In this work, we successfully fabricate a rapid, sensitive sensor for the detection of superoxide anions O2˙- based on graphene/DNA/Mn3(PO4)2 biomimetic enzyme. In the design, graphene is served as excellent carrier to improve the catalysis of Mn3(PO4)2 nanoparticles; and DNA adsorbed on graphene acts as medium to assist the growth of Mn3(PO4)2 on graphene. The fabricated graphene/DNA/Mn3(PO4)2 composites exhibit excellently electrochemical activity, significantly decrease the response time and increase the sensitivity of the sensor towards O2˙-. The successful detection of O2˙- released from cancer cell demonstrated its potential applications in biology and medicine.

As part of our interest in halogenobismuthate(iii) organic-inorganic hybrid materials, a novel compound named bis(4,4'-diammoniumdiphenylsulfone) hexadecaiodotetrabismuthate(III) tetrahydrate with the chemical formula (C12H14N2O2S)2[Bi4I16]·4H2O, abbreviated as (H2DDS)[Bi4I16], has been prepared by a slow evaporation method at room temperature. This compound was characterized by single crystal X-ray diffraction (SCXRD), spectroscopic measurements, thermal study and antimicrobial activity. The examination of the molecular arrangement shows that the crystal packing can be described as made of layers of organic [C12H14N2O2S]2+ entities and H2O molecules, between which tetranuclear [Bi4I16]4- units, isolated from each other, are inserted. The cohesion among the different molecules is assured by N-H⋯I, N-H⋯O and O-H⋯I hydrogen bonding interactions, forming a three-dimensional network. Room temperature IR, Raman spectroscopy of the title compound were recorded and analyzed. The optical properties were also investigated by both UV-vis and photoluminescence spectroscopy. Moreover, the synthesized compound was also screened for in vitro antimicrobial (Gram-positive and Gram-negative) and antioxidant activities (scavenging effect on DPPH free radicals, reducing power and total antioxidant capacity).

Cerium oxide (CeO2) nanoparticles (NPs) were synthesized using a modified conventional polyol method. The ratio of diethylene glycol (DEG) and water in the synthesis was varied, and three different cerium precursor salts (Ce(NO3)3, CeCl3, and Ce(CH3COO)3) were used. The structure, size, and morphology of the synthesized CeO2 NPs were studied. An average crystallite size of 13 to 33 nm was obtained from the XRD analysis. Spherical and elongated morphologies of the synthesized CeO2 NPs were acquired. Average particle sizes in the range of 16-36 nm were obtained by varying different ratios of DEG and water. The presence of DEG molecules on the surface of CeO2 NPs was confirmed using FTIR. Synthesized CeO2 NPs were used to study the antidiabetic and cell viability (cell cytotoxicity) properties. Antidiabetic studies were carried out using α-glucosidase enzymes inhibition activity. CeO2 synthesized using Ce(NO3)3 and CeCl3 precursors showed approximately 40.0% α-glucosidase enzyme inhibition activity, while CeO2 synthesized using Ce(CH3COO)3 showed the lowest α-glucosidase enzyme inhibition activity. Cell viability properties of CeO2 NPs were investigated using an in vitro cytotoxicity test. CeO2 NPs prepared using Ce(NO3)3 and CeCl3 were non-toxic at lower concentrations, while CeO2 NPs prepared using Ce(CH3COO)3 were non-toxic at all concentrations. Therefore, polyol-mediated synthesized CeO2 NPs showed quite good α-glucosidase inhibition activity and biocompatibility.

Chemosensing plays a very important role in the detection of essential/pollutant ions in aqueous media. In this manuscript, two tripodal ligands, i.e., 1-(2-hydroxybenzyl)-3-(4-nitrophenyl)-1-phenylurea (ligand 1) and 1-(2-hydroxybenzyl)-3-(4-nitrophenyl)-1-phenylthiourea (ligand 2) have been synthesised, which differ in the linker molecule, i.e., urea and thiourea in ligand 1 and ligand 2, respectively. The ligands were characterised by NMR, IR and mass spectroscopic techniques. Ligands 1 and 2 (2 mM) were further employed for the generation of their organic nanoparticles (ONPs) (0.01 mM) of size 20-25 nm and 30-35 nm, respectively, by the reprecipitation method. The chemosensing properties of 1-ONP and 2-ONP solutions were investigated. 1-ONP showed simultaneous recognition behaviour towards Cs(i) and Al(iii) with the limits of detection of ∼220 and ∼377 nM, respectively, in an aqueous medium, while 2-ONP did not show any recognition behaviour towards any ion.

Natural dolomite, an inexpensive and vastly available natural material, was demonstrated as a potential heterogeneous photocatalyst for the efficient removal of diphenhydramine (DP) from aqueous solution under simulated solar light in this study. About 65% DP removal and 14% mineralization were achieved with dolomite as a catalyst after 75 min irradiation. The electron spin resonance analysis and scavenger experiments verified that 1O2, ˙OH, and O2 -˙ produced in the dolomite system were the main reactive species responsible for DP degradation. Furthermore, first-principle calculations combined with deoxygenation experiments were employed to elucidate the photocatalytic mechanism. The results revealed that the dolomite changed from an insulator to a semiconductor after partial substitution of Mg2+ by Fe2+, suggesting that natural dolomite could act as a semiconductor photocatalyst in photoreactions. Under irradiation, photo-excited electrons and holes separate and migrate to the surface of dolomite, and subsequently react to form reactive species resulting in the DP degradation. Product studies demonstrated that the main degradation pathways of DP included hydroxylation of the aromatic ring as well as hydroxyl radical mediated oxidation of the alkylamine side chain. This work indicated that natural dolomite could be applied in water and wastewater treatment as a promising photocatalyst.

The purpose of the present study was to examine the effectiveness of 23 different synthesized ionic liquids (ILs) on Fusarium culmorum and Fusarium oxysporum growth rate. The strategy of IL synthesis was a structural modification of ionic liquids through changing the polarity of imidazolium and pycolinium cations and replacing halide anions with well known antifungal anions (cinnamate, caffeate and mandelate). The findings clearly suggest that the type of alkyl chain on the cation is the most determining factor for IL toxicity. In order to examine how IL structure affects their toxicity towards Fusarium genus, lipophilic descriptor A log P is calculated from density functional theory and correlated with Fusarium growth rate. All these results demonstrate the high level of the interdependency of lipophilicity and toxicity for investigated ILs towards the Fusarium genus. The data collected in this research suggest that the inhibitory influence of ILs is more pronounced in the case of F. oxysporum.

Arsenic (As) is a toxic metalloid that has drawn immense attention from the scientific community recently due to its fatal effects through its unwanted occurrence in ground water around the globe. The presence of an excess amount of water soluble arsenate and/or arsenite salt (permissible limit 10 μg L-1 as recommended by the WHO) in water has been correlated with several human diseases. Although arsenate (HAsO4 2-) is a molecular analogue of phosphate (HPO4 2-), phosphate is indispensable for life, while arsenic and its salts are toxic. Therefore, it is worthwhile to focus on the removal of arsenic from water. Towards this end, the design of peptide-based scaffolds for the recognition of arsenate and arsenite would add a new dimension. Utilizing the stereochemical similarity between arsenate (HAsO4 2-) and phosphate (HPO4 2-), we successfully investigated the recognition of arsenate and arsenite with a naturally occurring novel phosphate binding 'CαNN' motif and its related designed analogues. Using computational as well as biophysical approaches, for the first time, we report here that a designed peptide-based scaffold based on the 'CαNN' motif can recognize anions of arsenic in a thermodynamically favorable manner in a context-free system. This peptide-based arsenic binding agent has the potential for future development as a scavenger of arsenic anions to obtain arsenic free water.

A series of mononuclear gold(iii) complexes of the general formula [AuCl3(diazanaphthalene)], where diazanaphthalene is quinazoline (qz, 1), phthalazine (phtz, 2), 1,5-naphthyridine (1,5-naph, 3), 1,6-naphthyridine (1,6-naph, 4) or 1,8-naphthyridine (1,8-naph, 5), were prepared and fully characterized. The complexes 1-5 consist of discrete monomeric species with the Au(iii) cation in a square planar coordination geometry surrounded by three chloride anions and one diazanaphthalene ligand. Crystallographic studies indicate the presence of an extended 4 + 1 or 4 + 2 geometry around the square planar [AuCl3(diazanaphthalene)] center due to Au⋯Cl and Au⋯N interactions. The crystal structures of these complexes are controlled by a variety of intermolecular interactions that utilize the amphiphilic properties of the coordinated chloride anions and involve C-H groups, π-electrons, and an uncoordinated nitrogen atom of the diazanaphthalene ligand. The usual offset π-stacking between the N-heteroaromatic ligands appears to be completely hindered between the 1,5-naph fragments and significantly weakened between the 1,6-naph and 1,8-naph in their respective complexes 3, 4 and 5, for which the average molecular polarizability (α) values are the lowest in the series. It is remarkable that the [AuCl3(benzodiazine)] complexes 1 and 2 form centrosymmetric crystals, but the [AuCl3(naphthyridine)] complexes 3-5 assemble into non-centrosymmetric aggregates, making them potential alternatives to the previously studied systems for application in various fields by taking advantage of their polarity.

Hydrazine is a vital precursor used in several pharmaceuticals and pesticide industries and upon exposure can cause severe health hazards. Herein, a new AIEgen, tetraphenylethylene phthalimide (TPE-PMI), is synthesized in a one-step solvent-free mechanochemical approach exploiting the simple condensation between TPE-NH2 and phthalic anhydride and used for the selective and sensitive detection of hydrazine. TPE-PMI with an AIE-active TPE-moiety is non-emissive in the solid phase by design. Hydrazine performs the cleavage of TPE-PMI in a typical "Gabriel synthesis" pathway to release AIE-active TPE-NH2 in an aqueous solution to emit blue fluorescence. A gradual rise in fluorescence intensity at 462 nm was due to the increasing hydrazine concentration and TPE-PMI showed a linear relationship with hydrazine in the concentration range from 0.2 to 3 μM. The selectivity study confirmed that the probe is inert to amines, amino acids, metal anions, anions and even common oxidants and reductants. The detection limit is 6.4 ppb which is lower than the US Environmental Protection Agency standard (10 ppb). The practical utilities of TPE-PMI were successfully demonstrated through quantitative detection of hydrazine vapour on solid platforms like paper strips and TLC plates. Furthermore, on-site detection of hydrazine in the solid phase was demonstrated by spiking the soil samples with measured quantities of hydrazine and quantitation through image analysis. This cost-effective sensing tool was successfully utilized in in vitro detection of hydrazine in live HeLa cells.

A special fluorescent probe has been developed, one that demonstrated excellent "off-on-type" change in fluorescence with high selectivity toward Cu2+. Interestingly, the probe-Cu2+ complex could detect cysteine due to the ability of this amino acid to strongly coordinate Cu2+, and no obvious interference was observed from other amino acids and anions. According to the proposed mechanism, addition of cysteine induced decomplexation of the probe-Cu2+ form. Furthermore, the results of confocal microscopy experiments demonstrated the potential of using the probe to image Cu2+ in living cells and mice.

The zeolitic imidazolate framework ZIF-8 (Zn(mim)2, mim = 2-methylimidazolate) has recently been proposed as a drug delivery platform for anticancer therapy based on its capability of decomposing in acidic media. The concept presumes a targeted release of encapsulated drug molecules in the vicinity of tumor tissues that typically produce secretions with elevated acidity. Due to challenges of in vivo and in vitro examination, many studies have addressed the kinetics of ZIF-8 decomposition and subsequent drug release in phosphate buffered saline (PBS) with adjusted acidity. However, the presence of hydrogen phosphate anions [HPO4]2- in PBS may also affect the stability of ZIF-8. As yet, no separate analysis has been performed comparing the dissolving capabilities of PBS and various acidification agents used for regulating pH. Here, we provide a systematic study addressing the effects of phosphate anions with and without lactic acid on the degradation rate of ZIF-8 microcrystals. Lactic acid has been chosen as an experimental acidification agent, since it is particularly secreted by tumor cells. Interestingly, the effect of a lactic acid solution with pH 5.0 on ZIF-8 degradation is shown to be weaker compared to a PBS solution with pH 7.4. However, as an additive, lactic acid is able to enhance the decomposition efficacy of other solutions by 10 to 40 percent at the initial stage, depending on the presence of other ions. Additionally, we report mild toxicity of ZIF-8 and its decomposition products, as examined on HDF and A549 cell lines.

A novel near-infrared fluorescent probe (L) based on a 1,4-diethyl-1,2,3,4-tetrahydro-7H-pyrano[2,3-g]quinoxalin-7-one scaffold has been synthesized and characterized. Probe L displays highly selective and sensitive recognition to H2S over various anions and biological thiols with a large Stokes shift (125 nm) in THF/H2O (6/4, v/v, Tris-HCl 10 mM, pH = 7.4). This probe exhibits turn-on fluorescence for H2S through HS- induced thiolysis of dinitrophenyl ether. Confocal laser scanning micrographs of MCF-7 cells incubated with L confirm that L is cell-permeable and can successfully detect H2S in living cells.

A new probe (E)-7-(diethylamino)-3-(3-(thiophen-2-yl)acryloyl)-2H-chromen-2-one (ChC16) was synthesized and studied as a turn-on fluorescent probe, based on a Michael addition mechanism for sensing SO2 derivatives, which is favored in the presence of cationic micellar media such as cetylpyridinium bromide (CPB). The probe showed high selectivity and sensitivity toward bisulfite over other anions and biothiols, including cysteine (Cys), homocysteine (Hcy) and glutathione (GSH), with a detection limit of 240 nM. Moreover, the probe showed great potential for its practical application in the detection of bisulfite in real samples, such as dry white wine, and in bioimaging.

In this study, a naphthalene Schiff-base P which serves as a dual-analyte probe for the quantitative detection of Al3+ and Mg2+ has been designed. The proposed probe showed an ''off-on'' fluorescent response toward Al3+ in ethanol-water solution (1 : 9, v/v, pH 6.3, 20 mM HEPES) over other metal ions and anions, while the detection by the probe could be switched to Mg2+ by regulating the pH from 6.3 to 9.4. The sensing mechanisms of P to Al3+/Mg2+ are attributed to inhibition of the photo-induced electron transfer (PET) process by the formation of 1 : 1 ligand-metal complexes. More importantly, the probe was applied successfully in living cells for the fluorescent cell-imaging of Al3+ and Mg2+.

In this study carbon nanofibers (CNF) were phosphorylated by using ortho-phosphoric acid and applied for adsorptive remediation of uranium from water. The phosphorylated carbon nanofibers (PCNF) showed 96% removal of uranium as compared to 79% by CNF. The adsorption data from batch adsorption studies fitted well with the Langmuir model and a maximum adsorption capacity of 512.8 mg g-1 was obtained at pH 6.0 while the adsorption followed pseudo second order kinetics. A detailed characterisation of the adsorbent has been carried out using various analytical and spectroscopic tools. The application of the adsorbent to ground water samples exhibited promising results even in the presence of other interfering cations and anions which is imperative considering the toxic effects of uranium in ground water.

Donor-acceptor π-conjugated random copolymers based on regioregular poly(3-hexylthiophene), rr-P3HT, with unsymmetrical monothienoisoindigo moieties were obtained by direct arylation polycondensation of 2-bromo-3-hexylthiophene with unsymmetrical monothienoisoindigo motifs under the optimized conditions [palladium-immobilized on thiol-modified silica gel with chloride counter anions, PITS-Cl (2.5 mol%), PivOH (1.0 equiv.), K2CO3 (3.0 equiv.), DMAc, 100 °C, 24 h]. Incorporation of unsymmetrical monothienoisoindigo electron-acceptor units into the polymers tuned their highest occupied and lowest unoccupied molecular orbital levels, which were close to those of the hole transport material (PEDOT) and electron transport material (PCBM), respectively, in thin-film organic solar cells. Alkyl chains of the unsymmetrical monothienoisoindigo units in the polymers tuned their macrostructural order, resulting in the observation of crystalline patterns and specific absorption peaks in thin films. An organic solar cell containing the most crystalline random copolymer showed an efficiency of 1.91%.

Seven new metal coordination complexes, [NiC15H43N5O11] (I), [Co3C36H98N6O6] (II), [CuC14H32N2O6] (III), [Cu2C32H43Cl2N2O13] (IV), [Zn2C24H32Cl3N3O3] (V), [Co3C48H66Cl6N6O6] (VI), and [Zn (C18H45N3O3] (VII), have been synthesized from some direct reactions of amino-alcoholic ligands with metal salts in anhydrous methanol or ethanol medium. All the crystals of these seven complexes are crystallized in the chiral space groups (P212121 for (I), (IV), (VI) and (VII); P21 for (III) and (V); and C2 for (II), respectively). Their characteristic peaks were analyzed and assigned by FTIR, NMR, and UV-Vis and elemental analysis techniques. The anticancer activities of amino alcohol complexes (I)-(VII) showed cytotoxic effects against the human tumour cell line A549; among them, complex (V) showed the best activity with an IC50 value of 17.8. The higher biological activity should be related to its di-nuclear zinc(ii) unit in which one zinc is only four-coordinated by four small chloride anions.

The fluoride anion (F-) sensing abilities of 1-hydroxyl-3,4,9,10-tetra (n-butoxyloxycarbonyl) perylene (probe 1) and 1-hydroxyl-mono-five-membered S-heterocyclic annulated tetra (n-butoxyloxycarbonyl) perylene (probe 2) were studied through visual detection experiments, UV-Vis, fluorescence, and 1H NMR titrations. The probes were sensitive and selective for distinguishing F- from other anions (Cl-, Br-, I-, SO4 -, PF6 -, H2PO4 -, BF4 -, ClO4 -, OH-, CH3COO-, and HPO4 2-) through a change of UV-Vis and fluorescence spectra. The absorption and fluorescence emission properties of the probes arise from the intermolecular proton transfer (IPT) process between a hydrogen atom on the phenolic O position of probe and the F- anion. The sensing mechanism was supported by theoretical investigation. Moreover, probe-based test strips can conveniently detect F- without any additional equipment, and they can be used as fluorescent probes for monitoring F- in living cells.

Solid bifunctional catalysts based on cesium salts of V-containing heteropoly acids (CsHPA: Cs3.5H0.5PW11VO40, Cs4.5H0.5SiW11VO40, Cs3.5H0.5PMo11VO40) and Cs2.5H0.5PMo12O40 were used for studying one-pot hydrolysis-oxidation of potato starch to formic acid at 413-443 K and 2 MPa air mixture. It was shown that the optimum process temperature that prevents formic acid from destruction is 423 K. The studies were focused on the influence of the composition of heteropoly anions on the yield and selectivity of formic acid. Using W-V-P(Si) CsHPA results in the product overoxidation compared to Mo-V-containing CsHPA. The activity of Cs-PMo was significantly lower compared to Cs-PMoV. This may indicate that vanadium plays an important role in the oxidation process. The most promising catalyst was Cs3.5H0.5PMo11VO40 which provided the maximum yield of formic acid equal to 51%. Cs3.5H0.5PMo11VO40 was tested during nine cycles of starch hydrolysis-oxidation to demonstrate its high stability and efficiency.

The growing interest in the application of ionic liquids (ILs) with simultaneous sustainability draws attention to their environmental impact in general and their biodegradability in particular. Considering this, we designed a series of novel bio-ionic liquids based on natural, abundant compounds: a carbohydrate [Carb], as the cation, and amino acids [AA], as the anions; these ILs can serve as viable alternatives to the well-known and utile cholinium AAILs. Several [Carb][AA] ILs were characterized by 1H and 13C NMR, mass spectrometry, thermogravimetry (TGA) and differential scanning calorimetry (DSC). The biodegradability properties of the [Carb][AA] ILs were elucidated as well and showed biodegradation readily occurred, decomposing within 5-6 days. These novel materials were successfully utilized as catalysts for the Knoevenagel condensation reaction, where conversion values of 67-94% were achieved under exceptionally mild conditions using water as the solvent and reaction times as short as 15 minutes. These sugar based ILs were easily separated and recycled.