Organic upconversion is a unique process in which low-energy light (usually NIR light) is converted to high-energy light through either the two-photon absorption (TPA) mechanism or the triplet-triplet annihilation (TTA) mechanism. Both TPA upconversion (TPA-UC) and TTA upconversion (TTA-UC) have been actively investigated in recent years due to their intriguing applications in optics, biophotonics, and solar energy utilization. Although they show some similarity (i.e., belonging to the nonlinear two-quantum process and needing focused excitation light), TPA-UC and TTA-UC are very different, such as in mechanism, characteristics involved, molecular design and potential applications. Here, we collectively reviewed these two kinds of upconversion processes and compared their respective characteristics and merits. We also present recent advances made in the areas of TPA- and TTA-UC, the remaining challenges and opportunities, with particular emphasis on molecular engineering of these two active upconversion materials.
Self-powered operation, flexibility, excellent mechanical properties, and ultra-high sensitivity are highly desired properties for pressure sensors in human health monitoring and anthropomorphic robotic systems. Piezoelectric pressure sensors, with enhanced electromechanical performance to effectively distinguish multiple mechanical stimuli (including pressing, stretching, bending, and twisting), have attracted interest to precisely acquire the weak signals of the human body. In this work, we prepared a poly(vinylidene fluoride-trifluoroethylene)/ multi-walled carbon nanotube (P(VDF-TrFE)/MWCNT) composite by an electrospinning process and stretched it to achieve alignment of the polymer chains. The composite membrane demonstrated excellent piezoelectricy, favorable mechanical strength, and high sensitivity. The piezoelectric coefficient d33 value was approximately 50 pm/V, the Young’s modulus was ~0.986 GPa, and the sensitivity was ~540 mV/N. The resulting composite membrane was employed as a piezoelectric pressure sensor to monitor small physiological signals including pulse, breath, and small motions of muscle and joints such as swallowing, chewing, and finger and wrist movements. Moderate doping with carbon nanotubes had a positive impact on the formation of the β phase of the piezoelectric device, and the piezoelectric pressure sensor has the potential for application in health care systems and smart wearable devices.
A carboxymethyl chitosan and peptide-decorated PEEK ternary biocomposite showed enhanced antibacterial activity, in vitro osteogenic differentiation and in vivo osseointegration.
Electric potential plays an indispensable role in tissue engineering and wound healing. Piezoelectric nanogenerators based on direct piezoelectric effects can be self-powered energy sources for electrical stimulation and have attracted extensive attention. However, the accuracy of piezoelectric stimuli on piezoelectric polymers membranes in vitro during the dynamic condition is rarely studied. Here, a self-powered tunable electrical stimulation system for assisting the proliferation of preosteoblasts was achieved by well-aligned P(VDF-TrFE) piezoelectric nanofiber membrane (NFM) both as a nanogenerator (NG) and as a scaffold. The effects of electrospinning and different post-treatments (annealing and poling) on the surface wettability, piezoelectric β phase, ferroelectric properties, and sensing performance of NFMs were evaluated here. The polarized P(VDF-TrFE) NFM offered an enhanced piezoelectric value (d31 of 22.88 pC/N) versus pristine P(VDF-TrFE) NFM (d31 of 0.03 pC/N) and exhibited good sensing performance. The maximum voltage and current output of the P(VDF-TrFE) piezoelectric nanofiber NGs reached −1.7 V and 41.5 nA, respectively. An accurate electrical response was obtained in real time under dynamic mechanical stimulation by immobilizing the NGs on the flexible bottom of the culture plate, thereby restoring the real scene of providing electrical stimulation to the cells in vitro. In addition, we simulated the interaction between the piezoelectric nanofiber NG and cells through an equivalent circuit model. To verify the feasibility of P(VDF-TrFE) nanofiber NGs as an exact electrical stimulation, the effects of different outputs of P(VDF-TrFE) nanofiber NGs on cell proliferation in vitro were compared. The study realized a significant enhancement of preosteoblasts proliferation. This work demonstrated the customizability of P(VDF-TrFE) piezoelectric nanofiber NG for self-powered electrical stimulation system application and suggested its significant potential application for tissue repair and regeneration.
A new palladium-catalyzed tandem cyclization of various
alkene-tethered
aryl iodides has been presented. In this protocol, o-bromobenzoic acids are employed as coupling parters to achieve the
insertion of aromatic rings by the cleavage of C(sp2)–Br
and decarboxylation, thus assembling various dibenzoisoquinolinediones
and dibenzoisoquinolinones. In addition, a seven-membered ring
can be constructed by the use of 8-bromo-1-naphthoic acid. Notably,
this approach enables regioselective product formation and features
broad substrate scope.
Memristors will be critical components in the next generation of digital technology and artificial synapses. Researchers are investigating innovative mechanistic understanding of the memristor devices based on low-cost, solutionprocessable, and organic materials as promising candidates. Here, we demonstrate a novel polyelectrolyte-based memristor device, which is simply prepared by spin-coating poly(acrylic acid) (PAA) and polyethylenimine (PEI) on an indium tin oxide (ITO) substrate followed by a magnetron sputtering of the ITO as the top electrode. The device has a potential to achieve excellent resistive switching (RS) performance and synapse functionality as well as greater flexibility and transmittance when compared to the oxidebased memories. An on/off resistance ratio of 50 can be maintained without degradation for up to 20 000 cycles (flat state) and over 4000 cycles (bending to a 2 mm radius 10 000 times) in the DC sweep mode. Moreover, the device performs various synaptic functions, including spike-timing-dependent plasticity, pulse pair plasticity, and short-term and long-term plasticity in the potentiation and depression processes. The counterions and two oppositely charged polyelectrolyte chains can move in and out of each other depending on the applied electrical potential (pulse), resulting in a change in the potential drop at the interface of the polyelectrolyte bilayer and its electrodes, which can be attributed to the RS mechanism and various synaptic functions. This insight may accelerate the technological deployment of the organic resistive memories.
A novel
palladium-catalyzed cascade cyclization of alkene-tethered aryl halides
with o-bromobenzoic acids is described, which provides
an efficient avenue for building various fused hexacyclic scaffolds
containing indolo[2,1-a]isoquinoline in moderate
to excellent yield. The method enables the construction of three C–C
bonds through an intramolecular carbopalladation, C–H activation,
and a decarboxylation sequence. Furthermore, dihydrocyclohepta[de]naphthalene-fused indolo[2,1-a]isoquinolines
can be synthesized in moderate yield by constructing a seven-membered
ring.
A novel
palladium-catalyzed divergent decarboxylative cyclization
of 2-iodobiphenyls and α-oxocarboxylic acids utilizing the atmosphere
as a controlled switch is reported. Under the protection of a nitrogen
atmosphere, tribenzotropones are synthesized by a [4 + 3] decarboxylative
cyclization. Employing a palladium/O2 system enables a
[4 + 2] decarboxylative cyclization to assemble triphenylenes. Notably,
preliminary mechanistic studies indicate that the formation of triphenylenes
involves a double decarboxylation.
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