Magnetic graphene oxide-anchored Ni/Cu nanoparticles with a Cu-rich surface for transfer hydrogenation of nitroaromatics

The bimetallic nanoparticles compositing of Ni-rich core and Cu-rich shell(Ni/Cu NPs)were successfully synthesized by a liquid-phase thermal decomposition method.The content of copper and nickel in Ni/Cu NPs was controllable by adjusting the ratio of two metal precursors,copper formate(Cuf)and nickel acetate tetrahydrate(Ni(OAc)_(2)·4H_(2)O).Ni/Cu NPs were further anchored on graphene oxide(GO)to prepare a magnetic composite catalyst,called Ni/Cu-GO.The dispersibility of Ni/Cu NPs in solution was enhanced by GO anchoring to prevent the sintering and aggregation during the reaction process,thereby ensuring the catalytic and cycling performance of the catalyst.The catalytic transfer hydrogenation(CTH)reaction of nitroaromatics was investigated when ammonia borane was used as the hydrogen source.Cu dominated the main catalytic role in the reaction,while Ni played a synergistic role of catalysis and providing magnetic properties for separation.The Ni_(7)/Cu_(3)-GO catalyst exhibited the best catalytic performance with the conversion and yield of 99%and 96%,respectively,when 2-methyl-5-nitrophenol was used as the substrate.The Ni_(7)/Cu_(3)-GO catalyst also exhibited excellent cyclic catalytic performance with the 5-amino-2-methylphenol yield of above 90%after six cycles.In addition,the Ni_(7)/Cu_(3)-GO catalyst could be quickly recycled by magnetic separation.Moreover,the Ni_(7)/Cu_(3)-GO catalyst showed good catalytic performance for halogen-containing nitroaromatics without dehalogenation.

Effect of monotoxicity and mixtoxicity of nitroaromatics to the green algae, Scienedesmus obliquus

In general, many pollutants co\|exist in natural aquatic ecosystems. They affect each other and occur different results, such as synergism, addition and antagonism. So the research at mixtoxicity of contaminants to aquatic organism is more important than monotoxicity. In this paper, 50% effectual inhibition concentration 48h \%EC\%\-\{50\} values of 6 kinds of nitroaromatic compounds to the green algae, \%Scenedesmus obliquus,\% were investigated. Mixtoxic experiments, in which any combination of 2,4\|DNT and other 6 kinds of compounds, indicate: (1) synergisms between 2,4\|DNT and 4\|NAn, as well as 4\|NAnis, 1,4\|DNB; (2) antagonisms between 2,4\|DNT and 4\|NT, as well as 4\|NPh, 4\|NCB.

Tough lanthanide luminescent hydrogel for nitroaromatics detection

Luminescent hydrogels have received considerable attention in the application of sensors.Nitroaro matics are harmful to human health and can be carcinogenic.Some skin allergies and central nervous system injuries may also be attributed to the over exposure to nitroaromatics.Thus,nitroaromatics sensor with fast detection and low detection limit is highly desirable.Herein,novel tough hydrogels were prepared by introducing hydrogen bonds and covalent bonds into the interpenetrating networks of modified chitosan and poly(vinyl alcohol)(PVA) via frozen-thawing induced chemical cross-linking.The synthesized hydrogels exhibit high mechanical strength(0.23 MPa tensile strength at 140% tensile strain,1.0 MPa compressive strength at 80% compressive strain).Strong green emission was realized by energy transfer from the modified chitosan to Tb^(3+)via the so-called "antenna effect." The prepared luminescent hydrogels show an excellent detection effect on nitroaromatic compounds and its detection limit can reach ppm-level.The hydrogels also exhibit good reversibility and a fast "off-on" fluorescence switching process.This work may open up a new way for the development of stable,rapid,and reusable sensors for the detection of harmful nitroaromatics.

Nanostructured Ni-MoCx:An efficient non-noble metal catalyst for the chemoselective hydrogenation of nitroaromatics

Catalysts for chemoselective hydrogenation are of vital importance for the synthesis of various important chemicals and intermediates.Herein we developed a simple method for preparing a highly efficient Ni-MoC_(x)nanocomposite catalyst via temperature-programmed carburization of a polyoxometalate precursor.X-ray diffraction(XRD),scanning transmission electron microscopy(STEM),X-ray photoelectron spectroscopy(XPS),and X-ray absorption spectroscopy(XAS)analyses indicate that the resulting mesoporous nanocomposite catalyst is made up of well-dispersed metallic nickel particles embedded in a MoC_(x)matrix.This catalyst exhibits high activity and selectivity(>99%)in the hydrogenation of various substituted nitroaromatics to corresponding anilines.The high efficiency is attributed to the intimate contact of the constituents favoring electron transfer and hydrogen adsorption.Dihydrogen is physisorbed on the carbide support and dissociates on the nickel particles,as evidenced by Mo K-edge X-ray absorption near-edge structure(XANES)spectra,density functional theory(DFT),and hydrogen-deuterium exchange.The remarkable catalytic performance of the catalyst could be traced back to the synergistic interaction between the Ni particles and the carbide support.In-situ infrared spectroscopy and DFT simulations indicated that the adsorption/activation of the nitro group is favored compared to that of other substituents at the aromatic ring.In recyclability tests,the Ni-MoC_(x)nanocomposite showed no significant loss of catalytic performance in seven consecutive runs,indicating its robust nature.

2D/3D-QSAR comparative study on mutagenicity of nitroaromatics

Nitroaromatics are typical toxic organic pollutants and are ubiquitous in environment with diverse structures. They are widely used in many industries and formed during many natural and anthropogenic processes. Most of these pollutants are potentially carcinogenic and the as-sessment and prediction of the mutagenicity of nitroaromatics are of great interest. In this paper the structure-mutagenicity relationships of 219 nitroaromatics are investigated by molecular or-bital theory based classic structure-activity relationships and comparative molecular field analysis (CoMFA). A comparison is undertaken in respect of the interpretation of mechanism and predic-tive ability for these two categories of QSAR approaches and highly predictive QSAR models have been developed.

General Reductive Amination of Aldehydes and Ketones with Amines and Nitroaromatics under H2 by Recyclable Iridium Catalysts

Heterogeneous iridium catalysts were prepared and applied for the reductive amination of aldehydes and ketones with nitroaromatics and amines using H2. The iridium catalysts were prepared by pyrolysis of ionic liquid 1-methyl-3-cyanomethylimidazoulium chloride （[MCNI]C1） with iridium chloride （IrC13） in activated carbons. Iridium particles were well dispersed and stable in the N-doped carbon materials from [MCNI]C1 with activated carbon. The Ir@NC（600-2h） catalyst was found to be highly active and selective for the reductive amination of aldehydes and ketones using H2 and a variety of nitrobenzenes and amines were selectively converted into the corresponding secondary and tertiary amines. The Ir@NC（600-2h） catalyst can be reusable several times without evident deactivation.

Non-contact biomimetic mechanism for selective hydrogenation of nitroaromatics on heterogeneous metal nanocatalysts

While the enzymatic reduction of unsaturated compounds usually has high specificity,highly selective reduction processes are hardly realized by heterogeneous industrial catalysts,which is critical for the green production of many fine chemicals.Here,we report an unexpected discovery of a biomimetic behavior of dicyandiamide(DICY)-modified Pt nanocatalysts for the green hydrogenation of a wide range of nitroaromatics.We demonstrate that the surface modification by DICY not only prevents the direct contact of nitroaromatic reactants with Pt surface but also induces an effective non-contact hydrogenation mechanism mediated by protons and electrons.In such a process,the DICY layer serves as a“semi-permeable membrane”to allow the permeation of H_(2) molecules for being activated into electrons and protons at the Pt-DICY interface.With the generation of separated protons and electrons,the nitro group with strong electrophilic properties can be hydrogenated through the electron transfer followed by the proton transfer,which is facilitated by the hydrogen bonding network formed by protonated DICY.The unique mechanism makes it highly directional toward the hydrogenation of nitro groups without side reactions.Owing to its capability to largely eliminate the waste generation,the developed Pt-DICY catalysts have been successfully applied for the green industrial production of many important aniline intermediates.

Effects of Nitrobenzenes on DNA Damage in Germ Cells of Rats

The single cell gel electrophoresis （SCGE） technique was used to detect DNA damage in germ cells of rats, which was induced by five tested nitroaromatic compounds. Mixed cultures of Sertoli and germ cells were prepared from the rats testis and their responses to rn-dinitrobenzene （ m-DNB）, 2,4-dinitrotoluene （ 2,4-DNT）, 2,6-dinitroto-luene（2,6-DNT）, 4-nitrotoluene（4-NT） and 2,4-dinitroaniline（2,4-DNAn） were studied. The results show that all the five chemicals have a reproductive toxicity. Each dose group and the control group were significantly different （ P 〈 0. 01 ）. All of them can lead to the damage to DNA in the germ cells of Kunming male rats in the definite range of concentration（m-DNB ： 0. 04-25μmol/L; 2,4-DNT, 2,6-DNT and 4-NT： 0. 032-500μmol/L; 2,4-DNAn ：0. 8-20μmol/L）. When the concentration increases, the damage rate will become higher, which shows an evident logarithm dose-effect relationship.

Effect of background electrolytes on the adsorption of nitroaromatic compounds onto bentonite

To further elucidate interaction of nitroaromatic compounds with mineral surface, the sorption of m-dinitrobenzene （m-DNB） and nitrobenzene to original bentonite in aqueous solution containing different electrolytes （i.e., KCl, NH4Cl, CaCl2 and Tetramethylammonium bromide （TMAB）） was studied. The sorption of m-DNB was greatly enhanced with the presence of KCl and NH4Cl, while little influence was observed with CaCl2 and TMAB, following the order of KCl 〉 NH4Cl 〉〉 TMAB, CaCl2, or DI water. For nitrobenzene, sorption enhancement only occurred at high nitrobenzene concentrations in the presence of KCl, and the solute equilibrium concentration at inflexion point was lowered with increasing KCl concentration. These sorption enhancements were significantly promoted with the increase of electrolyte concentration. The salting-out effect is insufficient to account for the sorption enhancement by original bentonite with increasing KCI or NH4Cl concentration. X-ray diffraction patterns of bentonite suspensions indicated that the sorption enhancement of m-DNB was attributed to the intercalation of K^＋ or NH4^＋ into bentonite interlayer and then dehydration with m-DNB to form inner-sphere complexes, which caused previously expanded bentonite interlayers to collapse in aqueous suspension, thus further enhanced the interaction of phenyl with siloxane surface. In comparison, the sorption enhancement of NB is attributed to the formation of outer-sphere complexes with K^＋ at high solute-loadings （〉 20（0-400 mg/kg）. The sorption of m-DNB to initially modified TMA^＋-bentonite and K^＋-bentonite was almost the same as respective sorption to original bentonite in solution containing TMA^＋ and K^＋.

Structural Characterization and Acute Toxicity Simulation for Nitroaromatic Compounds

The three-dimensional holographic vector of atomic interaction field（3D-Ho VAIF） is used to characterize the molecular structures of 45 nitroaromatic compounds.Two quantitative structure-toxicity relationship（QSAR） models are built up by stepwise regression（SMR）,multiple linear regression（MLR） and partial least-squares regression（PLS）.The correlation coefficients（R） of the models are 0.960 and 0.961,respectively.Then the models are evaluated by performing the cross-validation with the leave-one-out（LOO） procedure and the correlation coefficients（RCV） are 0.949 and 0.941,respectively.The results show that the descriptors can successfully describe the structures of organic compounds.The stability and predictability of the model are satisfactory.

Quantitative structure activity relationships for carp kidney ATPase endpoint

The IC 50 values of 20 nitroaromatics were determined by the activity of ATPase of carp ( Cyprinus carpio ) kidney in vitro, and used to develop the quantitative structure activity relationship (QSAR) with 6 descriptors of 1 X v, Σσ -, I , 1 Ka , E LUMO , log P . A best equation was obtained by multiple regression analysis -log IC 50 =1 306 Σσ -+0 657 I +0 584E LUMO +2 852( r =0 925). Σσ - is the sum of substituent constants. I is the indicator variable. E LUMO is the energy of the lowest unoccupied orbital. Results showed that the Σσ -, I and E LUMO were closely correlated with toxicity of nitroaromatics. Some toxicity mechanisms by nitroaromatics are also discussed in this paper.

QSPR of Thermal Stability of Nitroaromatic Explosives Using Theoretical Descriptors Derived from Electrostatic Potentials on the Molecular Surface

In the present study,geometrical optimization and electrostatic potential calcula-tions have been performed for 22 nitroaromatic compounds at the HF/6-31G level of theory.A number of statistically based parameters have been obtained.Linear relationship between the decomposition enthalpy（taken as a macroscopic property related to explosibility） of nitroaromatic compounds and the structural descriptors have been established by multiple regression method.The result shows that the quantities derived from electrostatic potentialsΣ V sind＋,,Vsind- and Vs,max can be well used to express the quantitative structure-decomposition enthalpy relationship of nitroa-romatic compounds,which proves the general applicability of this parameter set to a great extent.Good predictive capabilities have also been demonstrated.

Reductive Metabolism of Nitroaromatic Compounds by Various Liver Microsomes

Nitroaromatic compounds were reductively metabolized to the corresponding amine compounds via the intermediate hydroxylamines by liver microsomes from pig,rat,chook,cattle,sheep,paralichthys olivaceus and cyprinoid in varied reactivity.Similar with baker＇s yeast,the pig,rat and sheep liver microsomes exhibited high reactivity toward 4-nitro-1,2-dicyanbenzen（1a）,while the cyprinoid liver microsomes were inefficient.Contrasted to compound 1a,monocyannitrobenzene（2a） was difficult to reduce by pig liver microsomes.In opposition to grape cells,pig liver microsomes exhibited activities toward some aromatic hydroxylamine compounds.

Linear and Nonlinear QSPR Models for Predicting Thermal Stabilities of Nitroaromatic Compounds

Quantitative structure-property relationships（QSPRs） have been developed to predict the thermal stability for a set of 22 nitroaromatic compounds by means of the theoretical descriptors derived from electrostatic potentials on molecular surface. Several techniques, including partial least squares regression（PLS）, least-squares support vector machine（LSSVM） and Gaussian process（GP） have been utilized to establish the relationships between the structural descriptor and the decomposition enthalpy. The nonlinear LSSVM and GP models have proven to own a better predictive ability than the linear PLS method. Moreover, owing to its ability to handle both linear- and nonlinear-hybrid relationship, GP gives a stronger fitting ability and a better predictive power than LSSVM, and therefore could be well applied to developing QSPR models for the thermal stability of nitroaromatic explosives.

通过与钌合金化来调控铂的电子结构促进以水为质子源的光催化选择性加氢

调控金属活性位点的电子结构来发展高活性的选择性加氢反应催化剂对于可持续有机合成非常重要.但时至今日,这仍然是非常具有挑战性的课题.在本文中,我们将具有电子结构调节特性的超细PtRu合金纳米颗粒负载在CdS纳米棒上,成功构建了PtRu/CdS复合催化剂并研究了其光催化芳香族硝基化合物氢化还原性能.我们发现当以水为质子源时,所得复合催化剂表现出高效的光催化加氢活性.超快光谱研究和密度泛函理论计算揭示了合金的形成促进了光生载流子的分离并降低了氢化还原反应中决速步的能垒,从而显著提高了加氢活性.本研究通过合金化效应调节助催化剂的电子结构,为高活性助催化剂/光催化剂体系的理性设计开辟了一条新途径.

Rational design of an AIE-active metal-organic framework for highly sensitive and portable sensing nitroaromatic explosives

Herein,we report a new metal-organic framework with an AIE ligand (H_(4)TCPP=2,3,5,6-tetra-(4-carboxyphenyl)pyrazine) and Mg^(2+) ions,that is,[Mg_(2)(H_(2)O)_(4)TCPP]·DMF·5CH_(3)CN (Mg-TCPP,TCPP=tetra-(4-carboxyphenyl)pyrazine) for detection of nitroaromatic explosives.Due to the coordination effect and restricted intramolecular rotation,Mg-TCPP exhibits bright blue light.As a fluorescent sensor,Mg-TCPP exhibits high selectivity and sensitivity for sensing 2,4,6-trinitrophenol (TNP) by quenching behaviors with the Stern-Volmer quenching constant (K_(SV)) of 3.63×10^(5)L/mol and achieves the low limit of detection of 25.6 ppb,which is beyond most of the previously reported fluorescent materials.Notably,the portable Mg-TCPP films are prepared and it can be used for rapid and sensitive TNP detection in a variety of environments including organic solvent and aqueous solution.Moreover,TNP vapor can be detected within 3 min by naked eye and the film could be regenerated under simple solvent cleaning.

A Fluorescent In (Ⅲ) Metal-Organic Framework for Explosives Detection

Anovel metal-organic framework{[In_(3)(TATAT)_(2)]·3CH_(3)NH_(3)·7NMF·8H_(2)O}[JLU-MOF101,H_(6)TATAT=5,5′,5″-(1,3,5-triazine-2,4,6-triyl)tris-(azanediyl)triisophthalate,NMF=N-methyl-formamide]with cor topology has been synthesized under solvothermal conditions.The framework of JLU-MOF101 is constructed by{In(COO)_(4)}-nodes and a hexacarboxylic organic ligand.JLU-MOF101 exhibits excellent fluorescence properties in N,N-dimethylformamide(DMF)solution,and its emission spectrum can be greatly overlapped with the ultraviolet absorption spectra of trinitrophenol(TNP)and 2,4-dinitrophenol(2,4-DNP).As a result,JLU-MOF101 exhibits excellent performance of fluorescence quenching for TNP and 2,4-DNP.In addition,we demonstrate the selective detection capability of JLU-MOF101 through a large number of anti-interference tests.

DFT Study on the QSAR of Nitroaromatic Compound Toxicity to the Fathead Minnow

The DFT-B3LYP method, with the basis set 6-311G, was employed to calculate the molecular geometries and electronic structures of 31 nitroaromatics. EHOMO, ELUMO, QC, QN. QNO2 and μ were selected as quantum chemical descriptors. The acute toxicity （-lg LC50） of these compounds to the fathead minnow along with the six descriptors was used to establish the quantitative structure-activity relationships （QSARs）, Through stepwise multiple linear regression analysis, a model was established as follows： -lg LC50=9.524-39.527ELUMO＋16.859EHOMO＋15.130QNO2＋4.166QC （n=28, R=0.912, SE=0.361, F=28.468）. The model was applied to predict and elucidate the toxicity of nitroaromatics successfully. Furthermore, a metabolic route of nitroaromatics in fathead minnow was proposed.

Ligand controlled structure of cadmium(Ⅱ) metal-organic frameworks for fluorescence sensing of Fe^(3+) ion and nitroaromatic compounds

Three cadmium(II) metal-organic frameworks(MOFs) based on tetracarboxylate ligands, namely[Cd_2(TTTA)(DMF)_3]·2 DMF(1),[Cd_2(TB)(H_2O)_4]·3DMF·H_2O(2)and [Cd(TEB)_(0.5)].2 DMF.4 H_2O(3) have been designed and synthesized. Complex 1 is a 2-dimensional(2 D) 3,4-connected network with 3,4 L13 topology, complex 2 features a 3-dimensional(3D) 3,4-connected tfa topology with a 2-fold interpenetrating structure and complex 3 has a 3D 4-connected dia topology with a 4-fold interpenetrating structure. Interestingly, 2 exhibits permanent pores and selective adsorption of CO_2 over CH_4. In addition, 2 shows fluorescence sensing of Fe^(3+) ion and rapid detection of nitroaromatic compounds(NACs) through fluorescence quenching.

Detection of Picric Acid by Terpy-Based Metallo- Supramolecular Fluorescent Coordination Polymers in Aqueous Media

The synthesis of two linear terpy-based metallo-supramolecular fluorescent coordination polymers through 1 ： 1 complexation of Zn^2＋ and Cd^2＋ ions with ditopic terpyridine ligand was reported. The dispersibility of P1 and P2 was significantly improved in organic solvent and water through the introduction of hydrophilic oligo-ethyoxy side chain. Two polymers displayed yellow light emission both in solution and the solid state due to the intra-ligand charge transfer （ILCT） between the d^10 metal ions and the conjugated spacer unit. These coordination polymers were explored as fluorescent chemosensors for detecting picric acid in aqueous media, displaying high sensitivity and good selectivity. In addition, test strips were prepared from these polymers and exhibited the practical potential of detecting the NACs pollutants in the outdoor water for public safety and security.