Multispectral and Circular Polarization-Sensitive Carbon Dot-Polydiacetylene Capacitive Photodetector (Small 31/2023)

Multispectral photodetectors (MSPs) and circularly polarized light (CPL) sensors are important in opto-electronics, photonics, and imaging. A capacitive photodetector consisting of an interdigitated electrode coated with carbon dot/anthraquinone-polydiacetylene is constructed. Photoexcitation of the carbon dots induces transient electron transfer to the anthraquinone moieties, and concomitant change in the film dielectric constant and recorded capacitance. This unique photodetection mechanism furnishes wavelength selectivity that is solely determined by the absorbance of the carbon dots incorporated in the anthraquinone-polydiacetylene matrix. Accordingly, employing an array of polymerized-anthraquinone photodetector films comprising carbon dots (C-dots) exhibiting different excitation wavelengths yielded optical “capacitive fingerprints” in a broad spectral range (350–650 nm). Furthermore, circular light polarization selectivity is achieved through chiral polymerization of the polydiacetylene framework. The carbon dot/anthraquinone-polydiacetylene capacitive photodetector features rapid photo-response, high fidelity, and recyclability as the redox reactions of anthraquinone are fully reversible. The carbon dot/anthraquinone-polydiacetylene platform is inexpensive, easy to fabricate, and consists of environmentally friendly materials.     

碳量子点的生物应用:成像、载药与毒性

碳量子点作为一种新型的纳米材料,具有荧光性能优异、尺寸小、毒性低等诸多优势,因而具有良好的应用前景,尤其在生物医学领域有突出的应用价值,近年来引起了科研者们的广泛关注。在介绍碳量子点光学性质的基础上,重点综述了碳量子点在生物成像、诊疗剂应用及碳量子点生物毒性等方面的最新研究进展,并探讨了碳量子点未来的发展方向和前景。     

Room Temperature Phosphorescence Carbon Dots: Preparations,Regulations, and Applications

Room temperature phosphorescence (RTP) materials have drawn considerable attention by virtue of their outstanding features. Compared with organometallic complexes and pure organic compounds, carbon dots (CDs) have emerged as a new type of RTP materials, which show great advantages, such as moderate reaction condition, low toxicity, low cost, and tunable optical properties. In this review, the important progress made in RTP CDs is summarized, with an emphasis on the latest developments. The synthetic strategies of RTP CDs will be comprehensively summarized, followed by detailed introduction of their performance regulation and potential applications in anti-counterfeiting, information encryption, sensing, light-emitting diodes, and biomedicine. Finally, the remaining major challenges for RTP CDs are discussed and new opportunities in the future are proposed.     

Carbon Dots‐in‐Matrix Boosting Intriguing Luminescence Properties and Applications

As a new class of luminescent nanomaterials, carbon dots (CDs) have aroused significant interest because of their fascinating photoluminescence properties and potential applications in biological, optoelectronic, and energy‐related fields. Strikingly, embedding CDs in host matrices endow them with intriguing luminescent properties, in particular, room temperature phosphorescence and thermally activated delayed fluorescence, due to the confinement effect of the host matrix and the H‐bonding interactions between CDs and the matrix. Here, the state‐of‐the‐art strategies for introducing CDs in various host matrices are summarized, such as nanoporous materials, polyvinyl alcohol, polyurethane, potash alum, layered double hydroxides, amorphous silica, etc. The resultant luminescent properties of the composites and their emission mechanisms are discussed. Their applications in bioimaging, drug delivery/release, sensing, and anticounterfeiting are also presented. Finally, current problems and challenges of CDs‐based composites are noted for future development of such luminescent materials.     

Glowing Graphene Quantum Dots and Carbon Dots: Properties,Syntheses, and Biological Applications

The emerging graphene quantum dots (GQDs) and carbon dots (C‐dots) have gained tremendous attention for their enormous potentials for biomedical applications, owing to their unique and tunable photoluminescence properties, exceptional physicochemical properties, high photostability, biocompatibility, and small size. This article aims to update the latest results in this rapidly evolving field and to provide critical insights to inspire more exciting developments. We comparatively review the properties and synthesis methods of these carbon nanodots and place emphasis on their biological (both fundamental and theranostic) applications.     

Rational Design of Covalent Bond Engineered Encapsulation Structure toward Efficient,Long-Lived Multicolored Phosphorescent Carbon Dots (Small 31/2023)

Multicolored phosphorescent materials based on carbon dots (CDs) constructed using the same or similar precursors with long lifetimes are conducive to their wide range of practical applications due to the developed compatibility. Herein, a universal method is developed to prepare long-lived multicolored phosphorescent CD-based composites for which heavy-metal doping is not required. The multicolored CDs are encapsulated in silica via silane hydrolysis, which forms many covalent Si O C and Si C bonds; hence, the vibrations and rotations of the luminescent centers on the CD surfaces are hindered. The transformation of Si O C to a more rigid Si C moiety occurs during high-temperature calcination. Furthermore, during calcination, the silica collapses, resulting in more tightly encapsulated CDs. The synergistic effect of these two calcination phenomena produces blue, green, yellow, and red phosphorescence, at wavelengths spanning 465 to 680 nm and with lifetimes of up to 2.11 s. Taking advantage of their superior phosphorescence performances, the CD-based composites are successfully applied to 3D multichannel information storage and encryption.     

Magnetic Polaron States in Photoluminescent Carbon Dots Enable Hydrogen Peroxide Photoproduction (Small 32/2023)

Photoactivation of aspartic acid-based carbon dots (Asp-CDs) induces the generation of spin-separated species, including electron/hole (e⁻/h⁺) polarons and spin-coupled triplet states, as uniquely confirmed by the light-induced electron paramagnetic resonance spectroscopy. The relative population of the e⁻/h⁺ pairs and triplet species depends on the solvent polarity, featuring a substantial stabilization of the triplet state in a non-polar environment (benzene). The electronic properties of the photoexcited Asp-CDs emerge from their spatial organization being interpreted as multi-layer assemblies containing a hydrophobic carbonaceous core and a hydrophilic oxygen and nitrogen functionalized surface. The system properties are dissected theoretically by density functional theory in combination with molecular dynamics simulations on quasi-spherical assemblies of size-variant flakelike model systems, revealing the importance of size dependence and interlayer effects. The formation of the spin-separated states in Asp-CDs enables the photoproduction of hydrogen peroxide (H₂O₂) from water and water/2-propanol mixture via a water oxidation reaction.     

Carbon Dots with Guanidinium and Amino Acid Functional Groups for Targeted Small Interfering RNA Delivery toward Tumor Gene Therapy (Small 31/2023)

Small interfering RNA (siRNA)-based gene therapy represents a promising strategy for tumor treatment. Novel gene vectors that can achieve targeted delivery of siRNA to the tumor cells without causing any side effects are urgently needed. To this end, the large amino acid mimicking carbon dots with guanidinium functionalization (LAAM GUA-CDs) are designed and synthesized by choosing arginine and dopamine hydrochloride as precursors. LAAM GUA-CDs can load siRNA through the multiple hydrogen bonds between their guanidinium groups and phosphate groups in siRNA. Meanwhile, the amino acid groups at the edges of LAAM GUA-CDs endow them the capacity to target tumors. After loading siBcl-2 as a therapeutic agent, LAAM GUA-CDs/siBcl-2 has a high tumor inhibition rate of up to 68%, which is twice more than that of commercial Lipofectamine 2000. Furthermore, LAAM GUA-CDs do not cause side effect during antitumor treatment owing to their high tumor-targeting ability, thus providing a versatile strategy for tumor-targeted siRNA delivery and cancer therapy.     

SMART Silly Putty: Stretchable,Malleable, Adherable,Reusable, and Tear-Resistible Hydrogels

Cell engineering, soft robotics, and wearable electronics often desire soft materials that are easy to deform, self-heal readily, and can relax stress rapidly. Hydrogels, a type of hydrophilic networks, are such kind of materials that can be made responsive to environmental stimuli. However, conventional hydrogels often suffer from poor stretchability and repairability. Here, hydrogels consisting of boronic ester dynamic covalent bonds in a double network of poly(vinyl alcohol)/boric acid and chitosan are synthesized, which demonstrate extreme stretchability (up to 310 times the original length), instant self-healing (within 5 s), and reusability and inherent adhesion. Their instant stress relaxation stems from a low activation energy of the boronic ester bond exchange (≤20 kJ mol⁻¹) and contributes to the extreme stretchability and self-healing behaviors. Various water-dispersible additives can be readily incorporated in the hydrogels via hand kneading for potential applications such as soft electronics, bio-signal sensing, and soft artificial joints.     

Robust Negative Electrode Materials Derived from Carbon Dots and Porous Hydrogels for High‐Performance Hybrid Supercapacitors

Hybrid supercapacitors generally show high power and long life spans but inferior energy densities, which are mainly caused by carbon negative electrodes with low specific capacitances. To improve the energy densities, the traditional methods include optimizing pore structures and modifying pseudocapacitive groups on the carbon materials. Here, another promising way is suggested, which has no adverse effects to the carbon materials, that is, constructing electron‐rich regions on the electrode surfaces for absorbing cations as much as possible. For this aim, a series of hierarchical porous carbon materials are produced by calcinating carbon dots–hydrogel composites, which have controllable surface states including electron‐rich regions. The optimal sample is employed as the negative electrode to fabricate hybrid supercapacitors, which show remarkable specific energy densities (up to 62.8–90.1 Wh kg^?1) in different systems.     

Co-Assembly of Carbon Nanotube Porins into Biomimetic Peptoid Membranes (Small 21/2023)

Robust and cost-effective membrane-based separations are essential to solving many global crises, such as the lack of clean water. Even though the current polymer-based membranes are widely used for separations, their performance and precision can be enhanced by using a biomimetic membrane architecture that consists of highly permeable and selective channels embedded in a universal membrane matrix. Researchers have shown that artificial water and ion channels, such as carbon nanotube porins (CNTPs), embedded in lipid membranes can deliver strong separation performance. However, their applications are limited by the relative fragility and low stability of the lipid matrix. In this work, we demonstrate that CNTPs can co-assemble into two dimension (2D) peptoid membrane nanosheets, opening up a way to produce highly programmable synthetic membranes with superior crystallinity and robustness. A combination of molecular dynamics (MD) simulations, Raman spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM) measurements to verify the co-assembly of CNTP and peptoids are used and show that it does not disrupt peptoid monomer packing within the membrane. These results provide a new option for designing affordable artificial membranes and highly robust nanoporous solids.     

Effect of Multiwalled Carbon Nanotubes on the Conductivity and Swelling Properties of Porous Polyacrylamide Hydrogels

Multiwalled carbon nanotubes (MWCNTs) were added to polyacrylamide (PAM) hydrogels in different proportions to tune their electrical and mechanical properties. The choice of MWCNTs as a reinforcement is justified by the fact that these are highly conducting, fairly stable and flexible particles. A series of MWCNT/PAM hydrogels were prepared by freezing method. The characteristic absorption peaks at 1480 and 1213 cm^?1 in the FTIR spectra reveal that MWCNTs are embedded in the PAM hydrogels. Powder x-ray diffractograms and thermogravimetric analysis (TGA) images show that the MWCNT/PAM hydrogels are crystalline, more thermally stable and have a higher electrical conductivity than a traditional PAM hydrogel. Scanning electron micrographs reveal about reduced pore size, homogeneous and denser texture. The swelling properties of all these hybrid hydrogels were found to be better than those of the parent PAM hydrogel. The Li–Tanaka equation was employed to produce the swelling parameters. The diffusion coefficients (D _c ) of PAM hydrogel is 10 times higher than the literature value. 0.8% MWCNTs reinforced PAM hydrogel has excellent τ_c and electrical conductivity (0.76 mS/cm) with improvements in all properties. Lower D _c of 0.8% MWCNTs/PAM hydrogel reveal that extent of crosslinking is much important than density of the system for a better collective diffusion of the respective solvent.     

P(AAM-co-NMA)/MWNTs-COOH复合水凝胶的制备和性能研究

采用自由基水溶液聚合法,分别合成了聚(丙烯酰胺-co-甲基丙烯酸钠)(P(AAM-co-NMA))水凝胶和不同MWNTs-COOH含量的新型聚(丙烯酰胺-co-甲基丙烯酸钠)/羧基碳纳米管(P(AAM-co-NMA)/MWNTsCOOH)复合水凝胶。结果发现,P(AAM-co-NMA)和羧基碳纳米管(MWNTs-COOH)之间表现出良好的兼容性。当MWNTs-COOH的含量为1.5%时,P(AAM-co-NMA)/MWNTs-COOH复合水凝胶表现出较高的膨胀性能和最佳的力学性能。同时发现这种复合水凝胶具有优良的pH值敏感性。因此MWNTs-COOH含量为1.5%的复合水凝胶有望被应用在药物控释和组织工程方面。     

Perforated Carbon Nanotube Film Assisted Growth of Uniform Monolayer MoS2 (Small 23/2023)

Scaling up the chemical vapor deposition (CVD) of monolayer transition metal dichalcogenides (TMDCs) is in high demand for practical applications. However, for CVD-grown TMDCs on a large scale, there are many existing factors that result in their poor uniformity. In particular, gas flow, which usually leads to inhomogeneous distributions of precursor concentrations, has yet to be well controlled. In this work, the growth of uniform monolayer MoS₂ on a large scale by the delicate control of gas flows of precursors, which is realized by vertically aligning a well-designed perforated carbon nanotube (p-CNT) film face-to-face with the substrate in a horizontal tube furnace, is achieved. The p-CNT film releases gaseous Mo precursor from the solid part and allows S vapor to pass through the hollow part, resulting in uniform distributions of both gas flow rate and precursor concentrations near the substrate. Simulation results further verify that the well-designed p-CNT film guarantees a steady gas flow and a uniform spatial distribution of precursors. Consequently, the as-grown monolayer MoS₂ shows quite good uniformity in geometry, density, structure, and electrical properties. This work provides a universal pathway for the synthesis of large-scale uniform monolayer TMDCs, and will advance their applications in high-performance electronic devices.     

Ag／PVA复合水凝胶的制备及其性能的研究

通过沉淀法制备Ag／PVA复合水凝胶，对复合水凝胶的微观结构进行了表征，并对其力学性能和抗菌性能进行了研究。结果表明，银微粒可以通过沉淀法均匀分散在水溶性的PVA中，形成Ag／PVA复合水凝胶，并且这种复合水凝胶具有抗菌性能，并改善了PVA水凝胶的力学性能。