A Fiber Optic Biosensor for Uric Acid Based on Immobilized Enzymes

Abstract

A simplified enzyme based fiber optic uric acid biosensor is reported. It is constructed by coimmobilizing uricase and horseradish peroxidase [HRP] to bovine albumin via glutaraldehyde. A new fluorimetric substrate, thiamine, is used to indicate the sensing process. Under optimized conditions, the linear range of uric acid concentration is 0.5 to 5.0 ug/mL with a correlation coefficient of 0.997, and the detection limit is 0.15 ug/mL with excellent reversibility and stability. The sensor can be used at least two months at room temperature. It is possibly to determine uric acid directly in serum and urine samples with satisfactory results.     

Silver nanoparticles plasmon resonance-based method for the determination of uric acid in human plasma and urine samples

We have developed a simple and sensitive colorimetric procedure for the quantification of trace amounts of uric acid. It is based on the finding that uric acid in a medium containing ammonia and sodium hydroxide at 65?°C can reduce silver ions to form yellow silver nanoparticles (Ag NPs). These are stabilized in solution by using poly(vinyl alcohol) as a capping agent. The yellow color of the solution that results from the localized surface plasmon resonance of Ag NPs can be observed by the bare eye. The absorbance at 415?nm is proportional to the concentration of uric acid which therefore can be determined quantitatively. The calibration curve is linear in the concentration range from 10 to 200?nM, with a limit of detection of 3.3?nM. The method was successfully applied to the determination of uric acid in human plasma and urine samples.

Synthesis and properties of mesogenic laterally fluorinated compounds containing benzoxazole unit

Series of mesogenic laterally fluorinated compounds, 2-(2′,3′-difluoro-4′-alkoxybiphenyl-4-yl)-benzoxazole derivatives (nB-Fx) bearing different substituents (H, CH₃, Cl, NO₂, coded as nB-FH, nB-FM, nB-FC and nB-FN, respectively) at 5-position, were prepared and characterised. Their phase transition behaviour was investigated by differential scanning calorimetry and polarising optical microscopy. nB-Fx with alkoxy chain lengths of 2 to 10 carbons exhibited enantiotropic mesophases, for which the mesophase ranges were 0°C–58°C and 0°C–71°C on heating and cooling for nB-FH, 41°C–93°C and 66°C–140°C for nB-FM, 44°C–133°C and 87°C–155°C for nB-FC, and 0°C–76°C and 0°C–95°C for nB-FN, respectively. Compared to non-fluorinated analogues, with the exception of nB-FC, fluorinated nB-Fx mainly exhibited nematic mesophase both in heating and cooling, which were attributed to the disruption of the side-to-side intermolecular packing caused by the two ortho-lateral fluoro substituents. For nB-Fx series, nB-FM, nB-FC and nB-FN exhibited a much wider mesophase range than the corresponding nB-FH series, which indicated that the substituent at benzoxazole moiety was helpful in increasing the mesophase stability. With the exception of nB-FN, the nB-Fx series displayed intense photoluminescence emission at 379–383 nm in methylene chloride solution, when it was excited at its absorption maxima.     

POLAROGRAPHIC INVESTIGATION OF THE SYSTEMS ARSENIC(III)-TARTARIC ACID AND ARSENIC(III)-1,2-DIAMINO-CYCLOHEXANE-N,N,N′,N′-TETRAACETIC ACID (DCTA)

Abstract

The reactions between As(III), tartaric acid (H₂T)and DCTA were investigated polarographically. The conditional stability constants of As(III)-complexes at a given pH-value and variable ligand concentration were calculated from the change of the limiting currents. The optimum conditions for calculating stability constants from the current were also discussed. It was found that DCTA (H₄L)formed the complex [As(OH)₂HL]^2- whose overall formation constant was lgβ111=(20.67 ±0.09)atμ=0.1 and t°- (25.0±0.2)°C, whereas the complex between As(III) and H₂T was [As(OH)₂T]^? with an overall stability constant 1gβ 101= 6.62 ±0.14 at μ=0.1 and t°= (25 ± 0.2)°C.     

Linear and Hyperbranched Poly(arylene ether)s from a New Semifluorinated AB Monomer

A new trifluoromethyl-activated AB monomer has been successfully synthesized by Pd-initiated coupling of 4-bromo anisole with 4-fluoro-3-trifluoromethylphenylboronic acid followed by demethylation. The monomer leads to a semifluorinated poly(arylene ether) by nucleophilic displacement polymerization reaction. The AB monomer has been further copolymerized with a corresponding AB ₂ monomer to form the corresponding semifluorinated hyperbranched (hb) poly(arylene ether). The resulting linear and hb poly(arylene ether)s exhibited weight average molecular weight of 75700 and 144100 g/mol, respectively. The hb copolymer exhibited better solubility in different organic solvents compared to the linear poly(arylene ether). The polymers showed excellent thermal stability up to 522°C at 10% wt loss in air and glass transition temperatures as high as 187°C. The mechanical properties of the linear poly(arylene ether) film 1a exhibited tensile strength at break of 89 MPa, elongation at break of up to 3% and a Young’s modulus value of 2.66 GPa. The films of the polymers were hydrophobic in nature and showed water contact angle as high as 93.6°.     

THE REACTION OF DIPHENYLPHOSPHINE OXIDE WITH DIPHENYLPHOSPHINOUS CHLORIDE IN THE ABSENCE OF BASE

Abstract

Diphenylphosphinous chloride (1) and diphenylphosphine oxide (2) (2 mol. equivalent) react to form diphenylphosphinic acid (4), together with tetraphenyldiphosphine (5) (at 80°C), or its hydrochloride (6) (at 20°C), as the only products.     

Complexation and Thermal Studies of Uric Acid with Some Divalent and Trivalent Metal Ions of Biological Interest in the Solid State

Nine new [metal uric acid] complexes [M(Ua) n ]°·XH 2 O have been synthesized. These complexes have been characterized by elemental analysis, X-ray diffraction (XRD), magnetic susceptibility ( w eff. ), FTIR spectra, thermal analysis (TG & DTA), and electronic spectra (UV/visible). Uric acid (HUa) coordinates as a bidentate ligand to Mn(II), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Al(III), Cr(III) and Fe(III) through the protonated N-7 within the imidazole ring and O-6 within the pyrimidine ring. Uric acid forms neutral metal urate complexes with all the above metal ions. The quantitative compositions were determined as [M(Ua) 2 ·(H 2 O) 2 ]°·XH 2 O where M(II)=Mn, Fe, Co, Ni, Cu, Zn and X=2, 4, 2, 4, 2, 2, respectively. The M(II) complexes exhibit an isostructural octahedral coordination with N-7, O-6 of two uric acid ligand molecules, and O of two water molecules. Compositions were also determined as [M(Ua) 3 ]°·YH 2 O where M(III)=Al, Cr, Fe and Y=6, 3, 3 respectively. All the M(III) complexes form an isostructural octahedral coordination with N-7 and O-6 of three uric acid ligand molecules. Iron(III) complexes prepared with N 1 , N 3 and N 9 -methyl uric acid yielded brown complexes with a metal ligand ratio of 1 3, while N 7 -methyl uric acid did not yield a complex due to blockage of N-7 with a methyl group.     

Synthesis and Characterization of Novel Poly(Arylene Ether)s from 1,3‐bis(4‐Hydroxyphenyl) Benzene

Abstract

Several poly(aryl ether)s have been prepared by the condensation of 1,3‐bis(4‐hydroxy phenyl) benzene with different trifluoromethyl activated bis‐fluoro compounds. IR, ¹H and ¹³C NMR, and elemental analyses have established the resulting polymer structures. The properties of the polymers have been evaluated by DSC, TGA, dynamic mechanical analysis (DMA) and stress–strain analysis. The polymers 1a and 1c showed semi‐crystalline behavior as evident by sharp crystalline melting peaks at 299°C and 330°C along with glass transitions at 202°C and 216°C, respectively. The polymers showed very good thermal stability in air, high modulus, and high tensile strength with low elongation at break.     

Simple,Safe, Large Scale Synthesis of 5-Arylmethyl-2,2-dimethyl-1,3-dioxane-4,6-diones and 3-Arylpropanoic Acids

Reaction of aryl aldehydes with Meldrum's acid 2 in the presence of formic acid and triethylamine gives 5-arylmethyl Meldrum's acid derivatives 4 at room temperature, whereas at 80–100°C 3-arylpropanoic acids 5 are formed.     

Some Recent Results on the Synthesis of Certain Aromatic Heterocyclic Polymers

Abstract

Continued research on poly(bisbenzimidazobenzophenanthrolines) from one-step condensation of 1, 4, 5, 8-naphthalene tetracarboxylic (NTA) acid and 3, 3′-diaminobenzidene in polyphosphoric acid (PPA) has led to good-quality fibers with outstanding resistance to high temperatures and Fade-O-Meter aging. The condensation of 4, 5-diamino-1, 8-naphthalene dicarboxylic acid derivatives produces low molecular weight polyperimidines which have good stability. The polyimide from condensation of 1, 1′, 5, 5′-diphenyldianhydride is insoluble in all solvents tried and shows moderate thermal stability. The completely soluble ladder polymer from condensation of 1, 4, 5, 8-naphthalene tetracarboxylic acid with 1,2,4,5-tetraamino benzene in polyphosphoric acid has been obtained in high molecular weight (intrinsic viscosities in methane sulfonic acid at 30°C of over 5 dl/g).     

A Uricase Method for the Peak Identification of Uric Acid Appeared in a Liquid Chromatogram Amperometrically Monitored

Abstract

A uricase method for the peak identification of uric acid appeared in a liquid chromatogram monitored by aid of an electrochemical detector has been developed. Uricase (EC 1.7.3.3, from Candida utilis) catalyzes the conversion of uric acid to allantoin. We have found that uric acid can be oxidized under the chromatographic conditions employed in this study, whereas allantoin cannot be oxidized. The complete disappearance of a uric acid peak in a chromatogram of a biological sample after the uricase treatment indicates that the uric acid peak does not contain any other electroactive components. We observed the complete disappearance of the uric acid peaks in the chromatograms of human serum and gastric body.     

Determination of Uric Acid in Human Serum: Reversed-Phase Liquid Chromatography with Electrochemical Detection

Abstract

A method for the simultaneous determination of uric acid in human serum by reversed-phase high-performance liquid chromatography with electrochemical detection has been developed. Human serum (0.5 ml) was mixed with 0.5 ml of 0.2 N perchloric acid solution and the mixture was centrifuged at 3,000 g for 20 min. An aliquot (10 μl) of the supernatant (deproteinized human serum) was injected into the chromatographic system employed in this study. The assay limit for quantitation was about 10 pg for uric acid. Complete separation of uric acid was achieved in about 8 min under the present chromatographic conditions.     

Photochemical behaviour of Schiff base liquid crystals based on isoxazole and isoxazoline ring. A kinetic approach

ABSTRACT

The kinetic study on the hydrolysis of Schiff bases (SBs) 1a-c and 2a-c induced by UV-vis was undertaken as a complementary study of the stability in solution and in bulk of the SBs. Solutions in chloroform were exposed to UV-vis and acquisition data occurred for 1a-c and for 2a-c in 21°C, 30 °C, 35°C and 40°C. Kinetic profile for 1a-c and 2a-c displayed the similar photochemical behaviour in that four temperature values. At 21°C, two kinetic regimes were observed where the decomposition of SBs is faster at the initial stage, with no linear plot of absorbance vs time, and after the kinetic profile obeyed a linear behaviour. A mathematical treatment of the experimental data was applied, which allowed associating the initial stage data with a second-order reaction, and the final stage of the hydrolysis with a first-order reaction. The mechanism of photochemical hydrolysis of SBs 1a and 2a was addressed. It was composed of three parts, the excitation, then the isomerisation and activation processes of tetrahedral intermediate and, the last process, a collapse of the intermediate to the yielded products of the hydrolysis aldehydes and amines which were detected by their UV-vis spectrum.     

Interaction of the general volatile anesthetic Enflurane with bacteriorhodopsin-DPPC proteoliposomes

Thermal decomposition of dried crystalline powder obtained from titanium(IV) bis(acetylacetonate) diisopropoxide (75% solution in 2-propanol) (1) was monitored by simultaneous TG/DTA, EGA-FTIR and EGA-MS measurements and the results were compared with those of amorphous powder obtained by gelling of acetylacetonate-modified titanium(IV) tetra-isopropoxide at molar ratio of 1:2 in boiling 2-methoxyethanol (2). Thermal degradation of 1 in the temperature range of 25–700°C consists of 5 steps with a total mass loss of 62.5%. EGA by FTIR and MS revealed the release of H₂O below 120°C; followed by an intensive evolution of acetylacetone around 245°C. The release of acetone and acetic acid occurs up to 270°C and that of CO and CO₂ up to 530°C.     

A New Route for the Synthesis of Alkali Polyphosphate from Economical Starting Materials: Preparation and Characterization of Sodium Cyclotriphosphate

Abstract

Thermal synthesis of sodium cyclotriphosphate (SCTP) – Na₃P₃O₉ was investigated in the temperature range of 150 °C to 750 °C using sodium chloride (NaCl) and 85 wt% orthophosphoric acid (H₃PO₄) as economical starting materials. Reaction temperature had a crucial impact on the chloride elimination rate and the formation of SCTP. The best result was obtained at 600 °C with 96% of elimination of the initial chloride as hydrochloric acid and 84% of selectivity in SCTP. At lower temperatures, residual chloride contents were high. At higher temperatures (650 °C and 750 °C), SCTP was melted and transformed into glassy products.     

Synthesis and phase behaviour of new biodegradable liquid crystalline polycarbonate derived from side chain cholesteryl derivative

A new cholesterol side-functionalised polycarbonate was synthesised through a coupling reaction between the terminal carboxyl group of the monomer 6-cholesteroxy-6-oxocaproic acid (COHA) and side hydroxyl group of the polycarbonate (PHTMC). The chemical structures of the intermediate compounds, monomers and polymers obtained in this study were characterised with FT-IR and ¹H NMR spectrum. Their phase behaviour and thermal stability were investigated using polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and thermogravimetric analysis. The monomer COHA showed a cholesteric phase, while the corresponding cholesterol side-functionalised polycarbonate P(TMC-g-COHA) revealed a smectic A phase. This behaviour was attributed to an increased density of the mesogenic units in side chain and hence an ordered organisation into the mesophase. Furthermore, P(TMC-g-COHA) could exhibit a liquid crystalline state below body temperature (≈37°C). This fact indicated it could be used clinically as a self-assemble material with orientational-order mesophase. In addition, P(TMC-g-COHA) had a good thermal stability, the corresponding thermal decomposition temperature was 241°C.     

Application of Ion-Exclusion Chromatography to the Study of Equilibria of Anionic Complexes

Abstract

An ion-exclusion chromatographic method for the determination of a stability constant of an anionic metal complex has been devised. The stability constants (1og β₁) of magnesium diphosphate and magnesium triphosphate complexes at 1=0.1 and 15°C were evaluated to be 5.06 and 5.89 in sodium chloride solution.     

Thermal stability of flexible polyurethane foams containing modified layered double hydroxides and zinc borate

Abstract

Flexible polyurethane foams (FPUFs) have been modified to contain layered double hydroxides (LDHs) by dihydrogen phosphate (H₂PO₄ ^?). The thermal stability of the prepared foams has been characterized using thermogravimetric analysis (TGA) at 5, 10, 20, 30, and 40?°C/min heating rates. The experimental data indicate that the temperature range for the two pyrolysis stages of FPUF is about 212–350?°C and 350–565?°C, respectively. Integral programmed decomposition temperature (IPDT) has been calculated according to the measured data, which was found that the IPDT of the modified FPUF was increased to 526?°C. Additionally, the thermal stability of FPUF composite has been also evaluated by the activation energy (E) on the basis of the pyrolysis kinetics of FPUF composites during thermal decomposition using Coats–Redfern integral method. These results manifest that the presence of intercalated LDHs enhances the thermal stability of FPUF.     

Chemical Condensation of Phosphoramidates with Acids

Abstract

Several phosphoramidates and its phenyl ester were reacted with hydrogen chloride, acetic acid, and oxalic acid at room temperature and/or 60 °C.     

Voltammetric oxidation of some biologically important xanthines at the pyrolytic graphite electrode

Linear and cyclic sweep voltammetry of some biologically important N-methylxanthines has been carried out. The principal and potential determining reaction for oxidation of xanthines is a 2 electron attack at the -N₉C_8⁻ double bond to give the appropriate uric acid, which is then immediately further oxidized to an intermediate 4,5-diol species. In many instances this 4,5-diol is sufficiently stable to be detected by fast sweep cyclic voltammetry as a small cathodic peak formed as a result of reduction of part of the 4,5-diol to the corresponding uric acid. The uric acid so formed can be reoxidized upon subsequent cycles at a potential close to that observed for reduction fo the 4,5-diol, so that most xanthines (and uric acids) show evidence for a reversible redox couple at about 0.4–0.55 V. Methylation at position N₇ decreases somewhat the stability of the intermediate 4,5-diol and dimethylation at N₃ and N₇ results in such a marked decreased in the stability of the diol that it cannot be observed by cyclic voltammetry.