Photochemical C(sp³)–H Activation for Diversity-Oriented Synthesis of 3‑Functionalized Oxindoles

Heteroatom-adjacent C­(sp3) radical cyclization of N-arylacrylamides provides a straightforward pathway to synthesize valuable 3-functionalized oxindoles. Traditional cyclization reactions normally require harsh conditions or transition-metal catalysts. Here, we developed a metal-free, diversity-oriented synthesis of 3-functionalized oxindoles via photochemically induced selective cleavage of C­(sp3)–H bonds. A variety of 3-substituted oxindoles with functionalities such as ethers, polyhalogens, benzyl, and formyl groups can be obtained by a rational design. This strategy is characterized by its simple operation and mild conditions, aligning well with the developmental requirements for sustainable chemistry. The gram-scale continuous-flow synthesis and efficient construction of bioactive molecules highlight its practical utility

Electroplating Sludge-Derived Multiple-Metal-Doped Spinel with Superior CO Selectivity in Reverse Water–Gas-Shift Reaction

At present, carbon reduction is one of the hottest topics and CO is the raw source of many industrial products. For the first time, this work reported CO2 conversion to CO with superior selectivity via hydrogenation using an electroplating sludge-derived catalyst. As a result, the optimized catalyst attained a best CO2 conversion of 45.88% and CO selectivity of 99.97% at 600 °C. What is more, the catalyst stably maintained a high conversion of 55.39% and selectivity of 99.68% for 100 h at 550 °C. At the same time, the total amount of byproducts was less than 0.32%. After detailed characterizations, the catalyst was featured by CuFeMn-doped ZnCr spinel, which had the ability of mild C–O dissociation and weak CO adsorption. After all, above results show that electroplating sludge is a good precursor for the synthesis of spinel for excellent catalytic CO2 conversion to CO

Photoinduced Phosphination of Arenes Enabled by an Electron Donor–Acceptor Complex Using Thianthrenium Salts

Herein, we describe a metal-free approach for the cross-coupling of arenes or styryl–thianthrenium salts (TTs) with diarylphosphines via an electron donor–acceptor (EDA) complex. Various tertiary phosphines were obtained with high site selectivity and good functional group tolerance. This method enables straightforward construction of C–P bonds via C–H activation of arenes and allows the late-stage functionalization of natural products or pharmaceutical molecules. Mechanistic studies support the approach involving a photoinduced EDA complex

Photosynthesis of C‑1-Deuterated Aldehydes via Chlorine Radical-Mediated Selective Deuteration of the Formyl C–H Bond

C-1-deuterated aldehydes are essential building blocks in the synthesis of deuterated chemicals and pharmaceuticals. This has led chemists to devise mild methodologies for their efficient production. Ideally, hydrogen–deuterium exchange (HDE) is the most effective approach. However, the traditional HDE for creating C-1-deuterated aldehydes often requires a complex system involving multiple catalysts and/or ligands. In this study, we present a mild photocatalytic HDE of the formyl C–H bond with D2O. This process is facilitated by chlorine radicals that are generated in situ from low-cost FeCl3. This strategy demonstrated a broad reaction scope and high functional group tolerance, affording good yields and ≤99% D incorporation. To bridge the gap between research and industrial applications, we designed a new flow photoreactor equipped with a high-intensity light-emitting diode bucket, enabling the synthesis of C-1-deuterated aldehydes on a scale of 85 g. Finally, we successfully produced several important deuterated aldehydes that are integral to the synthesis of deuterated pharmaceuticals

Data_Sheet_1_Childhood Experiences and Psychological Distress: Can Benevolent Childhood Experiences Counteract the Negative Effects of Adverse Childhood Experiences?.docx

BackgroundChildhood experiences can exert a huge impact on adult psychological conditions. Previous studies have confirmed the effects of adverse childhood experiences (ACEs) and benevolent childhood experiences (BCEs) on psychological distress (e.g., stress, depression, and suicidal ideation) separately, but few studies explored a combined effect of ACEs and BCEs on psychological distress. The aim of this study was to explore a combined effect of ACEs and BCEs on psychological distress among Chinese undergraduates.MethodsParticipants were undergraduates aged 17–24 years (N = 1,816) and completed a self-reported questionnaire. A series of regression analyses were conducted to examine the association between childhood experiences and psychological distress.ResultsA total of 65.7% of undergraduates had BCEs, 27.1% of undergraduates had ACEs, and 12.9% of undergraduates had ACEs and BCEs simultaneously. Logistic regression analysis indicated that undergraduates who experienced high ACEs were more likely to have a high risk of psychological distress [odds ratio (ORs) = 1.46, 1.84, and 3.15 for uncertainty stress, depressive symptoms, and suicidal ideation, respectively], while undergraduates who experienced High BCEs were less likely to have psychological distress (ORs = 0.33, 0.22, and 0.32 for uncertainty stress, depressive symptoms, and suicidal ideation, respectively) compared with Low-Both group. The combined effect of ACEs and BCEs (High-Both group) could also play as a protective factor in uncertainty stress (OR = 0.56) and depressive symptoms (OR = 0.47).ConclusionOur findings suggested that ACEs and BCEs could not only predict the psychological distress independently, but also BCEs could counteract the negative effect of ACEs in psychological problems. There is an even greater need to identify and support the victims of ACEs and to increase BCEs in early childhood.</p

Metal-Level Thermally Conductive yet Soft Graphene Thermal Interface Materials

Along with the technology evolution for dense integration of high-power, high-frequency devices in electronics, the accompanying interfacial heat transfer problem leads to urgent demands for advanced thermal interface materials (TIMs) with both high through-plane thermal conductivity and good compressibility. Most metals have satisfactory thermal conductivity but relatively high compressive modulus, and soft silicones are typically thermal insulators (0.3 W m–1 K–1). Currently, it is a great challenge to develop a soft material with the thermal conductivity up to metal level for TIM application. This study solves this problem by constructing a graphene-based microstructure composed of mainly vertical graphene and a thin cap of horizontal graphene layers on both the top and bottom sides through a mechanical machining process to manipulate the stacked architecture of conventional graphene paper. The resultant graphene monolith has an ultrahigh through-plane thermal conductivity of 143 W m–1 K–1, exceeding that of many metals, and a low compressive modulus of 0.87 MPa, comparable to that of silicones. In the actual TIM performance measurement, the system cooling efficiency with our graphene monolith as TIM is 3 times as high as that of the state-of-the-art commercial TIM, demonstrating the superior ability to solve the interfacial heat transfer issues in electronic systems

Metal-Level Thermally Conductive yet Soft Graphene Thermal Interface Materials

Along with the technology evolution for dense integration of high-power, high-frequency devices in electronics, the accompanying interfacial heat transfer problem leads to urgent demands for advanced thermal interface materials (TIMs) with both high through-plane thermal conductivity and good compressibility. Most metals have satisfactory thermal conductivity but relatively high compressive modulus, and soft silicones are typically thermal insulators (0.3 W m–1 K–1). Currently, it is a great challenge to develop a soft material with the thermal conductivity up to metal level for TIM application. This study solves this problem by constructing a graphene-based microstructure composed of mainly vertical graphene and a thin cap of horizontal graphene layers on both the top and bottom sides through a mechanical machining process to manipulate the stacked architecture of conventional graphene paper. The resultant graphene monolith has an ultrahigh through-plane thermal conductivity of 143 W m–1 K–1, exceeding that of many metals, and a low compressive modulus of 0.87 MPa, comparable to that of silicones. In the actual TIM performance measurement, the system cooling efficiency with our graphene monolith as TIM is 3 times as high as that of the state-of-the-art commercial TIM, demonstrating the superior ability to solve the interfacial heat transfer issues in electronic systems

Metal-Level Thermally Conductive yet Soft Graphene Thermal Interface Materials

Along with the technology evolution for dense integration of high-power, high-frequency devices in electronics, the accompanying interfacial heat transfer problem leads to urgent demands for advanced thermal interface materials (TIMs) with both high through-plane thermal conductivity and good compressibility. Most metals have satisfactory thermal conductivity but relatively high compressive modulus, and soft silicones are typically thermal insulators (0.3 W m–1 K–1). Currently, it is a great challenge to develop a soft material with the thermal conductivity up to metal level for TIM application. This study solves this problem by constructing a graphene-based microstructure composed of mainly vertical graphene and a thin cap of horizontal graphene layers on both the top and bottom sides through a mechanical machining process to manipulate the stacked architecture of conventional graphene paper. The resultant graphene monolith has an ultrahigh through-plane thermal conductivity of 143 W m–1 K–1, exceeding that of many metals, and a low compressive modulus of 0.87 MPa, comparable to that of silicones. In the actual TIM performance measurement, the system cooling efficiency with our graphene monolith as TIM is 3 times as high as that of the state-of-the-art commercial TIM, demonstrating the superior ability to solve the interfacial heat transfer issues in electronic systems

Metal-Level Thermally Conductive yet Soft Graphene Thermal Interface Materials

Along with the technology evolution for dense integration of high-power, high-frequency devices in electronics, the accompanying interfacial heat transfer problem leads to urgent demands for advanced thermal interface materials (TIMs) with both high through-plane thermal conductivity and good compressibility. Most metals have satisfactory thermal conductivity but relatively high compressive modulus, and soft silicones are typically thermal insulators (0.3 W m–1 K–1). Currently, it is a great challenge to develop a soft material with the thermal conductivity up to metal level for TIM application. This study solves this problem by constructing a graphene-based microstructure composed of mainly vertical graphene and a thin cap of horizontal graphene layers on both the top and bottom sides through a mechanical machining process to manipulate the stacked architecture of conventional graphene paper. The resultant graphene monolith has an ultrahigh through-plane thermal conductivity of 143 W m–1 K–1, exceeding that of many metals, and a low compressive modulus of 0.87 MPa, comparable to that of silicones. In the actual TIM performance measurement, the system cooling efficiency with our graphene monolith as TIM is 3 times as high as that of the state-of-the-art commercial TIM, demonstrating the superior ability to solve the interfacial heat transfer issues in electronic systems