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  • 1
    Language: English
    In: Chemistry - A European Journal, Dec 11, 2017, Vol.23(69), p.n/a(1)
    Description: To purchase or authenticate to the full-text of this article, please visit this link: http://onlinelibrary.wiley.com/doi/10.1002/chem.201786961/abstract Byline: Philipp Lang, Matthias Schwalbe Keywords: CO.sub.2 reduction; cooperativity; energy transfer; O.sub.2 reduction; water oxidation ***** No abstract is available for this article. *****
    Keywords: Catalysis
    ISSN: 0947-6539
    E-ISSN: 15213765
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  • 2
    Language: English
    In: Chemistry – A European Journal, 11 December 2017, Vol.23(69), pp.17398-17412
    Description: In this Concept article we present the syntheses and application of homo and heterodinuclear “Pacman” compounds. This architecture implies that two metal coordination fragments are brought in close vicinity to each other via a covalent linkage to either support energy transfer between the two units or cooperative transformation of a substrate. Nature has shown that the combination of metal fragments, in particular two different metals, can dramatically improve the efficiency of small molecule activation. We exemplify this strategy for the activation of water, dioxygen and carbon dioxide. Furthermore, we present artificial systems in which a positive effect on the catalytic performance because of the combination of two (different) metal centers could be observed. Thus, Pacman‐type compounds are very well suited as structural and functional models for their biological counterparts. ! (Hetero‐)Pacman architectures can be used to place two (different) metal coordination fragments in close vicinity to each other. This structural motif can either lead to energy or electron‐transfer interactions. In latter case the cooperative activation of small molecules becomes possible that can lead to catalytic applications such as water oxidation and CO or O reduction.
    Keywords: Co 2 Reduction ; Cooperativity ; Energy Transfer ; O 2 Reduction ; Water Oxidation
    ISSN: 0947-6539
    E-ISSN: 1521-3765
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  • 3
    Language: English
    In: Proceedings of the National Academy of Sciences of the United States, Dec 24, 2013, Vol.110(52), p.21089(6)
    Description: The immunological interactions that regulate the T-cell response to chronic viral infection are insufficiently understood. Here we study a cellular interaction that may enhance the antiviral immune response and constrain immunopathology. We analyze the contribution of Qa-1-restricted [CD8.sup.+] regulatory T cells (Treg cells) to antiviral immunity after infection by lymphocytic choriomeningitis virus. These [CD8.sup.+] Treg cells recognize and eliminate target cells through an interaction with the murine class Ib MHC molecule Qa-1 (HLA-E in humans). Using Qa-1 mutant mice (B6 X Qa-1-D227K [B6-DK]) that harbor a single mutation that abrogates binding of Qa-1 peptide to the CD8-TCR (T-cell receptor) complex, we show that disruption of immune suppression mediated by [CD8.sup.+] Treg cells results in robust antiviral immune responses in both acute and chronic viral infection. Enhanced antiviral responses of B6-DK mice were accompanied by increased control of virus, reduced tissue inflammation in the acute phase, and dramatic alleviation of disease in the chronic phase. In addition, [CD8.sup.+] effector T cells in B6-DK mice displayed a less exhausted phenotype characterized by decreased expression of programmed cell death 1 (PD-1), LAG3 (CD223), and 2B4 (CD244) and increased expression of NKG2D (CD314) and killer cell lectin-like receptor subfamily G member 1 (KLRG1). Enhanced antiviral immunity in B6-DK mice reflected, in part, reduced inhibition of [CD8.sup.+] effector cells by [CD8.sup.+] Treg cells. These findings indicate that direct inhibition of effector [CD8.sup.+] T cells by Qa-1-restricted [CD8.sup.+] Treg cells results in increased disease severity and delayed recovery. These data suggest that depletion or inactivation of [CD8.sup.+] Treg cells represents a potentially effective strategy to enhance protective immunity to chronic viral infection. T-cell exhaustion | killer cell Ig-like receptor | immune regulation www.pnas.org/cgi/doi/10.1073/pnas.1320999110
    Keywords: Virus Diseases -- Research ; Virus Diseases -- Analysis ; Virus Diseases -- Health Aspects ; T Cells -- Analysis ; T Cells -- Health Aspects ; Genetic Research -- Analysis ; Genetic Research -- Health Aspects ; Antiviral Agents -- Research ; Antiviral Agents -- Analysis ; Antiviral Agents -- Health Aspects ; Hla Antigens -- Analysis ; Hla Antigens -- Health Aspects ; Immune Response -- Analysis ; Immune Response -- Health Aspects
    ISSN: 0027-8424
    Source: Cengage Learning, Inc.
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  • 4
    Language: English
    In: Proceedings of the National Academy of Sciences of the United States of America, 09 July 2013, Vol.110(28), pp.11433-8
    Description: Protein ectodomain shedding by ADAM17 (a disintegrin and metalloprotease 17), a principal regulator of EGF-receptor signaling and TNFα release, is rapidly and posttranslationally activated by a variety of signaling pathways, and yet little is known about the underlying mechanism. Here, we report that inactive rhomboid protein 2 (iRhom2), recently identified as essential for the maturation of ADAM17 in hematopoietic cells, is crucial for the rapid activation of the shedding of some, but not all substrates of ADAM17. Mature ADAM17 is present in mouse embryonic fibroblasts (mEFs) lacking iRhom2, and yet ADAM17 is unable to support stimulated shedding of several of its substrates, including heparin-binding EGF and Kit ligand 2 in this context. Stimulated shedding of other ADAM17 substrates, such as TGFα, is not affected in iRhom2(-/-) mEFs but can be strongly reduced by treating iRhom2(-/-) mEFs with siRNA against iRhom1. Activation of heparin-binding EGF or Kit ligand 2 shedding by ADAM17 in iRhom2(-/-) mEFs can be rescued by wild-type iRhom2 but not by iRhom2 lacking its N-terminal cytoplasmic domain. The requirement for the cytoplasmic domain of iRhom2 for stimulated shedding by ADAM17 may help explain why the cytoplasmic domain of ADAM17 is not required for stimulated shedding. The functional relevance of iRhom2 in regulating shedding of EGF receptor (EGFR) ligands is established by a lack of lysophasphatidic acid/ADAM17/EGFR-dependent crosstalk with ERK1/2 in iRhom2(-/-) mEFs, and a significant reduction of FGF7/ADAM17/EGFR-stimulated migration of iRhom2(-/-) keratinocytes. Taken together, these findings uncover functions for iRhom2 in the regulation of EGFR signaling and in controlling the activation and substrate selectivity of ADAM17-dependent shedding events.
    Keywords: Adams ; Rhbdf1/2 ; Adam Proteins -- Physiology ; Carrier Proteins -- Physiology
    ISSN: 00278424
    E-ISSN: 1091-6490
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  • 5
    Language: English
    In: Fertility and Sterility, 2011, Vol.95(6), pp.2125.e1-2125.e3
    Description: To present a case of an acute hemoperitoneum caused by a ruptured ovarian cyst in a late twin pregnancy. Case report study. Department of Obstetrics and Gynecology, Medical University of Graz, Austria. A woman with a history of surgery for endometriosis and currently pregnant with dichorionic twins after IVF presented with acute abdominal pain. Serial ultrasound assessment revealed a massive hemoperitoneum that was caused by a ruptured endometriotic ovarian cyst. Emergency laparotomy was performed. Hemostasis. Laparotomy led to operative hemostasis and preterm cesarean section of healthy twins at 27 weeks of gestation. Endometriosis occurs in about 10% of women of reproductive age and carries an infertility rate of up to 50%. Severe endometriosis used to be a rare event in patients with spontaneously conceived pregnancies. However, during the last decade, the increased use of assisted reproductive technologies has led to higher fertility rates in patients with endometriosis and to a higher incidence of multiple gestations. Therefore, the number of pregnant women with endometriosis and associated complications may rise.
    Keywords: Hemoperitoneum ; Endometriosis ; Pregnancy ; Ultrasound ; in Vitro Fertilization ; Medicine
    ISSN: 0015-0282
    E-ISSN: 1556-5653
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  • 6
    Language: English
    In: Proceedings of the National Academy of Sciences of the United States of America, 24 December 2013, Vol.110(52), pp.21089-94
    Description: The immunological interactions that regulate the T-cell response to chronic viral infection are insufficiently understood. Here we study a cellular interaction that may enhance the antiviral immune response and constrain immunopathology. We analyze the contribution of Qa-1-restricted CD8(+) regulatory T cells (Treg cells) to antiviral immunity after infection by lymphocytic choriomeningitis virus. These CD8(+) Treg cells recognize and eliminate target cells through an interaction with the murine class Ib MHC molecule Qa-1 (HLA-E in humans). Using Qa-1 mutant mice (B6.Qa-1-D227K [B6-DK]) that harbor a single mutation that abrogates binding of Qa-1 peptide to the CD8-TCR (T-cell receptor) complex, we show that disruption of immune suppression mediated by CD8(+) Treg cells results in robust antiviral immune responses in both acute and chronic viral infection. Enhanced antiviral responses of B6-DK mice were accompanied by increased control of virus, reduced tissue inflammation in the acute phase, and dramatic alleviation of disease in the chronic phase. In addition, CD8(+) effector T cells in B6-DK mice displayed a less exhausted phenotype characterized by decreased expression of programmed cell death 1 (PD-1), LAG3 (CD223), and 2B4 (CD244) and increased expression of NKG2D (CD314) and killer cell lectin-like receptor subfamily G member 1 (KLRG1). Enhanced antiviral immunity in B6-DK mice reflected, in part, reduced inhibition of CD8(+) effector cells by CD8(+) Treg cells. These findings indicate that direct inhibition of effector CD8(+) T cells by Qa-1-restricted CD8(+) Treg cells results in increased disease severity and delayed recovery. These data suggest that depletion or inactivation of CD8(+) Treg cells represents a potentially effective strategy to enhance protective immunity to chronic viral infection.
    Keywords: T-Cell Exhaustion ; Immune Regulation ; Killer Cell Ig-Like Receptor ; Cd8-Positive T-Lymphocytes -- Immunology ; DNA Virus Infections -- Immunology ; Immunity, Cellular -- Genetics ; T-Lymphocytes, Regulatory -- Immunology
    ISSN: 00278424
    E-ISSN: 1091-6490
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  • 7
    Language: English
    In: Science (New York, N.Y.), 13 January 2012, Vol.335(6065), pp.229-32
    Description: Innate immune responses are vital for pathogen defense but can result in septic shock when excessive. A key mediator of septic shock is tumor necrosis factor-α (TNFα), which is shed from the plasma membrane after cleavage by the TNFα convertase (TACE). We report that the rhomboid family member iRhom2 interacted with TACE and regulated TNFα shedding. iRhom2 was critical for TACE maturation and trafficking to the cell surface in hematopoietic cells. Gene-targeted iRhom2-deficient mice showed reduced serum TNFα in response to lipopolysaccharide (LPS) and could survive a lethal LPS dose. Furthermore, iRhom2-deficient mice failed to control the replication of Listeria monocytogenes. Our study has identified iRhom2 as a regulator of innate immunity that may be an important target for modulating sepsis and pathogen defense.
    Keywords: Immunity, Innate ; Adam Proteins -- Metabolism ; Carrier Proteins -- Metabolism ; Lipopolysaccharides -- Immunology ; Listeriosis -- Immunology ; Shock, Septic -- Immunology ; Tumor Necrosis Factor-Alpha -- Metabolism
    ISSN: 00368075
    E-ISSN: 1095-9203
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  • 8
    Language: English
    In: Proceedings of the National Academy of Sciences of the United States of America, 28 April 2015, Vol.112(17), pp.5521-6
    Description: Urea cycle defects and acute or chronic liver failure are linked to systemic hyperammonemia and often result in cerebral dysfunction and encephalopathy. Although an important role of the liver in ammonia metabolism is widely accepted, the role of ammonia metabolizing pathways in the liver for maintenance of whole-body ammonia homeostasis in vivo remains ill-defined. Here, we show by generation of liver-specific Gln synthetase (GS)-deficient mice that GS in the liver is critically involved in systemic ammonia homeostasis in vivo. Hepatic deletion of GS triggered systemic hyperammonemia, which was associated with cerebral oxidative stress as indicated by increased levels of oxidized RNA and enhanced protein Tyr nitration. Liver-specific GS-deficient mice showed increased locomotion, impaired fear memory, and a slightly reduced life span. In conclusion, the present observations highlight the importance of hepatic GS for maintenance of ammonia homeostasis and establish the liver-specific GS KO mouse as a model with which to study effects of chronic hyperammonemia.
    Keywords: RNA Oxidation ; Glutamine ; Hepatic Encephalopathy ; Metabolic Zonation ; Oxidative Stress ; Glutamate-Ammonia Ligase -- Metabolism ; Hyperammonemia -- Enzymology ; Liver -- Enzymology
    ISSN: 00278424
    E-ISSN: 1091-6490
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  • 9
    Language: English
    In: Proceedings of the National Academy of Sciences of the United States of America, 25 January 2011, Vol.108(4), pp.1555-60
    Description: 14-3-3σ regulates cytokinesis and cell cycle arrest induced by DNA damage but its role in the immune system is unknown. Using gene-targeted 14-3-3σ-deficient (i.e., KO) mice, we studied the role of 14-3-3σ in B-cell functions. Total numbers of B cells were reduced by spontaneous apoptosis of peripheral B cells. Upon B-cell antigen receptor engagement in vitro, KO B cells did not proliferate properly or up-regulate CD86. In response to T cell-independent antigens, KO B cells showed poor secretion of antigen-specific IgM. This deficit led to increased lethality of KO mice after vesicular stomatitis virus infection. KO B cells showed elevated total FOXO transcriptional activity but also increased FOXO1 degradation. Coimmunoprecipitation revealed that endogenous 14-3-3σ protein formed a complex with FOXO1 protein. Our results suggest that 14-3-3σ maintains FOXO1 at a consistent level critical for normal B-cell antigen receptor signaling and B-cell survival.
    Keywords: 14-3-3 Proteins -- Immunology ; B-Lymphocytes -- Immunology ; Forkhead Transcription Factors -- Immunology ; Homeostasis -- Immunology
    ISSN: 00278424
    E-ISSN: 1091-6490
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  • 10
    Language: English
    In: Chemistry – A European Journal, 02 March 2018, Vol.24(13), pp.3225-3233
    Description: A series of heterodinuclear complexes, with M=H, Zn, Cu or Co, X=Cl or I, has been synthesized, and first results on their photocatalytic activity in visible light driven proton reduction are presented. The compounds are based on a phenanthroline extended ‐tetramesityl‐porphyrin bridging ligand () incorporating different metal centers in the porphyrin moiety, which functions as a photosensitizer unit. The well‐known catalytically active PtX fragment resides in the phenanthroline coordination pocket. The synthesis was optimized, compounds were fully characterized and a solid‐state structure could be obtained for selected complexes. Photocatalytic studies in acetonitrile/water mixtures using triethylamine as sacrificial electron donor showed that the activity of the complexes depends strongly on the metal center in the porphyrin moiety as well as the halogen ions bound at the platinum(II) center. : A series of hetero dinuclear phenanthroline‐extended porphyrin complexes was synthesized and fully characterized. Beside the discussion of the analytical data as well as two X‐ray structures, first photocatalytic experiments were implemented. Here we discuss the behavior during irradiation and compare the results with structurally related compounds.
    Keywords: Hydrogen Production ; Macrocycles ; Photocatalysis ; Platinum ; Porphyrins
    ISSN: 0947-6539
    E-ISSN: 1521-3765
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