Cyclic and acyclic acetals as safe, nonaqueous formaldehyde equivalents for the synthesis of pillararenes.

Pillar[5]arene was synthesized using acyclic acetals diethoxymethane and dimethoxymethane, and cyclic acetals 1,3-dioxolane and 1,3,5-trioxane as an alternative to paraformaldehyde. Both Lewis and Brønsted acids were effective in catalyzing the hydrolysis of acetal and initiating the Friedel-Crafts reaction in pillararene synthesis.

Reconfigurable Pickering Emulsions with Functionalized Carbon Nanotubes.

Pickering emulsions (PEs) achieve interfacial stabilization by colloidal particle surfactants and are commonly used in food, cosmetics, and pharmaceuticals. Carbon nanotubes (CNTs) have recently been used as stabilizing materials to create dynamic single emulsions. In this study, we used the formation of Meisenheimer complexes on functionalized CNTs to fabricate complex biphasic emulsions containing hydrocarbons (HCs) and fluorocarbons (FCs). The reversible nature of Meisenheimer complex formation allows for further functionalization at the droplet-water interface. The strong affinity of fluorofluorescent perylene bisimide (F-PBI) to the CNTs was used to enhance the assembly of CNTs on the FC-water interface. The combination of different concentrations of the functionalized CNTs and the pelene additive enables predictable complex emulsion morphologies. Reversible morphology reconfiguration was explored with the addition of molecular surfactants. Our results show that the interfacial properties of functionalized CNTs have considerable utility in the fabrication of complex dynamic emulsions.

Mortality in spontaneous coronary artery dissection: A systematic review and meta-analysis.

OBJECTIVE: The aim of this systematic review and meta-analysis was to provide a comprehensive estimate for spontaneous coronary artery dissection (SCAD) related mortality, and explore factors associated with an increased risk of death. BACKGROUND: SCAD is an infrequent but increasingly recognized cause of acute coronary syndrome. Despite a growing body of evidence, there have been few detailed examinations of SCAD associated mortality. METHODS: We searched MEDLINE, EMBASE, Cochrane, Web of Science and Google Scholar databases through May 7, 2020. We included studies reporting mortality data, confirmed SCAD with coronary angiography and included ≥10 participants. We excluded non-English studies, conference abstracts, review articles and duplicate datasets. Random-effects meta-analysis and meta-regression were used to evaluate estimates and predictors of mortality. RESULTS: From an initial 1,131 articles, 34 studies with 2,817 patients were eligible for inclusion. The weighted mean age was 50 years, and 84% of participants were female. The pooled estimate for SCAD mortality was 1% (Proportion 0.01; 95% CI, 0.00-0.02). The mean duration of follow-up was 33 months. Meta-regression showed male sex was associated with 3.5-fold increased odds of mortality (OR, 3.50; 95% CI, 1.22-10.03). In addition, smoking (current or previous) was associated with a 15-fold increased risk of mortality (OR 15.32; 95% CI, 2.88-81.41). CONCLUSIONS: This meta-analysis has shown that SCAD is associated with favorable survival outcomes with an estimated mortality of 1% over a mean follow-up period of 33 months. We also found male sex and smoking were associated with an increased risk of mortality.

Aryl Migration on Graphene.

The design and synthesis of molecular systems able to carry out movements resembling macroscopic objects is an exciting and challenging endeavor. Molecules that can walk covalently on a track have been demonstrated, and we now report how aryl groups that can migrate over a graphene surface. Specifically, we describe a system comprised of covalently functionalized aryl groups on graphene that undergo continuous aryl shifts. The dynamic aryl shift allows the aryl groups on graphene to effectively migrate step-by-step wherein each step involves reversible bond breaking and making that is initiated by a combination of an activated arene and p-doping of the graphene surface. Raman spectroscopic mapping of the distribution of the covalent attachment revealed that activated 4-methoxyphenyl groups migrate several microns from regions of high functionalization to regions with no prior functionalization.

Chemiresistive Carbon Nanotube Sensors for N-Nitrosodialkylamines.

N-Nitrosamines are environmental genotoxicants that are widely encountered in air, water, and food. Contamination of indoor and outdoor air with N-nitrosamines has been reported on many occasions. Conventional detection of airborne N-nitrosamines requires sophisticated instrumentation, field sampling, and laboratory analysis. Herein, we report ultrasensitive carbon nanotube based chemiresistive sensors utilizing a cobalt(III) tetraphenylporphyrin selector element for the detection of N-nitrosamines. Concentrations as low as 1 ppb N-nitrosodimethylamine, N-nitrosodiethylamine, and N-nitrosodibutylamine were detected. We also demonstrate the integration of these sensors with a field deployable sensing node wherein the sensor response can be read online remotely.

Carbon Nanotube Chemical Sensors.

Carbon nanotubes (CNTs) promise to advance a number of real-world technologies. Of these applications, they are particularly attractive for uses in chemical sensors for environmental and health monitoring. However, chemical sensors based on CNTs are often lacking in selectivity, and the elucidation of their sensing mechanisms remains challenging. This review is a comprehensive description of the parameters that give rise to the sensing capabilities of CNT-based sensors and the application of CNT-based devices in chemical sensing. This review begins with the discussion of the sensing mechanisms in CNT-based devices, the chemical methods of CNT functionalization, architectures of sensors, performance parameters, and theoretical models used to describe CNT sensors. It then discusses the expansive applications of CNT-based sensors to multiple areas including environmental monitoring, food and agriculture applications, biological sensors, and national security. The discussion of each analyte focuses on the strategies used to impart selectivity and the molecular interactions between the selector and the analyte. Finally, the review concludes with a brief outlook over future developments in the field of chemical sensors and their prospects for commercialization.

Resistive and Capacitive γ-Ray Dosimeters Based On Triggered Depolymerization in Carbon Nanotube Composites.

We report γ-ray dosimeters using carbon nanotubes wrapped with metastable poly(olefin sulfone)s (POSs) that readily depolymerize when exposed to ionizing radiation. New POSs, designed for wrapping single-walled carbon nanotubes (SWCNTs), are synthesized and characterized. The resulting POS-SWCNT composites serve as the active transducer in a novel class of γ-ray dosimeters. In our devices, polymer degradation results in immediate changes in the electronic potential of the POS-SWCNT active layers by decreasing the electron tunneling barriers between individualized tubes and by creating enhanced cofacial π-π electron contacts. By incorporating the SWCNT-POS composites into small resistive device platforms, we establish a rare example of real-time detection and dosimetry of radioactive ionizing radiation using organic-based materials. We show that the sensitivity of our platform closely depends on the intrinsic stability of the polymer matrix, the opacity toward γ-rays, and the dispersion efficiency (i.e., the individualization and isolation of the individual SWCNT charge carriers). Resistance decreases up to 65% after irradiation with a 40 krad dose demonstrates the high sensitivity of this novel class of γ-ray sensors. In addition, the detection mechanism was evaluated using a commercial capacitive device platform. The ease of fabrication and low power consumption of these small and inexpensive sensor platforms combined with appealing sensitivity parameters establishes the potential of the poly(olefin sulfone)-SWCNT composites to serve as a new transduction material in γ-ray sensor applications.

Hyperstage Graphite: Electrochemical Synthesis and Spontaneous Reactive Exfoliation.

Covalent modification of the π-electron basal planes of graphene enables the formation of new materials with enhanced functionality. An electrochemical method is reported for the formation of what is referred to as a Hyperstage-1 graphite intercalation compound (GIC), which has a very large interlayer spacing d001 > 15.3 Å and contains disordered interstitial molecules/ions. This material is highly activated and undergoes spontaneous exfoliation when reacted with diazonium ions to produce soluble graphenes with high functionalization densities of one pendant aromatic ring for every 12 graphene carbons. Critical to achieving high functionalization density is the Hyperstage-1 GIC state, a weakening of the van der Waals coupling between adjacent graphene layers, and the ability of reactants to diffuse into the disordered intercalate phase between the layers. Graphene functionalization with 3,5-dinitrophenyl groups provides for exceptional dispersibility (0.24 mg mL-1 ) in N,N-dimethylformamide and for conjugation with amines.

Room temperature amine sensors enabled by sidewall functionalization of single-walled carbon nanotubes.

A new series of sidewall modified single-walled carbon nanotubes (SWCNTs) with perfluorophenyl molecules bearing carboxylic acid or methyl ester moieties are herein reported. Pristine and functionalized SWCNTs (p-SWCNTs and f-SWCNTs, respectively) were characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and scanning electron microscopy (SEM). The nitrene-based functionalization provided intact SWCNTs with methyl 4-azido-2,3,5,6-tetrafluorobenzoate (SWCNT-N-C6F4CO2CH3) and 4-azido-2,3,5,6-tetrafluorobenzoic acid (SWCNT-N-C6F4CO2H) attached every 213 and 109 carbon atoms, respectively. Notably, SWCNT-N-C6F4CO2H was sensitive in terms of the percentage of conductance variation from 5 to 40 ppm of ammonia (NH3) and trimethylamine (TMA) with a two-fold higher variation of conductance compared to p-SWCNTs at 40 ppm. The sensors are highly sensitive to NH3 and TMA as they showed very low responses (0.1%) toward 200 ppm of volatile organic compounds (VOCs) containing various functional groups representative of different classes of analytes such as benzene, tetrahydrofurane (THF), hexane, ethyl acetate (AcOEt), ethanol, acetonitrile (CH3CN), acetone and chloroform (CHCl3). Our system is a promising candidate for the realization of single-use chemiresistive sensors for the detection of threshold crossing by low concentrations of gaseous NH3 and TMA at room temperature.

Bio-Inspired Carbon Monoxide Sensors with Voltage-Activated Sensitivity.

Carbon monoxide (CO) outcompetes oxygen when binding to the iron center of hemeproteins, leading to a reduction in blood oxygen level and acute poisoning. Harvesting the strong specific interaction between CO and the iron porphyrin provides a highly selective and customizable sensor. We report the development of chemiresistive sensors with voltage-activated sensitivity for the detection of CO comprising iron porphyrin and functionalized single-walled carbon nanotubes (F-SWCNTs). Modulation of the gate voltage offers a predicted extra dimension for sensing. Specifically, the sensors show a significant increase in sensitivity toward CO when negative gate voltage is applied. The dosimetric sensors are selective to ppm levels of CO and functional in air. UV/Vis spectroscopy, differential pulse voltammetry, and density functional theory reveal that the in situ reduction of FeIII to FeII enhances the interaction between the F-SWCNTs and CO. Our results illustrate a new mode of sensors wherein redox active recognition units are voltage-activated to give enhanced and highly specific responses.

E pluribus unum: isolation, structure determination, network analysis and DFT studies of a single metastable structure from a shapeshifting mixture of 852 bullvalene structural isomers.

Bullvalene is an organic molecule that spontaneously undergoes Cope rearrangements, resulting in a reconfiguration of its carbon framework. During our study of oligosubstituted bullvalenes, which are structurally dynamic shapeshifting molecules, we found that we could isolate one metastable isomer from the interconverting population of 1680 constitutional isomers (852 structures if enantiomeric pairs are counted once). The preferential formation and unexpected stability of this isomer led to many questions, which we have addressed in this report. (1) What is its structure? (2) How many rearrangements are required to form this isomer from the initial bullvalene structure? (3) Why is it the preferred isomer? (4) What is the role of the substituents in its energetic preference? Our answers required synthesis, HPLC isolation, NMR characterizations, network construction and analysis, and computational (DFT) studies. The results of these efforts revealed the remarkable interconversion network of bullvalene rearrangements. The formation of this metastable isomer is preferred by both thermodynamic and kinetic factors and the ester substituent amplifies the energy difference between various structural isomers of oligosubstituted bullvalenes. The shapeshifting nature of oligosubstituted bullvalene is a useful and unusual property that has many potential applications. Insights into their rearrangements, energy landscape and substituent effect will be important knowledge for the development of these molecules towards materials, sensors and biologically active compounds.

Racemization as a stereochemical measure of dynamics and robustness in shape-shifting organic molecules.

Bullvalene is a structurally unique dynamic molecule thought to interconvert among 1.2 million degenerate isomers. The incorporation of different chemical substituents onto the bullvalene core should lead to a "shape-shifting" molecule that can interconvert among thousands of discrete structural isomers. Previous NMR spectroscopy and HPLC studies on substituted bullvalenes ascertained the fact that these compounds are dynamic, but they could not attest to whether the molecules are only interconverting among only a few isomers or if a multitude of structures are being accessed. Here we confirm the remarkable shape-shifting property of a tetrasubstituted bullvalene by means of a racemization experiment. We show that a single, though fleeting, chiral, enantioenriched tetrasubstituted bullvalene isomer can spontaneously equilibrate to a racemic population of dynamic compounds. Despite the fact that conversion from one enantiomer of a bullvalene isomer to the other may require dozens or even hundreds of rearrangements and involve many potential pathways, CD spectroscopy and HPLC analysis of different bullvalene populations showed that multiple pathways exist and result in the complete racemization of an initial enantioenriched chiral bullvalene. These oligosubstituted bullvalenes represent a very rare example of an entity that can spontaneously transform itself into different discrete structures using ambient thermal energy. The confirmation that these shape-shifting organic molecules are chemically robust yet structurally dynamic is an important step toward their further use as materials, sensors, and biologically active compounds.

Julia Olefination as a General Route to Phenyl (alpha-Fluoro)vinyl Sulfones.

Mild and efficient synthesis of phenyl (alpha-fluoro)vinyl sulfones via condensation of aldehydes and a ketone with a novel benzothiazolyl based bis-sulfone reagent is reported and this proceeds with moderate to good Z-stereoselectivity.