Classes Of Polar Compounds Research Articles

Effect of anionic groups in zwitterionic hydrophilic stationary phases on their chromatographic characteristics

The structure of zwitterion has great impact on the separation properties of zwitterionic hydrophilic stationary phases. To better understand the role of anionic groups of zwitterions, a novel carboxybetaine-based zwitterionic monolithic column was first prepared through thermo-initiated copolymerization of functional monomer (3-acrylamidopropyl)-dimethyl-(2-carboxymethyl) ammonium (CBAA) and crosslinker ethylene dimethacrylate (EDMA) within 100 μm ID capillary. The optimal poly(CBAA-co-EDMA) monolithic column exhibited satisfactory mechanical and chemical stability, good repeatability, high column efficiency (96,000 plates/m), and excellent separation performance for different classes of polar compounds (i.e., phenols, monophosphate nucleotides, urea and allantoin). A comparative study was then performed among three zwitterionic hydrophilic stationary phases containing different anionic groups, i.e. poly(CBAA-co-EDMA) (carboxybetaine), poly(2-{2-(methacryloyloxy) ethyldimethylammonium}ethyl n-butyl phosphate-co-EDMA) (phosphocholine), and poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-N-(3-sulfopropyl) ammonium betaine-co-EDMA) (sulfobetaine) using benzoic acid derivatives, amine compounds, nucleobases and nucleosides as model analytes. The carboxybetaine-based monolithic column exhibited much higher positive zeta-potential and hydrophilicity, which endows it with a stronger retention capacity for acidic and neutral compounds, but sulfobetaine-based monolithic column exhibited much higher selectivity and retention capacity for the amines. Moreover, their enrichment efficiencies for N-glycopeptides were also evaluated based on their different hydrophilicity, and it was observed that the poly(CBAA-co-EDMA) monolithic material captured 4-8 times more N-glycopeptides compared to the other two materials.

Lipid biomarker comparison of relict and active microbial mats from the McMurdo Ice Shelf, Antarctica

Earth’s biota leave traces in the form of molecular fossils, typically from the membrane lipids of organisms, preserved in the sedimentary rock record. However, since the environmental conditions prevailing at the time can impact the nature of those remains, it is important to understand the diagenetic processes that occur under contrasting regimes. In this study, we investigated the preservation under cold and arid climatic conditions of intact polar lipids, bacteriohopanepolyols, and quinones preserved in a ∼700-year-old relict, desiccated microbial mat. We compared these to lipid signatures in actively growing counterparts from nearby meltwater ponds of McMurdo Ice Shelf in Antarctica. Substantial differences in lipid distribution were evident between active and relict mats, suggesting that significant diagenetic degradation of lipid biomarkers occurs within a short period, thereby illuminating the selective preservation of certain polar compound classes under cold and dry conditions.

Circular valorization of coffee silverskin through supercritical CO2 for the production of functional extracts

Supercritical CO2 efficiently extracts classes of polar compounds connected with the relevance of silverskin's phytochemical profile, justifying the valorization of this coffee waste towards added value products.

Systematic Evaluation of HILIC Stationary Phases for Global Metabolomics of Human Plasma.

Polar hydrophilic metabolites have been identified as important actors in many biochemical pathways. Despite continuous improvement and refinement of hydrophilic interaction liquid chromatography (HILIC) platforms, its application in global polar metabolomics has been underutilized. In this study, we aimed to systematically evaluate polar stationary phases for untargeted metabolomics by using HILIC columns (neutral and zwitterionic) that have been exploited widely in targeted approaches. To do so, high-resolution mass spectrometry was applied to thoroughly investigate selectivity, repeatability and matrix effect at three pH conditions for 9 classes of polar compounds using 54 authentic standards and plasma matrix. The column performance for utilization in untargeted metabolomics was assessed using plasma samples with diverse phenotypes. Our results indicate that the ZIC-c HILIC column operated at neutral pH exhibited several advantages, including superior performance for different classes of compounds, better isomer separation, repeatability and high metabolic coverage. Regardless of the column type, the retention of inorganic ions in plasma leads to extensive adduct formation and co-elution with analytes, which results in ion-suppression as part of the overall plasma matrix effect. In ZIC-c HILIC, the sodium chloride ion effect was particularly observed for amino acids and amine classes. Successful performance of HILIC for separation of plasma samples with different phenotypes highlights this mode of separation as a valuable approach in global profiling of plasma sample and discovering the metabolic changes associated with health and disease.

Discovery of amantadine formate: Toward achieving ultrahigh pyroelectric performances in organics

Pyroelectrics are a class of polar compounds that output electrical signals upon changes in temperature. With the rapid development of flexible electronics, organic pyroelectrics are highly desired. However, most organics suffer from low pyroelectric coefficients or low working temperatures. To date, the realization of superior pyroelectric performance in all-organics has remained a challenge. Here, we report the discovery of amantadine formate, an all-organic pyroelectric with ultrahigh voltage figures of merit (Fv), surpassing those of all other known organics and commercial triglycine sulfate, LiTaO3 as well around room temperature. The key to the high Fv is attributed to large pyroelectric coefficients in a favorable temperature range resulting from a ferroelectric-paraelectric phase transition of second order at 327 K, small dielectric constant, and moderate heat capacity. In addition, amantadine formate is relatively lightweight, soft, transparent, low-cost, and non-toxic, adding value to its potential applications in flexible electronics. Our results demonstrate that a new type of pyroelectrics can exist in organic compounds.

Profiling naphthenic acids in produced water using hollow fiber liquid-phase microextraction combined with gas chromatography coupled to Fourier transform Orbitrap mass spectrometry

In this study, we describe the development of an analytical method to profile naphthenic acids (NAs) from produced water (PW). The NAs were isolated by hollow fiber liquid-phase microextraction (HF-LPME). A microwave-assisted methylation method was used to convert the free acids into its corresponding naphthenic methyl esters (NAMEs). The best reaction conditions were ascertained using central composite design. The optimized sample preparation method exhibited an improved analytical eco-scale value (80 vs. 61) compared to conventional liquid-liquid extraction. Although the primary goal was qualitative analysis of NAMEs (e.g., group-type separation) in produced water, the quantitative performance was also evaluated for future investigations. The instrumental detection and quantification limits were 0.10 ng mL−1 and 0.16 ng mL−1, respectively, using full spectrum data acquisition. The accuracy and precision of the proposed method ranged from 90.4 to 96.6 % and 3.3 to 13.1 %, respectively, using matrix-matched working solutions (0.1, 0.5, and 1.0 µg mL−1). The monoisotopic masses of the adduct ions ([M+H]+) and its corresponding fine isotopic patterns were used to determine the elemental composition of the NAMEs in the PW samples. Qualitative analysis indicated the O2 class as the predominant class in all samples with carbon numbers ranging from C5 to C19 and double bond equivalent (DBE) values of 1 to 8. Additional classes of polar compounds, i.e., O3, O4 and nitrogen-containing classes, are reported for the first time by gas chromatography coupled to Fourier transform Orbitrap mass spectrometry and chemical ionization.

Simple, Expendable, 3D-Printed Microfluidic Systems for Sample Preparation of Petroleum.

In this study, we introduce a simple protocol to manufacture disposable, 3D-printed microfluidic systems for sample preparation of petroleum. This platform is produced with a consumer-grade 3D-printer, using fused deposition modeling. Successful incorporation of solid-phase extraction (SPE) to microchip was ensured by facile 3D element integration using proposed approach. This 3D-printed μSPE device was applied to challenging matrices in oil and gas industry, such as crude oil and oil-brine emulsions. Case studies investigated important limitations of nonsilicon and nonglass microchips, namely, resistance to nonpolar solvents and conservation of sample integrity. Microfluidic features remained fully functional even after prolonged exposure to nonpolar solvents (20 min). Also, 3D-printed μSPE devices enabled fast emulsion breaking and solvent deasphalting of petroleum, yielding high recovery values (98%) without compromising maltene integrity. Such finding was ascertained by high-resolution molecular analyses using comprehensive two-dimensional gas chromatography and gas chromatography/mass spectrometry by monitoring important biomarker classes, such as C10 demethylated terpanes, ααα-steranes, and monoaromatic steroids. 3D-Printed chips enabled faster and reliable preparation of maltenes by exhibiting a 10-fold reduction in sample processing time, compared to the reference method. Furthermore, polar (oxygen-, nitrogen-, and sulfur-containing) analytes found in low-concentrations were analyzed by Fourier transform ion cyclotron resonance mass spectrometry. Analysis results demonstrated that accurate characterization may be accomplished for most classes of polar compounds, except for asphaltenes, which exhibited lower recoveries (82%) due to irreversible adsorption to sorbent phase. Therefore, 3D-printing is a compelling alternative to existing microfabrication solutions, as robust devices were easy to prepare and operate.

Chromatographic behaviour of synthetic high pressure high temperature diamond in aqueous normal phase chromatography

The chromatographic properties of high pressure high temperature synthesised diamond (HPHT) are investigated under the conditions of hydrophilic interaction liquid chromatography (HILIC). A 50×4.6mm ID stainless steel column packed with HPHT particles of mean diameter 1.6μm and specific surface area 5.1m2g−1 is used. According to the results of acid-base titration with NaOH the purified HPHT batch contains 4.59μeqg−1 of protogenic, mainly carboxyl- and hydroxyl-, groups, which make this polar adsorbent suitable for use as a stationary phase in HILIC. The retention behaviour of several classes of polar compounds including benzoic and benzenesulfonic acids, nitro- and chlorophenols, various organic bases, and quaternary ammonium compounds are studied using acetonitrile and methanol based mobile phases containing 5–30v/v% of water. The effects of the buffer pH and concentration, column temperature and organic solvent content on retention of model compounds are also investigated. It is shown that both pH and acetonitrile/methanol ratio in the mobile phase can be used to vary the separation selectivity. Molecular adsorption mechanism (related to aqueous normal phase mode), rather than partitioning is established to be responsible for the retention.

Determination of Polar Compounds in Guava Leaves Infusions and Ultrasound Aqueous Extract by HPLC-ESI-MS

Literature lacks publications about polar compounds content in infusion or guava leaves tea. Because of that, a comparison between different times of infusion and a conventional ultrasound aqueous extract was carried out. Several polar compounds have been identified by HPLC-ESI-MS and their antioxidant activity was evaluated by FRAP and ABTS assays. Four different classes of phenolic compounds (gallic and ellagic acid derivatives, flavonols, flavanones, and flavan-3-ols) and some benzophenones were determined. The quantification results reported that the order, in terms of concentration of the classes of polar compounds in all samples, was flavonols > flavan-3-ols > gallic and ellagic acid derivatives > benzophenones > flavanones. As expected, the aqueous extract obtained by sonication showed the highest content in the compounds studied. Significative differences were noticed about the different times of infusion and five minutes was the optimal time to obtain the highest content in polar compounds using this culinary method. All the identified compounds, except HHDP isomers and naringenin, were positively correlated with antioxidant activity.

Analysis of chemical profiles of insect adhesion secretions by gas chromatography–mass spectrometry

This article reports on the chemical analysis of molecular profiles of tarsal secretions of the desert locust Schistocerca gregaria (Forsskål, 1775) by gas chromatography hyphenated with quadrupol mass spectrometry (GC–MS) as well as 1H-nuclear magnetic resonance (1H NMR) spectroscopy. Special focus of this study was to elaborate on sampling methods which enable selective microscale extraction of insect secretions in a spatially controlled manner, in particular tarsal adhesive secretions and secretions located on cuticle surfaces at the tibia. Various solvent sampling procedures and contact solid-phase microextraction (SPME) methods were compared in terms of comprehensiveness and extraction efficiencies as measured by signal intensities in GC–MS. Solvent sampling with water as extraction solvent gave access to the elucidation of chemical profiles of polar compound classes such as amino acids and carbohydrates, but is extremely tedious. Contact SPME on the other hand can be regarded as a simplified and more elegant alternative, in particular for the lipophilic compound fraction. Many proteinogenic amino acids and ornithine as well as carbohydrate monomers arabinose, xylose, glucose, and galactose were detected in tarsal secretions after acid hydrolysis of aqueous extracts. Qualitatively similar but quantitatively significantly different molecular profiles were found for the lipid fraction which contained mainly n-alkanes and internally branched monomethyl-, dimethyl-, and trimethyl-alkanes in the C23–C49 range as well as long chain fatty acids and aldehydes. Especially, hydrocarbons with >C40 carbon numbers have previously been rarely reported for insect secretions. The results suggest that the investigated insect secretions are complex emulsions which allow the attachment of tarsi on various otherwise incompatible materials of smooth and rough surfaces. The solid consistence of the established alkanes at ambient temperatures might contribute to a semi-solid consistence of the adhesive, amalgamating partly opposing functions such as slip resistance, tarsal release, desiccation resistance, and mechanical compliance. The methods developed can be extended to other similar applications of studying compositions of insect secretions of other species.

Recent progress in polar metabolite quantification in plants using liquid chromatography–mass spectrometry.

Metabolite analysis or metabolomics is an important component of systems biology in the post-genomic era. Although separate liquid chromatography (LC) methods for quantification of the major classes of polar metabolites of plants have been available for decades, a single method that enables simultaneous determination of hundreds of polar metabolites is possible only with gas chromatography–mass spectrometry (GC–MS) techniques. The rapid expansion of new LC stationary phases in the market and the ready access of mass spectrometry in many laboratories provides an excellent opportunity for developing LC–MS based methods for multi-target quantification of polar metabolites. Although various LC–MS methods have been developed over the last 10 years with the aim to quantify one or more classes of polar compounds in different matrices, currently there is no consensus LC–MS method that is widely used in plant metabolomics studies. The most promising methods applicable to plant metabolite analysis will be reviewed in this paper and the major problems encountered highlighted. The aim of this review is to provide plant scientists, with limited to moderate experience in analytical chemistry, with up-to-date and simplified information regarding the current status of polar metabolite analysis using LC–MS techniques.

Petroleomics by Traveling Wave Ion Mobility–Mass Spectrometry Using CO2as a Drift Gas

The technique of choice for petroleomics has been ultra-high-resolution and high-accuracy Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), but other techniques such as ion mobility have been shown to provide additional or alternative information about crude oil composition. Using the traveling wave ion mobility (TWIM) cell of a hybrid Q-TWIM-TOF first-generation Synapt instrument and electrospray ionization in both the positive and negative ion modes, different crude oil samples with different polar compound profiles and petro fuels (diesel and gasoline) with or without additives were analyzed using either CO2 or N2 as the drift gas. Parameters such as gas pressure, velocity, and wave height were optimized for each type of crude oil or fuel sample. The ability of TWIM–MS to separate crude oil components according to their classes was verified by comparison with FT-ICR data. Results showed separation of several classes of polar compounds (NO, O2, and N), and their separation was improved using CO2, which also enhanced the resolution between adjacent m/z species. Additives and contaminants presented in petro fuels could also be easily separated and characterized.

Quantitative profiling of polar primary metabolites using hydrophilic interaction ultrahigh performance liquid chromatography–tandem mass spectrometry

A hydrophilic interaction liquid chromatography (HILIC)-MS/MS profiling method was developed for the efficient separation and quantification of small polar molecules, mostly primary metabolites. The method was based on an ultrahigh performance liquid chromatography (UHPLC) separation system coupled with ESI mass spectrometry on a triple quadrupole mass spectrometer, operating in both positive and negative ionisation mode using rapid polarity switching. With the developed method quantitation of 135 compounds belonging in four major classes of polar compounds (sugars, aminoacids, organic acids and amines) was achieved in a single run of 30min. The method was applied to grape extracts from different varieties and provided information on primary metabolite content. Multivariate statistical analysis was applied using the concentrations found, with the aim of investigating the differences in metabolite profiles. Classification of grapes according to their skin colour was carried out using principle component analysis based on the concentration variation of a number of the metabolites studied.

Equilibrium Partition Coefficients of Diverse Polar and Nonpolar Organic Compounds to Polyoxymethylene (POM) Passive Sampling Devices

Equilibrium passive samplers (EPS) based on polyoxymethylene (POM) are increasingly used for determining freely dissolved water and pore water concentrations of hydrophobic organic compounds in the environment. Unlike other polymeric materials commonly used as EPS, namely poly(dimethylsiloxane) (PDMS) and low-density polyethylene (PE), POM is a polar polymer, containing repeating H-bond accepting ether units. Thus, POM is expected to be a more sensitive EPS than PDMS and PE for polar, H-bond donating compounds, such as many hormones, pharmaceuticals, and biocides. To better characterize the sorption capacity of POM for diverse polar and apolar compounds, equilibrium POM-water partition coefficients, K(POM/w), were measured for 56 compounds, including several classes of polar compounds and organochlorine pesticides. Using this data set and literature data, various POM-partitioning models were calibrated and validated for their ability to predict K(POM/w). The best performing models tested were an Abraham descriptor based polyparameter linear free energy relationship (PP-LFER) (SD = 0.24 log units) and COSMOthermX (SD = 0.37 log units). The performance of SPARC (SD = 0.61 log units) and log-log correlations with K(ow) (SD = 0.49 log units) were lower. A comparison with PDMS and PE confirmed expectations that POM exhibits a higher sensitivity for H-bond donating polar compounds than PDMS and PE do for these compounds. These findings expand the domain of chemicals for which POM can be used as an EPS sampler, and demonstrate that POM is as suitable a passive sampler for many polar organic compounds as it is for hydrophobic organic compounds.

Prediction of Absolute Solvation Free Energies using Molecular Dynamics Free Energy Perturbation and the OPLS Force Field.

The accurate prediction of protein-ligand binding free energies is a primary objective in computer-aided drug design. The solvation free energy of a small molecule provides a surrogate to the desolvation of the ligand in the thermodynamic process of protein-ligand binding. Here, we use explicit solvent molecular dynamics free energy perturbation to predict the absolute solvation free energies of a set of 239 small molecules, spanning diverse chemical functional groups commonly found in drugs and drug-like molecules. We also compare the performance of absolute solvation free energies obtained using the OPLS_2005 force field with two other commonly used small molecule force fields-general AMBER force field (GAFF) with AM1-BCC charges and CHARMm-MSI with CHelpG charges. Using the OPLS_2005 force field, we obtain high correlation with experimental solvation free energies (R(2) = 0.94) and low average unsigned errors for a majority of the functional groups compared to AM1-BCC/GAFF or CHelpG/CHARMm-MSI. However, OPLS_2005 has errors of over 1.3 kcal/mol for certain classes of polar compounds. We show that predictions on these compound classes can be improved by using a semiempirical charge assignment method with an implicit bond charge correction.

Characterization of polar organic compounds in the organic film on indoor and outdoor glass windows.

Organic films on an impervious surface (window glass) were sampled at paired indoor-outdoor sites in July 2000 and characterized for their paraffinic and polar organic compositions along an urban-rural transect. Four classes of polar compounds (C11-C31 aliphatic monocarboxylic, C6-C14 dicarboxylic, nine aromatic polycarboxylic, and five terpenoid acids) constituted between 81 and 95% (w/w) of the total organic fraction analyzed comprising n-alkanes (C10-C36), 46 PAH, 97 PCBs, and 18 OC pesticides. Concentrations of the polar compounds plus their precursors, n-alkanes, ranged from 8 to 124 microg m(-20 and were dominated by monocarboxylic acids (67-89%, w/w). On outdoor windows, n-alkanes, aromatic acids, and terpenoid acids decreased in concentration along the urban-rural transect. The carbon preference index values and the interpretations of individual compounds indicate that the main sources of n-alkanes were plant waxes followed by petrogenic sources; monocarboxylic and dicarboxylic acids were from plant waxes and animal fats. Results of principal component analysis showed closer correspondence between outdoor and indoor signatures than among locations. In outdoor films, these compounds are suggested to play an important role in mediating chemical fate in urban areas by air-film exchange and facilitating "wash-off" due to their surfactant-like properties. In indoor films, these compounds provide a medium for the accumulation of more toxic compounds.

Real-time detection of organic compounds in liquid environments using polymer-coated thickness shear mode quartz resonators

The selection of sensitive coatings is a critical task in the design and implementation of chemical sensors using coated thickness shear mode quartz crystal resonators (QCRs) for detection in liquid environments. This design or selection is performed through a study of the sorption process in terms of the partition coefficients of the analytes in the coatings. The partition coefficient, which is controlled by the chemical and physical properties of the coating materials, determines the inherent selectivity and sensitivity toward analyte molecules. The selection of the coatings is logically determined by the interactions between coating and target analyte molecules, but can also be made through a systematic variation of the coating's properties. The determination of the partition coefficients is only accurate if all contributions to the total measured frequency shifts, deltafs, of the coated QCR can be established. While mass loading is often assumed to be the dominant factor used in determining partition coefficients, viscoelastic effects may also contribute to deltafs. Both the effect of viscoelastic properties and the effect of mass loading on the sensor responses are investigated by using a network analyzer and oscillator circuit and by characterizing the total mechanical impedance of the loaded sensor. Different types of coatings including rubbery and glassy polymers are investigated, and the targeted analytes include classes of polar compounds (methanol), nonpolar compounds (toluene, xylenes), and chlorinated hydrocarbons (trichloroethylene, tetrachloroethylene, etc). It is seen that changes in viscoelastic properties due to analyte sorption may be significant enough to place the sensor in the nongravimetric regime. However, for most applications involving the detection of relatively low concentrations of organic compounds and the use of acoustically thin films, changes in the complex shear modulus of the coatings contribute less than 5% of the total shift in the series resonant frequency, depending on the coating. In that case, the measured deltafs and, hence, the calculated approximate classification and selection of the coatings for operation in a complex solution of water/analyte molecules.

Adsorptive capacity of active filter aids for used cooking oil

Many materials are purported to adsorb polar compounds that are the result of degradation of oils used for deep‐fat frying. In the present study, the capacity of several of these adsorbents in terms of the amount of polar oil degradation compounds adsorbed by a given weight of material was determined. A significant difference in the adsorptive characteristics and capacity of the materials tested was demonstrated. Adsorptive capacity varied from 0 to over 150 mg of total polar compounds per gram of adsorbent. Some of the materials demonstrated selective adsorption characteristics. For these materials, only one class of polar compounds was adsorbed.

石炭水添液化反応における循環溶剤の組成変化 ＩＩ 極性成分について

The composition changes of polar compounds in recycle solvents (S-1-6) derived from liquefaction experiment with Akabira coal are examined by means of HPLCGC/MS method.Using HPLC equipped with a Zorbax BP-NH2 column, polar compounds in recycle solvents were separated into three polar compound classes (Fr-B, N and A) in a stepwise elution system with different concentrations of solvents from hexane to chloroform.Major polar compound classes in hydrogenated anthracene oil (HAO), used as a starting solvent, were Fr-B (basic nitrogen compounds) and N (neutral hetero compounds), and were mainly composed of carbazoles, benzoquinolines and azapyrenes. However, very little Fr-A (acidic oxygen compounds) was contained in HAO.The amounts of Fr-N and of carbazoles in S-1 increased more than they did in HAO. But after the first recycle, their levels remained approximately constant regardless of recycling. The levels of anilines and indoles, little contained in HAO, increase with recycling. That is, nitrogen compounds with high molecular weight, such as carbazoles and benzoquinolines derived from coal were partially hydrogenated and cleavaged. Then, nitrogen compounds with low molecular weight, such as anilines and indoles, were produced and their levels increased with recycling.Fr-A accumulated in the recycle solvent in each recycle and was mainly composed of phenols, phenylphenols and indanols/tetrahydronaphthols.In general, the level of compounds with low-carbon number of alkyl side chains increased with recycling. This means that the reaction of dealkylation occurs in coal liquefaction.

Feeding preferences of eastern spruce budworm larvae in two‐choice tests with combinations of host‐plant extracts

AbstractThree extracts were obtained from each of four host plants: sugars/glycosides; amino acids/bases; and organic acids. The four hosts studied were balsam fir, black spruce, red spruce, and white spruce. The effects of recombined host plant extracts on the feeding behaviour of eastern spruce budworm larvae were examined in two‐choice tests. Results compare feeding preferences as well as feeding rates between combinations of extracts. The importance of each class of polar compounds is discussed.RÉSUMÉPréférences des larves de la tordeuse des bourgeons de l'épinette envers extraits combinés de leurs plantes‐hôtesTrois extraits ont été obtenus de chacune de quatre plantes‐hôtes: sucres/glycosides; acides aminées/bases organiques; acides organiques. Les quatre plantes‐hôtes étudiées furent le sapin baumier, et les épinettes blanc, noir, et rouge. Le comportement gustatoire des larves a été étudié en raison de l'effet de combinaisons d'extraits de chaque plante‐hôte. Les résultats comparent la préférence des larves ainsi que leur consommation totale envers ces extraits.