Hydrogen Oxalate Research Articles

Nucleation kinetics, chemical etching, hirshfeld surface, and photoluminescence of Rubidium hydrogen oxalate dihydrate NLO single crystal

The nucleation dynamics of a semi-organic Rubidium hydrogen oxalate dihydrate (RbHOH) crystal were assessed using double-distilled water as a solvent medium to obtain good quality crystal using the solution growth technique. Gravimetric analysis of solubility revealed that it has a positive temperature coefficient of solubility, which is appropriate for bulk growth. Other nucleation parameters such as metastable zonewidth, induction period, and interfacial energy were carried out using the classical theory of nucleation. The photoconductivity experiments reveal that the grown crystal exhibits a positive photoconductivity nature. Chemical etching and atomic force microscopy (AFM) experiments were performed on the produced crystal surface. From AFM experiments, effectively assessed amplitude parameters were calculated. Etching studies showed the presence of etch pit patterns such as tiny hillocks and rectangular shapes. Intermolecular interactions were analysed by using Hirshfeld surface analysis. In the photoluminescence (PL) studies, the grown crystal indicates green emission peaks at 519 nm, and the bandgap energy is found to be 4.8 eV. At room temperature, the refractive index of the RbHOH crystal was determined to be 1.669. The nonlinear optical (NLO) efficiency of the grown crystal was examined using a second harmonic generation efficiency test, and it was determined to be 0.58 times that of KDP.

L-Cysteine oxalates with dimeric and trimeric cations

Single crystals of two new compounds, (l-CysH···l-Cys)(HC2O4) (I) and (l-CysH···l-Cys···l-CysH)(HC2O4)2·0.5H2O (II), were obtained. Crystal structures were solved and refined using single-crystal X-ray diffraction, and compared with the previously known orthorhombic and monoclinic modifications of the simple salt (l-CysH)(HC2O4). Compound (I) crystallizes in the triclinic crystal system (space group P1, Z=2) and contains (l-CysH···l-Cys) dimeric cations with very short O···O interatomic distance of 2.434(2) Å. Hydrogen oxalate anions form head-to-tail type chains with very short hydrogen bonds, characterized by O···O distances of 2.422(2) Å and 2.417(3) Å. The crystal lattice of (II) is monoclinic with the space group C2, Z=4. It contains a new type of cation, that has never been observed before for cysteine salts, i.e. trimeric (l-CysH···l-Cys···l-CysH) cation. Protonated l-cysteinium cations are connected to the zwitterionic l-cysteine moiety through the same oxygen atom of the carboxylate group via hydrogen bonds, with O···O distances of 2.6410(18) Å and 2.4888(19) Å. Similar to the structure (I), the hydrogen oxalate anions form head-to-tail type chains linked by short hydrogen bonds with O···O distances of 2.4369(17) Å and 2.4330(17) Å, respectively. The crystals were characterized by IR and Raman spectroscopy. The batches obtained on crystallization were also characterized by X-ray powder diffraction, in order to check the phase purity of all the sample.

Efficacy of the new insecticide thiocyclam hydrogen oxalate in the control of rice striped stem borer Chilo suppressalis (Lepidoptera: Grambidae) under field conditions

Efficacy of the new insecticide thiocyclam hydrogen oxalate in the control of rice striped stem borer Chilo suppressalis (Lepidoptera: Grambidae) under field conditions

Indoxacarb resistance in Iranian populations of Tuta absoluta (Lepidoptera: Gelechiidae): Cross-resistance, biochemical and molecular mechanisms

Tuta absoluta (Meyrick) is an invasive tomato pest that occurs worldwide, including Iran. This study investigates the occurrence of resistance to indoxacarb, an oxadiazine insecticide, and the underlying mechanisms in Iranian populations of T. absoluta. Bioassays were performed on second-instar larvae using indoxacarb alone and in combination with three synergists: Piperonyl butoxide (PBO), diethyl maleate (DEM), and triphenyl phosphate (TPP). The activities of the main detoxification enzymes, including glutathione S-transferases (GST), general carboxylesterases (CarEs), and P450 monooxygenases (P450s), were evaluated. In addition, the presence of known amino acid substitutions in the IV segment 6 domain of the T. absoluta sodium channel was investigated. The results showed that resistance rates to indoxacarb in Iranian populations ranged from 2.37- to 14.45-fold. However, pretreatment with synergists did not significantly increase the toxicity of indoxacarb. Enzyme assays showed that Ardabil (Ar) and Kerman (Kr) populations had the highest CarEs activity, while Ar population showed the highest P450 activity. However, the observed increases in enzyme activities were <2-fold. Two indoxacarb resistance mutations, F1845Y and V1848I, were detected. Apart from a significant and positive correlation between LC50 values of indoxacarb and thiocyclam hydrogen oxalate, no cross-resistance between indoxacarb and other insecticides was detected. Overall, these results suggest that populations of T. absoluta in Iran have developed resistance to indoxacarb, primarily through changes at the target site.

N-Methyl-serotonin hydrogen oxalate.

The solid-state structure of N-methyl-serotonin {systematic name: [2-(5-hy-droxy-1H-indol-3-yl)eth-yl](meth-yl)aza-nium hydrogen oxalate}, C11H15N2O+·C2HO4 -, is reported. The structure possesses a singly protonated N-methylserotonin cation and one hydrogen oxalate anion in the asymmetric unit. In the crystal, the mol-ecules are linked by N-H⋯O and O-H⋯O hydrogen bonds into a three-dimensional network.

Phase transitions of L-histidinium hydrogen oxalate crystal under high pressures investigated by Raman spectroscopy

L-histidinium hydrogen oxalate (L-HisH)(HC2O4) crystal is formed from amino acid. L-histidine with oxalic acid whose vibrational high pressures behavior have not yet been investigated in the literature. Here we synthesized (L-HisH)(HC2O4) crystal by slow solvent evaporation method in a 1:1 ratio of L-histidine and oxalic acid. In addition, a vibrational study of (L-HisH)(HC2O4) crystal as a function of pressure was performed via Raman spectroscopy in the pressure range of 0.0–7.3 GPa. From analysis of the behavior of the bands within 1.5–2.8 GPa, characterized by the disappearance of lattice modes, the occurrence of a conformational phase transition was noted. A second phase transition, now from structural type, close to 5.1 GPa was observed due to the incidence of considerable changes in lattice and internal modes, mainly in vibrational modes related to imidazole ring motions.

Studies on the growth, structural, spectral and third order nonlinear optical properties of ethylammonium hydrogen oxalate hemihydrate crystal

Studies on the growth, structural, spectral and third order nonlinear optical properties of ethylammonium hydrogen oxalate hemihydrate crystal

Structural, spectral, and third-order nonlinear optical analysis of solution-grown allylammonium hydrogen oxalate hemihydrate crystal for laser applications

Structural, spectral, and third-order nonlinear optical analysis of solution-grown allylammonium hydrogen oxalate hemihydrate crystal for laser applications

N-Benzylethanolammonium Ionic Liquids and Molten Salts in the Synthesis of 68Ga- and Al18F-Labeled Radiopharmaceuticals

Ionic liquids (ILs), due to their structural features, have unique physical and chemical properties and are environmentally friendly. Every year, the number of studies devoted to the use of ILs in medicine and pharmaceutics is growing. In nuclear medicine, the use of ILs with self-buffering capacity in the synthesis of radiopharmaceuticals is extremely important. This research is devoted to obtaining new ionic buffer agents containing N-benzylethanolammonium (BEA) cations and anions of carboxylic acids. A series of new BEA salts was synthesized and identified by NMR (1H, 13C), IR spectroscopy and elemental and thermal analysis. The crystal structures of BEA hydrogen succinate, hydrogen oxalate and oxalate were determined by x-ray diffraction. Newly synthesized compounds were tested as buffer solutions in 68Ga- and Al18F-radiolabeling reactions with a series of bifunctional chelating agents and clinically relevant peptides used for visualization of malignancies by positron emission tomography. The results obtained confirm the promise of using new buffers in the synthesis of 68Ga- and Al18F-labeled radiopharmaceuticals.

Growth, structural, vibrational, characterization and DFT investigations of 2-methylimidazolium hydrogen oxalate dihydrate (2MIO) single crystal-towards third order NLO applications

We report the studies conducted on the single crystal of 2-methyimidazolium hydrogen oxalate dihydrate (2MIO) which was achieved by employing the solution growth technique of conventional slow evaporation wherein the solvent used was deionized water. The confirmation of the grown 2MIO crystal's lattice parameters were accomplished by the analysis of single-crystal X-ray diffraction (SCXRD). The powder sample was utilized for the studies of identifying its crystalline phase, composition, and NLO efficiency. The UV–Vis-NIR studies show that the 2MIO crystal has a better transmittance in the region of entire visible and the lower cut-off wavelength is 280 nm. The decomposition and dissociation points of the 2MIO were studied by employing thermal measurements. The nonlinear optical parameters were computed for 2MIO from the performed Z-scan study. Additionally, quantum chemical studies were carried out on 2MIO molecule which was performed by making use of density functional theory (DFT) at the B3LYP/6–311 G (d.p) method. The optimized geometrical parameters, the bond length and bond angles were compared with the observed experimental XRD data. Hirshfeld surface analysis featuring 2D fingerprint plots were analysed by using Crystal Explorer 3.1 such that it could confirm the intermolecular and weak interactions. Natural bond orbital (NBO) analysis was undertaken to evaluate the donor-accepter interactions and stabilization energies of the molecule. The HOMO-LUMO energy was analysed whereby the energy gap (ΔE) and other related properties of the molecules present in 2MIO were calculated. The first-order hyperpolarizability of 2MIO was measured from the computational studies with which it is established that the obtained value is 4.95 times than that of standard urea.

Systematic investigation and comparison of oxalic acid dihydrate, ammonium oxalate hydrate and ammonium hydrogen oxalate oxalic acid dihydrate single crystals

Semiorganic crystals are hybrid materials that have captured the interest of researchers due to their improved material characteristics and applications. In the current work, single crystals of oxalic acid dihydrate (OAD), Ammonium oxalate hydrate (AHO), and Ammonium hydrogen oxalate oxalic acid dihydrate (AHOOD) were grown using a slow evaporation method. Single crystal and powder XRD measurements were carried out to elucidate their unit cell parameters, crystal system, and structural information. To comprehend the interplay of light and matter, optical investigations like UV–Vis Spectroscopy and photoluminescence studies were performed. Interaction of ammonium with oxalic acid, and thus formed crystals, was investigated using impedance spectroscopy. Detailed dielectric parameters such as dielectric constant, dielectric loss, impedance, conductivity, and electric modulus were explored as a function of frequency. Vickers hardness test was used to calculate the hardness, Meyer's number, brittleness, and fracture toughness. The crystals were determined to be of the hard materials group.

DFT, hirshfeld and molecular docking studies of a hybrid compound - 2,4-Diamino-6-methyl-1,3,5-triazin-1-ium hydrogen oxalate as a promising anti -breast cancer agent

The six-membered heterocyclic ring - 1,3,5-triazine and its derivatives have garnered a lot of attention because they're good bioactive herbicides, cancer agents, and other things. One such triazine derivative, 2,4-diamino-6-methyl-1,3,5-triazin-1-ium hydrogen oxalate (DMTHO), was produced in this work, and the structure was optimised using density functional theory's B3LYP functional and the basis set 6–31++G (d,p). Additionally, the chemical underwent in-depth research using molecular docking analysis, Hirshfeld, and density functional theory. The electron densities distribution in the atoms is provided by natural orbital analysis, which also characterises the chemical bonding and reaction behaviour of the compound. The calculated HOMO and LUMO energies indicate that charge transfer occurs inside the molecule. Chemical reactivity traits including HOMO-LUMO energy gaps, softness, total energy, chemical hardness, electronic chemical potential, and electrophilicity of bioactive substances have all been subjected to analytical investigation. Total dipole moment (μ) and first-order hyperpolarizability (β) measurements for the investigated chemical indicate that DMTHO may exhibit microscopic nonlinear optical (NLO) behaviour with nonzero values. A quantitative description about intermolecular interactions in the produced crystal is provided by the Hirshfeld surface analysis. Further docking studies of the compound have been performed and the results reveals that the compound inhibit the breast cancer related protein - casein kinase (CK2) – and the possibility of developing as a potential anti breast cancer lead.

Protic Ionic Liquids Based on BIS‐TRIS Carboxylates: Synthesis, Structural Characterization and Buffer Activity

AbstractIonic liquids, which have their own buffer capacity, have been classified as Good's buffer ionic liquids (GB‐ILs). GB‐ILs have demonstrated their potential in biotechnology due to their biocompatibility and profitable self‐buffering properties. A number of new GB‐ILs based on BIS‐TRIS (bis(2‐hydroxyethyl)‐amino‐tris(hydroxymethyl)methane) carboxylates have been synthesized. IR, NMR (1H, 13C) spectroscopy, and thermal analysis data confirming the formation of new BIS‐TRIS salts are presented. The crystal structure of three BIS‐TRIS salts with salicylate, hydrogen oxalate, and oxalate anions was determined by single‐crystal X‐ray diffraction. Screening of synthesized BIS‐TRIS carboxylates as buffers in 68Ga‐radiolabeling reactions of the model chelator p‐SCN−Bn‐DOTA, which is prototype of DOTA‐modified (1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid) peptides, was carried out.

Departures from near inversion symmetry using amino acid hydrogen oxalate quasiracemates

Departures from near inversion symmetry using amino acid hydrogen oxalate quasiracemates

Structural and vibrational analysis of 2, 4-diamino-6-methyl-1, 3, 5-triazin-1-ium-hydrogen oxalate

An organic crystalline salt − 2,4-Diamino-6-methyl-1,3,5-triazin- 1-ium hydrogen oxalate (DMTO) has hydrogen interactions viz. NH⋯O, CH⋯O, NH⋯N and OH⋯O gives interesting vibrational effect. X-ray diffraction study reveals that DMTO is crystallized in triclinic centrosymmetric space group P-1 as expected. Structural as well as the vibrational spectra have been discussed on the basis of density functional theory (DFT) using B3LYP hybrid functional with the basis set 6–311++G(d,p).Acidic proton of the oxalic acid (OA) is transferred to 2,4-diamino-6-methyl-1,3,5-triazine (DAMT) and giving rise to singly protonated 2,4-diamino-6-methyl-1,3,5-triazinium ion.

Defect-induced measurements of semi-organic ammonium hydrogen oxalate oxalic acid dihydrate single crystals using gamma irradiation

The structural, optical, mechanical and electrical properties of pure and 5—20-kGy gamma-irradiated semi-organic single crystals of ammonium hydrogen oxalate oxalic acid dihydrate (NH4H3(C4O8).2H2O) are presented. The crystals were synthesized at room temperature using facile solvent evaporation technique. Powder XRD measurements indicate gradual enhancement in crystallinity and lattice defect annihilation for low radiation dosage. Radiation-induced increase in optical band gap (4.01–4.16 eV) indicates high damage threshold of the crystals. Quenching of photoluminescence is attributed to the lowering of surface defect density with radiation. The influence of gamma radiation on the functional vibrations of the crystals is studied using FTIR-Raman spectroscopy. Vickers microhardness measurements show gradual enhancement in crystal hardness with the increase in radiation. An increase in forward resistance with irradiation is observed from I–V measurements and is attributed to high transparency of the crystals. These results indicate the viability of NH4H3(C4O8) 2H2O crystals in potential space optoelectronic applications.

Structural, optical, mechanical, dielectric and nonlinear optical studies of rubidium hydrogen oxalate dihydrate (RbC4H7O10) single crystal

A transparent Rubidium hydrogen oxalate dihydrate (RbHOH) single crystal was synthesized by adopting the slow solvent evaporation method. RbHOH crystallizes in the triclinic structure with the P1‾ space group. The characteristic FTIR spectrum reflects the vibrational modes of water molecules and hydroxyl groups available in the material. From the absorption spectrum, the lower cutoff wavelength of RbHOH was at 260 nm with an energy gap of 4.74 eV. From TG/DSC, the thermal stability of RbHOH is around 91 °C. The normal indentation size effect of the material was verified with the help of Vickers microhardness analysis.Dielectric measurement has been performed over a wide range of temperature, as a function of frequencies. The third-order nonlinear susceptibility of RbHOH was calculated as 3.95242 × 10−6 esu.

Intramolecular Proton Transfer in the Hydrogen Oxalate Anion and the Cooperativity Effects of the Low-Frequency Vibrations: A Driven Molecular Dynamics Study.

We report first-principles molecular dynamics (MD) and dipole-driven molecular dynamics (μ-DMD) simulations of the hydrogen oxalate anion at the MP2/aug-cc-pVDZ level of theory. We examine the role of vibrational coupling between the OH stretching bands, that is, the fundamental and a few combination bands spanning the 2900-3100 cm-1 range, and several of the low-frequency bending and stretching fundamental modes. The low-frequency modes between 300 and 825 cm-1 play a crucial role in the proton-transfer motion. Strong involvement of CO2 and CCO bending and the CC stretching vibrations indicate that these large amplitude motions cause the shortening of the O···O distance and thus promote H+ transfer to the other oxygen by bringing it over the 3.4 kcal/mol barrier. Analysis of resonant μ-DMD trajectories shows that the complex spectral feature near 825 cm-1, closely corresponding to both an overtone of two quanta of 425 cm-1 and a combination band of low-frequency CO2 rocking (300 cm-1) and CCO bending (575 cm-1) modes, is involved in the proton transfer. μ-DMD shows that exciting the system at these mode combinations leads to faster barrier activation than exciting at the OH fundamental mode.

Bioefficacy of Thiocyclam Hydrogen Oxalate 50 SP against Major Pests of Rice

Bioefficacy of thiocyclam hydrogen oxalate 50 SP, a new molecule of nereistoxin group, was evaluated against three major pests of rice viz. stem borer, leaf folder and whorl maggot during Sali (Kharif) and Ahu (Rabi) seasons, 2016–2017 at Instructional Cum Research (ICR) farm of Assam Agricultural University, Jorhat. Cartap hydrochloride 50 EC and trizophos 40 EC were used as standard check along with three doses of thiocyclam hydrogen oxalate 50 SP viz., 200, 350 and 500 g ai ha−1. The result showed that thiocyclam hydrogen oxalate 50 SP @ 200 and 500 g ai ha−1 recorded the lowest dead heart (2.3 and 2.0%), white ear head (1.4 and 1.3%) and leaf folder infestation (3.0 and 2.8%) with highest yield (5069 and 5097 kg ha−1) in Sali (Kharif) season 2016. Similarly, in Ahu (Rabi) season of 2017, the thiocyclam hydrogen oxalate 50 SP @ 200 and 500 g ai ha−1 recorded the lowest dead heart (1.9 and 1.8%), white ear head (1.0 and 0.5%) and leaf damage by whorl maggot (2.2 and 2.1%) with highest yield (4691 and 4861 kg ha−1), respectively. Moreover, thiocyclam hydrogen oxalate did not show any deleterious effect on natural enemies population of rice ecosystem.

On the Hydrogen Oxalate Binding Motifs onto Dinuclear Cu and Ag Metal Phosphine Complexes.

We report the binding geometries of the isomers that are formed when the hydrogen oxalate ((CO2)2H=HOx) anion attaches to dinuclear coinage metal phosphine complexes of the form [M1M2dcpm2(HOx)]+ with M=Cu, Ag and dcpm=bis(dicyclohexylphosphino)methane, abbreviated [MM]+ . These structures are established by comparison of isomer‐selective experimental vibrational band patterns displayed by the cryogenically cooled and N2‐tagged cations with DFT calculations of the predicted spectra for various local minima. Two isomeric classes are identified that feature either attachment of the carboxylate oxygen atoms to the two metal centers (end‐on docking) or attachment of oxygen atoms on different carbon atoms asymmetrically to the metal ions (side‐on docking). Within each class, there are additional isomeric variations according to the orientation of the OH group. This behavior indicates that HOx undergoes strong and directional coordination to [CuCu]+ but adopts a more flexible coordination to [AgAg]+ . Infrared spectra of the bare ions, fragmentation thresholds and ion mobility measurements are reported to explore the behaviors of the complexes at ambient temperature.