Imidazole Nitrogen Research Articles

Metal Imidazole-Modified Covalent Organic Frameworks as Electrocatalysts for Alkaline Oxygen Evolution Reaction

Since the product contains no carbon-based substances and can be driven by non-carbon-based electricity, electrocatalytic water splitting is considered to be among the most effective strategies for alleviating the energy crisis and environmental pollution. This process helps lower greenhouse gas emissions while also supporting the shift toward renewable energy sources. The anodic oxygen evolution reaction (OER) involves a more complex multi-electron transfer process, which is the principal limiting factor in overall water splitting. Extensive research has demonstrated that the controlled design of effective electrocatalysts can address this limitation. In this study, a previously unreported covalent organic framework material (COF-IM) was synthesized via a post-synthetic modification strategy. Notably, COF-IM contains imidazole nitrogen metal active sites. Transition metal-coordinated COF-IM@Co can function as a highly effective electrocatalyst, exhibiting a lower overpotential (403.8 mV@10 mA cm−2) in alkaline electrolytes, thereby highlighting its potential for practical applications in energy conversion technologies. This study offers new perspectives on the design and synthesis of COFs, while also making substantial contributions to the advancement and application of OER electrocatalysts.

Silver(I) and gold(III) complexes with miconazole: The influence of the metal ion on the antimicrobial activity of the coordinated azole

To develop a new antimicrobial agent, we used the clinically approved antifungal azole, miconazole (mcz), as a ligand for the synthesis of silver(I) and gold(III) complexes. The new complexes [Ag(NO3-O)(mcz-N)2] (1) and [AuCl3(mcz-N)] (2) were synthesized and characterized by 1H NMR, IR and UV–Vis spectroscopy and mass spectrometry, while the crystal structure of 1 was determined by single-crystal X-ray diffraction analysis. From the results obtained, it can be concluded that in both complexes, mcz is monodentately coordinated to the silver(I) and gold(III) ions through the imidazole nitrogen atom N3. In the solid state, complex 1 contains two mcz ligands and monodentately coordinated nitrate in the third position, while in the case of 2 gold(III) ion is coordinated by one mcz and three chlorido ligands, resulting in the expected square-planar arrangement around the metal center. DFT and TDDFT calculations were employed to elucidate the electronic structures and thermodynamic stability of the synthesized complexes in solution to complement the experimental findings. The coordination of mcz to silver(I) and gold(III) ions leads to an enhancement of its activity against Gram-negative Escherichia coli and Pseudomonas aeruginosa strains, while against the panel of Staphylococcus aureus and Candida species, only 2 shows improved activity compared to mcz. Both complexes 1 and 2 were tested in vitro for their antimycobacterial activity against the strain Mycobacterium tuberculosis H37Rv and showed good growth inhibition with minimum inhibitory concentration (MIC) values of 3.12 and 8.69 μM, respectively, with complex 1 being twice effective as mcz (MIC = 7.50 μM). Complex 2 significantly reduced the production of pyocyanin, a virulence factor in P. aeruginosa controlled by quorum sensing, while this effect was not observed for 1.

Using dopants in the atmospheric pressure chemical ionization ion source to determine the site of protonation by ion mobility spectrometry.

Compounds like caffeine metabolites with more than one proton acceptor site can produce a mixture of isomeric protonated ions (protomers) in electrospray ionization and atmospheric pressure chemical ionization (APCI) ion sources. Discrimination between the protomers is of interest as the charge location influences ion structure and chemical and physical properties. Protonation of caffeine in an APCI ion source was studied using ion mobility spectrometry. The hydronium ions, H3O+(H2O)n, are the main reactant ions in the APCI ion source. Different dopant gases including NO2, NH3, and CH3NH2 were used to produce new reactant ions NO+, NH4 +, and CH3NH3 +, respectively. Density functional theory was employed to explain the experimental results and calculate the energies of the ionization reactions. The ion mobility spectrum of caffeine showed three peaks. In the presence of NO2 dopant and NO+ reactant ion, caffeine was ionized via charge transfer and formation of M+ ion. As NH3 and CH3NH2 are stronger bases than H2O, the reactant ions NH4 + and CH3NH3 + selectively protonated the more basic site of caffeine, that is, the imidazole nitrogen. Using these dopants, we could attribute the first ion mobility peak to M+ ion, the second peak to the protonation of caffeine at the carbonyl oxygen atom, and the third peak to the protonation of the imidazole nitrogen atom. The calculated collisional cross-sections of M+ and the protomers of caffeine confirmed the peaks' assignment. The criterion for the selection of an appropriate dopant is that its proton affinity (PA) should be between those of the proton acceptor sites of the molecule studied.

Zn(II) and Cu(II) Coordination Enhances the Antimicrobial Activity of Piscidin 3, but Not That of Piscidins 1 and 2.

Piscidins, antimicrobial peptides isolated from fish, are potent against a variety of human pathogens; they show minimum inhibitory concentration values comparable to those of commercially used antimicrobials. Piscidins 1 and 2 are generally more effective than piscidin 3 when applied alone; the contrary is observed for their metal complexes: Zn(II) and Cu(II) coordination does not enhance the efficacy of piscidins 1 and 2, while a moderate enhancement is observed for piscidin 3. All three piscidins bind Cu(II) in a so-called albumin-like binding mode, while for Zn(II) complexes, two coordination modes are observed: piscidins 1 and 2 bind Zn(II) by imidazole nitrogens from His4, His11, and His17 side chains; piscidin 3 coordinates Zn(II) by His3, His4, and His11 imidazole nitrogens and additionally supports the interaction, formed by carbonyl oxygen from His4. Most likely, the high antimicrobial activity of piscidin complexes is due to neither the stability of their complexes nor the change in their secondary structure. Copper(II) complexes with piscidins 1 and 2 can form hydroxyl radicals, which could be responsible for the antimicrobial membrane damaging activity of these complexes. Clearly, a different mechanism (most likely an intercellular targeted one) is observed for piscidin 3 metal complexes; in most cases, the coordination of Cu(II) and Zn(II) enhances the antimicrobial potency of piscidin 3, showing that not only piscidin 3 alone but also its metal complexes have a different mode of action than piscidins 1 and 2.

Co(II) Substitution Enhances the Esterase Activity of a de Novo Designed Zn(II) Carbonic Anhydrase.

Carbonic Anhydrases (CAs) have been a target for de novo protein designers due to the simplicity of the active site and rapid rate of the reaction. The first reported mimic contained a Zn(II) bound to three histidine imidazole nitrogens and an exogenous water molecule, hence closely mimicking the native enzymes' first coordination sphere. Co(II) has served as an alternative metal to interrogate CAs due to its d7 electronic configuration for more detailed solution characterization. We present here the Co(II) substituted [Co(II)(H2O/OH-)]N(TRIL2WL23H)3 n+ that behaves similarly to native Co(II) substituted human-CAs. Like the Zn(II) analogue, the cobalt-derivative at slightly basic pH is incapable of hydrolyzing p-nitrophenylacetate (pNPA); however, as the pH is increased a significant activity develops, which at pH values above 10 eventually yields a catalytic efficiency that exceeds that of the [Zn(II)(OH-)]N(TRIL2WL23H)3 + peptide complex. X-ray absorption analysis is consistent with an octahedral species at pH 7.5 that converts to a 5-coordinate species by pH 11. UV-vis spectroscopy can monitor this transition, giving a pKa for the conversion of 10.3. We assign this conversion to the formation of a 5-coordinate Co(II)(Nimid)3(OH)(H2O) species. The pH dependent kinetic analysis indicates the maximal rate (kcat), and thus the catalytic efficiency (kcat/Km), follow the same pH profile as the spectroscopic conversion to the pentacoordinate species. This correlation suggests that the chemically irreversible ester hydrolysis corresponds to the rate determining process.

Heme Spin Distribution in the Substrate-Free and Inhibited Novel CYP116B5hd: A Multifrequency Hyperfine Sublevel Correlation (HYSCORE) Study.

The cytochrome P450 family consists of ubiquitous monooxygenases with the potential to perform a wide variety of catalytic applications. Among the members of this family, CYP116B5hd shows a very prominent resistance to peracid damage, a property that makes it a promising tool for fine chemical synthesis using the peroxide shunt. In this meticulous study, we use hyperfine spectroscopy with a multifrequency approach (X- and Q-band) to characterize in detail the electronic structure of the heme iron of CYP116B5hd in the resting state, which provides structural details about its active site. The hyperfine dipole-dipole interaction between the electron and proton nuclear spins allows for the locating of two different protons from the coordinated water and a beta proton from the cysteine axial ligand of heme iron with respect to the magnetic axes centered on the iron. Additionally, since new anti-cancer therapies target the inhibition of P450s, here we use the CYP116B5hd system-imidazole as a model for studying cytochrome P450 inhibition by an azo compound. The effects of the inhibition of protein by imidazole in the active-site geometry and electron spin distribution are presented. The binding of imidazole to CYP116B5hd results in an imidazole-nitrogen axial coordination and a low-spin heme FeIII. HYSCORE experiments were used to detect the hyperfine interactions. The combined interpretation of the gyromagnetic tensor and the hyperfine and quadrupole tensors of magnetic nuclei coupled to the iron electron spin allowed us to obtain a precise picture of the active-site geometry, including the orientation of the semi-occupied orbitals and magnetic axes, which coincide with the porphyrin N-Fe-N axes. The electronic structure of the iron does not seem to be affected by imidazole binding. Two different possible coordination geometries of the axial imidazole were observed. The angles between gx (coinciding with one of the N-Fe-N axes) and the projection of the imidazole plane on the heme were determined to be -60° and -25° for each of the two possibilities via measurement of the hyperfine structure of the axially coordinated 14N.

Silver(I) complexes containing antifungal azoles: significant improvement of the anti-Candida potential of the azole drug after its coordination to the silver(I) ion.

Inspired by the emergence of resistance to currently available antifungal therapy and by the great potential of metal complexes for the treatment of various diseases, we synthesized three new silver(I) complexes containing clinically used antifungal azoles as ligands, [Ag(ecz)2]SbF6 (1, ecz is econazole), {[Ag(vcz)2]SbF6}n (2, vcz is voriconazole), and [Ag(ctz)2]SbF6 (3, ctz is clotrimazole), and investigated their antimicrobial properties. The synthesized complexes were characterized by mass spectrometry, IR, UV-vis and 1H NMR spectroscopy, cyclic voltammetry, and single-crystal X-ray diffraction analysis. In the mononuclear complexes 1 and 3 with ecz and ctz, respectively, the silver(I) ion has the expected linear geometry, in which the azoles are monodentately coordinated to this metal center through the N3 imidazole nitrogen atom. In contrast, the vcz-containing complex 2 has a polymeric structure in the solid state in which the silver(I) ions are coordinated by four nitrogen atoms in a distorted tetrahedral geometry. DFT calculations were done to predict the most favorable structures of the studied complexes in DMSO solution. All the studied silver(I) complexes have shown excellent antifungal and good to moderate antibacterial activities with minimal inhibitory concentration (MIC) values in the ranges of 0.01-27.1 and 2.61-47.9 μM on the selected panel of fungi and bacteria, respectively. Importantly, the complexes 1-3 have exhibited a significantly improved antifungal activity compared to the free azoles, with the most pronounced effect observed in the case of complex 2 compared to the parent vcz against Candida glabrata with an increase of activity by five orders of magnitude. Moreover, the silver(I)-azole complexes 2 and 3 significantly inhibited the formation of C. albicans hyphae and biofilms at the subinhibitory concentration of 50% MIC. To investigate the impact of the complex 3 more thoroughly on Candida pathogenesis, its effect on the adherence of C. albicans to A549 cells (human adenocarcinoma alveolar basal epithelial cells), as an initial step of the invasion of host cells, was studied.

Synthesis and Characterization Some Complexes of Mixed Ligand and Study Its Effects as Antioxidant and Anticancer

A series of mixed ligand complexes of Co(II), Ni(II), Cu(II), Zn (II),Cd(II), Fe (III ) andAu(III) were prepared and characterized. A new azo ligand derived from 4-methylimidazole with sulfadiazine and Schiff base derived from 4-(dimethylamino)-2-hydroxobenzaldehyde and 4-amino-3-hydroxy benzene sulfonamide. Ligands structures and their transitional metal mix-ligand complexes were characterized using various analytical techniques, including molar conductance, elemental analysis (C.H.N), electronic spectral, magnetic measurements, 1HNMR, IR spectral studies and mass spectra. The data shows that these complexes have composition of [ML1L2H2O] where M = Co(II), Ni(II), Cu(II), Zn(II) ,Cd(II) and Hg(II). [ML1L2Cl] where M=Fe(III). [ML1L2]Cl2 where M=Au(III). The magnetic susceptibility and electronic spectral data of the complexes indicate that the octahedral geometry of all complexes, except the complex of Au(III) indicates a square plane geometry. The IR results demonstrate that the co-ordination sites are imidazole nitrogen atom and the farthest azo nitrogen atom of L1 as natural bidentate with nitrogen the azomethine and oxygen atoms of Schiff base L4. Azo ligand and Schiff base behave as tridentate manner. All the compounds showed DPPH radical scavenging activity. In general, the results indicated that the complexes have potential and promising anti-oxidant activities.

Label-free multimodal analysis of copper ions at below permissible exposure limit in the aqueous medium

An anthraimidazoledione based amphiphilic dye molecule was synthesized that shows formation of tuneable charge-transfer state in solution, susceptible to change in pH, polarity and hydrogen bonding ability of the medium. The compound also showed formation of nanoscopic self-assembled structure in water medium. The probe molecule can achieve multimodal detection (colorimetric, fluorimetric and electrochemical) of copper ions as low as 0.3 ppm in the aqueous medium. Addition of copper leads to dose-dependent ratiometric change in solution color from yellow to purple. The mechanistic investigation indicates that the coordination of copper ions was possible via simultaneous engagement of both imidazole nitrogen ends and neighbouring hydroxyl unit. Not only optical property, the changes in microenvironment also influence the selectivity as well as sensitivity of the probe molecule towards Cu2+ ions. Further, the optical probe is used for detection as well as quantification of copper ions in natural water samples without any sample pretreatment. Low-cost, reusable paper strips are developed for rapid, on-location detection of residual Cu2+ in real-life samples.

Synthesis and Biological Evaluation of New Nitroimidazole Derivatives as Anti-Helicobacter pylori Agents Against Metronidazole-Resistant Strains

: Since several Helicobacter pylori strains have become resistant to metronidazole, new nitroimidazole derivatives based on metronidazole were designed and synthesized with different substituents on imidazole nitrogen. The activity of the synthesized compounds was evaluated against 20 clinically isolated metronidazole-resistant H. pylori strains. Some synthesized compounds were effective against those metronidazole-resistant H. pylori strains. Three compounds exhibited the most potent inhibitory activities (MIC50 = 8 µg/mL and MIC90 = 16 µg/mL).

Acidified Nitrogen Self-Doped Porous Carbon with Superprotonic Conduction for Applications in Solid-State Proton Battery.

Solid proton electrolytes play a crucial role in various electrochemical energy storage and conversion devices. However, the development of fast proton conducting solid proton electrolytes at ambient conditions remains a significant challenge. In this study, a novel acidified nitrogen self-doped porous carbon material is presented that demonstrates exceptional superprotonic conduction for applications in solid-state proton battery. The material, designated as MSA@ZIF-8-C, is synthesized through the acidification of nitrogen-doped porous carbon, specifically by integrating methanesulfonic acid (MSA) into zeolitic imidazolate framework-derived nitrogen self-doped porous carbons (ZIF-8-C). This study reveals that MSA@ZIF-8-C achieves a record-high proton conductivity beyond 10-2 Scm-1 at ambient condition, along with good long-term stability, positioning it as a cutting-edge alternative solid proton electrolyte to the default aqueous H2 SO4 electrolyte in proton batteries.

PH-dependent Synthesis and Interactions of Fluorescent L-Histidine Capped Copper Nanoclusters with Metal Ions.

In this work, L-Histidine-protected copper nanoclusters synthesized by changing the pH levels of precursor solution have been shown to display different emission wavelengths and intensities. As determined by mass spectrometry, nanoclusters Cu3L2 synthesized at acidic pH have 3 atoms in their core and emit in the greenish-yellow region, and nanoclusters Cu2L2, synthesized in the basic conditions have 2 atoms in their core and emit in the blue-green region. They are expected to have coordination through the carboxylate group and nitrogen of the imidazole ring of histidine ligand, respectively. Metal ions Mg2+, Mn2+, Zn2+, and Pb2+ selectively enhance the interaction between carboxylate - copper metal core and increase the emission intensity of Cu3L2. These metal ions weaken the interaction between imidazole nitrogen and copper metal core and quench the emission intensity of Cu2L2. As synthesized, nanoclusters exhibit good water solubility and photostability, they can act as fluorescent probes to sense the metal ions, therefore, they were utilized for the optical sensing of the mentioned metal ions. Fluorescent nanoclusters were found to sense even a very low concentration of metal ions with a limit of detection (3 σ/slope) in nanomolar range.

An Efficient Synthesis of Benzimidazole‐pyrazines via the Sequential Ugi/Hydroamination/Cyclization Reactions

AbstractThis study reported an efficient two‐step method based on the sequential post‐Ugi hydroamination reaction for synthesizing a novel class of benzimidazole‐pyrazines with high yields. First, a Ugi fourcomponent reaction (Ugi‐4CR) is carried out using readily available starting materials, i. e., 1H‐benzo[d]imidazole‐2‐carboxylic acid, aldehydes, propargylamine, and isocyanides, in methanol at ambient temperature. Afterward, the Ugi products undergoes a sequential intramolecular hydroamination/cyclization reaction between a nitrogen of imidazole and alkyne functional group in aqua media in the presence of AuCl3 as a catalyst to obtain benzimidazole‐pyrazine products. These heterocyclic compounds may have a potential to be utilized in designing modern drugs with desirable features.

Synthesis, characterization, and selective gas adsorption performance of hybrid NH2-MIL-101(Fe)/ZIF-8 metal organic framework (MOF)

In this paper, an efficient NH2-MIL-101(Fe)/ZIF-8 metal organic framework (MOF) with tunable pore architecture was synthesized by an internal extended growth approach, using polyvinylpyrrolidone (PVP) as a regulator. In the resultant structure, the larger-pore MOF (NH2-MIL-101(Fe)) provides the facilitated transport pathways and the smaller-pore MOF (ZIF-8) acts as the shell, enhancing the molecular sieving properties. The synthesized MOFs were characterized by FESEM, EDS, HRTEM, FTIR, XRD, TGA, and BET analyses, and the hybrid structure formation was accordingly approved. Furthermore, the pure gas adsorption measurements were conducted for CO2, N2, CH4, C2H6, and C2H4 gases at 298 and 328 K and equilibrium pressures up to 4 bar. The CO2 adsorption capacity of 3.982 mmol g−1 at 298 K for NH2-MIL-101(Fe)/ZIF-8 was obtained, which is ∼43% and ∼127% higher than the values for the individual MOFs, respectively. This increase is mainly attributed to the favorable CO2 interactions with the unpaired electrons of nitrogen (amine functional groups and imidazole nitrogen) as well as oxygen atoms along with unsaturated metal sites present in the both MOFs. In addition, the beneficial size exclusion effect of the shell MOF, resulted in improved gas adsorption selectivity values. The synthesized hybrid structure displayed considerably higher CO2/N2 and CO2/CH4 adsorption selectivities, which were ∼3.8 and 1.7 times greater than those of the pristine NH2-MIL-101(Fe) MOF, respectively. Furthermore, the C2H6/C2H4 selectivity of NH2-MIL-101(Fe)/ZIF-8 was raised by ∼48%, compared to the NH2-MIL-101(Fe) MOF, owning to the molecular sieving effect of ZIF-8 for C2H6 with larger kinetic diameter compared to C2H4.

Ligand-Structure Effects on N-Heterocyclic Carbene Rhenium Photo- and Electrocatalysts of CO2 Reduction.

Three novel rhenium N-heterocyclic carbene complexes, [Re]-NHC-1-3 ([Re] = fac-Re(CO)3Br), were synthesized and characterized using a range of spectroscopic techniques. Photophysical, electrochemical and spectroelectrochemical studies were carried out to probe the properties of these organometallic compounds. Re-NHC-1 and Re-NHC-2 bear a phenanthrene backbone on an imidazole (NHC) ring, coordinating to Re by both the carbene C and a pyridyl group attached to one of the imidazole nitrogen atoms. Re-NHC-2 differs from Re-NHC-1 by replacing N-H with an N-benzyl group as the second substituent on imidazole. The replacement of the phenanthrene backbone in Re-NHC-2 with the larger pyrene gives Re-NHC-3. The two-electron electrochemical reductions of Re-NHC-2 and Re-NHC-3 result in the formation of the five-coordinate anions that are capable of electrocatalytic CO2 reduction. These catalysts are formed first at the initial cathodic wave R1, and then, ultimately, via the reduction of Re-Re bound dimer intermediates at the second cathodic wave R2. All three Re-NHC-1-3 complexes are active photocatalysts for the transformation of CO2 to CO, with the most photostable complex, Re-NHC-3, being the most effective for this conversion. Re-NHC-1 and Re-NHC-2 afforded modest CO turnover numbers (TONs), following irradiation at 355 nm, but were inactive at the longer irradiation wavelength of 470 nm. In contrast, Re-NHC-3, when photoexcited at 470 nm, yielded the highest TON in this study, but remained inactive at 355 nm. The luminescence spectrum of Re-NHC-3 is red-shifted compared to those of Re-NHC-1 and Re-NHC-2, and previously reported similar [Re]-NHC complexes. This observation, together with TD-DFT calculations, suggests that the nature of the lowest-energy optical excitation for Re-NHC-3 has π→π*(NHC-pyrene) and dπ(Re)→π*(pyridine) (IL/MLCT) character. The stability and superior photocatalytic performance of Re-NHC-3 are attributed to the extended conjugation of the π-electron system, leading to the beneficial modulation of the strongly electron-donating tendency of the NHC group.

Novel Casein-Derived Peptide-Zinc Chelate: Zinc Chelation and Transepithelial Transport Characteristics

Casein-derived peptides are recognized as promising candidates for improving zinc bioavailability through the form of a peptide-zinc chelate. In the present work, a novel 11-residue peptide TEDELQDKIHP identified from casein hydrolysate in our previous study was synthesized to investigate the zinc chelation characteristics. Meanwhile, the digestion stability and transepithelial transport of TEDELQDKIHP-Zn were also investigated. The obtained results indicated that the carboxyl groups (from Asp and Glu), amino groups (from Lys and His), pyrrole nitrogen group of Pro, and imidazole nitrogen group of His were responsible for zinc chelation. The complexation with zinc resulted in a more ordered structure of TEDELQDKIHP-Zn. In terms of digestion stability, the chelate of TEDELQDKIHP-Zn could remain stable to a large extent after gastric (78.54 ± 0.14%) and intestinal digestion (70.18 ± 0.17%). Moreover, TEDELQDKIHP-Zn was proven to be a well-absorbed biological particle with a Papp value higher than 1 × 10-6 cm/s, and it could be transported across the intestine epithelium through transcytosis. TEDELQDKIHP-Zn exhibited more bioavailable effects on zinc absorption and ALP activity than inorganic zinc sulfate.

Ultra‐microporous MAF stu‐1 modified by ammonia for efficient CO2 capture

AbstractA series of ultra‐microporous rod‐shaped three‐dimensional metal organic frameworks MAF stu‐1 modified with different amounts of ammonia water were synthesized by solvothermal method using chelated nitrogen‐containing ligands, which was applied to CO2 capture and exhibited excellent adsorption performance and CO2/N2 (15:85, v/v) separation efficiency. MAF stu‐1‐C regulated by .13 mol NH3 had small pore size of 4.9 Å and uncoordinated imidazole nitrogen sites in the channel, which were beneficial to improving CO2 adsorption capacity and selectivity. The maximal CO2 adsorption capacity of MAF stu‐1‐C was 110 cm3/g, exhibiting excellent CO2 capture ability and cycle stability. The ideal adsorption solution theory (IAST) model was used to calculate the adsorption and separation ratio of CO2 to N2. The CO2 to N2 selectivity of the modified adsorbent was more than 100. Furthermore, the adsorption heat of MAF stu‐1‐C for CO2 was calculated to be about 35 kJ/mol by virial equation fitting method, indicating that the modified adsorbent also had remarkable regeneration performance.

Benzimidazole-based covalent organic polymer nanosheets incorporated in mesoporous organosilica nanoparticles with excitation-dependent fluorescence for sensing of Cu2+

A novel type of small-sized nanosheets (TD-Si) was prepared by chemical exfoliating stacked bulk materials of benzimidazole-based covalent organic polymer (TpDAB). Then TD-Si was used as organosiloxane precursor to incorporate into silica frameworks of mesoporous organosilica nanoparticles (TD-MONs) using CTAB as structural-directing agents. The obtained TD-MONs show a clearly hexagonal mesoporous structure with high surface area. Moreover, the optical properties of TD-MONs were measured with fluorescence and Ultraviolet–visible (UV–vis) spectroscopies. The results showed that TD-MONs possessed excitation wavelength dependent fluorescence and had better fluorescence properties due to the reduction of π-π stacking between nano-layers of TpDAB polymer. The emission peaks of TD-MONs were red-shifted as the excitation wavelength increases and TD-MONs exhibited the optimal fluorescence emission at 525 nm when excited at 400 nm. TD-MONs showed high selectivity, sensitivity and recyclability toward copper ions and could be used for the detection of Cu2+ with a low limit of detection (LOD) as low as 3.77 × 10−7 M. In addition, the coordination interaction between TD-MONs and copper ions was demonstrated by FT-IR spectra and high-resolution X-ray photoelectron spectra, and further proved that the binding sites were carbonyl oxygen atoms and imidazole nitrogen atoms in TD-MONs. Therefore, TD-MONs is expected to be a high-sensitive chemical sensor for detecting Cu2+.

Identification and Characterization of the Isomeric Impurity of the Fungicide "Cyazofamid".

Identification and characterization of biproducts/ impurities present in agrochemicals are critical in view of their efficacy and safety towards public health. We herein present our study on identification and characterization of an impurity, 5-chloro-2-cyano-N,N-dimethyl-4-p-tolylimidazole-1-sulfonamide (2) present in the fungicide, "cyazofamid". Intermittent HPLC analysis of the reaction of substituted imidazole (1) with N,N-dimethylsulfamoyl chloride suggested that 2 is formed during the reaction. Isolation by preparative HPLC and characterization by NMR, LC/HRMS, MS/MS and single crystal XRD analysis confirmed 2 as an isomer of cyazofamid, wherein the N,N-dimethyl sulfonamide group was positioned on the other nitrogen of imidazole in close proximity to chloride group. Computational studies further supported the formation of 2 and ruled out the other possible isomeric structures.

Stereochemistry of low-spin cobalt porphyrins. 9. Molecular stereochemistry of two picket fence cobalt(II) derivatives

The preparation and molecular structures of two five-coordinate cobalt(II) picket fence porphyrinates with imidazole ligands are described, [Co(TpivPP)(L)] (TpivPP, dianion of picket fence porphyrin). The ligands are the unhindered imidazole, 1-ethylimidazole, and the sterically hindered imidazole, 1,2-dimethylimidazole. Although the equatorial aspects of the geometry are quite equivalent, the axial coordination group geometry strongly reflects the differing steric requirements of the axial ligand. The hindering methyl group in 1,2-dimethylimidazole, adjacent to the coordinated imidazole nitrogen atom, leads to an increased CoNIm bond distance, a tilt of the CoN bond and unequal CoNCIm bond angles, all of which serve to reduce the steric strain when compared with the unhindered derivative.