Vaping cannabinoids in electronic (e)-cigarette devices is rapidly increasing in popularity, particularly among adolescents, although the chemistry affecting the composition of the vape aerosol is not well understood. This work investigates the formation of aerosol mass, bioactive hydroxyquinones, and harmful or potentially harmful carbonyls from the e-cigarette vaping of natural and synthetic cannabinoids e-liquids in propylene glycol and vegetable glycerin (PG/VG) solvent at a 50 mg/mL concentration in a commercial fourth-generation vaping device. The following cannabinoids were studied: cannabidiol (CBD), 8,9-dihydrocannabidiol (H2CBD), 1,2,8,9-tetrahydrocannabidiol (H4CBD), cannabigerol (CBG), and cannabidiolic acid (CBDA). Quantification of analytes was performed using liquid chromatography coupled to accurate mass spectrometry. The addition of cannabinoids significantly increased aerosol and carbonyl formation compared with the PG/VG solvent alone. All cannabinoids in the study formed hydroxyquinones during vaping (up to ∼1% mass conversion) except for CBDA, which primarily decarboxylated to CBD. Hydroxyquinone formation increased and carbonyl formation decreased, with a decreasing number of double bonds among CBD and its synthetic analogues (H2CBD and H4CBD). During the vaping process, ∼3-6% of the cannabinoid mass can be observed as carbonyls under the study conditions. Oxidation of the terpene moiety on the cannabinoids is proposed as a major contributor to carbonyl formation. CBD produced significantly higher concentrations of formaldehyde, acetaldehyde, acrolein, diacetyl, and methylglyoxal compared with the other cannabinoid samples. CBG produced significantly higher levels of acetone, methacrolein, and methylglyoxal. Conversion of CBD to tetrahydrocannabinol (THC) was not observed under the study conditions. The chemical mechanism basis for these observations is discussed. Compared with other modalities of use for CBD and other cannabinoids, vaping has the potential to adversely impact human health by producing harmful products during the heated aerosolization process.

Cannabidiol (CBD) use has grown exponentially more popular in the last two decades, particularly among older adults (>55 yr), though very little is known about the effects of CBD use during age-associated metabolic dysfunction. In addition, synthetic analogues of CBD have generated great interest because they can offer a chemically pure product, which is free of plant-associated contaminants. To assess the effects of a synthetic analogue of CBD (H4CBD) on advanced metabolic dysfunction, a cohort of 41-wk-old Otsuka Long-Evans Tokushima Fatty (OLETF) rats were administered 200 mg H4CBD/kg by oral gavage for 4 wk. Animals were fed ad libitum and monitored alongside vehicle-treated OLETF and Long-Evans Tokushima Otsuka (LETO) rats, the lean-strain controls. An oral glucose-tolerance test (oGTT) was performed after 4 wk of treatment. When compared with vehicle-treated, OLETF rats, H4CBD decreased body mass (BM) by 15%, which was attributed to a significant loss in abdominal fat. H4CBD reduced glucose response (AUCglucose) by 29% (P < 0.001) and insulin resistance index (IRI) by 25% (P < 0.05) compared with OLETF rats. However, H4CBD did not statically reduce fasting blood glucose or plasma insulin, despite compensatory increases in skeletal muscle native insulin receptor (IR) protein expression (54%; P < 0.05). H4CBD reduced circulating adiponectin (40%; P < 0.05) and leptin (47%; P < 0.05) and increased ghrelin (75%; P < 0.01) compared with OLETF. Taken together, a chronic, high dose of H4CBD may improve glucose response, independent of static changes in insulin signaling, and these effects are likely a benefit of the profound loss of visceral adiposity.NEW & NOTEWORTHY Cannabis product use has grown in the last two decades despite the lack of research on Cannabidiol (CBD)-mediated effects on metabolism. Here, we provide seminal data on CBD effects during age-associated metabolic dysfunction. We gave 41-wk-old OLETF rats 200 mg H4CBD/kg by mouth for 4 wk and noted a high dose of H4CBD may improve glucose response, independent of static changes in insulin signaling, and these effects are likely a benefit of loss of visceral adiposity.

Highly branched alkanes and cycloalkanes are produced via electrochemical processing of the renewable platform molecule mesityl oxide, which is a dimer of biogenic acetone. The final product is a sustainable, drop-in jet fuel.

Conjugated polymers are sequentially doped to control film conductivity and optical properties. (1) Carrier fractions (measured via optical absorbance), (2) polymer site densities, and (3) dopant volumes are used to calculate polaron densities.

Molecular doping of conjugated polymers causes bleaching of the neutral absorbance and results in new polaron absorbance transitions in the mid and near infrared. Here, the concentration dependent changes in the spectra for a series of molecularly doped diketopyrrolopyrrole (DPP) co‐polymers with a series of ultra‐high electron affinity cyanotrimethylenecyclopropane‐based dopants is analyzed. With these strong dopants the polaron mole fraction (Θ) reaches saturation. Analysis of the full spectrum enables separation of neutral and polaron signals and quantification of the polaron mole fraction using a simple noninteracting site model. The peak ratios for both neutral and polaron peaks change systematically with increasing polaron mole fraction for all measured polymers. Analysis of the spectral changes indicates that the polaron mole fraction can be quantified to within 5%. While the total change in the absorbance spectrum with increasing polaron mole fraction is linear, the lowest energy polaron peak (P1) grows nonlinearly, which indicates increased polarization/delocalization. Molecular doping of polymers that form either H‐ or J‐aggregates shows systematically different spectral changes in the vibronic peak ratios of the neutral spectra and provides insights into the polymer configuration at undoped sites in the film.

High electron affinity (EA) molecules p-type dope low ionization energy (IE) polymers, resulting in an equilibrium doping level based on the energetic driving force (IE-EA), reorganization energy, and dopant concentration. Anion exchange doping (AED) is a process whereby the dopant anion is exchanged with a stable ion from an electrolyte. We show that the AED level can be predicted using an isotherm equilibrium model. The exchange of the dopant anion (FeCl3-) for a bis(trifluoromethanesulfonamide) (TFSI-) anion in the polymers poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly[3-(2,2-bithien-5-yl)-2,5-bis(2-hexyldecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione-6,5-diyl] (PDPP-2T) highlights two cases in which the process is nonspontaneous and spontaneous, respectively. For P3HT, FeCl3 provides a high doping level but an unstable counterion, so exchange results in an air stable counterion with a marginal increase in doping. For PDPP-2T, FeCl3 is a weak dopant, but the exchange of FeCl3- for TFSI- is spontaneous, so the doping level increases by >10× with AED.

New organic-soluble dopants have record high electron affinity values and show outstanding doping performance with high ionization energy co-polymers.

Biobased 5-(chloromethyl)furoate and 5-methylfuroate esters can be deprotonated to function as furylogous lithium enolates, and the former can also undergo zinc insertion to access Reformatsky-type chemistry. Carbon nucleophilicity represents hitherto little-explored reactivity in these key carbohydrate-derived platform molecules, expanding their synthetic utility and potentially opening up new sustainable product markets (e. g., in epoxy resins or biobased dyes).

Sequential solution doping is a processing technique that allows a conjugated polymer film to be doped from a solvent that will not dissolve the polymer. We present here a method to predict the film doping level in cm-3 from the solution concentration used to dope the film. We show using four polymers and three different and newly synthesized dopants that the doping level can me modeled using a simple Langmuir isotherm. In addition, analysis of the UV/vis spectra shows filling of the density of states. Polymers with a sharper band edge demonstrate much high conductivity for the same hole density. We analyze a series of DPP polymers and show how the polymer order changes as a function of the doping level. A second recent discovery is that the anion in sequentially doped films can be exchanged with another anion after doping. This means that the reactive molecule used to doped the polymer can be removed and replaced with a different ion that is not reactive. We present a multi-ion Langmuir isotherm model and show that the film doping level in mixed ion solutions can also be predicted.

5-(Chloromethyl)furfural (CMF) is a cellulose derivative of increasing appeal as a renewable platform molecule. Although its role as an electrophile has been broadly studied, little is known about its potential utility as a carbon nucleophile. This work describes the preparation of organozinc reagents based on CMF by the insertion of zinc metal into the C-Cl bond. Reformatsky-type reactions are observed with a range of electrophiles under mild conditions in good to high yields. A kinetic study of zinc insertion shows the generation of this organometallic reagent from renewable furoate esters is a facile process. This method constitutes a practical tool in the synthetic repertory for the conversion of cellulosic biomass into useful organic molecules.

Molecular dopants are increasingly studied to enhance the conductivity of semiconducting polymers. Most available p-type dopants have low solubility in common solvents and moderate electron affinities (EA), which makes solution processing difficult and limits the range of semiconducting polymers that can be doped. Here, we describe the synthesis and characterization of the new molecular dopant TMCN3-CP, which has an EA of −5.5 eV. We show that high ionization energy alternating copolymers such as PDPP-4T, PDPP-3T, and PDPP-T-TT-T can be p-type doped and achieve high conductivities with TMCN3-CP using sequential solution processing. The main advantage of this new dopant is the ability to chemically tailor the ester groups, which we demonstrate here for sequential solution doping of films. Sequential solution processing allows a greater ability to control the film morphology and is also desirable for scale-up to large-area polymer electronics.

The introduction of functional groups with varying electron-donating/-withdrawing properties at the β-position of diketopyrrolopyrrole (DPP) has been shown to affect the optoelectronic properties of the polymers. We report the synthesis of a new diketopyrrolopyrrole monomer wherein a strong electron-donating substituent, a methoxy group, was incorporated at the β-position in an effort to modulate polymer properties. Homopolymers and co-polymers of the new β-methoxy DPP and nonderivatized DPP were synthesized, and their properties were measured by cyclic voltammetry and UV-vis-near-infrared. Density functional theory computations also were employed to predict the degree of planarity of β-methoxy oligomers to probe the significance of the newly introduced S-O conformational lock. The combined experimental and computational results showed a reduction in the gap between highest occupied molecular orbital/lowest unoccupied molecular orbital levels, a redshift toward the near-infrared region, and an increased planarity in the β-methoxy polymers.

The zirconium rac- and meso-complexes of the ansa-type that contain a 3-phenyl-6,7,8,9-tetrahydrocyclopenta[a] naphthalene fragment and a dimethylsilylene bridge are synthesized. The compounds obtained are characterized by NMR spectroscopy; the structure of rac-complex is studied by X-ray diffraction, which maked it possible to evaluate the steric availability of the zirconium center in the corresponding catalysts for the olefin polymerization.

A novel protocol for efficient coupling of nitrobenzene and aniline in poly(ethylene glycol) medium in the presence of KOH giving diphenylamine derivatives has been developed, to enable the exclusion of the toxic tetramethylammonium hydroxide catalyst commonly used in the rubber antidegradant industry.

Generally, the long-range electronic communication between spatially orthogonal orbitals is inefficient and limited to field and inductive effects. In this work, we provide experimental evidence that such communication can be achieved via intramolecular electron transfer between two degenerate and mutually orthogonal frontier molecular orbitals (MOs) at the transition state. Interaction between orthogonal orbitals is amplified when the energy gap between these orbitals approaches zero, or at an "orbital crossing". The crossing between two empty or two fully occupied MOs, which do not lead to stabilization, can be "activated" when one of the empty MOs is populated (i.e., electron injection) or one of the filled MOs is depopulated (i.e., hole injection). In reductive cycloaromatization reactions, such crossings define transition states with energies defined by both the in-plane and out-of-plane π-systems. Herein, we provide experimental evidence for the utility of this concept using orbital crossings in reductive C1-C5 cycloaromatization reactions of enediynes. Communication with remote substituents via orbital crossings greatly enhances regioselectivity of the ring closure step in comparison to the analogous radical cyclizations. We also present photophysical data pertaining to the efficiency of electron injection into the benzannelated enediynes.

The reaction of 2-perfluoroalkyl-substituted cyclic imines with arylhydrazines was investigated. We found that 2-perfluoroalkylated cyclic imines are highly reactive electrophiles that form, through ring opening, the corresponding hydrazones bearing an amine group at the end of the alkyl chain. Subsequent acidic treatment resulted in a Fischer rearrangement. Thus, a new synthesis of 2-perfluoroalkylated tryptamines and their homologues through a Fischer reaction was developed. The possibility of modification of the indole core of the 2-CF3-substituted tryptamine products was demonstrated, and various 2-trifluoromethylated tryptamines substituted at the 5-position were prepared.

A Friedel–Crafts-type alkylation reaction was studied between various pyrroles and α-polyfluoroalkylated cyclic imines that were activated by Lewis acids. The reaction proceeded under mild conditions and provided a high yielding synthesis of α-CF3-substituted pyrrolidines and piperidines as well as seven-membered analogues that contained a pyrrole ring. The unpredictably high β-selectivity for the aminoalkylation of both 1H-pyrrole and N-substituted pyrrole was observed as a result of a thermodynamically-controlled electrophilic substitution reaction. The computational data are in full agreement with the experimental results, which confirmed the observed regioselectivity as a result of the lower energy of the β-substituted pyrroles that contain α-trifluoromethyl-substituted pyrrolidine, piperidine, and azepane rings.

The reaction of cyclic ketimines with indoles was studied. A dramatic difference between the electrophilicity of perfluoroalkyl-substituted and non-fluorinated imines was demonstrated. In good agreement with our calculations, the Friedel-Crafts-type alkylation of indoles only takes place with alpha-polyfluoroalkylated cyclic imines that are activated by boron trifluoride-diethyl ether. The reaction proceeds under mild conditions and provides the opportunity to obtain promising alkaloid-like structures that contain a fluoroalkyl group. As a result, alpha-CF3- and alpha-C2F5-substituted pyrrolidines, piperidines, and azepanes that contain an indole moiety can be prepared efficiently.