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Binuclear Cu(i) complexes bearing N-heterocycles-containing phosphines function as luminescent sensors for N-nitrosamines.

We designed porous polymers with a tungsten-calix[4]arene imido complex as the nitrosamine receptor for the efficient extraction of tobacco-specific nitrosamines (TSNAs) from water. The interaction between the metallocalix[4]arene and the TSNA, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (nicotine-derived nitrosamine ketone, NNK) was investigated. We found that the incorporation of the nitrosamine receptor into porous polymers increased their selectivity toward NNK over nicotine. The polymer with an optimal ratio of calixarene-containing and porosity-inducing building blocks showed a high maximum adsorption capacity of up to 203 mg/g toward NNK under sonication, which was among the highest values reported. The adsorbed NNK could be removed from the polymer by soaking it in acetonitrile, enabling the adsorbent to be reused. A similar extraction efficiency to that under sonication could be achieved using the polymer-coated magnetic particles under stirring. We also proved that the material could efficiently extract TSNAs from real tobacco extract. This work not only provides an efficient material for the extraction of TSNAs but also offers a design strategy for efficient adsorbents.

ConspectusBottom-up materials design by the conceiving of new molecular building blocks is powerful and chemists are uniquely qualified to innovate. Liquid crystals (LCs) and related soft crystals, collectively called mesophases, naturally create materials with dynamic properties. The thermotropic LC state has a liquid-like intermolecular disorder, but the cooperative nature of these materials facilitates a long-range directional order (alignment) that couples strongly to applied electric/magnetic fields and interfaces. Thermotropic LCs are held together by mesogen cores, which are often unsaturated with anisotropic polarizability, and are appended with flexible (often

We describe the preparation of oil-in-water (o/w) colloidal particles with a polypyrrole (pPy) shell in which cyclodextrin has been incorporated at the oil-water interface

1,4-Dithiin and its dibenzo-analogue, thianthrene, represent a class of non-aromatic, sulfur-rich heterocycles. Their unique properties, stemming from both their non-planar structures and reversible one- and two-electron oxidations, serve as primary motivators for their use in the development of new materials. The applications of 1,4-dithiins and thianthrenes are rich and diverse, having been used for energy storage and harvesting, and the synthesis of phosphorescent compounds and porous polymers, among other uses. This review offers first an overview of the properties of 1,4-dithiin and thianthrene. Next, we describe enabling synthetic methodology to access 1,4-dithiins and thianthrenes with various substitution patterns. Lastly, the utility of 1,4-dithiin and thianthrene in the construction and design of new materials is detailed using select literature examples.1 Introduction2 Properties of 1,4-Dithiins and Thianthrenes3 Synthesis of 1,4-Dithiins and Thianthrenes3.1 Synthesis of 1,4-Dithiins3.2 Synthesis of Thianthrenes4 Application of 1,4-Dithiins and Thianthrenes in Materials4.1 Thianthrene-Containing Polymers4.2 Thianthrene in Redox-Active Materials4.3 Thianthrenes and 1,4-Dithiins in Supramolecular Chemistry and Self-Assembly4.4 Thianthrenes in Phosphorescent Materials4.5 Thianthrenes with Other Interesting Photophysical Properties4.6 Thianthrenes in the Synthesis of Non-natural Products5 Conclusion

Faraday rotation is a magneto-optical effect central to a number of commercial technologies including optical isolation and magneto-optical imaging. Today, the performance needs of these technologies are met by inorganic materials containing paramagnetic heavy elements. However, organic thin films are increasingly being evaluated as replacement materials, promising higher magneto-optical performance and facile fabrication of structures that enable expanded applications. Despite being an object of research for more than 175 years, our understanding of the Faraday effect in solid-state organic materials remains incomplete, hindering our attempts to methodically improve magneto-optical performance. This Perspective aims to place several recent advances in the field of thin-film organic Faraday rotators within the well-established theoretical framework developed by solution-state magnetic circular dichroism spectroscopists: the Faraday A, B, and C terms. Through careful consideration of these quantum mechanical mechanisms in example molecules, an intuitive understanding of the impact of chemical structure in thin-film Faraday rotators can be achieved, including the critical roles of molecular symmetry, rigidity, absorptivity, and magnetism. Future work seeking to maximize the magneto-optical performance of organic thin films may more readily evaluate candidate chromophores based on the Faraday A, B, and C term framework presented herein.

The design and synthesis of new macrocycles with well-defined cavities represent a promising avenue for the development of new supramolecular hosts. Moreover, the ability to diversify a macrocycle through chemical manipulations enables the fine-tuning and tailoring of properties. In this report, the synthesis and functionalization of thiapillar[6]arene, a pillar[6]arene analogue in which the bridging methylene groups are replaced by sulfurs, are described. First, we demonstrate the scalable synthesis of the parent thiapillar[6]arene. Next, the diversification of thiapillar[6]arene is demonstrated via functionalization of the phenols and oxidation of the sulfur atoms. The solid-state structures of two thiapillar[6]arene derivatives are reported, and the effect of sulfur oxidation state on the macrocyclic conformation is discussed. All sulfone derivatives described were found to demonstrate high luminescence quantum yields (ΦF = 0.43–0.66) in CH2Cl2 with emission maxima between λ = 404 and 462 nm. Lastly, assessment of the electrochemical properties of the sulfone derivatives by square-wave voltammetry revealed electron-accepting ability owing to the oxidation of the sulfur atoms, with four reduction events observed for the analogues surveyed. Overall, this work implicates thiapillar[6]arene as a modular scaffold amenable for further applications in host–guest chemistry and sensing.

The use of molecules as active components to build nanometer-scale devices inspires emerging device concepts that employ the intrinsic functionality of molecules to address longstanding challenges facing nanoelectronics. Using molecules as controllable-length nanosprings, here we report the design and operation of a nanoelectromechanical (NEM) switch which overcomes the typical challenges of high actuation voltages and slow switching speeds for previous NEM technologies. Our NEM switches are hierarchically assembled using a molecular spacer layer sandwiched between atomically smooth electrodes, which defines a nanometer-scale electrode gap and can be electrostatically compressed to repeatedly modulate the tunneling current. The molecular layer and the top electrode structure serve as two degrees of design freedom with which to independently tailor static and dynamic device characteristics, enabling simultaneous low turn-on voltages (sub-3 V) and short switching delays (2 ns). This molecular platform with inherent nanoscale modularity provides a versatile strategy for engineering diverse high-performance and energy-efficient electromechanical devices.

We recently used selective (2)H labeling of BDPA to investigate the Overhauser Effect (OE) dynamic nuclear polarization (DNP) mechanism in insulating solids doped with 1,3-bis(diphenylene)-2-phenylallyl (BDPA), and established that the α and γ (1)H spins on the fluorene rings are responsible for generating a zero quantum (ZQ) mediated positive bulk polarization. Here, we establish that the phenyl (1)H spins relax via double-quantum (DQ) processes and therefore contribute negative enhancements which attenuate the OE-DNP. With measurements at different magnetic field strengths, we show that phenyl-d(5)-BDPA offers >50% improvement in OE-DNP enhancement compared to h(21)-BDPA attaining a maximum of ~ 90 at 14.1 T and 5 kHz MAS, the highest observed OE-DNP enhancement to date under these conditions. The approach may be utilized to optimize other polarizing agents exhibiting an OE, an important DNP mechanism with a favorable field and spinning frequency dependence.

N-Nitrosamines are found in food, drugs, air, water, and soil. They pose a significant risk to human health because of their carcinogenicity; consequently, materials that can be used to selectively and sensitively detect nitrosamines are needed. In this work, we designed and synthesized two polymers bearing calix[4]arene or 4-tert-butylcalix[4]arene tungsten−imido complexes (PCalixH and PCalixtBu) as N-nitrosodimethylamine (NDMA) receptors. The interaction between metallocalix[4]arene monomers/polymers and NDMA was confirmed by (1)H NMR and IR spectroscopy. Single-crystal X-ray analysis further revealed that the host−guest interaction is based on binding of the terminal oxygen of NDMA to tungsten within the calixarene cavity. Gravimetric detection of NDMA was performed on a quartz crystal microbalance (QCM) in air. Both polymers show responses to NDMA, with PCalixtBu exhibiting a low theoretical limit of detection of 5 ppb for NDMA. The sensor also shows high selectivity toward NDMA and moderate humidity tolerance. This work provides a sensitive sensor for detection of NDMA and also offers a class of new, selective, and efficient NDMA receptors for the future design of NDMA sensors and NDMA extraction materials.

Installing fluoroalkyl chains on a molecule by the Heck reaction is a versatile method to transform the molecule’s properties that enable unique materials applications. This work further expands the scope of this reaction to thiophenes, which were able to undergo further functionalization and polymerization, highlighting the potential of these molecules in conjugated organic materials.

We report a chemiresistive cyclohexanone sensor on a flexible substrate based on single-walled carbon nanotubes (SWCNTs) functionalized with thiourea (TU) derivatives. A wrapper polymer containing both 4-vinylpyridine (4VP) groups and azide groups (P(4VP-VBAz)) was employed to obtain a homogeneous SWCNT dispersion via noncovalent functionalization of SWCNTs. The P(4VP-VBAz)-SWCNT composite dispersion was then spray-coated onto an organosilanized flexible poly(ethylene terephthalate) (PET) film to achieve immobilizing quaternization between the pyridyl groups from the polymer and the functional PET substrate, thereby surface anchoring SWCNTs. Subsequent surface functionalization was performed to incorporate a TU selector into the composites, resulting in P(Q4VP-VBTU)-SWCNT, for the detection of cyclohexanone via hydrogen bonding interactions. An increase in conductance was observed as a result of the hydrogen-bonded complex with cyclohexanone resulting in a higher hole density and/or mobility in SWCNTs. As a result, a sensor device fabricated with P(Q4VP-VBTU)-SWCNT composites exhibited chemiresistive responses (ΔG/G0) of 7.9 ± 0.6% in N2 (RH 0.1%) and 4.7 ± 0.4% in air (RH 5%), respectively, upon exposure to 200 ppm cyclohexanone. Selective cyclohexanone detection was achieved with minor responses (ΔG/G0 < 1.4% at 500 ppm) toward interfering volatile organic compounds (VOC). analytes. We demonstrate a robust sensing platform using the polymer-SWCNT composites on a flexible PET substrate for potential application in wearable sensors.

Porous organic polymers (POPs) with strong covalent linkages between various rigid aromatic structural units having different geometries and topologies are reported. With inherent porosity, predictable structure, and tunable functionality, POPs have found utility in gas separation, heterogeneous catalysis, sensing, and water treatment. Poly(arylene ether)s (PAEs) are a family of high-performance thermoplastic materials with high glass-transition temperatures, exceptional thermal stability, robust mechanical properties, and excellent chemical resistance. These properties are desirable for development of durable POPs. However, the synthetic methodology for the preparation of these polymers has been mainly limited in scope to monomers capable of undergoing nucleophilic aromatic substitution (S

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.

The spread of the COVID-19 pandemic around the world has revealed that it is urgently important to develop rapid and inexpensive assays for antibodies in general and anti-SARS-CoV-2 IgG antibody (anti-SARS-CoV-2 spike glycoprotein S1 antibody) in particular. Herein we report a method to detect the anti-SARS-CoV-2 spike antibody level by using Janus emulsions or Janus particles as biosensors. Janus emulsions are composed of two immiscible hydrocarbon and fluorocarbon oils. The hydrocarbon/water interfaces are functionalized with a secondary antibody of IgG protein and SARS-CoV-2 spike receptor binding domain (RBD), to produce two different Janus emulsions. Mixtures of these Janus droplets enable the detection of the anti-SARS-CoV-2 spike IgG antibody in an agglutination assay caused by the antibody’s binding to both the secondary antibody of IgG antibody and SARS-CoV-2 spike protein RBD. Both qualitative optical images and quantitative fluorescence spectra are able to detect the level of anti-SARS-CoV-2 spike antibody at concentrations as low as 0.2 μg/mL in 2 h. The detection results of clinical human serum samples using this agglutination assay confirm that this method is applicable to clinical samples with good sensitivity and specificity. The reported method is generalizable and can be used to detect other analytes by attaching different biomolecular recognition elements to the surface of the Janus droplets., An efficient, sensitive and less expensive method of using Janus emulsions or Janus particles for the detection of the anti-SARS-CoV-2 spike IgG antibody in human serum is described.

We describe a novel class of tetraphenylbenzene-based discotic molecules with exceptional self-assembling properties. Absorption and fluorescence studies confirmed the formation of J-type aggregates in solution. The discotic mesogens also show an enhancement of the emission upon aggregation. Interestingly, these discotic molecules displayed enantiotropic hexagonal columnar liquid crystal (LC) phases that can be switched into a helical columnar organization by application of an electric field. The helical columns arise from the electric-field-induced tilt of the polar fluorobenzene ring that directs all of the peripheral phenyl groups into a propeller-like conformation with respect to the central benzene core. A cooperative assembly process of these propeller-shaped molecules resolves into a helical columnar organization, in which the preferred helical sense is obtained from the stereogenic center proximate to the polar carbon-fluorine bond. The ease of inducing chirality in columnar LCs by an electric field presents opportunities to create next-generation chiral materials for a variety of applications.

Herein we describe a highly responsive optical biosensor based on dynamic complex liquid crystal (LC) emulsions. These emulsions are simple to prepare and consist of immiscible chiral nematic liquid crystals (N*) and fluorocarbon oils. In this work, we exploit the N* selective reflection to build a new sensing paradigm. Our detection strategy is based on changes in the LC/water interfacial activity of boronic acid polymeric surfactants caused by reversible interactions with IgG antibodies at the LC interface. Such biomolecular recognition events can vary the pitch length of the N* organization due to the presence of binaphthyl units in the polymeric structure, which are known to be powerful chiral dopants. We demonstrate that these interface-triggered reflection changes can be used as an effective optical read-out for the detection of the foodborne pathogen Salmonella.

Many biosensing methods rely on signals produced by enzyme-catalyzed reactions and efficient methods to detect and record this activity. Herein, we report a wireless lateral flow device and demonstrate the conversion of oxidase reactions to changes in the resonance of radio frequency identification (RFID) circuits. The detection is triggered by polyoxometalate-catalyzed oxidative doping of polypyrrole (pPy) when exposed to oxidase-generated H

The increasing demand for food production has necessitated the development of sensitive and reliable methods of analysis, which allow for the optimization of storage and distribution while ensuring food safety. Methods to quantify and monitor volatile and biogenic amines are key to minimizing the waste of high-protein foods and to enable the safe consumption of fresh products. Novel materials and device designs have allowed the development of portable and reliable sensors that make use of different transduction methods for amine detection and food quality monitoring. Herein, we review the past decade?s advances in volatile amine sensors for food quality monitoring. First, the role of volatile and biogenic amines as a food-quality index is presented. Moreover, a comprehensive overview of the distinct amine gas sensors is provided according to the transduction method, operation strategies, and distinct materials (e.g., metal oxide semiconductors, conjugated polymers, carbon nanotubes, graphene and its derivatives, transition metal dichalcogenides, metal organic frameworks, MXenes, quantum dots, and dyes, among others) employed in each case. These include chemoresistive, fluorometric, colorimetric, and microgravimetric sensors. Emphasis is also given to sensor arrays that record the food quality fingerprints and wireless devices that operate as radiofrequency identification (RFID) tags. Finally, challenges and future opportunities on the development of new amine sensors are presented aiming to encourage further research and technological development of reliable, integrated, and remotely accessible devices for food-quality monitoring. Made available in DSpace on 2022-09-28T20:05:36Z (GMT). No. of bitstreams: 1 P-Recent-Progress-in-Amine-Gas-Sensors-for-Food-Quality-Monitoring.pdf: 4506930 bytes, checksum: afd8070c0df98dba888f9ab63a3b7a3e (MD5) Previous issue date: 2022

The Faraday effect is a magneto-optical (MO) phenomenon that causes the plane of linearly polarized light to rotate when passing through a medium subjected to a parallel magnetic field. Informed by the established quantum mechanical model developed by Buckingham and Stephens, we sought to identify molecules that would exhibit large MO responses. Magnetic circular dichroism studies of ferrocenium in the 1970s revealed its potential as an MO material; however, it has not been evaluated in the context of Faraday rotation and thin-film optical applications. Herein, we report near-infrared (NIR) Faraday rotation in thin films of decamethylferrocenium/poly(methyl methacrylate) composites with maximum Verdet constants of -3.45 × 104 deg T-1 m-1 at 810 nm (absorbance = 0.09) and -1.44 × 104 deg T-1 m-1 at 870 nm (absorbance = 0.01). These polymer-metallocene thin films deliver larger Verdet constants than commercially used NIR inorganic Faraday rotators and are facile and inexpensive to produce. The temperature dependence and distinct lineshape of the MO responses observed in decamethylferrocenium radical cations, decamethylmanganocene, and chromocene are in accordance with the quantum mechanical model. The observation of a strong C-term Faraday rotation in solid-state organometallic materials provides the groundwork for the development of high-performance metallocene-based Faraday rotators.

The magneto-optical phenomenon known as Faraday rotation involves the rotation of plane-polarized light as it passes through an optical medium in the presence of an external magnetic field oriented parallel to the direction of light propagation. Faraday rotators find applications in optical isolators and magnetic-field imaging technologies. In recent years, organic thin films comprised of polymeric and small-molecule chromophores have demonstrated Verdet constants, which measure the magnitude of rotation at a given magnetic field strength and material thickness, that exceed those found in conventional inorganic crystals. We report herein the thin-film magnetic circular birefringence (MCB) spectra and maximum Verdet constants of several commercially available and newly synthesized phthalocyanine and porphyrin derivatives. Five of these species achieved maximum Verdet constant magnitudes greater than 105 deg T-1 m-1 at wavelengths between 530 and 800 nm. Notably, a newly reported zinc(II) phthalocyanine derivative (ZnPc-OT) reached a Verdet constant of -33 × 104 deg T-1 m-1 at 800 nm, which is among the largest reported for an organic material, especially for an optical-quality thin film. The MCB spectra are consistent with resonance-enhanced Faraday rotation in the region of the Q-band electronic transition common to porphyrin and phthalocyanine derivatives, and the Faraday A-term describes the electronic origin of the magneto-optical activity. Overall, we demonstrate that phthalocyanines and porphyrins are a class of rationally designed magneto-optical materials suitable for applications demanding large Verdet constants and high optical quality.

Hydrogen peroxide is a dynamic signaling molecule in biological systems. We report herein a versatile double emulsion sensor that can detect femtomolar quantities of aqueous hydrogen peroxide. The mechanism responsible for this sensitivity is a peroxide induced change in double emulsion structure, which results in a modified directional emission from dyes dissolved in the high index organic phase. The morphology (structure) of the double emulsion is controlled via interfacial tensions and a methyltrioxorhenium catalyzed sulfide oxidation results in an enhancement of the surfactant effectiveness. The incipient polar sulfoxide induced decrease of the interfacial tension at the organic-water (O-W) interface results in an increased interfacial area between the organic phase and water and a diminished emission perpendicular to the supporting substrate. The modularity of our sensory system is demonstrated through cascade catalysis between methyltrioxorhenium and oxidase enzymes, with the latter producing hydrogen peroxide as a byproduct to enable for the selective and sensitive detection of molecular and ionic enzymatic substrates.

Exciton migration to emissive defects in π-conjugated polymers is a robust signal amplification strategy for optoelectronic sensors. Herein we report end-capped conjugated polymers that show two distinct emissions as a function of interpolymer distances at the air–water and hydrocarbon–water interfaces. Amphiphilic poly(phenylene ethynylene)s (PPEs) end-capped with perylene monoimides display two distinct emission colors (cyan from PPE and red from perylene), the relative intensity of which depends on the surface pressure applied on the Langmuir monolayers. This behavior produces a ratiometric interfacial pressure indicator. Relative quantum yields are maintained at the different surface pressures and hence display no sign of self-quenching of the excitons in an aggregated state. These polymers can be organized at the micelle–water interface in lytropic liquid crystals, thereby paving the way for potential applications of end-capped amphiphilic conjugated polymers in biosensors and bioimaging.

Interactions between π-conjugated polymers are known to create ground-state aggregates, excimers, and exciplexes. With few exceptions, these species exhibit decreased fluorescence quantum yields relative to the isolated polymers in liquid or solid solutions. Herein, we report a method to assemble emissive conjugated polymer excimers and demonstrate their applicability in the detection of selected solvent vapors. Specifically, poly(phenylene ethynylene)s (PPEs) with amphiphilic side chains are organized in a Langmuir monolayer at the air-water interface. Compression of the monolayer results in the reversible conversion from a face-on organization of the π-system relative to the water to what appears to be an incline-stack conformation. The incline-stack organization creates a bright yellow emissive excimeric state with increases of 28% in relative fluorescence quantum yields to the face-on monolayer conformation. Multilayers can be transferred onto the glass substrate via a Langmuir-Blodgett method with preservation of the excimer emission. These films are metastable and the fluorescence reverts to a cyan color similar to the spectra obtained in solution and spin-cast films after exposure to selected solvent vapors. This behavior has practical utility as a fluorescence-based indicator for selected volatile organic compounds.

We report a versatile new synthetic route to poly(