Late-stage Functionalization using a Popular Titrating Agent: Aryl-Chlorides and -Fluorides Activation by the Diphenylacetic Acid Dianion.

Aryl-chlorides and -fluorides are common building blocks, but their use in synthesis is limited by the high stability of their Ar-X bonds. The generation of aryl radicals via activation of strong Ar-X bonds is possible through the irradiation of tailor-made organic anions, which become reductants stronger than lithium metal. We report that the combination of visible light with the cheap diphenylacetic acid dianion is an even better tool, showing excellent activity across a variety of complex substrates and providing opportunities for late-stage drug modification. Ar-X bonds are chemoselectively activated in the presence of more easily reducible functions, such as Alk-Cl ones and carbonyl groups. These results pave the way to original synthetic strategies that would be otherwise considered impossible.

Molecularly Imprinted Polypyrrole-Modified Screen-Printed Electrode for Dopamine Determination.

This paper introduces a quantitative method for dopamine determination. The method is based on a molecularly imprinted polypyrrole (e-MIP)-modified screen-printed electrode, with differential pulse voltammetry (DPV) as the chosen measurement technique. The dopamine molecules are efficiently entrapped in the polymeric film, creating recognition cavities. A comparison with bare and non-imprinted polypyrrole-modified electrodes clearly demonstrates the superior sensitivity, selectivity, and reproducibility of the e-MIP-based one; indeed, a sensitivity of 0.078 µA µM-1, a detection limit (LOD) of 0.8 µM, a linear range between 0.8 and 45 µM and a dynamic range of up to 350 µM are achieved. The method was successfully tested on fortified synthetic and human urine samples to underline its applicability as a screening method for biomedical tests.

Selective Oxidation of Alcohols to Carbonyls Under Decatungstate-Mediated Photoelectrochemical Conditions.

The oxidation of alcohols to the corresponding carbonyl derivatives has been realized under photoelectrochemical conditions in the presence of tetrabutylammonium decatungstate (TBADT) as the homogeneous photocatalyst. The protocol can be applied to both primary and secondary, benzylic and aliphatic alcohols. The desired products are obtained selectively, skipping the need for purposely added chemical oxidants. An in-depth study of photoelectrochemical conditions revealed that the protocol works best under amperostatic conditions in an undivided electrochemical cell irradiated with a 390 nm LED lamp. The comparison with analogous electrochemical and chemical oxidant-promoted photocatalytic transformations demonstrates the superior efficiency and selectivity of the hereby reported photoelectrochemical conditions.

An Optical Device Based on a Chemical Chip and Surface Plasmon Platform for 2-Furaldehyde Detection in Insulating Oil.

2-Furaldehyde (2-FAL) is one of the main by-products of the degradation of hemicellulose, which is the solid material of the oil-paper insulating system of oil-filled transformers. For this reason, it has been suggested as a marker of the degradation of the insulating system; sensing devices for 2-FAL analysis in a wide concentration range are of high interest in these systems. An optical sensor system is proposed; this consists of a chemical chip, able to capture 2-FAL from the insulating oil, coupled with a surface plasmon resonance (SPR) probe, both realized on multimode plastic optical fibers (POFs). The SPR platform exploits gold nanofilm or, alternatively, a double layer of gold and silicon oxide to modulate the sensor sensitivity. The capturing chip is always based on the same molecularly imprinted polymer (MIP) as a receptor specific for 2-FAL. The system with the SPR probe based on a gold nanolayer had a higher sensitivity and a lower detection limit of fractions of µg L-1. Instead, the SPR probe, based on a double layer (gold and silicon oxide), has a lower sensitivity with a worse detection limit, and it is suitable for the detection of 2-FAL at concentrations of 0.01-1 mg L-1.

Photodegradation of cannabidiol (CBD) and Δ9-THC in cannabis plant material.

Δ9-THC, the psychotropic cannabinoid in Cannabis sativa L., for many years has been the focus of all the pharmacological attention as the main promising principle of the plant. Recently, however, cannabidiol (CBD) has brought a sudden change in the scenario, exponentially increasing the interest in pharmacology as the main non-psychotropic cannabinoid with potential therapeutic, cosmetical and clinical applications. Although the reactivity of CBD and Δ9-THC has been considered, little attention has been paid to the possible photodegradation of these cannabinoids in the vegetal matrix and the data available in the literature are, in some cases, contradictory. The aim of the present work is to provide a characterization of the photochemical behaviour of CBD and Δ9-THC in three cannabis chemotypes, namely I (Δ9-THC 2.50%w/w), II (CBD:Δ9-THC 5.82%w/w:3.19%w/w) and III (CBD 3.02%w/w).

Easy and Accessible Synthesis of Cannabinoids from CBD.

Cannabidiol (CBD), a prominent phytocannabinoid found in various Cannabis chemotypes, is under extensive investigation for its therapeutic potential. Moreover, because it is nonpsychoactive, it can also be utilized as a functional ingredient in foods and supplements in certain countries, depending on its legal status. From a chemical reactivity point of view, CBD can undergo conversion into different structurally related compounds both during storage and after the consumption of CBD-based products. The analytical determination of these compounds is of paramount concern due to potential toxicity and the risk of losing the active ingredient (CBD) title. Consequently, the complete stereoselective total synthesis of representative CBD-derived compounds has become a matter of great interest. The synthesis of pure CBD-derived compounds, achievable in a few synthetic steps, is essential for preparing analytical standards and facilitating biological studies. This paper details the transformation of the readily available CBD into Δ8-THC, Δ9-THC, Δ8-iso-THC, CBE, HCDN, CBDQ, Δ6-iso-CBD, and 1,8-cineol cannabinoid (CCB). The described protocols were executed without the extensive use of protecting groups, avoiding tedious purifications, and ensuring complete control over the structural features.

Pervasiveness of inorganic gunshot residue (IGSR) in handguns after cleaning and conditioning procedures.

Memory effect in firearms that is, the possibility for a weapon to release inorganic particles whose elemental composition depends on its entire shooting history, is responsible for most of the interpretation difficulties encountered in forensic gunshot residue analysis. The presence of residues chemically inconsistent with the last discharged round, the creation of particles having unusual elemental profiles, and the dependence of residue population composition on the collection point are all manifestations of memory effect. The experimental results reported in this paper highlight the ineffectiveness of a wide number of gun cleaning procedures in reducing memory effect. Moreover, the common alternative of discharging batches of rounds having a "new" primer mixture does not fully eliminate the possibility to recover "old" residues at least from the shooter's hands. Two brand new pistols and ammunition having lead-based, leadless and heavy metal free primers were used. Specimens, collected both from the shooters' hands and from cotton targets set nearby the gun muzzle, were analyzed by SEM-EDS and by ICP-OES. After discharging 10's of new ammunitions, the number of old residues ejected from the gun muzzle indeed showed an asymptotic decrease to zero. In spite of this, the number of old residues recovered from the shooter's hands did not follow any predictable trend. These different behaviors suggest that all internal components of a gun, and not just the barrel, play a role in memory effect.

Molecularly Imprinted Polymer-based voltammetric sensor for amino acids/indazole derivatives synthetic cannabinoids detection.

BACKGROUND: Synthetic cannabinoids (SCs) are a broad class of illicit drugs that are classified according to the chemical structure of the aromatic core that they present (i.e., indole, imidazole, pyrrole) and their detection is still a challenge, despite their widespread diffusion. The identification of a specific class of SC in complex matrices, such as real samples with a rapid, economic analytical device useable directly in the field, is highly desirable, as it can provide immediate and reliable information that eventually addresses more targeted analyses. RESULTS: The present paper proposes a Molecularly Imprinted Polymer (MIP)-based voltammetric sensor for the rapid and selective detection of indazole-type SCs. In this context, a polyacrylate-based MIP was used to functionalize a Pt electrode. The MIP composition was optimized through a Design of Experiments approach, and for the sake of safety, a non-psychotropic compound structurally related to the selected SCs was employed as the template in the MIP formulation. A complete characterization of the electrochemical behavior of the selected SCs was performed, and differential pulse voltammetry (DPV) in acetonitrile/lithium perchlorate 0.1 M was the technique applied for their quantification. LOD around 0.01 mM and linearity up to 0.8 mM were found. Comparison with the non-imprinted (NIP) modified and bare electrodes showed better selectivity and reproducibility of the MIP-based sensor. Recovery tests (in the 70-115 % range) were performed on simulated pills and smoking mixtures to test the reliability of the proposed method. SIGNIFICANCE: The method proposed allows the identification and quantification of indazole-based SCs as a class in complex matrices. Due to the selectivity of the obtained device, no clean-up of the sample before analyses is needed. For the same reason, the interference of cutting substances and natural cannabinoids was negligible.

A new cysteamine-copper chemically modified screen-printed gold electrode for glyphosate determination.

A chemically modified screen-printed gold electrode has been prepared by covering the electrode surface with a cysteamine-copper self-assembled monolayer (SAM). The sensor was effective for the voltammetric sensing of glyphosate. The method exploits the interaction of glyphosate with copper ions complexed by cysteamine, which results in a decrease in the intensity of copper redox current. Cyclic voltammetry was employed as a measuring technique. When dealing with voltammograms with numerous peaks changing in shape and size, it is difficult to define which signal is the most significant for the analyte determination; in these cases, a helpful approach is chemometrics. In this work, PLS (Partial Least Square regression) has been applied to build models to correlate the signal with the glyphosate concentration in standard aqueous solutions and tap water samples (matrix-matched calibration). The method's figures of merits were evaluated, obtaining a limit of quantification of about 5 µM. The reliability of the proposed sensor was verified by analyzing tap water spiked with glyphosate; recoveries higher than 90 % were achieved.

Electrifying Friedel-Crafts Intramolecular Alkylation toward 1,1-Disubstituted Tetrahydronaphthalenes.

In this work, we successfully employed electrochemical conditions to promote a Hofer-Moest, intramolecular Friedel-Crafts alkylation sequence. The reaction proceeds under mild conditions, employing carboxylic acids as starting materials. Notably, the electrochemical process performed in batch was adapted to a continuous flow electrolysis apparatus to provide a significant improvement. This catalyst-free, electrochemical approach produces an array of tetrahydronaphthalenes that could be used for API synthesis.

Activation of Solid-State Emission and Photostability through Molecular Confinement: The Case of Triptycene-Fused Quinacridone Dyes.

We report the facile, metal-free convergent synthesis and the characterization of novel quinacridone dyes in which two triptycene units end-cap and sterically confine the quinacridone chromophore. A precise comparison of the confined dyes with their known homologues reveals that the reduction of π-π interactions in triptycene-fused quinacridone dyes compared to classical quinacridone results not only in an increase of solubility and processability but also in an enhancement of fluorescence quantum yield and photostability in the solid state.

Arylazo Sulfones as Nonionic Visible-Light Photoacid Generators.

The selective visible-light-driven generation of a weak acid (sulfinic acid, in nitrogen-purged solutions) or a strong acid (sulfonic acid, in oxygen-purged solutions) by using shelf-stable arylazo sulfones was developed. These sulfones were then used for the green, smooth, and efficient photochemical catalytic protection of several (substituted) alcohols (and phenols) as tetrahydropyranyl ethers or acetals.

Alkyl Radical Generation via C-C Bond Cleavage in 2-Substituted Oxazolidines.

There is an urgent need to develop uncharged radical precursors to be activated under mild photocatalyzed conditions. 2-Substituted-1,3-oxazolidines (E ox < 1.3 V vs SCE, smoothly prepared from the corresponding aldehydes) have been herein employed for the successful release of tertiary, α-oxy, and α-amido radicals under photo-organo redox catalysis. The reaction relies on the unprecedented C-C cleavage occurring from the radical cation of these heterocyclic derivatives. Such a protocol is applied to the visible-light-driven conjugate radical addition onto Michael acceptors and vinyl (hetero)arenes under mild metal-free conditions.

An Optical Fiber Sensor for Uranium Detection in Water.

An optical sensor for uranyl has been prepared based on a gold-plated D-shaped plastic optical fiber (POF) combined with a receptor consisting of a bifunctional synthetic molecule, 11-mercaptoundecylphosphonic acid (MUPA), with a phosphonic group for complexing the considered ion, and a sulfide moiety through which the molecule is fixed at the gold resonant surface as a molecular layer in an easy and reproducible way. The sensor is characterized by evaluating the response in function of the uranyl concentration in aqueous solutions of different compositions and real-life samples, such as tap water and seawater. The mechanism of the uranyl/MUPA interaction was investigated. Two different kinds of interactions of uranyl with the MUPA layer on gold from water are observed: a strong one and a weak one. In the presence of competing metal ions as Ca2+ and Mg2+, only the strong interaction takes place, with a high affinity constant (around 107 M-1), while a somewhat lower constant (i.e., around 106 M-1) is obtained in the presence of Mg2+ which forms stronger complexes with MUPA than Ca2+. Due to the high affinity and the good selectivity of the recognition element MUPA, a detection limit of a few µg L-1 is reached directly in natural water samples without any time-consuming sample pretreatment, making it possible for rapid, in situ controls of uranyl by the proposed sensor.

Carbon dioxide photoreduction in prebiotic environments.

The reduction of carbon dioxide is one of the hottest topics due to the concern of global warming. Carbon dioxide reduction is also an essential step for life's origins as photoautotrophs arose soon after Earth formation. Both the topics are of high general interest, and possibly, there could be a fruitful cross-fertilization of the two fields. Herein, we selected and collected papers related to photoreduction of carbon dioxide using compounds easily available on the Earth and considered of prebiotic relevance. This work might be useful also to scientists interested in carbon dioxide photoreduction and/or to have an overview of the techniques available.

Cathode Active Material Recycling from Spent Lithium Batteries: A Green (Circular) Approach Based on Deep Eutectic Solvents.

The transition to a circular economy vision must handle the increasing request of metals required to satisfy the battery industry; this can be obtained by recycling and feeding back secondary raw materials recovered through proper waste management. Here, a novel and green proof-of-concept was developed, based on deep eutectic solvents (DESs) to fully and easily recover valuable metals from various cathode active materials, including LiMn2 O4 , LiNi0.5 Mn1.5 O4 , and LiNi0.8 Co0.2 O2 . DES composed of choline chloride and lactic acid could leach Li, Mn, Co, and Ni, achieving efficiency of 100 % under much milder conditions with respect to the previous literature. For the first time, to our best knowledge, a two-step approach was reported in the case of LiNi0.8 Co0.2 O2 for selective recovery of Li, Co, and Ni with high yield and purity. Furthermore, other cathode components, namely aluminum current collector and binder, were found to be not dissolved by the proposed DES, thus making a simple separation from the active material possible. Finally, this strategy was designed to easily regenerate and reuse the leaching solvents for more than one extraction, thus further boosting process sustainability.

Photochemistry of Cannabidiol (CBD) Revised. A Combined Preparative and Spectrometric Investigation.

Cannabis is a plant with an astonishing ability to biosynthesize cannabinoids, and more than 100 molecules belonging to this class have been isolated. Among them in recent years cannabidiol (CBD) has received the interest of pharmacology as the major nonpsychotropic cannabinoid with many potential clinical applications. Although the reactivity of CBD has been widely investigated, only little attention has been given to the possible photodegradation of this cannabinoid, and the data available in the literature are outdated and, in some cases, conflicting. The aim of the present work is providing a characterization of the photochemical behavior of CBD in organic solvents, through a detailed GC-MS analyses, isolation, and NMR characterization of the photoproducts obtained.

Photoelectrochemical cross-dehydrogenative coupling of benzothiazoles with strong aliphatic C-H bonds.

A photoelectrochemical strategy for the cross-dehydrogenative coupling of unactivated aliphatic hydrogen donors (e.g. alkanes) with benzothiazoles is reported. We used tetrabutylammonium decatungstate as the photocatalyst to activate strong C(sp3)-H bonds in the chosen substrates, while electrochemistry scavenged the extra electrons.

Electrophysiological Responses of the Mediterranean Fruit Fly, Ceratitis capitata, to the Cera Trap® Lure: Exploring Released Antennally-Active Compounds.

The Mediterranean fruit fly (medfly), Ceratitis capitata, is a worldwide pest of agriculture able to use olfactory cues to locate habitat, food sources, mates and oviposition sites. The sensitivity of medfly olfaction has been exploited to develop olfactory-based attractants that are currently important tools for detection, control and eradication of its populations. Among these is Cera Trap® (BIOIBERICA, S.A.U.), a cost-effective bait. Here we used coupled gas chromatography/electroantennographic detection (GC-EAD) and GC/mass spectrometry (GC-MS) approaches to characterize the medfly antennally-active compounds released by this lure. We identified GC peaks corresponding to chemicals belonging to six different classes including heterocyclic aromatic compounds, aliphatic alcohols, aldehydes, esters, sesquiterpene hydrocarbons, and aromatic alcohols. We tested ten potential candidate volatiles belonging to these classes and predicted to be emitted by the lure and found that they were eliciting electroantennographic responses in medfly adults. These results will help in unravelling the physiological mechanisms of odor perception in both sexes, especially in relation to Cera Trap® attractant activity, which in the field has been shown to be female-specific. These findings and their developments will ultimately expand the toolbox for medfly control in the field.

Photochemistry of Tris(2,4-dibromophenyl)amine and its Application to Co-oxidation on Sulfides and Phosphines.

The photochemistry of tris(2,4-dibromophenyl)amine was investigated via time-resolved nanosecond spectroscopy. The tris(2,4-dibromophenyl)amine radical cation ("Magic Green") was immediately detected after the laser pulse; this intermediate then cyclizes to N-aryl-4a,4b-dihydrocarbazole radical cation. The latter transient reacted with molecular oxygen to provide the corresponding hydroperoxyl radical, which smoothly co-oxidize sulfides into sulfoxides. On the other hand, the photogenerated "Magic Green" was exploited to promote the co-oxidation of nucleophilic triarylphosphines to triarylphosphine oxides through an electron transfer process preventing the amine cyclization. In this case, the intermediate Ar3 POO•+ was found to play a key role in phosphine oxide formation.