The effects of high concentrations of aqueous tetramethylammonium chloride and other salts on the dissociation of phenylphosphonic acid and on the enolization of acetone

The dissociation constants of benzoic acid and phenylphosphonic acid have been determined in aqueous solutions containing tetramethylammonium chloride at concentrations up to 15 and 13 molal, respectively. The second dissociation constant of phenylphosphonic acid has also been determined in concentrated solutions of alkali halides. Whereas the organic electrolyte increases the observed pK values of the acids, the inorganic electrolyte idecrease them. The rate of enolization of acetone, catalyzed by phenylphosphonate dianion is increased by the presence of tetramethylammonium chloride, but is decreased by the presence of inorganic salts, in accordance with the changes in the apparent acidity constants of phenylphosphonate monoanion that the two different kinds of electrolyte bring about. The slope of the Brónsted plot for the inorganic salts is 0.76; that for the organic electrolyte is 0.46. Non-quaternary ammonium salts also increase the rate of the phenylphosphonate dianion catalyzed enolization of acetone, but this appears to be due to a considerable extent to the formation of reactive iminium ion intermediates.     

Synthesis and degradation of polyurethanes containing phosphorus—Part II: Thermal degradation of poly(butylene phenylphosphonate) and poly(butylene phenylphosphonate) bis(phenylcarbamate)

The principal characteristics and products of thermal degradation of an oligomeric phosphorus containing polyol, poly(butylene phenylphosphonate) (I), and the same compound endcapped with phenyl isocyanate, poly(butylene phenylphosphonate) bis(phenylcarbamate) (II) were studied. (I) and (II) are precursors of a high molecular weight phosphorus containing polyurethane.The products from (I) were butadiene, tetrahydrofuran, dihydrofuran, water, the cyclic ester of phenylphosphonic acid and 1,4-butanediol, phenylphosphonic acid and a linear diester of phenylphosphonic acid and butane diol. The residue at 550°C incorporated pyrophosphonic acid links. All these products were also formed from (II) with the addition of carbon dioxide and aniline.The products and characteristics of the reactions have been accounted for in terms of acceptable processes.     

Preparation of hybrid film of polyaniline and organically pillared zirconium phosphate nanosheet by electrodeposition

α-Zirconium phosphate was chemically modified with 1,2-bis(dimethylchlorosilyl)ethane to graft organic chain, and then it was used as host material for inorganic nanosheet-polyaniline hybrid. The grafted α-zirconium phosphate was exfoliated in an acetonitrile solution with tetrabutylammonium salt and aniline. The electrodeposition in the presence of aniline was performed, and then it resulted in a formation of higher-order structure in which phosphate nanosheet was propped up by 1,2-bis(dimethylchlorosilyl)ethane with intrusion of polyaniline into the nanospace. The gravimetric capacitance of the α-zirconium phosphate without grafts and polyaniline hybrid film was around 194 F/g with the base on the amount of polyaniline mass. On the other hand, the α-zirconium phosphate nanosheet with grafts and polyaniline hybrid film provided larger capacitance of around 350 F/g in maximum. The nanospace formed by grafted phosphate nanosheet with 1,2-bis(dimethylchlorosilyl)ethane molecules gives increased amounts of polyaniline included and diffusion paths for ions.     

层状α-氢型磷酸氢锆混合二氧化硅的交流电导

1 引言无定形和多晶粉末层状α-水合磷酸氢锆是一种固体质子电解质.多晶粉末层状α-水合磷酸氢锆的电导率随结晶度的提高而明显降低,但是其电导表观活化能相同而和结晶度无关.电导主要是由质子沿着微晶的水合表面迁移所致.因此,增大水合表面有可能提高多晶粉末层状α-磷酸氢锆的电导率.α-磷酸氢锆的层状结构由层间的磷氧基形成氢键     

Intercalation of n-Alkylamines and n-Alkyldiamines into γ-Zirconium Phenylphosphonate Phosphate

Crystalline -zirconium phenylphosphonate phosphate was prepared according to Yamanaka's method and the intercalation behavior of n-alkylamines and n-alkyldiamines were investigated. In the case of n-alkylamines, a linear increase in interlayer distance was observed up to a carbon atom number of 12, whereas in n-alkyldiamines, only two di-amines, ethylenediamine and propylenediamine, were intercalated with respective increases in the interlayer distance. The increment of interlayer distance in both monoamines and diamines indicates the formation of a monomolecular layer in the interlayer region of the host, in contrast to the case in -zirconium phosphate as a host.     

Layered calcium phenylphosphonate: Synthesis and properties

Calcium phenylphosphonate, Ca(HO₃PPh)₂, was synthesized by the reaction of calcium nitrate and phenylphosphonic acid. A thorough investigation was performed to study the effect of reaction parameters on the synthesis and growth of crystalline product in a high yield. The compound was structurally characterized by single-crystal X-ray diffraction technique. It consists of a layered structure with inorganic framework of CaO₈ polyhedra from which phenyl groups are pointing out. The inorganic framework is also stabilized by the OH⋯O hydrogen bonds. Results from thermal analysis by thermogravimetry and thermodiffractometry revealed that calcium phenylphosphonate is stable up to 300°C. The compound undergoes consequent thermal decomposition and phase transitions above 300°C temperatures until it converts to δ-Ca(PO₃)₂ at 620°C.     

层状苯膦酸-磷酸锆的合成与磺化研究

研究了制备苯膦酸-磷酸锆Zr(PO₄H)_2-n(PO₃Ph)_n的主要影响因素。在F^-/Zr⁴⁺=12和H₃PO₄/Zr⁴⁺=20条件下,通过改变苯膦酸用量获得了n=0～2的系列单一晶相层状苯膦酸-磷酸锆,其热稳定性达400℃以上。苯膦酸-磷酸锆的磺化试验表明层间苯环可被完全磺化,磺化产物Zr(PO₄H)_2-n(PO₃PhSO₃H)_n具有丰富的酸性位,其热稳定性亦可达到300℃以上。     

Kinetics of gas-solid reactions in α-zirconium phosphate. H+/Na+ mixed diffusion coefficients

The rates of reaction between gaseous HCl and sodium ion exchanged phases of α-zirconium phosphate have been measured. The reactions are diffusion controlled and were fit by an equation for diffusion in a sphere from a well stirred fluid of limited volume (Carman and Haul equation). Diffusion coefficients were of the order of 10⁻¹⁵–10⁻¹² cm²/sec in the temperature range 25°–220°C. These coefficients are in the same range as those determined from self-diffusion studies but are several orders of magnitude smaller than those obtained from rates of exchange. Possible reasons for this discrepency are given.     

An amperometric biosensor using toluidine blue as an electron transfer mediator intercalated in α-zirconium phosphate-modified horseradish peroxidase immobilization matrix

A novel H₂O₂ biosensor was constructed employing α-zirconium phosphate as a new support substrate to hold an electron shuttle toluidine blue between a glassy carbon electrode and horseradish peroxidase. Toluidine blue was intercalated into α-zirconium phosphate-modified horseradish peroxidase immobilization matrix cross-linked on a glassy carbon electrode surface via bovine serum albumin-glutaraldehyde. This co-immobilization matrix of the mediator and the enzyme was formed from the α-zirconium phosphate (α-ZrP)-toluidine blue (TB) inclusion colloid in which horseradish peroxidase (HRP) was dissolved. Intercalation of TB in layered α-ZrP was investigated by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and electrochemical measurements. TB immobilized in this way underwent a quasi-reversible electrochemical redox reaction at the electrode. Cyclic voltammetry and amperometric measurements demonstrated good stability and efficiently-shuttled electrons between HRP and the electrode. The sensor responded rapidly to H₂O₂ with a detection limit of 3.0 × 10^–7 mol/L.     

Synthesis of phosphorus‐containing vinyl ether monomers and oligomers and their photoinitiated polymerization

Divinyl ether monomers containing phosphorous residues were synthesized by the addition reaction of glycidyl vinyl ether (GVE) with various phosphonic dichlorides or dichlorophosphates with quaternary onium salts as catalysts. The reaction of GVE with phenylphosphonic dichloride gave bis[1‐(chloromethyl)‐2‐(vinyloxy)ethyl]phenylphosphonate ( 1a ) in a 77% yield. The polycondensation of 1a with terephthalic acid was also carried out with 1,8‐diazabicyclo[5.4.0]undecene‐7 (DBU) as a condensing agent to afford the corresponding phosphorus‐containing polyester. A multifunctional monomer containing both vinyl ether groups and methacrylate groups was prepared by the reaction of 1a with methacrylic acid with DBU. The photoinitiated cationic polymerization of these vinyl ether compounds proceeded rapidly with bis[4‐(diphenylsulfonio)phenyl]sulfide‐bishexafluorophosphate as the cationic photoinitiator without a solvent upon ultraviolet irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2031–2042, 2004     

季鏻阳离子柱撑磷酸锆的热稳定性及抗菌活性

采用离子交换法将不同含量的十二烷基三丁基溴化鏻(DDTB)插入层状磷酸锆得到一种耐高温且具有优良抗菌性能季鏻阳离子柱撑磷酸锆(DDTB-ZrPs)。通过热重分析(TGA)、红外分析(FTIR)、X射线衍射法(XRD)和透射电镜(TEM)对DDTB-ZrPs的结构进行了表征,并测定了DDTB-ZrPs的最低抑菌浓度。结果表明,季鏻盐已经成功插入层状α-鏻酸锆的层间,DDTB-ZrPs的层间距随着季鏻盐含量的增加而增加。DDTB-ZrP-1(DDTB含量为5.61wt%)的热稳定性最好,有机物失重5%时温度可达320℃,最大热分解率温度达384℃。DDTB-ZrP-6(DDTB含量为26.46wt%)显示出良好的长效抗菌活性,对大肠杆菌和金黄色葡萄球菌的最低抑菌浓度分别为80和15 mg·L-1。进一步的研究表明,随着DDTB含量的增加,DDTB-ZrPs的热稳定性降低而抗菌活性增强。     

Click-chemistry-based bis-triazolylpyridine diphosphonate ligand for the sensitized luminescence of lanthanides in the solid state within the layers of γ-zirconium phosphate

The synthesis by means of ‘click’ chemistry of a new ligand bearing the bis-triazolylpyridine motif and pendant phosphonate groups is described. The topotactic phosphate/phosphonate exchange of the ligand into gamma-zirconium phosphate led to an organic-inorganic-layered material which revealed an excellent matrix to achieve the efficient sensitization of emitting lanthanides.     

Online preconcentration of arsenic compounds by dynamic pH junction-capillary electrophoresis

An online preconcentration technique by dynamic pH junction was studied to improve the detection limit for anionic arsenic compounds by CE. The main target compound is roxarsone, or 3-nitro-4-hydroxyphenylarsonic acid, which is being used as an animal feed additive. The other inorganic and organoarsenic compounds studied are the possible biotransformation products of roxarsone. The arsenic species were separated by a dynamic pH junction in a fused-silica capillary using 15 mM phosphate buffer (pH 10.6) as the BGE and 15 mM acetic acid as the sample matrix. CE with UV detection was monitored at a wavelength of 192 nm. The influence of buffer pH and concentration on dynamic pH junction were investigated. The arsenic species focusing resulted in LOD improvement by a factor of 100-800. The combined use of C18 and anion exchange SPE and dynamic pH junction to CE analysis of chicken litter and soils helps to increase the detection sensitivity. Recoveries of spiked samples ranged between 70 and 72%.     

γ-Zirconium and γ-Titanium Phosphates Platinum Intercalation Compound Preparation, characterization and thermal behaviour

Inorganic ion-exchangers with a layered structure such as γ-zirconium and γ-titanium phosphates, intercalated with organic diamines, are able to exchange Pt²⁺ ions to give new intercalation compounds that can be utilized in heterogeneous catalysis. The experiments performed at different temperatures (25 and 45°C), show different ion uptakes, greater at 45°C and for the materials derived from γ-zirconium phosphate. After platinum exchange, all the materials show an amorphization in the XRD if compared with their precursors. The thermal behaviour of the platinum materials is specific, depending on the exchanger used and the ligand inside the exchanger. Pt²⁺ ion has a catalytic effect on ligand elimination in the γ-zirconium phosphate platinum compounds, but not in those derived from γ-titanium. All the obtained yellow materials show a small step in the TG curves and simultaneously we have the Pt²⁺→Pt⁰ reduction: this is confirmed by XRD registered at the temperatures of the thermal effect, showing peaks at d_hkl=2.27 and 1.95 Å. This revised version was published online in July 2006 with corrections to the Cover Date.     

氧化硅柱撑磺化磷酸-苯膦酸锆的合成及性能

以磷酸-苯膦酸锆为层板,合成并表征了硅柱撑的层柱磷酸-苯膦酸锆,并磺化了其中的苯环.磺化后的产物具有较高的酸量,在酯化反应中催化活性与硫酸相当.     

Incorporation of Cadmium Ions and Cadmium Sulfide Particles into Sol-gel Zirconium Phosphate. Synthesis,thermal behavior and X-ray characterization

The inorganic ion-exchanger α-zirconium phosphate was synthesized by the sol-gel method and its properties relating to the exchange of Cd²⁺ and the intercalation of CdS particles were studied. The Cd²⁺-exchange process is a fast process and the material obtained exhibits an increased interlayer distance d with respect to its precursor (9.56 vs. 7.56 Å). The resulting Cd-containing material was exposed to aH₂S gas flow to give CdS particles in the exchanger. The zirconium phosphate containing CdS particles still possesses a layered structure, with a pattern almost identical to that of the initial ion-exchanger precursor. Moreover, the material may exchange further Cd²⁺ and hence lead to a higher CdS particle content. The thermal behavior of this ion-exchangers containing Cd²⁺ or CdS particles was studied.     

超分子结构姜黄素插层镁铝水滑石的组装、结构及缓释性能

以镁铝水滑石为主体, 以中药提取物姜黄素为客体, 由共沉淀法、离子交换法和焙烧复原法三种不同方法组装得到超分子结构复合材料——姜黄素插层镁铝水滑石. 并用XRD, IR, HPLC等手段对该材料进行了表征. 结果表明, 共沉淀法和离子交换法成功组装得到两种不同结构的姜黄素插层产物, 使材料的层间距扩大为0.82～1.36 nm, 层间客体姜黄素阴离子是以平行或者单层垂直的定位方向排列于层间的. 考察了该材料在不同pH值的磷酸盐缓冲溶液中的缓释性能, 其缓释历程为客体阴离子与介质中 的离子交换过程. 该研究指出了阴离子层状材料——水滑石在中药释释剂领域的应用潜力.     

ESCA investigations of amorphous and crystalline zirconium acid phosphates

Amorphous and micro-crystalline α- and γ-zirconium acid phosphates have been investigated by the ESCA technique. α-zirconium phosphate has been also studied as a single crystal. Both the B.E. of zirconium and phosphorous electrons in zirconium phosphates are slightly higher than those reported for zirconium derivatives and trivalent metal phosphates, indicating a stronger polarization of the ZrO and PO bonds. Furthermore, it seems that some ESCA features of the zirconium phosphates investigated are structure dependent. However, no definitive conclusions have been drawn because of the lack of knowledge of the “charging-up” phenomena in protonic conductors such as zirconium phosphates. Satellite structures have been observed in the P_2s, P_2p, Zr_3d and Zr_4p regions. The position and the intensity of these “shake-up” effects are again dependent on the nature of the examined phase and they seem to be due to the presence of electron defect structures induced by X-rays or already present in the original samples.     

A controlled anion exchange strategy to synthesize Bi2S3 nanocrystals/BiOCl hybrid architectures with efficient visible light photoactivity

Bi(2)S(3) nanocrystals/BiOCl hybrid architectures with tunable band gaps were synthesized by a controlled anion exchange approach and they displayed highly efficient visible light photoactivities, which is associated with suitable energetics and structural topotactic relationship that can benefit the interfacial charge transfer.     

Tris-(8-hydroxy-quinoline) aluminium/zirconium phosphate: a novel hybrid assembly with strong luminescence and prolonged lifetime

A novel hybrid assembly of tris-(8-hydroxy-quinoline) aluminium intercalated into modified α-zirconium phosphate in aqueous media was fabricated successfully, resulting in the dramatically enhanced greenish-blue-light emission and prolonged excited-state lifetime.