A fluorescence-based sweat test sensor in a proof-of-concept clinical study for COVID-19 screening diagnosis.

During the corona virus disease 2019 (COVID-19) pandemic period, rapid screening of covid-19 patients has been of great interest by developing a fluorescent sensor for complexation with nonanal, which is a marker for Covid-19 detection in sweat. Solid phase micro-extraction gas chromatography-mass spectrometry (SPME GC-MS) was initially used to quantify nonanal in armpit sweat samples based on an external calibration curve. A sample containing a nonanal content above the threshold of 1.04 µL is expected to be COVID-19 positive with a sensitivity and specificity of 87% and 89%, respectively, validated by comparison with RT-PCR results. For more practical applications, helicene dye-encapsulated ethyl cellulose, namely EC@dyeNH, was applied to screen 140 sweat samples collected from the foreheads of volunteers. The mixed sensor and sweat solution droplets were then visualized and imaged under blacklight. The COVID-19 positive droplets exhibited yellow fluorescence emission, the brightness of which could be measured by using ImageJ in the grey scale. With the optimum color intensity of >73 for positive results, the screening performance was observed with a sensitivity and specificity of 96% and 93%, respectively. The overall test time of this method is approximately less than 15 min. This alternative method offers a promising practical screening approach for the diagnosis of COVID-19 in sweat.

3,12-Dimeth-oxy-5,6,9,10-tetra-hydro-[5]helicene-7,8-dicarbo-nitrile.

The complete molecule of the title compound, C26H20N2O2, is generated by a crystallographic twofold axis. The torsion angle between the terminal and central benzene rings is -32.5 (2)°. The torsion angle along the inner helical rim of the molecule is -18.8 (2)° with each other. The C⋯C distance between the terminal rings is 3.016 (2) Å. In the crystal, weak C-H⋯N hydrogen bonds are observed.

Crystal structure of 3,13-dimethoxy-5,6,10,11-tetrahydrofuro[3,4-i][5]helicene-7,9-dione.

The title compound, C26H20O5, crystallizes with two independent molecules (A and B) in the asymmetric unit, which differ primarily in the location of the -OCH3 groups. In the crystal, the mol-ecules form a layered structure parallel to (10-1) by C-H⋯O hydrogen-bonded networks. Adjacent layers are also linked by further C-H⋯O hydrogen bonds, forming a three-dimensional structure.

The evolution of multiplex detection of mycotoxins using immunoassay platform technologies.

Mycotoxins present serious threats not only for public health, but also for the economy and environment. The problems become more complex and serious due to co-contamination of multiple hazardous mycotoxins in commodities and environment. To mitigate against this issue, accurate, affordable, and rapid multiplex detection methods are required. This review presents an overview of emerging rapid immuno-based multiplex methods capable of detecting mycotoxins present in agricultural products and feed ingredients published within the past five years. The scientific principles, advantages, disadvantages, and assay performance of these rapid multiplex immunoassays, including lateral flow, fluorescence polarization, chemiluminescence, surface plasmon resonance, surface enhanced Raman scattering, electrochemical sensor, and nanoarray are discussed. From the recent literature landscape, it is predicted that the future trend of the detection methods for multiple mycotoxins will rely on the advance of various sensor technologies, a variety of enhancing and reporting signals based on nanomaterials, rapid and effective sample preparation, and capacity for quantitative analysis.

Helicene-Hydrazide Encapsulated Ethyl Cellulose as a Potential Fluorescence Sensor for Highly Specific Detection of Nonanal in Aqueous Solutions and a Proof-of-Concept Clinical Study in Lung Fluid.

Over the past years, lung cancer has been one of the vital cancer-related mortalities worldwide and has inevitably exhibited the highest death rate with the subsequent need for facile and convenient diagnosis approaches to identify the severity of cancer. Previous research has reported long-chain aldehyde compounds such as hexanal, heptanal, octanal, and nonanal as potential biomarkers of lung cancer. Herein, the helicene dye-encapsulated ethyl cellulose (EC@dye-NH) nanosensors have been applied for the potentially sensitive and specific detection of long-chain aldehydes in aqueous media. The sensors contain the intrinsic hydrazide group of dye-NH, which is capable of reacting an aldehyde group via imine formation and the EC backbone. This offers the synergistic forces of hydrophobic interactions with alkyl long-chain aldehydes, which could induce self-assembly encapsulation of EC@dye-NH nanosensors and strong fluorescence responses. The addition of long-chain aldehyde would induce the complete micellar-like nanoparticle formation within 15 min in acetate buffer pH 5.0. The limit of detection (LOD) values of EC@dye-NH nanosensors toward heptanal, octanal, and nonanal were 40, 100, and 10 µM, respectively, without interference from the lung fluid matrices and short-chain aldehydes. For practical applicability, this sensing platform was developed for quantification of the long-chain aldehydes in lung fluid samples with 98-101% recoveries. This EC@dye-NH nanosensor was applied to quantify nonanal contents in lung fluid samples. The results of this method based on EC@dye-NH nanosensors were then validated using standard gas chromatography-mass spectrometry (GC-MS), which gave results consistent with the proposed method. With intracellular imaging application, the EC@dye-NH nanosensors demonstrated excellent intracellular uptake and strong green fluorescence emission upon introducing the nonanal into the lung cancer cells (A549). Thus, the developed nanosensing approach served as the potential fluorescent probes in medical and biological fields, especially for lung cancer disease diagnosis based on highly selective and sensitive detection of long-chain aldehydes.

Bis[2,6-bis-(2-meth-oxy-phen-yl)pyridinium] di-µ-bromido-bis-[dibromidocuprate(II)].

The title salt, (C(19)H(18)NO(2))(2)[Cu(2)Br(6)], was obtained from an attempt to synthesize the copper(II) complex of 2,6-bis-(2-meth-oxy-phen-yl)pyridine (L) from a reaction between CuBr(2) and one equivalent of L in CH(2)Cl(2) at room temperature. The resulting compound is the salt of the 2,6-bis-(2-meth-oxy-phen-yl)pyridinium cation and 0.5 equivalents of a hexa-bromido-dicuprate(II) dianion. Both meth-oxy groups of the cationic pyridinium moiety are directed towards the N atom of the pyridine ring as a result of intra-molecular N-H⋯O hydrogen bonds. The centrosymmetric hexabromidodicuprate dianion possesses a distorted tetra-hedral geometry at the copper ion. The Cu-Br bond lengths are 2.3385 (7) and 2.3304 (7) Šfor the terminal bromides, whereas the bond length between the Cu atom and two bridging bromides is slightly longer [2.4451 (6) Å].

Development of a microarray lateral flow strip test using a luminescent organic compound for multiplex detection of five mycotoxins.

While lateral flow immunoassay (LFIA) is a simple technique that offers a rapid, robust, user friendly, and point-of-care test, its capacity for multiplex detection is rather limited. This study therefore combined the multiplexity of microarray technique and the simple and rapid characteristics of LFIA to enable simultaneous and quantitative detection of five mycotoxins, namely aflatoxin B1 (AFB1), deoxynivalenol (DON), fumonisin B1 (FUMB1), T-2 toxin (T-2), and zearalenone (ZON). In addition, we have synthesized a novel extra-large Stokes shift and strong fluorescence organic compound to be used as a reporter molecule which can be detected under UV light without light filter requirement. Many parameters including microarray spotting buffer, blocking buffer, and concentrations of mycotoxin antibodies were optimized for the microarray LFIA (µLFIA) construction. With the optimal conditions, the µLFIA could accurately and quantitatively detect multiple mycotoxins at the same time. The limits of detection of AFB1, DON, FUMB1, T-2, and ZON were 1.3, 0.5, 0.4, 0.4, and 0.9 ppb, respectively. The recoveries of these five mycotoxins were 70.7%-119.5% and 80.4%-124.8% for intra-assay and inter-assay, respectively. Combining the advantages of the novel reporter molecule and the multiplex capability of µLFIA test, this system could simultaneously detect multiple mycotoxins in one sample with high specificity and high sensitivity. Moreover, this system presents a promising affordable point-of-care platform to detect other analytes as well.

Detection of hazardous mercury ion using [5]helicene-based fluorescence probe with "TurnON" sensing response for practical applications.

A new fluorescence probe based on [5]helicene derivative (MT) was designed and synthesized. The chemical structure of the probe was fully characterized by NMR, mass spectrometry and X-ray crystallography. MT which is the combination of thioamide[5]helicene with Schiff base-thiophene moiety, exhibited a high selectivity to detect Hg2+ through irreversible desulfurization reaction with "TurnON" fluorescence response and large Stokes shift of 110 nm in aqueous methanol solution. The detection limit of MT was 1.2 ppb (6.0 × 10-3 µM), which is lower than the limit of Hg2+ level in drinking water, as specified by WHO (6.0 ppb) and U.S. EPA (2.0 ppb). The Hg2+ detection range of the probe was 0.07-1.6 µM with good linearity. Under UV irradiation, MT possessed the capability to detect Hg2+ in diverse context of real samples, including drinking and sea waters, vegetable tissue and brain tumor cell. In addition, MT could be used as a paper test strip for monitoring and screening of Hg2+ contamination in environment.

Dual-Analyte Fluorescent Sensor Based on [5]Helicene Derivative with Super Large Stokes Shift for the Selective Determinations of Cu2+ or Zn2+ in Buffer Solutions and Its Application in a Living Cell.

A new fluorescent sensor, M201-DPA, based on [5]helicene derivative was utilized as dual-analyte sensor for determination of Cu2+ or Zn2+ in different media and different emission wavelengths. The sensor could provide selective and bifunctional determination of Cu2+ in HEPES buffer containing Triton-X100 and Zn2+ in Tris buffer/methanol without interference from each other and other ions. In HEPES buffer, M201-DPA demonstrated the selective ON-OFF fluorescence quenching at 524 nm toward Cu2+. On the other hand, in Tris buffer/methanol, M201-DPA showed the selective OFF-ON fluorescence enhancement upon the addition of Zn2+, which was specified by the hypsochromic shift at 448 nm. Additionally, M201-DPA showed extremely large Stokes shifts up to ∼150 nm. By controlling the concentration of Zn2+ and Cu2+ in a living cell, the imaging of a HepG2 cellular system was performed, in which the fluorescence of M201-DPA in the blue channel was decreased upon addition of Cu2+ and was enhanced in UV channel upon addition of Zn2+. The detection limits of M201-DPA for Cu2+ and Zn2+ in buffer solutions were 5.6 and 3.8 ppb, respectively. Importantly, the Cu2+ and Zn2+ detection limits of the developed sensors were significantly lower than permitted Cu2+ and Zn2+ concentrations in drinking water as established by the U.S. EPA and WHO.

Excited state dynamics and structures of functionalized phthalocyanines. 1. Self-regulated assembly of zinc helicenocyanine.

Recently synthesized zinc helicenocyanine (ZnHc), where four helicene groups are fused with a phthalocyanine (Pc) core through all-carbon linkages, exhibits an unusually strong tendency of forming soluble molecular aggregates in organic solvents. The aggregation results in a strong optical absorption across most of the visible region, which is drastically different from that of its monomer. The aggregation is suppressed by dissolving ZnHc in a liquid crystal, octylbiphenylcarbonitrile (OBCN), where the monomer ZnHc dominates and exhibits a typical optical absorption spectrum of monomeric zinc phthalocyanine, except red shift in both Q- and B- bands due to pi-conjugation expansion. This study correlates optical properties and excited state dynamics of ZnHc with intra- and intermolecular electronic interactions, using quantum mechanical calculations and ultrafast transient absorption spectroscopy. Structural details of the aggregates are revealed by small-angle X-ray scattering (SAXS) to be uniformly dimers with alkoxy chains wrapped around the core of a face-to-face dimer. The results suggest that while the peripheral helicene moieties in ZnHc are electronically coupled to the Pc core via expansion of the pi-conjugation of the macrocycle, the coupling is attenuated by the "lock washer" conformation of the nonplanar peripheral helicenes which prevents pi-conjugation throughout the entire macrocycle. The interplay between pi-conjugation expansion in the macrocyle plane and the pi-pi stacking out of the macrocyle plane produces a structure that facilitates the unique optical properties and self-regulated assembly into nanoscale structures in solution. These novel optical properties are explored for potential applications in various areas.

[5]helicene-fused phthalocyanine derivatives. New members of the phthalocyanine family.

An efficient synthetic route to fuse [5]helicene moieties around the phthalocyanine core is reported. The helicene moiety was constructed by the Diels-Alder reaction of 3,4,3',4'-tetrahydro-1,1'-dinaphthyl and dibromobenzyne. Subsequent cyanation, oxidation, O-alkylation, and cyclic tetramerization resulted in octaalkoxy phthalocyanine derivatives which showed high solubility in common organic solvents and displayed strong absorption in the near-IR region.