp@Ir is an efficient catalyst for reducing nitroaromatics at ambient temperature with a minimal catalyst loading of 0.0025%. The complete conversion of 4-nitrophenol to 4-aminophenol took only 20 s with a minimal catalyst loading of 0.0025% and a rate constant of 0.0522 s-1. The high catalytic activity factor (1.040 s-1 mg-1) and high turnover frequency (9 min-1) obtained for Fe3O4@trp@Ir nanocatalyst highlight the possible synergistic effect of the two metals (Fe and Ir). The visible-light photocatalytic degradation of 4-NP was also investigated in the presence of Fe3O4@trp@Ir. The photocatalytic degradation of 4-NP by Fe3O4@trp@Ir is completed in 20 min with 95.15% efficiency, and the rate of photodegradation of 4-NP (0.1507 min-1) is about twice the degradation rate of 4-NP in the dark (0.0755 min-1). The catalyst was recycled and reused for five cycles without significant reduction in the conversion efficiency of the catalyst.

Cysteamine-decorated gold nanoparticles for plasmon-based colorimetric on-site sensors for detecting cyanide ions using the smart-phone color ratio and for catalytic reduction of 4-nitrophenol.

In this paper, we have reported the cyanide ions (CN-) sensing in environmental water samples using cysteamine-capped gold nanoparticles (Cyst-AuNPs) by spectrophotometric, colorimetric, and smartphone-based RGB color detection. The surface plasmon resonance shift at around 525 nm for the Cyst-AuNPs could be used to detect quantitatively the amounts of CN- with concomitant alteration of their color from wine red to purple visualized by the naked eye. For the first time, the Cyst-AuNPs-based visual sensing of CN- was performed using smartphone-based detection with its detection limit of 159 × 10-9 M, ten times lower than that of the highest tolerance level (2 × 10-6 M) permitted by the world health organization. The Cyst-AuNPs displayed excellent specificity for detecting the concentration of 30 × 10-6 M even amid the presence of other interfering inorganic anions with their concentrations about five times higher than it. Environmental real water samples were used to arrange the three different CN- concentrations for plasmon-based colorimetric detection and smartphone-based method. Additionally, the catalytic performance of Cyst-AuNPs was demonstrated for the fast catalytic conversion of hazardous 4-nitrophenol (selected environmental contaminant) to the analogous amino aromatic compounds. A chemical kinetic study showed the conversion rate to be estimated as 1.65 × 10-2 s-1. Cyst-AuNPs can find an application in colorimetric sensing of CN- while being able to be utilized as a catalytic nanomaterial for ecological remedies associated with health care.

Fluorometric Sensing and Detection of p-Nitroaniline by Mixed Metal (Zn, Ni) Tungstate Nanocomposite.

Aromatic amines are important chemical intermediates that hold an irreplaceable significance for synthesizing many chemical products. However, they may react with substances excreted from human bodies to generate blood poisoning, skin eczema, and dermatitis disease and even induce cancer-causing high risks to human health and the environment. Metal tungstates have been proven to be highly efficient materials for developing various toxic gases or chemical detection sensor systems. However, the major factors of the sensors, such as sensitivity, selectivity, stability, response, and recovery times, still need to be optimized for practical technological applications. In this work, Ni-doped ZnWO4 mixed metal tungstate nanocomposite material was synthesized by the hydrothermal method and explored as a sensor for the fluorometric determination of p-nitroaniline (p-NA). Transmission electron microscopy (TEM) was used for the elucidation of the optimized particle diameter. Scanning electron microscopy (SEM) was employed to observe the surface morphological changes in the material during the solid-state reactions. The vibration modes of as-prepared samples were analyzed using Fourier-transform infrared spectroscopy (FTIR). The chemical bonding and oxidation states of individual elements involved in material synthesis were observed using X-ray photoelectron spectroscopy (XPS). The PL activities of the metal tungstate nanoparticles were investigated for the sensing of p-nitroaniline (p-NA). The obtained results demonstrated that ZnNiWO4 was more effective in sensing p-NA than the other precursors were by using the quenching effect. The material showed remarkably high sensitivity towards p-NA in a concentration range of 25-1000 µM, and the limit of detection (LOD) value was found to be 1.93 × 10-8 M for ZnWO4, 2.17 × 10-8 M for NiWO4, and 2.98 × 10-8 M for ZnNiWO4, respectively.

Graphene-like wrapped Ni@C catalyst with magnetic recyclability for selective hydrogenation of nitro-aromatics.

The graphene-like wrapped Ni@C catalysts were facilely synthesized by a modified sol-gel method. Nickel nitrate and citric acid (CA) were adopted as the raw materials to form sol-gel mixture. Under the circumstances, the additive CA were employed not only as a complexing agent but also as a carbon source. It is found that the calcination temperature and the mole ratios between Ni and CA are the key factors affecting the physical property and the catalytic performance of catalysts in the conversion of nitroarenes into corresponding anilines. The results show that the Ni@C-500(1:1) catalyst exhibited the best performance in the hydrogenation ofo-chloronitrobenzenes (o-CNB) too-chloroanilines (o-CAN). The yield ofo-CAN was achieved at 100% wheno-CNB was completely converted at 40.0 °C under 2.0 MPa H2for 2.0 h. Furthermore, the Ni@C-500(1:1) catalyst could be separated and recovered easily after reaction by an external magnetic field. The investigated results indicate that the Ni@C-500(1:1) catalyst remained higher activity after using twelve times. More importantly, this kind of catalyst is also active for the selective hydrogenation of other nitroarenes into the corresponding anilines. This new synthetic method may pave a way for producing low-cost Ni@C catalysts on a large scale, which is attractive for industrial anilines applications.

Visible-Light-Driven Porphyrin-Based Bimetallic Metal-Organic Frameworks for Selective Photoreduction of Nitro Compounds under Mild Conditions.

Selective reduction of nitroaromatics to the corresponding amines generally requires complex conditions, involving pressurized hydrogen, higher temperatures, or organic acids. In this work, we successfully prepared a series of porphyrin-based MOF photocatalysts (Pd-PMOFs, In-PMOFs, and In/Pd-PMOFs) via a facile solvothermal method for the efficient selective reduction of nitroaromatics to corresponding anilines with deionized water as the hydrogen donor. Being a new structured material (monoclinic, C52H40InN6O8Pd), on account of the abundant pore channels, strong light absorption capability, well-matched bandgap, as well as the coordination of indium ions and palladium ions, In/Pd-MOFs have excellent migration efficiency of photo-induced electrons and holes. Specifically, the In/Pd-PMOF photocatalyst manifested superior conversion (100%) and selectivity (≥80%) toward the screened nitro compounds under mild conditions. This work avoids the use of strong reductants, organic acids, and pressurized hydrogen gas as hydrogen sources, providing a promising concept for developing green catalytic systems.

Lanthanide(III) Ions and 5-Methylisophthalate Ligand Based Coordination Polymers: An Insight into Their Photoluminescence Emission and Chemosensing for Nitroaromatic Molecules.

The work presented herein reports on the synthesis, structural and physico-chemical characterization, luminescence properties and luminescent sensing activity of a family of isostructural coordination polymers (CPs) with the general formula [Ln2(µ4-5Meip)3(DMF)]n (where Ln(III) = Sm (1Sm), Eu (2Eu), Gd (3Gd), Tb (4Tb) and Yb (5Yb) and 5Meip = 5-methylisophthalate, DMF = N,N-dimethylmethanamide). Crystal structures consist of 3D frameworks tailored by the linkage between infinite lanthanide(III)-carboxylate rods by means of the tetradentate 5Meip ligands. Photoluminescence measurements in solid state at variable temperatures reveal the best-in-class properties based on the capacity of the 5Meip ligand to provide efficient energy transfers to the lanthanide(III) ions, which brings intense emissions in both the visible and near-infrared (NIR) regions. On the one hand, compound 5Yb displays characteristic lanthanide-centered bands in the NIR with sizeable intensity even at room temperature. Among the compounds emitting in the visible region, 4Tb presents a high QY of 63%, which may be explained according to computational calculations. At last, taking advantage of the good performance as well as high chemical and optical stability of 4Tb in water and methanol, its sensing capacity to detect 2,4,6-trinitrophenol (TNP) among other nitroaromatic-like explosives has been explored, obtaining high detection capacity (with Ksv around 105 M-1), low limit of detection (in the 10-6-10-7 M) and selectivity among other molecules (especially in methanol).

Bacillus pumilus proteome changes in response to 2,4,6-trinitrotoluene-induced stress.

2,4,6-Trinitrotoluene (TNT) is the most widely used nitroaromatic compound and is highly resistant to degradation. Most aerobic microorganisms reduce TNT to amino derivatives via formation of nitroso- and hydroxylamine intermediates. Although pathways of TNT degradation are well studied, proteomic analysis of TNT-degrading bacteria was done only for some individual Gram-negative strains. Here, we isolated a Gram-positive strain from TNT-contaminated soil, identified it as Bacillus pumilus using 16S rRNA sequencing, analyzed its growth, the level of TNT transformation, ROS production, and revealed for the first time the bacillary proteome changes at toxic concentration of TNT. The transformation of TNT at all studied concentrations (20-200 mg/L) followed the path of nitro groups reduction with the formation of 4-amino-2,6-dinitrotoluene. Hydrogen peroxide production was detected during TNT transformation. Comparative proteomic analysis of B. pumilus showed that TNT (200 mg/L) inhibited expression of 46 and induced expression of 24 proteins. Among TNT upregulated proteins are those which are responsible for the reductive pathway of xenobiotic transformation, removal of oxidative stress, DNA repair, degradation of RNA and cellular proteins. The production of ribosomal proteins, some important metabolic proteins and proteins involved in cell division are downregulated by this xenobiotic.

Facile synthesis of green and efficient magnetic nanocomposites of carrageenan/copper for the reduction of nitrophenol derivatives.

A green and facile method for preparation of Kappa-Carrageenan or Iota-Carrageenan grafted N,N'-methylenebisacrylamide/Fe3O4/Cu nanoparticles (κC-g-MBA/MNPs/Cu and ιC-g-MBA/MNPs/Cu) catalysts was developed to place copper on a magnetic carrageenan surface. The structure and morphology of the prepared catalysts were identified using FT-IR, XRD, BET, VSM, TGA, EDX, mapping, FE-SEM, TEM, and ICP-OES analyses. The catalytic activity of the catalysts was investigated to reduce 4-nitrophenol, 2-nitrophenol, 3-nitroaniline, and 4-nitroaniline compounds using the UV-Vis spectrum. To reduce 4-nitrophenol using κC-g-MBA/MNPs/Cu and ιC-g-MBA/MNPs/Cu, the rate constants (Kapp) obtained were 0.37 and 0.25 min-1, and the activity factors (k') were 134 and 193 s-1 g-1, respectively. The catalysts had a good performance in reducing the nitrophenol compounds and due to the magnetic properties of the catalysts, they could easily be separated and used multiple times.