Selective Anchoring by Surface Sulfur Species Coupled with Rapid Interface Electron Transfer for Ultrahigh Capacity Extraction of Uranium from Seawater.

Improving the adsorption selectivity, enhancing the extraction capacity, and ensuring the structural stability of the adsorbent are the key to realize the high efficiency recovery of uranium. In this work, we utilized the strong Lewis acid-base interaction between S2- and U(VI)O22+ coupling rapid electron transfer at the MnS/U(VI)O22+ solid-liquid interface to achieve excellent selectivity, high adsorption capacity, and rapid extraction of uranium. The as-synthesized MnS adsorbent exhibited an ultrahigh uranium extraction capacity (2457.05 mg g-1) and a rapid rate constant (K = 9.11 × 10-4 g h-1 mg-1) in seawater with 100.7 ppm of UO2(NO3)2 electrolyte. The kinetic simulation reveals that this adsorption process is a chemical adsorption process and conforms to a pseudo-second-order kinetic model, indicating electron transfer at the MnS/U(VI)O22+ solid-liquid interface. The relevant (quasi) in situ spectroscopic characterization and theoretical calculation results further revealed that the outstanding uranium extraction property of MnS could be attributed to the highly selective UO22+ adsorption of MnS with lower adsorption energy as a result of the strong interaction between S2- and UO22+ and the rapid mass transfer and interface electron transfer from S2- and low-valent Mn(II) to U(VI)O22+.

Visualization of photothermal therapy by semiconducting polymer dots mediated photoacoustic detection in NIR II.

Visualization of photothermal therapy mediated by photothermal transduction agents (PTAs) is important to promote individual treatment of patients with low side effects. Photoacoustic detection has emerged as a promising noninvasive method for the visualization of PTAs distribution but still has limitations in temperature measurement, including poor measurement accuracy and low tissue penetration depth. In this study, we developed biocompatible semiconducting polymer dots (SPD) for in situ coupling of photothermal and photoacoustic detection in the near-infrared II window. SPD has dual photostability under pulsed laser and continuous-wave laser irradiation with a photothermal conversion efficiency of 42.77%. Meanwhile, a strong correlation between the photoacoustic signal and the actual temperature of SPD can be observed. The standard deviation of SPD-mediated photoacoustic thermometry can reach 0.13 °C when the penetration depth of gelatin phantom is 9.49 mm. Preliminary experimental results in vivo show that SPD-mediated photoacoustic signal has a high signal-to-noise ratio, as well as good performance in temperature response and tumor enrichment. Such a study not only offers a new nanomaterial for the visualization of photothermal therapy but will also promote the theranostic platform for clinical applications.

Strengthening Fe(II)/Fe(III) Dynamic Cycling by Surface Sulfation to Achieve Efficient Electrochemical Uranium Extraction at Ultralow Cell Voltage.

Electrochemically mediated Fe(II)/Fe(III) redox-coupled uranium extraction can efficiently reduce the cell voltage of electrochemical uranium extraction (EUE). How to regulate the surface structure to enhance the uranium acyl ion adsorption capacity and strengthen the Fe(II)/Fe(III) redox cycle process is crucial for EUE. In this work, we developed surface sulfated nanoreduced iron (S-NRI) for EUE and exhibited improved properties for EUE at an ultralow cell voltage (-0.1 V). Compared with a nanoreduced iron (NRI) adsorbent, S-NRI displayed faster electrochemical extraction kinetics properties and higher extraction efficiency and capacity for uranium. In a more complex seawater electrolyte containing uranyl ion concentration ranging from 1 to 20 ppm, the removal efficiency could reach almost ∼100% after EUE for 24 h. At a higher 50 ppm uranium acyl ion concentration in a seawater electrolyte, S-NRI exhibited higher extraction capacity (755.03 mg/g), which is better than 528.53 mg/g of NRI at a cell voltage of -0.1 V. Outstanding EUE property could be attributed to the fact that sulfate species (M-SO42-) on the S-NRI surface not only enhanced selective adsorption of uranyl ions but also strengthened the Fe(II)/Fe(III) redox cycle, which accelerated electron transfer between Fe(II) and U(VI), promoted the regeneration of Fe(II) active sites, and finally enhanced the EUE property.

Opto-acoustic synergistic irradiation for vaporization of natural melanin-cored nanodroplets at safe energy levels and efficient sono-chemo-photothermal cancer therapy.

Rationale: Insufficient penetration and accumulation of theranostic payloads in solid tumors greatly challenge the clinical translation of cancer nanomedicines. To address this challenge, we synthesized natural melanin-cored and doxorubicin-loaded perfluoropentane nanodroplets with good biocompatibility and self-assembling ability. Methods: We used an opto-acoustic synergistic irradiation (OASI) method that was effective at lower energy levels than ultrasound- or laser-only irradiation to safely vaporize the nanodroplets and to cavitate the generated microbubbles for mechanically enhancing intratumoral delivery. The delivered melanin and doxorubicin inside the tumors mediated secondary chemo-photothermal therapy under laser irradiation to fully kill cancer cells. Results:In vivo animal experiments demonstrated direct mechanical disruption of tumor structures (H&E staining), enhanced intratumoral penetration of melanin (photoacoustic imaging), and efficient intratumoral accumulation of doxorubicin (fluorescent imaging). Anti-tumor experiments demonstrated that the nanodroplets combined with OASI treatment and subsequent laser irradiation could efficiently eliminate melanoma tumors. Conclusion: Melanin-cored and doxorubicin-loaded perfluoropentane nanodroplets hold great promise for translational sono-chemo-photothermal cancer therapy.

Core-Satellite Polydopamine-Gadolinium-Metallofullerene Nanotheranostics for Multimodal Imaging Guided Combination Cancer Therapy.

Integration of magnetic resonance imaging (MRI) and other imaging modalities is promising to furnish complementary information for accurate cancer diagnosis and imaging-guided therapy. However, most gadolinium (Gd)-chelator MR contrast agents are limited by their relatively low relaxivity and high risk of released-Gd-ions-associated toxicity. Herein, a radionuclide-64 Cu-labeled doxorubicin-loaded polydopamine (PDA)-gadolinium-metallofullerene core-satellite nanotheranostic agent (denoted as CDPGM) is developed for MR/photoacoustic (PA)/positron emission tomography (PET) multimodal imaging-guided combination cancer therapy. In this system, the near-infrared (NIR)-absorbing PDA acts as a platform for the assembly of different moieties; Gd3 N@C80 , a kind of gadolinium metallofullerene with three Gd ions in one carbon cage, acts as a satellite anchoring on the surface of PDA. The as-prepared CDPGM NPs show good biocompatibility, strong NIR absorption, high relaxivity (r 1 = 14.06 mM-1 s-1 ), low risk of release of Gd ions, and NIR-triggered drug release. In vivo MR/PA/PET multimodal imaging confirms effective tumor accumulation of the CDPGM NPs. Moreover, upon NIR laser irradiation, the tumor is completely eliminated with combined chemo-photothermal therapy. These results suggest that the CDPGM NPs hold great promise for cancer theranostics.

The role of viscosity estimation for oil-in-gelatin phantom in shear wave based ultrasound elastography.

Shear wave based ultrasound elastography utilizes mechanical excitation or acoustic radiation force to induce shear waves in deep tissue. The tissue response is monitored to obtain elasticity information about the tissue. During the past two decades, tissue elasticity has been extensively studied and has been used in clinical disease diagnosis. However, biological soft tissues are viscoelastic in nature. Therefore, they should be simultaneously characterized in terms of elasticity and viscosity. In this study, two shear wave-based elasticity imaging methods, shear wave dispersion ultrasound vibrometry (SDUV) and acoustic radiation force impulsive (ARFI) imaging, were compared. The discrepancy between the measurements obtained by the two methods was analyzed, and the role of viscosity was investigated. To this end, four types of gelatin phantoms containing 0%, 20%, 30% and 40% castor oil were fabricated to mimic different viscosities of soft tissue. For the SDUV method, the shear elasticity µ1 was 3.90 ± 0.27 kPa, 4.49 ± 0.16 kPa, 2.41 ± 0.33 kPa and 1.31 ± 0.09 kPa; and the shear viscosity µ2 was 1.82 ± 0.31 Pa•s, 2.41 ± 0.35 Pa•s, 2.65 ± 0.13 Pa•s and 2.89 ± 0.14 Pa•s for 0%, 20%, 30% and 40% oil, respectively in both cases. For the ARFI measurements, the shear elasticity µ was 7.30 ± 0.20 kPa, 8.20 ± 0.31 kPa, 7.42 ± 0.21 kPa and 5.90 ± 0.36 kPa for 0%, 20%, 30% and 40% oil, respectively. The SDUV results demonstrated that the elasticity first increased from 0% to 20% oil and then decreased for the 30% and 40% oil. The viscosity decreased consistently as the concentration of castor oil increased from 0% to 40%. The elasticity measured by ARFI showed the same trend as that of the SDUV but exceeded the results measured by SDUV. To clearly validate the impact of viscosity on the elasticity estimation, an independent measurement of the elasticity and viscosity by dynamic mechanical analysis (DMA) was conducted on these four types of gelatin phantoms and then compared with SDUV and ARFI results. The shear elasticities obtained by DMA (3.44 ± 0.31 kPa, 4.29 ± 0.13 kPa, 2.05 ± 0.29 kPa and 1.06 ± 0.18 kPa for 0%, 20%, 30% and 40% oil, respectively) were lower than those by SDUV, whereas the shear viscosities obtained by DMA (2.52 ± 0.32 Pa·s, 3.18 ± 0.12 Pa·s, 3.98 ± 0.19 Pa·s and 4.90 ± 0.20 Pa·s for 0%, 20%, 30% and 40% oil, respectively) were greater than those obtained by SDUV. However, the DMA results showed that the trend in the elasticity and viscosity data was the same as that obtained from the SDUV and ARFI. The SDUV results demonstrated that adding castor oil changed the viscoelastic properties of the phantoms and resulted in increased dispersion of the shear waves. Viscosity can provide important and independent information about the inner state of the phantoms, in addition to the elasticity. Because the ARFI method ignores the dispersion of the shear waves, namely viscosity, it may bias the estimation of the true elasticity. This study sheds further light on the significance of the viscosity measurements in shear wave based elasticity imaging methods.