Environmental problems caused by the development of nanotechnology have threatened human health. Investigating the biomedical effects of nanomaterials can help to solve these environmental safety issues. In studies on the biomedical effects of nanomaterials, several types of novel nanoscale probes that allow reliable, sensitive, accurate and rapid biomedical detection have emerged. We summarize recent developments in three categories of these nanoprobes, including noble metal nanocluster probes, carbon-based nanostructured probes, and unnatural amino acid-based probes. Besides reviewing the utility of different nanoprobes in cell imaging and protein detection, we also discuss the molecular mechanism of nanoprobe detection. Perspectives of novel nanoprobe design based on molecular details of biomedical detection are presented.
ZnO-Au25 nanocomposites were synthesized by doping Au25 nanoclusters into the porous ZnO nanospheres. It was notable that the ultrasmall Au25 nanoclusters possessed uniform sizes and fine dispersibility on the porous ZnO supports. A considerable correlation between the loading of Au25 nanoclusters and the photocatalytic activity was found. Compared with the pure ZnO nanospheres, the ZnO-Au25 nanocomposites exhibited more efficient photocatalytic activity in terms of degradation of Rhodamine B (RhB) in an aqueous solution. In addition, the possible photocatalytic mechanisms are discussed in this work. This strategy may be helpful for preparing other novel hybrid nanocomposites with well-defined structures and superior performances.
As a novel class of metallic materials, bulk metallic glasses (BMGs) have attracted a great deal of attention owing to their technological promise for practical engineering applications. In nature, biological materials exhibit inherent multifunctional integration, which provides some inspiration for scientists and engineers to construct multifunctional artificial materials. In this contribution, inspired by superhydrophobic self-cleaning lotus leaves, multifunctional bulk metallic glasses (BMG) materials have been fabricated through the thermoplastic forming-based process followed by the SiO2/soot deposition. To mimic the microscale papillae of the lotus leaf, the BMG micropillar with a hemispherical top was first fabricated using micro-patterned silicon templates based on thermoplastic forming. The deposited randomly distributed SiO2/soot nanostructures covered on BMG micropillars are similar to the branch-like nanostructures on papillae of the lotus leaf. Micro-nanoscale hierarchical structures endow BMG replica with superhydrophobicity, a low adhesion towards water, and self-cleaning, similar to the natural lotus leaf. Furthermore, on the basis of the observation of the morphology of BMG replica in the Si mould, the formation mechanism of BMG replica was proposed in this work. The BMG materials with multifunction integration would extend their practical engineering applications and we expect this method could be widely adopted for the fabrication of other multifunctional BMG surfaces.
Separation of trivalent lanthanides (Ln(III)) and actinides (An(III)) is a key issue in the advanced spent nuclear fuel reprocessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK) process, the organophosphorus ligand HDEHP (di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(III) from An(III) with the combination of a holdback reagent in aqueous lactate buffer solution. In this work, the structural and electronic properties of Eu3+ and Am3+ complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory (DFT). It was found that HDEHP can coordinate with M(III) (M=Eu, Am) cations in the form of hydrogen-bonded dimers HL2- (L=DEHP), and the metal ions prefer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(III) complexes have higher interaction energies, the HL2- dimer shows comparable affinity for Eu(III) and Am(III) according to thermodynamic analysis, which may be attributed to the higher stabilities of Eu(III) nonahydrate. It is expected that this work could provide insightful information on the complexation of An(III) and Ln(III) with HDEHP at the molecular level.
Highly soluble multi-walled carbon nanotubes (MWNTs) were prepared by radiation-induced free radical graft polymerization of vinyl acetate (VAc) onto pristine MWNT surfaces. High resolution transmission electron microscopy (HR-TEM), Fourier transform infrared (FTIR) spectroscopy, and micro-Raman spectroscopy were used to confirm that poly(vinyl acetate) (PVAc) had been successfully grafted onto the surface of the MWNTs. The effects of experimental parameters on the degree of grafting (DG) of PVAc were also investigated, including adsorbed dose, dose rate, initial monomer concentration, and solvents. The grafted MWNTs (MWNTs-g-PVAc) exhibited good solubility in common organic solvents at high mass fraction. In addition, a superhydrophobic composite membrane could be readily fabricated by vacuum filtration of MWNTs-g-PVAc onto a supporting membrane, as was confirmed by water contact angle testing and visualization by scanning electron microscopy.
Hydrogen sulfide (H2S) has been found to be the third most important endogenous gaseous signaling molecule after nitric oxide (NO) and carbonic oxide (CO) and plays crucial roles in living organisms and biological systems. Here we use aggregation-induced emission (AIE) of a small organic molecule (TPE-indo) to detect H2S in both solution and living cells. TPE-indo can target mitochondria and aggregate to fluoresce, which can serve as a sensor for monitoring H2S in the mitochondria. We regulate the fluorescence of AIE molecules by tuning the viscosity of the solution to form TPE-indo nanoparticles, constructing a probe for H2S with good selectivity and high sensitivity. The nucleophilic addition of HS- to the TPE-indo is crucial for the rapid H2S detection. The imaging and analysis of H2S in mitochondria of living cells with the probe demonstrate potential biological applications.
The broad class of explosives includes nitro aromatics as well as challenging aliphatic nitro-organics whose detection is important from counter-terrorism and national security perspectives. Here we report a turn-on fluorescent sensor array based on aggregation-induced emission (AIE) fluorophores as receptors. To achieve a good sensing system with fast response, good sensitivity and low detection limit, three receptors with abundant chemical diversities for target analytes were synthesized. The turn-on response of the individual receptor showed highly variable and cross-reactive analyte-dependent changes in fluorescence. The excellent ability to identify a variety of explosives, especially the challenging aliphatic nitro-organics (2,3-dimethyl-2,3-dinitrobutane (DMNB), 1,3,5-trinitro-1,3,5-triazinane (RDX), cyclotetramethylene tetranitramine (HMX) and entaerythritol tetranitrate (PETN)), was demonstrated in qualitative and quantitative analyses with 100% accuracy. The fluorescence signal amplification in the presence of explosives allows for application of these receptors in a sensor microarray suitable for high-throughput screening. These results suggested that the cross-reactive sensor array based on AIE fluorophores could find a wide range of applications for sensing various analytes or complex mixtures.
A highly sensitive and selective two-photon sensing scheme for detection of cartap was developed by using Au@Ag bimetallic core-shell nanoparticles. Cartap was found to induce the aggregation of Au@Ag nanoparticles and up to 700-fold enhancement in two-photon photoluminescence. Huge enhancement in two-photon photoluminescence allows achieving a detection limit of as low as 0.0062 mg/kg, which is better than the conventional colorimetric methods. This two-photon sensing scheme has a broad dynamic range and displays excellent selectivity in detection of cartap against over other ten kinds of commonly used insecticides.
There are great needs for real-time detection of volatile organic amines (VOA) through low-cost detection methods in public health, food safety, and environmental monitoring area. Organic thin-film fluorescent probe (OTFFP) is expected to become a new and efficient means of detecting VOA because of its fast response, high sensitivity, no contamination to the analyte and ease to prepare a portable instrument. Compared with the mature detection methods in solution, research on solid fluorescence sensing has been less studied. In this article, we review recent progress in OTFFP research for VOA vapour. We mainly focus on the new fluorescent sensing mechanisms applied in solid state in recent years and the design principle of probes for different types of organic amines (such as primary amine, secondary amine, tertiary amine and aromatic amine). We also review the material structures of these probes and the strategies to enhance their sensitivity or selectivity.
Glutathione (GSH) plays a critical role in maintaining oxidation-reduction homeostasis in biological systems. Considering the detection of GSH by fluorescence sensors is limited by either the short wavelength emission or the poor photostability, a highly stable colorimetric and ratiometric NIR fluorescent sensor (DCM-S) for GSH detection has been constructed on the basis of dicyanomethylene-4H-pyran (DCM) chromophore. The specific disulfide bond is incorporated via a carbamate linker as the GSH responsive group, which simultaneously blue-shifts and quenches the fluorescence. Upon addition of GSH, DCM-S exhibits outstanding colorimetric (from yellow to red) and ratiometric fluorescent response with the 6-fold enhancement of NIR fluorescence at 665 nm in quantum yield. More importantly, the GSH-treated DCM-S (DCM-NH2 actually) possesses 20-fold longer fluorescence half-life period as well as much better photostability than the FDA-approved ICG. Finally, the ratiometric detection of GSH is also successfully operated in the living cell imaging, exhibiting NIR fluorescence and large Stokes shift (215 nm) with nearly no background fluorescence interference. As a consequence, DCM-S can be utilized as colorimetric and ratiometric NIR fluorescent sensor for GSH, with a great potential in the development of GSH-induced drug delivery system.
Fluorescent light-up probes comprising a tetraphenylethene unit with aggregation-induced emission (AIE) characteristics and a water-soluble peptide have been designed and synthesized which provide cell membrane and nuclear permeability to live cells. This strategy has offered new opportunities for the development of probes with light-up ability and good signal-to-noise ratio. The selectivity or targeting specificity is determined by the peptide sequence, i.e. a nuclear localization signal that leads to nucleus imaging and a cell biomarker targeting peptide that offers specific light-up imaging of HT-29 cells.
The ability to supply suitable blood vessel system is a major challenge for artificial thick tissue engineering. Angiogenesis is a key point during the process of microvascular formation. Many bioactive molecules such as extra cellular matrix (ECM) proteins and adhesion peptides derived from the ECM are applied to promote angiogenesis. In this work, two adhesion peptides, YIGSR and REDV, were selected to modify sodium alginate (ALG) to obtain YIGSR- and REDV-alginate conjugates (ALG-YIGSR, and ALG-REDV, respectively). We mixed the two peptide-conjugates together in a series of concentration ratios to prepare bioactive surfaces for in vitro studies and hydrogel scaffolds for in vivo studies. In vitro studies showed that surfaces modified with 1.09 pmol/mm2 peptide had the best affinity to human umbilical vein endothelial cells (HUVECs) than that with high or low concentrations of peptides. In addition, surfaces modified with dual peptides could significantly promote HUVECs proliferation, where ALG-YIGSR:ALG-REDV at a mole ratio of 5:1 exhibited the best enhancement ability. Furthermore, the in vivo angiogenesis results demonstrated that hydrogel scaffolds composed of mixed ALG-YIGSR and ALG-REDV at the 5:1 ratio had angiogenic induction potential by stimulating new blood vessel formation, and showed higher blood vessel density than scaffolds composed of a single peptide. These results demonstrated that a mixed combination of peptide alginate conjugates could be a potential scaffold to stimulate and induce angiogenesis in tissue engineering applications.
This study examined the total arsenic (Ast) and inorganic arsenic (Asi) content in the main rice growing area of China. The results were compared with other countries and then used for dietary exposure assessment. A total of 446 rice samples from 15 main rice-growing provinces and autonomous regions of China were collected and then divided into unpolished and polished rice. Total arsenic and arsenic species were analyzed in a total of 892 subsamples using inductively coupled plasma-mass spectrometry (ICP-MS) and high performance liquid chromatography (HPLC) coupled ICP-MS, respectively. National Ast means were 255 μg/kg of unpolished rice and 143 μg/kg of polished rice. Asi was found to be the predominant species and mean levels were 209 μg/kg of unpolished rice and 108 μg/kg of polished rice, respectively. Exposure assessment to Asi in polished rice has been calculated for the margin of exposure (MOE), which highlights the fact that Asi levels in the Chinese rice should arouse public health concern.
Transparent conductive electrodes play a significant role in the fabrication and development of optoelectronic devices. As next generation optoelectronic devices trend towards mobile and wearable devices, the added attribute of flexibility or stretchability for these electrodes becomes increasingly important. However, mechanical requirements aside, transparent conductive electrodes must still retain high transparency and conductivity, with the metrics for these parameters being compared to the standard, indium tin oxide. In the search to replace indium tin oxide, two materials that have risen to the forefront are carbon nanotues and silver nanowires due to their high transparency, conductivity, mechanical compliance, and ease of fabrication. This review highlights recent innovations made by our group in electrodes utilizing carbon nanotubes and silver nanowires, in addition to the use of these electrodes in discrete devices and integrated systems.
Plasmonic Pd nanosheets have been emerging as promising materials for application in near-infrared (NIR) photothermal therapy (PTT) of cancer. However, animal in mice studies indicated that the original synthesized poly(vinylpyrrolidone) (PVP)-protected small Pd nanosheets (Pd-PVP) and some further surface-modified small Pd nanosheets such as Pd-PEG(SH) easily accumulated in reticuloendothelial system (RES) organs (liver, spleen, etc.) and were difficult to be cleared from these organs quickly. In the work, we surprisingly found that glutathione (GSH) could promote the clearance of surface-modified small Pd nanosheets (e.g. Pd-PVP, Pd-PEG(SH) and Pd-GSH) from the RES organs efficiently. The effects of GSH on the bio-distribution and clearance of different surface-modified Pd nanosheets were investigated. Our results indicated that these surface-modified Pd nanosheets with or without GSH added caused no morbidity at target primary organs, and GSH can promote the clearance of different surface-modified Pd nanosheets in the order of Pd-PVP≈Pd-PEG(SH)>Pd-GSH. This study suggests that glutathione could be an attractive reagent for promoting nanomaterials eliminated from the reticuloendothelial systems (RES).
An air-stable supported Cu(I) catalyst, CuI@PS-Phen, was designed and synthesized. CuI@PS-Phen can efficiently catalyze the click polymerization of diynes a and diazides b to produce soluble and thermally stable polytriazoles with high molecular weights (Mw up to 30800), and low copper residue content (down to 190 ppm) in high yields (up to 94.2%) under mild reaction conditions without the exclusion of oxygen.
Multicomponent polymerizations have become powerful tools for the construction of sequence-defined polymers. Although the Passerini multicomponent reaction has been widely used in the synthesis of sequence-defined polymers, the tandem usage of the Passerini multicomponent reaction and other multicomponent reactions in one-pot for the synthesis of sequence-defined polymers has not been developed until now. In this contribution, we report the tandem usage of the Passerini three-component reaction and the three-component amine-thiol-ene conjugation reaction in one pot for the synthesis of sequence-defined polymers. The Passerini reaction between methacrylic acid, adipaldehyde, and 2-isocyanobutanoate was carried out, affording a new molecule containing two alkene units. Subsequently, an amine and a thiolactone were added to the reaction system, whereupon the three-component amine-thiol-ene conjugating reaction occurred to yield a sequence-defined polymer. This method offers more rapid access to sequence-defined polymers with high molecular diversity and complexity.
DNA computing, currently a hot research field in information processing, has the advantages of parallelism, low energy consumption, and high storability, therefore, it has been applied to a variety of complicated computational problems. The emerging field of DNA nanotechnology has also developed quickly; within it, the method of DNA strand displacement has drawn great attention because it is self-induced, sensitive, accurate, and operationally simple. This article summarizes five aspects of the recent developments of DNA-strand displacement in DNA computing: (1) cascading circuits; (2) catalyzed reaction; (3) logic computation; (4) DNA computing on surfaces; and (5) logic computing based on nanoparticles guided by strand displacement. The applications and mechanisms of strand displacement in DNA computing are discussed and possible future developments are presented.