The chemoselective transformation of diarylethanones via either aerobic oxidative cleavage to give arylmethanoic acids or tandem aerobic oxidation/benzilic acid rearrangement/decarboxylation to give diarylmethanones has been developed. The transformation is controllable and applicable to a broad spectrum of substrates and affords the desired products in good to excellent yields. Mechanistic insights with control reactions, 1H NMR tracking, and single-crystal X-ray diffraction reveal a complex mechanistic network in which two common intermediates, α-ketohydroperoxide and diarylethanedione, and three plausible pathways are proposed and verified. These pathways are interlinked and can be switched reasonably by changing the reaction conditions. This method enables scalable synthesis and access to a number of valuable compounds, including vitamin B3, diphenic acid, and the nonsteroidal anti-inflammatory drug ketoprofen. The present protocol represents a step forward in exploiting complex mechanistic networks to control reaction pathways, achieving divergent syntheses from the same class of starting materials.

Four cupric complexes (1–4) with a newly designed ligand – (fluorene-9,9-diyl)dipropanoic acid – were obtained under different pH conditions. These complexes exhibit pH-dependent supramolecular self-assembly morphologies as 0D, 1D and 2D architectures, among which 1D water channels are formed by a triple winding helical chain with opposite chiral configurations in 3.

•A nanofibrous membrane of fluorinated hyperbranched PU was prepared.•High fluorine content was achieved on fluorinated PU membrane surface.•Superhydrophobicity with high adhesion to water was fabricated by electrospinning.The fluorination of hyperbranched polyurethane (HPU) was achieved by atom transfer radical grafting polymerization (ATRgP) of dodecafluoroheptyl methacrylate that was initiated from 2-bromoisobutyryl bromide-modified end groups of HPU. The nanofibrous membrane of fluorinated HPU was prepared by electrospinning. The structure of fluorinated HPU was characterized by Fourier-transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectrum (1H NMR). The surface of nanofibrous membrane was investigated with scanning electron microscope (SEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS) and water contact angle (WCA) analysis, respectively. The results suggested that compared with the reported linear fluorine-containing polyurethane materials, rather high fluorine content up to 29.14% was achieved on the surface of fluorinated HPU nanofibrous membrane. Meanwhile, a superhydrophobic surface (WCA 159.7°) with high adhesion to water was successfully fabricated via a convenient electrospinning process. The prepared material is promising for the application in microfluidic devices.Graphical abstract

A one-pot palladium-catalyzed synthesis of symmetrical and unsymmetrical diarylmethanones using acetophenone and aryl bromides as raw materials has been developed. In this reaction, acetophenone acts as a latent carbonyl donor and two pathways of palladium-catalyzed sequential coupling and aerobic oxidation are identified. The reaction is applicable to a spectrum of substrates and delivers the products in moderate to good yields. This method can be used for the synthesis of ketoprofen, a nonsteroidal anti-inflammatory drug, in a two-step procedure and 45% overall yield.

This paper presents the fabrication of a molecularly imprinting sol–gel hybrid film by the one-step electrodeposition of the constitutional individuals including chitosan (CS), phenyltrimethoxysilane (PTMS), in situ formed gold nanoparticles (AuNPs) and template p-nitrophenol (p-NP). The electrodeposition was triggered by applying an optimal potential at −0.30 V vs. SCE, leading to the formation of the p-NP imprinting CS/PTMS/AuNPs hybrid film on a glassy carbon electrode (GCE) with a roughly architectural and conductive nature, as revealed by scanning electron microscopy and electrochemical impedance analysis. The mechanism of the hybrid film formation was discussed accordingly. Upon complete removal of the template molecules assisted by cyclic voltammetry, the p-NP imprinted film modified electrode exhibited differential pulse voltammetric (DPV) responses to p-NP in a linear range from 3.0 × 10−8 to 3.5 × 10−4 M with a detection limit of 5.0 × 10−9 M. The selectivity and reusability of the sensor was demonstrated by discriminating the p-NP response from its analogues and successive rebinding/debinding cycles, respectively. The methodology is extendable as a simple and general platform for developing hybrid film sensors for the specific determination of various electrochemically active species.

This article reports the fabrication of a nanocomposite biosensor for the sensitive and specific detection of methyl parathion. The nanocomposite sensing film was prepared via the formation of gold nanoparticles on silica particles, mixing with multiwall carbon nanotubes and subsequent covalent immobilization of methyl parathion hydrolase. The composite of the individual materials was finely tuned to offer the sensing film with high specific surface area and high conductivity. A significant synergistic effect of nanocomposites on the biosensor performance was observed in biosensing methyl parathion. The square wave voltammetric responses displayed well defined peaks, linearly proportional to the concentrations of methyl parathion in the range from 0.001 μg mL−1 to 5.0 μg mL−1 with a detection limit of 0.3 ng mL−1. The application of this biosensor in the analysis of spiked garlic samples was also evaluated. The proposed protocol can be used as a platform for the simple and fast construction of biosensors with good performance for the determination of enzyme-specific electroactive species.

An electrochemical strategy on the basis of rationally designed molecularly imprinted sol–gel polymer embedded with gold nanoparticles (AuNPs) is developed for the specific and sensitive determination of Sudan I. The rationally designed sensing Sudan I imprinted sol–gel was prepared by mixing Sudan I with 3-aminopropyltriethoxysilane, tetraethoxysilane, chitosan, and AuNPs, followed by copolymerization and extraction of the template molecules. The hybrid forming membrane was characterized by SEM and FTIR-ATR, and used for the linear sweep voltammetric (LSV) determination of Sudan I in water/ethanol solutions. The LSV responses exhibited high sensitivity and selectivity, as discriminated from Sudan I analogues. Under optimal experimental conditions, LSV peak currents were linearly proportional to the concentrations of Sudan I in the range from 0.1 × 10−7 to 1.0 × 10−5 M, with a detection limit of 2.0 × 10−9 M. The strategy is generally applicable in developing sensitive, selective, and moreover, reusable electrochemical sensors for quantitative determination of electroactive species.

The reaction of l-ascorbic acid with l-cysteine in heated aqueous solution (141 ± 1 °C) at five different pH values (5.00, 6.00, 7.00, 8.00, or 9.00) for 2 h, resulted in the formation of a complex mixture of aroma volatiles. The volatile compounds generated were analysed by SPME–GC–MS. The results gave 43 aroma compounds. The reaction between l-ascorbic acid and l-cysteine led mainly to the formation of alicyclic sulphur compounds, thiophenes, thienothiophenes, thiophenones, thiazoles and pyrazines, most of which contain sulphur. Many of these volatiles had meaty flavour. The origin of many of the compounds was explained. The studies showed that thienothiophenes and thienones were formed mainly at acidic pH. In contrast, higher pH values could promote the production of thiophenes, thiazoles and pyrazines.

The identification of aroma compounds, formed from the reactions of l-ascorbic acid with l-threonine/l-serine at five different pH values (5.00, 6.00, 7.00, 8.00, or 9.55) and 143 ± 2 °C for 2 h, was performed using a SPME–GC–MS technique, and further use of LRI. The results showed 35 aroma compounds. The reaction between l-ascorbic acid and l-threonine/l-serine led mainly to the formation of pyrazines. Many of these were alkylpyrazines, such as 2-methylpyrazine, 2,5-dimethylpyrazine, 2-ethylpyrazine, 2-ethyl-6-methylpyrazine, 2-ethyl-5-methylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2,3-diethyl-5-methylpyrazine, and 3,5-diethyl-2-methylpyrazine; other compounds identified were furans and aldehydes. More volatiles were generated in l-ascorbic acid with l-threonine systems than in l-ascorbic acid with l-serine systems. The studies showed that furans, such as furfural, 2-furanmethanol, benzofuran, 2,5-furandicarboxaldehyde and 2-furfurylfuran were formed mainly at acidic pH. In contrast, higher pH values could promote the production of pyrazines.

The labeling strategy with gold nanoparticles for the conventional surface plasmon resonance (SPR) signal enhancement has been frequently used for the sensitive determination of small molecules binding to its interaction partners. However, the influence of gold nanoparticles with different size and shape on SPR signal is not known. In this paper, three kinds of gold nanoparticles, namely nanorods, nanospheres, and nanooctahedrons with different size, were prepared and used to investigate their effects on the conventional SPR signal at a fixed excitation wavelength 670 nm. It was found that the SPR signal (i.e., resonant angle shift) was varied with the shapes and sizes of gold nanoparticles in suspension at a fixed concentration due to their different plasmon absorbance bands. For gold nanorods with different longitudinal absorbance bands, three conventional SPR signal regions could be clearly observed when the gold nanorod suspensions were separately introduced onto the SPR sensor chip surface. One region was the longitudinal absorbance bands coinciding with or close to the SPR excitation wavelength that suppressed the SPR angle shift. The second region was the longitudinal absorbance bands at 624 to 639 and 728 to 763 nm that produced a moderate increase on the SPR resonant angle shift. The third region was found for the longitudinal absorbance bands from 700 to 726 nm that resulted in a remarkable increase in the SPR angle shift responses. This phenomenon can be explained on the basis of calculation of the correlation of SPR angle shift response with the gold nanorod longitudinal absorbance bands. For nanospheres and nanooctahedrons, the SPR angle shift responses were found to be particle shape and size dependent in a simple way with a sustaining increase when the sizes of the nanoparticles were increased. Consequently, a guideline for choosing gold nanoparticles as tags is suggested for the SPR determination of small molecules with binding to the immobilized interaction partners.

The article presents a novel strategy for a sensitive investigation of the interaction between acetylcholinesterase (AChE) and its small molecular carbamate inhibitors. Two carbamate inhibitors with different ether linkages and the terminal lipoate were synthesized and labeled with gold nanoparticles (AuNPs). With the signal amplification of AuNPs, the specific interactions between the AuNPs labeled carbamate inhibitors (ALC1 and ALC2) and the immobilized AChE on sensor chip surface were readily examined. The detection sensitivities of ALC1 and ALC2 were 176 and 121 m°/nM, respectively, with the detection limits of 7.0 and 12 pM at a signal-to-noise ratio of 3. The association/dissociation constants for the binding interaction between carbamate inhibitors and AChE were reported for the first time. The affinity constants were estimated to be 3.13 × 106 and 6.39 × 105 M−1 for ALC1 and ALC2 respectively. This AuNPs labeling strategy is versatile and may be applicable for the direct or competitive SPR kinetic assay of the interaction between small molecule inhibitors and their target proteins with a high sensitivity.

Thin film of a molecular imprinted polymer based on electropolymerization method with sensitive and selective binding sites for dimethoate was developed. This film was cast on gold electrode by electrochemical polymerization in solution of o-phenylenediamine and template dimethoate via cyclic voltammetry scans and further deposition of Ag nanoparticles. The surface plasmon resonance and cyclic voltammetric signals were also recorded simultaneously during the electropolymerization, controlling the thickness of the polymer film to be 25 nm. The imprinted film showed high selectivity towards to dimethoate. The recognition between the imprinted sensor and target molecule was observed by measuring the variation amperometric response of the oxidation–reduction probe, K3Fe(CN)6, on electrode. Under the optimal experimental conditions, the peak currents were proportional to the concentrations of dimethoate in two ranges, from 1.0 to 1000 ng mL−1 and from 1.0 to 50 μg mL−1, with the detection limit of 0.5 ng mL−1. Due to the high affinity, selectivity and stability the imprinted sensor provides a simple detection platform for organophosphate compounds.

A simple method to immobilize acetylcholinesterase (AChE) on silica sol–gel (SiSG) film assembling gold nanoparticles (AuNPs) was proposed, thus a sensitive, fast and stable amperometric sensor for quantitative determination of organophosphorous insecticide was developed. The large quantities of hydroxyl groups in the sol–gel composite provided a biocompatible microenvironment around enzyme molecule and stabilized its biological activity to a large extent. The immobilized AChE could catalyze the hydrolysis of acetylthiocholine chloride (ATCl) with a Kmapp value of 450 μM to form thiocholine, which was then oxidized to produce detectable single with a linear range of 10–1000 μM. AuNPs catalyzed the electro-oxidation of thiocholine, thus increasing detection sensitivity. Based on the inhibition of organophosphorous insecticide on the enzymatic activity of AChE, using monocrotophos as a model compound, the conditions for detection of the insecticide were optimized. The inhibition of monocrotophos was proportional to its concentration ranging from 0.001 to 1 μg/ml and 2 to 15 μg/ml, with the correlation coefficients of 0.9930 and 0.9985, respectively. The detection limit was 0.6 ng/ml at a 10% inhibition. The developed biosensor exhibited good reproducibility and acceptable stability, thus providing a new promising tool for analysis of enzyme inhibitors.