3D printing of microneedle arrays for hair regeneration in a controllable region.

Hair loss is a common skin disease that causes intense emotional suffering. Hair regeneration in a personalized area is highly desirable for patients with different balding conditions. However, the existing pharmaceutical treatments have difficulty precisely regenerating hair in a desired area. Here, we show a method to precisely control the hair regeneration using customized microneedle arrays (MNAs). The MNA with a customized shape is fast fabricated by a static optical projection lithography process in seconds, which is a 3D printing technology developed by our group. In the mouse model, MNA treatment could induce hair regrowth in a defined area corresponding to the customized shape of MNA. And the regenerated hair promoted by MNAs had improved quality. Cellular and molecular analysis indicated that MNA treatment could recruit macrophages in situ and then initiate the proliferation of hair follicle stem cells, thereby improving hair regeneration. Meanwhile, the activation of the Wnt/ß-catenin signaling pathway was observed in hair follicles. The expressions of Hgf, Igf 1 and Tnf-α were also upregulated in the treated skin, which may also be beneficial for the MNA-induced hair regeneration. This study provides a strategy to precisely control hair regeneration using customized microneedle arrays by recruiting macrophages in situ, which holds the promise for the personalized treatment of hair loss.

Ultrasensitive SERS Analysis of Liquid and Gaseous Putrescine and Cadaverine by a 3D-Rosettelike Nanostructure-Decorated Flexible Porous Substrate.

Putrescine and cadaverine are toxic biogenic amines in spoiled food, which poses a serious threat to food security. In this work, we reported a highly sensitive three-dimensional (3D)-rosettelike surface-enhanced Raman spectroscopy (SERS) substrate functionalized with a p-mercaptobenzoic acid (p-MBA) monolayer to detect liquid and gaseous putrescine and cadaverine in pork samples. The SERS substrate was made by a combination of the merit of the 3D morphology of ZnO nanorod arrays on a flexible porous poly(vinylidene fluoride) (PVDF) membrane and the in situ chemical growth of Au nanoparticle seeds on Au film-coated ZnO nanorods, which produced a 3D-rosettelike BigAuNP/Au/ZnO/P heterostructure with abundant SERS-active hot spots that significantly enhanced the localized surface plasmonic resonance (LSPR) effect and charge-transfer (CT) effect of Raman enhancement. This SERS substrate showed high sensitivity, reproducibility, stability, and uniformity. With the p-MBA molecular monolayer as the sensing interface, our SERS substrate realized the highly sensitive and quantitative detection of liquid putrescine and cadaverine within 10 min, with a limit of detection (LOD) of 3.2 × 10-16 and 1.6 × 10-13 M, respectively. Additionally, the sensor showed efficient SERS responses to gaseous amine molecules at low concentrations (putrescine: 1.26 × 10-9 M, cadaverine: 2.5 × 10-9 M). Further, the sensor was successfully applied to determine the total content of putrescine and cadaverine. Moreover, the practicability of this SERS sensor was verified by the measurement of liquid and gaseous amines in pork samples, and it showed great potential applications for sensitive detection of food spoilage.

Continuous in situ portable SERS analysis of pollutants in water and air by a highly sensitive gold nanoparticle-decorated PVDF substrate.

The increasingly serious environmental pollution worldwide has posed a great threat to the ecosystem and human health, and yet the development of portable in situ monitoring techniques that are sensitive to gaseous and water pollutants remains incomplete. Herein, we report a highly active surface-enhanced Raman spectroscopy (SERS) substrate fabricated by immobilizing gold nanoparticles (AuNPs) onto a polyvinylidene fluoride (PVDF) membrane for continuous in situ SERS detection of pollutants in water and atmosphere. 4-Mercaptobenzoic acid (4-MBA) was adopted as a probe molecule to evaluate the performance of the substrate, and the results indicate that the polymer-based flexible substrate features high sensitivity, uniformity, and repeatability. The fabricated PVDF/SERS substrate was integrated with a portable Raman spectrometer operating under both passing-by and passing-through modes. The integrated system accomplishes quantitative detection and real-time online monitoring of pH in a liquid environment with a response speed of less than 10 s and the rapid SERS response to gas molecules at a low concentration within 30 s. We also demonstrated the highly sensitive detection for mainstream smoke (MS) and sidestream (SS) of cigarette smoke and verified their differences in the main constituent which contributes to the harmful secondhand smoke in public. The developed portable Raman system has excellent application prospects in online liquid and gas environmental detection.

Effect of reduced graphene oxide doping on photocatalytic reduction of Cr(VI) and photocatalytic oxidation of tetracycline by ZnAlTi layered double oxides under visible light.

The existence of Cr(VI) and antibiotics in the environment can form the joint contaminant which can be hazardous to the ecosystem. To deal with this, we have explored a plausible method to remove the Cr(VI) and tetracycline (TC) from water by visible light photocatalysis. In this study, a series of reduced graphene oxide@ZnAlTi layered double oxides (rGO@LDO) composites with different doping ratio of rGO were successfully synthesized, which were applied in photocatalytic reduction of Cr(VI) and oxidation of TC. Graphene acts as an electron donor and it can enhance the adsorption of Cr(VI) and TC on the surface of the composites. It's found that the obtained ZnAlTi-LDO composites doped with rGO have higher photo-responsiveness in the visible region. The best-performing rGO@LDO composite (i.e., CGL3) exhibited enhanced visible light-driven photocatalytic Cr(VI) reduction, which was about five times higher than those of ZnAlTi-LDO (without adding hole catcher). The rGO@LDO also showed a satisfactory performance for photocatalytic oxidation of TC with the total organic carbon removal of 80%. However, the doping of rGO did not significantly enhance the removal of TC. The experiment of pH effects demonstrated that acidic pH was favorable to photocatalytic reduction of Cr(VI), while neutral pH was favorable to photocatalytic oxidation of TC. The band structure of ZnAlTi-LDO was first identified, and the EVB and ECB of ZnAlTi-LDO are -2.32 and 0.72 V (vs. RHE). This research provides a feasible method to remove Cr(VI) and tetracycline from water by employing ZnAlTi-LDO doped with rGO as photocatalyst.

Simultaneous and efficient photocatalytic reduction of Cr(VI) and oxidation of trace sulfamethoxazole under LED light by rGO@Cu2O/BiVO4p-n heterojunction composite.

Antibiotics and heavy metals often coexist in polluted environment, and the harm of combined pollution is greater than that of single pollution. In this study, a series of graphene supported p-n heterojunction rGO@Cu2O/BiVO4 composites are synthesized with different Cu2O doping for simultaneous detoxification of Cr(VI) and antibiotics. The obtained photocatalysts (rGO@Cu2O/BiVO4) with proper loading amount of Cu2O shows the a high photocatalytic degradation activity for simultaneously efficient Cr(VI) reduction and sulfamethoxazole (SMZ) oxidation under LED light at neutral pH. The Cr(VI) was completely transformed to Cr(III) rather than simply Cr(VI) adsorbed on the surface of rGO@Cu2O/BiVO4. The photocatalytic activity of composites can be attributed to excellent electrical conductivity of rGO and the p-n heterojunction between Cu2O and BiVO4, which promotes the spatial separation of photogenerated charges at the heterojunction boundary and inhibits of the photogenerated h+ and e- recombination. It's confirmed that h+, O2- and OH are the main reactive species for the photocatalytic SMZ oxidation, and the most important reactive species is h+. Finally, the tentative degradation pathways of SMZ are proposed based on the liquid chromatography-triple quadrupole mass spectrometry analysis. This work provides an effective approach for the treatment of water that contains SMZ and Cr(VI) under LED light.