Dual ligand-capped gold nanoclusters for the smart detection of specific reactive oxygen species.

Quantitative detection of different types of reactive oxygen species (ROS) is vital for understanding the crucial roles of them in biological processes. However, few researches achieved the detection of multiple types of ROS with one probe until now. Given this, we designed and prepared fluorescent gold nanoclusters capped by dual ligand bovine serum albumin and lysozyme (BSA-LYS-AuNCs), which could detect 3 specific types of ROS based on its different fluorescent responses to H2O2, •OH and ClO-, respectively. The limit of detection (LOD) of H2O2, •OH, and ClO- was as low as 0.82 µM, 0.45 µM, and 0.62 µM. Moreover, as an important ROS type, ClO- was detected with high sensitivity and low LOD by BSA-LYS-AuNCs. It was also proved that the crosslinking of protein mainly contributed to the unique fluorescent characteristics of the probe exposing to ClO-. Furthermore, the fluorescent probe achieved the smart detection of hROS (including •OH and ClO-) and wROS (the form of H2O2) in the real sample, which could also been applied specifically to the detection of antioxidants, e.g. ascorbic acid. The gold nanoclusters developed have high potential for the smart detection of multiple ROS in the body fluid of organisms.

Ratiometric Fluorescent Detection of Ultrasound-Regulated ATP Release: An Ultrasound-Resistant Cu,N-Doped Carbon Nanosphere.

Focused ultrasound, as a protocol of cancer therapy, might induce extracellular adenosine triphosphate (ATP) release, which could enhance cancer immunotherapy and be monitored as a therapeutic marker. To achieve an ATP-detecting probe resistant to ultrasound irradiation, we constructed a Cu/N-doped carbon nanosphere (CNS), which has two fluorescence (FL) emissions at 438 and 578 nm to detect ultrasound-regulated ATP release. The addition of ATP to Cu/N-doped CNS was conducted to recover the FL intensity at 438 nm, where ATP enhanced the FL intensity probably via intramolecular charge transfer (ICT) primarily and hydrogen-bond-induced emission (HBIE) secondarily. The ratiometric probe was sensitive to detect micro ATP (0.2-0.6 µM) with the limit of detection (LOD) of 0.068 µM. The detection of ultrasound-regulated ATP release by Cu,N-CNS/RhB showed that ATP release was enhanced by the long-pulsed ultrasound irradiation at 1.1 MHz (+37%, p < 0.01) and reduced by the short-pulsed ultrasound irradiation at 5 MHz (-78%, p < 0.001). Moreover, no significant difference in ATP release was detected between the control group and the dual-frequency ultrasound irradiation group (+4%). It is consistent with the results of ATP detection by the ATP-kit. Besides, all-ATP detection was developed to prove that the CNS had ultrasound-resistant properties, which means it could bear the irradiation of focused ultrasound in different patterns and detect all-ATP in real time. In the study, the ultrasound-resistant probe has the advantages of simple preparation, high specificity, low limit of detection, good biocompatibility, and cell imaging ability. It has great potential to act as a multifunctional ultrasound theranostic agent for simultaneous ultrasound therapy, ATP detection, and monitoring.

Enhanced HIFU Theranostics with Dual-Frequency-Ring Focused Ultrasound and Activatable Perfluoropentane-Loaded Polymer Nanoparticles.

High-intensity focused ultrasound (HIFU) has been widely used in tumor ablation in clinical settings. Meanwhile, there is great potential to increase the therapeutic efficiency of temporary cavitation due to enhanced thermal effects and combined mechanical effects from nonlinear vibration and collapse of the microbubbles. In this study, dual-frequency (1.1 and 5 MHz) HIFU was used to produce acoustic droplet vaporization (ADV) microbubbles from activatable perfluoropentane-loaded polymer nanoparticles (PFP@Polymer NPs), which increased the therapeutic outcome of the HIFU and helped realize tumor theranostics with ultrasound contrast imaging. Combined with PFP@Polymer NPs, dual-frequency HIFU changed the shape of the damage lesion and reduced the acoustic intensity threshold of thermal damage significantly, from 216.86 to 62.38 W/cm2. It produced a nearly 20 °C temperature increase in half the irradiation time and exhibited a higher tumor inhibition rate (84.5% ± 3.4%) at a low acoustic intensity (1.1 MHz: 23.77 W/cm2; 5 MHz: 0.35 W/cm2) in vitro than the single-frequency HIFU (60.2% ± 11.9%). Moreover, compared with the traditional PFP@BSA NDs, PFP@Polymer NPs showed higher anti-tumor efficacy (81.13% vs. 69.34%; * p < 0.05) and better contrast-enhanced ultrasound (CEUS) imaging ability (gray value of 57.53 vs. 30.67; **** p < 0.0001), probably benefitting from its uniform and stable structure. It showed potential as a highly efficient tumor theranostics approach based on dual-frequency HIFU and activatable PFP@Polymer NPs.

Bovine hemoglobin adsorption onto modified silica nanoparticles: Multi-spectroscopic measurements based on kinetics and protein conformation.

Herein, the effects of bovine hemoglobin (BHb) binding to hydrophilic silica nanoparticles (SN1) and hydrophobic silica nanoparticles (SN2) were explored under physiological conditions. SEM and XRD were used to characterize silica nanoparticles (SNs). Zeta potential and DLS confirmed the formation of protein corona (PC), and SN2 showed more increase in their size after PC formation comparing with SN1. The adsorption isotherms were fitted well by the Freundlich model, and the kinetics tended to follow pseudo-second-order kinetics. Then, the second structure of BHb has been analyzed by UV-vis and FT-IR spectroscopy, which implied the impact of SN2 on the secondary structure of BHb was greater than that of SN1 on BHb. Moreover, fluorescence spectroscopy and Raman spectroscopy showed that SNs may induce heme degradation to form fluorescent heme product, resulting in increased fluorescence intensity. This investigation will be significant in exploring the toxicity profile of SNs for their in vivo.

Carbon quantum dots (CQDs) modified ZnO/CdS nanoparticles based fluorescence sensor for highly selective and sensitive detection of Fe(III).

A simple and fast spectrofluorimetric method coupled with carbon quantum dots (CQDs) modified ZnO/CdS nanoparticles was developed for the detection of Ferric iron (Fe(III)). The fluorescence of CQDs/ZnO/CdS NPs was effectively quenched by Fe(III) due to the strong interaction between the CQDs/ZnO/CdS NPs and Fe(III). In addition, the detection limit of Fe(III) was about 1.72×10-7M. The effect of foreign ions on the fluorescence intensity of CQDs/ZnO/CdS NPs showed that the interference response in detecting of Fe(III) ions was low. Moreover, the quenching of Fe(III) and CQDs/ZnO/CdS NPs was discussed to be a static quenching procedure, which was proved by quenching constant KSV and fluorescence lifetime τ. The study of thermodynamics showed that the values of entropy change (ΔS) and enthalpy change (ΔH) were both positive, and the value of free energy (ΔG) was negative, which implied that the weak interaction of the molecular between CQDs/ZnO/CdS NPs and Fe(III) was hydrophobic force, and the quenching process was endothermic and spontaneous.

Modulation of membrane properties by DNA in liposomes: A spectroscopic study.

Liposome mediated DNA transport possesses a number of preventing diseases in clinical trials, thus, the study of interaction between DNA and liposomes has become a hot research direction. In this paper, the adsorption behavior of DNA onto two representative lipids had been studied by the fluorescence spectrum measurement, Ultraviolet absorption spectrum and Langmuir-Blodgett technology. The results of fluorescence spectrum measurement indicated that the fluorescence liposomes were quenched statically by DNA at all three temperatures. Thermodynamic analysis displayed that the intermolecular forces between DNA and liposomes were van der Waals forces and Hydrogen bonding. The experimental results of Ultraviolet absorption spectrum and Langmuir-Blodgett technology further verified these mechanisms. This work provides useful theoretical basis for the development of novel DNA delivery materials.

Fabrication of graphene oxide and sliver nanoparticle hybrids for fluorescence quenching of DNA labeled by methylene blue.

Since graphene oxide­silver nanoparticles (GO-AgNPs) have special affinities to DNA, it become increasingly important in fields of biological analysis in which GO-AgNPs nanocomposites universally functioned as a quencher. In this paper, GO-AgNPs nanocomposites with different GO to AgNPs ratios were synthesized as a fluorescence quencher to interact with DNA labeled by methylene blue (MB). The results showed that the fluorescence intensity of DNA-MB system decreased with the increasing of GO-AgNPs nanocomposites concentration. The quenching phenomenon of DNA-MB by AgNPs and GO was not a simple additive effect but a synergistic effect. The quenching efficiency of synthesized GO-AgNPs nanocomposites with different ratios (1:1, 1:3, 1:5, 1:10) increased with the decrease of GO/Ag ratio. Thermodynamic analysis was employed to investigate the interaction of GO-AgNPs and DNA-MB, it can be concluded that the intermolecular force between GO-AgNPs and DNA-MB was hydrogen bonding. Our works will provide important theoretical and experimental bases for fluorescence sensing of DNA.

Interaction of graphene oxide with bovine serum albumin: A fluorescence quenching study.

Fluorescence quenching was used to elucidate the binding interaction mechanism between bovine serum albumin (BSA) and graphene oxide (GO). By analyzing the values of Stern-Volmer quenching constant (KSV) and binding constant (KA) which were affected by temperature, we supposed that the quenching process between GO and BSA was mainly determined by static quenching, combined with dynamic quenching. The study of thermodynamics showed that the values of enthalpy change (∆H), entropy change (∆S) and Free Energy (∆G) were all negative, which implied that the weak interaction of the molecular between BSA and GO was Van der Waals interaction or hydrogen bond, and the quenching process was exothermic and spontaneous. The red shift in the synchronous fluorescence spectra suggested that the conformation of tryptophan was changed in the presence of GO. According to Förster's non-radiative energy transfer theory, the distance r between BSA (donor) and GO (acceptor) was calculated and indicated the occurrence of energy transfer from BSA to GO had high probability. The AFM observation and Raman spectroscopy revealed that the interaction between BSA and GO has occurred. Compared with other literatures, the explosion of surface topography about BSA and GO was paid more attention on in this study.