Search

Comprehensive Summary: Organoborons are commonly used building blocks for rapidly increasing molecular complexity. Although significant progress has been made in the selective functionalization of mono‐organoborons, the site‐selective functionalization of poly(organoborons) has attracted substantial interest in organic synthesis, pharmaceuticals, and agrochemicals due to the presence of multiple potential reaction sites. This review discusses various activation modes of the target C–B bond, with diverse transformations being achieved in both a selective and efficient manner. Recent advances in the catalytic selective transformations of 1,n‐diboronates through ionic and radical pathways are highlighted. Furthermore, we summarize the existing challenges and future research directions in this field. Key Scientists: In 1993, Suzuki, Miyaura and coworkers developed a pioneering example of selective arylation towards cis‐1,2‐bis(boryl) alkenes, marking the inception of this field. The Morken group has made significant contributions to the asymmetric diboration of alkenes and realized elegant catalytic functionalization of these compounds since 2004. In 2016, Fernández and colleagues achieved the selective arylation of the internal C–B bond of tri(boronates). Since 2019, the Aggarwal group has developed efficient Giese‐type addition and selective arylation at the more substituted C–B bond of 1,2‐bis(boronic) esters through photoredox catalysis. The controllable regiodivergent alkynylation of 1,3‐bis(boronic) esters was developed by Gao and coworkers in 2023. Recently, Qin conducted elegant research on the programmable late‐stage functionalization of bridge‐substituted bicyclo[1.1.1]pentane (BCP) bis‐boronates. Since 2013, catalytic stereoselective transformations have been developed by several groups, including those led by Morken and Chen. This review summarizes the latest and most significant developments in this field since 1993. [ABSTRACT FROM AUTHOR]

The influence of annealing at various temperatures on the phase stability and microstructure of pulsed-wave laser mode (PW) 316L stainless steel fabricated via Directed Energy Deposition (DED) was systematically investigated. The microstructural alterations resulting from heat treatment were examined to clarify their influence on the mechanical properties of the specimens subjected to tensile loading. The results showed that cell size increased with annealing temperature, with the cellular microstructure disappearing at higher temperatures (T ≥ 1000 °C). A decrease in the mechanical strength of the specimens was observed as annealing temperature increased. Additionally, the influence of different laser pulse frequencies and duty cycles on residual stresses was examined, revealing that moderate laser frequencies and duty cycles effectively reduced residual stress levels. [ABSTRACT FROM AUTHOR]

Continuous-wave laser (CW) and pulsed-wave laser (PW) are the two laser modes in direct energy deposition (DED). This paper mainly reports on a study into the effects of the two laser modes on residual stresses with a given energy input. The contour method (CM) with non-uniform spatial distribution of inspection points was used to capture residual stress distributions in DED of Fe3000 on a substrate made of 316L stainless steel. Residual stresses in the transition zone between the deposit and the substrate were carefully examined to gain an understanding of cracks frequently observed at the connection between the substrate and the deposit. Furthermore, X-ray diffraction, along with successive material removal, was used to reveal residual stresses at various depths in the substrate. The results showed that significant tensile longitudinal stresses developed at the substrate–deposit junction for both CW and PW laser modes. It increased sharply (about 64%) with the increase in energy input for CW mode, while it showed the opposite trend for PW mode; the longitudinal residual stress decreased 13.2% with the increase in energy input. PW, however, introduced lower residual stress than that of CW under the condition of high-energy input; the maximum longitudinal residual stress decreased by about 10.4% compared to CW mode. This was due to stress relaxation at high-energy inputs in PW mode. In addition, residual stresses were found to be higher than the initial yield stress, and yielding occurred in the deposited part. The results determined by the CM and X-ray diffraction depth profiling were found to be consistent. [ABSTRACT FROM AUTHOR]

Directed energy deposition with laser beam (DED-LB) components experience significant residual stress due to rapid heating and cooling cycles. Excessive residual tensile stress can lead to cracking in the deposited sample, resulting in service failure. This study utilized digital image correlation (DIC) and thermal imaging to observe the in situ temporal evolution of strain and temperature gradients across all layers of a deposited 316 L stainless steel thin wall during DED-LB. Both continuous-wave (CW) and pulsed-wave (PW) laser modes were employed. Additionally, the characteristics of thermal cracks and geometric dislocation density were examined. The results reveal that PW mode generates a lower temperature gradient, which in turn reduces thermal strain. In CW mode, the temperature–stress relationship curve of the additive manufacturing sample enters the "brittleness temperature zone", leading to the formation of numerous hot cracks. In contrast, PW mode samples are almost free of cracks, as the metal avoids crack-sensitive regions during solidification, thereby minimizing hot crack formation. Overall, these factors collectively contribute to reduced residual stress and improved mechanical properties through the adjustment of pulsed-wave laser deposition. [ABSTRACT FROM AUTHOR]

In the process of directed energy deposition (DED), the grain structure of the deposited samples is determined by two aspects. The first is the initial solidification grain structure; the second is the effect of the upper thermal cycle on the solidified grain structure of the lower layer. Dynamic recrystallization and grain growth can be activated under suitable strain and the temperature resulting from thermal cycles. The evolution of grain size and the geometric dislocation density (GND) of austenitic stainless steel 316 L under different strains and temperatures caused by thermal cycles was investigated. It is found that dynamic recrystallization requires an appropriate level of accumulated strain, temperature, and initial grain size. Under <2% accumulated strain and 400–1200 °C conditions caused by 30 layers of thermal cycles, fully dynamic recrystallization occurs with coarse initial grains (CIG), leading to the complete coarsening of grains. However, relatively fine initial grains (FIG) under the same conditions only display partial dynamic recrystallization. The next 2–4% strain and 400–700 °C by 60 layers of thermal cycles make up the driving force of fully dynamic recrystallization, and the grains coarsen completely. Larger accumulated strain (4–6%) and lower temperature (400–600 °C) by 90 layers of thermal cycles and FIG provide more nucleation sites for dynamic recrystallization, which leads to little coarsening of grains even after fully dynamic recrystallization. Temperature, accumulated strain, and the amount of δ-ferrite promote the formation of sub-grains during dynamic recrystallization caused by thermal cycles, which leads to the increase in GND. [ABSTRACT FROM AUTHOR]

Pharmaceutical contaminants are causing great attention for the public people, urgently requiring to be eliminated from the environment. Herein, commercial pharmaceutical carbamazepine was chosen as a model to be degraded by a heterogeneous Fenton system using natural pyrite as catalyst. The catalyst was characterized by X‐ray diffraction apparatus, high‐resolution transmission electron microscopy, and X‐ray photoelectron spectroscopy. The elements composition and chemical states of pyrite changed significantly after the Fenton reaction, which promoted the production of active species in the electron transfer process. The degradation efficiency of carbamazepine (2.5 mg/L) can reach 99.71% after 30 min with 0.3 g/L of pyrite and 5 mM of H2O2, respectively. The reaction system was suitable for a wide range of pH (3–9). The environmental adaptability examination of pyrite showed that humic acid (HA) had inhibitory effects on the degradation of carbamazepine. While the changes of degradation efficiency of carbamazepine were inconspicuous in the presence of NO3− and SO42−, indicating strong anti‐interference to environment common anions. Free‐radical capturers suggested that hydroxyl radical (∙OH), superoxide radical (∙O2−), and singlet oxygen (1O2) participated in the degradation of carbamazepine. This research has offered a new strategy of "treating wastes with wastes" to use pyrite to remove emerging pollutants. [ABSTRACT FROM AUTHOR]

Background: Hepatocellular carcinoma (HCC) remains a leading cause of cancer-related mortality, underscoring the need for novel therapeutic targets. This study aimed to elucidate the role of endoplasmic reticulum membrane protein complex subunit 1 (EMC1) in HCC progression and its therapeutic potential. Methods: Publicly available sequencing data and biopsy specimens were analyzed to assess EMC's clinical value and functions in HCC. In vitro experiments validated EMC functions, and multiplex immunofluorescence analysis examined EMC-associated sorafenib resistance mechanisms. EMC1 expression was knocked down in HCC cell lines, followed by cell viability, wound healing, and transwell migration assays. Tumor growth and response to sorafenib treatment were evaluated in mouse models. Metabolomic analysis assessed changes in the TCA cycle. Results: EMC genes were aberrantly expressed in HCC, and high EMC1 expression correlated with poorer survival rates. EMC1 disruption enhanced HCC cells' sensitivity to sorafenib, reducing cell viability, increasing apoptosis, and decreasing tumor size and weight. EMC1 maintained cancer cell stemness and promoted M2 macrophage infiltration. Metabolomic analysis revealed significant changes in the TCA cycle, indicating EMC1's role in HCC metabolic reprogramming. Importantly, EMC1 is highly associated with sorafenib resistance, potentially linked to CTNNB1 mutation or activation. Conclusion: EMC1 plays a critical role in regulating the sorafenib resistance in HCC. Targeting EMC1 may improve HCC treatment efficacy. [ABSTRACT FROM AUTHOR]