CH2 COOH Research Articles

Oxidation of butane-2,3-dione at high pressure: Implications for ketene chemistry

Ketene (CH2CO) mechanism is a building block for developing combustion kinetic models of practical fuels. To revisit the combustion chemistry related to ketene, oxidation experiments of butane-2,3‑dione (diacetyl, CH3COCOCH3), considered as an effective precursor of CH2CO, are conducted in a jet-stirred reactor (JSR) at 10 bar and temperatures ranging from 650 to 1160 K. Identification and quantification of intermediates are achieved by Fourier transform infrared spectrometry, gas chromatography, and mass spectrometry. A kinetic model of diacetyl is constructed based on recent theoretical and modeling studies on diacetyl and ketene, which has been validated against the present data and experimental data of diacetyl and CH2CO in literature. Generally, the present model can adequately predict most of them, and better predict the methyl-related intermediates under wide pyrolysis and combustion conditions than previous models. Based on modeling analyses, the unimolecular decomposition reaction of diacetyl is the dominant reaction pathway for fuel consumption under different equivalence ratio conditions, especially at high temperatures. Under lean conditions, both the H-atom abstraction reactions by methyl (i.e. CH3COCOCH3 + CH3 = CH4 + CH2CO + CH3CO, R3) and by OH (i.e. CH3COCOCH3 + OH = H2O + CH2CO + CH3CO, R5) are important for diacetyl consumption, while under rich conditions R5 becomes negligible. As the most important intermediates in diacetyl oxidation, the main consumption pathways of CH2CO and CH3 are dependent on the equivalence ratio conditions. Under lean conditions, CH2CO mainly reacts with OH to produce CH2OH and CO (i.e. CH2CO + OH = CH2OH + CO, R10), while methyl reacts with HO2 to produce CH3O and OH (i.e. CH3 + HO2 = CH3O + OH, R20). In contrast, under rich conditions, the addition-elimination reaction between CH2CO and H becomes competitive with R10, while the CH3 self-combination producing C2H6 plays a more important role than the CH3 oxidation pathway R20. Sensitivity analysis of CH2CO shows that not only the reactions of CH2CO, but also those of CH3 are sensitive to CH2CO formation. This is because CH3 related reactions influence the distribution of radical pool, which determines the oxidation reactivity of the reaction system.

First-Principles Modeling of Bottom-Up Synthesis of Carbon Quantum Dots

In this work, we report the results of various scenarios related to the initial stages in the assembly of carbon quantum dots (CQDs) from citric acid (CA) or o-phenylenediamine (OPD). The results of the step-by-step simulations of the synthesis demonstrate that all possible scenarios of CQD assembly are different from those previously proposed. For example, in synthesizing CQDs from citric acid, each addition of a new carbon ring to the growing nanographene leads to the appearance of the carbonyl (C=O) groups on the edges and carboxyl (–COOH) groups in the interior parts of the nanographenes. Even the initial steps of CQD assembly from CA are accompanied by the formation of bushy structures from carboxyl and –CH2–COOH groups on the edges. On the other hand, in manufacturing CQDs from OPD, the formation of flat nanographenes is extremely energetically favorable. This result is in qualitative agreement with a very high yield of synthesized CQDs from OPD. However, the discussed process of nanographene formation proceeds simultaneously with the oxidation of newly formed nanographenes in a medium of superheated water accompanied by the appearance of C–OH bonds in the internal parts of newly formed sp2- carbon species or even in their etching. For both cases, the scenario of eliminating excessive carboxyl or hydroxyl groups by forming interlayer C–C bonds between two adjacent nanographenes is estimated as possible.

NMR and DFT studies of monounsaturated and ω-3 polyunsaturated free fatty acids in the liquid state reveal a novel atomistic structural model of DHA

Structures of low-energy conformers of caproleic acid (CA; 10:1 cis-9), oleic acid (OA; 18:1 cis-9), α-linolenic acid (ALA; 18:3 cis-9,12,15 ω-3), eicosapentaenoic acid (EPA; 20:5 cis-5,8,11,14,17 ω-3), and docosahexaenoic acid (DHA; 22:6 cis-4,7,10,13,16,19 ω-3) in the liquid state, based on detailed 1D NOE and density functional theory calculations of 1H NMR chemical shifts are presented. Transient 1D NOE experiments with variable mixing time showed significant through-space proximity of the CH2–COOH protons and the terminal CH3– groups. Variable temperature 1H NMR experiments revealed strong intermolecular centro-symmetric cyclic hydrogen bond interactions of the carboxylic groups of the monounsaturated oleic and caproleic acids (δ(COOH) ∼ 12.0–12.4 ppm), ALA and EPA (δ(COOH) ∼ 11.0 ppm). On the contrary, the carboxylic proton of DHA is strongly shielded with δ(COOH) ∼ 8.5 ppm. DFT calculations were interpreted in terms of aggregates of dimerized fatty acids with parallel and antiparallel interdigitated structures. The antiparallel arrangement was found to be in excellent agreement with experimental 1D NOE NMR data. For the dimeric DHA, a flip-flop process between a classical intermolecular centro-symmetric hydrogen bond through carboxylic groups and a novel intramolecular hydrogen bond between the carboxylic group and the terminal ω-3 double bond is demonstrated.

Development of a CH2-dependent analytical method using near-infrared spectroscopy via the integration of two algorithms: non-dominated sorting genetic-II and competitive adaptive reweighted sampling (NSGAII-CARS).

In most of the near-infrared studies, near-infrared spectra (NIRS) were often mathematically treated. However, these algorithms selected a large number of variables and latent variables, and they caused the over-fitting phenomenon, which became very common. The large number of variables made it impossible to extract the "chemical information" directly from the NIRS. To build robust and interpretable mathematical models, the non-dominated sorting genetic-II-competitive adaptive reweighted sampling (NSGAII-CARS) algorithm was proposed to determine influential functional groups for quantitative analysis. In this research, data on a primary mixture of two amino acids (AAs), namely NH2(CH2)3COOH and HOOC(NH2)CH(CH2)2COOH, was used to illustrate the algorithm. The principle of the algorithm was first to find out the different characteristic spectral regions of two amino acids by extreme points according to Non-dominated Sorting Genetic-II (NSGAII). Second, based on the absolute value of the regression coefficient, we found out [ν(CH2) + 2δ(CH2)] and [2ν(CH2)], where the wavenumber ranged from 6165 to 5683 cm-1, were the influential functional groups for quantitative analysis. Finally, the CARS (competitive adaptive reweighted sampling) algorithm was combined with NSGAII to find the specific fingerprint points for the determination of two AAs. Compared with the previous results, the NSGAII-CARS algorithm not only pointed out the influential quantitative functional groups but also used only 6 points for HOOC(NH2)CH(CH2)2COOH and 18 points for NH2(CH2)3COOH to achieve the full-spectrum quantitative effect. The results proposed a general algorithm for the quantitative analysis of NIRS obtained in the binary or ternary mixed systems. The MATLAB codes of the NSGAII-CARS algorithm are available on the website: https://github.com/Mark1988NK/NSGAII-CARS-Algorithm.git.

Judicious design functionalized 3D-COF to enhance CO2 adsorption and separation.

The effects of functional groups (including OH, OCH3 , NH2 , CH2 NH2 , COOH, SO3 H, OCO(CH2 )2 COOH(E-COOH), and (CH2 )4 COOH(c-COOH)) in 3D covalent organic frameworks (3D-COFs) on CO2 adsorption and separation are investigated by grand canonical Monte Carlo (GCMC) simulations and density functional theory calculations. The results indicate that interaction between CO2 and the framework is the main factor for determining CO2 uptakes at low pressure, while pore size becomes the decisive factor at high pressure. The binding energy of CO2 with functionalized linker is correlated to CO2 uptake at 0.3 bar and 298 K on 3D-COF-1, suggesting functional groups play a key role in CO2 capture in microporous 3D-COFs. Moreover, CO2 selectivity over CH4 , N2 , and H2 can be significantly enhanced by functionalization, where CH2 NH2 , COOH, SO3 H, and E-COOH enhance CO2 adsorption more effectively at 1 bar. Among them, SO3 H is the most promising functional group in 3D-COFs for CO2 separation.

Efficient Generation of Permutationally Invariant Potential Energy Surfaces for Large Molecules

An efficient method is described for generating a fragmented, permutationally invariant polynomial basis to fit electronic energies and, if available, gradients for large molecules. The method presented rests on the fragmentation of a large molecule into any number of fragments while maintaining the permutational invariance and uniqueness of the polynomials. The new approach improves on a previous one reported by Qu and Bowman by avoiding repetition of polynomials in the fitting basis set and speeding up gradient evaluations while keeping the accuracy of the PES. The method is demonstrated for CH3–NH–CO–CH3 (N-methylacetamide) and NH2–CH2–COOH (glycine).

Noncovalent Modification of Nanodiamonds with Tritium-Labeled Pantothenic Acid Derivatives

The efficiency of tritium labeling of salts of pantothenic (HO–R–COOH), hopantenic (HO–R–CH2–COOH), and 4-D-phosphopantothenic [(HO)2P(=O)–O–R–COOH] acids [R = CH2C(CH3)2CHOH–CONH(CH2)2] with thermal activation of tritium at target temperatures of 77 and 295 K was studied. The phosphate group inhibits the isotope exchange. The tritium-labeled compounds were used for studying the adsorption of pantothenic acid derivatives from aqueous solutions and in the presence of 0.9% NaCl at 297 ± 3 K onto nanodiamonds prepared by detonation synthesis (NDs). Preparation of stable ND suspensions in advance enhances the ability of NDs to adsorb the compounds studied. The parameters of the equation describing the sorption isotherms at different ionic strengths of the solution were calculated. The strength of the adsorbate retention in contact with water, 0.9% NaCl solution, 0.01 M HCl solution, and 40 g L−1 bovine serum albumin (BSA) solution was determined. The data obtained allow two mechanisms of the adsorbate retention on the ND surface to be considered: reversible adsorption due to ionic interactions and irreversible binding due to hydrophobic interactions. The strongly bound molecules undergo slow desorption in the presence of BSA. The revealed trends confirm high potential of NDs as a drug delivery platform.

Electrochemical lability of glycine in acid media

Electrochemical lability of different glycine species is considered on the basis of voltammetric data obtained for hydrogen evolution on the copper electrode in weakly acidic glycine solutions at different potential sweep rates (v). Voltammograms contain well-defined current peaks the height of which depends on both solution pH and glycine concentration. Current peaks and their potentials vary linearly with √−v and log v, respectively, this being typical of the electrochemical processes controlled by diffusion and charge transfer.To characterise system lability, peak coordinates and convolutive transforms of voltammograms are analysed. The results show that protons attached to different groups in a glycine molecule exhibit different mobility. In contrast to the protonated amino group, the release of a proton from the carboxylic group proceeds significantly faster. Consequently, protonated species +H3N–CH2–COOH can be treated as labile proton donors, whereas zwitterions +H3N–CH2–COO– do not fall into this category.

Intracrystalline diffusivity of lignin-derived benzene derivatives in silicalite-1 crystal in aqueous-phase system

Lignin is a renewable resource that can generate a variety of value-added benzene derivatives during hydrothermal and/or chemical hydrolysis treatment; the crucial task is to separate the targeted derivatives from the hydrolysate. This study aims to investigate the adsorption kinetics of lignin-derived benzene derivatives onto silicalite-1 crystal in an aqueous-phase system to examine the potential applicability of silicalite-1 to aqueous-phase kinetic separation. Functional groups substituted to benzene include –OH, –CH3, –CH2–CH3, –OCH3, –CHO, –COOH, and –CH2=CH2–COOH. First, the corrected diffusivity was compared among cresol isomers. Critical diameter of the isomers was found to be a key parameter, giving rise to significant differences in diffusivity. Interestingly, we also discovered a considerable difference (maximum over 4 orders of magnitude) in corrected diffusivity, even among mono- and para-substituted derivatives, although these sorbates have the same critical diameter. In particular, the carboxylic derivatives tended to exhibit extremely low diffusivities and to show S-shaped isotherms. The diffusivities were strongly affected by the melting point of the sorbates. These results indicate a strong sorbate-sorbate interaction (e.g., hydrogen-bonding between carboxylic groups) that considerably limits molecular mobility in the narrow channel. Our findings are relevant to research on silicalite-1 to aqueous-phase kinetic separation.

Averaged electron collision cross sections for thermal mixtures of β-alanine conformers in the gas phase

A theoretical study of elastic electron scattering by gas-phase amino acid molecule β-alanine (NH2–CH2–CH2–COOH) is presented. R-matrix calculations are performed for each of the ten lowest-lying, thermally-accessible conformers of β-alanine. Eigenphase sums, resonance features, differential and integral cross sections are computed for each conformer. The positions of the low-energy shape resonance associated with the unoccupied orbital of the −COOH group are found to vary from 2.5 to 3.3 eV and the resonance widths from 0.2 to 0.5 eV depending on the conformation. The temperature-dependent population ratios are derived, based on temperature-corrected Gibbs free energies. Averaged cross sections for thermal mixtures of the 10 conformers are presented. A comparison with previous results for the α-alanine isomer is also presented.

Quantum chemistry calculation of reaction pathways of carboxyl groups during coal self-heating

During coal self-heating, reactions of carboxyl groups feature in the evolution of the spontaneous combustion of coal. However, their elementary reaction pathways during this process still have not been revealed. This paper selected the Ar–CH2–COOH as a typical carboxyl group containing structure for the analysis of the reaction pathways and enhancement effect on the coal self-heating process by quantum chemistry calculations. The results indicate that the hydrogen atoms in carboxyl groups are the active sites, which undergo the oxidation process and self-reaction process during coal self-heating. They both have two elementary reactions, namely (i) the hydrogen abstraction of –COOH by oxygen and the decarboxylation of the –COO· free radical and (ii) the hydrogen abstraction of –COOH and its pyrolysis. The total enthalpy change and activation energy of the oxidation process are 76.93 kJ/mol and 127.85 kJ/mol, respectively, which indicate that this process is endothermic and will occur at medium temperatures. For the hydrogen abstraction of –COOH by hydrocarbon free radicals, the thermal parameters are 53.53 kJ/mol and 56.13 kJ/mol, respectively, which has the same thermodynamic properties as the oxidation process. However, for the pyrolysis, the thermal parameters are –42.53 kJ/mol and 493.68 kJ/mol, respectively, and is thus exothermic and would not occur until the coal reaches high temperatures. They affect heat accumulation greatly, generate carbon dioxide, and provide new active centers for enhancing the coal self-heating process. The results would be helpful for further understanding of the coal self-heating mechanism.

Ribonuclease A inhibition by carboxymethylsulfonyl-modified xylo- and arabinopyrimidines.

A group of acidic nucleosides were synthesized to develop a new class of ribonuclease A (RNase A) inhibitors. Our recent study on carboxymethylsulfonyl-modified nucleosides revealed some interesting results in RNase A inhibition. This positive outcome triggered an investigation of the role played by secondary sugar hydroxy groups in inhibiting RNase A activity. Uridines and cytidines modified with SO2 CH2 COOH groups at the 2'- and 3'-positions show good inhibitory properties with low inhibition constant (Ki ) values in the range of 109-17 μM. The present work resulted in a set of inhibitors that undergo more effective interactions with the RNase A active site, as visualized by docking studies.

Glycine combusted ZnFe2O4 gas sensor: Evaluation of structural, morphological and gas response properties

A simple and robust synthesis approach to zinc based spinel ferrite (ZnFe2O4) using the glycine combustion method is reported. The route utilizes divalent zinc nitrate (Zn(NO3)2·6H2O) and trivalent iron nitrate (Fe(NO3)3·9H2O) precursors in aqueous solution (distilled H2O). Glycine (NH2–CH2–COOH) acts as a fuel for the combustion process and subsequent ferrite (ZnFe2O4) formation. As produced material powder was sintered at 700°C in the pellet form and examined for LPG, acetone, ethanol and ammonia sensing properties in the temperature range of 200–450°C. XRD and TEM analyses revealed the formation of single phase nanocrystalline material with crystallite size in the range of 25–30nm. SEM analysis confirmed the coarse structural morphology due to auto-ignition during the combustion reaction. The produced ferrite showed maximum response to both acetone (57%) and LPG (54%) at operating temperatures of 250°C and 375°C, respectively. Further, the sensor showed decent stability and reproducibility towards LPG and acetone, over the period of 30 days, which was then decreased by 2% up to 45 days. The present study confirms that the as produced ZnFe2O4 is a promising candidate for fabricating high performance sensors towards LPG and acetone sensing, in practice.

Carboxylated graphene oxide–Mn2O3 nanorod composites for their electrochemical characteristics

Carboxylated-graphene–Mn2O3 (G-COOMn) nanocomposites were grown as Mn2O3 nanowires on graphene sheets by a one-step thermal method using graphene oxide–COOH (G-COOH) and Mn(NO3)2. Graphene oxide (G) was prepared by the Hummers method by using graphite flakes as a starting material. G-COOH sheets were synthesized using G and chloroacetic acid (Cl–CH2–COOH). G, G-COOH, and G-COOMn were characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, 13C-nuclear magnetic resonance, and Raman spectroscopy. The electrochemical properties of the fabricated G-COOMn supercapacitor were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge–discharge tests. The obtained results showed that the asymmetric supercapacitor had electrochemical capacitance performance within the potential range 0–0.7 V. The supercapacitor delivered a specific capacitance of ∼300 F g−1 at a current density of 50 mA cm−2. The method used in this work provides an easy and straightforward approach for depositing Mn2O3 nanowires on graphene sheets and may be readily extended to the preparation of other classes of hybrids based on G sheets for use in specific technological applications.

A pyridyl–carboxylate type linking ligand containing an intervening amide group and its cadmium and nickel coordination polymers: (3-py)–C(O)NH–C6H4–CH2–COOH (HL), {[CdL2](H2O)}∞, and {[NiL2(H2O)2](H2O)}∞

A new pyridyl–carboxylate type linking ligand with an intervening amide group, (3-py)–C(O)NH–C6H4–CH2–COOH (HL), was prepared from 4-aminophenylacetic acid and nicotinoyl chloride hydrochloride. By employing this ligand, two coordination polymers were prepared under hydrothermal conditions: {[CdL2](H2O)}∞ (1) and {[NiL2(H2O)2](H2O)}∞ (2). The ligand exhibits distinct coordination modes in polymers 1 and 2. These bonding modes result in the different topologies: a 2-D layer for polymer 1 and a 1-D double-chain for polymer 2. In the case of polymer 2, several types of hydrogen bonds connect the 1-D polymers to a 2-D network.

Facile and Mild Strategy Toward Biopolymer-Coated Boron Nitride Nanotubes via a Glycine-Assisted Interfacial Process

We report a simple way to obtain polymer-coated multiwalled boron nitride nanotubes (BNNTs) conducted under mild conditions compatible with fragile biopolymers. The approach converts aggregated pristine BNNTs into colloidally stable dispersions in water without requiring treatment at high temperature or in strongly oxidative conditions. The method relies on our experimental observation that glycine (NH2–CH2–COOH, Gly) interacts with BNNTs, in accordance with theoretical calculations. The role of glycine in this process is 2-fold: the Gly amine group binds to the B-sites of BNNTs, while the Gly carboxylic acid function provides ionic anchoring sites for interactions with polyelectrolytes. The formation of Gly-BNNTs proved to be essential, since they readily disperse in water as disentangled objects and spontaneously adsorb polycations, such as chitosan (CH), polyanions, such as hyaluronan (HA), and polyzwitterionic polymers, such as chitosan-phosphorylcholine (CH-PC). Treatment of aqueous dispersions of coarsely coated BNNTs with an immiscible solvent (hexane) resulted in the complete coverage of the BNNT surfaces via oil/water interfacial assembly. This work provides a rapid, mild, and scalable route to water-dispersible biofunctional BNNTs that may serve as drug delivery vehicles or scaffolds in tissue engineering.

Syntheses, structures, and magnetic properties of one-dimensional coordination polymers based on N-succinopyridine ligand

A series of one-dimensional (1-D) N-succinopyridine-based complexes: [Cu(L−)(H2O)2]Cl·2H2O (1), [Pr(L−)(H2O)4]Cl2 (2), [Ln(L−)(H2O)5]Cl2·3H2O (Ln = Eu (3), Gd (4)), and [Er(L−)(H2O)4]Cl2·H2O (5) (HL = N-succinopyridine (−OOC–CH(N+C5H5)–CH2–COOH)) have been prepared and characterized by single-crystal X-ray diffraction. The frameworks of complexes 1, 2 and 5 constructed from dinuclear metal building blocks exhibit 1-D double-strand loop-like chains; these chains are further connected to each other by hydrogen bonds forming a 3-D supramolecular architecture. Whereas complexes 3 and 4 feature hydrogen bonding 2-D supramolecular networks assembled from 1-D chains that are constructed from mononuclear metal building blocks. The effects of different metal ions, steric hindrance and coordination diversities of HL on the polymeric architectures have been discussed. In addition, thermogravimetric and magnetic properties of these complexes were also investigated in this paper.

Novel sulfur—containing benzophenone derivative as radical photoinitiator for photopolymerization

AbstractA novel, highly efficient, polymerizable sulfur‐containing photoinitiator for free radical polymerization, benzophenone thio‐acetic acid (BP‐S‐CH2‐COOH) was synthesized, characterized, and compared to photoinitiator parameters of the benzophenone (BP) and benzophenone/(phenylthio)acetic acid couple. The photoinitiator possesses a greatly redshifted UV maximal absorption in comparison to BP. Laser flash photolysis studies suggest that photoinitiator radicals are generated by photocleavage of CS bond. Photopolymerization of 2‐ethyl‐2‐(hydroxymethyl)‐1,3‐propanediol triacrylate (TMPTA) demonstrated that one‐component system BPSCH2COOH is more efficient for polymerization than two‐component system. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Experimental and Modeling Studies of the Pressure and Temperature Dependences of the Kinetics and the OH Yields in the Acetyl + O2 Reaction

The acetyl + O(2) reaction has been studied by observing the time dependence of OH by laser-induced fluorescence (LIF) and by electronic structure/master equation analysis. The experimental OH time profiles were analyzed to obtain the kinetics of the acetyl + O(2) reaction and the relative OH yields over the temperature range of 213-500 K in helium at pressures in the range of 5-600 Torr. More limited measurements were made in N(2) and for CD(3)CO + O(2). The relative OH yields were converted into absolute yields by assuming that the OH yield at zero pressure is unity. Electronic structure calculations of the stationary points of the potential energy surface were used with a master equation analysis to fit the experimental data in He using the high-pressure limiting rate coefficient for the reaction, k(∞)(T), and the energy transfer parameter, (ΔE(d)), as variable parameters. The best-fit parameters obtained are k(∞) = 6.2 × 10(-12) cm(-3) molecule(-1) s(-1), independent of temperature over the experimental range, and (ΔE(d))(He) = 160(T/298 K) cm(-1). The fits in N(2), using the same k(∞)(T), gave (ΔE(d))(N(2)) = 270(T/298 K) cm(-1). The rate coefficients for formation of OH and CH(3)C(O)O(2) are provided in parametrized form, based on modified Troe expressions, from the best-fit master equation calculations, over the pressure and temperature ranges of 1 ≤ p/Torr ≤ 1.5 × 10(5) and 200 ≤ T/K ≤ 1000 for He and N(2) as the bath gas. The minor channels, leading to HO(2) + CH(2)CO and CH(2)C(O)OOH, generally have yields <1% over this range.

Theoretical evaluation of corrosion inhibition performance of imidazoline compounds with different hydrophilic groups

Corrosion inhibition performance of four 1-R-2-undecyl-imidazoline compounds (R CH 2COOH (A), CH 2CH 2OH (B), CH 2CH 2NH 2 (C) and H (D)) for carbon steel was evaluated by quantum chemistry and molecular mechanics methods. Results indicated that the hydrophilic groups (R) have remarkable influence on molecular reactivity, binding strength between self-assembled monolayer (SAM) and Fe surface, and compactness of the inhibitor SAM. The inhibition efficiency evaluated via theoretical methods was well accorded with reported experimental ones, following the same order as A > B > C > D. This research might provide a theoretical inhibition performance evaluation approach for homologous inhibitors.