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.

Cs and Br tuning to achieve ultralow-hysteresis and high-performance indoor triple cation perovskite solar cell with low-cost carbon-based electrode.

With high efficacy for electron-photon conversion under low light, perovskite materials show great potential for indoor solar cell applications to power small electronics for internet of things (IoTs). To match the spectrum of an indoor LED light source, triple cation perovskite composition was varied to adjust band gap values via Cs and Br tuning. However, increased band gaps lead to morphology, phase instability, and defect issues. 10% Cs and 30% Br strike the right balance, leading to low-cost carbon-based devices with the highest power conversion efficiency (PCE) of 31.94% and good stability under low light cycles. With further improvement in device stack and size, functional solar cells with the ultralow hysteresis index (HI) of 0.1 and the highest PCE of 30.09% with an active area of 1 cm2 can be achieved. A module from connecting two such cells in series can simultaneously power humidity and temperature sensors under 1000 lux.

Robust perovskite formation via vacuum thermal annealing for indoor perovskite solar cells.

Perovskite materials are fascinating candidates for the next-generation solar devices. With long charge carrier lifetime, metal-halide perovskites are known to be good candidates for low-light harvesting. To match the irradiance spectra of indoor light, we configured a triple-cation perovskite material with appropriate content of bromide and chloride (FA0.45MA0.49Cs0.06Pb(I0.62Br0.32Cl0.06)3) to achieve an optimum band gap (Eg) of [Formula: see text]1.80 eV. With low photon flux at indoor condition, minimal recombination is highly desirable. To achieve such goal, we, for the first time, combined dual usage of antisolvent deposition and vacuum thermal annealing, namely VTA, to fabricate a high-quality perovskite film. VTA leads to compact, dense, and hard morphology while suppressing trap states at surfaces and grain boundaries, which are key culprits for exciton losses. With low-cost carbon electrode architecture, VTA devices exhibited average power conversion efficiency (PCE) of 27.7 ± 2.7% with peak PCE of 32.0% (Shockley-Queisser limit of 50-60%) and average open-circuit voltage (Voc) of 0.93 ± 0.02 V with peak Voc of 0.96 V, significantly more than those of control and the vacuum treatment prior to heat.

Four series of lanthanide coordination polymers based on the tetrabromobenzene-1,4-dicarboxylate ligand: structural diversity and multifunctional properties.

Four series of lanthanide-based coordination polymers (LnCPs), namely [Ln(Br4bdc)1.5(MeOH)3] (1Ln; Ln = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy), [Ln2(Br4bdc)2(NO3)2(MeOH)4] (2Ln; Ln = Ce, Pr, Nd, Sm), [Ln(Br4bdc)(NO3)(MeOH)] (3Ln; Ln = Gd, Tb, Dy), and [Ln2(Br4bdc)3(H2O)2.3(MeOH)2.7] (4Ln; Ln = Gd, Tb, Dy) have been synthesized by reacting hydrated lanthanide(III) salts with tetrabromobenzene-1,4-dicarboxylic acid (H2Br4bdc) in different solvents under solvothermal conditions. The structural diversity found in the system mainly resulted from the effects of anions, solvents, and the variation in the ionic radii of the lanthanide(III) ions. Compounds in series 1Ln feature a two-dimensional (2D) layered structure with sql topology based on {(Ln(COO)2)2(µ-COO)2} secondary building units (SBUs). Compounds in series 2Ln and 3Ln comprise, respectively, infinite uniform and alternate chains of {Ln(COO)2}n SBUs that are assembled into a similar network topology to 1Ln. Meanwhile, compounds in series 4Ln feature 3D coordination networks of a pcu α-Po topological net consisting of binuclear {Ln2(COO)3} SBUs. The formation of polymeric networks in series 1Ln-4Ln is facilitated by the numerous coordination sites of the ligand Br4bdc2- and the fact that its bromine atoms can participate in the formation of various types of intermolecular interactions. The solid-state photoluminescence studies on Eu- (1Eu) and Tb- (1Tb, 3Tb, 4Tb) containing compounds indicate that the Br4bdc2- ligands can efficiently sensitize Eu3+ and Tb3+ emission. Notably, such compounds exhibit highly sensitive fluorescence sensing for acetone, water, and Fe3+ ions via the fluorescence quenching effect. As the representatives of the series, activated 1Eu, 2Pr, 3Tb, and 4Tb show the maximum CO2 uptake capacities of 170.4, 273.7, 255.3, and 303.5 cm3 g-1, respectively, at 50 bar and 298 K with good repeatability of the adsorption-desorption properties. Magnetic studies indicate that the Gd- and Dy-based compounds 1Gd, 1Dy, 3Gd, 3Dy, and 4Gd show simple paramagnetic behaviours, whereas compound 4Dy exhibits weak ferromagnetic interactions.

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.

Graded multilayer triple cation perovskites for high speed and detectivity self-powered photodetector via scalable spray coating process.

Rapid advancements in perovskite materials have led to potential applications in various optoelectronic devices, such as solar cells, light-emitting diodes, and photodetectors. Due to good photoelectric properties, perovskite enables low-cost and comparable performance in terms of responsivity, detectivity, and speed to those of the silicon counterpart. In this work, we utilized triple cation perovskite, well known for its high performance, stability, and wide absorption range, which is crucial for broadband photodetector applications. To achieve improved detectivity and faster response time, graded multilayer perovskite absorbers were our focus. Sequential spray deposition, which allows stacked perovskite architecture without disturbing lower perovskite layers, was used to generate single, double, and triple-layer perovskite photodetectors with proper energy band alignment. In this work, we achieved a record on self-powered perovskite photodetector fabricated from a scalable spray process in terms of EQE and responsivity of 65.30% and 0.30 A W-1. The multilayer devices showed faster response speed than those of single-layer perovskite photodetectors with the champion device reaching 70 µs and 88 µs for rising and falling times. The graded band structure and the internal electric field generated from perovskite heterojunction also increase specific detectivity about one magnitude higher in comparison to the single-layer with the champion device achieving 6.82 × 1012 cmHz1/2 W-1.

The coordination chemistry of benzhydrazide with lanthanide(iii) ions: hydrothermal in situ ligand formation, structures, magnetic and photoluminescence sensing properties.

The influence of synthetic conditions on the solid-state structural formation of lanthanide(iii) complexes based on a hydrazide ligand have been investigated and reported. Depending on the solvents and reaction temperatures, the reactions of hydrated Ln(NO3)3 with a benzohydrazide (bzz) ligand afforded three classes of lanthanide(iii) coordination complexes viz. [Ln(bzz)(NO3)](NO3)2 (1Ln; Ln = Sm (1), Eu (2), Gd (3), Tb (4), Dy (5)), [Ln(bzz)(ben)3(H2O)]·H2O (2Ln; Ln = Pr (6), Nd (7), Sm (8), Eu (9), Gd (10), Tb (11), Dy (12), Er (13)), and [Ln3(ben)3] (3Ln; Ln = Eu (14), Gd (15), Tb (16), Dy (17), Er (18), Tm (19), Yb (20), Lu (21)). Complexes 1-5 in series 1Ln were isolated by slow evaporation of their isopropanol solutions at ambient temperature, and the complexes display similar discrete structures bearing distinct intermolecular N-H⋯O hydrogen bonds to generate a three-dimensional (3D) supramolecular architecture. Complexes 6-13 in series 2Ln were obtained under hydrothermal conditions at 110 °C where the in situ generated benzoate (ben) ligands participated in the formation of one-dimensional (1D) coordination polymers (CPs) with the bzz ligands. At a temperature of 145 °C the hydrothermal conditions result in the formation of the thermodynamically more stable products of 14-21 in series 3Ln, in which the bzz ligand underwent complete in situ hydrolysis to create the ben ligand. These coordination assemblies feature 1D zigzag chains that are formed by unusual low coordination numbers of the six- and seven-fold coordinated Ln3+ centers bridged by the ben ligands in µ 2- and µ 3-coordination modes. Notably, the chain structures of 2Ln can be transformed into the zigzag tape-like structures of 3Ln upon heating the crystalline samples to 400 °C in air. In the solid state at room temperature, the Eu- (2, 9, 14) and Tb- (4, 11, 16) containing complexes emit red and green light, respectively. The luminescence investigations show that the Eu- (9, 14) and Tb-(11, 16) based CPs could be used as fluorescent probes for acetone and Co2+ ions via an energy competition mechanism. Meanwhile, the Gd- (10, 15) and Dy- (12, 17) based CPs show typical antiferromagnetic interactions.

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.

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.

Modifying morphology and defects of low-dimensional, semi-transparent perovskite thin films via solvent type.

(PEA)2(MA) n-1Pb n I n+1Br2n perovskites are semi-transparent, color-tunable thin films with broader band gaps. They have the potential for semi-transparent solar cell and smart window applications. Solvent engineering significantly alters the morphology, absorbance, crystallinity, charge separation, and defects, thereby influencing the optoelectronic properties. Herein, we investigated the effect of the solvent type on the low dimensional, mixed halide perovskite thin films (n = 1, 3, and 5) and identified DMF : DMSO = 8 : 2 as the most suitable solvent. The mixed solvent regulated the growth rate of perovskites, which led to the smooth morphology and larger crystallite size. Through surface photovoltage spectroscopy and time resolved photoluminescence, good charge separation and low defects were linked to DD82 usage.

Eight combinatorial stacks of three layers of carbon black/PVA-carbon black/EVA composite as a vapor detector array.

Eight specimens of combinatorial stacking of 3 layers of carbon black/PVA-carbon black/EVA composite were prepared on substrate with interdigitated electrode. They were subjected to 15 solvent vapors with dielectric constants from 2-80,and their responses were processed for calculation of resolution factor (RF). If the detector responses are assumed to have a normal distribution, RF values of 1.0, 2.0, and 3.0 indicate the 76, 92, and 98% confidence, respectively, of correctly identifying one analyte from the other of a specific pair. Of the possible 105 pairs, 99 pairs have RF values of more than 3, 5 pairs have RF values of more than 1, and only one pair has an RF value of less than 1. The resolution factor was affected by both the dielectric constant and boiling point of tested solvents. Employing Fisher linear discrimination improves all RF values greater than 3, making confidence in resolving the pair reach almost 100%. Contributions from each combination were studied, and it was shown that diversity by combinatorial stacking is essential to the improvement of RF value. All of these capabilities are derived from combinatorial stacking of 3 layers of just two simple carbon black/polymer composites.

Highly effective discrimination of catecholamine derivatives via FRET-on/off processes induced by the intermolecular assembly with two fluorescence sensors.

We proudly presented the novel sensor system based on intermolecular assembled complexes of two fluorescence sensors and a suitable catecholamine acting as a guest linker by the reaction between boronic acid and aldehyde moieties of the sensors with the diol and amine units of catecholamines, respectively. The FRET-on/off induced by the assembly could discriminate structural similarity of catecholamines.