Water splitting is promising to realize a hydrogen‐based society. The practical use of molecular water‐splitting catalysts relies on their integration onto electrode materials. We describe herein the immobilization of cobalt corroles on carbon nanotubes (CNTs) by four strategies and compare the performance of the resulting hybrids for H2 and O2 evolution. Co corroles can be covalently attached to CNTs with short conjugated linkers (the hybrid is denoted as H1) or with long alkane chains (H2), or can be grafted to CNTs via strong π–π interactions (H3) or via simple adsorption (H4). An activity trend H1≫H3>H2≈H4 is obtained for H2 and O2 evolution, showing the critical role of electron transfer ability on electrocatalysis. Notably, H1 is the first Janus catalyst for both H2 and O2 evolution reactions in pH 0–14 aqueous solutions. Therefore, this work is significant to show potential uses of electrode materials with well‐designed molecular catalysts in electrocatalysis.

A cobalt complex of 5,15‐bis(pentafluorophenyl)‐10‐(4)‐(1‐pyrenyl)phenyl corrole that contains a triphenylphosphine axial ligand (1‐PPh3) was synthesized and examined as an electrocatalyst for the hydrogen evolution reaction (HER). If supported on graphene (G), the resulting 1‐PPh3/G material can catalyze the HER in aqueous solutions over a wide pH range of 0–14 with a high efficiency and durability. The significantly enhanced activity of 1‐PPh3/G, compared with that of its analogues 1‐py/G (the Co‐bound axial ligand is pyridine instead of triphenylphosphine) and 2‐py/G (Co complex of 5,10,15‐tris(pentafluorophenyl)corrole), highlights the effects of the pyrenyl substituent and the triphenylphosphine axial ligand on the HER activity. On one hand, the pyrenyl moiety can increase the π–π interactions between 1 and graphene and thus lead to a fast electron transfer from the electrode to 1. On the other hand, the triphenylphosphine axial ligand can increase the electron density (basicity) of Co and thus make the metal center more reactive to protons at the trans position through a so‐called “push effect”. This study concerns a significant example that shows the trans effect of the axial ligand on the HER, which has been investigated rarely. The combination of various ligand‐design strategies in one molecule has been realized in 1‐PPh3 to achieve a high catalytic HER performance. These factors are valuable to be used in other molecular catalyst systems.

Many researchers have considered how to exploit molecular properties, with their intrinsic diversity, to create molecular switches. The use of photochromic compounds, such as spiropyran and diarylethene, as photoswitching systems attracts much attention because of their potential ability for application in photonic devices, where each isomer of the photochromic compound can represent ª0º or ª1º of a digital binary code.[1] Raymo and Giordani [2] demonstrated the modulation of pyrene fluorescence in the presence of spiropyran under three external inputs (ultraviolet (UV) and visible (vis) light and protons) by taking advantage of the different absorption properties of three states of spiropyran, which was proposed for use in multichannel signal communication. Zhu and coworkers proposed a new molecular logic circuit based on the fact that the excimer fluorescence of bis-pyrene can be reversibly regulated by UV light, metal ions, and visible light in the presence of spiropyran. [3] However, these multi-channel signal communication systems relied on two molecules per system. In fact, one key aspect sought in the progress of molecular switching technology is the development of smarter systems that integrate several switchable functions into a single molecule.[4±6]1,2-Bis(thienyl)ethene derivatives (BTEs)±metalloporphy-rin switches, in which the transition metal is coordinated to the ends of the pyridyl-derived BTE, were suggested to achieve non-destructive readout using phosphorescence instead of fluorescence changes. [6a,b] The interaction between the metal ions located at both ends of the pyridyl groups of the diarylethene can be switched by irradiation, because the p-conjugated bond structures between the two aryl groups in the two isomers are different. [7,8] On the other hand, reversible changes of luminescence of BTEs are interesting from the viewpoint of applications for erasable memory media, optical switches, and fluorescence probes. Irie et al. [9] have shown that digital switching of the fluorescence of diarylethene molecules can be controlled by irradiation with UV/vis light at the single-molecule level. Based on the changes of near-infrared (IR) luminescence along with photochromism, a novel family of photochromic BTE-based tetraazaporphyrin or phthalocyanine hybrids was developed in our lab as excellent, non-destructive readout media for application in optical switches.[10]In this communication, a photochromic pyridine-tethered BTE (Py-BTE), namely bis(5-pyridyl-2-methylthien-3-yl)cyclopentene (see Scheme 1), [11a] is used as a photoswitch responding to metal ions, protons, and alternating UV/vis light irradiation. The compound Py-BTE has a special selective response to Zn 2+ and is also very sensitive to protons. The fluorescent properties, including the intensity and emission peak wavelengths of the compound, can be reversibly regulated by UV-vis light, Zn 2+ , and protons. Based on these results, a complicated molecular switch is proposed. To the best of our knowledge, it is the first time that o...

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The response of soil organic carbon (SOC) decomposition to global warming is a potentially major source of uncertainty in climate prediction. However, the magnitude and direction of SOC cycle feedbacks under climate warming remain uncertain because of the knowledge gap about the global‐scale spatial pattern and temperature sensitivity (Q10) mechanism of SOC decomposition. Here, we collected data of Q10 and corresponding soil variables from 81 peer‐reviewed papers using laboratory incubation to explore how Q10 varied among different ecosystems at the global scale and whether labile and recalcitrant SOC pools had equal Q10 values. Q10 with a global average of 2.41 substantially varied among different ecosystems, ranging from the highest in cropland soils (2.76) and the lowest in wetland soils (1.84). Hump‐shaped correlations of Q10 values with the maximum at SOC = 190 g/kg and the minimum at clay = 37% were observed. However, the main influencing factors of Q10 differed among various ecosystems. Q10 values showed a clear decrease with increasing incubation temperature but no significant decrease above 25°C. In general, labile SOC was less sensitive than recalcitrant SOC to warming. Structural equation model analyses showed that total N and SOC accounted for 53% and 46%, respectively, of the variation in Q10 of labile SOC and recalcitrant SOC. This finding suggested that Q10 values of labile and recalcitrant SOC pools had different controlling factors. Our findings highlighted the importance of Q10’s variations in ecosystem types and the response of recalcitrant SOC to warming in predicting the soil C cycling and its feedback to climate change. Therefore, ecosystem type and difference in Q10 of labile and recalcitrant SOC should be considered to precisely predict the soil C dynamics under global warming. A http://onlinelibrary.wiley.com/doi/10.1111/1365-2435.13256/suppinfo is available for this article.

A new bis(5-pyridyl-2-methylthien-3-yl)cyclopentene, as a photochromic bridging ligand, has been synthesized and the photocyclization quantum yield was found to increase in the presence of a metal ion.

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Background Alport syndrome (AS) is an inherited progressive renal disease caused by mutations in COL4A3, COL4A4, and COL4A5 genes. The large sizes of these genes and the absence of mutation hot spots have complicated mutational analysis by routine PCR‐based approaches. In recent years, the development of next‐generation sequencing (NGS) has made possible the time‐ and cost‐effective and accurate analysis of the three genes in a single step. Methods Here, we analyze COL4A3, COL4A4, and COL4A5 simultaneously in 29 AS patients using NGS. Candidate mutations were validated by classic Sanger sequencing and Real‐time PCR. Results Twenty two new mutations and 10 known mutations were detected. Of those novel mutations, 18, 3, and 1 mutations were detected in COL4A5, COL4A4, and COL4A3, respectively. Twenty six patients showed X‐linked inheritance, one showed autosomal recessive inheritance and two showed digenic inheritance (DI). Conclusion A comparison of the clinical manifestations caused by different types of mutations in COL4A5 suggested that large fragment mutations are relatively more severe than the other missense mutations and AS by some mutations may show inter‐ and intra‐familial phenotypic variability. It is important to consider these transmission patterns in the clinical evaluation according to the results of genetic testing, especially for DI. Twenty two new mutations can expand the genotypic spectrum of AS.