Organic solid-state luminescence switching (SLS) materials with the ability to reversibly switch the luminescence by altering the mode of molecular packing without changing the chemical structures of their component molecules have attracted considerable interest in recent years. In this work, we design and synthesize a new class of 2,7diphenylfluorenone derivatives (compounds 1−6) that exhibit prominent aggregation-induced emission (AIE) properties with high solid-state fluorescence quantum yields (29−65%). Among them, 2,7-bis(4-methoxyphenyl)-9H-fluoren-9-one (2) and 2,7-bis(4-ethylphenyl)-9H-fluoren-9-one ( 6) display reversible stimuli-responsive solid-state luminescence switching. Compound 2 transforms between red and yellow crystals (the emission wavelength switches between 601 and 551 nm) under the stimuli of temperature, pressure, or solvent vapor. Similarly, compound 6 exhibits SLS behavior, with luminescence switching between orange (571 nm) and yellow (557 nm). Eight X-ray single-crystal structures, characterization of the photophysical properties, powder X-ray diffraction, and differential scanning calorimetry provide insight into the structure−property relationships of the solid-state fluorescence behavior. The results indicate that the variable solid-state luminescence of the fluorenone derivatives is attributed to the formation of different excimers in different solid phases. Additionally, the stimuli-responsive reversible phase transformations of compounds 2 and 6 involve a structural transition between π−π stacking-directed packing and hydrogen bond-directed packing. The results also demonstrate the feasibility of our design strategy for new solid-state luminescence switching materials: introduction of both π−π stacking and hydrogen bonding into an AIE structure to obtain a metastable solid/crystalline state luminescence system.
Graphene oxides with different surface charges were fabricated from carboxylated graphene oxide by chemical modification with amino- (-NH2), poly-m-aminobenzene sulfonic acid- (-NH2/-SO3H), or methoxyl- (-OCH3) terminated functional groups. The chemically functionalized graphene oxides and the carboxylated graphene oxide were characterized by infrared spectroscopy, X-ray photoelectron spectroscopy, UV-Vis spectrometry, ζ potential measurements, field emission scanning electron microscopy, and contact angle analyses. Subsequently, the resulting graphene oxides were used as substrates for culturing primary rat hippocampal neurons to investigate neurite outgrowth and branching. The morphological features of neurons that directly reflect their potential capability in synaptic transmission were characterized. The results demonstrate that the chemical properties of graphene oxide can be systematically modified by attaching different functional groups that confer known characteristics to the substrate. By manipulating the charge carried by the functionalized graphene oxides, the outgrowth and branching of neuronal processes can be controlled. Compared with neutral, zwitterionic, or negatively charged graphene oxides, positively charged graphene oxide was found to be more beneficial for neurite outgrowth and branching. The ability to chemically modify graphene oxide to control neurite outgrowth could be implemented clinically, especially in cases wherein long-term presence of outgrowth modulation is necessary.
Photodynamic therapy (PDT) is a noninvasive and light-activated method for cancer treatment. Two of the vital parameters that govern the efficiency of PDT are the light irradiation to the photosensitizer and visual detection of the selective accumulation of the photosensitizer in malignant cells. Herein, we prepared an integrated nanoplatform for targeted PDT and imaging of cancer cells using folic acid and horseradish peroxidase (HRP)-bifunctionalized semiconducting polymer dots (FH-Pdots). In the FH-Pdots, meta-tetra(hydroxyphenyl)-chlorin (m-THPC) was used as photosensitizer to produce cytotoxic reactive oxygen species (ROS); fluorescent semiconducting polymer poly[2-methoxy-5-((2-ethylhexyl)oxy)-p-phenylenevinylene] was used as light antenna and hydrophobic matrix for incorporating m-THPC, and amphiphilic Janus dendrimer was used as a surface functionalization agent to conjugate HRP and aminated folic acid onto the surface of FH-Pdots. Results indicated that the doped m-THPC can be simultaneously excited by the on-site luminol-H2O2-HRP chemiluminescence system through two paths. One is directly through chemiluminescence resonance energy transfer (CRET), and the other is through CRET and subsequent fluorescence resonance energy transfer. In vitro PDT and specificity studies of FH-Pdots using a standard transcriptional and translational assay against MCF-7 breast cancer cells, C6 glioma cells, and NIH 3T3 fibroblast cells demonstrated that cell viability decreased with increasing concentration of FH-Pdots. At the same concentration of FH-Pdots, the decrease in cell viability was positively relevant with increasing folate receptor expression. Results from in vitro fluorescence imaging exhibited that more FH-Pdots were internalized by cancerous MCF-7 and C6 cells than by noncancerous NIH 3T3 cells. All the results demonstrate that the designed semiconducting FH-Pdots can be used as an integrated nanoplatform for targeted PDT and on-site imaging of cancer cells.
Controllable manipulation of fluid flow is crucial for efficient particle separation, which is associated with plenty of biomedical and industrial applications. Microfluidic technologies have achieved promising progress in particle positioning depending on inertial force with or without the help of the Dean effect. Herein, we describe an inertial microfluidic system containing a spiral microchannel for various highly efficient particle separations. We demonstrated that Dean-like secondary flow can be regulated by geometric confinement in the microchannel. On the introduction of a library of micro-obstacles into the spiral microchannels, the resulting linear acceleration of secondary flow can be applied to remarkably enhance particle focusing in time and space. Further, multiple separating and sorting manipulations of particles including polymeric particles, circulating tumor cells, and blood cells, can be successfully accomplished in the dimension-confined spiral channels in a sheathless, high-throughput (typically 3 ml min), long-term (at least 4 h), and highly-efficient (up to 99.8% focusing) manner. The methodological achievement pointing to ease-of-use, effective, and high-throughput particle manipulations is useful for both laboratory and commercial developments of microfluidic systems in life and material sciences.
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