Tetrazol-Cu(i) immobilized on nickel ferrite catalyzed green synthesis of indenopyridopyrimidine derivatives in aqueous media

After the initial study of different protocols in the synthesis of indeno[2′,1′:5,6]pyrido[2,3-d]pyrimidines, herein, a new method is presented using cheaper and more accessible starting materials to produce high-efficiency products. In this protocol, the novel nanocatalyst is very effective in the progression of the reaction and increasing the efficiency. This green approach in aqueous media has several advantages as compared with other methods, such as easier work-up, very mild reaction conditions, reusability of the catalyst, and eco-friendliness. The products of this four-component condensation were evaluated using IR, ¹H NMR, ¹³C NMR spectra, and C. H. N. analyses, and the catalyst structure was confirmed by FT-IR, XRD, SEM, EDX, TGA and VSM techniques.

In this protocol, a novel nanocatalyst was very effective in progression of the reaction and increasing efficiency. This green approach in aqueous media has several advantages compared with the reported methods.     

Basic ionic liquid as catalyst and surfactant: green synthesis of quinazolinone in aqueous media

Basic imidazolium-based ionic liquids not only possess the extraordinary physicochemical properties of ionic liquids, but also have excellent basicity and surfactivity. 1-Propyl-3-alkylimidazole hydroxide ionic liquids ([PRIm][OH]) were synthesized and their catalytic and surfactant behavior were studied in this work. [PRIm][OH] owned excellent surfactivity, and their alkyl chains and ion pairs benefit hydrophobicity and hydrophilicity respectively. The surfactivity of [PRIm][OH] increased with increasing alkyl chain length. [PRIm][OH] showed better catalytic performance than NaOH in the condensation of 2-aminobenzonitrile with cyclohexanone in aqueous medium, and the catalytic performance was well coincident with their surfactant behavior. [PRIm][OH] could decrease the interfacial tension of solvent effectively and form micelles in water. The formed micelles could solubilise more reactants into water and effectively increase the chance of contact between reactants and catalytic active sites. The catalyst dosage obviously affected catalytic performance. The catalytic system is a promising recyclable system.

[PRIm][OH] showed excellent catalytic properties in synthesis of quinazolinone in aqueous medium, owing to its excellent surfactivity and basicity.     

One-pot three component synthesis of 5-allyl-1,2,3-triazoles using copper(i) acetylides

One-pot three-component reactions using copper(i) acetylide, azide, allyl iodide, and NaOH have been developed. The reactions proceed smoothly at room temperature to afford 5-allyl-1,2,3-triazoles, which can be further transformed into a variety of 1,2,3-triazole-fused bi-/tricyclic scaffolds. This method offers the most efficient, convenient, and practical route towards useful polycyclic scaffolds in moderate to excellent yields.

A one-pot three-component synthetic route toward 5-allyl-1,2,3-triazoles using copper(i) acetylide has been developed, which allows further transformation to important tricyclic scaffolds.     

Electrochemical synthesis of copper(i) acetylides via simultaneous copper ion and catalytic base electrogeneration for use in click chemistry

We report an efficient and sustainable electrochemical synthesis of copper(i) acetylides using simultaneous copper oxidation and Hofmann elimination of quaternary ammonium salts. The electrochemically-generated base was also regenerated electrochemically, making it catalytic. A ‘Click test’ (CuAAC reaction) was performed to assess product purity and an electrochemically-promoted, one-pot CuAAC reaction was performed, which serves as a promising initial demonstration of this approach in a pharmaceutically-relevant reaction.

We report an efficient and sustainable electrochemical synthesis of copper(i) acetylides using simultaneous copper oxidation and Hofmann elimination of quaternary ammonium salts.     

Enantioselective one-pot synthesis of 4H-chromene derivatives catalyzed by a chiral Ni(ii) complex

A Ni(ii)–bis(oxazoline) complex and p-TSOH are used to form enantioenriched 4H-chromenes from ortho-quinone methides (o-QMs) and dicarbonyls, providing the desired products in up to 95% ee. The method is compatible with various β-ketoester substrates, and the products obtained could be converted into biologically active 4H-chromene derivatives.

A Ni(ii)–bis(oxazoline) complex and p-TSOH are used to form enantioenriched 4H-chromenes from ortho-quinone methides (o-QMs) and dicarbonyls, providing the desired products in up to 95% ee.

The chromene skeleton is widespread in natural products and medicinal agents,¹ and the diverse biological activities² of chromene derivatives have intrigued pharmacologists and chemists. In particular, 4H-chromene is a privileged core structure that has received increasing attention in recent years. Natural and synthetic functionalized 4H-chromenes (Fig. 1) display a broad spectrum of biological activities,³ including as cell-proliferation inhibitors (A), apoptosis inducers (B), and neuropeptide Y Y5 receptor antagonists (C), as well as improving cognitive deficit (D).Open in a separate windowFig. 1Natural and synthetic bioactive 4H-chromene compounds.Over the past decade, extensive efforts have been devoted to the synthesis of 4H-chromene compounds. Most of the synthetic methods furnished racemic products,^4,5 though enantioselective routes have recently been developed. In 2009 and 2011, Xie et al. and Wang et al.⁶ respectively, reported the organocatalytic synthesis of chiral 2-amino-4H-chromene derivatives from malononitrile. In 2011, Feng et al.⁷ explored the first Lewis acid-catalyzed one-pot synthesis of enantioenriched 2-amino-4H-chromenes bearing indolyl moieties from malononitrile, salicylaldehyde and indole. In 2014, Schneider et al.⁸ found the reaction of ortho-hydroxyl benzhydryl alcohols with β-diketones was catalyzed by a chiral phosphoric acid (CPA), giving rise to 4H-chromenes in high yield with excellent enantioselectivities (up to 98% ee); however, when the substrate was changed to ethyl acetoacetate, the ee value dropped to 84%. Subsequently, Rueping et al.⁹ employed a chiral binol based N-trifly phosphoramide to promote the in situ generation of ortho-quinone methides (o-QMs) and their subsequent reaction with 1,3-cyclohexanedione, providing the desired 4H-chromene products with excellent enantioselectivities (up to 95% ee). In 2017, the Schneider group reported the oxidation of 2-alkyl-substituted phenols in situ by Mn(dbm)₃ (dbm = dibenzoylmethane) to give o-QMs that, upon the CPA-catalyzed conjugate addition of β-dicarbonyls, afforded 4H-chromenes in up to 79% yield and up to 74% ee,¹⁰ indicating that the substrate structures have a remarkable influence on the reaction. Despite these notable advances, efficient and concise methods for the enantioselective synthesis of 4H-chromenes are still limited and highly desirable. o-QMs have been extensively applied in Michael additions and cycloadditions.^11,12 The reaction of some dicarbonyls with o-QMs generates chromene derivatives, and particularly the use of β-diketones has been well studied.However, few reports mention the use of asymmetric catalysis to construct 4H-chromenes from β-ketoesters.^8,13 As part of a continuing effort to develop efficient catalytic asymmetric methods using readily available catalyst systems,¹⁴ we explored the reaction of β-ketoesters with o-QMs catalyzed by a Ni(ii)–bis(oxazoline) complex and subsequent p-TSOH, which gave 4H-chromenes in good yields and up to 95% ee. This one-pot, three-step sequence of enantioselective Michael addition, intramolecular ketalization and dehydration, was accomplished under mild conditions. The products could be transformed into potentially bioactive 4H-chromene compounds.At the outset, ortho-quinone methide (o-QMs) 1a (PMP = p-MeOPh) and ethyl acetoacetate 2a were chosen as model substrates. The reaction was carried out in CHCl₃ at 0 °C in the presence of different metal complexes of ligand L1. For various Lewis acids including Cu(OTf)₂, Mg(OTf)₂, Zn(OTf)₂, Ni(OTf)₂ and Ni(ClO₄)₂, the reaction proceeded to completion within 5 minutes and giving product 3aa in moderate to high yields (†Optimization of the reaction condition^a

Microwave assisted one-pot green synthesis of cinnoline derivatives inside natural sporopollenin microcapsules

We present a green and efficient approach for the synthesis of novel cinnoline derivatives inside natural Lycopodium clavatum sporopollenin (LCS) microcapsules via a one-pot microwave (MW) assisted reaction for the first time. We also propose the concept that the robust micrometre-sized sporopollenin microcapsules can act as MW microreactors. We demonstrate the feasibility of this concept by in situ synthesising 8-hydroxy-7-nitro-6-(3-nitrophenyl)-3-oxo-2-(p-tolyl)-2,3,5,6-tetrahydrocinnoline-4-carbonitrile inside the LCS microcapsules via a microwave (MW) assisted reaction of ethyl 5-cyano-4-methyl-6-oxo-1-(p-tolyl)-1,6-dihydropyridazine-3-carboxylate with 1-nitro-2-phenylethylene in the presence of piperidine as a base at 100 °C for 20 minutes. The LCS microparticles are extensively characterised before and after the MW induced reaction using several techniques. The formation of the cinnoline compound inside the LCS microcapsules is confirmed by laser scanning confocal microscopy (LSCM), X-ray diffraction (XRD) and fourier-transform infrared spectroscopy (FTIR) analyses. Using liquid chromatography-mass spectrometry (LCMS) analyses, we show that the structural integrity of the cinnoline compound, recovered from the cinnoline loaded (cinn-loaded) LCS, is preserved. The pure cinnoline is found to show promising optical properties with two λ_max absorption peaks at 310 and 610 nm. Both the pure cinnoline and cinn-loaded LCS show promising antibacterial activity against Pseudomonas aeruginosa (Gram-negative) and Bacillus cereus (Gram-negative) human pathogenic bacterial strains. The successful MW induced reaction of the prominent cinnoline derivative inside the biocompatible LCS microreactors can open up intriguing applications in materials and pharmaceutical sciences.

We have achieved in situ microwave assisted green syntheses of a novel cinnoline derivative inside natural sporopollenin microreactors.     

Thermally activated delayed fluorescence in luminescent cationic copper(i) complexes

In this work, the photophysical characteristics of [Cu(N^N)₂]⁺ and [Cu(N^N)(P^P)]⁺ complexes were described. The concept of thermally activated delayed fluorescence (TADF) and its development throughout the years was also explained. The importance of ΔE_(S1–T1) and spin-orbital coupling (SOC) values on the TADF behavior of [Cu(N^N)₂]⁺ and [Cu(N^N)(P^P)]⁺ complexes is discussed. Examples of ΔE_(S1–T1) values reported in the literature were collected and some trends were proposed (e.g. the effect of the substituents at the 2,9 positions of the phenanthroline ligand). Besides, the techniques (or calculation methods) used for determining ΔE_(S1–T1) values were described. The effect of SOC in TADF was also discussed, and examples of the determination of SOC values by DFT and TD-DFT calculations are provided. The last chapter covers the applications of [Cu(N^N)₂]⁺ and [Cu(N^N)(P^P)]⁺ TADF complexes and the challenges that are still needed to be addressed to ensure the industrial applications of these compounds.

Bibliographic review of cationic Cu(i) complexes that undergo Thermally Activated Delayed Fluorescence (TADF). From the first findings found in the homoleptic and heteroleptic Cu(i)-TADF complexes to the use of this property in lighting devices.     

Bio-molecule functionalized rapid one-pot green synthesis of silver nanoparticles and their efficacy toward the multidrug resistant (MDR) gut bacteria of silkworms (Bombyx mori)

The present study aimed to synthesise bio-molecule functionalized silver nanoparticles (AgNPs) using leaf extract from mulberry variety S-1635 (Morus alba L.) and to explore its antibacterial efficacy against multidrug resistant (MDR) gut bacteria isolated from natural infection observed from silkworm larvae in rearing conditions. AgNPs formation was established by surface plasmon resonance at 480 nm. The crystallinity of the synthesised AgNPs was checked by HR-TEM and XRD analysis. SEM and TEM characterisation further exhibited the spherical, monodispersed, well scattered nature of the AgNPs with an average particle size of 11.8 nm ± 2.8. The presence of (111), (200), (220) and (311) planes in Bragg''s reflections confirmed the face-cantered-cubic crystalline silver. EDX analysis confirmed the presence of elemental silver. FT-IR spectra revealed functional groups were responsible for the reduction of silver ions. The zeta potential value of −17.3 mV and −25.6 mV was recorded in MH and DMEM/F-12 media, respectively. The LC-QTOF/MS and HRMS spectra disclosed the presence of bioactive compounds like flavonoid, gallic acid, and stigmasterol, which are probably involved in the reduction and functionalization of AgNPs. The antibacterial efficacy of bio-molecule functionalized AgNPs and the naked AgNPs was tested on Gram-positive and Gram-negative bacteria isolated from silkworms and characterized by using 16S rDNA and gyrB genes. The cytotoxicity of AgNPs was tested on WRL-68, HEK-293, ACHN, and HUH-7 cell lines using MTT assay. This study provides an insight into the application of bio-molecule functionalized AgNPs for combating various silkworm pathogens which severely affect the agro-rural economy of developing countries.

We aimed to synthesise bio-molecule functionalized silver nanoparticles using leaf extract from mulberry variety S-1635 (Morus alba L.) and to explore its antibacterial effect on multidrug resistant gut bacteria isolated from natural infection observed from silkworm larvae.     

Dihydropyrimidinones: efficient one-pot green synthesis using Montmorillonite-KSF and evaluation of their cytotoxic activity

A simple, efficient, cost-effective, recyclable and green approach has been developed for the synthesis of new dihydropyrimidinone analogs via the Biginelli reaction. The methodology involves a multicomponent reaction catalyzed by “HPA-Montmorillonite-KSF” as a reusable and heterogeneous catalyst. This method gives an efficient and much improved modification of the original Biginelli reaction, in terms of yield and short reaction times under solvent free conditions. All the derivatives were subjected to cytotoxicity screening against a panel of four different human cancer cell lines viz. colon (Colo-205), prostate (PC-3), leukemia (THP-1) and lung (A549) to check their effect on percentage growth. MTT [3-(4,5-dimethylthiazol-yl)-diphenyl tetrazoliumbromide] cytotoxicity assay was employed to check IC₅₀ values. Of the synthesized analogs, 16a showed the best activity with IC₅₀ of 7.1 ± 0.8, 13.1 ± 1.4, 13.8 ± 0.9 and 14.7 ± 1.1 μM against lung (A549), leukemia (THP-1), prostate (PC-3) and colon (Colo-205) cancer lines, respectively. The 16a analog was further checked for its effect on cancer cell properties through clonogenic (colony formation) and scratch motility (wound healing) assays and thereby was found that it reduced both the colony formation and migratory properties of the lung cancer cell line (A549). Further, molecular docking studies were performed with 16a to show its binding mode.

The general method for the preparation of DHPM analogs; cytotoxic activity and binding mode of the most active derivative against PI3Kγ and CDK2 targets.     

The shiny side of copper: bringing copper(i) light-emitting electrochemical cells closer to application

Heteroleptic [Cu(P^P)(N^N)][PF₆] complexes, where N^N is 5,5′-dimethyl-2,2′-bipyridine (5,5′-Me₂bpy), 4,5,6-trimethyl-2,2′-bipyridine (4,5,6-Me₃bpy), 6-(tert-butyl)-2,2′-bipyridine (6-tBubpy) and 2-ethyl-1,10-phenanthroline (2-Etphen) and P^P is either bis(2-(diphenylphosphino)phenyl)ether (POP, PIN [oxydi(2,1-phenylene)]bis(diphenylphosphane)) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos, PIN (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane)) have been synthesized and their NMR spectroscopic, mass spectrometric, structural, electrochemical and photophysical properties were investigated. The single-crystal structures of [Cu(POP)(5,5′-Me₂bpy)][PF₆], [Cu(xantphos)(5,5′-Me₂bpy)][PF₆], [Cu(POP)(6-tBubpy)][PF₆], [Cu(POP)(4,5,6-Me₃bpy)][PF₆]·1.5Et₂O, [Cu(xantphos)(4,5,6-Me₃bpy)][PF₆]·2.33CH₂Cl₂, [Cu(POP)(2-Etphen)][PF₆] and [Cu(xantphos)(2-Etphen)][PF₆] are described. While alkyl substituents in general exhibit electron-donating properties, variation in the nature and substitution-position of the alkyl group in the N^N chelate leads to different effects in the photophysical properties of the [Cu(P^P)(N^N)][PF₆] complexes. In the solid state, the complexes are yellow to green emitters with emission maxima between 518 and 602 nm, and photoluminescence quantum yields (PLQYs) ranging from 1.1 to 58.8%. All complexes show thermally activated delayed fluorescence (TADF). The complexes were employed in the active layer of light-emitting electrochemical cells (LECs). The device performance properties are among the best reported for copper-based LECs, with maximum luminance values of up to 462 cd m⁻² and device half-lifetimes of up to 98 hours.

Heteroleptic copper(i) complexes with bisphosphanes and astutely tuned N^N chelating ligands as emitters give bright LECs with record-breaking stability.     

Structure and emission properties of dinuclear copper(i) complexes with pyridyltriazole

A new series of five highly emissive binuclear heteroleptic pyridyltriazole-Cu(i)-phosphine complexes 1–5 was synthesized and examined by different experimental (IR, elemental and thermogravimetric analysis, single crystal X-ray diffraction technique, UV-vis and fluorescence spectroscopy) and quantum chemical aproaches. Complexes 1–5 exhibited excellent stimuli-responsive photoluminescent performance in the solid state at room temperature (quantum yield (QY) = 27.5–52.0%; lifetime (τ) = 8.3–10.7 μs) and when the temperature was lowered to 77 K (QY = 38.3–88.2; τ = 17.8–134.7 μs). The highest QY was examined for complex 3 (52%) that can be explained by the small structural changes between the ground S₀ and exited S₁ and T₁ states leading to the small S₁–T₁ triplet gap and efficient thermally-activated delayed fluorescence. Moreover, complex 4 demonstrates reversible mechanochromic and excitation dependent luminescence.

New highly emissive copper(i) complexes based on 3/4-pyridyltriazole have been synthesized and fully characterized. Photophysical properties and the mechanism of photo- and mechanochromic and excitation dependent luminescence are discussed.     

Rapid electrochemical sensor for uranium(vi) assessment in aqueous media

The significance of reliable monitoring of uranium levels in water recourses calls for the development of time-saving, robust, and accurate methods for its estimation. In this view, the current study describes the design and analytical parameters of a potentiometric membrane sensor for uranium(vi) ions. The sensor is based on a new Schiff base derivative, as an ionophore, that was synthesized and structurally characterized by elemental, FTIR, and ¹HNMR analyses. The impact of the membrane constituents was studied and the membrane composition of PVC (32.50) : o-NPOE (65.00) : ionophore (2.00) :  KTpClPB (0.50) (%, w/w) achieved the optimal performance. A Nernestian response was observed for uranium(vi) ions within the concentration range 1.00 × 10⁻⁶ to 1.00 × 10⁻¹ mol L⁻¹. The sensor revealed a low detection limit of 3.90 × 10⁻⁷ mol L⁻¹ with satisfactory reproducibility. Stable and reproducible potentials were obtained within a short time (9 s) over the pH range 2.10–4.21. The impact of possible competing ions was investigated and the selectivity coefficients revealed appropriate selectivity for uranium(vi) ions over various cations without significant interference. The sensor''s performance was examined by determining the amount of uranium(vi) in water samples and the results showed no significant differences from those obtained by the ICP-OES method.

A new Schiff base was synthesized and applied as ionophore to construct potentiometric sensor for uranium(vi) determination.     

A facile green and one-pot synthesis of grape seed-derived carbon quantum dots as a fluorescence probe for Cu(ii) and ascorbic acid

In this study, an on–off–on fluorescence probe for the detection of trace Cu(ii) and ascorbic acid (AA) based on biomass-derived sulfur and nitrogen double heteroatom-doped carbon dots (N,S-CDs) was designed. For the first time, the probe (N,S-CDs) was prepared from grape seeds and thiourea as the precursor. Cu(ii) was added to the carbon point solution, the fluorescence intensity (FL) of N,S-CDs was strongly quenched (switch OFF) and the fluorescence probe turned to “ON” (switch ON) with the addition of AA. Under the optimal conditions, the as-synthesized N,S-CDs had a good detection performance for Cu(ii) and AA assay with the linearity ranges from 150–500 μg mL⁻¹ and 0.1–400 μg mL⁻¹, and the LODs were 0.048 mg L⁻¹ and 0.036 mg L⁻¹, respectively. The as-prepared N,S-CDs exhibited a low cytotoxicity and a good biocompatibility, which show their potential for application in the biological imaging of living cells.

In this study, an on–off–on fluorescence probe for the detection of trace Cu(ii) and ascorbic acid (AA) based on biomass-derived sulfur and nitrogen double heteroatom-doped carbon dots (N,S-CDs) was designed.     

Eco-friendly polyethylene glycol (PEG-400): a green reaction medium for one-pot,four-component synthesis of novel asymmetrical bis-spirooxindole derivatives at room temperature

PEG-400 has been used as a green and biodegradable polymeric solvent for the one-pot, two-step, multi-component synthesis of novel asymmetrical bis-spirooxindole derivatives by the reaction of N-alkyl isatin, isatin derivatives, alkylmalonates and C–H activated carbonyl compounds in the presence of K₂CO₃ at room temperature. Using this procedure, all the products were obtained in good to excellent yields.

PEG-400 has been used for the synthesis of novel asymmetrical bis-spirooxindoles by the reaction of N-alkyl isatin, isatin derivatives, alkylmalonates and C–H activated carbonyl compounds in the presence of K₂CO₃ at room temperature.     

The anchoring of a Cu(ii)–salophen complex on magnetic mesoporous cellulose nanofibers: green synthesis and an investigation of its catalytic role in tetrazole reactions through a facile one-pot route

Today, most synthetic methods are aimed at carrying out reactions under more efficient conditions and the realization of the twelve principles of green chemistry. Due to the importance and widespread applications of tetrazoles in various industries, especially in the field of pharmaceutical chemistry, and the expansion of the use of nanocatalysts in the preparation of valuable chemical reaction products, we decided to use an (Fe₃O₄@NFC@NSalophCu)CO₂H nanocatalyst in this project. In this study, the synthesis of the nanocatalyst (Fe₃O₄@NFC@NSalophCu)CO₂H was explained in a step-by-step manner. Confirmation of the structure was obtained based on FT-IR, EDX, FE-SEM, TEM, XRD, VSM, DLS, TGA, H-NMR, and CHNO analyses. The catalyst was applied to the synthesis of 5-substituted-1H-tetrazole and 1-substituted-1H-tetrazole derivatives through multi-component reactions (MCRs), and the performance was assessed. With advances in science and technology and increasing environmental pollution, the use of reagents and methods that are less dangerous for the environment has received much attention. Therefore, following green chemistry principles, with the help of the (Fe₃O₄@NFC@NSalophCu)CO₂H salen complex as a nanocatalyst that is recyclable, cheap, safe, and available, the use of water as a green solvent, and reduced reaction times, the synthesis of tetrazoles can be achieved.

Due to the importance and widespread applications of tetrazoles, especially in pharmaceutical chemistry, and the expansion of the use of nanocatalysts in the preparation of valuable chemical reaction products, we decided to use a (Fe₃O₄@NFC@NSalophCu)CO₂H nanocatalyst.     

Effect of neocuproine, a copper(i) chelator, on rat bladder function

The effects of a specific copper(I)-chelator, neocuproine (NC), and a selective copper(II)-chelator, cuprizone, on nonadrenergic-noncholinergic transmitter mechanisms in the rat urinary bladder were studied by measuring nerve-evoked contractions of bladder strips and voiding function under urethane anesthesia. After blocking cholinergic and adrenergic transmission with atropine and guanethidine, electrical field stimulation induced bimodal contractions of bladder strips. An initial, transient contraction that was blocked by the purinergic antagonist, suramin, was significantly enhanced by NC (20 and 200 microM applied sequentially) but not affected by cuprizone. The facilitating effect, which was blocked by suramin and reversible after washout of the drug, did not occur following administration of neocuproine-copper(I) complex (NC-Cu). NC (20 microM) significantly increased the second, more sustained contraction, whereas 200 microM decreased this response. These effects of NC on the sustained contractions were not elicited by NC-Cu and not blocked by suramin. The nitric oxide synthase inhibitor, l-nitroarginine, did not alter the responses to NC. NC (20 microM) elicited a marked increase in basal tone of the strips. This effect was less prominent after the second application of 200 microMNC or with NC-Cu treatment or in the presence of suramin. In anesthetized rats, during continuous infusion cystometry, intravesical infusion of 50 microM NC but not NC-Cu or cuprizone significantly decreased the intercontraction interval (ICI) without changing contraction amplitude. The ICI returned to normal after washout of NC. Suramin blocked this effect. These results indicate that NC enhances bladder activity by facilitating purinergic excitatory responses and that copper(I)-sensitive mechanisms tonically inhibit purinergic transmission in the bladder.     

A facile one-pot green synthesis of gold nanoparticle-graphene-PEDOT:PSS nanocomposite for selective electrochemical detection of dopamine

A facile one-pot and green method was developed to prepare a nanocomposite of gold nanoparticle (AuNP), graphene (GP) and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS). Graphene was first electro-exfoliated in a polystyrene sulfonate solution, followed by a one-step simultaneous in situ formation of gold nanoparticle and PEDOT. The as-synthesized aqueous dispersion of AuNP-GP-PEDOT:PSS was thereafter used to modify the glassy carbon electrode (GCE). For the first time, the quaternary composite between AuNP, GP, PEDOT and PSS was used for selective determination of dopamine (DA) and uric acid (UA) in the presence of ascorbic acid (AA). In comparison to a bare GCE, the nanocomposite electrode shows considerably higher electrocatalytic activities toward the oxidation of DA and UA due to a synergistic effect between AuNP, GP, PEDOT and PSS. Using differential pulse voltammetry (DPV), selective determination of DA and UA in the presence of AA could be achieved with a peak potential separation of 110 mV between DA and UA. The sensor exhibits wide linear responses for DA and UA in the ranges of 1 nM to 300 μM and 10 μM to 1 mM with detection limits (S/N = 3) of 100 pM and 10 μM, respectively. Furthermore, the proposed sensor was also successfully used to determine DA in a real pharmaceutical injection sample as well as DA and UA in human serum with satisfactory recovery results.

A facile one-pot green synthesis of gold nanoparticle-graphene-PEDOT:PSS nanocomposite was successfully demonstrated.     

ZnCl2 loaded TiO2 nanomaterial: an efficient green catalyst to one-pot solvent-free synthesis of propargylamines

One-pot green synthesis of propargylamines using ZnCl₂ loaded TiO₂ nanomaterial under solvent-free conditions has been effectively accomplished. The aromatic aldehydes, amines, and phenylacetylene were reacted at 100 °C in the presence of the resultant catalyst to form propargylamines. The nanocrystalline TiO₂ was initially synthesized by a sol–gel method from titanium(iv) isopropoxide (TTIP) and further subjected to ZnCl₂ loading by a wet impregnation method. X-ray diffraction (XRD) patterns revealed the formation of crystalline anatase phase TiO₂. Field emission scanning electron microscopy (FESEM) showed the formation of agglomerated spheroid shaped particles having a size in the range of 25–45 nm. Transmission electron microscopy (TEM) validates cubical faceted and nanospheroid-like morphological features with clear faceted edges for the pure TiO₂ sample. Surface loading of ZnCl₂ on spheroid TiO₂ nanoparticles is evident in the case of the ZnCl₂ loaded TiO₂ sample. X-ray photoelectron spectroscopy (XPS) confirmed the presence of Ti⁴⁺ and Zn²⁺ species in the ZnCl₂ loaded TiO₂ catalyst. Energy-dispersive X-ray (EDS) spectroscopy also confirmed the existence of Ti, O, Zn and Cl elements in the nanostructured catalyst. 15% ZnCl₂ loaded TiO₂ afforded the highest 97% yield for 3-(1-morpholino-3-phenylprop-2-ynyl)phenol, 2-(1-morpholino-3-phenylprop-2-ynyl)phenol and 4-(1,3-diphenylprop-2-ynyl)morpholine under solvent-free and aerobic conditions. The proposed nanostructure-based heterogeneous catalytic reaction protocol is sustainable, environment-friendly and offers economic viability in terms of recyclability of the catalyst.

A one-pot green synthesis of propargylamines using nanostructured ZnCl₂–TiO₂ under solvent-free conditions has been effectively accomplished. The proposed reaction protocol is sustainable, environment-friendly and offers economic viability.     

A high-efficiency salamo-based copper(ii) complex double-channel fluorescent probe

In this paper, a salamo-based copper(ii) complex probe L-Cu²⁺ was synthesized, which combined with copper(ii) ions to form L-Cu²⁺ for the detection of S²⁻ and had a good fluorescence chemical response. Through spectral analysis, we found that S²⁻ could be identified with high sensitivity and selectivity in the presence of various anions and could be used for the detection of S²⁻ by the naked eye. With the addition of S²⁻, the solution color changed from colorless to bright yellow. UV absorption, fluorescence and other characterization methods were carried out, and the mechanism of action was determined. In addition, we performed a visual inspection of H₂S gas, and the probe L-Cu²⁺ could detect S²⁻ in the gas molecules, revealing its potential application value in biology and medicine.

A highly sensitive and selective salamo-based copper(ii) complex probe, L-Cu²⁺, was synthesized; it could be used for the detection of S²⁻ by UV and fluorescence spectroscopies. And it also could detect S²⁻ in gas molecules.