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      • Angiogenesis in Bone Regeneration: Tailored Calcium Release in Hybrid Fibrous Scaffolds

        Castañ,o, Oscar,Sachot, Nade&#x300,ge,Xuriguera, Elena,Engel, Elisabeth,Planell, Josep A.,Park, Jeong-Hui,Jin, Guang-Zhen,Kim, Tae-Hyun,Kim, Joong-Hyun,Kim, Hae-Won American Chemical Society 2014 ACS APPLIED MATERIALS & INTERFACES Vol.6 No.10

        <P>In bone regeneration, silicon-based calcium phosphate glasses (Bioglasses) have been widely used since the 1970s. However, they dissolve very slowly because of their high amount of Si (SiO<SUB>2</SUB> > 45%). Recently, our group has found that calcium ions released by the degradation of glasses in which the job of silicon is done by just 5% of TiO<SUB>2</SUB> are effective angiogenic promoters, because of their stimulation of a cell-membrane calcium sensing receptor (CaSR). Based on this, other focused tests on angiogenesis have found that Bioglasses also have the potential to be angiogenic promoters even with high contents of silicon (80%); however, their slow degradation is still a problem, as the levels of silicon cannot be decreased any lower than 45%. In this work, we propose a new generation of hybrid organically modified glasses, ormoglasses, that enable the levels of silicon to be reduced, therefore speeding up the degradation process. Using electrospinning as a faithful way to mimic the extracellular matrix (ECM), we successfully produced hybrid fibrous mats with three different contents of Si (40, 52, and 70%), and thus three different calcium ion release rates, using an ormoglass–polycaprolactone blend approach. These mats offered a good platform to evaluate different calcium release rates as osteogenic promoters in an in vivo subcutaneous environment. Complementary data were collected to complement Ca<SUP>2+</SUP> release analysis, such as stiffness evaluation by AFM, ζ-potential, morphology evaluation by FESEM, proliferation and differentiation analysis, as well as in vivo subcutaneous implantations. Material and biological characterization suggested that compositions of organic/inorganic hybrid materials with a Si content equivalent to 40%, which were also those that released more calcium, were osteogenic. They also showed a greater ability to form blood vessels. These results suggest that Si-based ormoglasses can be considered an efficient tool for calcium release modulation, which could play a key role in the angiogenic promoting process.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/aamick/2014/aamick.2014.6.issue-10/am500885v/production/images/medium/am-2014-00885v_0010.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/am500885v'>ACS Electronic Supporting Info</A></P>

      • SCISCIESCOPUS

        Syngas Purification by Porous Amino-Functionalized Titanium Terephthalate MIL-125

        Regufe, Maria Joã,o,Tamajon, Javier,Ribeiro, Ana M.,Ferreira, Alexandre,Lee, U-Hwang,Hwang, Young Kyu,Chang, Jong-San,Serre, Christian,Loureiro, Jose&#x301,M.,Rodrigues, Ali&#x301,rio E. American Chemical Society 2015 ENERGY AND FUELS Vol.29 No.7

        <P>The adsorption equilibrium of carbon dioxide (CO<SUB>2</SUB>), carbon monoxide (CO), nitrogen (N<SUB>2</SUB>), methane (CH<SUB>4</SUB>), and hydrogen (H<SUB>2</SUB>) was studied at 303, 323, and 343 K and pressures up to 7 bar in titanium-based metal–organic framework (MOF) granulates, amino-functionalized titanium terephthalate MIL-125(Ti)_NH<SUB>2</SUB>. The affinity of the different adsorbates toward the adsorbent presented the following order: CO<SUB>2</SUB> > CH<SUB>4</SUB> > CO > N<SUB>2</SUB> > H<SUB>2</SUB>, from the most adsorbed to the least adsorbed component. Subsequently, adsorption kinetics and multicomponent adsorption equilibrium were studied by means of single, binary, and ternary breakthrough curves at 323 K and 4.5 bar with different feed mixtures. Both studies are complementary and aim the syngas purification for two different applications, hydrogen production and H<SUB>2</SUB>/CO composition adjustment, to be used as feed in the Fischer–Tropsch processes. The isosteric heats were calculated from the adsorption equilibrium isotherms and are 21.9 kJ mol<SUP>–1</SUP> for CO<SUB>2</SUB>, 14.6 kJ mol<SUP>–1</SUP> for CH<SUB>4</SUB>, 13.4 kJ mol<SUP>–1</SUP> for CO, and 11.7 kJ mol<SUP>–1</SUP> for N<SUB>2</SUB>. In the overall pressure and temperature range, the adsorption equilibrium isotherms were well-regressed against the Langmuir model. The multicomponent breakthrough experimental results allowed for validation of the adsorption equilibrium predicted by the multicomponent extension of the Langmuir isotherm and validation of the fixed-bed mathematical model. To conclude, two pressure swing adsorption (PSA) cycles were designed and performed experimentally, one for hydrogen purification from a 30/70% CO<SUB>2</SUB>/H<SUB>2</SUB> mixture (hydrogen purity was 100% with a recovery of 23.5%) and a second PSA cycle to obtain a light product with a H<SUB>2</SUB>/CO ratio between 2.2 and 2.4 to feed to Fischer–Tropsch processes. The experimental cycle produced a light stream with a H<SUB>2</SUB>/CO ratio of 2.3 and a CO<SUB>2</SUB>-enriched stream with 86.6% purity as a heavy product. The CO<SUB>2</SUB> recovery was 93.5%.</P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/ef5b00975'>ACS Electronic Supporting Info</A></P>

      • SCISCIESCOPUS

        THE SCALING RELATIONS AND STAR FORMATION LAWS OF MINI-STARBURST COMPLEXES

        Nguye&#x302,̃,n-Lu’o, Quang,Nguye&#x302,̃,n, Hans V. V.,Motte, Fredé,rique,Schneider, Nicola,Fujii, Michiko,Louvet, Fabien,Hill, Tracey,Sanhueza, Patricio,Chibueze, James O.,Didelon, P American Astronomical Society 2016 The Astrophysical journal Vol.833 No.1

        <P>The scaling relations and star formation laws for molecular cloud complexes (MCCs) in the Milky Way are investigated. MCCs are mostly large (R> 50 pc), massive (similar to 106 M circle dot) gravitationally unbound cloud structures. We compare their masses M-gas, mass surface densities Sigma(Mgas), radii R, velocity dispersions sigma, star formation rates (SFRs), and SFR densities Sigma(SFR) with those of structures ranging from cores, clumps, and giant molecular clouds, to MCCs, and galaxies, spanning eight orders of magnitudes in size and 13 orders of magnitudes in mass. This results in the following universal relations: sigma similar to R-0.5, M-gas similar to R-2, Sigma(SFR) similar to Sigma(1.5)(Mgas) , SFR similar to M-gas(0.9) , and SFR similar to sigma(2.7) Variations in the slopes and coefficients of these relations are found at individual scales, signifying different physics acting at different scales. Additionally, there are breaks at the MCC scale in the sigma-R relation and between starburst and normal star-forming objects in the SFR-M-gas and Sigma(SFR)-Sigma(Mgas) gas relations. Therefore, we propose to use the Schmidt-Kennicutt diagram to distinguish starburst from normal star-forming structures by applying a SMgas threshold of similar to 100M circle dot pc (2) and a Sigma(SFR) threshold of 1M circle dot yr (1) kpc (2). Mini-starburst complexes are gravitationally unbound MCCs that have enhanced Sigma(SFR) (> 1M circle dot yr(-1) kpc(-2)), probably caused by dynamic events such as radiation pressure, colliding flows, or spiral arm gravitational instability. Because of dynamical evolution, gravitational boundedness does not play a significant role in regulating the star formation activity of MCCs, especially the mini-starburst complexes, which leads to the dynamical formation of massive stars and clusters. We emphasize the importance of understanding mini-starbursts in investigating the physics of starburst galaxies.</P>

      • SCISCIESCOPUS

        Local homeoprotein diffusion can stabilize boundaries generated by graded positional cues

        Quio&#x301,ñ,inao, Cristo&#x301,bal,Prochiantz, Alain,Touboul, Jonathan The Company of Biologists Limited 2015 Development (Cambridge) Vol.142 No.10

        <P>Boundary formation in the developing neuroepithelium decides on the position and size of compartments in the adult nervous system. In this study, we start from the French Flag model proposed by Lewis Wolpert, in which boundaries are formed through the combination of morphogen diffusion and of thresholds in cell responses. In contemporary terms, a response is characterized by the expression of cell-autonomous transcription factors, very often of the homeoprotein family. Theoretical studies suggest that this sole mechanism results in the formation of boundaries of imprecise shapes and positions. Alan Turing, on the other hand, proposed a model whereby two morphogens that exhibit self-activation and reciprocal inhibition, and are uniformly distributed and diffuse at different rates lead to the formation of territories of unpredictable shapes and positions but with sharp boundaries (the ‘leopard spots’). Here, we have combined the two models and compared the stability of boundaries when the hypothesis of local homeoprotein intercellular diffusion is, or is not, introduced in the equations. We find that the addition of homeoprotein local diffusion leads to a dramatic stabilization of the positioning of the boundary, even when other parameters are significantly modified. This novel Turing/Wolpert combined model has thus important theoretical consequences for our understanding of the role of the intercellular diffusion of homeoproteins in the developmental robustness of and the changes that take place in the course of evolution.</P><P><B>SUMMARY:</B> Mathematical modeling and simulations suggest that the local diffusion of homeoproteins during neuronal differentiation is enough to create smooth and reliable boundaries between cortical areas.</P>

      • Atomically Thin Ohmic Edge Contacts Between Two-Dimensional Materials

        Guimarã,es, Marcos H. D.,Gao, Hui,Han, Yimo,Kang, Kibum,Xie, Saien,Kim, Cheol-Joo,Muller, David A.,Ralph, Daniel C.,Park, Jiwoong American Chemical Society 2016 ACS NANO Vol.10 No.6

        <P>With the decrease of the dimensions of electronic devices, the role played by electrical contacts is ever increasing, eventually coming to dominate the overall device volume and total resistance. This is especially problematic for monolayers of semiconducting transition-metal dichalcogenides (TMDs), which are promising candidates for atomically thin electronics. Ideal electrical contacts to them would require the use of similarly thin electrode materials while maintaining low contact resistances. Here we report a scalable method to fabricate ohmic graphene edge contacts to two representative monolayer TMDs, MoS<SUB>2</SUB> and WS<SUB>2</SUB>. The graphene and TMD layer are laterally connected with wafer-scale homogeneity, no observable overlap or gap, and a low average contact resistance of 30 kΩ·μm. The resulting graphene edge contacts show linear current–voltage (<I>I</I>–<I>V</I>) characteristics at room temperature, with ohmic behavior maintained down to liquid helium temperatures.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/ancac3/2016/ancac3.2016.10.issue-6/acsnano.6b02879/production/images/medium/nn-2016-02879m_0007.gif'></P><P><A href='http://pubs.acs.org/doi/suppl/10.1021/nn6b02879'>ACS Electronic Supporting Info</A></P>

      • Solid State Luminescence Enhancement in π-Conjugated Materials: Unraveling the Mechanism beyond the Framework of AIE/AIEE

        Shi, Junqing,Aguilar Suarez, Luis E.,Yoon, Seong-Jun,Varghese, Shinto,Serpa, Carlos,Park, Soo Young,Lu&#x308,er, Larry,Roca-Sanjua&#x301,n, Daniel,Milia&#x301,n-Medina, Begoñ,a,Gierschner, Johan American Chemical Society 2017 JOURNAL OF PHYSICAL CHEMISTRY C - Vol.121 No.41

        <P>Solid state luminescence enhancement (SLE) of conjugated organic materials has had a great impact in materials science, but a deep understanding has been rather limited to date. Here, we investigate a prototype example of SLE materials, cyano-substituted distyrylbenzene (DCS), by varying systematically and subtly the substitution pattern (inter alia of the position of the cyano-substituent) to give largely different photoresponse in fluid and solid solution as well in the crystalline state. The combination of quantitative (ultra)fast optical spectroscopic techniques, appropriate quantum-chemical methods, and structural (X-ray) data allows us to elucidate and rationalize all details of the SLE process, including steric versus electronic factors, radiative versus nonradiative decay channels, and intra- versus intermolecular contributions, providing a first holistic picture of SLE.</P>

      • Numerical Modeling of the Releases of <sup>90</sup>Sr from Fukushima to the Ocean: An Evaluation of the Source Term

        Peria&#x301,ñ,ez, R.,Suh, Kyung-Suk,Byung-Il, Min,Casacuberta, N.,Masque&#x301,, P. American Chemical Society 2013 Environmental science & technology Vol.47 No.21

        <P>A numerical model consisting of a 3D advection/diffusion equation, including uptake/release reactions between water and sediments described in a dynamic way, has been applied to simulate the marine releases of <SUP>90</SUP>Sr from the Fukushima power plant after the March 2011 tsunami. This is a relevant issue since <SUP>90</SUP>Sr releases are still occurring. The model used here had been successfully applied to simulate <SUP>137</SUP>Cs releases. Assuming that the temporal trend of <SUP>90</SUP>Sr releases was the same as for <SUP>137</SUP>Cs during the four months after the accident simulated here, the source term could be evaluated, resulting in a total release of 80 TBq of <SUP>90</SUP>Sr until the end of June, which is in the lower range of previous estimates. Computed vertical profiles of <SUP>90</SUP>Sr in the water column have been compared with measured ones. The <SUP>90</SUP>Sr inventories within the model domain have also been calculated for the water column and for bed sediments. Maximum dissolved inventory (obtained for April 10th, 2011) within the model domain results in about 58 TBq. Inventories in bed sediments are 3 orders of magnitude lower than in the water column due to the low reactivity of this radionuclide. <SUP>90</SUP>Sr/<SUP>137</SUP>Cs ratios in the ocean have also been calculated and compared with measured values, showing both spatial and temporal variations.</P><P><B>Graphic Abstract</B> <IMG SRC='http://pubs.acs.org/appl/literatum/publisher/achs/journals/content/esthag/2013/esthag.2013.47.issue-21/es4031408/production/images/medium/es-2013-031408_0010.gif'></P>

      • Mesenchymal Cell–Specific MyD88 Signaling Promotes Systemic Dissemination of <i>Salmonella Typhimurium</i> via Inflammatory Monocytes

        Kim, Donghyun,Seo, Sang-Uk,Zeng, Melody Y.,Kim, Wan-Uk,Kamada, Nobuhiko,Inohara, Naohiro,Nu&#x301,u&#x301,ñ,ez, Gabriel The American Association of Immunologists, Inc. 2017 JOURNAL OF IMMUNOLOGY Vol.199 No.4

        <P>Enteric pathogens including Salmonella enteric serovar Typhimurium can breach the epithelial barrier of the host and spread to systemic tissues. In response to infection, the host activates innate immune receptors via the signaling molecule MyD88, which induces protective inflammatory and antimicrobial responses. Most of these innate immune responses have been studied in hematopoietic cells, but the role of MyD88 signaling in other cell types remains poorly understood. Surprisingly, we found that Dermo1-Cre;Myd88(fl/fl) mice with mesenchymal cell-specific deficiency of MyD88 were less susceptible to orogastric and i.p. S. Typhimurium infection than their Myd88(fl/fl) littermates. The reduced susceptibility of Dermo1-Cre; Myd88(fl/fl) mice to infection was associated with lower loads of S. Typhimurium in the liver and spleen. Mutant analyses revealed that S. Typhimurium employs its virulence type III secretion system 2 to promote its growth through MyD88 signaling pathways in mesenchymal cells. Inflammatory monocytes function as a major cell population for systemic dissemination of S. Typhimurium. Mechanistically, mesenchymal cell-specific MyD88 signaling promoted CCL2 production in the liver and spleen and recruitment of inflammatory monocytes to systemic organs in response to S. Typhimurium infection. Consistently, MyD88 signaling in mesenchymal cells enhanced the number of phagocytes including Ly6C(hi)Ly6G(-) inflammatory monocytes harboring S. Typhimurium in the liver. These results suggest that S. Typhimurium promotes its systemic growth and dissemination through MyD88 signaling pathways in mesenchymal cells.</P>

      • Dual-Color Emissive Upconversion Nanocapsules for Differential Cancer Bioimaging <i>In Vivo</i>

        Kwon, Oh Seok,Song, Hyun Seok,Conde, Joã,o,Kim, Hyoung-il,Artzi, Natalie,Kim, Jae-Hong American Chemical Society 2016 ACS NANO Vol.10 No.1

        <P>Early diagnosis of tumor malignancy is crucial for timely cancer treatment aimed at imparting desired clinical outcomes. The traditional fluorescence based imaging is unfortunately faced with challenges such as low tissue penetration and background autofluorescence. Upconversion (UC)-based bioimaging can overcome these limitations as their excitation occurs at lower frequencies and the emission at higher frequencies. In this study, multifunctional silica -based nanocapsules were synthesized to encapsulate two distinct triplet triplet annihilation UC chromophore pairs. Each nanocapsule emits different colors, blue or green, following a red light excitation. These nanocapsules were further conjugated with either antibodies or peptides to selectively target breast or colon cancer cells, respectively. Both in vitro and in vivo experimental results herein demonstrate cancer -specific and differential -color imaging from single wavelength excitation as well as far greater accumulation at targeted tumor sites than that due to the enhanced permeability and retention effect. This approach can be used to host a variety of chromophore pairs for various tumor -specific, color -coding scenarios and can be employed for diagnosis of a wide range of cancer types within the heterogeneous tumor microenvironment.</P>

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