Studies in the tetraarylborates : The preparation and reagent properties of sodium tetrakis(p-chlorophenyl)borate

Sodium tetrakis(p-chlorophenyl)borate was synthesized. It formed precipitates with K⁺, Rb⁺, Cs⁺, quarternary ammonium and protonated basic nitrogen compounds. The potassium salt was more soluble than potassium tetraphenylborate but flocculated more readily and filtered more easily. The salts formed with nitrogen compounds offer possibilities as derivatives suitable for qualitative analysis.     

Determination of phosphatidylcitoline in serum with use of a choline-sensitive membrane electrode

A choline-sensitive membrane electrode made with potassium tetrakis(p-chlorophenyl) borate as the exchanger and o-nitrophenyl phenyl ether as membrane solvent in poly (vinyl chloride) was almost insensitive to the surfactant sodium deoxycholate. By using this electrode, choline ( 10^?5 M) formed by the enzymatic hydrolysis of phosphatidylcholine with phospholipase D in the presence of sodium deoxycholate as activator was successfully measured. The method was applied to the determination of phosphatidylcholine in serum.     

Studies in the tetraarylborates: Part 8. The synthesis and reagent properties of tetrathienylborates

The following cesium tetrathienylborates were synthesized and screened for gravimetric reagent properties: tetrakis(2-thienyl), tetrakis(3-thienyl), tetrakis(5-bromo-2-thienyl), tetrakis(5-chloro-2-thienyl),tetrakis(2,5-dimethyl-3-thienyl), tetrakis(5-ethyl-2-thienyl), tetrakis(5-methyl-2-thienyl), and tetrakis(5-t-butyl-2-thienyl). Of these, the tetrakis(5- alkyl-2-thienyl) borates were not sufficiently stable for complete characterization. The following are possible reagents for cesium and quaternary ammonium cations: sodium tetrakis(2-thienyl), tetrakis(3-thienyl), and tetrakis(2,5-dimethyl-3-thienyl)borates.     

Lead-selective fluorescent optode membrane based on 3,3′,5,5′-tetramethyl-N-(9-anthrylmethyl)benzidine

A new proton-selective fluorescing indicator, 3,3′,5,5′-tetramethyl-N-(9-anthrylmethyl)benzidine (TMANB) has been synthesized and applied in an optode membrane for the determination of lead ion that works on the basis of a cation-exchange mechanism. When embedded in a plasticized poly(vinyl chloride) (PVC) membrane containing lead ionophore (tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide)) and a lipophilic anionic site [potassium tetrakis(4-chlorophenyl)borate], TMANB shows a significant fluorescence signal change on exposure to aqueous HCl solution containing lead ion, which exhibits the theoretically expected fluorescence response to lead ion concentration. The selectivity, response time, reproducibility and reversibility, and lifetime of the optode membrane were discussed.     

A sodium ion selective optode based on fluorescein octadecyl ether octadecyl ester and application in beverage and urine assay

A fast responsive sodium ion selective fluorescent optode membrane mounted on an optical fiber has been developed. The sensing membrane contained fluorescein octadecyl ether octadecyl ester (FODEE), potassium tetrakis(4-chlorophenyl) borate (KTpClPB) and a calix[4]arene tetraester in a plasticized poly(vinyl chloride) (PVC) matrix. It exhibited a reversible response to Na⁺ in 0.5 mol/l of HCl in the concentration range of 1.0×10⁻⁶ to 0.1 mol/l. The selectivity, response time, reproducibility and lifetime of the optode membrane were discussed. The practical use of this sensor was demonstrated by real sample analysis in complex sample solutions such as beverage and urine samples.     

Synthesis and Investigation of Energetic Boron Compounds for Pyrotechnics

The energetic boron esters tris(1‐ethyl‐5‐aminotetrazolyl) borate, tris(2‐ethyl‐5‐aminotetrazolyl) borate, tris(1‐ethyltetrazolyl) borate, tris(2‐ethyltetrazolyl) borate, and tris(2‐(3‐nitro‐1, 2,4‐triazolyl)ethyl) borate were synthesized and analyzed by NMR and IR spectroscopy, elemental analysis, and mass spectrometry. Two tetracoordinate borates potassium tetrakis(3‐nitro‐1, 2,4‐triazolyl)borate and potassium bis(4, 4′,5, 5′‐tetranitro‐2, 2′‐bisimidazolyl)borate were synthesized and fully characterized as well. Moreover, the energetic and thermal properties of the energetic boron esters and tetracoordinate borates were determined. The ¹¹B NMR chemical shifts of potassium tetrakis(3‐nitro‐1, 2,4‐triazolyl)borate and potassium bis(4, 4′,5, 5′‐tetranitro‐2, 2′‐bisimidazolyl)borate were calculated and compared to the experimental values. Tris(1‐ethyl‐5‐aminotetrazolyl) borate was tested as colorant in pyrotechnic formulations with respect to the combustion behavior and color properties as well as the energetic and thermal properties.     

Evaluation of the optimum composition of neutral-carrier membrane electrodes with incorporated cation-exchanger sites

Selectivities were measured for membrane electrodes containing a given amount of a neutral carrier (ETH 1692) and varying amounts of the additive potassium tetrakis(p-chlorophenyl)borate. The pronounced selectivity changes induced by the additive agreed with a theoretical model. Both theory and experiment confirmed that an optimum composition of the membrane exists. Ideally, sensors for monovalent cations should contain only small amounts of the additive, whereas sensors for divalent cations should contain a molar ratio of additive/carrier of about 0.7 (for 1:2 cation/carrier complexes). Also described are the new desk-computer programs used for the reduction, evaluation, and graphical presentation of ion-selective electrode data.     

Novel quaternary ammonium borates as latent catalysts for epoxy–phenolic resins

Novel tetrabutylammonium tetrakis(substituted benzoyloxy)borate salts ( 1a – 1d ) were synthesized by the reaction of tetrabutylammonium tetraphenylborate and corresponding substituted benzoic acids. Polyaddition reactions of diglycidyl ether of bisphenol A (DGEBA) and 4,4′‐bisphenol F (44BPF) or bisphenol F (BPF‐D) with the ammonium borates were investigated as model reactions of epoxy/phenol–novolac resin systems with respect to the thermal latency and storage stability of the catalyst. The polyaddition of DGEBA/44BPF with the ammonium borates in diglyme at 150 °C for 6 h proceeded up to 84–94% conversions and gave polymers with number‐average molecular weights of 3750–5750, whereas the polyaddition at 80 °C for 6 h gave less than 9% conversions. The catalytic activity of ammonium borates 1a – 1d depended on the substituent of the phenyl group of the borates, and the order of activity was 1b (p‐OMe) > 1a (? H) > 1c (p‐NO₂) > 1d [3,5‐(NO₂)₂]. The ammonium borate catalyst with the substituent that yielded lower acidity of the corresponding substituted benzoic acid tended to reveal higher activity. In comparison with tetrabutylammonium bromide (TBAB) as a conventional ammonium salt, 1a – 1d revealed better thermal latency. The storage stability of DGEBA/BPF‐D with the ammonium borate catalysts in bulk at 40 °C was better than that with TBAB. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2689–2701, 2002     

Tetrazoles: XLIX. Alkylation of tetrazoles with tetrakis(chloroacetoxymethyl)methane

Alkylation of 1-aryl-4,5-dihydro-1H-tetrazol-5-ones and 1-phenyl-4,5-dihydro-1H-tetrazole-5-thione with tetrakis(2-chloroacetoxymethyl)methane in boiling acetonitrile in the presence of potassium bromide and triethylamine gives tetrakis[2-(4-aryl-5-oxo-4,5-dihydro-1H-tetrazol-1-yl)acetoxymethyl]-methanes and tetrakis[2-(1-phenyl-1H-tetrazol-5-ylsulfanyl)acetoxymethyl]methane, respectively. The alkylation process is considerably accelerated under microwave irradiation.     

Solid contact PVC membrane electrodes based on neutral or charged carriers for the selective reading of anionic sulfamethoxazole and their application to the analysis of aquaculture water

Sulfamethoxazole (SMX) is among the antibiotics employed in aquaculture for prophylactic and therapeutic reasons. Environmental and food spread may be prevented by controlling its levels in several stages of fish farming. The present work proposes for this purpose new SMX selective electrodes for the potentiometric determination of this sulphonamide in water. The selective membranes were made of polyvinyl chloride (PVC) with tetraphenylporphyrin manganese (III) chloride or cyclodextrin-based acting as ionophores. 2-nitrophenyl octyl ether was employed as plasticizer and tetraoctylammonium, dimethyldioctadecylammonium bromide or potassium tetrakis (4-chlorophenyl) borate was used as anionic or cationic additive. The best analytical performance was reported for ISEs of tetraphenylporphyrin manganese (III) chloride with 50% mol of potassium tetrakis (4-chlorophenyl) borate compared to ionophore. Nersntian behaviour was observed from 4.0?×?10^?5 to 1.0?×?10^?2?mol/L (10.0 to 2500?µg/mL), and the limit of detection was 1.2?×?10^?5?mol/L (3.0?µg/mL). In general, the electrodes displayed steady potentials in the pH range of 6 to 9. Emf equilibrium was reached before 15?s in all concentration levels. The electrodes revealed good discriminating ability in environmental samples. The analytical application to contaminated waters showed recoveries from 96 to 106%.     

Anthracene‐sensitized polymerization of vinyl ethers by onium tetrakis(pentafluorophenyl)borate initiators

Cationic photopolymerization of vinyl ethers by the sensitized photolysis of onium tetrakis(pentafluorophenyl)borate initiators has been investigated in this study. The onium borates were sensitized by anthracene and initiated the photopolymerization of the vinyl ethers. The rate of polymerization increased with the decrease in the free‐energy change from the excited singlet state of anthracene to the onium cation of the onium borates. The acid generated by the decomposition of the onium borates formed nonacidic products by heating. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 982–987, 2000     

Development of a new fluorimetric bulk optode membrane based on 2,5-thiophenylbis(5-tert-butyl-1,3-benzexazole) for nickel(II) ions

A highly sensitive and selective fluorimetric optode membrane for the determination of ultra trace amounts of Ni²⁺ ions was prepared. The plasticized PVC-membrane incorporating potassium tetrakis(p-chlorophenyl)borate (KTpClPB) and 2,5-thiophenylbis(5-tert-butyl-1,3-benzexazole) (TTBB), as a highly fluorescent chromoionophore, displays a calibration response for Ni²⁺ ions over a wide concentration range of 1.0×10⁻³ to 1.0×10⁻⁸ M. It has a relatively fast response of <40 s. In addition to high stability and reproducibility, and relatively long working lifetime, the sensor possesses good selectivity for nickel ions over several common diverse ions. The fluorescence signal of the optode membrane can be easily recovered by immersion in EDTA solution. The optode was applied successfully to the determination of traces of Ni²⁺ ion in edible oil and a wastewater sample from nickel electroplating industries.     

Towards Reversibility of Ion Transfer Across the Interface between Valinomycin Membranes and Aqueous Electrolyte Solutions

Valinomycin-based potassium-selective membranes doped with potassium tetrakis(4-chlorophenyl)borate (KClTPB) or sodium tetrakis(4-fluorophenyl)borate (NaFTPB) are studied in KCl, NaCl, and CaCl₂ solutions by potentiometric and electrochemical impedance methods. Before contact with KCl, membranes doped with NaFTPB provide Nernstian potentiometric response to Na⁺ ions, which is lost after conditioning the membranes in KCl. The membranes doped with KClTPB even before contact with KCl give no Nernstian response to Na⁺ ions. In CaCl₂ solutions, none of the membranes provide a regular potentiometric response. Despite the difference in potentiometric behavior, the impedance spectra of the membranes are very similar in all solutions regardless of prior conditioning of the membranes. No evidence for a hindrance towards charge transfer processes is observed. The results suggest that the membrane/solution interface is reversible for interfering ions as well as for potassium, and the contamination of solutions with the latter is the sole reason for the lack of Nernstian response in the interfering electrolytes.     

Self‐crosslinking borate anions for the production of tough UV‐cured polyelectrolyte surfaces

The first anion with four polymerizable groups has been synthesized and used to produce durable, crosslinked polyelectrolyte (PE) coatings in a single step. Sodium tetrakis(4‐vinylphenyl)borate (NaBSty₄) was produced by the reaction of BCl₃ and the Grignard of 4‐bromostyrene. The full series of borates NaBPh_xSty_4?x, x = 1?3, were also synthesized analogously by reaction of the styryl‐Grignard and PhBCl₂, Ph₂BCl, or Ph₃B. Anion exchange of the borates with tributyl 4‐vinylbenzylphosphonium chloride gave a family of organic salts developed for applications in photopolymerized coatings. The percent UV cure of the polymer films was determined by infrared spectroscopy and this relative level of curing was corroborated by differential scanning calorimetry analysis. The degree of crosslinking imparted to the polymer films by the different monomers has resulted in varied mechanical properties, which were probed by diamond tip scratch tests and nanoindentation. These clearly demonstrated that as the number of polymerizable groups increased, the film hardness increased correspondingly. The final hardness of the films exceeds those of other related systems and identifies styryl borates as viable crosslinking additives in UV curable technologies, especially in the production of durable PE films. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Vibrational spectra and factor group analysis of rare-earth chromium borates,RCr3(BO3)4, with R = La–Ho

Anhydrous orthoborates RM₃(BO₃)₄, where R = Y, La–Lu, M = Al, Ga, Cr, Fe, with huntite structure type are considered as multifunctional laser materials. The crystal structure of these borates is either rhombohedral with space group R32 (D₃⁷) (Z = 3) or monoclinic with space group C2/c (C_2h⁶) (Z = 4) depending on the growth conditions. Both modifications have very close polytypic structures, and it is difficult to identify them by powder diffraction data. In this context, double borates of rare-earth cations and Cr³⁺ have been grown from high-temperature solutions and are characterized by Raman and infrared spectroscopy in a crystalline state in combination with factor group analysis of vibrational modes. The assignment for the stretching and bending vibrations of BO₃³⁻ groups and external modes has been made. Some external modes have been identified by study of mass effect (Al–Cr, La–Ho). Comparison of the Raman spectra of these borates shows redistribution of band intensities of two spectral modifications, related to different symmetry groups. As predicted by factor group analysis, the number of IR-active vibrational modes of stretching and bending vibrations of BO₃³⁻ units significantly increases in infrared spectra of monoclinic borates in comparison with rhombohedral ones. The dependence of the realized borate space group on the crystal growth conditions and the sort of rare-earth atom was revealed. Both GdCr₃(BO₃)₄ and EuCr₃(BO₃)₄ borates crystallize in space group R32 irrespective of growth conditions. The borates with the large rare-earth elements La–Nd always form the monoclinic structures, irrespective of crystallization temperature. The borates SmCr₃(BO₃)₄, TbCr₃(BO₃)₄ and DyCr₃(BO₃)₄ have been obtained in two modifications in dependence of crystalline borate substance/solvent ratio and related temperature of crystallization.     

A PVC-based 1,8-diaminonaphthalen electrode for selective determination of vanadyl ion

A PVC membrane vanadyl (VO²⁺) ion-selective electrode was constructed using 1,8-diaminonaphthalen (DAN) as a neutral carrier. The electrode shows good Nernstian response for VO²⁺ ions over a wide concentration range (1.0×10⁻¹-1.0×10⁻⁵ M). The optimum composition of the membrane was 55 wt.% poly(vinylchloride), 35 wt.% 2-nitrophenyl octyl ether (NPOE), 5 wt.% ionophore, and 5 wt.% potassium tetrakis(p-chlorophenyl)borate (KTpClPB). It has relatively fast response time and can be used at least for 5 weeks without any considerable divergence in potentials. The proposed electrode revealed relatively good selectivity for VO²⁺ over wide variety of other metal ions. The electrode was used for the potentiometric titration of VO²⁺ ions with EDTA.     

An effective BINAP and microwave accelerated palladium-catalyzed amination of 1-chloroisoquinolines in the synthesis of new 1,3-disubstituted isoquinolines

A facile and microwave accelerated reaction of 1-chloro-3-(4-chlorophenyl)isoquinoline with various heterocyclic amines, catalyzed by Pd, in the presence of BINAP additive and sodium carbonate as the base, leads to the formation of 3-(4-chlorophenyl)-1-(1H-1,2,3-triazol-1-yl)isoquinoline, 3-(4-chlorophenyl)-1-(1H-imidazol-1-yl)isoquinoline and 3-(4-chlorophenyl)-1-(1H-1,2,4-triazol-1-yl)isoquinoline via Buchwald protocol in good yields. Similarly pyrazolylisoquinolines are also reported.     

Magnesium-selective test strip

A selective test strip based on an ion-exchange mechanism to determine magnesium is described. This optical and reversible test strip, made on a transparent polyester sheet, has a circular polymeric film of plasticised PVC that contains all of the reagents necessary to produce a response to magnesium, namely, a cation-selective neutral ionophore, 2-amino-N,N′-diheptyl-N,N′-dimethyl-butanediamide, a chromoionophore, N,N-diethyl-5-(octadecanoylimino)-5H-benzo[a]phenoxazine-9-amine, and potassium tetrakis (4-chlorophenyl)borate (TCPB) as a lipophilic salt, which is evaluated by absorbance measurement at 655 nm in a standard photometer. The experimental variables that influence test strip response, especially in terms of selectivity and response time, have been studied. The test strip responded linearly to magnesium between 0.009 and 160 mM in activities. The reproducibility intermembrane at a medium level of the range was 8.0%, as R.S.D., of log aMg2+, and 5.9% as R.S.D. intramembrane. The procedure was applied to the determination of magnesium in different types of waters (tap, well and mineral) validating the results against a reference procedure. This proposed method is quick, inexpensive, selective and sensitive and uses only conventional instrumentation.     

The effects of substituents,molecular symmetry,ionic radius of the rare earth metal,and macrocycle on the electronic absorption spectra characteristics of sandwich-type bis(phthalocyaninato) and mixed (phthalocyaninato)(porphyrinato) rare earth complexes

The electronic absorption spectroscopic data for two series of 60 unsubstituted/substituted bis(phthalocyaninato) and mixed [tetrakis(4-chlorophenyl)porphyrinato](phthalocyaninato) rare earth complexes M(Pc)₂, M(Pc^∗)₂ and M(TClPP)(Pc) [M = Y, La…Lu except Pm; Pc^∗ = dianion of 2,3,9,10,16,17,23,24-octakis(4-methoxyphenoxy)phthalocyanine [Pc(MeOPhO)₈], dianion of 3(4),12(13),21(22),30(31)-tetra(tert-butyl)phthalocyanine (TBPc) and TClPP = tetra(4-chloro)phenylporphyrin] have been measured in CHCl₃. In this paper, the influence of the symmetry of macrocycle rare earth molecules, the effects of ionic radius of the rare earth metal and the influence of substituent species (tert-butyl and 4-methoxyphenoxy groups) onto the peripheral benzene rings on the electronic absorption characteristics of sandwich-type compounds have also been tentatively studied in detail.     

Infrared spectroscopy and the structure of polytypic modifications of RM<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> borates (R — Nd,Gd, Y; M — Al,Ga, Cr,Fe)

By means of IR spectroscopy with the use of factor group analysis for vibrations of the B-O bond, rare-earth borates with a general formula of RM₃(BO₃)₄ (R is Nd, Gd, and Y; M is Al, Ga, Cr, and Fe) and related polytypic structures are assigned to space groups R32 or 2/c. Compounds with both almost homogeneous structures and with inclusions of the monoclinic polytype are revealed among rhombohedral borates. The latter is most typical of phases with a small octahedral Al cation. It is shown that in the monoclinic modification of NdAl and NdCr borates fragments of the rhombohedral phase are always present. Alternation of differently ordered structural fragments is determined by temperature conditions of crystallization.