Carboxylate Oxygen Research Articles

Synthesis, structure and topological analysis of glycine templated highly stable cadmium sulfate framework: A New Lewis Acid catalyst

One new open-framework two-dimensional layer, [Cd(NH3CH2COO)(SO4)], I, has been synthesized using amino acid as templating agent. Single crystal structural analysis shows that the compound crystallizes in monoclinic cell with non-centrosymmetric space group P21, a = 4.9513(1) Å, b = 7.9763(2) Å, c = 8.0967(2) Å, β = 105.917(1)° and V = 307.504(12) Å3. The compound has connectivity between the Cd-centers and the sulfate units forming a two-dimensional layer structure. Sulfate unit is coordinated to metal center with η3, μ4 mode possessing a coordination free oxygen atom. The zwitterionic form of glycine molecule is present in the structure bridging with two metal centers through μ2-mode by carboxylate oxygens. The topological analysis reveals that the two-dimensional network is formed with a novel 4- and 6-connected binodal net of (32,42,52)(34,44,54,63) topology. Although one end of the glycine molecule is free from coordination, the structure is highly stable up to 350 °C. Strong N-H⋯ O hydrogen bonding interactions play an important role in the stabilization and formation of three-dimensional supramolecular structure. The cyanosilylation of imines using the present compounds as heterogeneous catalyst indicates good catalytic behavior. The present study illustrates the usefulness of the amino acid for the structure building in less studied sulfate based framework materials as well as designing of new heterogeneous catalysts for the broad application. The compound has also been characterized through elemental analysis, PXRD, IR, SEM and TG-DT studies.

Identification and Functional Mechanism of Novel Angiotensin I Converting Enzyme Inhibitory Dipeptides from Xerocomus badius Cultured in Shrimp Processing Waste Medium.

ACE inhibitory dipeptides from Xerocomus badius fermented shrimp processing waste were isolated with ethanol, macroporous resin, chloroform, and Sephadex G-10 in sequence and identified by LC-MS/MS system coupled with electrospray ionization source. Molecular docking was performed for exploring the mechanism of their inhibitions. The results showed that the identified ACE inhibitory dipeptides were Cys-Cys and Cys-Arg with IC50 values of 4.37 ± 0.07 and 475.95 ± 0.11 μM, respectively. The difference between ACE inhibitor potency of Cys-Cys and Cys-Arg could be explained by results of molecular docking. Cys-Cys formed crucial coordination between carboxyl oxygen and Zn(II), hydrogen bonds with residues Ala354(O), Ala356(HN), and Tyr523(OH), and a bump with the residue His387(NE2) at the active site of ACE. There was no coordination, except for 5 hydrogen bonds (at residues His353, Ala354, Glu384, Glu403, and Arg522) and a bump (Glu411) between Cys-Arg and active site of ACE. These findings highlighted that Cys-Cys could be considered as a novel potent ACE inhibitor, and coordination between its carboxyl oxygen and Zn(II) played significant role in defining its ACE inhibitor potency.

Synthesis and Structural Analysis of Ammonium Orotate Hydrate Crystal

Single crystals of the title molecular salt, NH4 +. C5H3N2O4 ‒ . H2O, were isolated from the reaction of orotic acid, Dysprosium (III) Nitrate in a 1:1 molar ratio in 5 ml water 25% ammonia solution by hydrothermal reaction at 120oC for 3 days. In the crystal, the cations and anions are positioned alternately along an infinite helical chain and linked together through N---H...O hydrogen bonds between carboxylate oxygen and carbonyl oxygen of orotate ion. The water molecules of crystallization link the chains into (101) bilayers, with the cations organized in an isotactic manner.

Synthesis, Spectral Characterization and Thermal Behavior of Newly Derived La(III), Co(III) and Mn(II) Complexes with Schiff Base Derived from Methionine and Salicylaldehyde

Many metal complexes of Schiff base derived from different amino acids are widely employed as biologically active materials, especially as antibacterial agents. Three new metal [Co(III), Mn(II) and La(III)] complexes with the Schiff base (L) derived from salicylaldehyde and amino acid (methionine) were synthesized and investigated by using various physico-chemical techniques such as elemental analysis, FTIR, UV-visible spectroscopy, magnetic measurement, thermo gravimetric analysis (TGA) and X-ray powder diffraction (XRD) method. From spectral studies, it has been concluded that the synthesized ligand acts as a tetra-dentate molecule, coordinates metal through azomethine nitrogen, sulfur, phenolic oxygen and carboxylate oxygen. UV-visible spectrophotometry showed the characteristic absorption bands corresponding to a square planar geometry for La(III) and Mn(II) metal complexes and tetrahedral geometry for Co(III) complex. The XRD data demonstrated that the manganese and cobalt complexes were crystalline but the lanthanum complex was amorphous in nature. The empirical formula of the synthesized complexes based on analytical data were [Co(C12H13SNO3)]·(NO3), [La(C12H13SNO3)](Cl)(H2O) and [Mn (C12H13SNO3)].

Stability and Hydration/Dehydration Mechanisms of a Carboxylate-Containing Metal-Organic Framework

Metal-organic frameworks (MOFs) are promising functional compounds; however, they are known to be moisture sensitive. Here, we investigate the hydration and dehydration processes of the carboxylate-containing MOFs [Ni2(nic)4(H2O)]n (nic = nicotinic acid) and the mononuclear complex [Ni(nic)2(H2O)4], respectively. X-ray single crystal diffraction reveals that the hydrogen bonds between water and carboxylic oxygen play a key role in these processes. Molecular-level mechanisms of reversible hydration and dehydration are proposed, based on the competition between water and carboxylic oxygen for coordination with Ni. This study provides important information for future studies on the hydrolytic stability of MOFs in moisture.

Highly selective sensing of Fe3+ by an anionic metal-organic framework containing uncoordinated nitrogen and carboxylate oxygen sites.

Fast and highly selective detection of trace amounts of metal ions has become one of the most urgent issues concerning public security and living systems. However, developing a highly efficient fluorescent sensor for metal ions still remains a great challenge. Metal-organic frameworks (MOFs) are a promising class of porous fluorescent sensors towards ion detection. Herein, the anionic MOF FJI-C8 based on the π-conjugated aromatic ligand H6TDPAT (2,4,6-tris(3,5-dicarboxylphenylamino)-1,3,5-triazine) containing uncoordinated nitrogen and carboxylate oxygen atoms was chosen as highly efficient sensor for selective detection of Fe3+. Due to the strong interaction between Fe3+ and Lewis base sites (uncoordinated nitrogen and carboxylate oxygen atoms), the high overlap between the emission spectrum of the anionic FJI-C8 and the absorption spectrum of Fe3+, and the good overlap of the excitation spectrum of the host material FJI-C8 with the absorption spectrum of Fe3+, FJI-C8 exhibited a high sensitivity (0.0233 mM of Fe3+) and extra selectivity (Ksv = 8245 M-1) for the rapid detection (less than 30 s) of Fe3+ with low usage (0.04 mg mL-1 of FJI-C8 suspension). To the best of our knowledge, this is the first example of a luminescent MOF chemosensor based on a trefoil ligand with the highest density of uncoordinated N and carboxylate O atoms for the highly selective detection of Fe3+. It is also crucial to note that this is a first time detection of Fe3+ using both FJI-C8 suspension and solid after filtration, and the results indicate that the detection of Fe3+ using the FJI-C8 suspension is better. This study will pave the way for designing luminescent MOF chemosensors for the detection of Fe3+ ion.

Structural characterization of aluminium(iii) and iron(iii) complexes of coumarinic acid in aqueous solutions from combined experimental and theoretical investigations

The Al(iii) ion forms bidentate complexes involving a 6-membered ring by binding both the carboxyl oxygens of the ligand. In contrast, the Fe(iii) ion preferentially forms monodentate tetrahedral complexes.

In vitro digestion profile and calcium absorption studies of a sea cucumber ovum derived heptapeptide-calcium complex.

In this study, a novel calcium-binding heptapeptide (NDEELNK) that is released during the trypsin hydrolysis of sea cucumber ovum was identified by peptidomics. The calcium binding mode, in vitro digestion profile and calcium absorption of the NDEELNK-calcium complex were investigated. The NDEELNK peptide could spontaneously bind calcium with a 1 : 1 stoichiometry, and the calcium-binding site might involve the carboxyl oxygen and amino nitrogen atoms of two glutamic acid and one aspartic acid residues in the NDEELNK peptide. The NDEELNK-calcium complex underwent disaggregation and self-aggregation in a mesh of smaller size during simulated gastrointestinal digestion, clarified by dynamic light scattering and confocal laser-scanning microscopy. In addition, the NDEELNK-calcium complex could be conducive to calcium absorption across Caco-2 cell monolayers. The findings from this research suggest possible utilization of hydrolyzed peptides from sea cucumber ovum as dietary supplements to improve calcium absorption.

Synthesis, Structural Characterization, and Antibacterial Activity of Novel Erbium(III) Complex Containing Antimony.

The novel 3D edta-linked heterometallic complex [Sb2Er(edta)2(H2O)4]NO3·4H2O (H4edta = ethylenediaminetetraacetic acid) was synthesized and characterized by elemental analyses, single-crystal X-ray diffraction, powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and thermal analysis. The complex crystallizes in the monoclinic system with space group Pm. In the complex, each erbium(III) ion is connected with antimony(III) ions bridging by four carboxylic oxygen atoms, and in each [Sb(edta)]− anion, the antimony(III) ion is hexacoordinated by two nitrogen atoms and four oxygen atoms from the edta4− ions, together with a lone electron pair at the equatorial position. The erbium(III) ion is octacoordinated by four oxygen atoms from four different edta4− ions and four oxygen atoms from the coordinated water molecules. The carboxylate bridges between antimony and erbium atoms form a planar array, parallel to the (1 0 0) plane. There is an obvious weak interaction between antimony atom and oxygen atom of the carboxyl group from the adjacent layer. The degradation of the complex proceeds in several steps and the water molecules and ligands are successively emitted, and the residues of the thermal decomposition are antimonous oxide and erbium(III) oxide. The complex was evaluated for its antimicrobial activities by agar diffusion method, and it has good activities against the test bacterial organisms.

Quantum chemical calculation of imidization mechanism of polyamic acid

In this paper, the imidization mechanism of polyamic acid to prepare polyimide has been studied by the density functional theory (DFT) method. Our results have shown that the imidization would proceed via two different reaction paths. The activation barrier via hydrogen transfer to closer carboxylate oxygen in the COOH is 220.35 kJ/mol while the activation barrier via hydrogen transfer to hydroxyl oxygen in the COOH is 220.70 kJ/mol. Both reaction paths would run in the actual thermal imidization process with closer high activation barriers. The high energy barrier interpreted the fact that additional energy or catalyst is usually needed during imidization. Moreover, the intrinsic imidization mechanism indicated is critical to further improve the imidization process.

Towards the systematic crystallisation of molecular ionic cocrystals: insights from computed crystal form landscapes.

The underlying molecular and crystal properties affecting the crystallisation of ionic cocrystals (ICCs) with the general formula A-B+N (A- = anion, B+ = cation and N = neutral acid molecule; 1 : 1 : 1 stoichiometry) are reported for a limited set of known crystal structures determined following the cocrystallisation of either 4-aminopyridine (which forms salts) or 4-dimethylaminopyridine (which forms salts and ICCs) with the same set of monoprotic acids with a single hydroxy or halogen substitution at the ortho or para position. Periodic density functional theory calculations (PBE + D2) on the energetic driving force for ICC crystallisation for a set of known crystal structures with well characterised acid, salt and ICC structures show that all but 1 of the 7 experimental ICC structures surveyed were more stable than the sum of their component salt and acid structures with 4 displaying relative stabilities (ΔEICC) ranging from 2.47-8.02 kJ mol-1. The majority of molecular ICCs that are more stable with respect to their component salt and acid structures display the formation of discrete intermolecular O-HacidOanion hydrogen bonds with the D11(2) graph set between the carboxylic acid OH donor and the carboxylate oxygen acceptor of the anion. Computed crystal form landscapes for model 1 : 1 salts derived from acid-base pairs (involving 4-dimethylaminopyridine) known to form molecular ICCs show that on average the most stable predicted polymorphs of the 1 : 1 salts have efficient packing of the ions with packing coefficients in the range 65-80% and this is comparable to the packing coefficients of the most stable predicted polymorphs of 1 : 1 salts (involving 4-aminopyridine) that have no ICCs reported. This suggests that the cocrystallisation of equimolar amounts of the 1 : 1 salt and the acid to form a 1 : 1 : 1 molecular ICC is a complicated phenomenon that cannot be explained on the basis of inefficiencies in the crystal packing of the salt ions.

Carboxylic Acid Group-Induced Oxygen Vacancy Migration on an Anatase (101) Surface.

Dye-sensitized solar cells (DSSCs) have aroused intensive interest for the replacement of conventional crystalline silicon solar cells. Through carboxylic acid groups, the dyes attach to the TiO2 anatase (101) surface, on which the subsurface oxygen vacancies (Vosubs) are predominant. The performance of DSSCs can be affected by the presence and positions of oxygen vacancies (Vos). By applying density functional theory calculations, we found that the adsorption of a carboxylic acid group-decorated dye molecule reverses the relative stability between the surface oxygen vacancy (Vosurf) and Vosub on the anatase (101) surface, which facilitates the migration of the Vo from the subsurface to the surface by overcoming an energy barrier of less than 0.16 eV, which is significantly lower than the 1.01 eV energy barrier on the clean surface. Further, ab initio molecular dynamics simulations indicate that the Vosub can easily migrate to the surface at room temperature. This dynamic interplay between the Vo of the anatase (101) surface and the carboxylic acid group would be important for future studies concerning the stability and photovoltaic efficiency of the solar cells.

Oxygen‐Rich Carbon Quantum Dots as Catalysts for Selective Oxidation of Amines and Alcohols

AbstractMetal‐free carbocatalysis has been widely utilized for aerobic oxidative reactions. Here, we report that oxygen‐rich carbon quantum dots (O‐CQDs) demonstrate a catalytic performance superior to graphene oxide, if used as a metal‐free nanocatalyst for the direct transformation of amines and alcohols, under mild and solvent‐free conditions. O‐CQDs show a yield of 75 % for the oxidative coupling of amine to imine (with 5 wt % catalyst loading) and a conversion of 3.8 % for benzyl alcohol (with 2 wt % catalyst loading). The catalytic activities of thermally treated O‐CQDs are further improved for benzylamine, for example, indicated by a yield of up to 98 % with 4 wt % catalyst loading. In addition, O‐CQDs show a photoenhanced catalytic ability of amine (98 % yield with 5 wt % catalyst loading for 6 h reaction). Characterizations and simulations show that numerous carboxyl oxygen functional groups and unpaired electrons at the edge sites of O‐CQDs are likely involved in the aerobic oxidation of amines.

A Novel Coordination Polymer Constructed by Hetero−Metal Ions and 2,3-Pyridine Dicarboxylic Acid: Synthesis and Structure of [NiNa2(PDC)2(μ-H2O)(H2O)2] n

A novel coordination polymer containing hetero-metal ions, [NiNa2(PDC)2(μ-H2O)(H2O)2] n , where PDC is 2,3-pyridine dicarboxylate ion, has been synthesized. In the structure, the PDC ligand chelates and bridges two Ni(II) and two Na(I) centers. Two kinds of metal centers are connected by μ4-PDC and μ2-H2O to form 2D coordination layers. Hydrogen bonds between coordination water molecules and carboxylate oxygen atoms further link these 2D coordination layers to form 3D supramolecular network.

A new Cu(II) three-dimensional network with 4,4′-oxybis benzoic acid: structural diversity, EPR, and magnetism

The copper derivative {[Cu4(oba)4(H2O)4]∙H2O}n (1) has been hydro(solvo)thermally synthesized by combining flexible 4,4′-oxybis benzoic acid (oba) and divalent copper nitrate. As a result of the potential coordination modes of carboxylate oxygens from the oba ligand, the aforementioned complex leads to the formation of an interesting 3D framework, as evidenced by single-crystal X-ray diffractometry. Concerning the topology in 1, the dimers [Cu2C4O8] are nodes of a 5-fold 4-connected uninodal net of the type lvt, with point symbol {42.84} and vertex symbol [4.4.84.84.88.88]. The encapsulation of the copper coordination polymer displays a moderate luminescent property. On temperature-dependent magnetic study, it reveals that the magnetic behaviour of 1 can be associated to a strong antiferromagnetic coupling between the two Cu(II) ions.

Neutral Luminescent Metal-Organic Frameworks: Structural Diversification, Photophysical Properties, and Sensing Applications.

Utilizing flexible bis(tridentate)polypyridyl ligands, the two new luminescent 2D metal organic frameworks {Zn2(tpbn)(2,6-NDC)2}n (1) and {[Zn2(tphn)(2,6-NDC)2]·4H2O}n (2), where tpbn = N,N',N″,N‴-tetrakis(2-pyridylmethyl)-1,4-diaminobutane, tphn = N,N',N″,N‴-tetrakis(2-pyridylmethyl)-1,6-diaminohexane, and 2,6-H2NDC = 2,6-naphthalenedicarboxylic acid, have been isolated in good yields under solvothermal conditions. Their solid-state molecular structures have been determined by single-crystal X-ray diffractometry. Both 1 and 2 have pentacoordinated Zn(II) centers with an N3O2 environment from three nitrogen atoms of the tpbn or tphn ligand and two carboxylate oxygen atoms from two different 2,6-NDC linkers. However, the binding modes of the tridentate part of polypyridyl ligands to the Zn(II) center are different in 1 and 2-meridional (tpbn) vs facial (tphn) due to an increase (1.5 times) in the methylene chain length. Thus, the binding mode of 2,6-NDC to the Zn(II) center differs: bis(monodentate) syn-anti in 1 and bis(monodentate) syn-syn in 2. This difference in binding modes of the components has a profound effect on the conformation of the six-membered ring (metal centers are considered as the vertices in it) within the 2D framework: honeycomb vs chair form for 1 and 2, respectively. In addition to further characterization by elemental analysis and UV-vis and FT-IR spectroscopy, their framework stabilities in water and thermal properties have been studied by powder X-ray diffraction and thermogravimetric analysis, respectively. On the basis of thermodiffractometry, 1 and 2 retain their crystallinity and overall structure up to 350 and 325 °C, respectively. Their luminescent properties have been utilized to demonstrate sensing of various solvents as well as nitro-aromatic compounds in water, which correlate well with their structural differences. Through the spectral overlap, lifetime measurements, and nature of the Stern-Volmer plots, the fluorescence quenching pathway for the nitro-analytes, particularly 2,4,6-trinitrophenol (TNP), is established for 1 and 2. Their recyclability and stability after sensing experiments are found to be excellent.

Determination of Protonation Constants of O-Phospho-l-serine in Aqueous Solution: Potentiometry, Microcalorimetry, NMR Spectroscopy and Quantum Chemical Calculations

O-Phospho-l-serine is one of the naturally occurring phosphorylated amino acids, having important pharmacological activity and bioactivity. The protonation constants of O-phospho-l-serine were determined by means of potentiometric titrations at 25 °C and ionic strength of 0.5 mol·L−1 (NaCl). The heat effects of the protonation reaction of the O-phospho-l-serine were measured by direct calorimetry. NMR spectroscopy has demonstrated that the first protonation site occurs at the nitrogen atom in the amino group, followed by one of the oxygen atoms in the phosphono group, and finally the carboxyl oxygen atom. This trend is in good agreement with the enthalpy of protonation and quantum chemical calculations. These data will help to predict the speciation of O-phospho-l-serine in physiological systems.

Two Coordination Polymers Constructed from Pentanuclear Zinc Clusters with Triazolate and Benzenecarboxylate Ligands: Selective Gas Adsorption

Reactions of Zn(NO3)2·6H2O with 1,2,4-triazole (Htrz) and 1,3,5-benzenetricarboxylic acid (H3BTC) or 5-sulfoisophthalic acid (5-H3SIP) afforded two coordination polymers, {[Zn5(μ3-OH)2(trz)2(BTC)2(DMF)2]·x(solvent)}n (1) and {[Zn7(trz)8(5-SIP)2(H2O)4]·4(H2O)}n (2). Compound 1 has pentanuclear [Zn5(μ3-OH)2] clusters, which are linked by the triazolate ligands to give a 2D layer. The 2D layer is further bridged by BTC3− ligands to form a 3D framework. The 3D framework of 1 has 1D channels filled by solvent molecules. Desolvated 1 shows a moderate CO2 uptake and high CO2/CH4 and CO2/N2 adsorption selectivities due to its carboxylate oxygen decorated pore environment. Compound 2 contains a rare 3D zinc-triazolate framework constructed from a pentanuclear [Zn5(trz)8] cluster wherein the five zinc atoms are arranged linearly. The 3D zinc-triazolate substructure has 1D open channels filled by 5-SIP3− ligands, which interact with the zinc-triazolate framework through Zn–O bonds, leading to a non-porous 3D structure of 2. Introduction of BTC3− into the zinc-triazolate system gave the porous structure of 1. While a variation of BTC3−, 5-SIP3− was introduced into the zinc-triazolate system yielding a non-porous structure of 2, demonstrating that the secondary ligands play an important role in the formation of the final structures.

First Mononuclear Lanthanide Imidazolium Carboxylates

The synthesis and structural analysis of six new lanthanide imidazolium carboxylates are discussed. The first mononuclear lanthanide imidazolium carboxylate salts, [{(L)2M}3+{NO3−}3], M=Sm (1), Gd (2), Dy (3) and Y (4), were synthesized from the reaction between zwitterionic tris-imidazolium carboxylate and corresponding metal nitrate salts. The presence of monodentately coordinating carboxylate groups in 1–4 are confirmed by FT-IR spectra. The isostructural salts 1–4 are discrete tricationic monomer. To the best of our knowledge, the ionic salts 1–4 are the first structurally characterized mononuclear lanthanide imidazole carboxylates. The coordination environment of M(III) is fulfilled by six carboxylate oxygen atoms of ligands in distorted octahedron geometry.

An Exploration of the Calcium-Binding Mode of Egg White Peptide, Asp-His-Thr-Lys-Glu, and In Vitro Calcium Absorption Studies of Peptide-Calcium Complex.

The binding mode between the pentapeptide (DHTKE) from egg white hydrolysates and calcium ions was elucidated upon its structural and thermodynamics characteristics. The present study demonstrated that the DHTKE peptide could spontaneously bind calcium with a 1:1 stoichiometry, and that the calcium-binding site corresponded to the carboxyl oxygen, amino nitrogen, and imidazole nitrogen atoms of the DHTKE peptide. Moreover, the effect of the DHTKE-calcium complex on improving the calcium absorption was investigated in vitro using Caco-2 cells. Results showed that the DHTKE-calcium complex could facilitate the calcium influx into the cytosol and further improve calcium absorption across Caco-2 cell monolayers by more than 7 times when compared to calcium-free control. This study facilitates the understanding about the binding mechanism between peptides and calcium ions as well as suggests a potential application of egg white peptides as nutraceuticals to improve calcium absorption.