Acidic Methanol Solution Research Articles

Synthesis of a New Imidazole Amino Acid Ionic Liquid Polymer and Selective Adsorption Performance for Tea Polyphenols.

A series of imidazolium ionic liquid monomers with L-Proline anions (ViImCn-L-Pro and (ViIm)2Cn(L-Pro)2) were firstly synthesized, after which new copolymer materials were prepared by polymerization of the ionic liquid monomers with N,N′-methylene diacrylamide (MBA). Polymerization conditions, including the ratio of Ils(ViImCn-L-Pro or (ViIm)2Cn(L-Pro)2) and MBA, solvent, ionic liquids and initiator’s amount, were investigated and found to have an important effect on the adsorption capacity. Polymerization conditions were shown to have more significant impacts on adsorption capacities in the following order: the ratio of Ils and MBA > the amount of initiator > ionic liquids > solvent. The polymers were characterized by IR, EA, SEM, particle size distribution and TG. One of the polymers exhibited the highest selective adsorption capacity of tea polyphenols (521 mg/g). which was significantly higher than other adsorption media. The absorbed tea polyphenols could be desorbed readily with 2% hydrochloric acid methanol solution as eluent. The polymer material could maintain a higher adsorption capacity after four reuses. Based on this polymer, a new method for the efficient separation of tea polyphenols from tea water could be developed.

Green analytical methods for simultaneous determination of compounds having relatively disparate absorbance; application to antibiotic formulation of azithromycin and levofloxacin

Green validated spectrophotometric methods are developed for simultaneous determination of Azithromycin (AZI) and Levofloxacin (LEVO) antibiotic mixture. Determination of AZI presents a real analytical challenge as its structure lacks any chromophore, and hence it cannot be determined by direct spectrophotometry. However, the reaction of AZI with perchloric acid produces a green product that can be accurately determined spectrophotometrically. Thus, the work presented demonstrates simple green and sensitive methods for the simultaneous determination of AZI and LEVO mixture. Method I depends on direct measurement of absorbance of azithromycin and levofloxacin in perchloric acid methanolic solution at 482 nm and 224 nm, respectively. While, Method II depends on measuring the first derivative spectrophotometric peak-to-peak amplitudes of AZI and LEVO in perchloric acid methanolic solution at 475–490 nm and 280–253 nm, respectively. Regression analysis shows good linearity for AZI and LEVO over the concentration ranges of 5–50 and 2.5–20 μg/mL for method I and 5–50 and 5–40 μg/mL for method II for AZI and LEVO, respectively. The proposed methods were validated in compliance with ICH guidelines. The suggested procedures are successfully applied for the assay of AZI and LEVO mixture in bulk powder and laboratory-prepared tablets. Greenness profile of the proposed methods were compared with other published methods through applying the Eco-scale protocol. Assessment results demonstrated that the proposed methods are greener than other reported methods. Moreover, upon comparison with other methods, the proposed methods showed better or comparable sensitivity in addition to being selective and rapid with no requirement for laborious extraction techniques. These advantages encourage the application of the proposed methods in routine analysis of AZI and LEVO in quality control laboratories as green and simple analytical tool.

Corrosion inhibition of methanol towards stainless steel bipolar plate for direct formic acid fuel cell

The corrosion properties of AISI316L stainless steel (316 L SS) as bipolar plates are investigated under aqueous acid methanol solutions (0.05 M H2SO4 + 2 ppm HF + 10 M HCOOH + x M CH3OH (x = 0, 3, 6 and 9) solutions at 70 °C) to simulate the varied anodic operating conditions of direct formic acid fuel cells (DFAFCs). When the methanol content is higher, the potentiodynamic, potentiostatic polarisation and EIS tests of the 316 L SS bipolar plates all show excellent corrosion resistance. The surface morphology and the glow discharge mass spectrometer (GDMS) illustrate that the surface corrosion on 316 L SS bipolar plates is slowed down when the methanol concentration is increased. These results indicate the methanol plays the role in retarding the corrosion rate of the 316 L SS in simulated DFAFCs anodic operating conditions by restricting the proton conductivity in the test solutions. The sample tested in higher content methanol solution has smoother corroded surface and thinner passivation film, which contributes to a lower interfacial contact resistances (ICR) value.

A LC-MS/MS method for determination of 73 synthetic cathinones and related metabolites in urine

Synthetic cathinones, which are a group of β-keto analogs of phenethylamine, have been reported as the most emerging new psychoactive substances in the past decade. The quantity and variety of synthetic cathinones have continued to increase, which poses considerable risks to public health and social security. In this study, an analytical method based on liquid chromatography-tandem mass spectrometry (LCMS/MS) was established for the simultaneous determination of 73 synthetic cathinones and related metabolites in urine. The chromatographic analysis was performed using a Kinetex® Biphenyl column (10 cm ×2.1 mm, 1.7 μm), applying a gradient mobile phase, comprising 0.1 % formic acid aqueous solution with 5 mM ammonium acetate and 0.1 % formic acid methanolic solution; the entire run time of the analysis was within 8 min. The multiple reaction monitoring (MRM) mode was employed to collect the monitoring and quantitative ion pairs. Intra-day/inter-day precision and accuracy were less than 10 % for all the studied analytes. The limits of detection and quantification for all the analytes were 0.1–0.5 ng/mL and 0.5–1.0 ng/mL, respectively. The matrix effect was satisfactory for all the analytes, with a deviation lower than 20 %. The present method was further applied to 67 authentic urine samples in which 13 different synthetic cathinones were detected from 32 positive samples. The abuse of poly-synthetic cathinones was examined that up to seven items was detected in one case from authentic samples in this study.

PtCo/N-doped carbon sheets derived from a simple pyrolysis of graphene oxide/ZIF-67/H2PtCl6 composites as an efficient catalyst for methanol electro-oxidation

Many alloy catalysts have been developed for methanol electro-oxidation, but most synthetic methods are complicated. Herein, PtCo alloy catalysts supported on N-doped carbon sheets (PtCo/NCS) are successfully prepared by a simple pyrolysis of graphene oxide/ZIF-67/H2PtCl6 composites at different temperatures (700, 800, 900 °C) under a gas flow of H2/Ar, in which ZIF-67 is served as Co and N sources. SEM, TEM, XRD, XPS and electrochemical characterization are employed to study as-prepared catalysts. In acidic methanol solution, the area-specific activity (1.25 mA cm−2 Pt) of PtCo alloy catalyst obtained at 800 °C (PtCo/NCS-800) is 2.6 times of commercial Pt/C (0.48 mA cm−2 Pt), and the area-specific activity of PtCo/NCS-800 is 3.5 times of Pt/C after 1000 cycles. Furthermore, an improved CO-tolerance of Pt is confirmed. The electronic effect and synergistic effect of metallic elements are responsible for outstanding performance of as-prepared catalysts. This work provides a simple approach to obtain high performance alloy catalysts.

Isolation of an isoflavonoid and a terpenoid from the heartwood of Baphia nitida Lodd. (camwood)

Abstract Chromatographic separation of methanolic extract of Baphia nitida heartwood gave two crystalline solids characterized as 3,9-dimethoxy-6aR,11aR-dihydro-6H-benzofuro(3,2-C)[1]benzopyran (also known as homopterocarpin) with molecular formula C17H16O4 (1.57% yield) and 2,4-dimethoxybenzaldehyde C9H10O3 (2.27% yield). Each of the isolated compounds showed a single spot on developed thin layer chromatographic plate under ultra-violet light (254 nm) and spray reagent (10% sulfuric acid in methanol solution). Structural elucidation was achieved using Fourier transform infrared (FT-IR) spectroscopy, one and two-dimension nuclear magnetic resonance (NMR) techniques. Distortionless enhancement by polarization transfer-edited-heteronuclear single quantum coherence (DEPT-ed-HSQC) was also a useful tool that aided the characterization of the two secondary metabolites isolated from Baphia nitida heartwood.

New members of the polynuclear manganese family: MnMn single-molecule magnets and MnMn antiferromagnetic complexes. Synthesis and magnetostructural correlations.

The synthesis, crystal structures and magnetic properties are reported for three novel mixed-valence tetranuclear [MnII2MnIII2(HBuDea)2(BuDea)2(EBA)4] (1), [MnII2MnIII2(HBuDea)2(BuDea)2(DMBA)4] (2) and undecanuclear [MnII3MnIII8O4(OH)2(BuDea)6(DMBA)8] (3) clusters, where H2BuDea is N-butyldiethanolamine, HEBA is 2-ethylbutyric acid and HDMBA is 2,2-dimethylbutyric acid. The compounds have been prepared through self-assembly reactions of manganese(ii) chloride with H2BuDea and respective carboxylic acid in methanol solution in air, affording 1 with HEBA, and 2 or 3 with HDMBA, depending on the experimental conditions. The single crystal X-ray analysis reveals that 1 and 2 have similar centrosymmetric structures based on the {M4(μ3-O)2(μ-O)4} core, while 3 discloses the unprecedented {M11(μ-O)4(μ3-O)12} one. The Mn4 complexes display single-molecule magnet (SMM) behavior with a S = 9 spin ground state and a high energy barrier Ueff/kB of up to 51 K. The magnetic properties of 2 are successfully modeled with JMnIII-MnIII/hc = 25.7 cm-1 and two JMnIII-MnII/hc constants of 3.1 and -0.93 cm-1 (data correspond to the Ĥ = -Jŝ1·ŝ2 formalism). The Mn11 cluster exhibits a paramagnetic behavior with dominant antiferromagnetic coupling. A possible influence of intermolecular effects and of different peripheries of the magnetic cores designed by using 2-ethylbutyrate (in 1) or 2,2-dimethylbutyrate (in 2) on the magnetic properties of 1 and 2 is discussed. The experimental magnetostructural correlations for the {MnII2MnIII2(μ3-O)2(μ-O)4} cores, supported by broken symmetry DFT calculations, disclose the X-MnIIIMnIII angle and MnIII-O distance (where MnIII-X and MnIII-O are axial Jahn-Teller bonds) as the structural factors having the strongest influence on JMnIII-MnIII exchange coupling. It is shown that two JMnIII-MnII constants are necessary for the correct description of magnetic exchange couplings in the {MnII2MnIII2(μ3-O)2(μ-O)4} tetranuclear unit.

Synthesis and characterization of 1,3,5-triarylpyrazol-4-ols and 3,5-diarylisoxazol-4-ols from chalcones and theoretical studies of the stability of pyrazol-4-ol toward acid dehydration

The synthesis of diverse pyrazol-4-ol and isoxazole-4-ol heterocycles involving only 3 reaction steps is reported in this study. However, the synthesis of carboxamide pyrazol-4-ol has failed in the conditions used in the synthesis, acid methanol solution. The carboxamide pyrazol-4-ol decomposes via dehydration, forming the respective pyrazol. Theoretical calculations were used to elucidate the dehydration reaction. We have found a mechanism for acid-catalyzed dehydration that can explain the experimental observations. The calculated free energy profile for acid-catalyzed dehydration of the carboxamide pyrazol-4-ol and phenylpyrazole-4-ol point out that the latter is more stable in relation dehydration, with a dehydration rate 100 times smaller in acid methanol solution.

Diblock Copolymer Core–Shell Nanoparticles as Template for Mesoporous Carbons: Independent Tuning of Pore Size and Pore Wall Thickness

Latex templating using core-shell particles represents a unique opportunity to design mesoporous carbons with a high level of control on textural properties. This new class of organic colloid templates is synthesized by polymerization-induced self-assembly (PISA) in which a solvophilic poly(hydroxyethyl acrylate) (PHEA) homopolymer is chain extended with a solvophobic polystyrene (PS) via a photomediated reversible-addition-fragmentation-transfer (RAFT) polymerization. The resultant PHEA-b-PS diblock copolymer nanoparticles exhibit a PS core stabilized by a PHEA shell, with two blocks characterized by a low molecular weight dispersity (1.1-1.3) and an adjustable degree of polymerization (DP). The core-shell structured nanoparticles are used as soft template for the formation of mesostructured carbons from phloroglucinol and glyoxylic acid in methanol solution. A micro- and mesostructured cellular foam is obtained having uniform, interconnected, and narrowly distributed mesopores ranging between 15 and 30 nm in diameter, a specific surface area up to 719 m2 g-1, and a total pore volume of (0.4-1.3) cm3 g-1. The mesopore size can be controlled by adjusting the diameter of the PS core (16-29 nm), while the wall thickness can be tailored independently by varying the size of the solvated PHEA shell (5-25 nm). An increase of PHEA block's DP from 25 to 85 gradually extends the stabilizing shell dimension, thus increasing the wall thickness up to 10 nm, and causing the shift from interconnected to isolated mesopores. By comparison, much thinner walls (2-3 nm) are obtained with conventional latex templates such as polystyrene nanoparticles or colloidal silica. Decreasing PHEA DP to 17 induces the formation of copolymer vesicles that can be used as template to create mesoporous carbons with nonspherical mesopores.

Simultaneous determination of metolazone and losartan in their combined tablets using synchronous fluorescence spectroscopy

Synchronous spectrofluorimetry is utilized to carry out a rapid, sensitive and reliable method for determination of the binary mixture of metolazone (MTL) and losartan potassium (LSP). Under optimized experimental conditions, the synchronized fluorescence spectra of the two drugs were measured at Δλ=80nm in acidic methanolic solution and intensities were recorded at 260nm for MTL and 335nm for LSP. Linear correlation between fluorescence intensity and concentration were obtained through the ranges 0.02-0.2μg/mL and 0.2-2.0μg/mL for MTL and LSP, respectively. Limits of detection were 3.02 and 0.12ng/mL, whereas limits of quantification were 9.16 and 0.35ng/mL for MTL and LSP, respectively. The designated procedure was easily and successfully adopted to determine the two compounds in their single, as well as in co-formulated, tablets and the results showed high precision and accuracy without any significant interference from common tablet excipients. A comparison of the obtained results with a published reference method was carried out and both showed good agreement with respect to accuracy and precision.

Simultaneous quantitation of aconitum alkaloids from You-Gui-yin in rat plasma by UPLC–ESI–MS and its application to a pharmacokinetic study

You-Gui-Yin (YGY), a famous traditional Chinese medicine, has been widely used in clinics for the treatment of kidney-yang deficiency, yang deficiency caused by excessive yin, and osteoporosis. A rapid and sensitive ultraperformance liquid chromatography–electrospray ionization–mass spectrometry (UPLC–ESI–MS) method for simultaneous determination of six Aconitum alkaloids including aconitine (AC), hypaconitine (HA), mesaconitine (MA), benzoylaconine (BAC), benzoylhypaconine (BHA), and benzoylmesaconine (BMA) in rat plasma after oral administration of YGY was developed in this study. Chromatographic separation was performed on an ACQUITY UPLC™ BEH C18 column (2.1 × 100 mm, 1.7 μm) using gradient elution with the mobile phase consisting of 2 mmol/L ammonium formate in 0.05% formic acid aqueous solution and 0.05% formic acid methanol solution, at a flow rate of 0.20 mL/min. MS detection was performed in the positive ion mode. The calibration curves were linear in the concentration range of 0.04160–41.60 ng/mL, 0.1070–107.0 ng/mL, 0.07358–73.50 ng/mL, 0.03228–32.28 ng/mL, 0.01809–18.09 ng/mL, and 0.1320–132.0 ng/mL for AC, HA, MA, BAC, BHA, and BMA, respectively. The intra- and inter-day precisions (relative standard deviation [RSD]) were less than 11.6% and 12.6%, respectively. The accuracies Relative Error (RE) ranged from −10.2% to 5.6%, while the recoveries ranged from 70.4% to 99.3%. The method for simultaneous quantitation of Aconitum alkaloids of You-Gui-Yin in rat plasma is accurate and repeatable, and this method was successfully applied to investigate the pharmacokinetics of the six Aconitum alkaloids in rat plasma after oral administration of YGY. For the pharmacokinetic study, the pharmacokinetics of the six Aconitum alkaloids were best described by a two-compartment open model.

Magnetic solid-phase extraction of quercetin on magnetic-activated carbon cloth (MACC)

Magnetic-activated carbon cloth (MACC) was synthesized, characterized, and used as magnetic adsorbent in magnetic solid-phase extraction of quercetin prior to UV–visible spectrophotometric determination. Different parameters such as pH, amount of MACC, effect of volume, and elution time were optimized for the determination of quercetin using UV–visible spectrophotometer at 370 nm. In this procedure, quercetin molecules in aqueous sample phase were adsorbed on the 10 mg of the adsorbent at pH 4.0 and desorbed with acidic methanol solution by using vortex mixer. Limit of detection (LOD), limit of quantification (LOQ), and relative standard deviation were found as 1.4 ng mL−1, 4.8 ng mL−1 and lower than 10%, respectively. The applicability of the developed magnetic solid-phase extraction method was proved on onion samples.

Continuous flow HER and MOR evaluation of a new Pt/Pd/Co nano electrocatalyst

A new protocol of synthesis (e.g. choose of the solvent, precursors and amount and type of reducing agents) has been designed to prepare a Pt/Pd/Co alloy with a desired metals ratio. The stability of the alloy has been monitored after an acidic washing, to remove, if present, unalloyed metals and pre-leach the surface. An excellent combination of performance, e.g. Tafel slope lower than 30 mV/dec and a negligible overpotential, were measured for our Pt/Pd/Co NPs, with an atomic ratio (7:3:3) in a flow system. Very high hydrogen production rate of 7.09 mL cm−2 h−1 at −0.05 V was measured. The electrochemical production of hydrogen from liquid methanol in acidic solution was also investigated. The Pt/Pd/Co NPs exhibit an anodic current density of 560 mA/mgPt during methanol oxidation in acidic solution at 0.45 V and an If/Ib ratio of 1.96. A quantitative evaluation of the performance of the electrode in the two different processes has been made, too.

Programmable Payload Release from Transient Polymer Microcapsules Triggered by a Specific Ion Coactivation Effect.

Stimuli-responsive materials activated by a pair of molecular or ionic species are of interest in the design of chemical logic gates and signal amplification schemes. There are relatively few materials whose coactivated response has been well-characterized. Here, we demonstrate a specific ion coactivation (SICA) effect at the interfaces of transient polymer solids and liquid solutions. We found that depolymerization of the transient polymer, cyclic poly(phthalaldehyde) (cPPA), exhibited a SICA effect when the cPPA core-shell microcapsules were suspended in ion-containing acidic methanol solutions. Significant acceleration in cPPA depolymerization rate is triggered by the combination of acid and ion coactivators. Intriguingly, the SICA effect is related to the Hofmeister behavior. The SICA effect is primarily determined by anions, and cations exhibit a secondary effect that modulates the coactivation strength. Based on these observations, we developed cPPA programmable microcapsules whose payload release rates depend on the composition and concentration of the salt/acidic-methanol solutions.

Efficient Capture and Effective Sensing of Cr2O72– from Water Using a Zirconium Metal–Organic Framework

Highly efficient decontamination of heavily toxic Cr2O72- from water remains a serious task for public health and ecosystem protection. An easily regenerative and reused sorbent with suitable porosity may address this task. Herein, a series of water-stable and ecofriendly metal-organic frameworks (MOFs) with large surface areas were assessed for their ability to adsorb and separate Cr2O72- from aqueous solutions. Among these tested MOFs, NU-1000 shows an extraordinary capability to efficiently capture (within 3 min) Cr2O72- with a sorption capacity of up to 76.8 mg/g, which is the largest one for the neutral MOF-based Cr2O72- sorbents. NU-1000 also shows remarkable selectivity for Cr2O72- capture and can effectively reduce the Cr(VI) concentration from 24 ppm to 60 ppb, which is below the acceptable limit for the drinking water standard (100 ppb by the U.S. Environmental Protection Agency). Moreover, this adsorbent can be easily regenerated by Soxhlet extraction with an acidic methanol solution (2.5 M HCl) and can be reused at least three times without a significant loss of it adsorption ability. More intriguingly, NU-1000 can also serve as an efficient photoluminescent probe for the selective detection of Cr2O72- in aqueous media. The Cr2O72- detection limit is as low as 1.8 μM, and the linear range is from 1.8 to 340 μM. Our work shows that NU-1000 is a unique material combining both efficient sorption and exceptional fluorescent sensing of Cr2O72- in aqueous media.

Crystal structure of ebastinium 3,5-di-nitro-benzoate.

Ebastine, 4-(benzhydr-yloxy)-1-[4-(4-tert-butyl-phen-yl)-4-oxobut-yl]piperidine, reacts with 3,5-di-nitro-benzoic acid in methanol solution to give the title 1:1 salt, ebastinium 3,5-di-nitro-benzoate, C32H40NO2+·C7H3N2O6-. In the cation, the disubstituted aryl ring exhibits orientational disorder over two sets of atomic sites having occupancies 0.706 (4) and 0.294 (6), with a dihedral angle of 41.2 (5)° between the two orientations: the bulky Ph2CH-O- substituent occupies an axial site on the piperidine ring. The two ions in the selected asymmetric unit are linked by a nearly linear N-H⋯O hydrogen bond and this, in combination with two C-H⋯O hydrogen bonds, links the ions into complex sheets.

Synthesis of a Novel Double Salt: Ammonium 3,4‐Diamino‐1,2,4‐triazolium Styphnate

Nitrogen‐rich double salt ammonium 3,4‐diamino‐1,2,4‐triazoliumstyphnate (NH4·DATr·TNR) (2) with good thermal stability was successfully synthesized by reacting 3,4‐diamino‐1,2,4‐triazolium chloride aqueous solution with styphnic acid methanol solution under the reaction medium of aqueous ammonia. The title double salt was characterized by elemental analysis (EA), Fourier transformation infrared spectrum (FT‐IR), and X‐ray single‐crystal diffraction. It crystallizes in the monoclinic crystal system with space group P21/n. Its density is 1.780 g·cm–3. Compound 2 is thermal stable below 200 °C by the differential scanning calorimetry (DSC) test. The non‐isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa‐Doyle's method, respectively. In addition, compound 2 showed low friction and impact sensitivities.

Development and validation of a stability indicating HPLC method to determine diltiazem hydrochloride in tablets and compounded capsules

A stability indicating HPLC method to determine diltiazem hydrochloride (DTZ) in tablets and compounded capsules was developed and validated according to Brazilian and the International Conference on Harmonization (ICH) guidelines. The separation was carried out on a Purospher Star® C18 (150 x 4.6 mm i.d., 5 µm particle size, Merck Millipore) analytical column. The mobile phase consisted of a 0.05% (v/v) trifluoroacetic acid aqueous solution and a 0.05% trifluoroacetic acid methanolic solution (44:56, v/v). The flow rate was 1.0 mL.min-1 with a run time of 14 minutes. The detection of DTZ and degradation products (DP) was performed at 240 nm, using a diode array detector. The method proved to be linear, precise, accurate, selective, and robust, and was adequate for stability studies and routine quality control analyses of DTZ in tablets and compounded capsules.

Impact of treatment with HCL/alcoholic in the modification of corn starch

The physical, chemical, or enzymatic modified starches are well suited for industrial applications. Acid hydrolysis changes the physicochemical properties without impairing the granular structure of starch. The acid hydrolysis in alcoholic solution can recover the granule starches after modification. Starch, the most abundant carbohydrate in grains, roots and tubers, is composed by amylose and amylopectin. Corn starch represents 85% of the global starch market. The aim of this study was to evaluate the effects of soft acid, acid–ethanol and acid methanol solutions, considering its application in the paper industry. One sample remained as native. The other six samples were modified with acid, acid–ethanol and acid–methanol solutions, at concentrations of 0.1 and 0.5 mol L−1 (hydrochloric acid). The acid treatment changed the thermal (TG) and rheological (RVA) properties of the corn starch. The TG/DTG results showed shifted (up to 8 °C) stability temperature ranges for the samples treated with a higher concentration of HCl in ethanol and methanol solutions. The RVA results for final viscosity of the treated samples showed an intense reduction of 1405 cP related to the native sample. DSC curves demonstrated that the treatments slightly modified the gelatinization behavior of the starch. The micrographs showed small changes in granules average diameter size after the modification process. Acid hydrolysis did not change the crystalline pattern of corn starch, and its relative crystallinity was slightly affected. According to the results obtained for the acid/alcohol, modified starches present suitable properties for their application in the paper industry.

Electrochemical performance of Mo2C@PtRu synthesized by electrochemical deposition method on methanol oxidation

The electrodeposition of Platinum and Ruthenium nanoparticles into Molybdenum carbide/ glassy carbon electrodes and their catalytic activity for the oxidatlon of methanol are described. These Mo2C@PtRu electrodes exhibit good activity with respect to the catalytic oxidation of methanol. The electrodes exhibited excellent long term stabilty in the acidic methanol solutions.