Zinc(II)-MOF: A Versatile Luminescent Sensor for Selective Molecular Recognition of Flame Retardants and Antibiotics.

An exceptional Zinc(II)-organic framework with the formula [{Zn(L4-py)(bdc)}·DMF]n (Zn-MOF) has been constructed solvothermally using a novel linker L4-py {2,7-bis(3-(pyridin-4-ylethynyl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone}, coligand H2bdc (1,4-benzenedicarboxylic acid), and ZnBF4·xH2O. The ligand L4-py has been fabricated after functionalization of NDA (1,4,5,8-naphthalenetetracarboxylic dianhydride) core with 3-(pyridin-4-ylethynyl)phenyl group. The single-crystal X-ray analysis reveals that Zn-MOF exhibits a comprehensive three-dimensional (3D) framework architecture and features (4)-connected uninodal dia; 4/6/c1; sqc6 topology with point symbol {66} and two-dimensional (2D) + 2D, parallel polycatenation. Notably, Zn-MOF displayed excellent fluorescence phenomenon and stability in water as well as in methanol solvents and was harnessed as a versatile sensor, demonstrating selective and sensitive molecular recognition of flame retardants and antibiotics. Notably, Zn-MOF displayed 57 and 49.5% quenching efficiency for the flame-retardant pentabromophenol (PBP) and 3,3',5,5'-tetrabromobisphenol A (TBPA), respectively. Whereas an outstanding 90% quenching efficiency was observed for antibiotics, tetracycline (TC) and secnidazole (SD). The mechanistic investigations of this luminescence quenching suggest that this might be primarily occurring via the Fourier resonance energy transfer (FRET) and photoinduced electron transfer (PET) mechanisms, which might be assisted by the competitive absorption and host-guest interactions. The π-electron-rich framework structure of sensor Zn-MOF activates this mechanism.

Metal-Organic Framework-Based Selective Molecular Recognition of Organic Amines and Fixation of CO2 into Cyclic Carbonates.

Synthesis and structural depiction of two new metal-organic frameworks (MOFs), namely, [{Zn(L)(oba)}·4H2O]α (Zn-MOF-1) and [{Cd1/2(L)1/2(nipa)1/2(H2O)1/2}·(DMF)1/2(H2O)]α (Cd-MOF-2) (where L = N2,N6-di(pyridin-4-yl)naphthalene-2,6-dicarboxamide, 4,4'-H2oba = 4,4'-oxybisbenzoic acid, and 5-H2nipa = 5-nitroisophthalic acid) are reported. Both Zn-MOF-1 and Cd-MOF-2 have been prepared by reacting ligand L and coligand 4,4'-H2oba or 5-H2nipa with the respective dihydrates of Zn(OAc)2 and Cd(OAc)2 (OAc = acetate). Crystal structure X-ray analysis discloses that Zn-MOF-1 displays an overall 2D → 3D interpenetrated framework structure. The topological analysis by ToposPro suggests a (4)-connected uninodal sql topology with a point symbol of {44·62} having 2D + 2D parallel polycatenation. However, crystal packing of Cd-MOF-2 adapted a porous framework architecture and was topologically simplified as (3,4)-connected binodal 2D net. In addition, both Zn-MOF-1 and Cd-MOF-2 were proved to be multifunctional materials for the recognition of organic amines and in the fixation of CO2 to cyclic carbonates. Remarkably, Zn-MOF-1 and Cd-MOF-2 showed very good fluorescence stability in aqueous media and have shown 98 and 97% quenching efficiencies, respectively, for 4-aminobenzoic acid (4-ABA), among all of the researched amines. The mechanistic study of organic amines recognition proposed that fluorescence quenching happened mainly through hydrogen-bonding and π-π stacking interactions. Additionally, cycloaddition of CO2 to epoxide in the presence of Zn-MOF-1 and Cd-MOF-2 afforded up to 96% of cyclic carbonate within 24 h. Both Zn-MOF-1 and Cd-MOF-2 exhibited recyclability for up to five cycles without noticing an appreciable loss in their sensing or catalytic efficiency.

Coordination Polymers as a Functional Material for the Selective Molecular Recognition of Nitroaromatics and ipso-Hydroxylation of Arylboronic Acids.

We report the synthesis and structural characterization of two coordination polymers (CPs), namely; [{Zn(L)(DMF)4 } ⋅ 2BF4 ]α (1) and [{Cd(L)2 (Cl)2 } ⋅ 2H2 O]α (2) (where L=N2 ,N6 -di(pyridin-4-yl)naphthalene-2,6-dicarboxamide). Crystal packing of 1 reveals the existence of channels running along the b- and c-axis filled by the ligated DMF and lattice anions, respectively. Whereas, crystal packing of 2 reveals that the metallacycles of each 1D chain are intercalating into the groove of adjacent metallacycles resulting in the stacking of 1D loop-chains to form a sheet-like architecture. In addition, both 1 and 2 were exploited as multifunctional materials for the detection of nitroaromatic compounds (NACs) as well as a catalyst in the ipso-hydroxylation of aryl/heteroarylboronic acids. Remarkably, 1 and 2 showed high fluorescence stability in an aqueous medium and displayed a maximum 88% and 97% quenching efficiency for 4-NPH, respectively among all the investigated NACs. The mechanistic investigation of NACs recognition suggested that the fluorescence quenching occurred via electron as well as energy transfer process. Furthermore, the ipso-hydroxylation of aryl/heteroarylboronic acids in presence of 1 and 2 gave up to 99% desired product yield within 15 min in our established protocol. In both cases, 1 and 2 are recyclable upto five cycles without any significant loss in their efficiency.

UV-FIA: UV-induced fluoro-immunochemical assay for ultra-trace detection of PETN, RDX, and TNT.

Fluorescence quenching based immunoassay format for the detection of a trace amount of some nitro-explosives with a high degree of selectivity is reported in this study. The immunoassay comprises anti-explosive antibodies functionalized microtitre strips specific to the targeted explosives, pentaerythritol tetranitrate (PETN), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and 2,4,6-trinitrotoluene (TNT). UV induced photolysis of nitro-explosive bound to targeted antibodies generates primarily nitrite ions which after the quick reaction with the detector molecule, 2,3-diaminonaphthalene (DAN), a fluorophore, quenches its fluorescence intensity, however, proportionately undergo cyclization to produce a highly fluorescent product, 2,3-naphthotriazole (NAT). The synthesized product, NAT, was verified using various chromatographic and spectrophotometric techniques. This newly developed antibody-based detection method, utilizing DAN dye, demonstrated a high selectivity towards PETN, RDX, and TNT. This method can be used as an economical testing kit for direct quantification of explosives, implying the great potential for quick, low-cost trace detection of explosives.

Trace detection of some nitro-explosives using thermal mediated immunochemical defragmented method.

A new immunoassay format using thermally induced defragmentation of some nitro-explosives with a high degree of selectivity is reported. Specific antibodies against three widely used explosives, 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitroperhydro-1,3,5-triazine (RDX), and pentaerythritol tetranitrate (PETN) were generated by designing suitable haptens using geometry optimization modules. These in-house generated antibodies were used in a newly developed thermal mediated immunochemical biosensing technique which involves the binding of specific antibodies to respective nitro-explosives on a microtiter strip, resulting in the formation of specific immunocomplex. Heating the specific immuno-complex formed on microtiter wells resulted in thermal lysis of nitro-explosives to generate nitrite ions. These ions react with Griess reagent to form a colored chromophore which correlates the concentration of individual explosive in the sample. The present work fulfills the need for an improved explosive detecting system that is highly specific and capable of quickly determining the presence of nitrate containing explosives from a mixture pool.

Toxicological responses of surfactant functionalized selenium nanoparticles: A quantitative multi-assay approach.

The utilization of selenium nanomaterials (Se Nps) in material and biological science is quickly growing, crafting an imperative need for toxicological evaluation of the exposure prospective and environmental consequences of Se Nps. The combination of quantitative multi-assay approach into environmental toxicological analysis has provided novel opportunities to build up effective markers and scrutinize the means of venomous nature of Se Nps in the current study. In the present work, we analyzed the toxicological effect of bare and surface functionalized Se Nps by using multi assay viz. seed germination studies as a function of concentration of SeNps and by using antifungal assays. The influence of SeNps on bacterial activities were also investigated by using the S. aureus, E. coli, P. aeruginosa and S. typhi bacterial strains as widespread marker species for antibacterial studies. The ocular assessment of chlorophyll content was maximum for Brij coated Se NPs (98%) as compared to bare (20%), SDS (45%) and CTAB (38%) coated SeNps. The existence of chromosomal aberrations in root meristems of A. cepa(A. cepa) with computed MI values of 16, 25, 33 and 52% for bare, CTAB, SDS and Brij coated particles has indicated the genotoxic effects of SeNps. The biocompatible nature of Brij coated Se Nps was observed from the faster mobility of DNA in gel electrophoresis studies. The investigational studies in the current work appraise the toxicity and measure the competence of obtained data to characterize possibilities of probable threats, prominence of data requirement and breaches that must be filled to diminish the ambiguities about the safe use of Se Nps.

Chemical Sensing Applications of ZnO Nanomaterials.

Recent advancement in nanoscience and nanotechnology has witnessed numerous triumphs of zinc oxide (ZnO) nanomaterials due to their various exotic and multifunctional properties and wide applications. As a remarkable and functional material, ZnO has attracted extensive scientific and technological attention, as it combines different properties such as high specific surface area, biocompatibility, electrochemical activities, chemical and photochemical stability, high-electron communicating features, non-toxicity, ease of syntheses, and so on. Because of its various interesting properties, ZnO nanomaterials have been used for various applications ranging from electronics to optoelectronics, sensing to biomedical and environmental applications. Further, due to the high electrochemical activities and electron communication features, ZnO nanomaterials are considered as excellent candidates for electrochemical sensors. The present review meticulously introduces the current advancements of ZnO nanomaterial-based chemical sensors. Various operational factors such as the effect of size, morphologies, compositions and their respective working mechanisms along with the selectivity, sensitivity, detection limit, stability, etc., are discussed in this article.

Facile synthesis, structural evaluation, antimicrobial activity and synergistic effects of novel imidazo[1,2-a]pyridine based organoselenium compounds.

A simple and efficient method has been described to synthesize the hitherto unknown imidazo[1,2-a]pyridine selenides (5a-l) by reaction of 2-chloroimidazo [1,2-a]pyridines with aryl/heteroaryl selenols, generated in situ by reduction of various diselenides with hypophosphorous acid. The crystal structures of 3-nitro-2-(phenylselanyl)-imidazo[1,2-a]pyridine (5a), 2-(mesitylselanyl)-3-nitro-imidazo[1,2-a]pyridine (5d) and 3-nitro-2-(pyridin-2-ylselanyl)-imidazo[1,2-a]pyridine (5e) were confirmed by X-ray crystallography and the DFT calculations were performed to determine various structural parameters which were correlated with the X-ray crystal structures. The synthesized compounds were subjected to antimicrobial evaluation and it was found that compounds 5a and 5j were active against gram negative bacterium Escherichia coli whereas compound 5e was active against different fungal strains. Time kill assay was performed to understand the microbial activity of synthesized organoselenium compounds and the toxicity of these compounds was evaluated against human cell lines. Synergistic effects of active compounds 5a and 5e were tested with existing antibiotic drugs which exhibited that the antibiotic combination with synthesized organoselenium compounds efficiently enhanced the antimicrobial activity.

Hybrid aptamer-antibody linked fluorescence resonance energy transfer based detection of trinitrotoluene.

Combining synthetic macromolecules and biomolecular recognition units are promising in developing novel diagnostic and analysis techniques for detecting environmental and/or clinically important substances. Fluorescence resonance energy transfer (FRET) apta-immunosensor for explosive detection is reported using 2,4,6-trinitrotoluene (TNT) specific aptamer and antibodies tagged with respective FRET pair dyes in a sandwich immunoassay format. FITC-labeled aptamer was used as a binder molecule in the newly developed apta-immunoassay format where the recognition element was specific anti-TNT antibody labeled with rhodamine isothiocyanate. The newly developed sensing platform showed excellent sensitivity with a detection limit of the order of 0.4 nM presenting a promising candidate for routine screening of TNT in samples.

CdTe nanobioprobe based optoelectrochemical immunodetection of diabetic marker HbA1c.

Highly luminescent water soluble CdTe quantum dots (QDs) were synthesized and conjugated with anti-HbA1c antibody to generate specific nanobioprobe. A sandwich immunoassay model was employed using capture HbA1c antibody as a specific receptor molecule and the QD-labeled secondary antibody as a dual (fluorescence cum electrochemical) tracer to quantify the concentration of HbA1c. A linear increase in current was observed for HbA1c analytical standards with a R(2) value of 0.990 and coefficient of variance ~5%. A comparison between HPLC and dual immunoassay for clinical samples showed a correlation coefficient of 89% and 96% for fluorescence and electrochemical detection methods respectively. The QD-based immunoassay shows great promise for rapid reproducible and cost effective analysis of HbA1c in clinical samples.

2-(Phenyl-selenon-yl)pyridine.

In the title compound, C11H9NO2Se, the pyridine and phenyl rings are almost perpendicular, with the dihedral angle between their mean planes being 79.16 (7)°. In the crystal, the mol-ecules pack so as to form ruffled sheets in the (110) plane connected by weak C-H⋯O inter-actions. In addition, there are weak π-π inter-actions between the mean planes of both the phenyl [centroid-centroid perpendicular distance of 3.591 (2) Šand slippage of 1.854 (2) Å] and pyridine rings [centroid-centroid perpendicular distance of 3.348 (2) Šand slippage of 1.854 (2) Å].

Nucleation and growth of surfactant-passivated CdS and HgS nanoparticles: Time-dependent absorption and luminescence profiles.

In this study, we have monitored the formation of CdS and HgS nanoparticles (NPs) using a precipitation method in the presence of surface-active agents. Three surfactants were tested to analyze the dependence of various parameters such as size, growth rate, photoluminescence (PL) emission and polydispersity of NPs on surfactant structure. Optical absorption spectroscopy was mainly used to estimate the optical bandgap and the size of NPs. The surfactant-induced quenching of PL intensity was found to be consistent with the different tendencies of the surfactants to act as Lewis acids towards these surfaces. The time-evolution of the absorbance suggested that the nucleation and growth rates markedly vary in a first-order fashion w.r.t. Cd(2+) and Hg(2+) salt concentration in excess of sulfide ions. The differences in the stabilization ability of the surfactants are discussed in reference to their structure-dependent adsorption behavior onto the particles. The comparative aspects of the different properties of CdS and HgS NPs prepared with identical methodology are presented in terms of metal cation-surfactant interactions. Changes in UV-vis and PL spectra during nucleation and growth of NPs were used to establish the possible mechanisms for the adsorption of surfactant molecules on the particle surface to restrict the unlimited growth.

Zeta potential based colorimetric immunoassay for the direct detection of diabetic marker HbA1c using gold nanoprobes.

A one-step homogeneous colorimetric immunoassay format coupled with zeta potential measurements for determination of specific diabetic biomarker glycated hemoglobin (HbA1c) using functionalised gold nanoparticles as bioprobes is reported. The assay exhibited an excellent sensitivity based on absorbance and zeta potential measurements showing the dynamic response range from 0.001-0.004 mg mL(-1) for HbA1c with a detection limit of 0.0015 mg mL(-1).

Tween-embedded microemulsions--physicochemical and spectroscopic analysis for antitubercular drugs.

The microemulsion composed of oleic acid, phosphate buffer, ethanol, and Tween (20, 40, 60, and 80) has been investigated in the presence of antitubercular drugs of extremely different solubilities, viz. isoniazid (INH), pyrazinamide (PZA), and rifampicin (RIF). The phase behavior showing the realm of existence of microemulsion has been delineated at constant surfactant/co-surfactant ratio (K (m) = 0.55) with maximum isotropic region resulting in the case of Tween 80. The changes in the microstructure of Tween 80-based microemulsion in the presence of anti-TB drugs have been established using conductivty (sigma) and viscosity (eta) behavior. The optical microscopic images of the system help in understanding the effect of dilution and presence of drug on the structure of microemulsion. Partition coefficient, particle size analysis, and spectroscopic studies (UV-visible, Fourier transform infrared, and 1H NMR) have been performed to evaluate the location of a drug in the colloidal formulation. To compare the release of RIF, PZA, and INH from Tween 80 formulation, the dissolution studies have been carried out. It shows that the release of drugs follow the order INH>PZA>RIF. The kinetics of the release of drug has been analyzed using the Korsmeyer and Peppas equation. The results have given a fair success to predict that the release of PZA and INH from Tween 80 microemulsion is non-Fickian, whereas RIF is found to follow a Fickian mechanism.

Entrapment of multiple anti-Tb drugs in microemulsion system: quantitative analysis, stability, and in vitro release studies.

The use of multiple drug regimes for the treatment of tuberculosis is restricted because of the degradation of Rifampicin in the presence of Isoniazid. In the present report, the microemulsion comprising Tween 80/ethanol/oleic acid/Buffer (pH 7.4) has been investigated for encapsulating Rifampicin (RIF), Isoniazid (INH), and Pyrazinamide (PZA) in different combinations. The main idea is to use the compartment of different domains of microemulsion for encapsulating drugs of different solubilties. The structural changes in the microstructure of microemulsion have been investigated in the light of the changes occurring in the presence of ATDs (anti-Tb drugs) in binary or ternary mixtures through conductivity and viscosity. Optical microscopy and (1)H NMR helped in estimating the shape and location of ATDs in microemulsion system. Electronic spectroscopy has been utilized qualitatively and quantitatively for understanding the stability and release of RIF from the composed formulation with various binary or ternary mixtures. Dissolution and release kinetics have been carried out to get an idea on the release of drugs from microemulsion formulation. ATDs in single and mixed drug formulations followed non-Fickian release behavior except for RIF in pH 7.4 release medium. The investigations employed have given us a fair success to predict not only the stability but also the release mechanism of ATDs in single and mixed drug formulations.

Solubilization, microstructure, and thermodynamics of fully dilutable U-type Brij microemulsion.

A U-type microemulsion of Brij 96 has been characterized with respect to the change in cosurfactant, oil chain length on dilution, water solubility, and water solubilization capacity. The phase behavior of the systems has been mapped with different oils. Several techniques, viz., conductivity, optical microscopy, dilution method, absorption, and FT-IR spectroscopy, have been used for microemulsion analysis. The equilibrium within the microemulsion droplets and liquid crystals has been visualized using optical microscopy. The microemulsions have evidenced volume-induced conductance percolation in all the cosurfactants (n2-n6 alcohols). The energetics of transfer of alcohol from the bulk oil to the interface has been determined through dilution method. To gain insight into the microenvironment of microemulsion, two optical probes, hydrophilic (Methyl orange) and hydrophobic (Nile red), have been utilized in absorption spectroscopy. Lastly, FT-IR has been explored to observe the state and dissolution behavior of water with increasing weight fraction.

Mixed surfactant based microemulsions as vehicles for enhanced solubilization and synthesis of organoselenium compounds.

We exploited the added degree of compositional freedom provided by mixed AOT/lecithin surfactants in reverse isooctane microemulsion to demonstrate that a small amount of added lecithin significantly enhances the solubility of organodiselenides over that in AOT reverse isooctane microemulsions alone. Conductivity results show that the added lecithin significantly increases the solubility of four different organodiselenides and raises the temperature required to induce percolation. FTIR, (1)H NMR, and UV-visible techniques were utilized to gain insight into the interactions of organodiselenides, AOT and lecithin headgroups with water in the micellar core. The information obtained from these experiments was used to design a novel synthetic route for preparing 4-chloro-2-(naphthalen-2-ylselanyl) pyrimidine in reverse microemulsion.

Mixed anionic and zwitterionic surfactant based microemulsions as vehicles for solubilizing organodiselenides.

Spectral and physiochemical behavior of water/sodium bis-(2-ethylhexyl)sulfosuccinate (AOT)/isooctane (ME-I) and water/AOT+lecithin (LC)/isooctane (ME-II) microemulsions has been investigated in the presence of organodiselenides. It was found that the OH, CO and C-O-C FTIR stretching frequency of the formulated microemulsions change with the addition of organodiselenides. Interaction with Acridine Orange (AO) indicates organodiselenide presence at the interface. Estimates of the micropolarities of the microemulsions at different water contents were carried out in terms of an empirical polarity parameter E(T)(30). The values increase with the increase in omega = [H(2)O]/[surfactant]. The emission spectra of AO reveal the quenching capacities of the added organodiselenides. The temperature induced percolation process has also been studied. The results indicate a subsequent increase in solubilization of organodiselenide in ME-II as compared to ME-I.

Facile solubilization of organochalcogen compounds in mixed micelle formation of binary and ternary cationic-nonionic surfactant mixtures.

This study investigated the water solubility enhancements of organochalcogen compounds, viz. bis(diphenylmethyl)diselenide [(C6H5)2CHSe]2 and 3,3'-dibromo-4,4'-dimethyl-2-dipyridyl diselenide [C12H10N2Se2Br2] in micellar media. Two cationic and one nonionic surfactants possessing the same hydrocarbon tail, namely hexadecyltrimethylammonium bromide (C16Br), hexadecyltrimethylammonium chloride (C16Cl), and polyoxyethylene(20)mono-n-hexadecyl ether (Brij 58), in their single as well as equimolar binary and ternary mixed states have been used. Solubilization capacity has been evaluated in terms of the molar solubilization ratio and the micelle water partition coefficients. The association constants between the solubilizate molecules and that of micelle and the average number of solubilizate molecules per micelle have also been quantified. The results showed that cationic surfactants exhibit less solubilization as compared to nonionic surfactant. The mixing effects of surfactants on micelle formation and solubilization efficiencies have also been discussed. It has been observed that cationic-nonionic binary combinations showed better solubilization capacity as compared to pure cationic, nonionic, or cationic-cationic binary mixtures. An equimolar cationic-cationic-nonionic ternary surfactant system provides higher solubilization than cationic-cationic but lowers than their cationic-nonionic counterpart. In addition, Fourier transform infrared has been employed with fair success to predict the information regarding the aggregates and the mechanism of docking of the surfactant and the chalcogenides in the system. The analysis has provided valuable information for the selection of mixed surfactants for solubilizing water-insoluble compounds. Certainly the solubilization ability of these surfactants is not simply related to molar capacity. The results give sufficient encouragement to warrant more detailed investigation of the features of surfactant properties that affect solubilization.