Effects of electrolytes on the reduction of 2,4‐dinitrotoluene by zero‐valent iron

BACKGROUND: Dinitrotoluenes (DNTs) are environmentally persistent, making the remediation of contaminated streams and groundwater difficult. Zero‐valent iron (Fe⁰) can be used as an electron source for the reduction of recalcitrant DNTs in waste‐water and thus enhance their biodegradability. However, little is known about the qualitative effects of major anions and cations present in waste‐water on the reduction of DNTs by Fe⁰. RESULTS: The presence of Na₂SO₄ and NaCl at levels between 0.25 and 2 mmol L^?1 was observed to enhance the reactivity of Fe⁰ towards 2,4‐DNT. The positive effect of K₂SO₄ is stronger than that of Na₂SO₄ at the same level (1 mmol L^?1). Varying (NH₄)₂SO₄ from 0.1 to 1.0 mmol L^?1 improved the efficiency of 2,4‐DNT degradation by Fe⁰. The effects of varying NaNO₃ and NaNO₂ from 0 mmol L^?1 to 4.7 mmol L^?1 and 0 mmol L^?1 to 5.8 mmol L^?1, respectively, were also investigated. Both NaNO₃ and NaNO₂ at low concentration improved the efficiency of 2,4‐DNT degradation by Fe⁰, however, at high concentration, inhibiting effects appeared. CONCLUSION: SO₄^2?, Cl^?, Na⁺, K⁺ and NH₄⁺ notably enhanced 2,4‐DNT reduction by Fe⁰ at the tested concentrations. The positive effect of K⁺, Cl^? was relatively stronger than that of Na⁺ and sulfate (SO₄^2?). However, the effect of NH₄⁺ was relatively weaker at concentrations greater than 1.0 mmol L^?1. The presence of low concentrations of NO₃^? and NO₂^? promoted 2,4‐DNT reduction by Fe⁰ and inhibited the reaction. The results suggest that 2,4‐DNT reduction by Fe⁰ can be controlled by the ions composition of the waste‐water. Copyright © 2010 Society of Chemical Industry     

The effect of three chemical oxidants on subsequent biodegradation of 2,4‐dinitrotoluene (DNT) in batch slurry reactors

BACKGROUND: Recent studies indicate that chemical oxidation may be compatible with subsequent biodegradation in contaminated soils. To test this, soil contaminated with 2,4‐dinintrotoluene (2,4‐DNT) was treated in batch slurry reactors with (1) ozone, (2) modified Fenton chemistry (MFC), and (3) iron‐activated sodium persulfate (SPS). Chemical and subsequent biological oxidation were monitored, and compared with biodegradation alone. Release of nitrite and nitrate distinguished biological from chemical oxidation of 2,4‐DNT, respectively. DNT‐degrading microorganisms were enumerated. The disappearance of volatile fatty acids (VFAs) accumulated during chemical oxidation was also monitored. RESULTS: In the biological reactor 66% of the 2,4‐DNT was degraded, but further biodegradation was inhibited by nitrite concentrations approaching 18 mmol L^?1. At the doses tested, all oxidants achieved chemical oxidation followed by biodegradation, resulting in 98% DNT removal overall. Ozone achieved the greatest DNT removal (70%), but also caused the greatest reduction in DNT degraders and the longest rebound time (60 days) before biodegradation of the remaining DNT and VFAs. SPS resulted in the least DNT removal by chemical oxidation (37%), but showed no obvious rebound period for DNT degraders, and even signs of co‐existing chemical and biological oxidation. By releasing nitrate, which is less toxic than nitrite, the oxidants kept nitrite levels below 18 mmol L^?1, enabling the follow‐on biodegradation step to attain lower concentrations of 2,4‐DNT than biodegradation alone. CONCLUSIONS: All three chemical oxidants were compatible with biodegradation of residual 2,4‐DNT. Post‐oxidation bioremediation should be included in remedial designs. Copyright © 2009 Society of Chemical Industry     

Characterization of 4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine

4,6‐Diazido‐N‐nitro‐1,3,5‐triazine‐2‐amine (DANT) was prepared with a 35 % yield from cyanuric chloride in a three step process. DANT was characterized by IR and NMR spectroscopy (¹H, ¹³C, ¹⁵N), single‐crystal X‐ray diffraction, and DTA. The crystal density of DANT is 1.849 g cm⁻³. The cyclization of one azido group and one nitrogen atom of the triazine group giving tetrazole was observed for DANT in a dimethyl sulfoxide solution using NMR spectroscopy. An equilibrium exists between the original DANT molecule and its cyclic form at a ratio of 7 : 3. The sensitivity of DANT to impact is between that for PETN and RDX, sensitivity to friction is between that for lead azide and PETN, and sensitivity to electric discharge is about the same as for PETN. DANT′s heat of combustion is 2060 kJ mol⁻¹.     

Molecular Recognition of Two 2,4‐syn‐Functionalized (S)‐Glutamate Analogues by the Kainate Receptor GluK3 Ligand Binding Domain

The kainate receptors are the least studied subfamily of ionotropic glutamate receptors. These receptors are thought to have a neuromodulatory role and have been associated with a variety of disorders in the central nervous system. This makes kainate receptors interesting potential drug targets. Today, structures of the ligand binding domain (LBD) of the kainate receptor GluK3 are only known in complex with the endogenous agonist glutamate, the natural product kainate, and two synthetic agonists. Herein we report structures of GluK3 LBD in complex with two 2,4‐syn‐functionalized (S)‐glutamate analogues to investigate their structural potential as chemical scaffolds. Similar binding affinities at GluK3 were determined for the 2‐(methylcarbamoyl)ethyl analogue (K_i=4.0 μM ) and the 2‐(methoxycarbonyl)ethyl analogue (K_i=1.7 μM ), in agreement with the similar positioning of the compounds within the binding pocket. As the binding affinity is similar to that of glutamate, this type of Cγ substituent could be used as a scaffold for introduction of even larger substituents reaching into unexplored binding site regions to achieve subtype selectivity.     

Elaboration and thermal analysis of nanocomposites based on poly(methyl methacrylate‐co‐4‐vinylpyridine) and Maghnia bentonite

Nanocomposites based on an organically modified bentonite, from Maghnia Algeria (OBT) and a copolymer of methyl methacrylate with 4‐vinylpyridine (PMM4VP) synthesized in dioxan at room temperature using a neutral Ni(II)α‐benzoinoxime complex as a single component initiator, were elaborated via solution intercalation method and characterized by several techniques. X‐ray diffraction and transmission electron microscopy investigations indicate that mainly exfoliated and intercalated PMM4VP/OBT nanocomposites were elaborated and that the degree of exfoliation decreases with an increase of the OBT loading. Thermal analyses of these nanocomposites compared with their virgin copolymer confirmed a significant improvement of their thermal stability as evidenced by an increase of 28°C in their onset degradation temperatures. In addition, differential scanning calorimetry displayed an increase in the range of 12–18°C in their glass transition temperatures relative to their virgin copolymer. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The fate of iron during the alkali‐activation of synthetic (CaO‐)FeOx‐SiO2 slags: An Fe K‐edge XANES study

Slags from the nonferrous metals industry have great potential to be used as feedstocks for the production of alkali‐activated materials. Until now, however, only very limited information has been available about the structural characteristics of these materials. In the work presented herein, synthetic slags in the CaO–FeO_x–SiO₂ system, representing typical compositions of Fe‐rich slags, and inorganic polymers (IPs) produced from the synthetic slags by activation with alkali silicate solutions have been studied by means of X‐ray absorption near‐edge structure (XANES) spectroscopy at the Fe K‐edge. The iron in the slags was largely Fe²⁺, with an average coordination number of approximately 5 for the iron in the amorphous fraction. The increase in average oxidation number after alkali‐activation was conceptualized as the consequence of slag dissolution and IP precipitation, and employed to calculate the degrees of reaction of the slags. The degree of reaction of the slags increased with increasing amorphous fraction. The iron in the IPs had an average coordination number of approximately 5; thus, IPs produced from the Fe‐rich slags studied here are not Fe‐analogs of aluminosilicate geopolymers, but differ significantly in terms of structure from the latter.     

Preparation of polystyrene/toluene‐2,4‐ di‐isocyanate–modified montmorillonite hybrid

A novel selective interlamellar modification of cetyltrimethylammonium bromide‐exchanged montmorillonite (MMT) by toluene‐2,4‐di‐isocyanate (TDI) has been successfully obtained, and a polystyrene/TDI‐modified MMT hybrid has been prepared. After the interlamellar modification, TDI was grafted to hydroxyl groups of the MMT, and the orientation of cetyltrimethylammonium in the interlayer space changed from a bilayer lying flat structure to a double‐layer inclined one. The structures of the TDI‐modified MMT and the hybrid were characterized by Fourier transform infrared (FTIR) spectra, powder X‐ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. A schematic model of the TDI‐modified MMT structure was also presented. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2201–2205, 2000     

Synthesis and Characterization of 3,4,5‐Triamino‐1,2,4‐Triazolium 5‐Nitrotetrazolate

3,4,5‐Triamino‐1,2,4‐triazolium 5‐nitrotetrazolate ( 2 ) was synthesized in high yield from 3,4,5‐triamino‐1,2,4‐triazole (guanazine) ( 1 ) and ammonium 5‐nitrotetrazolate. The new compound 2 was characterized by vibrational (IR and Raman) and multinuclear NMR spectroscopy (¹H, ¹³C, ¹⁵N), elemental analysis and single crystal X‐ray diffraction (triclinic, P(‐1), a=0.7194(5), b=0.8215(5), c=0.8668(5) nm, α=75.307(5), β=70.054(5), γ=68.104(5)°, V=0.4421(5) nm³, Z=2, ϱ=1.722 g cm⁻¹, R₁=0.0519 [F>4σ(F)], wR₂(all data)=0.1154). The ¹⁵N NMR spectrum and X‐ray crystal structure (triclinic, P‐1, a=0.5578(5), b=0.6166(5), c=0.7395(5) nm, α=114.485(5)°, β=90.810(5)°, γ=97.846(5)°, V=0.2286(3) nm³, Z=2, ϱ=1.658 g cm⁻¹, R₁=0.0460 [F>4σ(F)], wR₂(all data)=0.1153) of 1 were also determined.     

Preparation and characterization of ceria nanoparticles supported on poly(4‐vinyl pyridine‐co‐divinyl benzene)

Formation of ceria nanoparticles in 2% divinyl benzene (dvb) crosslinked 4‐vinyl pyridine (4vp) polymer [poly(4vp‐co‐dvb)] microspheres was investigated. The polymer was prepared by free radical suspension polymerization method. Poly(4vp‐co‐dvb)/ceria nanocomposites were prepared by reacting CeCl₃·7H₂O and NaOH in the presence of poly(4vp‐co‐dvb) at room temperature in aqueous media. The mole ratio of the metal to polymer was varied from 2.5 to 10% with an increment of 2.5. The polymer and nanocomposities were characterized by various spectrochemical methods. The coordination of nitrogen atoms of the polymer with Ce(IV) of ceria (CeO₂) has been confirmed from X‐ray photoelectron spectroscopy (XPS). The method has yielded ceria nanoparticles in an average size of 15 nm according to transmission electron microscopy. Differential scanning calorimetry, thermogravimetric analysis, X‐ray diffractometry and XPS analysis with respect to mole percentage of ceria in the composite are discussed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3439–3445, 2006     

Structural Investigation of the Binding of 5‐Substituted Swainsonine Analogues to Golgi α‐Mannosidase II

Golgi α‐mannosidase II (GMII) is a key enzyme in the N‐glycosylation pathway and is a potential target for cancer chemotherapy. The natural product swainsonine is a potent inhibitor of GMII. In this paper we characterize the binding of 5α‐substituted swainsonine analogues to the soluble catalytic domain of Drosophila GMII by X‐ray crystallography. These inhibitors enjoy an advantage over previously reported GMII inhibitors in that they did not significantly decrease the inhibitory potential of the swainsonine head‐group. The phenyl groups of these analogues occupy a portion of the binding site not previously seen to be populated with either substrate analogues or other inhibitors and they form novel hydrophobic interactions. They displace a well‐organized water cluster, but the presence of a C(10) carbonyl allows the reestablishment of important hydrogen bonds. Already approximately tenfold more active against the Golgi enzyme than the lysosomal enzyme, these inhibitors offer the potential of being extended into the N‐acetylglucosamine binding site of GMII for the creation of even more potent and selective GMII inhibitors.     

The influence of thermal treatment and processing on the structure and morphology of poly(propylene‐ran‐1‐butene) copolymers

New poly(propylene‐ran‐1‐butene) copolymers were analyzed to study the influence of different processing techniques on their structure and morphology. Wide‐angle X‐ray diffraction allowed determination of the percentage of the γ form and the crystallinity in the samples and also the influence of the percentage of 1‐butene on the cell parameters. Furthermore, it was possible to appraise the contributions of different stacks of lamellae to the small‐angle X‐ray diffraction patterns. © 2001 Society of Chemical Industry     

Kinetics of reductive degradation of Orange II in aqueous solution by zero‐valent iron

The reductive degradation of Orange II in aqueous solution by zero‐valent iron was investigated. The degradation of Orange II followed pseudo‐first‐order kinetics at various pH values and initial Orange II levels, but the formation of sodium sulfanilate, a major reductive product of Orange II, followed zero‐order kinetics. Copyright © 2004 Society of Chemical Industry     

Carbon/carbon composites derived from poly(ethylene oxide)‐modified novolac‐type phenolic resin: Microstructure and physical,and morphological properties

A poly(ethylene oxide) (PEO) novolac‐type phenolic resin blend was prepared by the physical blending method. The modified novolac‐type phenolic resin with various PEO contents was used as a matrix precursor to fabricate carbon/carbon composites. The effect of the PEO/phenolic resin mixing ratio on the change of the density and of the porosity was studied. The flexural strength and interlaminar shear strength of the PEO/phenolic resin blend‐derived carbon/carbon composites were also investigated. The results show that the density of the PEO/phenolic resin blend‐derived carbon/carbon composites decreases with the PEO content. The X‐ray diffraction and Raman spectra studies showed that the carbon fiber in the samples will affect the growth of the ordered carbon structure. From SEM morphological observation, it is shown that the fracture surface of specimens is smooth. Also, there is less fiber pull‐out and fiber breakage on the fracture surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1609–1619, 2002; DOI 10.1002/app.10407     

Eu2+‐doped strontium aluminum silicon nitrides having α‐SiAlON and polytypoid structures

Yellow single crystals of aluminum silicon nitrides containing strontium and europium were prepared by heating starting mixtures of Sr₃N₂, Si₃N₄, AlN, and EuN at 2050°C and 0.85 MPa of N₂ for 8 hours. Single‐crystal X‐ray diffraction revealed that prismatic crystals 20‐100 μm in size were Sr_0.31Al_0.62Si_11.38N₁₆:Eu (trigonal, a=7.7937(2) Å, c=5.6519(2) Å, space group P31c), which are isotypic with Sr‐α‐SiAlON, Sr_m/2Al_m+nSi_12?m?nN_16?nO_n, with m=0.62 and n=0. The Eu²⁺ content was approximately 1 at.% of Sr contained in the framework of corner‐sharing (Al/Si)N₄ tetrahedra with an occupancy of 0.154(2). Block‐shaped crystals with a side length of 50‐300 μm were a new polytypoid of Sr‐α‐SiAlON, Sr_2.97Eu_0.03Al₆Si₂₄N₄₀. Streak lines were observed in the direction of the c* axis in the X‐ray oscillation photographs, indicating stacking faults of the structure. The fundamental X‐ray reflections were indexed with a hexagonal cell (a=7.9489(3) Å, c=14.3941(6) Å). The structure was analyzed with a model of space group P in which one of the six Al/Si sites was statistically split into two sites with occupancies of 0.673(5) and 0.227(5). The atomic arrangements in the layers of the structure were similar to those of Sr‐α‐SiAlON, but the stacking sequences of the layers were different. The peak wavelengths and full widths at half maximum of emission spectra measured for the single crystals of Sr_0.31Al_0.62Si_11.38N₁₆:Eu and Sr_2.97Eu_0.03Al₆Si₂₄N₄₀ were 583 nm and 87 nm, and 584 nm and 91 nm, respectively, under 400 nm wavelength light excitation at room temperature.     

Structure and characterization of poly[(vinylidene fluoride)‐co‐hexafluoropropene]–(dibutyl phthalate) blends

Blends of poly[(vinylidene fluoride)‐co‐hexafluoropropene] with dibutyl phthalate were examined by wide‐ and small‐angle X‐ray scattering, differential scanning calorimetry and dynamic mechanical spectroscopy, in order to study the influence of amount of plasticizer and the crystallization rate on the crystallinity and lamellar morphology of the copolymer. The dibutyl phthalate seems, at least for the cooling and heating rates used, simply to dilute the crystalline phase without affecting the amount of polymer that is able to crystallize. Furthermore, the small‐angle X‐ray scattering technique points out that the plasticizer mostly enters the amorphous phase either outside or inside the lamellar stacks. © 2001 Society of Chemical Industry     

Low‐temperature thermal graft copolymerization of 1‐vinyl imidazole on fluorinated polyimide films with simultaneous lamination of copper foils

A simple technique of thermal graft copolymerization of 1‐vinyl imidazole (VIDZ) on pristine and argon plasma pretreated fluorinated polyimide (FPI) films with simultaneous lamination of copper foils was demonstrated. The simultaneous thermal grafting and lamination process was carried out in the temperature range of 80–140°C under atmospheric conditions and in the complete absence of a polymerization initiator. Three different FPI samples of different chemical structures were employed in the present study. An optimum T‐peel strength about 15 N/cm was achieved for the copper/FPI laminate. The adhesion strength, however, decreased with increasing fluorine content in the FPI film. The onset of cohesive failure occurred in the FPI film for assemblies with T‐peel strength greater than 6 N/cm. The T‐peel strengths are reported as a function of the argon plasma pretreatment time of the FPI films and thermal lamination temperature. The adhesion strengths were compared to that of the similarly prepared copper/polyimide (Kapton HN) laminate. Time‐dependent water contact angle (Θ) measurements indicated that the surfaces of FPI films are significantly more hydrophobic and more resistant to water diffusion or hydration than the Kapton HN films. The surface compositions of the pristine FPI films, as well as the delaminated FPI films and copper foils were studied by X‐ray photoelectron spectroscopy. The thickness of the graft VIDZ polymer layer was in the order of 200 nm, as derived from the cross‐sectional view of the scanning electron micrograph. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1478–1489, 1999     

Structure of Urethane Copolymers of 3,3‐Bis(azidomethyl)oxetane and 3‐Azidomethyl‐3‐methyloxetane

Polyurethane copolymers of 3,3‐bis (azidomethyl) oxetane (BAMO) and 3‐azidomethyl‐3‐methyloxetane (AMMO) with molecular structures of types B(AB)n, A(AB)n, (BB)n and ABn with different ratios of oligomeric units were investigated, where A is the non‐crystallizable “soft” block of oligoAMMO and B is the “hard” block of oligoBAMO and the included urethane diol fragments. The amorphous‐crystalline structures of copolymers BAMO and AMMO were elucidated by wide angle X‐ray diffraction measurements. The influences of the molecular structure and the ratio of oligomeric units on the structural parameters were identified. The degree of crystallinity is in a range from 8 to 22 % and sizes of the crystallites were determined. The defectivenesses of first and second kind in the structure were evaluated, which show high values of the first kind defectiveness (approx. 20 %), which describes the displacement of theoretical lattice sites and the existence of unequal sizes of the lattice sites, and minor values for the second kind defectiveness (approx. 3 %), which describes the lattice site disorder in large distances. Small‐angle X‐ray diffraction measurements were used to investigate the domain structures of copolymers BAMO and AMMO. The distribution and sizes of the crystallites in the structures of the copolymers were calculated.