HPLC Determination of Amino And Carbonyl Compounds with Dabsyl Chloride and Dabsyl Hydrazine

The new chromophoric reagent, 4-dimethylaminoazobenzene-4′-sulfonyl chloride (dabsyl chloride) was synthesized by reaction of sodium 4-dimethylaminoazobenzene 4′-sulfonate with phosphorus pentachloride. Dabsyl chloride reacted rapidly with all amino acids, aliphatic amines, and polyamines to form the corresponding dabsyl derivatives. The dabsyl amino acids (10^?11 mol) were visualized on thin layer plates and found to be photo-stable. During the last 12 years, in combination with HPLC, this newly developed labeling reagent has been shown to be very promising for microdetermination of amino acids, aliphatic amines and polyamines. Recently, another new chromophoric reagent, dabsylhydrazine, was synthesized from the reaction of dabsyl chloride with hydrazine. This reagent reacted readily with monosaccharides and carbonyl compounds to form the corresponding chromophoric dabsylhydrazones with strong absorbance at 425 nm. The application of this new reagent in HPLC analysis of monosaccharides was discribed. By use of Nova-PAK C₁₈ reverse-phase column and a concave gradient system of water and acetonitrile as eluent, the detection limits of monosaccharides in the range of 10 pmol have been reached.     

Facile Synthesis of N‐Carboranyl Amines through an ortho‐Carboryne Intermediate

The efficient o‐carboryne precursor 1‐Li‐2‐OTf‐o‐C₂B₁₀H₁₀ reacts with lithium amides at room temperature to give a series of N‐carboranyl amines in moderate to high isolated yields. This reaction is compatible with a broad substrate scope from primary to secondary, alkyl to aryl amines. The reaction mechanism is also proposed on the basis of experimental results and DFT calculations. This represents the first general and efficient method for the synthesis of 1‐NR¹R²‐o‐carboranes.     

Detector supports: application to aliphatic amines in wastewater

Solid support assisted derivatization coupled to diffuse reflectance spectroscopy (DRS) was proposed and proved useful for the detection and quantification of aliphatic amines in water as an example. Dabsyl chloride (DBS), ninhydrin and sodium 1,2-naphtoquinone 4-sulphonate (NQS) were assayed as derivatization reagents. C₁₈ and SDB-XC disks and C₁₈ cartridges were tested for amine retention and after that derivatization. The decrease of the orange colour of dabsyl chloride on SBD-XC disks produced by the formation of its derivative with methylamine in the support (10 min at 100 °C) allowed the selective determination of the amine at concentration level equal or higher than 0.5 mg L⁻¹. Ninhydrin can be used for methylamine, ethylamine, propylamine, butylamine and pentylamine (between 5 and 15 mg L⁻¹) by measuring the diffuse reflectance produced by the brown derivative formed in C₁₈ extraction disks after 15 min at 100 °C. NQS and C₁₈ SPE columns can be also employed to estimate amines, but the detection limits were higher than those provided by DBS and Ninhydrin, around 10 mg L⁻¹. As an example, found concentration of methylamine or total amines (expressed as -NH₂-N mg L⁻¹) in a wastewater sample is given employing dabsyl chloride or ninhydrin reagents, respectively with satisfactory results.     

Pentacoordinated Carboxylate π‐Allyl Nickel Complexes as Key Intermediates for the Ni‐Catalyzed Direct Amination of Allylic Alcohols

Direct amination of allylic alcohols with primary and secondary amines catalyzed by a system made of [Ni(1,5‐cyclooctadiene)₂] and 1,1′‐bis(diphenylphosphino)ferrocene was effectively enhanced by adding nBu₄NOAc and molecular sieves, affording the corresponding allyl amines in high yield with high monoallylation selectivity for primary amines and high regioselectivity for monosubstituted allylic alcohols. Such remarkable additive effects of nBu₄NOAc were elucidated by isolating and characterizing some nickel complexes, manifesting the key role of a charge neutral pentacoordinated η³‐allyl acetate complex in the present system, in contrast to usual cationic tetracoordinated complexes earlier reported in allylic substitution reactions.     

Kinetics and Mechanism of the Reactions of N-Pentafluorocarbonimidoyl Dihalides with Aliphatic Amines in Acetonitrile

A mechanism is proposed for the substitution of the first halogen atom in N-pentafluorophenylcarbonimidoyl dihalides (Ar_FN=CX₂, X = Cl, Br) by aliphatic amines and includes a tetrahedral intermediate (T _E ). In the case of the reactions of primary and secondary amines the rate-limiting stage is the formation of the intermediate, and in the case of tertiary amines it is stereomutation of the intermediate (T _E ) to the thermodynamically more stable configuration (T _Z ). In the case of all the amines the final product (the Z isomer) is formed from the configuration (T _Z ).     

Post‐functionalization of perfluorophenyl ester‐functional acyclic diene metathesis polymer

The acyclic diene metathesis (ADMET) polymerization was utilized for the design of the ADMET polymer (M_n = 21,200 g/mol, M_w/M_n = 1.74) with pendant perfluorophenyl ester functionality using Grubbs first generation catalysis overnight in bulk at 80 °C. Next, a wide variety of functional groups, like benzyl, octyl, propargyl, allyl, and furfuryl was quantitatively incorporated to the ADMET polymer backbone through various amines using activated ester substitution reaction. The ADMET polymers studied in this work were characterized using ¹H, ¹³C, and ¹⁹F NMR, GPC and DSC and displayed a monomodal distribution and a rather broad polydispersity index in the range of ?1.33 to 1.90. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2593–2598     

Effect of solvent on the free energy of activation of S_N2 reaction between phenacyl bromide and amines

The kinetics of SN2 reaction between phenacyl bromide and various amines in 12 different solvents were studied. Solvent effects on the rate of this reaction and free energy of activation, ΔG# , were interpreted by applying the Abraham-Kam-let-Taft (AKT) equation. UK solvent polarity (π1*), solvent hydrogen-bond basicity (β1) and Hildebrand cohesive density energy (δH2) are those parameters which increase the rate constant and decrease ΔG# , while solvent hydrogen-bond acidity (α1) will have the compensatory effect. A comparison among obtained values of second rate constants, k2, for different amines in a given solvent indicates that the amine reactivities are highly dependent on their structures. The consequent decrease of the rate constant for different amines in any given solvent was found to be: primary > secondary> tertiary. This order results from steric effects of amines.     

Oxidation of UO2(s) in aqueous solution

In this review the kinetics and mechanism of oxidative dissolution of UO₂(s), mainly under conditions of relevance for the safety assessment of a deep geological repository for spent nuclear fuel, are discussed. Rate constants for the elementary processes involved (oxidation of UO₂ and dissolution of oxidized UO₂) are used to calculate the rates of oxidative UO₂(s) dissolution under various conditions (type of oxidant, oxidant concentration and HCO₃ ⁻/CO₃ ²⁻ concentration) for which experimental data are also available. The calculated rates are compared to the corresponding experimental values under the assumption that the experimental numbers reflect the steady-state conditions of the system. The agreement between the calculated rates and the corresponding experimental ones is very good, in particular for the higher rates. In general, the calculated rates are somewhat higher than the experimental numbers. This can be due partly to the use of initial concentrations rather than steady-state concentrations in the calculations. The kinetic data are also used to quantitatively discuss the dynamics of spent nuclear fuel dissolution under deep geological repository conditions.      

Axial Ligand Coordination Tuning of the Electrocatalytic Activity of Iron Porphyrin Electrografted onto Carbon Nanotubes for the Oxygen Reduction Reaction

The oxygen reduction reaction (ORR) is essential in many life processes and energy conversion systems. It is desirable to design transition metal molecular catalysts inspired by enzymatic oxygen activation/reduction processes as an alternative to noble-metal-Pt-based ORR electrocatalysts, especially in view point of fuel cell commercialization. We have fabricated bio-inspired molecular catalysts electrografted onto multiwalled carbon nanotubes (MWCNTs) in which 5,10,15,20-tetra(pentafluorophenyl) iron porphyrin (iron porphyrin FeF₂₀TPP) is coordinated with covalently electrografted axial ligands varying from thiophene to imidazole on the MWCNTs’ surface. The catalysts’ electrocatalytic activity varied with the axial coordination environment (i. e., S-thiophene, N-imidazole, and O-carboxylate); the imidazole-coordinated catalyst MWCNTs-Im-FeF₂₀TPP exhibited the highest ORR activity among the prepared catalysts. When MWCNT-Im-FeF₂₀TPP was loaded onto the cathode of a zinc−air battery, an open-cell voltage (OCV) of 1.35 V and a maximum power density (P_max) of 110 mW cm⁻² were achieved; this was higher than those of MWCNTs-Thi-FeF₂₀TPP (OCV=1.30 V, P_max=100 mW cm⁻²) and MWCNTs-Ox-FeF₂₀TPP (OCV=1.28 V, P_max=86 mW cm⁻²) and comparable with a commercial Pt/C catalyst (OCV=1.45 V, P_max=120 mW cm⁻²) under similar experimental conditions. This study provides a time-saving method to prepare covalently immobilized molecular electrocatalysts on carbon-based materials with structure–performance correlation that is also applicable to the design of other electrografted catalysts for energy conversion.     

Thermal characterization and kinetic analysis of nano‐ and micro‐Al/NiO thermites: Combined experimental and molecular dynamics simulation study

In the experimental part of this study, thermal properties of the Al and NiO composites in micro‐ and nano‐sized Al are investigated. Differential scanning calorimetry (DSC) analysis of the onset temperatures of ignition, activation energy (E_a), frequency factor (A), rate constant (k), critical ignition temperature of thermal explosion (T_b), and self‐accelerating decomposition temperature (T_SADT), as well as the thermodynamic parameters (ΔS^≠ , ΔH^≠ , and ΔG^≠ ) are used to explore the thermal behavior and analyze the kinetics. Thermal analysis suggests that the mechanism is based on solid–solid diffusion and liquid–gas for the nano‐ and micro‐Al/NiO composite, respectively. Our results indicate that the incorporation of nano‐Al particles can significantly reduce the ignition temperature, E_a, A, k, T_b, and T_SADT. In the second part of this work, molecular dynamics (MD) simulation is used to investigate the behavior of Al/NiO thermite reaction using the Reaxff force field to evaluate the experimental results. Theoretically, MD results show 1,154 K as the reaction ignition temperature, which is in reasonably good agreement with experimental temperature of 893°C (1,166 K). The radial distribution function (RDF) shows that no reaction occurs at 500 K but it is complete at 1,200 K.     

Unraveling the Mechanism of Water Oxidation Catalyzed by Nonheme Iron Complexes

Density functional theory (DFT) is employed to: 1) propose a viable catalytic cycle consistent with our experimental results for the mechanism of chemically driven (Ce^IV) O₂ generation from water, mediated by nonheme iron complexes; and 2) to unravel the role of the ligand on the nonheme iron catalyst in the water oxidation reaction activity. To this end, the key features of the water oxidation catalytic cycle for the highly active complexes [Fe(OTf)₂(Pytacn)] (Pytacn: 1‐(2′‐pyridylmethyl)‐4,7‐dimethyl‐1,4,7‐triazacyclononane; OTf: CF₃SO₃^?) ( 1 ) and [Fe(OTf)₂(mep)] (mep: N,N′‐bis(2‐pyridylmethyl)‐N,N′‐dimethyl ethane‐1,2‐diamine) ( 2 ) as well as for the catalytically inactive [Fe(OTf)₂(tmc)] (tmc: N,N′,N′′,N′′′‐tetramethylcyclam) ( 3 ) and [Fe(NCCH₃)(^MePy₂CH‐tacn)](OTf)₂ (^MePy₂CH‐tacn: N‐(dipyridin‐2‐yl)methyl)‐N′,N′′‐dimethyl‐1,4,7‐triazacyclononane) ( 4 ) were analyzed. The DFT computed catalytic cycle establishes that the resting state under catalytic conditions is a [Fe^IV(O)(OH₂)(LN₄)]²⁺ species (in which LN₄=Pytacn or mep) and the rate‐determining step is the O?O bond‐formation event. This is nicely supported by the remarkable agreement between the experimental (ΔG^≠=17.6±1.6 kcal mol^?1) and theoretical (ΔG^≠=18.9 kcal mol^?1) activation parameters obtained for complex 1 . The O?O bond formation is performed by an iron(V) intermediate [Fe^V(O)(OH)(LN₄)]²⁺ containing a cis‐Fe^V(O)(OH) unit. Under catalytic conditions (Ce^IV, pH 0.8) the high oxidation state Fe^V is only thermodynamically accessible through a proton‐coupled electron‐transfer (PCET) process from the cis‐[Fe^IV(O)(OH₂)(LN₄)]²⁺ resting state. Formation of the [Fe^V(O)(LN₄)]³⁺ species is thermodynamically inaccessible for complexes 3 and 4 . Our results also show that the cis‐labile coordinative sites in iron complexes have a beneficial key role in the O?O bond‐formation process. This is due to the cis‐OH ligand in the cis‐Fe^V(O)(OH) intermediate that can act as internal base, accepting a proton concomitant to the O?O bond‐formation reaction. Interplay between redox potentials to achieve the high oxidation state (Fe^V?O) and the activation energy barrier for the following O?O bond formation appears to be feasible through manipulation of the coordination environment of the iron site. This control may have a crucial role in the future development of water oxidation catalysts based on iron.     

Colloid chemical characterisation of layered titanates,their hydrophobic derivatives and self-assembled films

Na₂Ti₃O₇, with layered structure, was prepared from a 1:3 molar mixture of powdered Na₂CO₃ and TiO₂ by heating at 800 °C for 2 h. The Na⁺ ions were exchanged for H⁺ ions by hydrochloric acid treatment; next, n-butylamine, n-octylamine, n-decylamine or n-dodecylamine were incorporated at pH=3.6–3.8. It was proven by XRD measurements that, as the length of the alkyl chain of the amines was increased, smaller amounts of amines were intercalated under identical conditions. H₂Ti₃O₇ samples dispersed in liquids of various compositions and polarities were used for the preparation of self-assembled titanate/polymer films for further sensor applications. Titanates, their composites with alkyl amines and the self-assembled hybrid structures were characterized by X-ray diffraction, thermoanalytical, optical, electron and atomic force microscopic measurements.     

Efficient Synthesis of Readily Water-Soluble Amides Containing Sulfonic Groups

A series of various readily water-soluble amides were synthesized by different procedures. These compounds are useful chemical tracers for assessing the cooling progress in a georeservoir during geothermal power plant operation. Acylation of primary amines was carried out by basically employing the Schotten–Baumann method. As a second method a single-phase solvent system consisting of ethyl acetate as an organic solvent and triethylamine as a catalyst was used. Products were characterized by ¹H NMR and ¹³C NMR.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Nucleosides. Part LVI. Aminolysis of carbamates of adenosine and cytidine

The 2-(4-nitrophenyl)ethoxycarbonyl(npeoc) group, introduced 1984 as protecting group for exocyclic amino functions of nucleic-acid bases, reacts with amines under mild conditions to urea derivatives. Treatment of 2′,5′-di-O-acetyl-N⁶-[2-(4-nitrophenyl) ethoxycarbonyl]cordycepin ( 3 ) with NH₃/MeOH overnight at room temperature affords cordycepin ( 4 ) and N₆-carbamoylcordycepin ( 5 ). Preliminary investigations towards the elucidation of the reaction mechanism indicate that the aminolysis proceeds via an addition-elimination or an isocyanate mechanism, depending on the reaction conditions. The phenoxycarbonyl (phoc) group at N⁶ or N⁴ was chosen to study the mild conversion of carbamates with aromatic amines into ureas of adenosine and cytidine, respectively.     

The kinetics and mechanism of polymer-based NHC-Pd-pyridine catalyzed heterogeneous Suzuki reaction in aqueous media

One of the most important challenges of the Suzuki reaction is a green synthesis of reaction products. In terms of economy and ecology, the Suzuki reaction details must be characterized for the industrial-scale Suzuki reaction processes. In this paper, for the first time, a kinetic and mechanistic study on the Suzuki reaction catalyzed with hydrogel-supported PEPPSI (pyridine-enhanced precatalyst preparation stabilization (and) initiation) type NHC-Pd-pyridine composite has been investigated. To determine the rate-limiting step, the effects of reactants and experimental conditions on the heterogeneous Suzuki reaction have been experimentally defined. The experimental results demonstrated that it is possible to reach 100% yield under the optimum reaction conditions, which were found as 75 × 10⁻³ mol/L of phenylboronic acid (FBA), 50 × 10⁻³ mol/L of bromoacetophenone (Brac), 125 × 10⁻³ mol/L of K₂CO₃, 1 g/L of catalyst, 80°C of reaction temperature, 400 rpm of mixing rate, and 3 h of reaction time. The transmetalation step in the cycle was defined as the rate-limiting step. On the basis of kinetic results, a mathematical reaction rate expression was presented assuming the steady-state approach to steps of the catalytic cycle. The activation energy (E_a) of the reaction was estimated to be 34.88 kJ/mol.     

New Mechanistic Aspects of the Fenton Reaction

The kinetics of the Fenton reaction was studied in detail. A second reaction step in the presence of excess H₂O₂ is attributed to formation of the complex Fe^III(^?O₂H)_aq. Therefore, the reaction of Fe(H₂O)₆²⁺ with Fe^III(^?O₂H)_aq in the presence of Fe^II to form Fe^III_aq (k=(7.7±1.5)×10⁵ M ^?1 s^?1) may contribute to the overall Fenton reaction, and could account for some of the debate in the literature concerning its detailed mechanism. If this is correct for LFe^III(^?O₂H)_aq also, then it might be of significant biological importance. The activation parameters ΔH^≠, ΔS^≠, and ΔV^≠ for the Fenton reaction were measured under various experimental conditions, and are used in the mechanistic interpretation.     

Dabsyl chloride derivatisation of melamine followed by high-performance liquid chromatography determination in water samples

A new and sensitive precolumn derivatisation with dabsyl chloride was developed for the analysis of melamine in water samples by high-performance liquid chromatography (HPLC) with visible detection. Derivatisation with dabsyl chloride leads to improving sensitivity and hydrophobicity of melamine. Under optimum conditions of derivatisation and microextraction, the method yielded a linear calibration curve ranging from 10 to 2000 µg L^?1 with a determination coefficient (R²) of 0.9952. Limit of detection (LOD) and limit of quantification (LOQ) were 2.0 and 6.0 µg L^?1, respectively. The relative standard deviation per cent (RSD%) for intraday and inter-day extraction and determination at 20 and 200 µg L^?1 levels of melamine was less than 8.2% (n = 6). Finally, the proposed method was successfully applied for the determination of melamine in different water samples and satisfactory results were obtained (relative recovery ≥91%).     

Facile and Versatile Synthesis of Alkyl and Aryl Isothiocyanates by Using Triphosgene and CoSolvent

A mild and efficient method for the conversion of alkyl and aryl amines to isothiocyanates via dithiocarbamates has been developed using (CH₃)₂CO-CS₂ as co-solvent and triphosgene as dehydrosulfurization reagent. High yields, mild reaction conditions and excellent functional group compatibility make it become a versatile synthetic method for the preparation of isothiocyanates compared with reported methods.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

STUDIES ON REVERSE OSMOSIS SEPARATION OF AQUEOUS ORGANIC SOLUTIONS BY PAA/PSF COMPOSITE MEMBRANE

The reverse osmosis (RO) separation of aqueous organic solutions, such as alcohols, amines, aldehydes, acids,ketones, and esters etc., by PAA (polyacrylic acid)/PSF (polysulfone) composite membrane has been studied. It was foundthat the separation results for aliphatic alcohols, amines and aldehydes are satisfactory, the solute rejection (R_a) and thevolume fluxes of solutions (J_v) for 1000 ppm ethanol, ethylamine and ethyl aldehyde are 66.2%, 61.0%, 84.0% and 0.90×10~(-6), 0.35×10~(-6), 0.40×10~(-6) m~3/m~2·s, respectively, at 5.0 MPa and 30℃. R_a increased with increasing molecular weights ofalcohols, amines and aldehydes, and the R_a for n-amyl alcohol, n-butylamine and n-butyl aldehyde reached 94.3%, 88.6%and 96.0%, respectively. Satisfactory separation results (R_a>70%) for ketones, esters, phenols and polyols have beenobtained with the PAA/PSF composite membrane. The effect of operating pressure on the properties of reverse osmosis hasalso been investigated. Analysis of experimental data with Spiegler-Kedem's transport model has been carried out and themembrane constants such as reflection coefficient σ, solute and hydraulic permeabilities ω and L_p for several organic soluteshave been obtained.