Wide Range Of Polarities Research Articles

Predicting dielectric constants of pure liquids: fragment-based Kirkwood-Fröhlich model applicable over a wide range of polarity.

In view of developing a procedure to predict the dielectric constant (εr) of pure liquids from molecular structure, a thorough analysis of prominent factors affecting this property is carried out. The results suggest that the orientational dipolar parameter gμ2 involved in the Kirkwood-Fröhlich theory may be estimated as a sum of additive contributions (gμ2)i associated with suitably defined polar fragments i. Associated with third-party models for the molar volume Vm and the refractive index nD, this provides a practical route to predicting εr for new compounds. Advantages over previous methods include: simplicity, as the present model relies on fragment-additivity and does not require 3D structures; sound physical bases; demonstrated applicability to polar liquids with εr values up to 200; predictive ability extensively demonstrated against large datasets (for a total of 1220 compounds) covering a broad structural diversity, resulting in values of the root mean square deviation/average percent error as low as 3.7/10% for data sets focused on simple organic compounds as considered in previous studies, although the inclusion of many alcohols in the data set leads to poorer statistics (5.0/32%) due to the lack of specific parameters for hydroxyl groups in distinct environments. The approach should be of special interest in the current search for new aprotic electrolytes aimed at improving the performances of electrochemical energy storage systems. Although its reliance on many fitting parameters restricts its domain of applicability, the present implementation is recommended over current procedures whenever possible. A Python script is provided to allow its straightforward application.

Solid-phase extraction method for stable isotope analysis of pesticides from large volume environmental water samples.

Compound-specific isotope analysis (CSIA) is a valuable tool for assessing the fate of organic pollutants in the environment. However, the requirement of sufficient analyte mass for precise isotope ratio mass spectrometry combined with prevailing low environmental concentrations currently limits comprehensive applications to many micropollutants. Here, we evaluate the upscaling of solid-phase extraction (SPE) approaches for routine CSIA of herbicides. To cover a wide range of polarity, a SPE method with two sorbents (a hydrophobic hypercrosslinked sorbent and a hydrophilic sorbent) was developed. Extraction conditions, including the nature and volume of the elution solvent, the amount of sorbent and the solution pH, were optimized. Extractions of up to 10 L of agricultural drainage water (corresponding to up to 200 000-fold pre-concentration) were successfully performed for precise and sensitive carbon and nitrogen CSIA of the target herbicides atrazine, acetochlor, metolachlor and chloridazon, and metabolites desethylatrazine, desphenylchloridazon and 2,6-dichlorobenzamide in the sub-μg L-1-range. 13C/12C and 15N/14N ratios were measured by gas chromatography-isotope ratio mass spectrometry (GC/IRMS), except for desphenylchloridazon, for which liquid chromatography (LC/IRMS) and derivatization-GC/IRMS were used, respectively. The method validated in this study is an important step towards analyzing isotope ratios of pesticide mixtures in aquatic systems and holds great potential for multi-element CSIA applications to trace pesticide degradation in complex environments.

Sensitive detection of topiramate degradation products by high-performance liquid chromatography/electrospray ionization mass spectrometry using ion-pairing reagents and polarity switching.

The chromatographic analysis of topiramate and its degradation products is challenging due to the absence of chromophoric moieties in their structures, the wide polarity range of the compounds and their ionization differences. This work proposes two new mass spectrometry approaches for evaluating these analytes. Based on the calculated experimental limit of detection (LOD), a highly sensitive high-performance liquid chromatography (HPLC) paired-ion electrospray ionization mass spectrometry (PIESI-MS) method was developed for the determination of topiramate inorganic degradation products. The influence of different solvent systems on the LODs for topiramate and its main degradation products was determined in both positive/negative ionization modes. In addition, a HPLC method to analyze both organic and inorganic degradation products was proposed by mass spectrometry with positive/negative ion switching electrospray ionization. A sensitive HPLC/PIESI-MS method was achieved for the efficient separation of topiramate inorganic degradation products. Both sulfate and sulfamate were detected in the positive selected ion monitoring (SIM) mode with an increased sensitivity compared with the negative SIM mode. The HPLC/ESI-MS analysis with positive/negative ion switching allowed the simultaneous separation and detection of the major degradation products of topiramate in a 10-min run using a single column and a single detector. Two new alternative MS approaches for analyzing the main degradation products of topiramate were developed. The proposed methods are considered advantageous over the existing methods and can be applied to quality control studies of topiramate.

Elucidation of diazinon metabolites in rice plants by liquid ‎chromatography ion-trap mass spectrometry

ABSTRACTA fast, selective and sensitive reversed-phased liquid chromatography coupled to ion-trap mass spectrometry has been developed to elucidate and confirm the diazinon metabolites with a wide range of polarity in the rice plant samples. Sample extraction and purification were performed with a QuEChERS-based (Quick, Easy, Cheap, Effective, Rugged, and Safe) procedure. To boost all metabolism sensitivities, all rice extracts were concentrated under vacuum to near dryness and taken up into initial mobile phase. Careful optimisation of the LC–MS/MS parameters were achieved in order to attain a fast separation with the best sensitivity. The detection was carried out on an ion-trap mass spectrometer by electrospray ionisation in positive ion mode (ESI+) with multiple reaction monitoring.

Finite-Temperature Equation of State of Polarized Fermions at Unitarity

We study in a nonperturbative fashion the thermodynamics of a unitary Fermi gas over a wide range of temperatures and spin polarizations. To this end, we use the complex Langevin method, a first principles approach for strongly coupled systems. Specifically, we show results for the density equation of state, the magnetization, and the magnetic susceptibility. At zero polarization, our results agree well with state-of-the-art results for the density equation of state and with experimental data. At finite polarization and low fugacity, our results are in excellent agreement with the third-order virial expansion. In the fully quantum mechanical regime close to the balanced limit, the critical temperature for superfluidity appears to depend only weakly on the spin polarization.

Alkanethiol-functionalized organosilicon monoliths for nano-reversed-phase liquid chromatography.

Organosilicon monoliths carrying chromatographic ligands with different alkyl chain lengths were obtained by thiol-methacrylate photopolymerization. The use of thiol-ene chemistry in the presence of a main monomer with a series of methacrylate functionality (i.e., methacrylate substituted polyhedral oligomeric silsesquioxane) allowed the synthesis of organosilicon monoliths with high cross-linking density and carrying hydrophobic alkyl-chain ligands by a one-pot process. In the synthesis runs, 1-butanethiol, 1-octanethiol, and 1-octadecanethiol were used as the hydrophobic thiol ligands with the number of methylene units between 4 and 18. The selectivity analysis performed using cytosine/uracil retention ratio showed that alkanethiol-attached organosilicon monoliths exhibited hydrophobicity close to octadecyl-attached silica-based RP columns. In the RP, chromatographic runs performed in nano-liquid chromatography, phenols, alkylbenzenes, and PAHs were used as the analytes. Among the synthesized monoliths, retention-independent plate height behavior and the smallest plate heights were obtained with 1-octadecanethiol-attached organosilicon monolith for the analytes in a wide polarity range. With this monolith, the mobile phases prepared with ACN contents ranging between 35 and 85% v/v could be used for satisfactory separation of analytes in a wide polarity range.

Simultaneous Separation of Water- and Fat-Soluble Vitamins by Selective Comprehensive HILIC × RPLC (High-Resolution Sampling) and Active Solvent Modulation

The simultaneous liquid chromatographic analysis of water- and fat-soluble vitamins is challenging because of their wide polarity range. Typically, water-soluble vitamins are separated and analyzed by hydrophilic interaction chromatography (HILIC) while fat-soluble vitamins are analyzed by reversed-phase liquid chromatography (RPLC). The combination of these two retention principles in a column coupling or multidimensional liquid chromatography approach seems to be a logical consequence to solve the problem. In this work, a selective comprehensive HILIC × RPLC 2D-LC approach is investigated. In this method, the polar water-soluble vitamins are resolved in the first dimension (1D) on a 2-pyridylurea mixed-mode phase operated by a HILIC gradient and the coeluted fat-soluble vitamins in the early part of the chromatogram are comprehensively transferred in ten 40-µL fractions into a second dimension (2D) separation by RPLC on a C8 core–shell column. This mode of separation is also known as high-resolution sampling. The separations in 1D and 2D were optimized systematically and the retention mechanism on the mixed-mode column interpreted by support of these chromatographic data. The solvent incompatibility of 1D HILIC and 2D RPLC conditions due to sampling of acetonitrile-rich fractions from 1D into 2D RPLC led to severe peak broadening when a direct fraction transfer was carried out. An isocratic refocusing step could partly improve the situation for the stronger retained fat-soluble vitamins. Active solvent modulation with a specifically designed valve which allows a bypass of the weak eluent from the 2D pump to the column head and dilution of the fractionated sample from the sampling loop completely solved the problem and provided perfect peak shapes and chromatographic efficiencies.

Dried urine swabs as a tool for monitoring metabolite excretion.

We tested a large set (n=181) of wet urine and dried urine samples spotted on regular cosmetic cotton swabs for comparative UHPLC-MS/MS analysis of various metabolites across a wide polarity and structural range. Results/methodology: The agreement of measurements between conventional 24h urines and dried urine spots made from them in situ was evaluated by Passing-Bablok regression and Bland-Altman analysis after creatinine correction. There was full agreement in qualitative results but quantitative analysis revealed underestimation of dried urine spots in some cases. The dried urine samples contained analytes at measurable levels for at least 9months. Although this technique seems very promising more methodological studies have to be conducted in order to improve applicability of dried urine microvolume fluidic sampling for quantitative analysis.

Insights into Excited State Intramolecular Proton Transfer: An Alternative Model for Excited State Proton Transfer of Green Fluorescence Protein

The excited state intramolecular proton transfer (ESIPT) that occurs in the o-sulfonamide analogue ( o-TsABDI) of the green fluorescent protein (GFP) chromophore provides an alternative model to get insights into the excited state proton transfer (ESPT) related photophysics of GFP. In this article, we explored the ESIPT-related photophysics of o-TsABDI by electronic absorption and fluorescence emission spectra in a wide polarity range of solvents, cis- trans photoisomerization experiment, and Coulomb-attenuating method (CAM)/time-dependent (TD) density functional theory (DFT) calculations. We found that the whole ESIPT process involves four steps. The first step is photoexcitation of o-TsABDI, which does not involve charge transfer (CT). The second step is ESIPT and accompanying electron transfer from the n orbital of the sulfonamide nitrogen to the half-filled π orbital of the 4-benzylideneimidazolone moiety. The third step is fluorescence emission of the zwitterionic o-TsABDI and accompanying CT from the π* orbital of the 4-benzylideneimidazolone moiety to the half-filled n orbital of the sulfonamide nitrogen. The last step involves irreversible and barrierless proton recombination. In contrast to the isolated GFP chromophore and its p- and m-amino analogues, the S1 excited state of o-TsABDI does not relax by way of cis- trans photoisomerization through the S1/S0 conical intersection CI(I) by rotating around the I-bond, but follows the ESIPT pathway. The low fluorescence quantum yield of the zwitterionic o-TsABDI might be due to (1) the fluorescence that involves the low-probability π* → n charge transfer and (2) nonradiative relaxation through the S1/S0 conical intersection CI(P″) by rotating around the P-bond.

Fluorescence quenching of a biologically active boronic acid derivative by aniline in different solvents

Boronic acid derivatives are novel biologically active fluorescent molecules with numerous applications in various fields. A study of their fluorescent properties reveals some information that can be utilized in sensor design. One such study is fluorescence quenching. Here fluorescence quenching of 2-methoxypyridin-3-yl-3-boronic acid (2MPBA) in different solvents of a wide range of polarities has been carried out at room temperature by steady state fluorescence measurements. Aniline is used as the quencher. The positive deviation observed in Stern–Volmer (S-V) plots is analyzed using different quenching models. Various quenching parameters like S-V constant (KSV), quenching rate parameter (kq), volume constant (V), and kinetic distance (r) have been estimated using extended S-V equations. KSV is found to vary from 12.94 to 62.49 (mol/L)−1 with respect to solvents. From the calculated values of these parameters it is concluded that the static quenching mechanism is active in the studied system. However the reactions are diffusion-limited, which is confirmed by invoking the finite sink approximation model.

Physicochemical properties of betaine monohydrate-carboxylic acid mixtures

Green solvents are widely used to minimize environmental problems associated with the use of volatile organic solvents in many industries. DES are new green solvents in recent. The physicochemical properties of DES can be varied by properly combining of salts with different hydrogen bond donors. The objective of this work is to investigate the effect of varying molar ratios on the physicochemical properties of betaine monohydrate-carboxylic acid (i.e,. propionic or acetic acid) mixtures. Properties of mixtures were measured at 40°C. The viscosity, polarity scale (ENR), density, pH, and water content tend to decrease with the decrease in a molar ratio of betaine monohydrate to acid. Conversely, the ionic conductivity was increased. The physicochemical properties of these mixtures depend on the hydrogen bonding interactions between betaine, water and acid molecules. Betaine monohydratecarboxylic acid mixtures have wide range of polarity, low viscosity, high ionic conductivity, and density higher than 1 g·cm-3 that make them fit for numerous various applications. Additionally, due to these mixtures have acidic pH, it should be properly selected of metal type to minimize corrosion problems in industrial application.

Coumarin/BODIPY Hybridisation for Ratiometric Sensing of Intracellular Polarity Oscillation.

With different polarity responses, coumarin and 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) were hybridised to construct polarity fluorescent sensors, CBDP and iso-CBDP, to overcome the disadvantages of solvatochromic sensors in ratiometric polarity sensing. Only CBDP displayed an emission ratio (ICou /IBDP , coumarin to BODIPY emissions) that increased with an exponential dependence on medium relative permittivity over a wide polarity range (ϵr <57.9). This sensing ability of CBDP was not affected by medium pH; viscosity; and most intracellular species, especially reactive oxygen, nitrogen, and sulfur species. Apart from local cytoplasmic polarity quantification through lambda imaging, CBDP enables real-time ratiometric imaging for intracellular polarity oscillation induced by oxidative stimulation. Ratiometric polarity flow cytometry was developed, for the first time, with CBDP, which demonstrated that a high concentration H2 O2 induced cytoplasmic polarity enhancement, whereas pre-incubation with N-acetyl-l-cysteine inhibited this effect.

Tunable Polarity Carbon Fibers, a Holistic Approach to Environmental Protection.

The pollution of environmental resources is an issue of social concern worldwide. Chemistry is essential for the design of decontamination strategies and analytical approaches to detect and monitor the contamination. Sorptive materials are usually required in both approaches and green synthesis should be used to minimize their own environmental impact. Carbon fibers (CFs) obtained by the pyrolysis of natural cellulose-rich materials fulfill these requirements. In this article, thirty CFs obtained under different conditions are chemically characterized and their sorption ability towards selected pollutants, covering a wide range of polarity, is evaluated. This study provides more profound knowledge related to the polarity of these materials, their interactions with chemical substances and allows the prediction of more appropriate materials (pyrolysis temperature and time) in order to remove the given pollutant. Furthermore, the use of CFs as sorptive materials for the extraction of contaminants from water samples to assist with their instrumental detection is outlined. In this sense, the use of CFs and gas chromatography with mass spectrometric detection allows the detection of selected pollutants in the low ng/mL range. Thus, this article provides an integrated approach to the potential of CFs for environmental protection.

Superacid-derived surface passivation for measurement of ultra-long lifetimes in silicon photovoltaic materials

Accurate measurements of bulk minority carrier lifetime are essential in order to determine the true limit of silicon's performance and to improve solar cell production processes. The thin film which forms when silicon wafers are dipped in solutions containing superacids such as bis(trifluoromethane)sulfonimide (TFSI) has recently been found to be effective at electronically passivating the silicon surface. In this paper we first study the role of the solvent in which TFSI is dissolved for the passivation process. We study ten solvents with a wide range of relative polarities, finding TFSI dissolved in hexane provides improved temporal stability, marginally better passivation and improved solution longevity compared to dichloroethane which has been used previously. Sample storage conditions, particularly humidity, can strongly influence the passivation stability. The optimised TFSI-hexane passivation scheme is then applied to a set of 3 Ω cm n-type wafers cut from the same float-zone ingot to have different thicknesses. This enables the reproducibility of the scheme to be systematically evaluated. At 1015 cm−3 injection the best case effective surface recombination velocity is 0.69 ± 0.04 cm/s, with bulk lifetimes measured up to the intrinsic lifetime limit at high injection and >43 ms at lower injection. Immersion of silicon in superacid-based ionic solutions therefore provides excellent surface passivation, and, as it is applied at room temperature, the effects on true bulk lifetime are minimal.

Aramid fiber with excellent interfacial properties suitable for resin composite in a wide polarity range

The weak interfacial adhesion of aramid fiber with resin matrix is believed as a major limitation for its wide application. In this study, a nondestructive grafting method was applied for surface modification of benzimidazole-contained aramid fiber. Using the NH in benzimidazole unit as active sites, aramid fiber surface was firstly decorated with densely SiO2 structure, and a rough surface was obtained. Then, high density of NH2 and C=C groups were introduced on fiber surface by the reaction with silane coupling agents. These functionalized NH2/C=C groups endow the fiber with the ability to chemically bonding with resin in a wide polarity range, including rubber, bismaleimide and epoxy resin. Also, the SiO2-decorated rough surface improves the level of mechanical interlocking with them. Experimental results show that the interfacial shear strength of functionalized fiber with natural rubber, bismaleimide and epoxy resin correspondingly increases 117%, 166% and 43%, compared with that of untreated fibers. Meanwhile, the grafting method is confirmed as nondestructive, and the superior mechanical property of aramid fiber is preserved. In all, the study presents a new effective method for the preparation of aramid fiber with excellent interfacial properties suitable for resin composite in a wide polarity range.

Study of a complex secondary metabolites with potent anti-radical activity by two dimensional TLC/HPLC coupled to electrospray ionization time-of-flight mass spectrometry and bioautography

The high performance liquid chromatography (HPLC) coupled to electrospray ionization (ESI) octopole orthogonal acceleration time-of-flight (TOF) mass spectrometry (MS) was developed to separate secondary metabolites belonging to different groups of compounds with a wide range of polarity, i.e. phenolic acids, flavonoids, sesquiterpenes and others present in minute amounts, in a single run.Moreover, application of ESI-TOF-MS with a simple in source type of fragmentation and high mass accuracy measurements (around 2 ppm) in both positive and negative ionization modes with different and optimized fragmentor voltages, enabled the identification of each single compound based on proposed fragmentation patterns. In this way a total number of 14 compounds in methanolic and water-methanolic (1:1, v/v) extract from fruits of Eryngium amethystinum and 6 compounds in extract from fruits of E. planum have been identified for the first time.Additionally, two dimensional thin layer chromatography/high performance liquid chromatography/electrospray-ionization-time-of-flight mass spectrometry (TLC/HPLC/ESI-TOF-MS) system was developed for identification of compounds with the highest anti-radical activity revealed in TLC-DPPH bioauthographic test. This on-line procedure enables significant improvement in terms of efficiency and faster structural analysis of the potential antioxidant natural compounds directly in the plant extracts screened for bioactivity tests. This effect – directed analysis (EDA) method enables separation, identification and preliminary screening of plant extracts for anti-radical properties and can be easily adopted for other bioactivities.

Terpene-Based Sustainable Elastomers: Vulcanization and Reinforcement Characteristics

Allured by the quest to fabricate sustainable elastomers having tangible applications, the present work reports the study of vulcanization and reinforcement characteristics of several sustainable elastomers derived from β-myrcene—a naturally occurring “waste” monoterpene from plant. The elastomers were synthesized by the environmentally benign and industrially robust emulsion polymerization method. Conventional elastomer processing techniques were employed for the compounding and vulcanization of the synthesized elastomers. The vulcanization characteristics of the synthesized sustainable elastomers are similar to natural rubber. Polymer microstructure, molecular weight, and type and amount of comonomer influence the curing characteristics and physico-mechanical properties of the elastomer vulcanizates. An attempt has been made to elucidate the plausible network structure of the polymyrcene vulcanizate. Because of wide range of polarity, these sustainable elastomers could also aid in dispersion of function...

Fabric phase sorptive extraction-high performance liquid chromatography-photo diode array detection method for simultaneous monitoring of three inflammatory bowel disease treatment drugs in whole blood, plasma and urine

This paper reports a novel fabric phase sorptive extraction-high performance liquid chromatography-photodiode array detection (FPSE-HPLC-PDA) method for the simultaneous extraction and analysis of three drug residues (ciprofloxacin, sulfasalazine, and cortisone) in human whole blood, plasma, and urine samples, generally administered in human patients to treat inflammatory bowel disease (IBD).The drugs of interest were well resolved using a Luna C18 column (250 mm × 4.6 mm; 5 μm particle size) in gradient elution mode within 20 min. The analytical method was optimized and validated in the range 0.05–10 μg/mL for whole blood, 0.25–10 μg/mL for human plasma, and 0.10–10 μg/mL for human urine. Blank human whole blood, plasma, and urine were used as the sample matrix for the method development and validation; while methyl-p-hydroxybenzoate was used as the internal standard (IS). Weighted-matrix matched standard calibration curves showed a good linearity up to a concentration of 10 μg/mL. The intra- and inter-day accuracy values (precision and trueness) were found in the range from −10.9% to 12.3%, and the performances of the validated FPSE-HPLC-PDA were further tested on real IBD patient samples.This is the first FPSE procedure applied simultaneously to whole blood, plasma, and urine samples for the determination of residual IBD drugs, which possess a wide range of polarity (logP values ranging from 2.30 for Ciprofloxacin, to 1.66 for Cortisone, and 2.92 for Sulfasalazine). The new approach exhibits high potential for immediate adoptation as a rapid, robust and green analytical tool for future clinical and pharmaceutical applications.

3D-QSAR modeling of maximum steady-state fluxes of some substituted benzenes and quinolone derivatives through polydimethylsiloxane membrane

The maximum steady-state flux of 79 compounds (substituted benzenes, and quinolones and their derivatives) with a wide range of polarity through a PDMS membrane was predicted using a comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) methods. Moreover, the contribution of partial atomic charge to mass transport phenomena was further verified by the correlation of atomic charge to apparent permeability through polydimethylsiloxane (PDMS) membranes. The obtained results indicated superiority of CoMSIA model over CoMFA model. The best CoMSIA model is developed based on the combination of electrostatic and hydrophobic and H-bond acceptor fields (CoMSIA-EHA). The contour maps of electrostatic and hydrophobic and H-bond acceptor fields of CoMSIA model provide an interpretable and logical relationship between chemicals structure and their fluxes, which give useful insights for designing new compounds with higher penetration through the membranes.

Performance enhancement in organic solvent nanofiltration by double crosslinking technique using sulfonated polyphenylsulfone (sPPSU) and polybenzimidazole (PBI)

In this paper, we report a new technique to design highly stable and selective organic solvent nanofiltration (OSN) membranes with enhanced solvent permeance by manipulating the crosslinking reactions. The new technique consists of three steps: (1) membrane fabrication via non-solvent induced phase inversion by blending sulfonated polyphenylsulfone (sPPSU) and polybenzimidazole (PBI) polymers, followed by (2) crosslinking the PBI part using α,α′-dibromo-p-xylene (DBX) to make the membrane chemically stable, and (3) ionically crosslinking the sPPSU part with hyperbranched polyethylenimine (HPEI) to narrow down the membrane pore size without affecting the permeance significantly. Crosslinking reactions have been confirmed by FTIR and XPS analyses. The OSN performance of the double crosslinked membranes was determined by measuring the permeance of various organic solvents and the rejection rates of tetracycline (Mw = 444 g mol−1) as a model pharmaceutical. Depending on the testing solvents, the permeances ranged from 2 to 11.8 L m−2 h−1 bar−1, while the rejection rates of tetracycline varied from 67% to 97%. Considering the outstanding OSN performance and the great chemical stability in a wide range of solvent polarities, this novel double crosslinking technique represents a step forward in the fabrication of high performance OSN membranes.