We present the first examples of CO electro-reduction catalysts that feature charged imidazolium groups in the secondary coordination sphere. The functionalized Lehn-type catalysts display significant differences in their redox properties and improved catalytic activities as compared to the conventional reference catalyst. Our results suggest that the incorporated imidazolium moieties do not solely function as a charged tag but also alter mechanistic aspects of catalysis.

The electrocatalytic reduction of carbon dioxide (CO2) could be a powerful tool for generating chemical fuels and feedstock molecules relevant to the chemical industry. One of the major challenges for molecular catalysts remains the necessity of high overpotentials, which can be overcome by identifying novel routes that improve the energetic reaction trajectory of critical intermediates during catalysis. In this combined experimental and computational study, we show that imidazolium functionalization of molecular fac-Mn­(CO)3 bipyridine complexes results in CO2 reduction at mild electrochemical potentials in the presence of H2O. Importantly, our studies suggest that imidazolium groups in the secondary coordination sphere promote the formation of a local hydration shell that facilitates the protonation of CO2 reduction intermediates. As such, we propose a synergistic relationship between the functionalized catalyst and H2O, which stands in contrast to other systems in which the presence of H2O frequently has detrimental effects on catalysis.

MIL-101 and MIL-101-NH 2 were partially modified to incorporate various functional groups that are capable of forming hydrogen bonds with water. Specifically, MIL-101-NH 2 was partially functionalized with -NHCONHCH 2 CH 3 (-UR2), -NHCOCHCHCOOH (-Mal), or -NH(CH 2 ) 3 SO 3 H (-3SO 3 H) and MIL-101 was partially functionalized with -COOH in order to investigate the effect of these groups on the water sorption properties when compared to the pristine versions. The MIL-101 derivatives were synthesized by either post-synthetic modification of MIL-101-NH 2 or through direct synthesis using a mixed linker strategy. The ratios of the incorporated functional groups were determined by 1 H-NMR analyses and the porosity changes were revealed by N 2 gas adsorption measurements at 77 K. Water sorption isotherms at 298 K conclude that the incorporation of -3SO 3 H enhances the water vapour uptake capacity at a low relative pressure (P/P 0 ¼ 0.30), whereas -UR2 and -Mal retard water adsorption in MIL-101-NH 2 . The partial incorporation of -COOH in MIL-101 exhibits a steeper water uptake at lower pressure (P/P 0 ¼ 0.40) than MIL-101-NH 2 . Interestingly, a greater -COOH content within the MIL-101 framework reduces the water uptake capacity. These results indicate that even partial functionalization of MIL-101 induces noticeably large changes in the water adsorption properties.

The functionalization of UiO-67 with -NH2 groups enhances CO2 and CH4 adsorption at 1 bar and 298 K and positively influences the framework's interaction with water as evidenced by the significant enhancement of water vapour adsorption at 0.1 < P/P0 < 0.3 and 298 K.

This tutorial review gives a synthetic chemistry perspective of magnetic relaxation phenomena through the lens of the reaction-coordinate diagram.

A porous organic framework (PAF-5) impregnated with a polyethylenimine (PEI) displays excellent properties for post-combustion CO2 capture.

Viruses utilize numerous mechanisms to counteract the host's immune response. Interferon production is a major component of the host antiviral response. Many viruses, therefore, produce proteins or RNA molecules that inhibit interferon-induced signal transduction pathways and their associated antiviral effects. Surprisingly, some viruses directly induce expression of interferon-induced genes. SM, an early lytic Epstein-Barr virus (EBV) nuclear protein, was found to specifically increase the expression of several genes (interferonstimulated genes) that are known to be strongly induced by alpha/beta interferons. SM does not directly stimulate alpha/beta interferon secretion but instead induces STAT1, an intermediate step in the interferon signaling pathway. SM is a posttranscriptional activator of gene expression and increases STAT1 mRNA accumulation, particularly that of the functionally distinct STAT1␤ splice variant. SM expression in B lymphocytes is associated with decreased cell proliferation but does not decrease cell viability or induce cell cycle arrest. These results indicate that EBV can specifically induce cellular genes that are normally physiological targets of interferon by inducing components of cytokine signaling pathways. Our findings therefore suggest that some aspects of the interferon response may be positively modulated by infecting viruses. Epstein-Barr virus (EBV), a human gammaherpesvirus, is the agent of infectious mononucleosis and is associated withBurkitt lymphoma, nasopharyngeal carcinoma, and lymphomas in immunosuppressed hosts (for a review, see reference 32). Infection by human herpesviruses of all classes specifically modulates cellular-gene expression. Because herpesviruses establish lifelong infections in the face of a competent immune system, many of the cellular genes affected are components of the innate or adaptive immune response. For example, an EBV immediate-early gene product inhibits gamma interferon (IFN-␥) signaling and down-regulates expression of the IFN-␥ receptor (42).The EBV SM protein is a posttranscriptional gene regulatory protein expressed early during lytic replication (9,12,14,53,66). Homologues of SM are found in herpes simplex virus (HSV), human cytomegalovirus (CMV), varicella-zoster virus, and Kaposi's sarcoma-associated virus (human herpesvirus 8) and act as transcriptional and posttranscriptional regulators (2,10,17,26,29,33,40). During lytic EBV replication, SM is expressed prior to other early genes but after the immediateearly genes BRLF1 and BZLF1. SM enhances the expression of several EBV genes and heterologous genes in cotransfection assays (30,31,39,52,55). Its ability to activate expression of cotransfected genes in a promoter-independent fashion has led to it being described as a promiscuous transactivator. Further studies demonstrated that several genes containing introns were inhibited by SM, whereas intronless genes were activated by SM (52). The majority of cellular genes and latent EBV genes are spliced, whereas most lytic EBV genes are n...

[1] Recently, Shinbori et al. (2004) examined the electric field variations associated with geomagnetic sudden commencements (SC) by using data from the Akebono satellite in the inner magnetosphere (L < 5) and reported the following characteristics of the SC-associated electric field variations. (1) The electric field shows a bipolar change. (2) The initial excursion of the electric field tends to be directed westward. (3) The electric field amplitude does not show a dependence on magnetic local time. By using a global three-dimensional MHD simulation model, we examine how and where such SC-associated electric field variations are established. In our study, we used the SC event that occurred on 21 October 1999, which was caused by a sudden increase in the solar wind dynamic pressure from $3 to $13 nPa. The solar wind and interplanetary magnetic field conditions observed from the Wind satellite near GSM (x, y, z) $ (22, À62, 20) R E are used as the simulation input parameters. The numerical simulation shows that inward flow is first excited near local noon and then flow vortex is generated near the flankside as the solar wind discontinuity is passing over the magnetosphere. Thus, the convection electric field variations change with local time. The vortical structure has a duration of 3-4 min and propagates with a flow speed of $75% of the solar wind speed. The electric fields associated with flow vortices show a bipolar structure. We suggest that the flow vortex in our simulation is associated with the main impulse of SC and that the SC-associated electric fields observed at Akebono are due to the convection electric field.