Ion-pair Research Articles

A Reverse Thinking Based on Partially Methylated Aldononitrile Acetates to Analyze Glycoside Linkages of Polysaccharides Using Liquid Chromatography-Multiple Reaction Monitoring Mass Spectrometry.

Glycoside linkage analyses of medicine and food homologous plant polysaccharides have always been a key point and a difficulty of structural characterization. The gas chromatography-mass spectrometry (GC-MS) method is one of the commonly used traditional techniques to determine glycoside linkages via partially methylated alditol acetates and aldononitrile acetates (PMAAs and PMANs). Due to the simplicity of derivatization and the highly structural asymmetry of PMANs, reverse thinking is proposed using liquid chromatography-electrospray ionization-multiple reaction monitoring mass spectrometry (LC-ESI-MRM-MS) for the first time to directly determine the neutral and acidic glycosyl linkages of polysaccharides. The complete characterization of glycoside linkages deduced from PMANs was achieved using a combination of tR values, characteristic MRM ion pairs, diagnostic ESI+-MS/MS fragmentation ions (DFIs), and optimal collision energy (OCE). The DFI and OCE parameters were confirmed to be effective for the auxiliary discrimination of some isomers of the PMANs. The practicality of LC-ESI+-MRM-MS was further verified by analyzing the glycoside linkages of polysaccharides in five medicine and food homologous plants. This method can serve as an alternative to GC-MS for the simultaneous determination of neutral and acidic glycosyl linkages in polysaccharides.

Structure and interactions of CO2 with reline (a 1:2 choline chloride – Urea mixture) according to quantum chemical calculations and molecular dynamics simulation

Quantum chemical DFT calculations [B3LYP+GD3/6-311++g(2d,2p)] of the structure and interactions in various complexes of CO2 molecule with a choline cation, a chloride anion, urea molecules, a choline chloride ion pair and a 1:2 choline chloride – urea complex were carried out. The contributions of Coulomb and van der Waals interactions were calculated. The QTAIM method was used to evaluate the strength of various bonds. A molecular dynamics simulation of CO2 molecules in reline in the NPT ensemble (1 atm, 298 K) was also carried out. The radial distribution functions of the particle centers of mass, local mole fraction functions, spatial distribution functions, and density profiles were calculated. Stronger interactions, compared to the other DES components, were observed in case of the chloride anion and the CO2 molecule according to the DFT calculations. However, in the system, stronger interactions were observed between the chloride anion and the system components, namely NHCl and OHCl hydrogen bonds. This made the chloride anion inaccessible and unable to interact with the CO2 molecule, according to the MD simulation results. Additionally, the presence of a fairly extensive surface layer containing DES and CO2 molecules was shown.

Generic method for the detection of short & long chain PFAS extended to the lowest concentration levels of SERS capability

The detection of the highly toxic per- and polyfluoroalkyl substances, PFAS, constitutes a challenging task in terms of developing a generic method that could be rapid and applicable simultaneously to both long and short-chain PFAS at ppt concentration level. In the present study, the method introduced by the USA Environmental Protection Agency, EPA, to detect surfactants, using methylene blue, MB, which is identified an ideal candidate for PFAS-MB ion pairing, is extended at the lowest concentration range by a simple additional step that involves the dissociation of the ion pairs in water. In this work, Surface Enhanced Raman Scattering, SERS, is applied via Ag nanocolloidal suspensions to probe MB and indirectly either/or both short-chain (perfluorobutyric acid, PFBA) and long-chain (perfluoloctanoic acid, PFOA) PFAS downt to 5 ppt. This method, which can be further optimized to sub-ppt level via a custom-made SERS-PFAS dedicated Raman system, offers the possibility to be applied to either specific PFAS (both short and long-chain) in a targeted analysis or to total PFAS in a non-targeted analysis at very low detection limits, following any type of MB detection method in aqueous solutions and obviously with any type of SERS substrate.

Bulk or supported tungstophosphates? Antioxidant and antimicrobial activities following pesticide removal

The study evaluates caesium, potassium, silver, and zinc tungstophosphates synthesized in bulk and Y zeolite-supported forms through a two-step process. Spectral investigation reveals the impact of cation size on tungstophosphates formation. The large cations form ion-ion interaction with the Keggin ion, while smaller cations form hydrogen bonds between the cation hydration sphere and terminal oxygens in the Keggin ion. Supported salts formation proceeds without Keggin ion distortion. Zeta potential showed the absence of particle aggregation for caesium and potassium tungstophosphate. Nicosulfuron removal by the supported salt exhibits enhanced retention, with the exception observed for zinc tungstophosphate suggesting a decomposition mechanism. Antimicrobial evaluations reveal silver salt's potency, especially in zeolite-supported form, emphasizing the role of zeolite support. In the presence of pesticide molecules, the antimicrobial activity of salts lowers, with the exception seen for fungus strain. The antioxidant assessments demonstrate superior inhibition for insoluble bulk salts, with caesium tungstophosphate exhibiting the highest inhibition, while supported silver salt enhances bulk salt performance. The presence of pesticides affects both antimicrobial and antioxidant activities, while a complex relationship with radical scavenging ability in bulk and supported salts is independent of their pesticide adsorption capacities. The study broadens the range of the versatile applications of tungstophosphates, highlighting their specific interactions with pesticides and their impact on bioactivity and environmental remediation.

A green, fluorescent probe employing erythrosine-B for tracing the accidental administration of levamisole in milk and plasma samples.

A simple and sensitive fluorescent probe has been developed and optimized to detect the non-intentional administration of levamisole (LVM). LVM is used as an anthelmintic therapy in cows, and hence, its residues appear in the drained milk until 60 hours after administering the drug. Meanwhile, levamisole is known to be an adulterant to cocaine and could be detected in addicts' plasma samples. Owing to its severe side effects, including agranulocytosis, which is lethal in many cases, detection and quantification of LVM in milk and plasma samples are of utmost importance. Therefore, a sensitive and selective analytical method is required for this purpose. This work develops a highly fluorescent probe obtained through the reaction between LVM and erythrosine-B in an acidic medium, where the produced ion pair complex has been measured at 553 nm after excitation at 528 nm. The proposed method provides linearity over the concentration range of 0.5-2.0 μg mL-1 for LVM, with a corresponding detection and quantitation limit of 0.5 and 0.3 μg mL-1. Full validation was performed, permitting the application of the suggested method to perform simple extraction steps. All the applied procedures followed the guidelines offered by green analytical chemistry, where the Green Analytical Procedure Index (GAPI) assessed the greenness of the proposed tool, and the yielded pictograms proved the eco-friendliness of the offered tool.

Catalysis of an SN2 pathway by geometric preorganization.

Bimolecular nucleophilic substitution (SN2) mechanisms occupy a central place in the historical development and teaching of the field of organic chemistry1. Despite the importance of SN2 pathways in synthesis, catalytic control of ionic SN2 pathways is rare and notably uncommon even in biocatalysis2,3, reflecting the fact that any electrostatic interaction between a catalyst and the reacting ion pair necessarily stabilizes its charge and, by extension, reduces polar reactivity. Nucleophilic halogenase enzymes navigate this tradeoff by desolvating and positioning the halide nucleophile precisely on the SN2 trajectory, using geometric preorganization to compensate for the attenuation of nucleophilicity4. Here we show that a small-molecule (646 Da) hydrogen-bond-donor catalyst accelerates the SN2 step of an enantioselective Michaelis-Arbuzov reaction by recapitulating the geometric preorganization principle used by enzymes. Mechanistic and computational investigations show that the hydrogen-bond donor diminishes the reactivity of the chloride nucleophile yet accelerates the rate-determining dealkylation step by reorganizing both the phosphonium cation and the chloride anion into a geometry that is primed to enter the SN2 transition state. This new enantioselective Arbuzov reaction affords highly enantioselective access to an array of H-phosphinates, which are in turn versatile P-stereogenic building blocks amenable to myriad derivatizations. This work constitutes, to our knowledge, the first demonstration of catalytic enantiocontrol of the phosphonium dealkylation step, establishing a new platform for the synthesis of P-stereogenic compounds.

An energy-efficient cyclic amine system developed for carbon capture from both flue gas and air

High energy consumption is a major barrier to the large-scale deployment of carbon capture processes from flue gases or air (direct air capture, DAC). The non-aqueous amines reported in literature possess a high energy efficiency for CO2 capture from flue gases, they struggle with gas streams containing ultra-dilute CO2, like air, due to poor absorption kinetics. This study developed novel 2-PE (2-piperidineethanol)/APZ (Aminoethylpiperazine) based CO2 absorbents to address these problems. The experiments and MD simulation results showed that the 2-PE/APZ-based absorbents possessed a superior absorption performance both in flue gas and air. Among the developed absorbents, when 2-PE/APZ mixed with DMF (Dimethylformamide), the CO2 loading reached to 1.004 mol/mole, as the theoretical maximum. In DAC tests, 87.31 % CO2 from the air was captured in 24 h experiments. The regeneration heat duty of 2-PE/APZ/DMF decreased to 1.694 KJ/g CO2, a 55.89 % reduction compared to the benchmark 30 wt% MEA. The CO2 absorption/desorption mechanism was analysed by NMR, In-situ FT-IR, and DFT calculation. It indicated that this significant improvement in CO2 absorption performance and the reduction in energy consumption are due to the synergistic effect of 2-PE and APZ. During CO2 absorption, CO2 reacts with APZ forming APZ zwitterion rapidly, then deprotonation to the 2-PE. The formation of protonated 2-PEH+ ion pairs with APZCOO- reduces hydrogen bonds and van der Waals forces among the amine-CO2 complex, facilitating easy regeneration at mild conditions while maintaining high reactivity. The combination of theoretical and experimental results indicates that 2-PE/APZ-based absorbents can serve as a promising alternative for carbon capture from flue gas to air with low energy usage.

Uncovering the binding nature of thiocyanate in contact ion pairs with lithium ions.

Ion pair formation is a fundamental molecular process that occurs in a wide variety of systems, including electrolytes, biological systems, and materials. In solution, the thiocyanate (SCN-) anion interacts with cations to form contact ion pairs (CIPs). Due to its ambidentate nature, thiocyanate can bind through either its sulfur or nitrogen atoms, depending on the solvent. This study focuses on the binding nature of thiocyanate with lithium ions as a function of the solvents using FTIR, 2D infrared spectroscopy (2DIR) spectroscopies, and theoretical calculations. The study reveals that the SCN- binding mode (S or N end) in CIPs can be identified through 2DIR spectroscopy but not by linear IR spectroscopy. Linear IR spectroscopy shows that the CN stretch frequencies are too close to one another to separate N- and S-bound CIPs. Moreover, the IR spectrum shows that the S-C stretch presents different frequencies for the salt in different solvents, but it is related to the anion speciation rather than to its binding mode. A similar trend is observed for the anion bend. 2DIR spectra show different dynamics for N-bound and S-bound thiocyanate. In particular, the frequency-frequency correlation function (FFCF) dynamics extracted from the 2DIR spectra have a single picosecond exponential decay for N-bound thiocyanate and a biexponential decay for S-bound thiocyanate, consistent with the binding mode of the anion. Finally, it is also observed that the binding mode also affects the line shape parameters, probably due to the different molecular mechanisms of the FFCF for N- and S-bound CIPs.

Charge Transfer and Intersystem Crossing in Compact Naphthalenediimide-Phenothiazine Triads: Synthesis and Study of the Photophysical Property with Transient Optical and Electron Paramagnetic Resonance Spectroscopic Methods.

In order to obtain a long-lived charge separation (CS) state in compact electron donor-acceptor molecular systems, we prepared a series of naphthalenediimide (NDI)-phenothiazine (PTZ) triads, with phenylene as the linker between the donor and acceptor. Conformation restriction is imposed to control the mutual orientation of the NDI and PTZ units by attaching methyl groups on the phenylene linker to tune the electronic coupling between the donor and the acceptor. Moreover, the PTZ moiety was oxidized to sulfoxide to tune the ordering of the CS state and the 3LE state (LE: locally excited state). UV-vis absorption spectra indicate electronic coupling between NDI with the phenylene linker as well as the PTZ units, manifested by the appearance of a charge-transfer (CT) absorption band, whereas this coupling is devoid in the triads with conformation restriction imposed. Fluorescence is strongly quenched in the triads compared to the reference compound, indicating electron transfer upon photoexcitation. Femtosecond transient absorption spectra indicate that the CS takes 0.8 ps, and then the 3LE state is formed by charge recombination in 83 ps. Nanosecond transient absorption (ns-TA) spectra show that the 3NDI state was observed in nonpolar solvents such as cyclohexane (triplet state lifetime: 95.7 μs), whereas the CS state was observed in more polar solvents. The CS state lifetimes are up to 1.2 μs (in toluene). Time-resolved electron paramagnetic resonance spectra of the triads in toluene consist of two types of signals: CS states (narrower signals, ∼10 mT) and 3LE states (broader signals, ∼50 to 200 mT). In the spectra of the triads containing PTZ, the CS state signals dominate, whereas for the triads containing oxidized PTZ, the 3NDI signals (zero-field splitting D ≈ 2000 MHz) prevail, both observations being in agreement with the ns-TA spectral studies. The electron spin polarization phase pattern of the 3NDI states of the triads indicates that the intersystem crossing (ISC) mechanism is spin-orbit charge-transfer ISC. Considering the 3CS state as ion pairs, the electron-exchange energy (J) is determined to be -39 to -59 MHz, and the electron spin dipolar interaction is 83-92 MHz.

Chiral Diselenophosphoric Acids for Ion Pair Catalysis: A Novel Approach to Enhance Both Proton Donating and Proton Accepting Properties.

The activation of poorly reactive substrates via strong chiral acids is a central topic in asymmetric ion pair catalysis these days. Despite highly successful scaffolds such as N-triflylphosphoramides, these catalysts either lack C2-symmetry or provide multiple H-bond acceptor sites, leading to lower ee values for certain reactions. We present BINOL-based diselenophosphoric acids (DSA) as an extremely promising alternative. Using an intertwined approach of synthesis and NMR studies, we developed a synthetic approach to DSA with up to 98 % NMR yield. The obtained acids provide both very high proton donor and proton acceptor properties, a bifunctionality, which is key to catalytic applications. Indeed, first reactivity test proved the much higher acidity of DSA and its ability to initiate Mukaiyama-Mannich reaction and protodesilylation of silyl ethers. Together with their C2-symmetry, the single donor and single acceptor situation, the decreased tendency of self-association, and the straightforward synthesis with potential 3,3'-substitution, the DSA provide all features ideal for the further development of ion pair catalysis.

Laser driven wake wave in pair-ion electron plasma with inclusion of ion dynamics

The generation of laser driven plasma wake wave has been investigated in hydrogen pair-ion electron plasma. The consideration of dynamics of the positive and negative ion pair have been adopted. Inclusion of the ion motion has the effect of modifying the electric field and density profiles of the wake wave. This has been demonstrated by observing the variation of the electron density and electric field profiles with the change in positive ion/negative ion concentration. High density spikes and sawtooth like electric field profiles (indication of wave breaking) are observed to transform into sinusoidal electric field profile and low amplitude density profile when the positive ion density in the plasma system is kept higher. Furthermore, we observe the variation of the electric field amplitude of the wake wave with the laser pulse width. This feature is the indication of the possibility of hybrid acceleration (Direct Laser Acceleration and wake field acceleration) of accelerated beam. The results are quite relevant in laser plasma interaction field in experimental physics and also in planetary environment.

Stability‐Indicating HPLC Method Development and Validation for the Quantification of Tofacitinib Citrate and Its Related Substances Using Hydrophilic Liquid Interaction Chromatography

ABSTRACTA new stability‐indicating RPHPLC method with short run time has been developed and validated for tofacitinib citrate and its related substances. The novel HPLC method integrates hydrophilic interaction liquid chromatography (HILIC) technology as the stationary phase and employs a mobile phase composed of phosphate buffer (pH 7.0) and acetonitrile (45:55, %v/v) at a flow rate of 0.5 mL/min under isocratic elution. Analytes were monitored via a UV detector at 210 nm and with the column oven temperature at 30°C for a 20‐min analysis. Precision (%RSD) for Impurity‐A and Impurity‐B and tofacitinib met specifications at 2.4%, 0.8%, and 0.0%, respectively. Accuracy ranged from 86% to 100% for impurities, with LOD at 0.03% and LOQ at 0.05%–0.06%. Correlation coefficients exceeded 0.999 for impurities and tofacitinib citrate. Solution stability was confirmed for 24 h at room temperature. The method range was extended from LOQ to ∼1.5% for impurities and LOQ to ∼150% for tofacitinib citrate. The method's stability was evaluated under acid and base hydrolysis, oxidative and water hydrolysis, and thermal and photolytic degradation. Introducing HILIC as the stationary phase for this work proved effective, eliminating the need of ion pair reagents, reducing analysis time, and ensuring consistent results.

Nor-LAAM loaded PLGA microparticles for treating opioid use disorder

The treatment landscape for opioid use disorder (OUD) faces challenges stemming from the limited efficacy of existing medications, poor adherence to prescribed regimens, and a heightened risk of fatal overdose post-treatment cessation. Therefore, there is a pressing need for innovative therapeutic strategies that enhance the effectiveness of interventions and the overall well-being of individuals with OUD. This study explored the therapeutic potential of nor-Levo-α-acetylmethadol (nor-LAAM) to treat OUD. We developed sustained release nor-LAAM-loaded poly (lactic-co-glycolic acid) (PLGA) microparticles (MP) using a hydrophobic ion pairing (HIP) approach. The nor-LAAM-MP prepared using HIP with pamoic acid had high drug loading and exhibited minimal initial burst release and sustained release. The nor-LAAM-MP was further optimized for desirable particle size, drug loading, and release kinetics. The lead nor-LAAM-MP (F4) had a relatively high drug loading (11 wt%) and an average diameter (19 μm) and maintained a sustained drug release for 4 weeks. A single subcutaneous injection of nor-LAAM-MP (F4) provided detectable nor-LAAM levels in rabbit plasma for at least 15 days. We further evaluated the therapeutic efficacy of nor-LAAM-MP (F4) in a well-established fentanyl-addiction rat model, and revealed a marked reduction in fentanyl choice and withdrawal symptoms in fentanyl-dependent rats. These findings provide insights into further developing long-acting nor-LAAM-MP for treating OUD. It has the potential to offer a new effective medication to the existing sparse armamentarium of products available to treat OUD.

The use of amines as steel corrosion inhibitors in butanol-gasoline blends

Butanol is an interesting component used for blending gasoline fuels. However, the polar nature of butanol allows the solubility of water and ionic compounds in butanol-gasoline blends (BGBs) making them aggressive to mild steel. Amines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentaamine, morpholine, piperazine, and hexamethylenediamine, were tested as corrosion inhibitors for mild steel in BGBs. Additionally, the influence of the acetic acid and sodium chloride concentrations on the inhibition efficiency was examined. Electrochemical impedance spectroscopy andpotentiodynamic polarization were employed for the measurements, complemented by static immersion testing and an XPS surface analysis. The highest inhibition efficiency was demonstrated for diethylenetriamine, triethylenetetramine, andhexamethylenediamine, achieving a value of 95 % or more at aconcentration of 100 mg/L. The formation of ionic pairs involving protonated amines andchlorides was also confirmed. The XPS analysis revealed a very thin passive layer of iron oxides, which may form in the presence of amines, protecting mild steel in BGBs.

Implementation of ICRU report 90 to re-evaluate the dosimetry standards in Taiwan

The purpose of this investigation is to re-evaluate primary dosimetry standards at the National Radiation Standard Laboratory (NRSL/INER) according to the recommendation of the International Commission on Radiation Units and Measurements Report 90 (ICRU Report 90). These standards are air kerma (Kair) in X-rays, 60Co and 137Cs beams, absorbed dose to water (DW) in 60Co beam, as well as reference air kerma (RAKR) in 192Ir beam for brachytherapy in Taiwan.However, the Consultative Committee for Ionizing Radiation (CCRI) summarized the expected changes in ICRU Report 90 to primary standards. These include modifications to the mean excitation energy of water (Iw) and graphite (Ig), the application of the density effect correction for graphite, new combined correction factors and the uncertainty related to the average energy required to create an ion pair in air (Wair), improved calculations of the stopping power, and the adoption of renormalized photoeffect cross-section. The recommendations of the CCRI were adopted for recalculation regarding correction factors and radiation-matter interaction constants for NRSL/INER primary standards. Furthermore, a newer version of Monte Carlo software and the alternative measurements with new ionization chambers (ICs) of a similar design were used to reassess the impact on the NRSL/INER standards. Consequently, the impact of the new ICRU recommendation on dosimetry standards ranged from -0.8% to 0.1%. The changes to the primary standards are in good correlation with similar changes implemented for the BIPM primary standards. For international comparisons of these standards, adoption of the ICRU Report 90 would not change significantly the degree of equivalence stated in the Asia-Pacific Metrology Programme (APMP) key and supplementary comparison database considering the impacts of the BIPM standards in the comparisons of APMP.RI(I)-K3, APMP.RI(I)-K1.1, APMP.RI(I)-K4, APMP.RI(I)-K8 and APMP.RI(I)-S3. Therefore, the NRSL/INER has formally implemented the re-evaluation standards on the 1st January 2024.

Dynamic Ion Gels from the Complex Coacervation of Oppositely Charged Poly(ionic liquid)s.

A cationic poly(ionic liquid) (PIL) with pendent butyl imidazolium cations and free bis(trifluoromethylsulfonyl)imide (TFSI) anions and an anionic PIL with pendent TFSI anions and free 1-butyl-3-methylimidazolium cations are synthesized by postpolymerization chemical modification and reversible addition-fragmentation chain-transfer radical copolymerization, respectively. Upon mixing solutions of these two PILs in acetone with stoichiometric amounts of ion pairs, ionic exchanges induce coacervation and, after solvent evaporation, lead to the formation of a dynamic ion gel (DIG) and the concomitant release of free [1-methyl-3-butyl imidazolium]TFSI ionic liquid (IL). A comparison of thermal (Tg), ion conducting (σDC), and viscoelastic (elastic moduli (G')) properties for DIGs and their parent polyelectrolytes, as well as extracted and IL-doped DIGs, demonstrates the formation of ionic cross-links and the ability to easily produce polymer electrolytes with enhanced ionic conductivity (σDC up to 4.5 × 10-5 S cm-1 at 30 °C) and higher elastic moduli (G' up to 4 kPa at 25 °C and 1 rad s-1), making them highly desirable in many electrochemical applications, including supercapacitors, soft robotics, electrochromic devices, sensors, and solar cells.

Dual tobramycin and docosahexaenoic acid loaded nanoemulsions combating Pseudomonas aeruginosa-induced pulmonary infection

Pseudomonas aeruginosa (P. aeruginosa) typically forms biofilms in vivo, which exhibit high resistance and complicate eradication efforts. Additionally, persistent inflammation and excessive oxidative stress can lead to severe lung dysfunction, facilitating bacterial colonization and infection. Herein, we prepared oil-in-water (O/W) nanoemulsions (TD-αT NEs) by using PEG5k-block-PCL5k and α-tocopherol to encapsulate tobramycin (TOB). To enhance TOB’s drug load, a hydrophobic ion pair (TDIP) composed of TOB and docosahexaenoic acid (DHA) was pre-prepared. TD-αT NEs was not only easily prepared and aerosolized, but stable in both physics and chemistry. The negatively charged TD-αT NEs facilitated penetration through mucus, reaching infection sites. Subsequently, TD-αT NEs permeated biofilms due to their small size and released drugs via lipase-triggered carrier dissociation, aiding in eradicating internal bacteria within biofilms (with a 16-fold reduction in CFU vs. free TOB group). TD-αT NEs simultaneously exerted superior anti-inflammatory effects, reducing levels of pro-inflammatory cytokines (NO, IL-6, IL-8, and TNF-α) while increasing the level of anti-inflammatory cytokine (IL-10). It was achieved through the upregulation of PPAR-γ and downregulation of NF-κB signaling, thus mitigating the lung damage. In addition, TD-αT NEs demonstrated strong antioxidant activity, alleviating the oxidative stress induced by P. aeruginosa. Notably, when administered via inhalation, TD-αT NEs significantly reduced the lung bacterial burden, lung inflammation, and oxidative stress in vivo compared to TOB solution. TD-αT NEs could prove beneficial in treating chronic pulmonary infections induced by P. aeruginosa through a comprehensive strategy, specifically enhancing biofilm eradication, reducing inflammation, and alleviating oxidative stress.

Selective Profiling of Carboxylic Acid in Crude Oil by Halogen Labeling Combined with Liquid Chromatography and High-Resolution Mass Spectrometry.

Carboxylic acids are a small but essential compound class within petroleum chemistry, influencing crude oil behaviors in production and processing and causing environmental impacts. Detailed structural information is fundamental to understanding their influence on petroleum characteristics. However, characterizing acids in crude oil remains challenging due to matrix effects, structural diversity, and low abundance. In this work, we present a new methodology for profiling carboxylic acids by liquid-liquid extraction and selective derivatization using 4-bromo-N-methylbenzylamine (4-BNMA) followed by liquid chromatography and electrospray ionization Orbitrap mass spectrometry (LC-ESI-Orbitrap MS). The fragmentation of 4-BNMA derivatives produces a unique product ion pair, m/z 169/171, enabling the identification of chromatographic fractions containing carboxylic acids. The mass spectra of the corresponding fractions are extracted, and the acids are further computationally isolated based on the isotopic pattern. The method was optimized and validated using acid standards and systematic experimental designs, assuring robustness and sensitivity for nontarget screening purposes. This method detected up to 380 carboxylic acids in six Danish North Sea crude oils, with up to two carboxyl and other heteroatom functionalities (NSO). The results indicated that the most populated species are fatty acids (double bond equivalent (DBE) = 1) and small aromatic acids (DBE = 2-6). The predominance and diversities of compound classes in different samples are consistent with their corresponding bulk properties. Polyfunctional acids (Ox, NxOx, and SxOx) were observed due to exposure to oxidation and biodegradation. Also, the approach's applicability benefits high-resolution MS analysis by simplifying data processing for crude oil and potentially other high-organic and aqueous samples.

Highly stable energy-storage performance of donor-acceptor co-doped TiO2 films

Energy-storage films that remain stable at high temperatures and frequencies are crucial for various applications. In this study, we demonstrated that donor-acceptor co-doped simple oxide TiO2 films, viz. V5+-Cr3+ co-doped TiO2 [(V0.5Cr0.5)xTi1-xO2] films, can exhibit highly stable energy-storage performance. The co-doped TiO2 films exhibited high breakdown strength and polarization owing to the local polarization induced by the V5+-Cr3+ ionic pairs. The energy-storage density of the (V0.5Cr0.5)0.02Ti0.98O2 film was approximately 48.93 J/cm3 at room temperature, which is approximately 195 times higher than that of the pure TiO2 film (0.25 J/cm3). In addition, the (V0.5Cr0.5)0.02Ti0.98O2 film exhibited excellent temperature stability from 303 K to 403 K, frequency stability from 0.5 kHz to 7.5 kHz, and fatigue durability over 107 charge-discharge cycles. The proposed strategy can effectively improve the stable energy-storage performance of lead-free donor-acceptor co-doped TiO2 films, which are in high demand in various applications.

Crystal structure of the 1:1 co-crystal 4-(di-methylamino)-pyridin-1-ium 8-hy-droxy-quinoline-5-sulfonate-N,N-di-methyl-pyridin-4-amine.

The asymmetric unit of the title compound is composed of two independent ion pairs of 4-(di-methyl-amino)-pyridin-1-ium 8-hy-droxy-quinoline-5-sulfonate (HDMAP+·HqSA-, C7H11N2 +·C9H6NO4S-) and neutral N,N-di-methyl-pyridin-4-amine mol-ecules (DMAP, C7H10N2), co-crystallized as a 1:1:1 HDMAP+:HqSA-:DMAP adduct in the monoclinic system, space group Pc. The compound has a layered structure, including cation layers of HDMAP+ with DMAP and anion layers of HqSA- in the crystal. In the cation layer, there are inter-molecular N-H⋯N hydrogen bonds between the protonated HDMAP+ mol-ecule and the neutral DMAP mol-ecule. In the anion layer, each HqSA- is surrounded by other six HqSA-, where the planar network structure is formed by inter-molecular O-H⋯O and C-H⋯O hydrogen bonds. The cation and anion layers are linked by inter-molecular C-H⋯O hydrogen bonds and C-H⋯π inter-actions.