One‐pot synthesis of carbon dots@ZrO2 nanoparticles with tunable solid‐state fluorescence

In recent years, fluorescent carbon dots (CDs) have been developed and showed potential applications in biomedical imaging and light‐emitting diodes (LEDs) for their excellent fluorescent properties. However, it still remains a challenge to incorporate fluorescent CDs into the host matrix in situ to overcome their serious self‐quenching. Herein, a one‐pot hydrothermal method is used to prepare nano‐zirconia with CDs (CDs@ZrO₂) nanoparticles. During the reaction, CDs and nano‐zirconia are generated simultaneously and connected with silane coupling agent. The CDs@ZrO₂ nanoparticles exhibit tunable emission wavelength from 450 to 535 nm emission by regulating the content of citric acid in the feed. The quantum yield of the CDs@ZrO₂ is up to 23.8%. Furthermore, the CDs@ZrO₂ nanoparticles with regulable fluorescence emission can be used for the fluorescent material to prepare white LEDs. The prepared LED has significant white light emission with color coordinates of (0.30, 0.37) and its color rendering index (CRI) is 67.1. In summary, we have developed the solid‐state CDs@ZrO₂ nanoparticles with tunable emission by a valuable strategy, that is, one‐pot method, for white LEDs.     

Carbon Dots Derived from Coffee Residue for Sensitive and Selective Detection of Picric Acid and Iron(III) Ions

Afacile method was developed to prepare carbon dots(CDs) by pyrolysis and etching of coffee residue. The as-prepared CDs show uniform spherical nanoparticles with an average size of 2.3 nm and exhibit excitation-dependent fluorescence emissions. Moreover, CDs also exhibit strong fluorescence quenching to nitro compounds and metal ions in both water and ethanol solutions, which could act as a platform for dual detection of PA(picric acid) and Fe³⁺ ions with low detection limits of 0.26 and 0.83 μmol/L, respectively. This work provides a novel method for preparation of environmental-friendly fluorescent CDs and shows their potential applications in photoluminescence sensors.     

Preparation and Characterization of Uniform Near IR Polystyrene Nanoparticles

Biomaterials for in vivo fluorescence imaging are required to be biocompatible, nontoxic, photostable and highly fluorescent. Fluorescence must be in the near infrared (NIR) region of the electromagnetic spectrum to avoid absorption and autofluorescence of endogenous tissues. NIR fluorescent polystyrene nanoparticles may be considered ideal biomaterials for in vivo imaging applications. These NIR nanoparticles were prepared by a swelling process of polystyrene template nanoparticles with a hydrophobic NIR dye dissolved in a water‐miscible swelling solvent, a method developed for preparation of nonbiodegradable nanoparticles, for NIR fluorescent bioimaging applications. This method overcomes common problems that occur with dye entrapment during nanoparticle formation such as loss of fluorescence and size polydispersity. Fluorescence intensity of the nanoparticles was found to be size dependent, and was optimized for differently sized nanoparticles. The resulting NIR nanoparticles were also found to be more fluorescent and highly photostable compared to the free dye in solution, showing their potential as biomaterials for in vivo fluorescence imaging.     

Synthesis and Applications of Red‐Emissive Carbon Dots

Carbon dots (CDs), a new class of fluorescent carbon nanoparticles (less than 10 nm in size), have been widely applied in various fields, including sensors, bioimaging, catalysis, light‐emitting devices (LEDs), and photoelectronic devices, owing to their unique properties such as low toxicity, bio‐compatibility, high photostability, easy surface modification, and up‐conversion fluorescence, over the past decades. Recently, multiple‐color‐emissive CDs, especially red‐emissive CDs (RCDs), have drawn much attention owing to their unique advantages, like the ability to penetrate the animal bodies without the disturbance of strong tissue autofluorescence, multiple‐color fluorescence displaying or sensing, and the capacity to be one essential component to obtain white LED (WLED). In this review, we focused on the progress of recently‐emerging RCDs in the past five years, including their synthetic methods (hydrothermal, solvothermal, reflux condensation and microwave techniques), influencing factors (precursors, solvents, elements doping, surface chemistry) and various applications (bioimaging, sensor, photocatalysis and WLEDs), with a perspective on the future advancements.     

Reversible Phase Transfer of Carbon Dots between an Organic Phase and Aqueous Solution Triggered by CO2

Carbon dots (CDs) have attracted increasing attention in applications such as bio‐imaging, sensors, catalysis, and drug delivery. However, unlike metallic and semiconductor nanoparticles, the transfer of CDs between polar and non‐polar phases is little understood. A class of amine‐terminated CDs is developed and their phase transfer behavior has been investigated. It is found that these CDs can reversibly transfer between aqueous and organic solvents by alternatively bubbling and removing CO₂ at atmospheric pressure. The mechanism of such CO₂‐switched phase transfer involves reversible acid–base reaction of amine‐terminated CDs with CO₂ and the reversible formation of hydrophilic ammonium salts. By using the CDs as catalysts, the phase transfer is applied in the Knoevenagel reaction for efficient homogeneous reaction, heterogeneous separation, and recycling of the catalysts.     

Dramatic Fluorescence Enhancement of Bare Carbon Dots through Facile Reduction Chemistry

Reduction of bare carbon dots (CDs) in aqueous NaBH₄ solution is a facile and effective approach to enhance their fluorescence without any surface coverage. CDs are treated with dilute aqueous NaBH₄ solutions, enhancing their quantum yields (QYs) successfully from 1.6 % to 16 % which is comparable to semiconductive QDs in aqueous environments. If pristine CDs are treated hydrothermally prior to reduction by NaBH₄, QYs reach 40.5 %. This value is among the highest QYs reported for bare CDs in the literature. The approach to enhance fluorescence through chemical reduction is generally applicable to other kinds of CDs synthesized by various methods. Alteration of the chemical structure of the CDs by NaBH₄‐reduction is analyzed by ¹³C NMR, X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy, which demonstrate that the carbonyl group content is decreased after NaBH₄‐reduction, whereas the number of sp³‐type carbon defects is increased. The valence‐band maxima (VBM) near the surface related to the surface energy bands of the CDs are estimated by XPS. VBM data show a semiconducting layer on the surface of the CDs, and the VBM of the CDs decrease with increasing NaBH₄‐reduction time. The layered graphite structures in the cores of the CDs are clearly observed by transmission electron microscopy (TEM). CDs could perhaps be regarded as semiconductive surface defect layers formed by chemical erosion over conductive graphite cores. Chemical reduction by NaBH₄ changes the surface‐energy bands of the CDs, thus, enhances their fluorescence. The fluorescence properties of aqueous NaBH₄‐reduced CDs are also studied for possible biological applications.     

Fluorescence Intensity Enhancement of Green Carbon Dots: Synthesis,Characterization and Cell Imaging

The hydrothermal treatment of green carbon dots (CDs) is an appropriate fluorescent probe synthesis method. CDs are exploited as biological staining agents, especially for cellular detection and imaging. The nitrogen-doped green carbon dots (N-CDs) formation can improve the fluorescence intensity property in a one-step process. Here, we report two N-CDs from lemon and tomato extraction in the presence of hydroxylamine. Lemon and tomato N-CDs showed the blue fluorescence under ultraviolet radiation of about 360 nm. The characterization of CDs and N-CDs showed the presence of N-H and C–N bonds which enhanced the fluorescence efficiency. The mean size of lemon and tomato N-CDs were about 2 and 3 nm with an increased quantum yield (QY) of 5% and 3.38%, respectively. The CDs and N-CDs cytotoxicity assay exhibited high cell viability approximately 85% and 73%, respectively. N-CDs show superior fluorescent intensity in different solvents and significant stability under long-time UV irradiation, different PH and high ionic strength. Our results indicated that the use of N-CDs in cell imaging can lead to fluorescence intensity enhancement as well as proper biocompatibility. Therefore, the safe and high fluorescence intensity of green N-CDs can be utilized for fluorescent probes in biolabeling and bioimaging applications.     

Chinese Oak Tasar Silkworm Antheraea pernyi Silk Proteins: Current Strategies and Future Perspectives for Biomedical Applications

Chinese nonmulberry temperate oak tasar/tussah, Antheraea pernyi (Ap) silk is a natural biopolymer that has attracted considerable attention as a biomaterial. The proteinaceous components of Ap silk proteins, namely fibroin and sericin may represent an alternative over mulberry Bombyx mori silk proteins. In fact, the silk fibroin (SF) of Ap is rich in Arginyl‐Glycyl‐Aspartic acid (RGD) peptides, which facilitate the adhesion and proliferation of various cell types. The possibility of processing Ap silk proteins into different distinct 2D‐ and 3D‐based matrices is described in earlier studies, such as membranes, nanofibers, scaffolds, and micro/nanoparticles, contributing to a different rate of degradation, mechanical properties, and biological performance useful for various biomedical applications. This review summarizes the current advances and developments on nonmulberry Chinese oak tasar silk protein (fibroin and sericin)‐based biomaterials and their potential uses in tissue engineering, regenerative medicine, and therapeutic delivery strategies.     

Motion Control of Polymeric Nanomotors Based on Host–Guest Interactions

Controlling the motion of artificial self‐propelled micro‐ and nanomotors independent of the fuel concentration is still a great challenge. Here we describe the first report of speed manipulation of supramolecular nanomotors via blue light‐responsive valves, which can regulate the access of hydrogen peroxide fuel into the motors. Light‐sensitive polymeric nanomotors are built up via the self‐assembly of functional block copolymers, followed by bowl‐shaped stomatocyte formation and incorporation of platinum nanoparticles. Subsequent addition of β‐cyclodextrin (β‐CD) leads to the formation of inclusion complexes with the trans‐isomers of the azobenzene derivatives grafted from the surfaces of the stomatocytes. β‐CDs attachment decreases the diffusion rate of hydrogen peroxide into the cavities of the motors because of partly blocking of the openings of the stomatocyte. This results in a lowering of the speed of the nanomotors. Upon blue light irradiation, the trans‐azobenzene moieties isomerize to the cis‐form, which lead to the detachment of the β‐CDs due to their inability to form complexes with the cis‐isomer. As a result, the speed of the nanomotors increases accordingly. Such a conformational change provides us with the unique possibility to control the speed of the supramolecular nanomotor via light‐responsive host–guest complexation. We envision that such artificial responsive nano‐systems with controlled motion could have potential applications in drug delivery.     

Rapid and Large‐Scale Production of Multi‐Fluorescence Carbon Dots by a Magnetic Hyperthermia Method

The intrinsic low yield of carbon dots (CDs) is a barrier that limits practical application. Now, a magnetic hyperthermia (MHT) method is used to synthesize fluorescent CDs on a large scale (up to 85 g) in one hour (yield ca. 60 %). The reaction process is intensified by MHT since the efficient heating system enhances the energy transfer. CDs with blue, green, and yellow luminescence are synthesized by using carbamide and citrate with three different cations (Zn²⁺, Na⁺, K⁺), respectively. The CDs exhibit bright fluorescence under UV light and show excellent monodispersity and solubility in water. The alternation of photoluminescence (PL) emissions of these CDs is probably due to the difference in particle sizes and surface state. A bar coating technique is used to construct large‐area emissive polymer/CDs films. CDs can insert themselves into the polymer chains by hydrogen bonding and electrostatic interactions. Wound healing efficiency can be enhanced by the Zn‐CDs/PCL nanofibrous scaffold.     

Synthesis of high performance,conductive PEDOT‐coated polyester yarns by OCVD technique

Production of high performance conductive textile yarn fibers for different electronic applications has become a prominent area of many research groups throughout the world. We have used oxidative chemical vapor deposition (OCVD) technique to coat flexible and high strength polyester yarns with conjugated polymer, poly(3,4‐ethylenedioxythiophene) (PEDOT) in presence of ferric (III) chloride (FeCl₃) oxidant. OCVD is an efficient solvent free technique used to get uniform, thin, and highly conductive polymer layers on different substrates. In this paper, PEDOT‐coated polyester (PET) yarns were prepared under specific reaction conditions, and the electrical, mechanical and thermal properties were compared to previously studied PEDOT‐coated viscose yarns. Scanning electron microscopy (SEM) and FT‐IR analysis revealed that polymerization of PEDOT on the surface of the polyester yarns has been taken place successfully and structural analysis showed that PEDOT has strong interactions with viscose yarns as compared to PET yarns. The voltage–current (V–I) characteristics showed that PET yarns are more conductive than PEDOT‐coated viscose yarns. The variation in the conductivity of PEDOT‐coated yarns and the heat generation properties during the flow of current through coated yarns for longer period of time, was studied by time–current (t–I) characteristics. Thermogravimeteric analysis (TGA) was employed to investigate the thermal properties and the amount of PEDOT in PEDOT‐coated PET yarns compared to PEDOT‐coated viscose. The effect of PEDOT coating and ferric (III) chloride concentration on the mechanical properties of coated yarns was evaluated by tensile testing. The obtained PEDOT‐coated conductive polyester yarns could be used in smart clothing for medical and military applications. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and Characterization of Fluorescent Silica Nanoparticles Functionalized with Collagens of Variable Lengths

Collagen, the most abundant protein in human body, has been widely used as an excellent natural material for diverse biomedical applications due to its superior properties such as ample biological interaction sites, minimal immunogenicity and high biocompatibility. Collagens of different lengths are produced by recombinant technology and utilized to functionalize fluorescent silica nanoparticles (FNPs). The collagen‐functionalized FNPs display mono‐disperse distribution, but their sizes are dependent on the length of collagen. These modified FNPs all show nice fluorescence profile as well as low cytotoxicity, suggesting promising applications in bioimaging. We have demonstrated that various types of collagen, conveniently produced by recombinant technology, can be used to modify silica nanoparticles with nice characteristics such as mono‐dispersion, non‐interference in fluorescence and low toxicity. It may endow fluorescent silica nanoparticles with broad biological applications.     

Photoactivated Fluorescence Enhancement in F,N‐Doped Carbon Dots with Piezochromic Behavior

Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co‐doped carbon dots (F,N‐doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N‐doped CDs increases with UV light irradiation (5 s–30 min), accompanied with a blue‐shift of the fluorescence emission from 586 nm to 550 nm. F,N‐doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N‐doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high‐pressure conditions and enhances their anti‐photobleaching.     

Advances,opportunities, and challenge for full-color emissive carbon dots

Carbon dots(CDs), novel luminescent zero-dimensional carbon nanomaterials, have been widely applied due to their low toxicity, optimal optical properties, and easy modification. However, the current controllable equipment and mechanism explanation of CDs are relatively vague and require urgent resolution.Full-color emission CDs, an essential CDs category, have attracted people’s attention given their light and color-tunable properties. In addition to a wider range of biological and optoelectroni...     

A Host‐Guest‐Recognition‐Based Electrochemical Sensor for Sequence‐Specific DNA Detection

We herein constructed a sensor that converts target DNA hybridization‐induced conformational transformation of the probe DNA to electrochemical response based on host‐guest recognition and nanoparticle label. In the sensor, the hairpin DNA terminal‐labeled with 4‐((4‐(dimethylamino)phenyl)azo)benzoic acid (dabcyl) and thiol group was immobilized on Au electrode surface as the probe DNA by Au‐S bond, and the CdS nanoparticles surface‐modified with β‐cyclodextrins (CdS‐CDs) were employed as electrochemical signal provider and host‐guest recognition element. Initially, the probe DNA immobilized on electrode kept the stem‐loop configuration, which shielded dabcyl from docking with the CdS‐CDs in solution due to the steric effect. After target hybridization, the probe DNA underwent a significant conformational change, which forced dabcyl away from the electrode. As a result, formerly‐shielded dabcyl became accessible to host‐guest recognition between β‐cyclodextrin (β‐CD) and dabcyl, thus the target hybridization event could be sensitively transduced to electrochemical signal provided by CdS‐CDs. This host‐guest recognition‐based electrochemical sensor has been able to detect as low as picomolar DNA target with excellent differentiation ability for even single mismatch.     

Photoluminescent chiral carbon dots derived from glutamine

The integration of luminescence and chirality in carbon dots (CDs) encourages candidates to explore novel functions and applications of CDs, however, the preparation of chiral CDs is very limited. Herein, we report a hydrothermal method to fabricate chiral CDs by utilizing amino acid enantiomers as the precursors. LGln-CDs or DGln-CDs with uniform size of 3–4 nm show excitation-dependent blue fluorescence in solutions. Circular dichroism measurement confirms the opposite optical rotation of chiral CDs in the region from 200 nm to 300 nm, and the signals can be regulated by concentrations of CDs solution. Time-dependent density functional calculation reveals that polypeptides may exist on the surface of CDs due to the polycondensation of L/DGln at high temperature, and the optical activity of CDs originates from the stacking of neighboring carbonyl groups. The facile synthetic methodology proposed will provide potential opportunities for the preparation and application of chiral and chiroptical CDs-based materials.     

Metal‐Enhanced Fluorescence of CdTe Nanocrystals in Aqueous Solution

Metal‐enhanced fluorescence of semiconductor nanocrystals (NCs) is investigated. There is very little attention paid to the metal‐enhanced fluorescence in aqueous solution, which has great potential applications in bioscience. In this work, we directly observe metal‐enhanced fluorescence of CdTe NC solution by simply mixing CdTe NCs and Au nanoparticles, both of which are negatively charged. In order to study this kind of photoluminescence enhancement in aqueous solutions, we propose a calibration method, which takes into account the light attenuation in solutions. After consideration of the light weakening in transmission, the maximal PL enhancement is about 3 times as large as the ones without Au NPs. Some factors related to the enhanced magnitude of fluorescence, for instance, the concentration and the molar feed ratio of CdTe NCs and Au NPs, are studied in detail. Furthermore, the decreased lifetimes of CdTe NCs induced by Au NPs are also obtained, which are in accord with the enhancement of the photoluminescence.     

Photoswitchable Fluorescent Nanoparticles: Preparation,Properties and Applications

This minireview highlights recent advances of research dedicated to photoswitchable fluorescent nanoparticles and their applications. Recently, several strategies have been developed to synthesize nanoparticles with optically switchable emission properties: either fluorescence on/off or dual‐alternating‐color fluorescence photoswitching. The underlying mechanisms of fluorescence photoswitching enable many different types of photoswitchable fluorescent nanoparticles to change fluorescence colors, thus validating the basis of the initial photoswitching design. Among all possible applications, the usage of photoswitchable fluorescent nanoparticles to empower super‐resolution fluorescence imaging and to label biological targets was subsequently reviewed. Finally, we summarize the important areas regarding future research and development on photoswitchable fluorescent nanoparticles.     

Red,Green, and Blue Luminescence by Carbon Dots: Full‐Color Emission Tuning and Multicolor Cellular Imaging

A facile approach for preparation of photoluminescent (PL) carbon dots (CDs) is reported. The three resulting CDs emit bright and stable red, green and blue (RGB) colors of luminescence, under a single ultraviolet‐light excitation. Alterations of PL emission of these CDs are tentatively proposed to result from the difference in their particle size and nitrogen content. Interestingly, up‐conversion (UC)PL of these CDs is also observed. Moreover, flexible full‐color emissive PVA films can be achieved through mixing two or three CDs in the appropriate ratios. These CDs also show low cytotoxicity and excellent cellular imaging capability. The facile preparation and unique optical features make these CDs potentially useful in numerous applications such as light‐emitting diodes, full‐color displays, and multiplexed (UC)PL bioimaging.     

Carbon dots as a fluorescent probe for label-free detection of physiological potassium level in human serum and red blood cells

A unique photoluminescence carbon dots (CDs) with larger size were prepared by microwave-assisted method. Complex functional groups on the surface of the CDs facilitate the nanoparticles to form affinity with some metal ions. Taking advantage of the effective fluorescence quenching effect of K⁺, a highly sensitive CD-based fluorescence analytical system for label-free detection of K⁺ with limit of detection (LOD) 1.0 × 10⁻¹² M was established. The concentrations of potassium ion in biological samples such as human serum are usually found at millimolar levels or even higher. The proposed method begins with a substantial dilution of the sample to place the K⁺ concentration in the dynamic range for quantification, which covers 3 orders of magnitude. This offers some advantages: the detection of K⁺ only needs very small quantities of biological samples, and the dilution of samples such as serum may effectively eliminate the potential interferences that often originate from the background matrix. The determined potassium levels were satisfactory and closely comparable with the results given by the hospital, indicating that this fluorescent probe is applicable to detection of physiological potassium level with high accuracy. Compared with other relative biosensors requiring modified design, bio-molecular modification or/and sophisticated instruments, this CD-based sensor is very simple, cost-effective and easy detection, suggesting great potential applications for successively monitoring physiological potassium level and the change in biological system.