Carboxylic Acid Functional Groups Research Articles

Synthesis and properties of responsive self-healing polyurethane containing dynamic disulfide bonds

The polymers with pH responsiveness and temperature sensitivity exhibit important applications in many fields. To endow the responsive polymers with self-healing is meaningful work, which contributes to increase their service life and reduce waste of resources significantly. In this research, a series of pH-responsive polyurethanes containing dynamic disulfide bonds and carboxylic acid functional groups were prepared by mixing polycaprolactone diol (PCL), hexamethylene diisocyanate (HDI), 2,2-dimethylolbutyric acid, and bis(2-hydroxyethyl) disulfide. The structure of the polymer was confirmed by some characterization methods such as infrared absorption spectroscopy, Raman scattering spectroscopy, X-ray diffraction, and differential scanning calorimetry. Many performances of the polymer such as the contact angle, thermal stability, mechanics, and self-healing properties can be adjusted by changing the functional units of polyurethanes. The dynamic disulfide bonds in the main chain were observed no harm to the pH response performance, instead which were beneficial to the promotion of heat resistance, tensile properties, and self-healing performance of polyurethane. The elongation at break and the tensile strength are increased by 85.3% and 54.9%, respectively. All the polyurethane exhibited considerable self-healing effects at 110°C, with the highest healing efficiency reaching 93.7%, as a result of the dissociation of hydrogen bonds and the exchange reaction of disulfide bonds.

MetFish: a Metabolomics Pipeline for Studying Microbial Communities in Chemically Extreme Environments.

ABSTRACTMetabolites have essential roles in microbial communities, including as mediators of nutrient and energy exchange, cell-to-cell communication, and antibiosis. However, detecting and quantifying metabolites and other chemicals in samples having extremes in salt or mineral content using liquid chromatography-mass spectrometry (LC-MS)-based methods remains a significant challenge. Here, we report a facile method based on in situ chemical derivatization followed by extraction for analysis of metabolites and other chemicals in hypersaline samples, enabling for the first time direct LC-MS-based exometabolomics analysis in sample matrices containing up to 2 M total dissolved salts. The method, MetFish, is applicable to molecules containing amine, carboxylic acid, carbonyl, or hydroxyl functional groups, and it can be integrated into either targeted or untargeted analysis pipelines. In targeted analyses, MetFish provided limits of quantification as low as 1 nM, broad linear dynamic ranges (up to 5 to 6 orders of magnitude) with excellent linearity, and low median interday reproducibility (e.g., 2.6%). MetFish was successfully applied in targeted and untargeted exometabolomics analyses of microbial consortia, quantifying amino acid dynamics in the exometabolome during community succession; in situ in a native prairie soil, whose exometabolome was isolated using a hypersaline extraction; and in input and produced fluids from a hydraulically fractured well, identifying dramatic changes in the exometabolome over time in the well.IMPORTANCE The identification and accurate quantification of metabolites using electrospray ionization-mass spectrometry (ESI-MS) in hypersaline samples is a challenge due to matrix effects. Clean-up and desalting strategies that typically work well for samples with lower salt concentrations are often ineffective in hypersaline samples. To address this gap, we developed and demonstrated a simple yet sensitive and accurate method—MetFish—using chemical derivatization to enable mass spectrometry-based metabolomics in a variety of hypersaline samples from varied ecosystems and containing up to 2 M dissolved salts.

Enantioselective Self-Assembled Nanofibrillar Network with Glutamide-Based Organogelator.

A chiral molecular gelation system, as a chiral host, was used to effectively realize enantioselectivity using the simple carboxylic acid functional group. For this purpose, an L-glutamic-acid-based lipidic amphiphile (G-CA) with a carboxylic head group was selected and its responsiveness to cationic guest molecules was investigated. The dispersion morphology of G-CA in its solution state was examined by confocal and transmission electron microscopies, while interactions between the G-CA, as the host system, and guest molecules were evaluated by UV-visible, circular dichroism, and fluorescence spectroscopies. As a result, enantioselectivity was effectively induced when G-CA formed highly ordered aggregates that provide negatively charged surfaces in which carboxyl groups are assembled in highly ordered states, and when the two cationic groups of the guest molecule are attached to this surface through multiple interactions.

The Decade-long Evolution and Toxicity of Oil Transformation Compounds in Louisiana Salt Marsh Sediments Revealed by FT-ICR Mass Spectrometry

The 2010 explosion of the Deepwater Horizon (DWH) drilling rig provides a unique opportunity to advance the understanding of the evolution of lingering oil in Louisiana salt marshes for nearly a decade after the initial spill. After an oil spill, petroleum hydrocarbons undergo physical and chemical processes that transform the native oil composition to a polyfunctional oxygenated hydrocarbon matrix that contains ketones, hydroxyl, and carboxylic acid functional groups. Preliminary analysis of saltmarsh sediments impacted by the DWH spill between 2010–2014 identifies highly polar oxygenated hydrocarbons with carboxylic acid functionalities. These highly polar, high molecular weight compounds are not detectable by conventional gas chromatography (GC) based techniques. Here, we employ advanced analytical technologies such as targeted fractionation and isolation methods with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to document and catalog oil transformation compounds detected in oiled saltmarsh sediments. The toxicities of these environmental transformation products are determined by commercial Microtox bioassay. Samples have been continuously collected from 21 previously established sampling stations located in northern Barataria Bay for the past ten years post-spill. The concentration of oil contamination from heavily and moderately oiled sites exceed non-oiled reference sites for years after the spill. Combining chromatographic fractionation, conventional GC MS, and ultrahigh-resolution FT-ICR Mass Spectrometry analyses, we identified tens-of-thousands of biotic and abiotic crude oil transformation products that remain persistent and keep evolving in the environment. Heavily oxygenated transformation products, which are mostly only accessible by FT-ICR MS, span a wide range of chemical functionalities. Toxicity of the non-GC amenable fraction of oil contaminants was measured to determine the health risk of weathered oil residues left in the salt marsh environment. The current study creates a decade-long assessment record, and a comprehensive understanding of petroleum compounds evolution of oil-impacted wetlands ecosystem.

Energy/Charge Transfer Modulation with Spacer Ligands for Highly Emissive Quantum Dot-Polymer Blend.

A blend of perovskite quantum dots (QDs) and a hole transport layer (HTL) is a feasible candidate to solve the long-standing issues in light-emitting diodes (LEDs) such as charge injection, energy state matching, and defect passivation. However, QD:HTL blend structures for QD-based LEDs suffer from fast charge and energy transfers due to an inhomogeneous distribution of QDs and the HTL matrix. Here we report new cross-linkable spacer ligands between QDs and TFB that result in a highly emissive QD:TFB-blended LED device. We synthesize three representative spacer ligands to control the charge and energy transfers between QDs and the HTL. The first spacer ligand is used for controlling the molecular distance between QDs and TFB, and the second spacer ligand is designed to investigate how molecular interaction between QDs and the spacer ligand affects the optical property of the QD:TFB blend. Subsequently, the best spacer ligand, a 10-((2-benzoylbenzoyl)oxy)decanoic acid, is designed to anchor TFB (via a benzophenone group) and simultaneously bond to QDs (with a carboxylic acid functional group). The carboxylic acid group strongly interacts with QDs, dramatically improving the cross-linking rate between QDs and TFB. Due to the direct interaction between QDs and TFB, hole carriers can be effectively injected to perovskite QDs through the conductive backbone of TFB, resulting in the highest luminance values of 10917 cd/m2 at 7.4 V due to carrier injection balance. This is at least 10 times better LED performance compared with a pristine QD device.

On the properties of nanosilicate-based filled dental adhesives: Synthesis, characterization, and optimized formulation

ObjectiveIn this study, we incorporated hybrid nanoparticles (poly (acrylic acid)-grafted nanoclay/nanosilica, respectively, with platelet and spherical morphologies, abbreviated as PAA-g–NC–Sil) in different concentrations (0, 0.2, 0.5, 1, 2 and 5 wt%) to an experimental dentin bonding system and investigated the physical properties of the filled adhesive and its shear bond strength (μ-SBS) to dentin. We subsequently compared the properties of the adhesives containing PAA-g–NC–Sil with previously studied adhesives containing poly (methacrylic acid)-g-nanoclay (PMA-g-NC) (Solhi et al., 2012a), poly (acrylic acid)-g-nanoclay (PAA-g-NC) (Solhi et al., 2012b), and the hybrid poly (methacrylic acid)-grafted-nanoclay-nanosilica (PMA-g–NC–Sil) (Solhi et al., 2020). Materials and methodsIn a set of previous publications and the present paper, we grafted poly (acrylic acid) (PAA) or poly (methacrylic acid) (PMA) onto the surface of pristine Na-MMT nanoclay (Cloisite® Na+) through free radical polymerization of monomer in an aqueous media in the presence or absence of nanosilica particles. We characterized the resulting modified nanoparticles (PMA-g-NC, PAA-g-NC, PMA-g–NC–Sil and PAA-g–NC–Sil) using GPC, FTIR, TGA, and XRD. We then incorporated the modified particles as functionalized fillers to experimental dentin adhesives in different concentrations and studied the stability of modified fillers dispersion by separation analysis. We also studied the properties of the photo-cured adhesive matrices using FTIR, TEM, SEM, EDXA, and XRD. We examined the shear bond strength of the adhesives (containing different contents of each modified filler, separately) to human premolar teeth. The results were analysed and compared statistically. ResultsThe results confirmed that the polymers have been grafted onto the surface of nanoclay. An exfoliated structure for the nanoclay platelets in the photo-cured adhesive containing PAA-g–NC–Sil was observed. Addition of 0.5 wt% of PAA-g–NC–Sil to the experimental adhesive increased the shear bond strength and the dispersion stability in comparison to unfilled adhesive. The same trend was also observed for adhesives containing PMA-g-NC, PAA-g-NC, and PMA-g–NC–Sil. The adhesive containing PAA-g–NC–Sil showed the best dispersion stability and subsequently the highest shear bond strength in the optimal concentration among adhesives containing the four available fillers (PMA-g-NC, PAA-g-NC, PMA-g–NC–Sil and PAA-g-NC-Sil). SignificanceAddition of poly (acrylic acid) modified nanoparticles to the experimental dentin adhesives resulted in higher shear bond strength due to the potential interactions between the carboxylic acid functional groups on the surface of the modified particles and the dentin structure. Between the poly (acrylic acid) and poly (methacrylic acid), the former acid with higher PKa performed better. Addition of the spherical nanosilica particles to the adhesives containing platelet nanoclay helped to better exfoliate the platelets resulting in improved μ-SBS and dispersion stability.

FTIR spectral band shifts explained by OM–cation interactions

AbstractBackground: The organic matter (OM) in soils interacts with polyvalent cations such as Ca2+ through hydroxyl (OH), carboxylic acid, ester, keto, aldehyde (summarized as C=O), and carboxylate (COO−) functional groups. Such interactions affect the bonding strength of the double bond between the C and the O atom in the functional groups, which is assumed to shift the wavenumber (WN) region of O–H (hydroxyl), C=O, COO−, and OMcat (i.e., C=O interacting with cations plus O–H groups) absorption band maxima in the Fourier transform infrared (FTIR) spectra. Such band shifts limit the evaluation of spectral information on OM in soil samples.Aims: The objective of this study was to analyze the extent of band shifts and the changes in absorption band intensities for relations with cation concentrations, and to estimate effects of band shifts on OM properties such as potential wettability of OM evaluated from FTIR absorption band ratios.Methods: Polygalacturonic acid (PGA) solutions were mixed with a CaCl2 solution at different relations. The freeze‐dried mixtures were analyzed with FTIR spectroscopy in the mid‐infrared spectral range by using KBr‐technique. The FTIR spectra were interpreted with respect to O–H, C=O, COO−, and OMcat bands, the latter reflecting the formation of PGA‐Ca2+ complexes.Results: The FTIR spectra of the PGA–Ca mixtures compared to that of pure PGA indicate band shift effects by CaCl2 addition on both, intensity and WN value of the OMcat, C=O and COO− absorption band maxima. The COO−/C–O–C ratio increased with Ca2+ concentration while the C–H/C–O–C ratio decreased. Furthermore, the C=O and COO− absorption band maxima were shifted towards lower WN values, while the OMcat absorption band was shifted towards higher WN values. The shift of OMcat band maxima was two times higher than that of the C=O band maximum and increased with Ca2+ concentration.Conclusion: Spectral band shifts depend on polyvalent cation concentration and limit automated interpretations of FTIR spectra without prior soil‐specific spectral corrections.

Synthesis of end group-functionalized PGMA-peptide brush platforms for specific cell attachment by interface-mediated dissociative electron transfer reversible addition-fragmentation chain transfer radical (DET-RAFT) polymerization

Polymer brush synthesis is a powerful approach to fabricate functional bio-interfaces. To enhance the control over brush synthesis and end groups, we have synthesized poly(glycidyl methacrylate) PGMA brushes with carboxylic acid end functional groups by interface-mediated dissociative electron transfer reversible addition-fragmentation chain transfer radical (DET-RAFT) polymerization on titanium surfaces. This method does not require the use of metals and occurs under mild conditions. The brushes obtained were analyzed comprehensively in order to understand how to control cell attachment behavior. The PGMA brushes synthesized by DET-RAFT polymerization were characterized by X-ray photoelectron spectroscopy (XPS), grazing angle Fourier transform infrared (GA-FTIR) spectroscopy, water contact angle measurements and variable angle spectroscopic ellipsometry. The terminal carboxylic acid functional groups were covalently conjugated with arginine-glycine-aspartic acid (RGD) and arginine-alanine-aspartic acid (RAD, negative control) peptides in one step. RGD selective attachment of NIH 3T3 fibroblasts was observed exclusively on PGMA-RGD brushes. Thus, a new versatile strategy has been validated to obtain functional biointerfaces for selective cell attachment in the absence of any metallic catalyst.

Postsynthetically Modified Polymers of Intrinsic Microporosity (PIMs) for Capturing Toxic Gases.

Polymers of intrinsic microporosity (PIMs) are promising materials for gas adsorption because of their high surface area, processability, and tailorable backbone. Specifically, nitrile groups on the backbone of PIM-1, an archetypal PIM, can be converted to other functional groups to selectively capture targeted gas molecules. Despite these appealing features of PIMs, their potential has mainly only been realized for the separation of nontoxic gases. Here, we prepared PIM-1 materials modified with carboxylic acid and amidoxime functional groups and investigated their performance as adsorbents for the capture of ammonia (NH3) and sulfur dioxide (SO2) gases. After determining the Brønsted acidity or basicity of the PIMs from potentiometric acid-base titrations, which can be correlated with affinity for acidic or basic toxic gases, we explored the uptake capacity toward NH3 and SO2, respectively. Gas sorption studies revealed that the carboxylated PIM showed higher affinity toward NH3 through the incorporation of Brønsted acid sites, while the amidoxime functionalized PIM exhibited affinity toward SO2 through the installed of slightly basic functional groups. Overall, this study highlights new insight into PIMs as solid sorbent materials for capturing toxic gases, which can be transferred to their potential use in practical applications, such as personal protective equipment or air filtration.

Magnetic Solid-Phase Extraction of Drugs and Pesticides from Human Plasma Using COOH-mMWCNTs.

Carbon nanotubes (CNTs) are useful for extracting chemical compounds due to their properties, such as surface area and the potential for chemical modification. Especially the formation of CNTs with carboxylic acid functional group makes them disperse in water-based samples and have strong interaction forces with cationizable analytes. Based on these features, carboxylic acid functionalized multi-walled CNTs (COOH-MWCNTs) have been used as extraction sorbents. CNT can also be gathered using an external magnet by forming complex with iron oxide (Fe3O4) magnetic nanoparticles (MNPs). In this study, COOH-MWCNTs with MNPs were subjected to magnetic solid-phase extraction (mSPE) in order to extract the targeted substances such as diphenhydramine, doxylamine, tramadol, escitalopram, zolpidem, diphenamid, paclobutrazol, hexaconazole, cyproconazole and mepronil from human plasma samples. The following five factors were optimized: (i) the ratio of COOH-MWCNTs to MNPs as a sorbent from 1:1 to 1:4; (ii) sorbent amount starting from 12.5 to 75%; (iii) sample pH tested pH2 to pH10 with 1N hydrochloride and 1N sodium hydroxide; (iv) agitating time from 0 to 4min and (v) elution solvent. Limit of detection of 10 targeted substances in human plasma were in the range of 0.1-0.4mg/L. The recovery of targeted substances (except diphenamid) in human plasma was 73.06-110.28% for intra-day and 83.00-107.70% for inter-day and the precision (relative standard deviation, %) in human plasma was 0.3-13.3% for intra-day and 2.9-15.6% for inter-day. The method was applied to nine authentic biological samples from overdose patients in the emergency room of Chungnam National University Hospital. The performance of mSPE was compared with the liquid-liquid extraction method using ethyl acetate. The results showed that the newly developed method in this study can be used for screening analysis in forensic and clinical toxicology.

Extraction and detection of quaternary ammonium ionic liquid cations in water samples

The recent development of ionic liquids may induce environmental pollution, yet there is a lack of sensitive analytical methods to detect traces of ionic liquids, notably for quaternary ammonium ionic liquids. Here, we set up a method based on solid-phase extraction and ion chromatography combined to analyze quaternary ammonium ionic liquid cations in river water samples. Cations included tetramethylammonium, tetraethylammonium, tetrapropylammonium and tetrabutylammonium. We used methanesulfonic acid–acetonitrile as mobile phase in a cation-exchange column with carboxylic acid functional groups. A strong acid cation-exchange solid-phase extraction column was used for extraction and enrichment, then water–methanol was eluted to wash impurities, and finally the analytes were eluted with H3PO4–KH2PO4 buffer solution because this buffer has a low conductivity signal which avoids interferences with cation detection. We obtained a detection limit of 0.003 mg/L for river samples. Precision and accuracy met the requirements of quantitative analysis.

Antimicrobial Properties of Mandelic Acid, Gallic Acid and their Derivatives.

Alpha-hydroxy acids (AHAs) are one of the classes of hydroxy acids being beneficial for human health. The manuscript summarizes the biological properties of two popular members of AHAs, i.e., Mandelic Acid (MA) and Gallic Acid (GA), with particular emphasis on antimicrobial properties. Moreover, attempts to design new derivatives improving the natural properties of AHAs by using the chemical and physical approach are discussed. Antimicrobial properties of MA, an arylalkyl AHA containing phenyl group attached to α- carbon, and GA, an aromatic trihydroxybenzoic acid containing the phenolic ring and carboxylic acid functional group, and their derivatives against common human and plant pathogenic fungi have been reviewed. The antimicrobial activity of MA and GA is a complex phenomenon strictly correlated with other properties exhibited by these acids, e.g., pro-oxidative activity and hydrophobicity. In most cases, the acids derivatives exhibited higher antimicrobial activity than the acids themselves. This is probably because of the higher lipophilicity of moiety that allows better penetration through the cell membrane. MA and GA present an excellent health-promoting tool and are valuable starting materials for the design of new compounds such as metal complexes with alkali, or alkali earth metals. The lipophilic, antimicrobial, and pro-oxidative properties act synergistically, supporting the pharmacological and therapeutic effect of acids and their derivatives.

Green Synthesis of Silver Nanoparticles Using <i>Euphorbia hirta</i> Leaf Extract and the Determination of Their Antimicrobial Activity

Nanotechnology is a fast-growing field of science. Nanoparticles get much attention due to their unique physicochemical, optical and thermal activities. Silver nanoparticles have been used in experiments to treat infectious diseases. The goal of the research was to make silver nanoparticles using <i>Euphorbia hirta</i> extract, physically characterize the nanoparticles obtained and, to evaluate silver nanoparticles' antibacterial properties. The leaf extract of <i>E. hirta</i> (asthma weed) was used for the reduction of 1 mM silver nitrate (AgNO₃) solution to silver nanoparticles (SNPs). SNPs were made by combining 50 mL of aqueous plant extract with 250 mL of AgNO₃ solution to make SNPs. The mixture was monitored for two hours. The synthesized SNPs were characterized by UV-Vis, FTIR spectroscopy and particle size. The antimicrobial activity of the SNPs was tested against <i>Escherichia. coli, Pseudomonas. aeruginosa, Salmonella. typhi, Bacillus. subtilis </i>and<i> Candida. albicans</i>. The reaction medium's hue shifted from yellow to brown. The results of the UV-vis analysis of the particles showed that at 430 nm the particles had the maximum absorption (λ max) within 2 hours. The FTIR identified carboxylic acid and other functional groups. The polydispersity index (PDI) and Z-average particle size were found to be 0.426 and 274 nm, respectively. The results of the antimicrobial studies showed sufficient growth inhibition of the bacteria by the SNPs the minimum inhibitory concentration (MIC) ranging from 7 µg-10 µg. It was concluded that SNPs were synthesized using <i>E. hirta</i> leaf extract. The synthesized SNPs possess good activity against pathogenic microorganisms.

The removal of Pb2+ ion by MnFe2O4/waste tea leaves biochar and mechanism of adsorption

In order to transform waste tea leaves into a useful/valuable material for removal of Pb2+ ions from wastewater, MnFe2O4/biochar was synthesized. The tea waste was pyrolyzed at 500 °C to obtain the biochar. Effects of the composition of tea leaves on the physicochemical properties of biochar were evaluated. Biochar and MnFe2O4/biochar were mainly organic matter. Regarding inorganic components, aside from Fe and Mn there were considerable albeit small amounts of the mineral elements K and Ca in the MnFe2O4/biochar. The MnFe2O4/biochar is porous with a specific surface area of 24.38 m2 g−1, and the surface is loaded with MnFe2O4 and amorphous MnO2 particles. Also carboxylic acid, hydroxyl, and carbonyl functional groups were formed on the MnFe2O4/biochar surfaces. The surface area and pore volume characteristics of the MnFe2O4/biochar were also increased compared with the baseline biochar, and the prepared MnFe2O4/biochar had mesostructure. The modification of biochar into MnFe2O4/biochar improved adsorption of Pb2+ ions with the removal increased to ∼98%. The Freundlich isotherm and the pseudo-second order kinetic models matched well Pb2+ adsorption onto the MnFe2O4/biochar.

Effect of acyl chloride functionalized carbon black on mechanical and thermal properties of acrylonitrile butadiene styrene/polyaniline blend

Pristine Carbon Black (CB) has been first oxidised to introduce carboxylic acid functional group on the surface of CB, followed by treating with thionyl chloride. The presence of acyl chloride group in the resultant product has been ascertained by FTIR spectroscopy. The acyl chloride functionalized CB (CB-Ac) has been used as a filler in Acrylonitrile Butadiene Styrene (ABS)/Polyaniline (PANI) blend to improve the mechanical and thermal properties. Further addition of Nanoclay (NC) in the blend has improved the dispersion of fillers in the polymer matrix as confirmed by FESEM images and XRD pattern. The Ultimate Tensile Analysis (UTA) and Dynamic mechanical analysis (DMA) have been studied. The Young modulus has shown increment of 48% and 66% in case of CB-Ac and CB-Ac/NC filled blend, respectively. The ultimate tensile strength has also been found to be increased in CB-Ac and CB-Ac/NC filled blends. DMA has given the insight about the excellent improvement in damping properties of the composites due to filler addition. Themo gravimetric analysis (TGA) and Differential scanning calorimetry (DSC) has been carried out to ascertain the thermal properties. TGA has revealed the excellent augmentation in the flame retardancy and heat resistance of the composites due to CB-Ac/NC loading. DSC study has further verified the improvement in degree of crystallinity due to interfacial attraction between fillers and polymer matrix.

Method Validation of Gamma-Hydroxybutyrate Detection upon Herpes Simplex Virus-Type 1 Infection using LC-MRM-MS with 3-Nitrophenylhydrazine Derivatization

Volatile organic compounds (VOCs) release triggered by infection of DNA virus has not been studied extensively. Previously, we reported that gamma-butyrolactone (GBL), a VOC, was released upon Herpes Simplex Virus Type-1 (HSV-1) acute infection. Based on the metabolic pathway and chemical conversion of GBL, we hypothesized that infected cells produce gammahydroxybutyrate (GHB) as a key pathway intermediate for the subsequent production of GBL. An analytical technique for the rapid detection of GHB is crucial for further understanding its role in the cellular response to HSV-1 infection. To address this, we developed a sensitive, reliable and specific method for the detection and quantification of GHB in mammalian cell culture using a pre-column derivatization approach. Our data showed that the carboxylic acid functional group of GHB could be derivatized with 3-nitrophenylhydrazine hydrochloride (3NPH) to produce its hydrazineyl derivative. Unlike GHB, the derivative could be detected seamlessly in HPLC-MS. We also demonstrate quantitive conversion of GHB into the derivative with over 95% yield at a range of 1 μg/mL- 6 μg/mL GHB concentration. This method offers a rapid quantification of GHB in aqueous mixtures, especially in cultured extracts.

7-Alkoxy-appended coumarin derivatives: synthesis, photo-physical properties, aggregation behaviours and current-voltage (I-V) characteristic studies on thin films.

In this study, we designed and synthesised a series of coumarin derivatives appended with a long alkoxy chain on the seventh position of the coumarin-3-carboxylate/carboxylic acid core to make thin film materials. Synthesised compounds were characterized by their UV and fluorescence spectra in solutions as well as their films prepared by both LB and spin-coated methods. The surface morphology and electrical behaviour of thin films were judged by AFM, SEM and I–V characteristic mapping respectively. Isotherm, UV-Vis absorption and fluorescence spectroscopic investigations revealed the formation of aggregates on thin films. The result of SEM and AFM images provides the information about the length and height of aggregates on the thin films of coumarin derivatives. From I–V characteristics, it was found that at room temperature, the spin-coated films of coumarin derivatives containing an ester functional group exhibited a threshold switching behaviour, whereas derivatives containing the carboxylic acid functional group showed both threshold and bipolar switching behaviours. We also noticed that the I–V characteristic features of synthesized materials depended on the length of the alkyl chain of individual series.

A thermodynamic atlas of carbon redox chemical space

Redox biochemistry plays a key role in the transduction of chemical energy in living systems. However, the compounds observed in metabolic redox reactions are a minuscule fraction of chemical space. It is not clear whether compounds that ended up being selected as metabolites display specific properties that distinguish them from nonbiological compounds. Here, we introduce a systematic approach for comparing the chemical space of all possible redox states of linear-chain carbon molecules to the corresponding metabolites that appear in biology. Using cheminformatics and quantum chemistry, we analyze the physicochemical and thermodynamic properties of the biological and nonbiological compounds. We find that, among all compounds, aldose sugars have the highest possible number of redox connections to other molecules. Metabolites are enriched in carboxylic acid functional groups and depleted of ketones and aldehydes and have higher solubility than nonbiological compounds. Upon constructing the energy landscape for the full chemical space as a function of pH and electron-donor potential, we find that metabolites tend to have lower Gibbs energies than nonbiological molecules. Finally, we generate Pourbaix phase diagrams that serve as a thermodynamic atlas to indicate which compounds are energy minima in redox chemical space across a set of pH values and electron-donor potentials. While escape from thermodynamic equilibrium toward kinetically driven states is a hallmark of life and its origin, we envision that a deeper quantitative understanding of the environment-dependent thermodynamic landscape of putative prebiotic molecules will provide a crucial reference for future origins-of-life models.

STUDY CYTOTOXICITY, ANTIBACTERIAL ACTIVITY, AND COMPOSITIONS BY FT-IR AND GC-MS FOR ORGANIC EXTRACT OF WHITE IRAQI DESERT TRUFFLE TIRMANIA NIVEA

The purpose of the present work aimed at exploring the potential biochemical components and biological activities of an organic extract of the white truffle Tirmania nivea collected from the Iraqi desert, then test the organic extract against the Cytotoxicity on Human Larynx carcinoma cells and selected strains of pathogenic bacteria. Fourier transform infrared spectroscopy (FTIR) and gas chromatography-mass spectrometry GC/MSS were used to analyze mycochemical compositions. The antibacterial activity and Minimum Inhibitory Concentration (MIC) and Minimum Bactericidal Concentration (MBC) was investigated using a disk diffusion agar method. The truffle extract's cytotoxicity effect against the larynx cell line (Hep-2) was assessed by the MTT assay (in vitro). FTIR results provided the presence of phenol, carboxylic acid, and alkane's functional group, The GC-MS analysis of T. nivea disclose the existence of nineteen compounds that can contribute to the pharmaceutical properties of the truffle. As for antibacterial activity result, A growth inhibition activity of truffle extract at (18-40 mm inhibition zones) against the tested pathogenic bacterial strains was detected, which minimum inhibitory concentration values ranged from 3.12 to 6.25 mg/mL for Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 25923) Respectively. The results of cytotoxicity shown that the organic truffle extract exhibited a high inhibitory rate (52.685%) against cell line (Hep-2) at a concentration of 1.56 ?g/mL. In this work, the results showed that the organic extracts of T. nivea are very promising as cancer cytotoxicity and antibacterial agent for future medical applications.

Multifunctional Binding Sites on Nitrogen-Doped Carboxylated Porous Carbon for Highly Efficient Adsorption of Pb(II), Hg(II), and Cr(VI) Ions.

Heavy metal ions represent one of the most toxic and environmentally harmful pollutants of water sources. This work reports the development of a novel chelating nitrogen-doped carboxylated porous carbon (ND-CPC) adsorbent for the effective removal of the heavy metal ions Pb(II), Hg(II), and Cr(VI) from contaminated and polluted water sources. The ND-CPC adsorbent is designed to combine four different types of nitrogen functional groups (graphitic, pyrrolic, pyridinic, and pyridine oxide) with the carboxylic acid functional groups within a high surface area of 1135 ± 20 m2/g of the porous carbon structure. The ND-CPC adsorbent shows exceptionally high adsorption affinity for Pb(II) with a capacity of 721 ± 14 mg/g in addition to high uptake values of 257 ± 5 and 104 ± 2 mg/g for Hg(II) and Cr(VI), respectively. The high adsorption capacity is also coupled with fast kinetics where the equilibrium time required for the 100% removal of Pb(II) from 50 ppb and 10 ppm concentrations is 30 s and 60 min, respectively. Even with the very high concentration of 700 ppm, 74% uptake of Pb(II) is achieved within 90 min. Removal efficiencies of 100% of Pb(II), 96% of Hg(II), 91% of Cu(II), 82% of Zn(II), 25% of Cd(II), and 13% of Ni(II) are achieved from a solution containing 10 ppm concentrations of these ions, thus demonstrating excellent selectivity for Pb(II), Hg(II), and Cu(II) ions. Regeneration of the ND-CPC adsorbent shows excellent desorption efficiencies of 99 and 95% for Pb(II) and Cr(VI) ions, respectively. Because of the fast adsorption kinetics, high removal capacity and excellent regeneration, stability, and reusability, the ND-CPC is proposed as a highly efficient remediation adsorbent for the solid-phase removal of Pb(II), Hg(II), and Cr(VI) from contaminated water.