Qing（黄庆） Huang

Destructive extraction of phospholipids from Escherichia coli membranes by graphene nanosheets

Understanding how nanomaterials interact with cell membranes is related to how they cause cytotoxicity and is therefore critical for designing safer biomedical applications. Recently, graphene (a two-dimensional nanomaterial) was shown to have antibacterial activity on Escherichia coli, but its underlying molecular mechanisms remain unknown. Here we show experimentally and theoretically that pristine graphene and graphene oxide nanosheets can induce the degradation of the inner and outer cell membranes of Escherichia coli, and reduce their viability. Transmission electron microscopy shows three rough stages, and molecular dynamics simulations reveal the atomic details of the process. Graphene nanosheets can penetrate into and extract large amounts of phospholipids from the cell membranes because of the strong dispersion interactions between graphene and lipid molecules. This destructive extraction offers a novel mechanism for the molecular basis of graphenes cytotoxicity and antibacterial activity.

Single Gold Nanoparticles as Real‐Time Optical Probes for the Detection of NADH‐Dependent Intracellular Metabolic Enzymatic Pathways

Plasmonics, is an emerging subfield of nanophontonics, and it attracts increasing attention because of its potential applications in controlling and manipulating light at nanoscale dimensions. The advent of dark-field microscopy (DFM) has enabled the study of plasmonic nanoparticles, especially the coinage metals and the effects of their size, shape, composition as well as the local environment, which further facilitate its use in biological-labeling and detection. DFM provides a direct means to probe chemical reactions, real-time optical sensing with high sensitivity, and the in vivo imaging of cancer cells. Recently, redox reactions were directly monitored on single gold nanocrystals using DFM. Actually, every individual nanoparticle (NP) in the assembly could potentially act as an independent probe. Single-nanoparticle sensing platforms offer advantages since they are readily implemented in multiplex detection. Single nanoparticle probes offer improved absolute detection limits and also enable higher spatial resolution. Single nanoparticles have promising applications for measurements in vitro and in vivo events that are non-reachable by fixed solid array. However, the use of plasmonic nanoparticles for the detection of biomolecules or biological processes is still scarce. Nicotinamide adenine dinucleotide/reduced nicotinamide adenine dinucleotide (NAD/NADH) plays an important role as cofactor in numerous biocatalyzed processes, including energy metabolism, mitochondrial responses, immunological functions, aging and cell death. The catalytic deposition of copper on gold nanoparticles (AuNPs) by the NADH cofactor has been applied for the optical and electrochemical detection of NADH and NAD-dependent biocatalytic processes. Herein, we describe a novel method to detect enzymatic activity at the single particle level inside and outside cells by DFM. To our knowledge, it is the first time to monitor the intracellular metabolism and the effect of anticancer drugs on the cell metabolism using copper growth on the AuNP probes. To investigate the application of single Au@Cu nanoparticles for nano-sensing, the plasmon resonance Rayleigh scattering (PRRS) spectra lmax of a single particle was used to probe the gold-catalyzed reduction of Cu ions on AuNPs by NADH or by NAD-cofactor-dependent enzyme/substrate system that generates NADH (Scheme 1). Compared with the scattering spectra in the absence of NADH, the scattering spectra acquired with NADH exhibit a distinct peak shift

Water‐Dispersed Near‐Infrared‐Emitting Quantum Dots of Ultrasmall Sizes for In Vitro and In Vivo Imaging

Near-infrared (NIR)-fluorescence imaging is widely recognized as an effective method for high-resolution and highsensitivity bioimaging because of its minimized biological autofluorescence background and the increased penetration of excitation and emission light through tissues in the NIR wavelength window (700–900 nm). There have been tremendous efforts to develop high-efficiency fluorescent biological probes for NIR-fluorescence imaging. Semiconductor quantum dots (QDs) have attracted much recent attention as a new generation of fluorescent probes because of their unique optical properties such as strong luminescence, high photostability, and size-tunable emission wavelength. While QDs emitting in the range of 450–650 nm have been well developed, NIR-emitting QDs have been much less explored because of their relatively complicated synthesis and post-treatment manipulations. Furthermore, NIR-emitting QDs are usually prepared in organic phase, and additional surface modification is employed to render them waterdispersible for biological applications. The relatively complicated surface modification often results in an increase in size of the QDs. Only recently, water-dispersed NIRemitting CdTe/CdS QDs with tetrahedral structure were directly prepared in aqueous phase through the epitaxialshell-growth method. Despite these advances, much work is still needed to obtain NIR-emitting QDs that can be facilely synthesized in aqueous phase for high-sensitivity and specific bioimaging. Herein, we report the first example of ultrasmall-sized NIR-emitting CdTe QDs with excellent aqueous dispersibility, robust storage, chemical, and photostability, and strong photoluminescence (photoluminescent quantum yield (PLQY): 15–20%). Significantly, the NIR QDs are directly synthesized in aqueous phase through a facile one-step microwave-assisted method (see the Supporting Information for experimental details and mechanisms) by utilizing several attractive properties of microwave irradiation such as prompt startup, easy heat control (on and off), prompt and homogeneous heating, and so forth. More importantly, highly spectrally and spatially resolved bioimaging was possible, and efficient tumor passive targeting in live mice was shown by using the prepared QDs. QDs with different emission wavelengths in the NIR range (lmax= 700–800 nm) can be readily prepared through fine adjustment of the experimental conditions (e.g., reaction time and temperature). Figure 1a,b displays the normalized ultraviolet photoluminescence (UV-PL) spectra for a series of as-prepared QDs with controllable maximum emission wavelength ranging from 700 to 800 nm in aqueous solution. Such QD solutions are transparent under ambient light conditions, suggesting the as-prepared QDs are well-dispersed in aqueous phase without further treatment (Figure 1c). The excellent aqueous dispersibility of the QDs arises from the surfacecovering mercaptopropionic acid (MPA) that acts as a stabilizer because of the presence of negatively charged carboxylic groups. Under UV irradiation the fluorescence of the as-prepared QDs became darker and the emission wavelength gradually shifted out of the visible region (Figure 1d). The transmission electron microscopy (TEM) and highresolution TEM (HRTEM) images reveal that the NIRemitting QDs are spherical particles with good monodispersibility (Figure 2a,b). The existence of a well-resolved crystal lattice in the HRTEM image further confirms the highly crystalline structures of the QDs (Figure 2b inset). Furthermore, the size distribution histogram (Figure 2c), which was determined by measuring more than 250 particles, shows that the average size and standard deviation of the as-prepared NIR-emitting QDs is (3.74 0.67) nm. Comparatively, the [*] Prof. Y. He, Y. L. Zhong, Dr. Y. Y. Su, Y. M. Lu, Z. Y. Jiang, F. Peng, T. T. Xu, Dr. S. Su Institute of Functional Nano & Soft Materials (FUNSOM) and Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University Suzhou, Jiangsu 215123 (China) Fax: (+86)512-6588-2846 E-mail: yaohe@suda.edu.cn

Graphene Oxide-Based Antibacterial Cotton Fabrics

Graphene oxide (GO) is an excellent bacteria-killing nanomaterial. In this work, macroscopic applications of this promising nanomaterial by fixing GO sheets onto cotton fabrics, which possess strong antibacterial property and great laundering durability, are reported. The GO-based antibacterial cotton fabrics are prepared in three ways: direct adsorption, radiation-induced crosslinking, and chemical crosslinking. Antibacterial tests show that all these GO-containing fabrics possess strong antibacterial property and could inactivate 98% of bacteria. Most significantly, these fabrics can still kill >90% bacteria even after being washed for 100 times. Also importantly, animal tests show that GO-modified cotton fabrics cause no irritation to rabbit skin. Hence, it is believed that these flexible, foldable, and re-usable GO-based antibacterial cotton fabrics have high promise as a type of new nano-engineered antibacterial materials for a wide range of applications.

Regenerable electrochemical immunological sensing at DNA nanostructure-decorated gold surfaces

A regenerable electrochemical immunosensor with novel 3D DNA nanostructure-decorated gold surfaces was developed by taking advantage of DNA-directed antibody conjugation and high resistance to non-specific protein adsorption.

Graphene-templated formation of two-dimensional lepidocrocite nanostructures for high-efficiency catalytic degradation of phenols

Graphene is a two-dimensional nanomaterial with exceptionally interesting physical and chemical properties, which has been actively explored in nanoelectronics, nanodevices and nanoscale catalysis. Here we report a graphene-templated route toward mild, solution-phase synthesis of ultrathin single crystal lepidocrocite (γ-FeOOH) nanosheets with high aspect ratio. We find that when reduced graphene oxide (rGO) was incubated with FeCl3 of 20 wt% at 80 °C and in the presence of reducing reagents (e.g.hydrazine hydrate), close-spaced 2D nanosheets of γ-FeOOH was formed on the surface of rGO, with the average thickness of 2.1 nm. This ultrathin nanomaterial was characterized via a range of complementary techniques, transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Mossbauer spectroscopy and synchrotron-based scanning transmission X-ray microscopy (STXM), which confirmed the formation of γ-FeOOH 2D nanosheets. Importantly, we explore the application of this novel nanomaterial as an efficient and stable catalyst for phenol treatment in wastewater.

A methylation-stimulated DNA machine: an autonomous isothermal route to methyltransferase activity and inhibition analysis

The operation of DNA nanomachines is generally triggered by either conformational changes of DNA nanostructure or external environmental stimuli. In the present study, we demonstrate an alternative driving force, DNA methylation, to stimulate DNA machine operation. DNA methylation changes neither DNA sequence and conformation nor external environment, however, blocks its cleavage by corresponding methylation-sensitive restriction endonuclease. We thus designed a strand displacement amplification DNA machine, which could be stimulated upon DNA methylation and then autonomously generates accumulated amounts of peroxidase-mimicking DNAzyme signaling machine products in an isothermal manner. The machine product DNAzyme could catalyze the H2O2-mediated oxidation of 2,2′-azino-bis(3-ethylbenzo thiazoline-6-sulfonic acid) (ABTS2−) to a colored product ABTS·−. This methylation-stimulated DNA machine was further used as a colorimetric assay for analysis of methyltransferases activities and screening of methylation inhibitors. As compared with classical methylation assay, this facile isothermal DNA machine avoids the introduction of methylation-specific polymerase chain reaction and radioactive labels, which might be employed as an effective tool for DNA methylation analysis.

Universal optical assays based on multi-component nanoprobes for genomic deoxyribonucleic acid and proteins

In this report, we developed a universal assay method for both genomic DNA and proteins by using enzyme-based multi-component optical nanoprobes. The nanoprobes are gold nanoparticles assembled with bio-recognizing and signaling elements. We firstly demonstrated that the nanoprobes could detect unpurified asymmetric polymerase chain reaction (PCR) product from genomic DNA of Escherichia coli, with the sensitivity approximately 10 times higher than that of quantitative real-time PCR assay. The limit of detection (LOD) of our nanoprobe-based method is less than 10 pg template DNA (target DNA). Using DNA aptamers as recognition elements, we also showed that as few as 0.1 nM thrombin could be colorimetrically detected with high specificity. These results indicated that the enzyme-based multi-component nanoprobes have the capability to work with real biological samples, and have the potential in various biological and clinical applications.