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.

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.