A Schiff base expanded porphyrin macrocycle that acts as a versatile binucleating ligand for late first-row transition metals

The coordination chemistry of the Schiff base polypyrrolic octaaza macrocycle 1 toward late first-row transition metals was investigated. Binuclear complexes with the divalent cations Ni(II), Cu(II), and Zn(II) and with the monovalent cation Cu(I) were prepared and characterized. Air oxidation of the Cu(I) ions in the latter complex to their divalent oxidation state resulted in a change in the coordination mode relative to the macrocycle.     

Potentiometric determination of acids and bases using a silica gel based carbon-epoxy indicator electrode

The construction and the application of a silica gel based carbon-epoxy indicator electrode for the potentiometric determination of acids and bases are described. The effect of composition of silica gel and carbon-epoxy, slope (mV/pH), linear response (pH range) and the use for acid-base titrations were investigated. The data obtained for the acid-base titrations were compared with those obtained using a glass electrode in the same conditions. The electrode showed a linear response in the pH 2 to 13 range with a slope of -40.5 +/- 0.4 mV/pH (at 25 degrees C) and a response time of less than 15 s. The lifetime of the electrode was higher than one year (over 6000 determinations) with a decrease of only 5% of the initial potentiometric response. The silica gel based carbon-epoxy electrode showed excellent results in the end-point indication potentiometric titrations in determination of acids and bases. The miniaturization of the proposed electrode for flow injection analysis was investigated.     

Potentiometric determination of acids and bases using a silica gel based carbon-epoxy indicator electrode

The construction and the application of a silica gel based carbon-epoxy indicator electrode for the potentiometric determination of acids and bases are described. The effect of composition of silica gel and carbon-epoxy, slope (mV/pH), linear response (pH range) and the use for acid-base titrations were investigated. The data obtained for the acid-base titrations were compared with those obtained using a glass electrode in the same conditions. The electrode showed a linear response in the pH 2 to 13 range with a slope of –40.5 ± 0.4 mV/pH (at 25 °C) and a response time of less than 15 s. The lifetime of the electrode was higher than one year (over 6000 determinations) with a decrease of only 5% of the initial potentiometric response. The silica gel based carbon-epoxy electrode showed excellent results in the end-point indication potentiometric titrations in determination of acids and bases. The miniaturization of the proposed electrode for flow injection analysis was investigated. Received: 11 August 1999 / Revised: 4 October 1999 / Accepted: 7 October 1999     

Solid ink-printed filter paper as a green adsorbent material for the solid-phase extraction of UV filters from water samples

This work describes the development of a new green solid-phase extraction approach, which is based on the use of low-cost extraction discs composed of plain filter papers that are covered with a synthetic wax-like coating. The filter papers are printed in a commercial solid ink printer, which dispenses a synthetic wax-like ink on the surface of the paper, to cover the hydrophilic cellulose fibre matrix with an interface of lipophilic domains where non-polar analytes can partition through hydrophobic interactions. The modified paper filters were used to extract hydrophobic organic compounds from water samples following the customary procedure of solid-phase extraction without sorbent preconditioning and needless of high-vacuum sources. As a proof-of-concept application, a series of non-polar organic UV filters were used as model analytes to optimise the extraction parameters and evaluate the performance of the method in spiked water samples. Based on this principle, a new sample preparation platform with low environmental footprint has been developed that enables extraction to be carried out using low-cost, environmental benign and non-toxic conventional materials. The advantages and disadvantages of the method, alongside with its future prospects towards the development of custom-made ‘printed extraction kits’, are envisioned and discussed.     

Fix L, a haemoglobin that acts as an oxygen sensor: signalling mechanism and structural basis of its homology with PAS domains

Fix L, which contains a haemoglobin domain homologous to the PAS family and a histidine kinase domain, forms, with Fix J, a two-component signalling complex that regulates expression of nitrogenase genes in Rhizobium. Spin transitions of its haem iron trigger stereochemical changes in and around the haem that, together with steric effects, control the activity of the kinase. Homology with the PAS family is based on a common core of about 20 structurally equivalent sites from which polar residues are excluded.     

Reduction of nitrous acid with a macrocyclic rhodium complex that acts as a functional model of nitrite reductase

Nitrous acid reacts with L(2)(H(2)O)Rh(2+) (L(2) = meso-hexamethylcyclam) in acidic aqueous solutions to generate a strongly absorbing intermediate Int-1 (λ(max) 400 nm, ε = 1200 M(-1) cm(-1)). The reaction follows a mixed second order rate law with k = (6.9 ± 0.3) × 10(4) M(-1) s(-1), independent of [H(+)]. The lack of acid dependence shows that Int-1 is a rhodium(II) complex of HNO(2), most reasonably assigned as L(2)(H(2)O)Rh(HNO(2))(2+). This species is analogous to the early iron and copper intermediates in the reduction of nitrite by nitrite reductases and by deoxyhemoglobin. In the presence of excess L(2)(H(2)O)Rh(2+), the lifetime of Int-1 is about 1 min. It decays to a 1:1 mixture of L(2)(H(2)O)RhNO(2+) and L(2)Rh(H(2)O)(2)(3+) with kinetics that are largely independent of the concentration of excess L(2)(H(2)O)Rh(2+) and of [H(+)] at [H(+)] < 0.03 M. At [H(+)] > 0.03 M, an acid-catalyzed pathway becomes effective, suggesting protonation and dehydration of Int-1 to generate L(2)(H(2)O)RhNO(3+) (Int-2) followed by rapid reduction of Int-2 by excess L(2)(H(2)O)Rh(2+). Int-2, which was generated and characterized independently, is an analog of the electrophilic intermediates in the mechanism of biological reduction of nitrite to (?)NO. Excess nitrite greatly reduces the lifetime of Int-1, which under such conditions decomposes on a millisecond time scale by nitrite-catalyzed disproportionation to yield L(2)(H(2)O)RhNO(2+) and L(2)Rh(III). This reaction provides additional support for the designation of Int-1 as a Rh(II) species. The complex reaction mechanism and the detection of Int-1 demonstrate the ability of inorganic complexes to perform the fundamental chemistry believed to take place in the biological reduction of HNO(2) to NO catalyzed by nitrite reductases or deoxyhemoglobin.     

Liquid-liquid interfaces as potentiometric ion-sensors-I The n-butanol-water interface as indicating sensor for the potentiometric titration of some acids and bases

The property that liquid-liquid interfaces modify their electrical charge as a function of the composition of the two phases in contact has been used to detect the end-points in a series of acid-base titrations in the aqueous phase. Although the titration curves are not classical in shape, the equivalence points can be located if the solutions are not too dilute. Good results for concentrations down to 10(-3)N have been obtained. The electrode has a fast response. The influence of surface-active substances on the titration has also been investigated.     

A heteronuclear bidentate Lewis acid as a phosphorescent fluoride sensor

Reaction of dimesityl-1,8-naphthalenediylborate (1) with C6F5HgCl results in the formation of a B/Hg heteronuclear bidentate Lewis acid (2), which complexes fluoride to afford [2-mu2-F]-. Structural and photophysical studies carried out in solution and in the solid state indicate that 2 is a highly selective and sensitive phosphorescent fluoride sensor. The proximity of the two Lewis acidic sites enforced by the 1,8-naphthalenediyl backbone promotes fluoride anion chelation and is, therefore, responsible for the high binding constant. The interplay of conjugative and spin-orbit coupling effects mediated by the boron and mercury atoms, respectively, results in the phosphorescent signaling of fluoride binding. Remarkably, fluoride binding occurs in partially aqueous solutions and results in a drastic change of the phosphorescence observed when the solutions are frozen.     

A ferrocene-modified platinum electrode as a potentiometric sensor for l-ascorbic acid

A half-oxidized platinum electrode modified with a monolayer of ferrocene is proposed as a potentiometric sensor for l-ascorbic acid in an aqueous glycine buffer pH 2.2. The ferrocene was covalently attached to the surface by a silane carbon chain. The potentials of 15 electrodes were measured and a slope of (50 ± 8.8) mV per decade change in concentration of ascorbic acid was obtained over the concentration range 10^?3-10^?6 M. Recovery experiments with pure l-ascorbic acid solutions showed a relative standard deviation of 1.9%, in the analysis of fresh orange juice, the relative standard deviation was 6.1%.     

Nitrogen Alkylation of schiff bases and amidines as a route to N-alkyl amino acids

Schiff base and amidine ester $\text{3}$ are alkylated and then hydrolyzed to yield N-alkyl amino acids $\text{4}$ in 41–75% yield with high to complete retention of optical activity.     

Immbolization of uricase enzyme in Langmuir and Langmuir-Blodgett films of fatty acids: possible use as a uric acid sensor

Preserving the enzyme structure in solid films is key for producing various bioelectronic devices, including biosensors, which has normally been performed with nanostructured films that allow for control of molecular architectures. In this paper, we investigate the adsorption of uricase onto Langmuir monolayers of stearic acid (SA), and their transfer to solid supports as Langmuir-Blodgett (LB) films. Structuring of the enzyme in β-sheets was preserved in the form of 1-layer LB film, which was corroborated with a higher catalytic activity than for other uricase-containing LB film architectures where the β-sheets structuring was not preserved. The optimized architecture was also used to detect uric acid within a range covering typical concentrations in the human blood. The approach presented here not only allows for an optimized catalytic activity toward uric acid but also permits one to explain why some film architectures exhibit a superior performance.     

Anthranilamide: a simple, removable ortho-directing modifier for arylboronic acids serving also as a protecting group in cross-coupling reactions

Anthranilamide (AAM) serves as a bifunctional modifier on the boron atom in catalytic transformations of arylboronic acids. It makes boronyl groups unreactive in Suzuki-Miyaura coupling and promotes Ru-catalyzed ortho-silylation. Suzuki-Miyaura coupling of AAM-modified bromophenylboronic acids with tolylboronic acid gave 1,1'-biaryl-4-boronic acid bearing AAM on the boron atom, which subsequently underwent Ru-catalyzed ortho-silylation at the 3-position by virtue of the ortho-directing effect of the AAM group.     

Influence of organic bases on the partition of indicator acids (and vice-versa) in a water-chloroform system: Analytical applications

The influence of organic bases on the partition of bromothymol blue between water of varying H-ion concentration and chloroform was studied quantitatively. A principle for the accurate determination of minute quantities of organic bases by a colorimetric procedure has been established by this research and by the method developed the reverse influence could further be investigated. A number of analytical applications follow.     

A dinuclear ruthenium(II) complex that functions as a label-free colorimetric sensor for DNA

A dinuclear ruthenium(II) complex groove binds to DNA and this interaction results in distinctive color changes that are dependent on both DNA sequence and structure.     

Unsaturated dicarboxylic acids as substrates in oscillating reactions involving bromate, sulfuric acid and a catalyst

A new type of homogeneous oscillating reaction has been observed in the potassium bromate-acetylenedicarboxylic acid-ferroin-sulfuric acid system. This proves that the presence of an active methylene group is not a necessary condition for oscillating reactions involving carboxylic acids. Malonic acid can be partly replaced by maleic and fumaric acid in the Belousov reaction. Under the mild experimental conditions of the oscillating reaction, maleic acid undergoes isomerization to fumaric acid.

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Metal-organic framework as a multi-component sensor for detection of Fe3+, ascorbic acid and acid phosphatase

In this research,a hydroxyl group functionalized metal-organic framework(MOF),UiO-66-(OH)₂,was synthesized as a "on-off-on" fluore scent switching nanoprobe for highly sensitive and selective detection of Fe³⁺,ascorbic acid(AA) and acid phosphatase(ACP).UiO-66-(OH)₂ emits yellow-green light under ultraviolet light,when Fe³⁺ was added,Fe³⁺ was chelated with hydroxyl group,the electrons in the excited state S_1 of the MOF transferred to the half-filled 3 d orbits of Fe³⁺,resulting in fluorescence quenching because of the nonradiative electron/hole recombination annihilation.AA could reduce Fe³⁺ to Fe²⁺,which can destroy the electron transfer between UiO-66-(OH)₂ and Fe³⁺ after AA adding,resulted in nonoccurrence of the nonradiative electron transfer,leading to the recovery of UiO-66-(OH)₂ fluorescence intensity.The probe can also be used to detect ACP based on the enzymolysis of 2-phospho-L-ascorbic acid(AAP) to produce AA.Benefitting from the hydroxyl group and the characteristics of UiO-66,including the high porosity and large surface area,the developed UiO-66-(OH)₂ showed extensive advantages as a fluorescent probe for detection of multi-component,such as high sensitivity and selectivity,colorimetric detection,fast response kinetics and easy to operate,economical and secure.This is the first time to use active group functionalized MOFs as a multicomponent sensor for these three substances detection.     

A novel chiral terpyridine macrocycle as a fluorescent sensor for enantioselective recognition of amino acid derivatives

Terpyridine macrocycle 1 is shown to be a strong chelating agent for organic ammonium salts and also a useful chromophore in fluorescent sensing. It exhibits very good enantioselectivity (K(obs)(S)/K(obs)(R)= 3.8) in chiral discrimination of alpha-phenylglycine methyl ester hydrochloride (PhEtOMe).     

A deuterium-palladium electrode as a new sensor in non-aqueous solutions: potentiometric titration of weak acids in acetonitrile and benzonitrile

A deuterium-palladium electrode was employed as a new indicator electrode for the titration of weak acids in acetonitrile and benzonitrile. The investigated electrode showed a linear dynamic response for p-toluenesulfonic acid in the concentration range from 0.001 M to 0.1 M with a Nernstian slope of 48 mV in acetonitrile. Sodium methylate, potassium hydroxide and tetrabutylammonium hydroxide proved to be very suitable titrating agents for these titrations. The response time was less than 10-11 s and the lifetime of the electrode was limitless. Advantages of the electrode are: long-term stability, fast response, reproducibility, easy preparation and low cost.     

Optical sensor for salicylic acid and aspirin based on a new lipophilic carrier for aromatic carboxylic acids

Summary The optode with fair selectivity for salicylate and aspirin is based on the use of a new lipophilic carrier for aromatic carboxylic acids, namely (±) n-butyl O-(1-naphthylaminocarbonyl) lactate (BNAL). The sensing scheme involves co-extraction of both salicylate anion and a proton from the aqueous sample medium into a pvc layer using BNAL as a salicylate carrier, and a pH-sensitive dye as a lipoid proton carrier, both contained in the pvc membrane. BNAL transports the salicylate anion into the pvc lipid membrane. In order to maintain electro-neutrality, the proton carrier dye simultaneously extracts a proton into the pvc membrane, thereby becoming protonated. As a result, the dye undergoes a colour change which is detected via measurement of fluorescence intensity. The sensor is fully reversible and has a dynamic range from 0.1 to 30 mmol/l salicylate at pH 5.00, but the response function is highly pH-dependent. The effect of 25 interfering anions was investigated, and optical selectivity coefficients were determined. It is also shown that by proper variation of the membrane composition, selectivities for other carboxy anions can be obtained. The method has been applied to determine aspirin in tablets using flow injection analysis, and the results were found to be satisfactory.On leave of absence from the Department of Chemistry, Nankai University, CN-300071 Tianjin, P. R. China