Enhanced degradation of reactive black 5 via persulfate activation by natural bornite: Influencing parameters, mechanism and degradation pathway

Reactive black 5 (RBk5) is a refractory azo dye that constitutes a serious threat to the environment and humans. Herein, natural bornite (Nbo) was utilized to activate persulfate (PDS) for the RBk5 removal. The particle size of the Nbo catalyst was optimized and the RBk5 degradation rate constant that responded positively to the particle size of the Nbo catalyst was exhibited. Then, the operational factors affecting RBk5 removal were comprehensively investigated. With the addition of 1.5 g·L−1 Nbo and 1.5 mM PDS, 99.05% of the RBk5 (20 mg·L−1) was removed in 150 min compared with 0.46% removal with PDS only, which was caused by the additional reactive oxygen species (ROS) produced by the synergistic action of Fe-Cu bimetallic metal and reductive sulfur species. The Nbo catalyst presented high stability and reusability toward RBk5 removal. Identification of reactive oxygen species revealed that SO4·−, ·OH, O2·− and 1O2 collectively participated in RBk5 removal. Additionally, a possible degradation pathway for RBk5 was proposed, including cleavage of the azo, C-S and S-O bonds, hydroxylation, hydrolyzation, direct oxidation and other pathways. This work developed a highly effective and low-cost natural mineral-based bimetallic sulfide material for PDS activation for the degradation of contaminants and environmental remediation.</p

Crystal Structure and Optical Properties Characterization in Quasi-0D Lead-Free Bromide Crystals (C₆H₁₄N)₃Bi₂Br₉·H₂O and (C₆H₁₄N)₃Sb₃Br₁₂

Low dimensional organic inorganic metal halide materials have shown broadband emission and large Stokes shift, making them widely used in various fields and a promising candidate material. Here, the zero-dimensional lead-free bromide single crystals (C6H14N)3Bi2Br9·H2O (1) and (C6H14N)3Sb3Br12 (2) were synthesized. They crystallized in the monoclinic crystal system with the space group of P21 and P21/n, respectively. Through ultraviolet–visible–near-infrared (UV–vis–NIR) absorption analysis, the band gaps of (C6H14N)3Bi2Br9·H2O and (C6H14N)3Sb3Br12 are found to be 2.75 and 2.83 eV, respectively. Upon photoexcitation, (C6H14N)3Bi2Br9·H2O exhibit broad-band red emission peaking at 640 nm with a large Stokes shift of 180 nm and a lifetime of 2.94 ns, and the emission spectrum of (C6H14N)3Sb3Br12 are similar to those of (C6H14N)3Bi2Br9·H2O. This exclusive red emission is ascribed to the self-trapping exciton transition caused by lattice distortion, which is confirmed through both experiments and first-principles calculations. In addition, due to the polar space group structure and the large spin–orbit coupling (SOC) associated with the heavy elements of Bi and Br of crystal 1, an obvious Rashba effect was observed. The discovery of organic inorganic metal bromide material provides a critical foundation for uncovering the connection between 0D metal halide materials’ structures and properties

Hemostatic Effects of Microbubble-Enhanced Low-Intensity Ultrasound in a Liver Avulsion Injury Model

<div><p>Objectives</p><p>Microbubble-enhanced therapeutic ultrasound (MEUS) can block the blood flow in the organs. The aim of this study was to evaluate the hemostatic effect of microbubble-enhanced pulsed, low-intensity ultrasound in a New Zealand White rabbit model of avulsion trauma of the liver. The therapeutic ultrasound (TUS) transducer was operated with the frequency of 1.2 MHz and an acoustic pressure of 3.4 MPa. Microbubble-(MB) enhanced ultrasound (MEUS) (n = 6) was delivered to the distal part of the liver where the avulsion was created. Livers were treated by TUS only (n = 4) or MB only (n = 4) which served as controls. Bleeding rates were measured and contrast enhanced ultrasound (CEUS) was performed to assess the hemostatic effect, and liver hemoperfusion before and after treatment. Generally, bleeding rates decreased more than 10-fold after the treatment with MEUS compared with those of the control group (P<0.05). CEUS showed significant declines in perfusion. The peak intensity value and the area under the curve also decreased after insonation compared with those of the control group (P<0.05). Histological examination showed cloudy and swollen hepatocytes, dilated hepatic sinusoids, perisinusoidal spaces with erythrocyte accumulation in small blood vessels, obvious hemorrhage around portal areas and scattered necrosis in liver tissues within the insonation area of MEUS Group. In addition, necrosis was found in liver tissue 48 h after insonation. We conclude that MEUS might provide an effective hemostatic therapy for serious organ trauma such as liver avulsion injury.</p></div

CEUS images after insonation.

<p><b>a, b</b>, Uniform perfusion of contrast agent in the MB group; <b>c, d</b>, A representative CEUS image showed a perfusion defect (arrow indicates the trauma, breakage the wound, and dotted line shows the range of defects. The area beyond the dotted line also showed an irregular defect) in MEUS group.</p

Images of procedure for application of microbubble-enhanced therapeutic ultrasound.

<p><b>a</b>’, active bleeding of the wound before insonation; <b>b</b>, Direct insonation of the wound by a transducer during injection of microbubbles; <b>c</b>, <b>c’,</b> small exudates over the wound after insonation; <b>d</b>, The liver wound were smooth and no bleeding after 48 h.</p

A comparison of bleeding visual scores before and after insonation.

<p>*P<0.05 indicates a significant difference between before and after insonation of MEUS group. ⁺P<0.05 indicates a significant difference between MEUS group and the controls.</p

Correlation between bleeding rates and acoustic density analysis, bleeding visual score before and after insonation.

<p>PI means the peak intensity value, and AUC means the area under the curve.</p

Representative histological HE sections after insonation of the TUS, and, MB groups.

<p>Hepatic cord and plate structure were clear, and blood cells were scattered in the sinusoids (<b>a,b</b>); In the MEUS group, hepatocytes swelled, and erythrocytes accumulated in the sinusoids (<b>c</b>), the swollen hepatocytes deformed and compressed the sinusoids and perisinusoidal space. A large number of erythrocytes accumulated in the central veins (<b>d</b>), periportal connective tissue hemorrhaged (<b>e</b>). The targets showed map-like necrosis in the MEUS group after 48 h (<b>f</b>).</p

DataSheet_1_Tumor microenvironment features decipher the outperformance of neoadjuvant immunochemotherapy over chemotherapy in resectable non-small cell lung cancer.docx

This study evaluated the efficacy of neoadjuvant immunochemotherapy (Io+Chemo) versus chemotherapy alone (Chemo) in resectable non–small cell lung cancer (NSCLC) in a real-world setting. The association of tumor immune microenvironment (TIME) with pathologic response to different neoadjuvant therapies was also explored.Stage I−III NSCLC patients who received Io+Chemo or Chemo alone followed by surgery were included in the study. Tumor tissues collected during surgery were subjected to TIME evaluation using multiplex immunohistochemistry to measure immune cell subsets, including T cells, B cells, NK cells, and macrophages. Fifty-five patients were included, including 24 treated with neoadjuvant Io+Chemo and 31 with Chemo alone. Io+Chemo induced significantly higher major pathologic response (MPR) (75.0% vs. 38.7%, P = 0.0133) and numerically better pathologic complete response (pCR) (33.3% vs. 12.9%, P = 0.1013) than Chemo. Compared with tumors with Chemo, tumors with Io+Chemo demonstrated a significantly higher ratio of M1 macrophage density in the tumor to that in the stroma (P = 0.0446), more abundant CD8+ cells in the stroma (P = 0.0335), and fewer PD-L1+CD68+ cells in both tumor and stroma. pCR/MPR patients displayed significantly higher density of CD3+, CD3+CD4+, CD20+, CD56 bright cell subsets and more tertiary lymphoid structures and significantly lower density of PD-L1+CD68+ and CD3+CD4+Foxp3+cells in the tumor or stroma. This study favored neoadjuvant Io+Chemo over Chemo and revealed the TIME features underlying the outperformance of Io+Chemo over Chemo.</p