Presence Of Azide Research Articles

Synthesis, Molecular, and Supramolecular Structures of Two Azide-Bridged Cd(II) and Cu(II) Coordination Polymers

Two 1D coordination polymers were synthesized by reaction of two ligands, 2-amino-4-picoline (2A4Pic) and quinoline-6-carboxylic acid (Qu-6-COOH) with two metal (II) nitrate (M = Cd and Cu) in the presence of azide as a linker. The synthesized metal complexes [Cd(2A4Pic)2(N3)2]n; (1) and [Cu(Qu-6-COO)(N3)(H2O)]n; (2) were isolated in single crystals and their X-ray structures revealed a 1D polymeric structure. Due to symmetry considerations, the asymmetric formula is half a [Cd(2A4Pic)2(N3)2] unit for 1 and one [Cu(Qu-6-COO)(N3)(H2O)] unit for 2. In complex 1, the Cd(II) is hexa-coordinated with two 2A4Pic molecules and four μ(1,1) azide units. Hence, the CdN6 coordination environment has a slightly distorted octahedral geometry. In 2, the Cu(II) is hexa-coordinated with three different ligands (Qu-6-COO¯, H2O and μ(1,1) N3¯) where all are connectors between the crystallographically related Cu(II) sites. Additionally, complex 2 distorted CuN2O4 octahedral geometry. In both complexes, the polymer arrays are connected by N…H hydrogen bonds and π–π stacking interactions. Based on Hirshfeld analysis, the percentages of N…H contacts are 43.1 and 27.4% for 1 and 2, respectively, while %C...C are 5.6 and 9.3%, respectively. Analysis of Cu-N, Cu-O, and Cd-N bonds using DFT calculations showed predominantly closed-shell coordination interactions with little covalent characters. Additionally, the negatively charged ligand groups were found to compensate the positive charge of the central metal ion to a larger extent than the electrically neutral ligands.

Synthesis, Supramolecular Structural Investigations of Co(II) and Cu(II) Azido Complexes with Pyridine-Type Ligands

Two new Co(II) and Cu(II) azido complexes with 4-picoline (4-Pic) and pyridine-2-carboxaldoxime (HAld) were synthesized by self-assembly of the organic ligand and the M(II) nitrate in the presence of azide as a co-ligand. Their structures were determined to be [Co(4-Pic)4(H2O)(N3)]NO3*H2O*4-Pic (1) and [Cu(HAld)(Ald)(N3)] (2) using X-ray single crystal diffraction. In complex 1, the coordination geometry is a slightly distorted octahedron with a water molecule and azide ion located trans to one another. On the other hand, complex 2 has a distorted square pyramid CuN5 coordination sphere with N-atoms of the organic ligand as a basal plane and azide ion as apical. All types of intermolecular contacts and their contributions in the molecular packing were analyzed using Hirshfeld analysis. The intermolecular contacts, H…H (53.9%), O…H (14.1%), N…H (11.0%) and H…C (18.8%) in 1, and H…H (27.4%), N…H (27.7%), O…H (14.7%) and H…C (13.6%) in 2 have the largest contributions. Of all the contacts, the O…H, N…H and C…C interactions in 2 and the O…H, N…H and H…C in 1 are apparently shorter than the van der Waals radii sum of the interacting atoms. Atoms in molecules (AIM) topological parameters explained the lower symmetry of the coordinated azide in 1 than 2.

Visible-Light-Mediated Oxidative Debenzylation Enables the Use of Benzyl Ethers as Temporary Protecting Groups.

The cleavage of benzyl ethers by catalytic hydrogenolysis or Birch reduction suffers from poor functional group compatibility and limits their use as a protecting group. The visible-light-mediated debenzylation disclosed here renders benzyl ethers temporary protective groups, enabling new orthogonal protection strategies. Using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as a stoichiometric or catalytic photooxidant, benzyl ethers can be cleaved in the presence of azides, alkenes, and alkynes. The reaction time can be reduced from hours to minutes in continuous flow.

A bile acid-based pyridino-triazole ligand for Cu(I)-stabilization and its application in Cu(I) catalyzed click reactions

A bile acid based pyridino-triazole ligand to stabilize Cu(I) state has been developed. The ligand was found to catalyze click reactions of a number of alkynes and azides in presence of Cu(CH3CN)4.BF4 at very low catalyst loading and under milder reaction conditions.

Thermoresponsive Nanogels of Modified Poly((di(ethylene glycol) methyl ether methacrylate)-co-(2-aminoethyl methacrylate))s

A series of copolymers of di(ethylene glycol) methyl ether methacrylate (D) and 2-aminoethyl methacrylate (A) (P(D-co-A)) with variable ratios of comonomers were synthesized using atom transfer radical polymerization. Then, the amino groups of obtained copolymers were modified to clickable azide or prop-2-yn-1-yl carbamate groups. A thermoresponsive copolymers were obtained with the value of cloud point temperature (TCP) dependent on the type and number of functional groups in the copolymer and on the concentration of solutions. For P(D-co-A) copolymers, the TCP increased with increasing content of 2-aminoethyl methacrylate comonomer. The presence of azide and prop-2-yn-1-yl carbamate groups caused the changes of TCP of modified copolymers. All studied copolymers in dilute aqueous solutions aggregated above TCP to nanoparticles with sizes dependent on the solution concentration, heating procedures, and types and numbers of functional groups present in a copolymer chain. The presence of hydrophilic elements in the chain and the increase in the copolymer concentration led to the enlargement of the particle sizes. Aggregates were crosslinked using click reaction between an azide and prop-2-yn-1-yl carbamate groups that led to stable thermoresponsive nanogels. A systematic study of the behavior of copolymers allowed the determination of the chains useful for possible application in drug delivery.

Generation of Singlet Molecular Oxygen by Lipid Hydroperoxides and Nitronium Ion†.

Singlet molecular oxygen is a reactive species involved in biological oxidative processes. The major cellular targets of singlet molecular oxygen are unsaturated fatty acids in the membrane, as well as nucleic acids and proteins. The aim of this study was to investigate whether lipids and commercial hydroperoxides generate singlet molecular oxygen, in presence of nitronium and activated nitronium ion. For this purpose, monomol light emitted in the near-infrared region (λ=1270nm) was used to monitor singlet molecular oxygen decay in different solvents, with different hydroperoxides and in the presence of azide. Direct measurements of the singlet molecular oxygen spectrum at 1270nm recorded during the reaction between lipids and commercial hydroperoxides and nitronium ions unequivocally demonstrated the formation of this excited species.

Synthesis of a Pseudodisaccharide Suitable for Synthesis of Ring I Modified 4,5-2-Deoxystreptamine Type Aminoglycoside Antibiotics.

To facilitate the synthesis of paromomycin and/or neomycin analogues, we describe a cleavage of ring I from paromomycin that proceeds in the presence of azides and affords a glycosyl acceptor for the installation of a modified ring I. A paromomycin 4',6'-diol is oxidized by the Dess-Martin periodinane followed by m-chloroperoxybenzoic acid. Base treatment then affords a protected pseudodisaccharide, which functions as a glycosyl acceptor. The method should also apply to the cleavage of pyranosyl 4,6-diols from oligosaccharides and glycoconjugates.

Anion Binding and Oxidative Modification at the Molybdenum Cofactor of Formate Dehydrogenase from Rhodobacter capsulatus Studied by X-ray Absorption Spectroscopy.

Formate dehydrogenase (FDH) enzymes are versatile catalysts for CO2 conversion. The FDH from Rhodobacter capsulatus contains a molybdenum cofactor with the dithiolene functions of two pyranopterin guanine dinucleotide molecules, a conserved cysteine, and a sulfido group bound at Mo(VI). In this study, we focused on metal oxidation state and coordination changes in response to exposure to O2, inhibitory anions, and redox agents using X-ray absorption spectroscopy (XAS) at the Mo K-edge. Differences in the oxidative modification of the bis-molybdopterin guanine dinucleotide (bis-MGD) cofactor relative to samples prepared aerobically without inhibitor, such as variations in the relative numbers of sulfido (Mo═S) and oxo (Mo═O) bonds, were observed in the presence of azide (N3-) or cyanate (OCN-). Azide provided best protection against O2, resulting in a quantitatively sulfurated cofactor with a displaced cysteine ligand and optimized formate oxidation activity. Replacement of the cysteine ligand by a formate (HCO2-) ligand at the molybdenum in active enzyme is compatible with our XAS data. Cyanide (CN-) inactivated the enzyme by replacing the sulfido ligand at Mo(VI) with an oxo ligand. Evidence that the sulfido group may become protonated upon molybdenum reduction was obtained. Our results emphasize the role of coordination flexibility at the molybdenum center during inhibitory and catalytic processes of FDH enzymes.

Chemical rescue of H+ delivery in proton transfer mutants of reaction center of photosynthetic bacteria

In the native and most mutant reaction centers of bacterial photosynthesis, the electron transfer is coupled to proton transfer and is rate limiting for the second reduction of QB− → QBH2. In the presence of divalent metal ions (e.g. Cd2+) or in some (“proton transfer”) mutants (L210DN/M17DN or L213DN), the proton delivery to QB− is made rate limiting and the properties of the proton pathway can be directly examined. We found that small weak acids and buffers in large concentrations (up to 1 M) were able to rescue the severely impaired proton transfer capability differently depending on the location of the defects: lesions at the protein surface (proton gate H126H/H128H + Cd2+), beneath the surface (M17DN + Cd2+, L210DN/M17DN) or deep inside the protein (L213DN) could be completely, partially or to very small extent recovered, respectively. Small zwitterionic acids (azide/hydrazoic acid) and buffers (tricine) proved to be highly effective rescuers consistent with their enhanced binding affinity and access to any of the proton acceptors (including QB− itself) in the pathway. As a consequence, back titration of the protons at L212Glu could be observed as a pH-dependence of the rate constant of the charge recombination in the presence of azide or formate. Model calculations support the collective influence of the acid cluster on the change of the protonation states upon extension of the cluster with the bound small acid. In proton transfer mutants, the rescuing agents decreased the free energy of activation together with their enthalpic and entropic components. This is in agreement with the hypothesis that they function as protein-penetrating protonophores delivering protons into the chain and select dominating paths out of many alternate routes. We estimate that the proton delivery will be accelerated in one pathway out of 100–200 alternate pathways. The implications for design of the chemical recovery of impaired intra-protein proton transfer pathways in proton transfer mutants are discussed.

Multicomponent click reaction catalyzed by organic surfactant-free copper sulfide (sf-CuS) nano/micro flowers

The azide-alkyne cycloaddition (Huisgen reaction) is one of the most powerful and widely used copper-mediated reactions. In many such reactions, use of metal or metal oxide nanoparticles as the catalyst is more appealing because of the increased catalytic activity attributed to the large surface to volume ratio. However, the nano/micro particles are synthesized often in the presence of long chain organic molecules as capping or stabilizing agents. These organic molecules cover the active centers and restrict or reduce their catalytic activity. Therefore, we have synthesized the copper sulfide (sf-CuS) nano/micro particles without having organic surfactant molecules as the capping agent. These particles with a flower-like architecture (micro flowers, mf) were obtained readily under the supersaturated condition at room temperature. In these particles, the surface was freely available for adsorption and desorption reactions. When utilized as a catalyst in multicomponent cycloaddition reactions, the sf-CuS mf exhibited excellent catalytic activity compared with some other nanoparticles with surfactants. This sf-CuS mf catalyzed the one-pot synthesis of 1,2,3-triazole and β-hydroxy-1,2,3-triazole effectively from a variety of benzyl bromide derivatives epoxides respectively. Both these reactions proceeded in the presence of azide and phenylacetylene in the water at room temperature. The catalyst was reusable, and there was no catalyst leaching observed during reactions. Synthesis of β-hydroxy triazoles and 1,2,3-triazoles under exceptionally mild conditions with high yields proved the sf-CuS mf as the catalyst as a robust and recyclable catalyst.

Synthesis And Characterization of Two Types of Heterogeneous Rings Derived from Sulfamethoxazole and Evaluation Their Bacterial Activity

In this research include preparation three steps of the new derivatives of Sulfamethoxazole drug, the first step involved converting Sulfamethoxazole to Schiff’s bases (1), by reaction Sulfamethoxazole with different specific aldehydes in ethanol, presence in glacial acetic acid. While the second step involved reaction Schiff’s bases (1) with sodium azide in presence of Benzene (dry) to give new tetrazole derivatives (2). Finally, The third reaction requires synthesis of thiazolidine (3) by reaction of Schiff’s bases (1) with 2-mercaptoacetic acid. The prepared compounds were characterized by physical properties, and somewhat of them by IR, 1H-NMR spectroscopy, and study biologic efficacy against two types of bacteria.

Three-component solvent-free synthesis of 5-substituted-1H-tetrazoles catalyzed by unmodified nanomagnetite with microwave irradiation or conventional heating

A convenient, rapid, and highly efficient procedure for synthesis of 5-substituted-1H-tetrazoles was developed via multicomponent domino Knoevenagel condensation/1,3-dipolar cycloaddition reaction between aromatic aldehydes, malononitrile, and sodium azide in presence of Fe3O4 magnetic nanoparticles, using microwave irradiation and conventional heating, under solvent-free conditions. The procedure is efficient due to the low cost and nontoxicity of the catalyst, elimination of volatile and toxic solvents, very short reaction time, excellent product yield, easy methodology, and simple workup. The magnetite catalyst was recycled using an external magnet and could be reused in at least five consecutive runs, delivering high product yield. We illustrate that green, efficient, and recoverable Fe3O4 magnetic nanoparticles can catalyze Knoevenagel condensation/1,3-dipolar cycloaddition of aromatic aldehydes, malononitrile, and NaN3 to synthesize 5-substituted-1H-tetrazoles using microwave irradiation and conventional heating.

2-Iodo benzoic acid: An unconventional precursor for the one pot multi-component synthesis of quinoxaline using organo Cu (II) catalyst

This is the first reported, unconventional, efficient strategy for the synthesis of quinoxaline from 2 to iodo benzoic acid and sodium azide in presence of organo Cu (II) catalyst. Herein, a very simple, versatile one pot multi-component protocol for the synthesis of biologically active compound, quinoxaline has been described via Schmidt reaction and the nucleophilic substitution reaction. The isolated compounds were characterized by 1H NMR, 13C NMR. Our reported organo catalyst was characterized by single crystal XRD, SEM.

One pot three-component synthesis of 5-substituted 1H-tetrazole from aldehyde

A versatile, robust and efficient strategy for the synthesis of vast range of highly functionalized 5-substituted 1H-tetrazole derivatives by using one pot three-component synthesis from various aldehydes, hydroxylamine hydrochloride and sodium azide in presence of a catalytic amount of ceric ammonium sulphate, a non toxic, easily available, inexpensive, unexplored and reusable catalyst is reported. This one-pot synthesis has several advantages such as mild reaction conditions, shorter reaction time, low catalyst loading, good to moderate yields and functional group tolerance making this methodology practically feasible. The synthesized compounds were characterized by 1H NMR, 13C NMR and HRMS.

Zinc‐Mediated Efficient and Selective Reduction of Carbonyl Compounds

We herein describe for the first time that an optimized combination of Zn and NH4Cl can be used for the selective reduction of aldehydes and ketones to the corresponding alcohols. The aldehyde and keto groups are selectively reduced in the presence of azide, cyano, epoxy, ester, and carbon–carbon double‐bond functional groups. A broad functional‐group compatibility, chemoselective reduction of aldehydes in the presence of ketones, and selective reduction of isatins at the C3 carbonyl group are the highlights of the present method.

Synthesis, crystal structure and antibacterial activity of azido complexes of cobalt(III) containing heteroaromatic Schiff bases

Three new Schiff base complexes of cobalt(III) viz. [Co(L1)(N3)]2 (1), [Co(L2)2(N3)2]NO3 (2) and [Co(L3)2(N3)2]ClO4 (3), where H2L1=N,N′-propane-1,3-diylbis[1-(pyrrol-2-yl)methanimine], L2=1-[(thiophen-2-ylmethylidene)amino]propan-2-amine and L3=1-[(3-methylthiophen-2-ylmethylidene)amino]propan-2-amine, have been prepared and characterized. The syntheses have been achieved by the reaction of cobalt(II) nitrate or perchlorate with the tetradentate Schiff base (H2L1) or the bidentate ligands L2 and L3 in presence of azide. All the complexes 1–3 have been characterized by microanalytical, spectroscopic, single crystal X-ray diffraction and other physicochemical studies. Structural studies reveal that all the complexes contain CoN6 chromophore in which the central Co(III) ions adopt distorted octahedral geometry. While 1 is a binuclear end-on bis(μ-azido) complex, both of 2 and 3 are mononuclear with two terminal azide ions disposed in cis positions. Structural studies reveal that weak intermolecular H-bonding or π…π interactions are operative to bind the complex units or the anions in the solid state. The antibacterial activity of all the complexes and their constituent Schiff base ligands has been tested against some Gram(+) and Gram(−) bacteria.

Role of oxygen and DOM in sunlight induced photodegradation of organophosphorous flame retardants in river water

The wide use of organophosphorous flame retardants (OPFR) and plasticizers causes a continuous release of large quantities into natural waters. One of the main contributors to micropollutants depletion in surface water is sunlight induced phototransformations. This study aims to elucidate whether alkyl, chloroalkyl and aryl organophosphorus flame retardants undergo phototransformations in river water. To perform the experiments, nine OPFR were subjected to natural sunlight, Xe lamp (simulated sunlight) and UV-C irradiations in ultra-pure Milli-Q water, Milli-Q water with humic acid and river water. Experiments demonstrated that OPFR achieve an important degree of photodegradation noticeable at long irradiation time, although direct photolysis did not account as the main photodegration mechanism. Results indicated that sunlight absorbing OPFR exhibited photosensitizing activity. The presence of azide in ultra- pure water inhibited some OPFR photodegration by singlet oxygen (1O2) scavenging, and the absence of dissolved oxygen significantly depleted most of OPFR removal. In the conditions studied, humic acid inhibited OPFR phototransformations, while river water enhanced their removal. Results from this study point out the need to further investigate the role of some OPFR as photosensitizers, which are important for fate and ecological risk assessment of flame retardants and other micropollutants in water.

Divergent ynamide reactivity in the presence of azides - an experimental and computational study.

An unusually divergent reactivity of ynamides in the presence of azides is reported. This new keteniminium-based methodology, which only requires triflic acid as promoter, facilitates access to β-enaminoamides and biologically important oxazolidine-2,4-diones in a highly selective, divergent manner that is fully controllable by the present azide. A mechanistic rationale for these divergent reaction pathways is delineated and supported by extensive density functional theory analyses, as well as selected mechanistic experiments.

Synthesis, characterization and rheology of tetrafunctional glycidyl azide polymer vis-à-vis difunctional GAP

Glycidyl azide polymer (GAP) with hydroxyl functionality of two is a potential energetic binder for explosive and propellant formulations. To improve its curing behavior and mechanical properties, the synthesis of multifunctional GAP has been attempted. In the present paper, a tetrafunctional GAP (t-GAP) was synthesized by epoxidation of linear difunctional polyepichlorohydrin (PECH-diol) having molecular weight ~1700 and then epoxy ring opening in the presence of water to obtain tetrafunctional PECH (t-PECH) followed by azidation with sodium azide in presence of aprotic solvent. Both t-PECH and t-GAP were characterized by FTIR, NMR, molecular weight, viscosity and hydroxyl value. The viscosity built up and curing reaction with different curator was monitored by rheometer. Viscosity of t-GAP was found to be higher as compared to difunctional GAP. The decomposition pattern of t-GAP, as determined by DSC, was similar to GAP-diol with exothermic decomposition at 254 °C. Clean and void-free curing of t-GAP was achieved using IPDI only as a curator and the curing profile was recorded on rheometer. The curing of t-GAP has been compared with GAP-diol which was cured with mixture of IPDI and triisocyanate (Desmedour N-100). It was observed that t-GAP gave clean and void-free curing with single isocyanate, where as difunctional GAP did not cure with single isocyanate without additive. The mechanical properties for both the cured samples were determined and compared. The t-GAP showed almost fourfold increase in tensile strength when compared with difunctional GAP cured with mixed isocyanate.

Ligand Binding to Chlorite Dismutase from Magnetospirillum sp.

Chlorite dismutase (Cld) catalyzes the reduction of chlorite to chloride and dioxygen. Here, the ligand binding to Cld of Magnetospirillum sp. (MaCld) is investigated with X-ray crystallography and electron paramagnetic resonance (EPR). EPR reveals a large heterogeneity in the structure of wild-type MaCld, showing a variety of low- and high-spin ferric heme forms. Addition of an axial ligand, such as azide or imidazole, removes this heterogeneity almost entirely. This is in line with the two high resolution crystal structures of MaCld obtained in the presence of azide and thiocyanate that show the coordination of the ligands to the heme iron. The crystal structure of the MaCld-azide complex reveals a single well-defined orientation of the azide molecule in the heme pocket. EPR shows, however, a pH-dependent heme structure, probably due to acid-base transitions of the surrounding amino-acid residues stabilizing azide. For the azide and imidazole complex of MaCld, the hyperfine and nuclear quadrupole interactions with the close-by (14)N and (1)H nuclei are determined using pulsed EPR. These values are compared to the corresponding data for the low-spin forms observed in the ferric wild-type MaCld and to existing EPR data on azide and imidazole complexes of other heme proteins.