Molecular Viscosity Sensors with Two Rotators for Optimizing the Fluorescence Intensity-Contrast Trade-Off.

A series of fluorescent molecular rotors obtained by introducing two rotational groups ("rotators"), which exhibit different rotational and electron-donating abilities, are discussed. Whereas the control molecular rotor, PH, includes a single rotator (the widely used phenyl group), the PO molecular rotors consist of two rotators (a phenyl group and an alkoxy group), which exhibit simultaneous strongly electron-donating and easy rotational abilities. Compared with the control rotor PH, PO molecular rotors exhibited one order of magnitude higher quantum yield (fluorescence intensity) and simultaneously exhibited significantly higher fluorescence contrast. These properties are directly related to the strong electron-donating ability and low energy barrier of rotation of the alkoxy group, as confirmed by dynamic fluorescence experiments and quantum chemical calculations. The PO molecular rotors exhibited two fluorescence relaxation pathways, whereas the PH molecular rotor exhibited a single fluorescence relaxation pathway. Cellular fluorescence imaging with PO molecular rotors for mapping cellular viscosity was successfully demonstrated.

Enhancement of the Mechanical Properties in Al⁻Si⁻Cu⁻Fe⁻Mg Alloys with Various Processing Parameters.

In this research, various processing conditions were implemented to enhance the mechanical properties of Al-Si alloys. The silicon content was varied from hypoeutectic (Si-10 wt.%) to eutectic (Si-12.6 wt.%) and hypereutectic (Si-14 wt.%) for the preparation of Al-XSi-3Cu-0.5Fe-0.6 Mg (X = 10⁻14%) alloys using die casting. Subsequently, these alloys were hot-extruded with an optimum extrusion ratio (17:1) at 400 °C to match the output extruded bar to the compressor size. An analysis of the microstructural features along with a chemical compositional analysis were carried out using scanning electron microscope along with energy dispersive X-ray spectroscopy and transmission electron microscope. The SEM micrographs of the extruded samples displayed cracks in primary Si, and the intermetallic (ß-Al5FeSi) phase was fragmented accordingly. In addition, the silicon phase was homogenously distributed, and the size remained constant. The mechanical properties of the extruded samples were enhanced by the increase of silicon content, and consequently the ductility decreased. By implementing proper T6 heat treatment parameters, coherent Al2Cu phases were formed in the Al matrix, and the Si phase was gradually increased along with the silicon content. Therefore, high tensile strength was achieved, reaching values for the Al-XSi-3Cu-0.5Fe-0.6Mg (X = 10⁻14%) alloys of 366 MPa, 388 MPa, and 420 MPa, respectively.

Enhanced Photodynamic Cancer Treatment by Mitochondria-Targeting and Brominated Near-Infrared Fluorophores.

A noninvasive and selective therapy, photodynamic therapy (PDT) is widely researched in clinical fields; however, the lower efficiency of PDT can induce unexpected side effects. Mitochondria are extensively researched as target sites to maximize PDT effects because they play crucial roles in metabolism and can be used as cancer markers due to their high transmembrane potential. Here, a mitochondria targeting photodynamic therapeutic agent (MitDt) is developed. This photosensitizer is synthesized from heptamethine cyanine dyes, which are conjugated or modified as follows. The heptamethine meso-position is conjugated with a triphenylphosphonium derivative for mitochondrial targeting, the N-alkyl side chain is modified for regulation of charge balance and solubility, and the indolenine groups are brominated to enhance reactive oxygen species generation (ROS) after laser irradiation. The synthesized MitDt increases the cancer uptake efficiency due to the lipo-cationic properties of the triphenylphosphonium, and the PDT effects of MitDt are amplified after laser irradiation because mitochondria are susceptible to ROS, the response to which triggers an apoptotic anticancer effect. Consequently, these hypotheses are demonstrated by in vitro and in vivo studies, and the results indicate strong potential for use of MitDts as efficient single-molecule-based PDT agents for cancer treatment.

High-Performance Visible-Blind UV Phototransistors Based on n-Type Naphthalene Diimide Nanomaterials.

This study investigates the performance of single-crystalline nanomaterials of wide-band gap naphthalene diimide (NDI) derivatives with methylene-bridged aromatic side chains. Such materials are found to be easily used as high-performance, visible-blind near-UV light detectors. NDI single-crystalline nanoribbons are assembled using a simple solution-based process (without solvent-inclusion problems), which is then applied to organic phototransistors (OPTs). Such OPTs exhibit excellent n-channel transistor characteristics, including an average electron mobility of 1.7 cm2 V-1 s-1, sensitive UV detection properties with a detection limit of ∼1 µW cm-2, millisecond-level responses, and detectivity as high as 1015 Jones, demonstrating the highly sensitive organic visible-blind UV detectors. The high performance of our OPTs originates from the large face-to-face π-π stacking area between the NDI semiconducting cores, which is facilitated by methylene-bridged aromatic side chains. Interestingly, NDI-based nanoribbon OPTs exhibit a distinct visible-blind near-UV detection with an identical detection limit, even under intense visible light illumination (for example, 104 times higher intensity than UV light intensity). Our findings demonstrate that wide-band gap NDI-based nanomaterials are highly promising for developing high-performance visible-blind UV photodetectors. Such photodetectors could potentially be used for various applications including environmental and health-monitoring systems.

Benzothiazolium Single Crystals: A New Class of Nonlinear Optical Crystals with Efficient THz Wave Generation.

Highly efficient nonlinear optical organic crystals are very attractive for various photonic applications including terahertz (THz) wave generation. Up to now, only two classes of ionic crystals based on either pyridinium or quinolinium with extremely large macroscopic optical nonlinearity have been developed. This study reports on a new class of organic nonlinear optical crystals introducing electron-accepting benzothiazolium, which exhibit higher electron-withdrawing strength than pyridinium and quinolinium in benchmark crystals. The benzothiazolium crystals consisting of new acentric core HMB (2-(4-hydroxy-3-methoxystyryl)-3-methylbenzo[d]thiazol-3-ium) exhibit extremely large macroscopic optical nonlinearity with optimal molecular ordering for maximizing the diagonal second-order nonlinearity. HMB-based single crystals prepared by simple cleaving method satisfy all required crystal characteristics for intense THz wave generation such as large crystal size with parallel surfaces, moderate thickness and high optical quality with large optical transparency range (580-1620 nm). Optical rectification of 35 fs pulses at the technologically very important wavelength of 800 nm in 0.26 mm thick HMB crystal leads to one order of magnitude higher THz wave generation efficiency with remarkably broader bandwidth compared to standard inorganic 0.5 mm thick ZnTe crystal. Therefore, newly developed HMB crystals introducing benzothiazolium with extremely large macroscopic optical nonlinearity are very promising materials for intense broadband THz wave generation and other nonlinear optical applications.