Simple optical determination of silver ion in aqueous solutions using benzo crown-ether modified gold nanoparticles

We describe a method for the modification of gold nanoparticles (Au-NPs) with benzo-15-crown-5 that led to the development of a colorimetric assay for Ag(I) ion. The brown color of a solution of the modified Au-NPs turns to purple on addition of Ag(I) ion. The ratio of the UV–vis absorption at 600 nm and 525 nm is proportional to the concentration of Ag(I) ions in the range from 20 to 950 nM, and the detection limit is 12.5 nM. Other metal ions do not interfere if present in up to millimolar concentrations. The method enables a rapid determination of Ag(I) in lake and drinking water and is amenable to bare-eye readout.

One-pot synthesis of 4,5-dihydro-1H-pyrrol-3-carboxamide derivatives via a four-component reaction

An effective route to functionalized 4,5-dihydro-1H-pyrrol-3-carboxamide derivatives is described. This involves reaction of N-alkyl-3-oxobutanamides, which result from the addition of an amine to the diketene, and a primary amine in the presence of dibenzoylacetylene. The 1,3-dicarbonyl compounds obtained from the addition of an amine to diketene were trapped with a primary amine to produce (Z)-3-(alkylamino)-N¹-alkyl-2-butenamide, which reacts with dibenzoylacetylene to produce 4,5-dihydro-1H-pyrrol-3-carboxamide derivatives.     

Efficient synthesis and metal cations complexation of some novel dinaphthosulfide-substituted macrocyclic diamides

Some dinaphthosulfide aza macrocycles (3–9) were synthesized based on the conventional route from the reaction of corresponding dinaphthosulfide diester and aliphathic diamines in refluxing methanol in good yields. Dinaphthosulfide diester were synthesized from the reaction of 1,1′-thiobis (2-hydroxy naphthalene) and methyl chloroacetate. The structures of these compounds were confirmed using IR, ¹H NMR, ¹³C NMR, MASS spectroscopy and elemental analysis. Conductometric studies of the complexation of some metal ions with aza derivative 8 (TDN) in methanol as solvent implied the formation of 1:1 complexes. The stability of the 1:1 complexes of TDN decreases in the order Hg²⁺ >> Pb²⁺ > Cu²⁺ > Zn²⁺ > Ca²⁺ > Mg²⁺ > Cd²⁺ > Sr²⁺ > Ag⁺ > Ba²⁺.     

Electrically induced fluorescence Fe sensing behavior of nanostructured Tiron doped polypyrrole

Nanostructured polypyrrole (PPy) film doped with Tiron was electrodeposited from aqueous solution on the surface of transparent electrode and used for sensitive, selective and rapid electrically controlled fluorescence detection of Fe³⁺ in aqueous media. The fluorescence intensity of PPy-Tiron film decreases linearly in the presence of Fe³⁺ by applying negative potential over a concentration range from 5.0 × 10⁻⁸ to 1.0 × 10⁻⁶ mol L⁻¹, with a relatively fast response time of less than 30 s at pH 7.4. The detection is not affected by the coexistence of other competitive metal ions such as Al³⁺, Ce³⁺, Tl³⁺, La³⁺, Bi³⁺, Cr²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Pb²⁺, Na⁺, K⁺, Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺. The proposed electro-fluorescence sensor has a potential application to the determination of Fe³⁺ in environmental and biological systems. The fluorescent thin film sensor was also used as a novel probe for Fe³⁺/Fe²⁺ speciation in aqueous solution.     

Electron Transport in Quasi‐Two‐Dimensional Porous Network of Titania Nanoparticles,Incorporating Electrical and Optical Advantages in Dye‐Sensitized Solar Cells

The integration of fast electron transport and large effective surface area is critical to attaining higher gains in the nanostructured photovoltaic devices. Here, we report facilitated electron transport in the quasi‐two‐dimensional (Q2D) porous TiO₂. Liquid electrolyte dye‐sensitized solar cells were prepared by utilizing photoanodes based on the Q2D porous substructures. Due to electron confinement in a microscale porous medium, directional diffusion toward collecting electrode is induced into the electron transport. Our measurements based on the photocurrent and photovoltage time‐of‐flight transients show that at higher Fermi levels, the electron diffusion coefficient in the Q2D porous TiO₂ is about one order of magnitude higher when compared with the conventional layer of porous TiO₂. The results show that microstructuring of the porous TiO₂ leads to an approximately threefold improvement in the electron diffusion length. Such a modification may considerably affects the electrical functionality of moderate or low performance dye‐sensitized solar cells for which the internal gain or collection efficiency is typically low.     

The helical melamine–Keggin hybrid nanorods: syntheses and characterizations with two strategies,one-step solid-state chemical reaction and experimental solvent diffusion method

Two new Melamine-Keggin hybrid nanorods, MELH-PMo₁₂ and MELH-PW₁₂, for the first time are successfully synthesized by two chemical methods, one-step solid-state chemical reaction method and experimental solvent diffusion method at room temperature. One-step solid-state reactions involve grounded nanorod materials along with grinding of row material and with solvent diffusion method these nanorods synthesized in single crystals form. These compounds crystallized in trigonal space groups P-3. Elemental analysis, infrared spectroscopy, UV spectroscopy and XRD analysis results prove that the samples still possess Keggin type structure. Transmittance electron microscopy and single-crystal X-ray have shown that the samples have nanorod structures.     

A stoichiometric imprinted chelating resin for selective recognition of copper(II) ions in aqueous media

This work reports the preparation of a new copper(II) ion-imprinted polymer (IIP) material, using 5,6;14,15-dibenzo-1,4-dioxa-8,12-diazacyclopentadecane-5,14-diene (DBDA15C4) and 2-vinylpyridine (VP) as a non-vinylated chelating agent and a functional vinyl monomer, respectively. The Cu²⁺ ion can form stable complexes with DBDA15C4 and VP. The stoichiometries of Cu²⁺-DBDA15C4 and ternary Cu²⁺-DBDA15C4-VP complexes were elucidated using conductometric and spectrophotometric methods, and found to be Cu²⁺(DBDA15C4), Cu²⁺(DBDA15C4)₂ and Cu²⁺(DBDA15C4)(VP)₂. The results obtained from solution studies were also supported by ab initio theoretical calculations. The resulting ternary complex Cu²⁺(DBDA15C4)(VP)₂ was copolymerized with ethyleneglycoldimethacrylate, as a cross-linking monomer, via bulk polymerization method. The imprinted copper ion was removed from the polymeric matrix by 0.1 M HNO₃. The Cu²⁺-imprinted polymer particles were characterized by IR spectroscopy and elemental analysis. Optimum pH range for rebinding of Cu²⁺ on the IIP and equilibrium binding time were 7.0-7.5 and 45 min, respectively. Sorbent capacity and enrichment factor for Cu²⁺ were obtained as 75.3 ± 1.9 μmol g⁻¹ and 100, respectively. In selectivity study, it was found that imprinting results in increased affinity of the material toward Cu²⁺ ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for five times without a significant decrease in polymer binding affinities.     

From Oncogenic Signaling Pathways to Single-Cell Sequencing of Immune Cells: Changing the Landscape of Cancer Immunotherapy

Over the past decade, there have been remarkable advances in understanding the signaling pathways involved in cancer development. It is well-established that cancer is caused by the dysregulation of cellular pathways involved in proliferation, cell cycle, apoptosis, cell metabolism, migration, cell polarity, and differentiation. Besides, growing evidence indicates that extracellular matrix signaling, cell surface proteoglycans, and angiogenesis can contribute to cancer development. Given the genetic instability and vast intra-tumoral heterogeneity revealed by the single-cell sequencing of tumoral cells, the current approaches cannot eliminate the mutating cancer cells. Besides, the polyclonal expansion of tumor-infiltrated lymphocytes in response to tumoral neoantigens cannot elicit anti-tumoral immune responses due to the immunosuppressive tumor microenvironment. Nevertheless, the data from the single-cell sequencing of immune cells can provide valuable insights regarding the expression of inhibitory immune checkpoints/related signaling factors in immune cells, which can be used to select immune checkpoint inhibitors and adjust their dosage. Indeed, the integration of the data obtained from the single-cell sequencing of immune cells with immune checkpoint inhibitors can increase the response rate of immune checkpoint inhibitors, decrease the immune-related adverse events, and facilitate tumoral cell elimination. This study aims to review key pathways involved in tumor development and shed light on single-cell sequencing. It also intends to address the shortcomings of immune checkpoint inhibitors, i.e., their varied response rates among cancer patients and increased risk of autoimmunity development, via applying the data from the single-cell sequencing of immune cells.     

All-solid-state Cr(III)-selective potentiometric sensor based on Cr(III)-imprinted polymer nanomaterial/MWCNTs/carbon nanocomposite electrode

A novel potentiometric sensor, based on carbon paste electrode (CPE), modified with ion-imprinted polymer (IIP) and multi-walled carbon nanotubes (MWCNTs), is introduced for detection of chromium (III). The IIP nanomaterial was synthesised and characterised by using scanning electron microscopy and Fourier Transform Infrared. The modification of the CPE with the IIP (as a ionophore) resulted in an all-solid-state Cr(III)-selective sensor. However, the presence of appropriate amount of MWCNTs in the electrode composition was found to be necessary to observe Nernstian response. The optimised electrode composition was 76.7% graphite, 14.3% binder, 5% IIP, and 4% CNT. The proposed sensor exhibited Nernstian slope of 20.2 ± 0.2 mV decade^?1 in the working concentration range of 1.0 × 10^?6?1.0 × 10^?1 mol L^?1 (52 µg L^?1–5.2 g L^?1), with a detection limit of 5.9 × 10^?7 mol L^?1 (30.68 µg L^?1) and a fast response time of less than 40 s. It displayed a stable potential response in the pH range of 2–5. It exhibited also high selectivity over some interfering ions. The proposed sensor was successfully applied for the determination of Cr(III) in real samples (sea, river water and soil).     

One-step in-syringe dispersive liquid–liquid microextraction and GC-FID determination of trace amounts of di(2-ethylhexyl) phthalate and its metabolite in human urine samples

Di(2-ethylhexyl) phthalate (DEHP) is used as plasticizer in polyvinylchloride (PVC) plastics. Its metabolites and the parent phthalates are considered toxic. As the DEHP plasticizers are not chemically bound to PVC, they can migrate, evaporate or be leached into indoor air and atmosphere, foodstuff, and other materials. We have reported a novel, easy and available analytical method for the determination of DEHP and its metabolite, mono(2-ethylhexyl) phthalate (MEHP) in human urine samples by the in-syringe dispersive liquid–liquid microextraction method coupled with gas chromatography with flame ionization detector. The limits of detection and precision (RSD) were 2.5 μg/L and 1.4% for DEHP and 1.1 μg/L and 3.0% for MEHP, respectively. This method could be utilized for routine monitoring of the trace DEHP and MEHP in urine of human exposure to plasticizers.