Spectrophotometric Evaluation of Acidity Constants of Biacetylmonoxime Nicotinylhydrazone

Abstract

The spectrophotometric evaluation of acidity constants of biacetylmonoxime nicotinylhydrazone is reported in this paper.     

Evaluation of Acidity Constants of Amphoteric Substances by the Corresponding Solubilities Method

Abstract

A simple method for the evaluation of acidity constants of amphoteric substances (HR) is reported in this paper. The method is based on the use of pH values which have corresponding solubilities and has been checked against the p-diethylaminobenzylidenrhodanine system. In order to apply the method it is not necessary to know the intrinsic solubility of HR.     

A Three Equation Method for the Numerical Evaluation of Acidity Constants of Single Equilibria from Spectrophotometric Data

Abstract

In this paper we devise a numerical method for the evaluation of acidity constants of single equilibria suitable for use when the limit absorbance of the pure species are unavailable since these species cannot be obtained pure in solutions. The method has been applied to the evaluation of the first acidity constant of methylglyoxal bis (4-pheny1-3-thiosemicarbazone) (MGBPT).     

A Bilogarithmic Method for the Evaluation of Distribution Constant (Partition Coefficient) and Acidity Constants of Amphoteric Substances from Liquid-Liquid Distribution Measurements

Abstract

In this report we present a convenient method for evaluating the distribution constant (partition coefficient) and acidity constants of amphoteric substances by analyzing the pH dependence of the distribution ratio against pH curves. The bilogarithmic method devised has been applied to previous data reported for 8-hydroxyquinoline (oxine) in order to demonstrate its utility.     

Acidity Constants of Supported Salts of Heteropoly Acids Using a Methodology Related to the Potentiometric Mass Titration Technique

Using a potentiometric mass titrationmethod, the pK_a values of 12-molybdophosphoric acid (MPA) and 12-tungstophosphoric acid (TPA) were determined in aqueous solution and as a solid suspension in acetonitrile. The results were compared with the earlier reported values obtained using other methods like calorimetry and adsorption (Cal-ad). The acidity values in terms of pK_a and the number of acid sites were determined for the ammonium salts of MPA and TPA, and ammonium salts incorporated with vanadium and ammonium salts impregnated on a ZrO₂ support. The effect of the amount of the salt or acid in the suspension of acetonitrile on the potentiometric titration behavior was also studied and it was found that 0.1 g of the substance gives a good neutralization jump in the titration curve.     

A Calibration‐Base Method for the Evaluation of the Detection Limit of an Electrochemical Biosensor

The method based on the confidence limits of a regression straight line is applied to the linear portion of the calibration curve of a biosensor in order to determine the limit of detection. A practical application gives a detection limit of an ethanol biosensor greater than that calculated by using the method of the signal‐to‐noise‐ratio, S/N=3, but the value is more reliable because it accounts for the variability in the response at analyte additions. A simple approximation of the method is also presented.     

Limit cycles in the presence of convection: a first-order analysis

We consider a diffusion model with limit cycle reaction functions. In an unbounded domain, diffusion spreads pattern outwards from the source. Convection adds instability to the reaction–diffusion system. We see the result of the instability in a readiness to create pattern. In the case of strong convection, we consider that the first-order approximation may be valid for some aspects of the solution behaviour. We employ the method of Riemann invariants and rescaling to transform the reduced system into one invariant under parameter change. We carry out numerical experiments to test our analysis. We find that most aspects of the solution do not comply with this, but we find one significant characteristic which is approximately first order. We consider the correspondence of the Partial Differential Equation with the Ordinary Differential Equation along rays from the initiation point in the transformed system. This yields an understanding of the behaviour.     

Strange Case of Signor Volta and Mister Nicholson: How Electrochemistry Developed as a Consequence of an Editorial Misconduct

This Essay tells the colourful history of the invention of the pile by Alessandro Volta and of the subsequent discovery by William Nicholson of the electrolysis of water, carried out with the Voltaic pile (1800). Indeed, as a result of the dissemination of Volta's paper among London scientists, favoured by an incorrect behaviour of the President of the Royal Society, the article by Nicholson was published months before the publication of Volta's letter. The outstanding news that electricity could be generated by a simple and easy to build instrument (the pile) was printed also by daily newspapers, which favoured its spreading all over Europe and stimulated a multitude of enthusiast practitioners and amateurs to construct their own pile and to carry out the electrical decomposition of a variety of aqueous electrolytes. The correct chemical interpretation of the pile and of electrolysis had to wait for nearly one century, but in 1800 electrochemistry was born.     

Spectrophotometric Study of the Complexation of Some Lanthanide (III) Ions with a Series of 18-Crowns-6 in DMSO Solution Using Murexide as a Metallochromic Indicator

The complexation of La(III), Ce(III), Pr(III) and Er(III) with 18-crown-6(18C6), dibenzo-18-crown-6 (DB18C6), dicyclohexano-18-crown-6 (DCY18C6) anddibenzopyridino-18-crown-6 (DBPY18C6) has been studied in dimethylsulfoxide(DMSO) by means of a competitive spectrophotometric method using murexide asa metal ion indicator. The formation constants of the 1 : 1 complexeswere found tovary in the order La(III) > Ce(III) > Pr(III) > Er(III). It was foundthat the structure influences the formation and stability of the resultingcomplexes. The effects ofvarious parameters on complexation are discussed. The order of the stabilityconstants of each lanthanide ion with these macrocycles are18C6 > DC18C6 > DB18C6 > DBPY18C6.     

On the tautomerism of pyrazolones: the geminal J[pyrazole C-4,H-3(5)] spin coupling constant as a diagnostic tool

The tautomerism of pyrazolones unsubstituted at position 3(5) has been investigated by ¹³C- and ¹H NMR spectroscopic methods. Apart from chemical shift considerations and NOE effects the magnitude of the geminal ²J[pyrazole C-4,H3(5)] spin coupling constant permits the unambiguous differentiation between 1H-pyrazol-5-ol (OH) and 1,2-dihydro-3H-pyrazol-3-one (NH) forms. Whereas 1H-pyrazol-5-ols and 2,4-dihydro-3H-pyrazol-3-ones (CH-form) exhibit ²J values of approximately 9-11 Hz, in 1,2-dihydro-3H-pyrazol-3-ones this coupling constant is considerably reduced to 4-5 Hz. This can be mainly attributed to the removal of the lone-pair at pyrazole N−1 in the latter due to protonation or alkylation. According to the data obtained, 2-substituted 4-acyl-1,2-dihydro-3H-pyrazol-3-ones exist predominantly as pyrazol-5-ols in CDCl₃ or benzene-d₆ solution, whereas in DMSO-d₆ also minor amounts of NH tautomer may contribute to the tautomeric composition. 2,4-Dihydro-2-phenyl-3H-pyrazol-3-one (1-phenyl-2-pyrazolin-5-one) exists in benzene-d₆ solely in the CH-form, in CDCl₃ as a mixture of CH and OH-form, whereas in DMSO-d₆ a fast equilibrium between OH and NH isomer (with the former far predominating) is probable. For 11 compounds, including neutral and protonated molecules, we have calculated at the B3LYP/6-311++G** level, the ²J(¹H,¹³C) coupling constants which are in good agreement with those measured experimentally.     

Elongated dihydrogen versus compressed dihydride complexes: the temperature dependence of the H-D spin-spin coupling constant as a criterion to distinguish between them

To be able to propose experimental tests to distinguish elongated dihydrogen transition-metal complexes from compressed dihydride transition-metal complexes, a thorough density functional study of the electronic structure in combination with quantum nuclear dynamics calculations have been performed for complexes [Cp*Ru(H2PCH2PCH2(H2)]+ and [CpRe(CO)2H2]. The results of this study suggest that elongated dihydrogen complexes and compressed dihydride complexes have different properties and that it should be possible to distinguish between them experimentally. In particular, different behavior is predicted with respect to 1) the sign of the isotope geometric effect on the H-H distance at 0 K, 2) the temperature dependence of the H-H distance, and 3) the temperature dependence of the H-D spin-spin coupling constant in 1H NMR spectroscopy.     

Simple DPPH.‐Based Electrochemical Assay for the Evaluation of the Antioxidant Capacity: a Thorough Comparison with Spectrophotometric Assays and Evaluation with Real‐World Samples

An assay based on the electrochemical detection of 2,2‐diphenyl‐1‐picrylhydrazyl radical (DPPH^.) for the evaluation of the total antioxidant capacity (TAC) was optimized. The assay is interchangeable with the classic spectrophotometric tests for TAC based on the same radical. In addition, it can be used for the analysis of dilute samples with low antioxidant capacities. A good linear correlation (R²=0.97) was obtained between the results obtained with the proposed electrochemical assay and the Trolox Equivalent Antioxidant Capacity test based on ABTS radical. The assay was successfully used to evaluate the antioxidant capacity of two red wines obtained by six different maceration‐fermentation techniques.     

A Bioinspired Peptide in TIR Protein as Recognition Molecule on Electrochemical Biosensors for the Detection of E. coli O157:H7 in an Aqueous Matrix

Currently, the detection of pathogens such as Escherichia coli through instrumental alternatives with fast response and excellent sensitivity and selectivity are being studied. Biosensors are systems consisting of nanomaterials and biomolecules that exhibit remarkable properties such as simplicity, portable, affordable, user‑friendly, and deliverable to end‑users. For this, in this work we report for the first time, to our knowledge, the bioinformatic design of a new peptide based on TIR protein, a receptor of Intimin membrane protein which is characteristic of E. coli. This peptide (named PEPTIR‑1.0) was used as recognition element in a biosensor based on AuNPs‑modified screen‑printed electrodes for the detection of E. coli. The morphological and electrochemical characteristics of the biosensor obtained were studied. Results show that the biosensor can detect the bacteria with limits of detection and quantification of 2 and 6 CFU/mL, respectively. Moreover, the selectivity of the system is statistically significant towards the detection of the pathogen in the presence of other microorganisms such as P. aeruginosa and S. aureus. This makes this new PEPTIR‑1.0 based biosensor can be used in the rapid, sensitive, and selective detection of E. coli in aqueous matrices.     

General Method for the 11C‐Labeling of 2‐Arylpropionic Acids and Their Esters: Construction of a PET Tracer Library for a Study of Biological Events Involved in COXs Expression

Cyclooxygenase (COX) is a critical enzyme in prostaglandin biosynthesis that modulates a wide range of biological functions, such as pain, fever, and so on. To perform in vivo COX imaging by positron emission tomography (PET), we developed a method to incorporate ¹¹C radionuclide into various 2‐arylpropionic acids that have a common methylated structure, particularly among nonsteroidal anti‐inflammatory drugs (NSAIDs). Thus, we developed a novel ¹¹C‐radiolabeling methodology based on rapid C‐[¹¹C]methylation by the reaction of [¹¹C]CH₃I with enolate intermediates generated from the corresponding esters under basic conditions. One‐pot hydrolysis of the above [¹¹C]methylation products also allows the synthesis of desired ¹¹C‐incorporated acids. We demonstrated the utility of this method in the syntheses of six PET tracers, [¹¹C]Ibuprofen, [¹¹C]Naproxen, [¹¹C]Flurbiprofen, [¹¹C]Fenoprofen, [¹¹C]Ketoprofen, and [¹¹C]Loxoprofen. Notably, we found that their methyl esters were particularly useful as proradiotracers for a study of neuroinflammation. The microPET studies of rats with lipopolysaccharide (LPS)‐induced brain inflammation clearly showed that the radioactivity of PET tracers accumulated in the inflamed region. Among these PET tracers, the specificity of [¹¹C]Ketoprofen methyl ester was demonstrated by a blocking study. Metabolite analysis in the rat brain revealed that the methyl esters were initially taken up in the brain and then underwent hydrolysis to form pharmacologically active forms of the corresponding acids. Thus, we succeeded in general ¹¹C‐labeling of 2‐arylpropionic acids and their methyl esters as PET tracers of NSAIDs to construct a potentially useful PET tracer library for in vivo imaging of inflammation involved in COXs expression.     

Iodine as a versatile reagent for the Prins-cyclization: an expeditious synthesis of 4-iodotetrahydropyran derivatives

Iodine is found to be an efficient reagent for the coupling of homoallylic alcohols with aldehydes under mild conditions to produce 4-iodotetrahydropyran derivatives in excellent yields in a short reaction time with high selectivity. The use of iodine makes this procedure simple, convenient and cost-effective.