The size of C-nanodots can be electrochemically tuned by changing the applied potential during their preparation. The higher the applied potential, the smaller the resulting C-nanodots. Moreover, the surface oxidation degree of the C-nanodots can also be electrochemically tuned. The red-shift of emission independent of the size provides an insight into the luminescence mechanism of C-nanodots.

The photoluminescence of carbon nanodots (C-dots) can be tuned by changing their surface chemistry or size because the photoluminescence is a function of the surface-state electronic transitions. Increasing the degree of surface oxidation leads to a narrowing of the energy gap of the surface; meanwhile, larger C-dots with an extensive π-electron system, which can couple with surface electronic states, can also lead to a narrowing of the energy gap of the surface states.

Nanodroplets on a solid surface (i.e., surface nanodroplets) have practical implications for high-throughput chemical and biological analysis, lubrications, laboratory-on-chip devices, and near-field imaging techniques. Oil nanodroplets can be produced on a solidliquid interface in a simple step of solvent exchange in which a good solvent of oil is displaced by a poor solvent. In this work, we experimentally and theoretically investigate the formation of nanodroplets by the solvent exchange process under well-controlled flow conditions. We find significant effects from the flow rate and the flow geometry on the droplet size. We develop a theoretical framework to account for these effects. The main idea is that the droplet nuclei are exposed to an oil oversaturation pulse during the exchange process. The analysis shows that the volume of the nanodroplets increases with the Peclet number Pe of the flow as ∝ Pe 3=4 , which is in good agreement with our experimental results. In addition, at fixed flow rate and thus fixed Peclet number, larger and less homogeneously distributed droplets formed at less-narrow channels, due to convection effects originating from the density difference between the two solutions of the solvent exchange. The understanding from this work provides valuable guidelines for producing surface nanodroplets with desired sizes by controlling the flow conditions. N anoscale droplets on a substrate (1) are an essential element for a wide range of applications, namely laboratory-on-chip devices, simple and highly efficient miniaturized reactors for concentrating products, high-throughput single-bacteria or singlebiomolecular analysis, encapsulation, and high-resolution imaging techniques, among others (2-5). These droplets are of great interest also because they can have a payload and can flow internally in response to external flow. As a consequence, such droplets are widely exploited in formulation industries. Quite some effort has been devoted to produce a large amount of nanodroplets in a controlled way. The current techniques include trapping by microcavities, emulsion direct adsorption, microprinting, and others (6). The solvent exchange process is a simple and generic approach for producing droplets or bubbles at solid-liquid interfaces that are only several tens to hundreds of nanometers in height, or a few femtoliters in volume (7-11). The approach has attractive advantages, such as its capability of producing a large number of nanodroplets in one simple step, and its generality in chemical composition of the droplet liquid, and flexibility in aspect ratio of the droplets and spatial structure or size of the substrate (9, 12).For the formation of surface nanodroplets by solvent exchange, a hydrophobic substrate is exposed sequentially to two miscible solutions of oil, where the second solvent has a lower solubility of oil than the first. Such solubility difference leads to supersaturation of the liquid with oil during the solvent exchange and consequently to the nucleation of nanodroplets on...

Spatiotemporal control of singlet oxygen ((1)O2) release is a major challenge for photodynamic therapy (PDT) against cancer with high therapeutic efficacy and minimum side effects. Here a selenium-rubyrin (NMe2Se4N2)-loaded nanoparticle functionalized with folate (FA) was designed and synthesized as an acidic pH-activatable targeted photosensitizer. The nanoparticles could specifically recognize cancer cells via the FA-FA receptor binding and were selectively taken up by cancer cells via receptor-mediated endocytosis to enter lysosomes, in which NMe2Se4N2 was activated to produce (1)O2. The pH-controllable release of (1)O2 specially damaged the lysosomes and thus killed cancer cells in a lysosome-associated pathway. The introduction of selenium into the rubyrin core enhanced the (1)O2 generation efficiency due to the heavy atom effect, and the substitution of dimethylaminophenyl moiety at meso-position led to the pH-controllable activation of NMe2Se4N2. Under near-infrared (NIR) irradiation, NMe2Se4N2 possessed high singlet oxygen quantum yield (ΦΔ) at an acidic pH (ΦΔ = 0.69 at pH 5.0 at 635 nm) and could be deactivated at physiological pH (ΦΔ = 0.06 at pH 7.4 at 635 nm). The subcellular location-confined pH-activatable photosensitization at NIR region and the cancer cell-targeting feature led to excellent capability to selectively kill cancer cells and prevent the damage to normal cells, which greatly lowered the side effects. Through intravenous injection of FA-NMe2Se4N2 nanoparticles in tumor-bearing mice, tumor elimination was observed after NIR irradiation. This work presents a new paradigm for specific PDT against cancer and provides a new avenue for preparation of highly efficient photosensitizers.

Ni-rich materials are appealing to replace LiCoO as cathodes in Li-ion batteries due to their low cost and high capacity. However, there are also some disadvantages for Ni-rich cathode materials such as poor cycling and rate performance, especially under high voltage. Here, we demonstrate the effect of dual-conductive layers composed of LiPO and PPy for layered Ni-rich cathode material. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy show that the coating layers are composed of LiPO and PPy. (NH)HPO transformed to LiPO after reacting with surface lithium residuals and formed an inhomogeneous coating layer which would remarkably improve the ionic conductivity of the cathode materials and reduce the generation of HF. The PPy layer could form a uniform film which can make up for the LiPO coating defects and enhance the electronic conductivity. The stretchy PPy capsule shell can reduce the generation of internal cracks by resisting the internal pressure as well. Thus, ionic and electronic conductivity, as well as surface structure stability have been enhanced after the modification. The electrochemistry tests show that the modified cathodes exhibited much improved cycling stability and rate capability. The capacity retention of the modified cathode material is 95.1% at 0.1 C after 50 cycles, whereas the bare sample is only 86%, and performs 159.7 mAh/g at 10 C compared with 125.7 mAh/g for the bare. This effective design strategy can be utilized to enhance the cycle stability and rate performance of other layered cathode materials.

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We presented a new aptamer biosensor for thrombin in this work, which was based on fluorescence resonance energy transfer (FRET) from upconverting phosphors (UCPs) to carbon nanoparticles (CNPs). The poly(acrylic acid) (PAA) functionalized UCPs were covalently tagged with a thrombin aptamer (5'-NH(2)- GGTTGGTGTGGTTGG-3'), which bound to the surface of CNPs through π-π stacking interaction. As a result, the energy donor and acceptor were taken into close proximity, leading to the quenching of fluorescence of UCPs. A maximum fluorescence quenching rate of 89% was acquired under optimized conditions. In the presence of thrombin, which induced the aptamer to form quadruplex structure, the π-π interaction was weakened, and thus, the acceptor was separated from the donor blocking the FRET process. The fluorescence of UCPs was therefore restored in a thrombin concentration-dependent manner, which built the foundation of thrombin quantification. The sensor provided a linear range from 0.5 to 20 nM for thrombin with a detection limit of 0.18 nM in an aqueous buffer. The same linear range was obtained in spiked human serum samples with a slightly higher detection limit (0.25 nM), demonstrating high robustness of the sensor in a complex biological sample matrix. As a practical application, the sensor was used to monitor thrombin level in human plasma with satisfactory results obtained. This is the first time that UCPs and CNPs were employed as a donor-acceptor pair to construct FRET-based biosensors, which utilized both the photophysical merits of UCPs and the superquenching ability of CNPs and thus afforded favorable analytical performances. This work also opened the opportunity to develop biosensors for other targets using this UCPs-CNPs system.

Understanding the electrically active defects in kesterite Cu2ZnSn(S,Se)4(CZTSSe) is critical for the continued development of solar cells based on this material, but challenging due to the complex nature of this polycrystalline multinary material. A comparative study of CZTSSe alloys with three different bandgaps, made by introducing different fractions of sulfur during the annealing process, is presented. Using admittance spectroscopy, drive level capacitance profiling, and capacitance‐voltage profiling, the dominant defect energy level present in the low sulfur content device is determined to be 0.134 eV above the valence band maximum, with a bulk defect density of 8 × 1014 cm−3, while the high sulfur content device shows a deeper defect energy level of 0.183 eV and a higher bulk defect density, 8.2 × 1015 cm−3. These findings are consistent with the current density–voltage characteristics of the resulting solar cells and their external quantum efficiency. It suggests that as the sulfur content increases, the bandgap of the absorber is enlarged, leading to an increasing open‐circuit voltage (Voc), that is accompanied by stronger recombination due to the higher defect density of the sulfur‐rich absorber. This is reflected in large Voc deficit and poor carrier collection of the high sulfur content device.