Formic Aqueous Solution Research Articles

NMR spectroscopy of Cu(II) complexes with acrylamide and sodium acrylate copolymer and ω-amino acids

Macromolecular complexes of acrylamide and sodium acrylate copolymer with microelements, including Cu(II), may form at preparation of crop protection and stimulation compositions, where the copolymer serves as an adhesive, water-retaining and film-forming agent. Preparations for crop production may also contain amino acids that protect plants under stressful conditions (cold, dry, etc.). Carboxylic groups of copolymer, carboxylic and amino groups of amino acids may be involved in mixed Cu(II) ions complexes formation. Number of methylene groups separating carboxylic and amino group of amino acids affects its ability to form a stable chelate cycle and, therefore, ligand composition of mixed Cu(II) ions complexes with acrylamide and sodium acrylate copolymer and amino acid. This work is aimed at determining the ligand composition of mixed macromolecular Cu(II) ion complexes with acrylamide and sodium acrylate copolymer and ω-amino acids (β-alanine, γ-aminobutyric acid, ε-aminocaproic acid). 13C and 1H NMR spectroscopy was used to clarify complexes composition. A complex where carboxylic groups of amino acids are ligands has been found to form in aqueous solutions of Cu(II) ions and ω-amino acid (β-alanine, γ-aminobutyric acid, ε-aminocaproic acid) at molar ratio of Cu(II) ions – amino acid equal to 1 : 6. A chelate complex where both carboxylic and amino groups of β-alanine are involved in coordination has been discovered to form in the solution containing Cu(II) ions, β-alanine, as well as acrylamide and sodium acrylate copolymer at molar ratio of Cu(II) – β-alanine – copolymer COO− equal to 1 : 6 : 30. Carboxylic groups of copolymer participate in complex formation as well. Carboxylic groups of both amino acids and the copolymer have been shown to participate in complex formation in aqueous solutions containing Cu(II) ions, either γ-aminobutyric or ε-aminokaproic acid and also acrylamide and sodium acrylate copolymer.

Atomistic simulation studies of ionic cyanine dyes: self-assembly and aggregate formation in aqueous solution.

Cyanine dyes are known to form large-scale aggregates of various morphologies via spontaneous self-assembly in aqueous solution, akin to chromonic liquid crystals. Atomistic molecular dynamics simulations have been performed on four cyanine dyes: pseudoisocyanine chloride (PIC), pinacyanol chloride (PCYN), 5,5',6,6'-tetrachloro-1,1',3,3'-tetraethylbenzimidazolylcarbocyanine chloride (TTBC) and 1,1'-disulfopropyl-3,3'-diethyl-5,5',6,6'-tetrachloro-benzimidazolylcarbocyanine sodium salt (BIC). Simulations employed an optimised general AMBER force field and demonstrate the organisation of the dyes into stacked structures at dilute concentrations. The thermodynamics of self-assembly was studied by calculating potentials of mean force for n-mers (n = 2, 3 or 4), from which the free energies of association are determined. We report binding free energies in the range of 8 to 15kBT for dimerisation, concordant with typical values for ionic chromonics (7 to 14kBT), and examine the enthalpic and entropic contributions to the aggregation process. The self-assembly of these dyes yields two distinct classes of structures. We observe the formation of H-aggregate stacks for PCYN, with further complexity in these assemblies for PIC; where the aggregates contain shift and Y junction defects. TTBC and BIC associate into a J-aggregate sheet structure of unimolecular thickness, and is composed of a brickwork arrangement between molecules. These sheet structures are characteristic of the smectic chromonic mesophase, and such assemblies provide a route to the emergence of nanoscale tubular architectures.

Amide bond formation in aqueous solution: direct coupling of metal carboxylate salts with ammonium salts at room temperature.

Herein, we report a green, expeditious, and practically simple protocol for direct coupling of carboxylate salts and ammonium salts under ACN/H2O conditions at room temperature without the addition of tertiary amine bases. The water-soluble coupling reagent EDC·HCl is a key component in the reaction. The reaction runs smoothly with unsubstituted/substituted ammonium salts and provides a clean product without column chromatography. Our reaction tolerates both carboxylate (which are unstable in other forms) and amine salts (which are unstable/volatile when present in free form). We believe that the reported method could be used as an alternative and suitable method at the laboratory and industrial scales.

Comment on “Topography of the free energy landscape of Claisen–Schmidt condensation: solvent and temperature effects on the rate-controlling step” by N. D. Coutinho, H. G. Machado, V. H. Carvalho-Silva and W. A. da Silva, Phys. Chem. Chem. Phys., 2021, 23, 6738

The referenced article in PCCP presents calculations of solvent kinetic isotope effects that indicate that the rate-limiting step in base-catalyzed chalcone formation in aqueous solution becomes the second enolization.

Probe metal binding mode of imine covalent organic frameworks: cycloiridation for (photo)catalytic hydrogen evolution from formate.

Metalation of covalent organic frameworks (COFs) is a critical strategy to functionalize COFs for advanced applications yet largely relies on the pre-installed specific metal docking sites in the network, such as porphyrin, salen, 2,2′-bipyridine, etc. We show in this study that the imine linkage of simple imine-based COFs, one of the most popular COFs, readily chelate transition metal (Ir in this work) via cyclometalation, which has not been explored before. The iridacycle decorated COF exhibited more than 10-fold efficiency enhancement in (photo)catalytic hydrogen evolution from aqueous formate solution than its molecular counterpart under mild conditions. This work will inspire more functional cyclometallated COFs to be explored beyond catalysis considering the large imine COF library and the rich metallacycle chemistry.

Homogeneous hydrogenation of saturated bicarbonate slurry to formates using multiphase catalysis

A highly efficient bicarbonate hydrogenation catalyst system based on ppm concentrations of a Ru-PNP pincer complex is presented. It allows converting supersaturated bicarbonate slurries to aqueous formate solutions up to 12 M in molarity.

Research Requirements to Move the Bar forward Using Aqueous Formate Salts as H2 Carriers for Energy Storage Applications

In this perspective on hydrogen carriers, we focus on the needs for the development of robust active catalysts for the release of H2 from aqueous formate solutions, which are non-flammable, non-toxic, thermally stable, and readily available at large scales at reasonable cost. Formate salts can be stockpiled in the solid state or dissolved in water for long term storage and transport using existing infrastructure. Furthermore, formate salts are readily regenerated at moderate pressures using the same catalyst as for the H2 release. There have been several studies focused on increasing the activity of catalysts to release H2 at moderate temperatures, i.e., < 80 °C, below the operating temperature of a proton exchange membrane (PEM) fuel cell. One significant challenge to enable the use of aqueous formate salts as hydrogen carriers is the deactivation of the catalyst under operating conditions. In this work we provide a review of the most efficient heterogeneous catalysts that have been described in the literature, their proposed modes of deactivation, and the strategies reported to reactivate them. We discuss potential pathways that may lead to deactivation and strategies to mitigate it in a variety of H2 carrier applications. We also provide an example of a potential use case employing formate salts solutions using a fixed bed reactor for seasonal storage of energy for a microgrid application.

Radiolytic degradation of formic acid and formate in aqueous solution: modeling the final stages of organic mineralization under advanced oxidation process conditions

The successful use of advanced oxidation processes to treat aqueous solutions containing undesirable organic species requires the degradation of these species to lower molecular weight, lower hazard compounds. Safe application of this technology requires a thorough understanding of the mechanisms of degradation. These oxidative transformations are mainly initiated by the reactions of reactive oxygen species, particularly hydroxyl radicals. These react with organic molecules to generate carbon-centered radicals. In the presence of dissolved oxygen, the carbon-centered radicals are next converted to peroxyl radicals, which then decay to lower molecular weight species by multiple mechanistic pathways. Formic acid and its conjugate base formate are the last stable chemical species produced immediately before the complete mineralization of any organic molecule undergoing oxidative degradation in aqueous solution. Once understood, the radical-induced chemistry of formic acid/formate under these conditions has wide applicability in all advanced oxidation technologies. To develop this quantitative knowledge, we have performed a series of 60Co gamma irradiation studies on aqueous formic acid/formate over different pH and solution conditions. The measured species concentration changes, as a function of applied dose, are compared with the predictions of a kinetic computer model constructed from literature reactions and reported rate coefficients. The excellent agreement found between the results and modeling gives confidence in the mechanism presented here and provide the first complete computer model for the radiolytic degradation of formic acid in water.

Guanidinylated Amphiphilic Polycarbonates with Enhanced Antimicrobial Activity by Extending the Length of the Spacer Arm and Micelle Self-Assembly.

Nine guanidinylated amphiphilic polycarbonates are rationally designed and synthesized. Each polymer has the same biodegradable backbone but different side groups. The influence of the hydrophobic/hydrophilic effect on antimicrobial activities and cytotoxicity is systematically investigated. The results verify that tuning the length of the spacer arm between the cationic guanidine group and the polycarbonate backbone is an efficient design strategy to alter the hydrophobic/hydrophilic balance without changing the cationic charge density. A spacer arm of six methylene units (CH2 )6 shows the best antimicrobial activity (minimum inhibitory concentration, MIC = 40 µg mL-1 against Escherichia coli, MIC = 20 µg mL-1 against Staphylococcus aureus, MIC = 40 µg mL-1 against Candida albicans) with low hemolytic activity (HC50 > 2560 µg mL-1 ). Furthermore, the guanidinylated polycarbonates exhibit the ability to self-assemble and present micelle-like nanostructure due to their intrinsic amphiphilic macromolecular structure. Transmission electron microscopy and dynamic light scattering measurements confirm polymer micelle formation in aqueous solution with sizes ranging from 82 to 288 nm.

Thermodynamics and Structure of Neptunium(V) Complexes with Formate. Spectroscopic and Theoretical Study.

The temperature and ionic strength dependences of the complex formation of NpO2+ with formate in aqueous solution are studied by absorption spectroscopy (Im = 0.5-4.0 mol kg-1, T = 20-85 °C, [Form-]total = 0-0.65 mol kg-1), extended X-ray absorption fine structure spectroscopy (EXAFS) and quantum chemical methods. The complex stoichiometry and the thermodynamic functions of the complexation reactions are determined by peak deconvolution of the absorption spectra and slope analyses. Besides the solvated NpO2+ ion, two NpO2+ formate species (NpO2(Form)n1-n; n = 1, 2) are identified. Application of the law of mass action yields the temperature dependent conditional stability constants log β'n(T) at a given ionic strength. These data are extrapolated to IUPAC reference state conditions (Im = 0) using the specific ion interaction theory (SIT). The results show, that log β01(20 °C) = 0.67 ± 0.04 decreases by approximately 0.1 logarithmic units with increasing temperature, log β02(20 °C) = 0.11 ± 0.11 increases by about 0.2 logarithmic units. The temperature dependence of the log β0n(T) values is modeled with the integrated Van't Hoff equation yielding the standard reaction enthalpy ΔrH0 and entropy ΔrS0 of the complexation reactions. The results show that the formation of NpO2(Form) is exothermic (ΔrH01 = -2.8 ± 0.9 kJ mol-1) whereas the formation of NpO2(Form)2- is endothermic (ΔrH02 = 6.7 ± 4.1 kJ mol-1). Furthermore, the binary ion-ion interaction coefficients εT(i,k) of the formed complexes are determined in NaClO4 and NaCl media as a function of the temperature. The coordination mode of formate toward the metal ion is investigated by EXAFS spectroscopy and quantum chemical calculations. A coordination of the ligand via only one O atom of formate to the metal ion is identified.

Supramolecular solvents formation in aqueous solutions containing primary amine and monoterpenoid compound: Liquid phase microextraction of sulfonamides

A phenomenon of supramolecular solvents formation in aqueous solutions containing primary amine and monoterpenoid compound is presented for the first time. A novel supramolecular solvent-based liquid phase microextraction was developed. In an aqueous phase primary amine formed isotropic solution due to formation of amphiphile supramolecular assembly. The phase separation was achieved by a coacervation process. The monoterpenoid phenol (thymol) acted as a coacervation agent and induced spontaneous in situ formation of tiny supramolecular solvent droplets. The applicability of the proposed microextraction procedure was demonstrated for the separation of sulfonamides from biological fluids (human plasma and serum). An obtained composition of supramolecular solvent (1-decylamine, thymol, water) promoted satisfactory extraction of polar analytes from aqueous phase. The calibration graphs were linear over the concentration ranges of 0.06–50 mg L−1 for sulfamethoxazole, sulfamethazine and sulfapyridine. The limit of detection calculated from the blank tests based on 3σ was 0.02 mg L−1 for all analytes. The total analysis time was 15 min.

Release and stability of water dispersible biochar colloids in aquatic environments: Effects of pyrolysis temperature, particle size, and solution chemistry

Pathways for the physical disintegration of biochar (BC) and the release of water dispersible BC colloids (WDBC) have received much attention due to their unique impacts on carbon loss and contaminant. However, the current understanding of the mechanisms involved in WDBC formation and associated influencing factors is rather limited. This study systematically explored the effects of pyrolysis temperature, initial particle size, and solution chemistry on WDBC formation in aqueous solutions and examined the formation and colloidal stability of WDBC in natural solutions. Results showed that pyrolysis temperature determined the abrasion resistance of pyrolyzed BC, and the submicron fragment rate decreased in the order 400 °C (BC400) > 700 °C (BC700) > 200 °C (BC200). The WDBC yield decreased in the order BC400 (77.5–331 mg g−1) > BC700 (33.5–173 mg g−1) > BC200 (16.8–125 mg g−1) depending on BC size at a solution ionic strength (IS) ≤ 1 mM, which was positively correlated with the submicron fragment rate of bulk BC. With the exception of BC200, increasing IS (0.1–20 mM) and decreasing pH (3.0–10.0) significantly inhibited WDBC yield. Release and sedimentation dominated the WDBC formation processes with the former being more susceptible to solution chemistry. Derjaguin-Landau-Verwey-Overbeek interactions properly explained the effect of IS on WDBC from BC400 and BC700, while the steric resistance of abundant dissolved organic carbon on BC200 was mainly responsible for the high formation of WDBC at high IS (20–50 mM). WDBC had high colloidal stability and could form and stabilize well in natural surface waters and soil solutions, suggesting the relevant risk of long-distance migration of WDBC in environments. These findings represent new knowledge regarding the physical decomposition and the fate of BC in the environment.

A ratiometric fluorescence sensor based on enzymatically activatable micellization of TPE derivatives for quantitative detection of alkaline phosphatase activity in serum.

A novel ratiometric fluorescence assay via enzymatically activatable micellization in aqueous solution was devised for quantitative detection of alkaline phosphatase (ALP) activity. We demonstrated that the dephosphorylation of the water-soluble, phosphate-functionalized, fluorophore monomer P-TPE-TG, induced by an enzymatic reaction of ALP, leads to micelle formation in aqueous solution because its water-soluble functionality is reduced. The dephosphorylation-induced micellization of P-TPE-TG exhibited a ratiometric sensing response for various ALP concentrations (10–200 mU mL−1) and provided a suitable sensing platform for naked eye detection with increased fluorescence quantum yield (Φ = 3.2%), even compared to a typical TPE-based sensor (Φ = 1.0%), where ALP can be sensed with a detection limit of 0.034 mU mL−1. In addition, P-TPE-TG displayed excellent sensing performance at concentrations from 0 to 50 mU mL−1 in diluted human serum (10%), which offers the capability to exploit ratiometric responses for bioactive substances under practical conditions.

Toward novel sulphur-containing derivatives of tetraazacyclododecane: synthesis, acid–base properties, spectroscopic characterization, DFT calculations, and cadmium(ii) complex formation in aqueous solution

New sulphur derivatives of cyclen, with potential complementary properties with respect to known compounds, have been synthesized and studied.

Proton-Conductive 3D LnIII Metal-Organic Frameworks for Formic Acid Impedance Sensing.

Metal-organic frameworks (MOFs) as new classes of proton-conducting materials have been highlighted in recent years. Nevertheless, the exploration of proton-conducting MOFs as formic acid sensors is extremely lacking. Herein, we prepared two highly stable 3D isostructural lanthanide(III) MOFs, {(M(μ3 -HPhIDC)(μ2 -C2 O4 )0.5 (H2 O))⋅2 H2 O}n (M=Tb (ZZU-1); Eu (ZZU-2)) (H3 PhIDC=2-phenyl-1H-imidazole-4,5-dicarboxylic acid), in which the coordinated and uncoordinated water molecules and uncoordinated imidazole N atoms play decisive roles for the high-performance proton conduction and recognition ability for formic acid. Both ZZU-1 and ZZU-2 show temperature- and humidity-dependent proton-conducting characteristics with high conductivities of 8.95×10-4 and 4.63×10-4 S cm-1 at 98 % RH and 100 °C, respectively. Importantly, the impedance values of the two MOF-based sensors decrease upon exposure to formic acid vapor generated from formic aqueous solutions at 25 °C with good reproducibility. By comparing the changes of impedance values, we can indirectly determine the concentration of HCOOH in aqueous solution. The results showed that the lowest detectable concentrations of formic acid aqueous solutions are 1.2×10-2 mol L-1 by ZZU-1 and 2.0×10-2 mol L-1 by ZZU-2. Furthermore, the two sensors can distinguish formic acid vapor from interfering vapors including MeOH, N-hexane, benzene, toluene, EtOH, acetone, acetic acid and butane. Our research provides a new platform of proton-conductive MOFs-based sensors for detecting formic acid.

Ion‐Enhanced Conversion of CO2 into Formate on Porous Dendritic Bismuth Electrodes with High Efficiency and Durability

Facile synthesis of efficient electrocatalysts that can selectively convert CO2 to value-added chemicals remains a challenge. Herein, the electrochemical synthesis of porous Bi dendrite electrodes and details of their activity toward CO2 conversion to formate in aqueous solutions of bicarbonate are presented. The as-synthesized multilayered, porous, dendritic Bi electrodes exhibit a faradaic efficiency (FE) of approximately 100 % for formate production. Added halides and cations significantly influence the steady-state partial current density for formate production JFM (Cl- >Br- ≈I- ; Cs+ >K+ >Li+ ). DFT calculations revealed that the reaction pathway involving the species *OCOH occurs predominantly and the presence of both Cs+ and Cl- makes the overall reaction more spontaneous. Photovoltaic-cell-assisted electrocatalysis produced formate with an FE of approximately 95 % (JFM ≈10 mA cm-2 ) at an overall solar conversion efficiency of approximately 8.5 %. The Bi electrodes maintain their activity for 360 h without a change in the surface states.

The micelle thermodynamics and mixed properties of sulfobetaine-type zwitterionic Gemini surfactant with nonionic and anionic surfactants

The surface tension curves of three zwitterionic Gemini surfactants (GCS12, GCS14, and GCS16) were measured at different temperatures. According to the values of critical micelle concentration (cmc) and γcmc, the thermodynamic parameters of these surfactants were calculated. As temperature increases, the cmc values decrease, and the surface activities increase. The thermodynamic parameters indicate that the micellization and adsorption of these surfactants are spontaneous, endothermic and entropy-driven. The process of micellization and adsorption features an enthalpy-entropy compensation phenomenon. The compensation temperatures of micellization are in the range of 311.2~312.8 K, while those of adsorption are between 310.2 K and 312.2 K. Among these surfactants, GCS14 aggregates most easily into micelles, and the micelles of GCS14 are the most stable. Moreover, the mixed properties of GCS14 with anionic surfactant (SDS) and nonionic surfactant (CDA) were investigated, respectively. The GCS14/SDS mixtures exhibit excellent surface activities, and GCS14 plays an essential role in the mixtures. At αGCS14 = 0.8, the cmc and γcmc values reach a minimum. According to the regular solution theory, the great absolute values of βσ (for mixed monolayer formation at the aqueous solution/air interface) and βm (for mixed micelle formation in aqueous solution) indicate the strong attraction between GCS14 and SDS. The GCS14/SDS mixtures show synergistic effects in three properties, including the efficiency in surface tension reduction, the ability of micelle formation, and the ability of surface tension reduction. Also, the mixtures of GCS14 and CDA feature excellent surface activities. At αGCS14 = 0.8, the cmc and γcmc values reach a minimum. For the GCS14/CDA mixtures, the great absolute values of βσ and βm suggest these mixtures exhibit the synergistic effect in the surface tension reduction and the formation of the micelles. Zwitterionic Gemini surfactant GCS14 reveals stronger synergistic effects in the formation of mixed micelle and mixed monolayers with anionic surfactant (SDS) than with the nonionic surfactant (CDA). The molecule attraction between GCS14 and SDS or CDA in the mixed films is stronger than in the micelles.

Guanine-guided time-resolved luminescence recognition of DNA modification and i-motif formation by a terbium(III)-platinum(II) complex

Site-specific recognition of DNA modification or the formation of noncanonical structures has important applications in molecular biology, disease diagnosis, and gene expression analysis. In this study, we introduce a guanine-guided sensing tool using a terbium(III)-platinum(II) complex (TPC) as a time-resolved luminescence probe to site-specifically recognize DNA modification and i-motif formation in aqueous solution. The probe is composed of a TbIII center as the luminescent reporter and two PtII units as the receptor for guanine (G) nucleobase. TPC exhibits remarkable reaction selectivity for guanine nucleotides over other nucleotides, giving rise to a significant increase in luminescence. The luminescence enhancement of TPC is mainly attributed to an energy transfer from G base to the TbIII center after the specific coordination of PtII with N7 of guanine (N7-G), which would be facilitated by the phosphates through promoting the departure of coordinated water and bringing G closer to TbIIIvia noncovalent interactions. Based on such sensing feature, the enhanced luminescence of TPC sensitized by G nucleotides can correspondingly decrease upon N7-G modifications of DNA or i-motif formation through constructing simple guanine-guided sensing tools. This probe would provide a useful strategy for site-specific recognition of DNA for extensive purposes.

PH-triggered prodrug micelles for cisplatin delivery: Preparation and In Vitro/Vivo evaluation

A novel copolymers based on glycidyl azide polymer (GAP) and polyethylene glycol (PEG) with comb-linear-comb architecture were synthesized via atom transfer radical polymerization (ATRP) and then linear GAP segment modified to generate polymers with pendant thiol groups. Subsequent thiol-ene reaction with maleic anhydride leads to polymers with carboxylate functionalities, which were conjugated with cisplatin to generate polymer-cisplatin conjugates (PCPtCs). Due to the hydrophobicity of the drug conjugated block, the copolymers took on amphiphilic character leading to micelle formation in aqueous solution with an average diameter of 142 nm. As an environmentally sensitive drug delivery vehicle, these conjugates can potentially minimize the drug loss during PCPtCs circulation in the blood, where the pH value is neutral, and trigger rapid intracellular drug release after the PCPtCs are endocytosed by the target cells. This characteristic drug release profile holds the promise to suppress cancer cell chemoresistance by rapidly releasing a high dose of chemotherapy drugs inside the tumor cells, thereby improving the therapeutic efficacy of the drug payload. In addition, PCPtCs also showed excellent cytotoxicity effect on MCF-7 cell line whereas the copolymer had no significant toxicity effects on MCF-7 cell line due to which cell viability maintain over 80% at all concentration. As well as, the copolymer did not show noticeable toxicity on A. salina and synthesized PCPtCs showed hemolysis effect lower than 9%. Moreover, this result was repeat in LD50 and all mice which treat with 5000 mg/Kg were still alive after 24 and 168 h, which confirmed the safety of the carrier. All of these results show that this unique pH sensitive PCPtCs may offer a very promising approach for drug delivery of cisplatin.

Association behavior of bile salts binary mixtures in an aqueous system: A tensiometric and fluorometric study

AbstractBile salts are steroidal surfactants consisting of 2 to 12 monomers to form a micelle. The most important physiological property of bile salts is the solubilization of cholesterol. The bile salts make mixed micelle with phospholipids that enhance the bile salts ability to solubilize cholesterol. The mixed micelle formation in aqueous solution between two bile salts (sodium taurocholate [NaTC] and sodium deoxycholate [NaDC]) mixtures has been studied by tensiometric and fluorometric studies. The nonideal mixing behavior was examined for mixed systems, and synergism was found for the current mixed systems. Rubingh and Rosen models were used to analyze the bile salt‐bile salt binary mixtures, and the interaction parameters, as well as mixed micelle compositions at bulk and interface, have been computed as well as discussed one by one. The values of were achieved to be negative for all studied systems. In the solution mixtures, as the content of NaTC increases, the formation of micelles becomes slightly less favorable.