Synthesis and spectroscopic studies of new adducts of organotin(IV) chlorides with a polydentate N,S ligand

The reaction of a polydentate N,S ligand, 1′-amino-1′-cyclohexyl 2-cyclohexylideneamino-1-cyclohexene-1-dithiocarboxylate (ACCCD), with Ph₂SnCl_2, Ph₃SnCl and Me₂SnCl₂ was investigated. The new adducts have been characterized by UV–Vis, ¹H NMR, IR, mass spectroscopy and elemental analysis. These data are consistent with 1:1 adducts. The ligand behaves as a bidentate and shows both nitrogen and sulfur coordination. There is also evidence that the ligand ACCCD exhibits some interest in forming possible inter-/intra-molecular hydrogen bonds through ClH₂N interactions in Me₂SnCl₂ and Ph₂SnCl₂ adducts. The UV–Vis spectra indicate that the compounds partially dissociate in chloroform.     

Chemical characterization and agronomic effectiveness of phosphorus applied as a polyphosphate-chitosan complex

This work was undertaken to characterize a chitosan-polyphosphate complex (CH-PP) and to evaluate its agronomic effectiveness as a source of phosphorus for ryegrass (Lolium perenne) grown on loamy and clayey soils. High resolution solid state³¹P and¹³C nuclear magnetic resonance were used to characterize this complex and to monitor the structural changes occurring to it during an 8-week incubation period in a loamy soil. A pot experiment was conducted on the two soils after labelling the available P with³²PO₄ ions. This experiment allowed for the determination of the agronomic effectiveness of the chitosan-polyphosphate complex compared to polyphosphate and to monocalcium phosphate. Results showed that chitosan immobilized up to 147 mg P kg^–1 as pyrophosphate and hexametaphosphate. This reaction did not involve major structural changes in the pyrophosphate or hexametaphosphate groups nor in the chitosan. The chitosan-polyphosphate complex was as efficient as the polyphosphate alone to sustain the P nutrition of ryegrass. The relative agronomic effectiveness of these P sources was slightly lower compared to that of monocalcium phosphate. The high P fertilizing value of the chitosan-polyphosphate complex was attributed to its gradual hydrolysis in the soil. The potential interest of chitosan to remove polyphosphates from waste waters while preserving the high P fertilizing value of polyphosphates was addressed.     

Ion-Exchange Behavior of New and Novel Zirconium(IV)-Based Composite Cation-Exchangers

The synthesized polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers were characterized by Fourier transform infrared spectroscopy, UV spectra, X-ray diffraction, scanning electron microscope, thermogravimetric analysis, and conductivity studies. The ion-exchange capacities, effect of eluent concentration, elution time, elution behavior, and pH on ion-exchange capacity were also studied to exploit the ion-exchange capability of the composites. The study revealed that polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate ion exchangers are having excellent ion-exchange capacity values for K⁺ ion 1.36 and 1.44?meq?g^?1, respectively. The organic polymeric part of the composites provides mechanical and chemical stability, whereas the inorganic part supports the ion-exchange behavior and thermal stability. The increase in electrical conductivity is due to the inorganic and organic parts. A mechanism for the formation of the polyaniline-Zr(IV) selenoiodate and polyaniline-Zr(IV) selenomolybdate composite ion exchangers is discussed, which may also be applied for the preparation of other composite ion exchangers. Sorption behavior of metal ions on the composites was studied in different solvent systems. On the basis of distribution coefficient values (K_d), it has been found that the cation-exchange materials are highly selective for Pb(II)-ions. Such modified composite materials can be applied as an electrochemically switchable ion exchanger for water treatment, especially water softening.     

Syntheses, characterization and biological activity of diorganotin(IV) derivatives of 2-amino-6-hydroxypurine (guanine)

Novel organotin(IV) derivatives of guanine of the general formula, R₂Sn(HGu)₂ (where, R = Me (1), n-Bu (2) and Ph (3)) have been synthesized by the reaction of R₂SnCl₂ with sodium salt of guanine (H₂Gu or 2-amino-6-hydroxypurine). The IR spectral studies suggest that guanine acts as a monobasic ligand coordinating through N(9) after its deprotonation. The weak bonding through C(6)O may also be evidenced, whereas ¹¹⁹Sn Mössbauer data suggest that the coordination number of tin is superior than four. The polyhedron around tin in R₂Sn(HGu)₂ is distorted trigonal–bipyramidal or pseudo-tetrahedral involving very weak interaction from CO group of neighboring molecule leading to polymerized structure. All the compounds exhibited potent anti-inflammatory activity with no appreciable side effects on blood pressure as evidenced by their very mild cardiovascular activity.     

Highly isotactic poly(vinyl alcohol) derived from tert-butyl vinyl ether. Part IV. Some physical properties, structure and hydrogen bonding of highly isotactic poly(vinyl alcohol) films

Some basic physical properties, structure and hydrogen bonding have been characterized for different stereoregular PVA films including highly isotactic PVAs (HI-PVAs), which were recently succeeded in synthesis, as functions of the mm fraction by using different analytical methods. The melting temperature, degree of crystallinity, and ¹³C spin-lattice relaxation time of the crystalline component are found to have their own clear minima at the mm fraction of about 0.4-0.5. This fact suggests that structural disordering associated with the decrease in crystallinity may be most strongly induced at this mm fraction. The formation of the new crystal form of PVA has been reconfirmed for HI-PVAs with the mm fractions higher than about 0.55 by FTIR spectroscopy and the structure and hydrogen bonding have been investigated in detail by solid-state ¹³C NMR spectroscopy. It is found that all OH groups are allowed to form successive intramolecular hydrogen bonding along the respective chains in the crystalline region for HI-PVAs with the mm fractions higher than about 0.7. Since these chains should contain some amount of r units even in the crystalline region, a slightly helical structure with a considerably long period may be adopted by them as an energetically stable state. On the basis of the line shape analysis of the CP/MAS ¹³C NMR spectra of the crystalline components, structural causes of the appearance of the minima of the physical values described above are also discussed in relation to the introduction of disordered units mainly associated with hydrogen bonding to the syndiotactic or isotactic sequences forming successive intermolecular or intramolecular hydrogen bonding, respectively.     

Heterogenization of 12-tungstophosphoric acid on stabilized zeolite Y

Topics in Catalysis - 12-tungstophosphoric acid (PW12) has been supported on dealuminated zeolite Y, containing a secondary pore system with the predominant pore radii of 15 Å. The interaction...     

Solid-state nuclear magnetic resonance (NMR): Application to precursors of ceramics—Polycarbosilane

The chemical structures of oxidation- and electron irradiation-cured polycarbosilane fibers has been studied by IR and chemical analysis, but its structure has not been identified in detail. In this work, the chemical structure and curing mechanism was examined by solid-state high-resolution NMR spectroscopy. From the analysis of NMR spectra, it is explained that (i) in oxidation curing of PCS fibers, oxygen attacks first the SiC₃H bond and forms the SiC₃O bond and, next, the SiC₄ backbone bond and forms the SiC₂O₂ units; (ii) in electron irradiation curing, the signal intensity of SiC₃H units decreases with the increase in dose, the increase in the signal being due to the formation of SiC₄ units; (iii) solid-state²⁹Si high-resolution (CP/MAS) NMR spectroscopy is a powerful tool for investigating the chemical structure and curing mechanism of PCS fibers complementing infrared and solid-state¹³C high-resolution NMR spectroscopy; and (iv)¹H CRAMPS NMR spectroscopy is very useful for investigating the chemical structure and curing mechanism of PCS fibers.     

Solvent Extraction Investigations on Pu(IV) and Th(IV) Complexes with Hydrophilic SO3-Ph-BTP and SO3-Ph-BTBP Ligands

ABSTRACT

Complexation of Pu(IV) and Th(IV) cations by the title ligands – hydrophilic sulfophenyl triazinyl derivatives of bis-triazinyl-pyridine and -bipyridine – was studied in solvent extraction systems containing a TODGA extractant and one of these hydrophilic ligands. Stoichiometries and stability constants of the complexes formed in an acidic (HNO₃) aqueous phase have been determined. The Pu(IV) complexes are significantly stronger than their Th(IV) analogues. Only two complexes of each metal with SO₃-Ph-BTP (1:1 and 1:2) have been detected, and only one (1:1) with SO₃-Ph-BTBP; both numbers being less than expected based on the coordination numbers of the metal ions and on the denticities of the ligands. Possible reasons of this discrepancy are discussed.     

Elongation-induced phase separation of poly(vinyl alcohol)/poly(acrylic-acid) blends as studied by C CP/MAS NMR and wide-angle X-ray diffraction

The membrane samples of poly(vinyl alcohol)/poly(acrylic-acid) (PVA/PAA) blend with different draw ratios were studied by both ¹³C CP/MAS NMR and wide-angle X-ray diffraction (WAXD) measurements. Phase separation induced by elongation of the sample was observed and the change of the phase structure with draw ratio was found to be dependent on the composition of the blend samples.     

Poly(di(ω-alkylphenyl)stannane)s

Poly(di(ω-alkylphenyl)stannane)s, [Sn(C _n H_2n Ph)₂] _m with n = 2–4, and a copolymer of di(3-propylphenyl)stannane and dibutylstannane of weight-average molar masses of 2–8 · 10⁴ g/mol were synthesized by dehydropolymerization of stannanes of the composition H₂SnR₂ using Wilkinson’s catalyst [RhCl(PPh₃)₃]. At least two methylene groups were required as spacers between the phenyl group and the tin atom for polymerization to occur. The polystannanes were characterized by, among other techniques, ¹H, ¹³C and ¹¹⁹Sn NMR spectroscopy, thermal analysis and X-ray diffraction. The polymers featured properties different from those of the corresponding poly(dialkylstannane)s. Specifically, the [Sn(C _n H_2n Ph)₂] _m family displayed glass transitions at remarkably low temperatures, down to ca. −50 °C, and a lower value for a copolymer (−68 °C). Polymers [Sn(C_nH_2nPh)₂]_m with n = 2 and 3 and a copolymer at room temperature were of a gel-like concistence, which enabled facile orientation with shear forces. Finally, the temperature-dependent electrical conductivity was determined for poly(di(3-propylphenyl)stannane), which followed the law of typical semiconductors, with an activation energy for conduction of 0.12 eV.     

Forms and exchangeability of inorganic phosphate in composted solid organic wastes

Switzerland yearly produces more than 260,000 Mg of compost, two thirds of which is recycled in agriculture and horticulture. This research was undertaken to examine the forms and availability of inorganic P (Pi) in Swiss composts made from solid kitchen and garden wastes using the isotopic exchange kinetic technique, a sequential Pi extraction and magic angle spinning (MAS) solid-state ³¹P nuclear magnetic resonance (NMR) spectroscopy. The different approaches described in this paper demonstrate the presence of a complex mixture of Pi species in the studied composts. Isotopic exchange experiments and sequential extraction showed that these composts contained relatively large concentrations of rapidly available Pi. Significant correlations were observed between the concentration of water-soluble Pi (Cp), and the total N, C and P content of composts suggesting that organic substances partly controlled the amount of rapidly available Pi. Significant correlations were observed in alkaline composts between the amount of Pi which can not be exchanged within 3 months and the total P and Ca content. In alkaline composts solid-state MAS ³¹P NMR results suggested the presence of a range of slightly soluble and poorly crystallized Ca-P compounds such as apatites or octacalcium phosphates and of organic P compounds. The slowly or non-exchangeable Pi present in these composts could therefore be bound to Ca in the form of apatites or octacalcium phosphates.     

Synthesis, X-ray structure and Hg, Se CP MAS NMR studies on the first tris(imidazolidine-2-selone) mercury complex: {Chloro-tris[N-methyl-2(3H)-imidazolidine-2- selone]mercury(II)}chloride

A novel cationic Hg(II) complex has been synthesized with N-methyl-imidazolidine-2-selone ligand. The tris(N-Methyl-imidazolidine-2-selone) mercury(II) complex, [(MeImSe)₃HgCl]⁺Cl⁻ (1), has been characterized by single crystal X-ray analysis and CP MAS ¹⁹⁹Hg and ⁷⁷Se NMR.     

CP/MAS C NMR analysis of the structure and hydrogen bonding of melt-crystallized poly(vinyl alcohol) films

The structure and hydrogen bonding of the melt-crystallized atactic poly(vinyl alcohol) (A-PVA) films, which were carefully prepared without significant thermal degradation, have been characterized by CP/MAS ¹³C NMR spectroscopy. The ¹³C spin-lattice relaxation analysis has revealed that there exist three components with different T_1C values, the crystalline, less mobile noncrystalline and mobile noncrystalline components, in good accord with the results for different PVA samples previously reported. It should be noted that the T_1C values of the crystalline and noncrystalline components are appreciably smaller for the melt-crystallized films than those for the un-annealed and annealed samples prepared by casting from the aqueous solution. The ¹³C NMR spectra of the crystalline and noncrystalline components are separately recorded by using the difference in T_1C and their CH lines are successfully resolved into three and seven constituent lines by the least-squares curve fitting, respectively. Moreover, the statistical analysis of the integrated intensities of the constituent lines thus obtained enables to determine the probability f_a for the formation of intramolecular hydrogen bonding in the successive two OH groups along each chain and another probability f_t of the trans conformation for the crystalline and noncrystalline components. It is found that the f_a value is relatively larger for the melt-crystallized films than those for the un-annealed and annealed samples. On the basis of these results, the features of the melt-crystallization and the resulting crystalline-noncrystalline structure are discussed by particularly considering effects of intra- and inter-molecular hydrogen bonding on the crystallization.     

Note: Zr(IV)-Immobilized Resin Prepared by Surface Template Polymerization for Fluoride Ion Removal

Abstract

A novel adsorbent Zr(IV)-immobilized resin was prepared to remove fluoride ions from tap water and industrial wastewater. In order to enhance both the kinetics and efficiency, large pathways were formed in the resin for fluoride ion adsorption and the Zr(IV)-phosphate complexes were immobilized on the polymer surface by surface-template polymerization. The Zr(IV)-immobilized resin had a fluoride adsorption capacity of 0.30 mmol/g. The morphology of the Zr(IV)-immobilized resin was evaluated by measuring the specific surface area, pore volume, and pore size distribution. The resin possessed large amounts of large macropores with diameters around 300 nm. The molecular structure at the fluoride adsorption sites was investigated by measuring the amounts of phosphorus, zirconium, and fluoride ion in the resin, and developing a model complex using computational chemistry. On the polymer surface, a fluoride ion/Zr(IV)/dioleyl phosphoric acid complex with an ideal F:Zr:P mole ratio of 3:1:3 could be formed.     

Sn(IV)-Porphyrin-Based Nanostructures Featuring Pd(II)-Mediated Supramolecular Arrays and Their Photocatalytic Degradation of Acid Orange 7 Dye

Two robust Sn(IV)-porphyrin-based supramolecular arrays (1 and 2) were synthesized via the reaction of trans-Pd(PhCN)₂Cl₂ with two precursor building blocks (SnP¹ and SnP²). The structural patterns in these architectures vary from 2D to 3D depending on the axial ligation of Sn(IV)-porphyrin units. A discrete 2D tetrameric supramolecule (1) was constructed by coordination of {(trans-dihydroxo)[5,10-bis(4-pyridyl)-15,20-bis(phenyl) porphyrinato]}tin(IV) (SnP¹) with trans-PdCl₂ units. In contrast, the coordination between the {(trans-diisonicotinato)[5,10-bis(4-pyridyl)-15,20-bis(phenyl)porphyrinato]}tin(IV) (SnP²) and trans-PdCl₂ units formed a divergent 3D array (2). Axial ligation of the Sn(IV)-porphyrin building blocks not only alters the supramolecular arrays but also significantly modifies the nanostructures, including porosity, surface area, stability, and morphology. These structural changes consequently affected the photocatalytic degradation efficiency under visible-light irradiation towards acid orange 7 (AO) dye in an aqueous solution. The degradation efficiency of the AO dye in the aqueous solution was observed to be between 86% to 91% within 90 min by these photocatalysts.     

Interaction between two anti-graffiti treatments and cement mortar (paste)

Much of the twentieth century's built heritage is made of concrete, which is particularly susceptible to graffiti “attacks”. Since the traditional methods used to remove spray paint are not particularly effective on this type of material, the adoption of preventive measures by applying a new type of protective treatments, known as anti-graffiti coatings, may be a good way to tackle the problem. The present study aimed to evaluate the physical properties of a cement mortar coated with two such products and to study the possible molecular interactions between the coatings and the cement paste. Neither product induced chromatic changes on the surface of the material, while both made it water repellent. ²⁹Si MAS NMR analysis detected a lower Q¹/Q² ratio, indicative of a longer chain length, in the C-S-H gel in the cement paste mixed with the anti-graffiti products.     

Evaluation of strong acid properties of layered HNbMoO6 and catalytic activity for Friedel–Crafts alkylation

The acid properties and catalytic activity of layered HNbMoO₆ for liquid-phase Friedel–Crafts alkylation are examined. ³¹P MAS NMR spectroscopy using trimethylphosphine oxide as a probe molecule reveals that HNbMoO₆ possesses strong acid sites in the interlayer region. Layered HNbMoO₆ is demonstrated to display remarkable catalytic performance for this reaction, substantially exceeding the activities of niobic acid, niobium–molybdenum mixed oxide, ion-exchange resins, and zeolites. It is determined that benzyl alcohol is intercalated into the HNbMoO₆ interlayer during alkylation to form a monolayer configuration, allowing the strong interlayer acid sites to participate in the reaction.     

Solid-state C NMR investigation of the structure and hydrogen bonding for stereoregular poly(vinyl alcohol) films in the hydrated state

The structure and hydrogen bonding of the hydrated stereoregular poly(vinyl alcohol) (PVA) films have been investigated by high-resolution solid-state ¹³C NMR spectroscopy. It is found by the ¹³C spin-lattice relaxation analysis that there exist three components with different T_1C values assigned to the crystalline, less mobile and mobile components for the hydrated syndiotactic PVA (S-PVA) and highly isotactic PVA (HI-PVA) films. The line shape analysis indicates that the probability of intramolecular hydrogen bonding is appreciably increased in the crystalline region for the S-PVA films by the hydration but a slightly helical structure, which is probably allowed by the formation of the successive intramolecular hydrogen bondings along the chains in the crystalline region, seems not to undergo any significant change by the hydration for HI-PVA. This fact indicates that intramolecular hydrogen bonding is more stable in the hydrated state in the crystalline region. As for the less mobile component, the line shape of the CH resonance line for the hydrated S-PVA or HI-PVA films is found to be very similar to that of the corresponding crystalline component, probably being due to the successive formation of intermolecular or intramolecular hydrogen bonding in the interfacial region, which mainly contributes to the less mobile component, for the S-PVA or HI-PVA films even in the hydrated state. The mole fractions of the mm, mr and rr sequences are also estimated for the mobile component that is produced in each stereoregular PVA sample by swelling with water and it is concluded that no prominent preferential partitioning of the mm, mr and rr sequences occurs in the crystalline and noncrystalline regions for the PVA films with different tacticities.     

Carbonization mechanisms resulting from intumescence association with the ammonium polyphosphate-pentaerythritol fire retardant system

In this work we study the thermal behavior of an ammonium polyphosphate-pentaerythritol mixture, fire-retardant additive for polyolefins and most particularly the carbonization process resulting from an intumescent phenomenon. The study has been carried out using Micro-Raman and ¹³C, ¹H, ³¹P NMR of the solid state spectroscopies. It is shown that the structure consists in phoscarbonaceous and polyaromatic species. These latter form an anisotropic structure above 280°C. This structure grows when the temperature increases. Finally, a reactional scheme of the carbonization of the intumescent system is proposed.