5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis,Crystal Structures and Performances

A new structural type for melt cast materials was designed by linking nitrotetrazole ring with 1,2,4-oxadiazole through a N-CH₂-C bridge for the first time. Three N-CH₂-C linkage bridged energetic compounds, including 3-((5-nitro-2H-tetrazol-2-yl) methyl)-1,2,4-oxadiazole (NTOM), 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-(trifluoromethyl)-1,2,4 -oxadiazole (NTOF) and 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-amine-1,2,4-oxadiazole (NTOA), were designed and synthesized through a two-step reaction by using 2-(5-nitro-2H-tetrazole -2-yl)acetonitrile as the starting material. The synthesized compounds were fully characterized by NMR (¹H, ¹³C), IR spectroscopy and elemental analysis. The single crystals of NTOM, NTOF and NTOA were successfully obtained and investigated by single-crystal X-ray diffraction. The thermal stabilities of these compounds were evaluated by DSC-TG measurements, and their apparent activation energies were calculated by Kissinger and Ozawa methods. The crystal densities of the three compounds were between 1.66 g/cm³ (NTOA) and 1.87 g/cm³ (NTOF). The impact and friction sensitivities were measured by standard BAM fall-hammer techniques, and their detonation performances were computed using the EXPLO 5 (v. 6.04) program. The detonation velocities of the three compounds are between 7271 m/s (NTOF) and 7909 m/s (NTOM). The impact sensitivities are >40 J, and the friction sensitivities are >360 N. NTOM, NTOF and NTOA are thermally stable, with decomposition points > 240 °C. The melting points of NTOM and NTOF are 82.6 °C and 71.7 °C, respectively. Hence, they possess potential to be used as melt cast materials with good thermal stabilities and better detonation performances than TNT.     

Crystallization of polypropylenewith a minute amount of β-nucleator

Triammonium-N-dithiocarboxyiminodiacetate, (NH₄)₃L, a new dithiocarbamato derivative of iminodiacetate, has been synthesized. The coordination properties of the ligand were tested in reactions with copper(II), nickel(II) and palladium(II) salts in acidic solutions. Complexes with a general formula M(H₂L)₂ were obtained, with the coordination taking place through the sulfur atoms of the dithiocarbamate moiety. The new compounds were characterized by elemental analysis, UV/VIS and IR spectroscopy, thermal analysis and magnetic measurements. In addition, the ligand was characterized by ¹H- and ¹³C-NMR spectroscopy and molar conductivity measurements. The copper(II) complex is paramagnetic, while the nickel(II) and palladium(II) compounds are diamagnetic. The thermal decomposition of all compounds is continuous and the thermal stability of the complexes is higher than that of the ligand, as expected.     

Thermal,Spectral and Antimicrobial Properties of New Zinc(II) Isobutyrate Compounds: Part I. Papaverine,Phenazone

Zinc carboxylate complexes with N-donor ligands exhibit antimicrobial and antifungal effects. The preparation and thermal properties of complex compounds Zn(isobut)₂ and Zn(isobut)₂L(isobut=(CH₃)₂CHCOO^–, L=papaverine — pap, phenazone — phen) are described in this paper. The newly synthesized compounds were characterized by elemental analysis, IR spectroscopy and TG/DTG, DTA methods.During the thermal treatment it was found that the release of organicligands (pap, phen) was followed by pyrolysis of zinc(II) isobutyrate. (C₃H₇)₂CO and CO₂ were found as gaseous products and zinc oxide as the final product of thermal decomposition. Gaseous and solid products of thermal decomposition were confirmed by chemical analysis, IR spectra and X-ray powder diffraction.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal expansion properties of organic crystals: a CSD study

The thermal expansion properties of crystalline organic compounds are investigated by data mining of the Cambridge Structural Database (CSD). The mean volumetric thermal expansion coefficient is 168.8 × 10⁻⁶ K⁻¹ and the mean uniaxial thermal expansion coefficient is 71.4 × 10⁻⁶ K⁻¹, based on 745 and 1129 different observations, respectively. Normal and anomalous coefficients can be identified using these values and the associated standard deviations. The anisotropy of the thermal expansion is also evaluated and found to have a very broad distribution. 4719 different structures, comprising 4093 different molecular compounds and 626 additional polymorphs have been analyzed on their thermal expansion properties. Approximately 34% of these structures may have at least one orthogonal axis with negative thermal expansion, much more than generally believed. Moreover 127 structures have been identified which could have negative volumetric thermal expansion. Experimental validation using a robust protocol with data collected at more than 2 different temperatures is required to validate these cases.

The thermal expansion properties of crystalline organic compounds are investigated by data mining of the Cambridge Structural Database (CSD). Negative uniaxial thermal expansion is much more common than generally believed.     

Analysis of inorganic mercury species associated with airborne particulate matter/aerosols: method development

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP–MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg⁰, HgCl₂, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50° min^–1, different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg⁰, HgCl₂, HgO, and HgS species from these samples were detected.     

31P NMR investigation of the structure of silica surfaces modified by phosphorus trichloride

The structure of the surface chemical compounds on modified pyrogenic silica has been studied in this work by ³¹P magic-angle-spinning NMR spectroscopy. It has been established that the surface silyl dichlorophospite groups (186 ppm) obtained as a result of the reaction of PCl³ with dehydrated silica are hydrolyzed upon the adsorption of water vapor with the formation of phosphorus acid. The thermal treatment of such samples in a vacuum is accompanied by the formation of condensed polyhydrophosphoryl structures.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 24, No. 5, pp. 629–633, September–October, 1988.     

The Solvent Effect on Composition and Dimensionality of Mercury(II) Complexes with Picolinic Acid

Three new mercury(II) coordination compounds, {[HgCl(pic)]}_n (1), [HgCl(pic)(picH)] (2), and [HgBr(pic)(picH)] (3) (picH = pyridine-2-carboxylic acid, picolinic acid) were prepared by reactions of the corresponding mercury(II) halides and picolinic acid in an aqueous (1) or alcohol–methanol or ethanol (2 and 3) solutions. Two different types of coordination compounds were obtained depending on the solvent used. The crystal structures were determined by the single-crystal X-ray structural analysis. Compound 1 is a one-dimensional (1-D) coordination polymer with mercury(II) ions bridged by chelating and bridging N,O,O′-picolinate ions. Each mercury(II) ion is four-coordinated with a bidentate picolinate ion, a carboxylate O atom from the symmetry-related picolinate ion and with a chloride ion; the resulting coordination environment can be described as a highly distorted tetrahedron. Compounds 2 and 3 are isostructural mononuclear coordination compounds, each mercury(II) ion being coordinated with the respective halide ion, N,O-bidentate picolinate ion, and N,O-bidentate picolinic acid in a highly distorted square-pyramidal coordination environment. Compounds 1–3 were characterized by IR spectroscopy, PXRD, and thermal methods (TGA/DSC) in the solid state and by ¹H and ¹³C NMR spectroscopy in the DMSO solution.     

Thermal and electrical studies on quinoxaline compounds of some first row transition metal ions

The chloro and bromo compounds of quinoxaline with manganese(II), cobalt(II), nickel(II) and copper(II) have been prepared in ethanolic solution. The thermal behaviour of these compounds was studied by thermogravimetry (TG) and differential thermal analysis (DTA). The thermal decomposition studies show that the compounds dichlorobis(quinoxaline) cobalt(II), dibromobis(quinoxaline) cobalt(II) and dibromobis(quinoxaline) manganese(II) form intermediate compounds before the metal halide is produced. The other compounds undergo decomposition with loss of organic ligand and the formation of the metal halide. Electrical conductivities at room temperature range from 1.4 × 10⁻⁶ Ω⁻¹ m⁻¹ for MnCl₂Q to 2.3 × 10⁻³ Ω⁻¹ m⁻¹ for both CoCl₂Q₂ and CoBr₂Q₂. There appears to be a correlation between electrical conductivity and coordination number of the metal atom. From the temperature dependence of conductivity, information has been obtained for donor or acceptor ionization energies. Decomposition temperature, as electrically determined, is in good agreement with the TG method.     

Validated Stability-Indicating GC-MS Method for Characterization of Forced Degradation Products of Trans-Caffeic Acid and Trans-Ferulic Acid

When dealing with simple phenols such as caffeic acid (CA) and ferulic acid (FA), found in a variety of plants, it is very important to have control over the most important factors that accelerate their degradation reactions. This is the first report in which the stabilities of these two compounds have been systematically tested by exposure to various different factors. Forced degradation studies were performed on pure standards (trans-CA and trans-FA), dissolved in different solvents and exposed to different oxidative, photolytic and thermal stress conditions. Additionally, a rapid, sensitive, and selective stability-indicating gas chromatographic-mass spectrometric method was developed and validated for determination of trans-CA and trans-FA in the presence of their degradation products. Cis-CA and cis-FA were confirmed as the only degradation products in all the experiments performed. All the compounds were perfectly separated by gas chromatography (GC) and identified using mass spectrometry (MS), a method that additionally elucidated their structures. In general, more protic solvents, higher temperatures, UV radiation and longer storage times led to more significant degradation (isomerization) of both trans-isomers. The most progressive isomerization of both compounds (up to 43%) was observed when the polar solutions were exposed to daylight at room temperature for 1 month. The method was validated for linearity, precision as repeatability, limit of detection (LOD) and limit of quantitation (LOQ). The method was confirmed as linear over tested concentration ranges from 1−100 mg L⁻¹ (r²s were above 0.999). The LOD and LOQ for trans-FA were 0.15 mg L⁻¹ and 0.50 mg L⁻¹, respectively. The LOD and LOQ for trans-CA were 0.23 mg L⁻¹ and 0.77 mg L⁻¹, respectively.     

Elaboration and Characterisation of Hybrid Materials of Polymethylhydrosiloxane Modified by Diamines of Various Lengths

The polymethylhydrosiloxane (PMHS) modified by bifunctional organic compounds (diamines), offer the possibility of producing organic-inorganic hybrid materials. These materials present excellent opto-electronic properties and find numerous applications such as the manufacture of electroluminescent diodes and ion or radiation sensors.This work shows that monolithic and transparent hybrid gels were obtained by reaction at room temperature of PMHS with diamines in tetrahydrofuran, using hexachloroplatinic acid (H₂PtCl₆·6H₂O) as catalyst. The products have been characterized by infrared and ²⁹Si MAS-NMR spectroscopy. The results show that the diamines have reacted with the PMHS leading to the monolithic and transparent gels in which both organic-inorganic —Si—(H)N—(CH₂) _n —N(H)—Si— bridges are formed (n = 3, 4 and 6). The thermal analysis of the xerogels was determined by TGA and DTA. The structure and texture of the obtained materials, were studied by Chemical Analysis and the Brunauer-Emmett-Teller (BET) method.     

Phenolic-iodine Redox Products: Mass Spectrometry,Thermal and Other Physico-chemical Methods of Analyses

Three interesting new compounds formed as a result of phenols-iodine redox reactions were investigated by mass spectral fragmentation (MS) and thermal analyses (TA) as well as some other physicochemical methods as microanalysis and infra-red spectroscopy to elucidate their structures. The characterization of the compounds was satisfactorily achieved by using the above analytical tools and their proposed general formulae, were found to be C₂₄H₁₅O₈I (PC-IO ₃ ^– ), C₂₄H₁₄O₁₂ I₂ (PG-IO ₃ ^– ) and C₁₂H₈O₆I₂ (PG-IO ₄ ^– ).The fragmentation pathways of PC-IO ₃ ^– , PG-IO ₃ ^– and PG-IO ₄ ^– have been examined using electron ionization (EI) mass spectrometry in comparison with thermal analyses (TG and DTA). Both decomposition modes were investigated, and the fragmentation pathways were suggested. The combined application of mass spectrometry and thermogravimetry (MS and TG) in the analysis of the products allowed the characterization of the fragmentation pathway in MS.The major pathway in both techniques of PC-IO ₃ ^– is due to the loss of CHO followed by CH₃I+2H₂O. It is due to the loss of 2H₂O followed by the loss of 2CH₃I for PG-IO ₃ ^– . While for PG-IO ₃ ^– it is related to the loss of 2H₂O followed by loss of 2CH₃I molecule stepwise. Different stabilities for initial products and some fragments are discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Meloxicam and Study of Their Antimicrobial Effects against Phyto- and Human Pathogens

Recently, the design of new biological metal-ligand complexes has gained a special interest all over the world. In this research, new series of mixed ligand complexes from meloxicam (H₂mel) and glycine (Gly) were synthesized. Structures of the compounds were investigated employing elemental analyses, infrared, electronic absorption, ¹H NMR, thermal analyses, effective magnetic moment and conductivity. The estimated molar conductivity of the compounds in 1 × 10⁻³ M DMF solution indicates the non-electrolyte existence of the examined complexes. Additionally, the effective magnetic moment values refer to the complexes found as octahedral molecular geometry. The data of the infrared spectra showed the chelation of H₂mel and Gly with metal ions from amide oxygen and nitrogen of the thyizol groups of H₂mel and through nitrogen of the amide group and oxygen of the carboxylic group for Gly. Thermal analyses indicated that the new complexes have good thermal stability and initially lose hydration water molecules followed by coordinated water molecules, Gly and H₂mel. The kinetic parameters were calculated graphically using Coats–Redfern and Horowitz–Metzeger methods at n = 1 and n ≠ 1. The density functional theory (DFT) calculations were performed at B3LYP levels. The optimized geometry of the ligand and its complexes were obtained based on the optimized structures. The data indicated that the complexes are soft with η value in the range 0.114 to 0.086, while η = 0.140 for free H₂mel. The new prepared complexes were investigated as antibacterial and antifungal agents against some phyto- and human pathogens and the minimum inhibitory concentration (MIC) data showed that complex (A) has the lowest MIC for Listeria and E. coli (10.8 µg/mL).     

Synthesis of new cyclotriphosphazene derivatives bearing Schiff bases and their thermal and absorbance properties

In this study, a series of cyclotriphosphazene derivatives containing a Schiff base (3a–3d) were synthesized by the reactions of hexachlorocyclotriphosphazene (1) with bis-aryl Schiff bases ( 2a – 2d ) having different terminal groups (H, F, Cl, and Br). The products ( 3a – 3d ) were characterized by elemental and mass analyses, FT-IR, and ¹ H, ¹³ C, and ³¹ P NMR spectroscopies. Furthermore, the structure of compound 3a was also determined by X-ray crystallography. The thermal behaviors and the spectral properties of the new cyclotriphosphazene compounds ( 3a – 3d ) were investigated and the results were compared in the series.     

Application of a data-processing model to determine the optimal sampling conditions for liquid phase trapping of atmospheric carbonyl compounds

The reactivity of two fluorescent derivatization reagents, 2-diphenyl-1,3-indandione-1-hydrazone (DIH) and 2-aminooxy-N-[3-(5-dimethylamino-naphtalene-1-sulfonamino)-propyl]-acetamide (dansylacetamidooxyamine, DNSAOA), was studied towards selected atmospheric carbonyl compounds. The results were compared to those obtained using the 2,4-dinitrophenylhydrazine (2,4-DNPH) UV–vis reagent, a standard well-established technique used to detect atmospheric carbonyl compounds. The experimental rate constant were integrated into a data-processing model developed in the laboratory to simulate the trapping efficiencies of a mist chamber device as a function of temperature, reagent and solvent type among others. The results showed that in an aqueous solution, DNSAOA exhibits a higher reactivity towards carbonyl compounds without the addition of an acidic catalyst than 2,4-DNPH. It was observed that DNSAOA can trap efficiently water-soluble gaseous compounds (for example formaldehyde). However, because of a high initial contamination of the reagent caused by the synthesis procedure used in this work, DNSAOA cannot be used in high concentrations. As a result, very low trapping efficiencies of less reactive water-insoluble gaseous compounds (acetone) using DNSAOA are observed. However, the use of an organic solvent such as acetonitrile improved the trapping efficiencies of the carbonyl compounds. In this case, using DIH as the derivatization reagent (DNSAOA is not soluble in acetonitrile), trapping efficiencies greater than 95% were obtained, similar to 2,4-DNPH. Moreover, fluorescence associated with DIH derivatives (detection limits 3.33 × 10⁻⁸ M and 1.72 × 10⁻⁸ M for formaldehyde and acetone, respectively) is further advantage of this method for the determination of carbonyl compounds in complex matrix compared to the classical UV–vis detection method (detection limits 3.20 × 10⁻⁸ M and 2.9 × 10⁻⁸ M for formaldehyde and acetone, respectively).     

A novel general method for the synthesis of nitrones by reaction of nitroso compounds with anions of aliphatic nitro compounds

Anions of aliphatic nitro compounds R¹R²C=NO₂ ^– react with nitroso compounds RNO to give nitrones R¹R₂C=N(O)R. Salts of nitro compounds with metals and Et₃N, as well as trimethylsilyl nitronates in the presence of F^–, can serve as the sources of the anions. The structure of the nitrones was established by NMR spectroscopy. 1,3-Dipolar cycloaddition of a series of the nitrones obtained to olefins was investigated.For a brief communication see Ref. 1Translated from IzvestiyaAkademii Nauk. Seriya Khimicheskaya, No. 4, pp. 901–907, April, 1996.     

Enthalpies of combustion and formation of 2-acetylpyrrole, 2-acetylfuran and 2-acetylthiophene

The combustion energies for 2-acetylpyrrole (cr) and 2-acetylfuran (cr) were determined using a static bomb calorimeter, whereas the combustion energy of 2-acetylthiophene (l) was determined with a rotating bomb calorimeter; both calorimeters have been recently described. The molar combustion energies obtained were: −(3196.1 ± 0.6) kJ mol⁻¹ for 2-acetylpyrrole, −(2933.8 ± 0.7) kJ mol⁻¹ for 2-acetylfuran, and −(3690.4 ± 0.8) kJ mol⁻¹ for 2-acetylthiophene. From these combustion energy values, the standard molar enthalpies of formation in the condensate phase were obtained as: −(163.51 ± 0.97) kJ mol⁻¹, −(283.50 ± 1.06) kJ mol⁻¹ and −(123.93 ± 1.15) kJ mol⁻¹, respectively. The obtained values of combustion and formation enthalpies of 2-acetylthiophene are in concordance with the reported previously. For the two last compounds, polyethene bags were used as an auxiliary material in the combustion experiments. The heat capacities and purities of the compounds were determined using a differential scanning calorimeter.     

Phosphorus Modified Cardanol: A Greener Route to Reduce VolaTile Organic Compounds and Impart Flame Retardant Properties to Alkyd Resin Coatings

Novel phosphorylated cardanol molecules based on phosphonate (PO₃CR) and phosphate (PO₄CR) functions were synthetized. Those molecules have two main actions which are described in this article: the reduction in volatile organic compounds (VOC) and the development of flame retardant (FR) properties conferred on alkyd resins used as coatings for wood specimen. Phosphorylated cardanol compounds have been successfully grafted by covalent bonds to alkyd resins thanks to an auto-oxidative reaction. The impact of the introduction of PO₃CR and PO₄CR on the film properties such as drying time and flexibility has been studied and the thermal and flame retardant properties through differential scanning calorimeter, thermogravimetric analysis and pyrolysis-combustion flow calorimeter. These studies underscored an increase in the thermal stability and FR properties of the alkyd resins. In the cone calorimeter test, the lowest pHRR was obtained with 3 wt% P of phosphate-cardanol and exhibited a value of 170 KW.m⁻², which represented a decrease of almost 46% compared to the PO_xCR-free alkyd resins. Moreover, a difference in the mode of action between phosphonate and phosphate compounds has been highlighted. The most effective coating which combined excellent FR properties and good coating properties has been obtained with 2 wt% P of phosphate-cardanol. Indeed, the film properties were closed to the PO_xCR-free alkyd resin and the pHRR decreased by 41% compared to the reference alkyd resin.     

Umbu Fruit Peel as Source of Antioxidant,Antimicrobial and α-Amylase Inhibitor Compounds

Herein, the extraction of bioactive compounds from umbu fruit peel was optimized using thermal-assisted solid–liquid extraction. In parallel, antioxidant, antimicrobial, and inhibitory effects against α-amylase of optimized extract were also evaluated. The combination of operational conditions including the temperature (32–74 °C), ethanol concentration (13–97%), and solid/liquid ratio (1:10–1:60; w/v) was employed using a rotational central composite design for optimization. The extracts were evaluated for total phenolic compounds (TPC), total flavonoid compounds (TFC) and antioxidant capacity by ABTS^•+, DPPH^• and FRAP assays. The bioactive profile of the optimized extract was obtained by ultra-performance liquid chromatography coupled to quadrupole/time-of-flight mass spectrometry in electrospray ionization in both negative and positive modes. The statistically evaluated results showed that the optimal operational conditions for the recovery of bioactive compounds from umbu fruit peel included 74 °C, 37% ethanol, and a solid–liquid ratio of 1:38. Under these conditions, the obtained values were 1985 mg GAE/100 g, 1364 mg RE/100 g, 122 µmol TE/g, 174 µmol/TE g and 468 µmol Fe²⁺/g for TPC, TFC, ABTS^•+, DPPH^•, and FRAP assays, respectively. In addition, the optimized extract was effective against Gram-positive and Gram-negative bacteria (MBC ranged from 0.060 to 0.24 mg GAE/mL), as well as it was effective to inhibit α-amylase (IC₅₀ value of 0.076 mg GAE/mL). The optimized extract showed to be mainly constituted by phenolic acids and flavonoids.     

Searching for high performance asymmetrically substituted teterazine energetic materials based on 3-hydrazino-6-(1H-1,2,3,4-tetrazol-5-ylimino)-s-tetrazine

Tetrazine compounds are promising candidates of high performance energetic materials (EMs). For the purpose of exploring high performance asymmetrically substituted teterazine explosives, 3-hydrazino-6-(1H-1,2,3,4-tetrazol-5-ylimino)-s-tetrazine was selected as the precursor and a series of teterazine EMs were prepared based on three synthetic strategies. All the obtained compounds were fully characterized and the crystal structures of seven compounds were further confirmed by single crystal X-ray diffraction. The thermal dynamics and thermal safety parameters, the detonation properties and impact sensitivities were also obtained. The results revealed that compounds 15–17 show excellent energetic properties (detonation velocities > 9000 m·s^?1, detonation pressures > 30 GPa) and have impact sensitivities (8–12 J) that comparable or lower than RDX. Compounds 9–13 are insensitive to impact and have detonation velocities range from 8452 to 8775 m·s^?1. These compounds can be good candidates of high performance secondary explosives or insensitive EMs.     

Ion Selective Electrode Determination of Free Versus Total Fluoride Ion in Simple and Fluoroligand Coordinated Hexafluoropnictate (PnF<Subscript>6</Subscript><Superscript>−</Superscript>, Pn = P,As, Sb,Bi) Salts

Interpretation of the results of determinations of free fluoride (F_f⁻) and total fluoride (F_t⁻) obtained with fluoride ISE while conducting elemental chemical analysis of bulk material of newly synthesized inorganic fluoride compounds is of crucial importance for the purpose of determination of purity and stoichiometry of these compounds. Knowledge of the properties and behavior of these compounds in aqueous media is therefore essential. Observations are presented on the determinations of the amounts of F_t⁻ and F_f⁻ in fluorinated compounds, in the particular hexafluoropnictate salts (PnF₆⁻, Pn = P, As, Sb, Bi) as found in aqueous media and in some compounds with XeF₂, AsF₃ ligands. A critical look at the determined amounts of F_f⁻, F_t⁻and calculated amounts of bound fluoride (F_b⁻) is provided.