pinecone/core-2020-05-10-deduplication huggingface dataset:
PST-1: A Synthetic Small-Pore Zeolite that Selectively Adsorbs H2

Angewandte Chemie, International Edition 2009, 48, 6647-6649. Includes supplementary information. This is the pre-peer reviewed version of the following article: FULL CITE, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/anie.200903336/fullA synthetic potassium gallosilicate natrolite with Si/Ga = 1.28 denoted PST-1 was found to selectively adsorb the smallest gases, especially H2, and hence to discriminate them from slightly larger molecules like Ar or CO2. Due to the remarkable easiness of its dehydration and great (hydro)thermal stability, PST-1 could be a potential candidate for fast, selective H2 and/ or He separation processes based on PSA or membrane technology.KOSEF (R0A-2007-000-20050-0) and CDRSRC (16-2008-02-005-01)Peer reviewe
Mechanistic Insights into the Formation of InP Quantum Dots

The molecular mechanism of InP colloidal quantum dot (QD) syntheses was investigated by NMR spectroscopy. Unlike methods for monodisperse PbSe and CdSe, existing InP syntheses result in total depletion of molecular phosphorous species following nucleation, so QD growth is due exclusively to non-molecular ripening. Amines inhibit precursor depletion by solvation (see picture), contrary to previous reports.MIT-Harvard Center for Cancer Nanotechnology Excellence (National Institutes of Health (U.S.) 1U54-CA119349)United States. Army Research Office (ISN W911NF-07-D-0004)Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (CHE-980806)Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (DBI-9729592)National Science Foundation (U.S.). Graduate Research Fellowship Progra
A Secreted Enzyme Reporter System for MRI

An important goal in modern biology is to understand how molecular processes commonly studied at the cellular level give rise to physiological functions in complex tissues and organisms. Non-invasive imaging of gene-expression patterns in whole animals could provide information critical to this end, but current methods lack sensitivity and spatiotemporal precision. Enzymatic reporter systems detectable by magnetic resonance imaging (MRI) address these limitations by combining the relatively high spatial and temporal resolution of MRI with the ability of each genetically expressed enzyme to generate many MRI-detectable product molecules.1, 2 A challenge with the imaging-based detection of some of the most popular reporter enzymes is the need to deliver MRI probes to their sites of action within cells. Herein we describe a new reporter-gene system for MRI that relieves this problem by harnessing an extracellular enzyme, the mammalian secreted alkaline phosphatase (SEAP).National Institutes of Health (U.S.) (grant DP2-OD002114
Selective knockout of gold active sites

This is the final manuscript version, made available by kind permission of Wiley-VCH Verlag GmbH & Co. KGaA. The definitive version is available at: http://doi.wiley.com/10.1002/anie.201000485It has long been known that defects on a gold surface play an important role in\ud
electrocatalysis, but the precise mechanism has always been unclear. This work\ud
indicates that the defect sites provide partially filled d-orbitals that stabilize freeradical\ud
intermediates. Strong evidence for this hypothesis is that the sites can be\ud
selectively knocked out by treatment with OH• radicals generated by Fenton's reagent.\ud
The knockout effect is demonstrated using oxygen reduction, hydrogen reduction, and\ud
the redox electrochemistry of hydroquinone
Reversible switching of surface texture by hydrogen intercalation

The interaction of atomic hydrogen with a single layer of hexagonal boron
nitride on rhodium leads to a removal of the h-BN surface corrugation. The
process is reversible as the hydrogen may be expelled by annealing to about 500
K whereupon the texture on the nanometer scale is restored. This effect is
traced back to hydrogen intercalation. It is expected to have implications for
applications, like the storage of hydrogen, the peeling of sp2-hybridized
layers from solid substrates or the control of the wetting angle, to name a
few.Comment: 4 pages and 4 figure
Anomalous Surface Compositions of Stoichiometric Mixed Oxide Compounds

The surface compositions of bulk mixed metal oxides stoichiometric vanadate and molybdate compounds have been systematically examined, for the first time, by combined synchroton-based depth-resolved XPS profile analysis, conventional XPS and LEIS spectroscopy. The outer surfaces of many, but not all, of the bulk mixed vanadates and molybdates tend to be enriched with surface VOx and MoOx species approaching monolayer coverage. Furthermore, this surface enrichment phenomenon can be dramatically enhanced in the presence of minor amount of alkali impurities. These new findings have significant implications for the fundamental understanding of how bulk mixed oxide materials function in numerous technical applications.Fil: Merzlikin, Sergiy V. . Ruhr-Universitt Bochum, Lehrstuhl fr Technische Chemie; AlemaniaFil: Tolkachev, Nikolay N. . Russian Academy of Sciences, N. D. Zelinsky Institute of Organic Chemistry; RusiaFil: Briand, Laura Estefania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas; ArgentinaFil: Strunskus,Thomas . Ruhr-Universitt Bochum, Lehrstuhl Physikalische Chemie; AlemaniaFil: Wöll, Christof. Ruhr-Universitt Bochum, Lehrstuhl Physikalische Chemie; AlemaniaFil:  Wachs, Israel E..  Lehigh University 
Bethlehem, Department of Chemical Engineering, Operando Molecular Spectroscopy and Catalysis Laboratory; Estados UnidosFil: Grüenert, Wolfgang . Ruhr-Universitt Bochum, Lehrstuhl fr Technische Chemie; Alemani
The next generation of advanced spectroscopy : surface enhanced raman scattering from metal nanoparticles

Surface enhanced Raman scattering (SERS) has enjoyed an ever growing research base since its discovery with the number of papers published using the technique and investigating the basis behind it growing exponentially year by year.[1] SERS is an advancement of Raman scattering which overcomes some of the limitations of normal Raman scattering. Raman scattering is a vibrational spectroscopy which gives molecularly specific information relating to specific molecular species. The disadvantage of Raman scattering is that it is an inherently weak process, however it can be used in aqueous solutions, due to water being a weak Raman scatterer, lending itself to analysis and study of molecules in aqueous solution including the study of biomolecules. Another major disadvantage is the fluorescence which often accompanies Raman scattering and can sometimes overwhelm the bands in the spectrum rendering the experiment useless. To overcome this, the phenomenon of surface enhanced Raman scattering can be used
A role for microbial palladium nanoparticles in extracellular electron transfer.

Herein we have demonstrated a DET mechanism used by D. desulfuricans; where the periplasmic cytochromes and hydrogenases play an important role, and Pd nanoparticles bound to the microbes may participate in the electron transfer process. The present work is of importance not only for the fundamental studies of electron transfer processes in microbial physiology and ecology, but also for increased understanding and improvement of the performance of bioelectrochemical techniques e.g. precious metals are extensively used and important catalysts, and therefore present in many industry processing wastewaters. Bio-nanoparticles can oxidize in situ metabolites e.g. H2, formate and ethanol in the anode chambers, while also acting as cathodic catalysts for the oxygen reduction reaction[23]. In addition, this study indicates the feasibility of using bioelectrochemical systems for metal immobilization, recovery or detoxificatio
A Nanoparticle Size Series for In Vivo Fluorescence Imaging

A nanoparticle toolset was created within the size limits of 10–150 nm for probing size-dependent nanoparticle distribution in solid tumors. By using multiphoton intravital microscopy, the particles were tracked both spatially and temporally in the same tumor grown in a transparent window model.National Cancer Institute (U.S.) (Grant R01-CA126642)MIT-Harvard Center for Cancer Nanotechnology Excellence (National Institutes of Health (U.S.) 1U54-CA119349)Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (CHE-980806)Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (DBI-9729592)Massachusetts Institute of Technology. Institute for Soldier Nanotechnologies (W911NF-07-D-0004)National Science Foundation (U.S.). Materials Research Science and Engineering Centers (Program) (DMR-0117795)National Science Foundation (U.S.). Climate Research Division (CHE-0714189)National Science Foundation (U.S.). Graduate Research Fellowship ProgramNovartis Foundation (Fellow of the Life Sciences Research Foundation
Alkyl-Alkyl Suzuki Cross-Coupling of Unactivated Secondary Alkyl Chlorides

No such thing as a problem substrate! In a reaction designed specifically for the title substrates C-C coupling with alkyl boranes occurred in good yield at room temperature with commercially available catalyst components (see scheme). This versatile method is also suitable for Suzuki reactions of secondary and primary alkyl bromides and iodides, as well as primary alkyl chlorides.National Institute of General Medical Sciences (U.S.) (Grant R01-GM62871)Eli Lilly and Company (Fellowship)Martin Family Society of Fellows for Sustainability (Fellowship)Merck Research LaboratoriesNovartis (Firm
Ligand-clustered “patchy” nanoparticles for modulated cellular uptake and in vivo tumor targeting

A matter of presentation: The manner in which polyvalent ligands are presented to a cell—homogeneously or in spatially defined groupings on a nanoparticle surface—may play an important role in cellular uptake. This aspect is investigated for the first time using a linear dendritic polymer construct to pattern the surfaces of nanoparticles with variable-sized ligand clusters in different spatial arrangements.Author Manuscript: 2012 August 05.National Institutes of Health (U.S.) (NIH NIBIB Grant 5R01EB008082-02)MIT-Harvard Center of Cancer Nanotechnology ExcellenceNational Science Foundation (U.S.
Chemistry and the Worm: Caenorhabditis elegans as a Platform for Integrating Chemical and Biological Research

This Review discusses the potential usefulness of the worm Caenorhabditis elegans as a model organism for chemists interested in studying living systems. C. elegans, a 1 mm long roundworm, is a popular model organism in almost all areas of modern biology. The worm has several features that make it attractive for biology: it is small (<1000 cells), transparent, and genetically tractable. Despite its simplicity, the worm exhibits complex phenotypes associated with multicellularity: the worm has differentiated cells and organs, it ages and has a well-defined lifespan, and it is capable of learning and remembering. This Review argues that the balance between simplicity and complexity in the worm will make it a useful tool in determining the relationship between molecular-scale phenomena and organism-level phenomena, such as aging, behavior, cognition, and disease. Following an introduction to worm biology, the Review provides examples of current research with C. elegans that is chemically relevant. It also describes tools—biological, chemical, and physical—that are available to researchers studying the worm.Chemistry and Chemical Biolog
Safe and Efficient Tetrazole Synthesis in a Continuous Flow Microreactor

Safer flow: The synthesis of 5-substituted tetrazoles in flow (see scheme) is safe, efficient, scalable, requires no metal promoter, and uses a near-equimolar amount of NaN[subscript 3], yet nonetheless displays a broad substrate scope. The hazards associated with HN[subscript 3] are essentially eliminated, shock-sensitive metal azides such as Zn(N[subscript 3])[subscript 2] are avoided, and residual NaN[subscript 3] is quenched in-line with NaNO[subscript 2].Novartis Foundation (MIT Center for Continuous Manufacturing
Mild and selective H/D exchange at the β position of aromatic α-olefins by N-heterocyclic carbene-hydride-rhodium catalysts

Pacman bites selectively! Stable rhodium(III)-N-heterocyclic carbene-hydride complexes (Pacman-like catalysts) are highly active and selective catalysts for H/D exchange at the β position of aromatic α-olefins (see picture). The interplay between bulky N-heterocyclic carbene and quinolinate ligands determines the size of the steric window responsible for this selectivity.Financial support from the MICINN of Spain (project numbers CTQ2009-08089 and CTQ2010-15221), the ARAID Foundation under the program “jóvenes investigadores”, and CONSOLIDER INGENIO-2010 program, under the projects MULTICAT (CSD2009-00050) and Factoría de Cristalización (CSD2006-0015) is gratefully acknowledged. R.C. thanks the CSIC and the European Social Fund for his Research Contract in the framework of the “Ramón y Cajal” program.Peer Reviewe
Light-Triggered Myosin Activation for Probing Dynamic Cellular Processes

Shining light on myosin: The incorporation of a caging group onto the essential phosphoserine residue of myosin by protein semisynthesis enables light-triggered activation of the protein (see picture). Caging eliminates the myosin activity, but exposure to 365 nm light restores its function to native levels. The caged protein can also be introduced into cells to facilitate studies of myosin with precise spatial and temporal resolution.American Heart Association (Fellowship)National Institutes of Health (U.S.) (NIH Cell Migration Consortium (GM064346))National Institute of General Medical Sciences (U.S.) (Biotechnology Training Grant
Use of Thin Sectioning (Nanoskiving) to Fabricate Nanostructures for Electronic and Optical Applications

This Review discusses nanoskiving—a simple and inexpensive method of nanofabrication, which minimizes requirements for access to cleanrooms and associated facilities, and which makes it possible to fabricate nanostructures from materials, and of geometries, to which more familiar methods of nanofabrication are not applicable. Nanoskiving requires three steps: 1) deposition of a metallic, semiconducting, ceramic, or polymeric thin film onto an epoxy substrate; 2) embedding this film in epoxy, to form an epoxy block, with the film as an inclusion; and 3) sectioning the epoxy block into slabs with an ultramicrotome. These slabs, which can be 30 nm–10 μm thick, contain nanostructures whose lateral dimensions are equal to the thicknesses of the embedded thin films. Electronic applications of structures produced by this method include nanoelectrodes for electrochemistry, chemoresistive nanowires, and heterostructures of organic semiconductors. Optical applications include surface plasmon resonators, plasmonic waveguides, and frequency-selective surfaces.Chemistry and Chemical Biolog
Pan-Src Family Kinase Inhibitors Replace Sox2 during the Direct Reprogramming of Somatic Cells

Small molecules do the job: Somatic cells are reprogrammed into iPS cells upon ectopic expression of Oct4, Sox2, Klf4 and c-Myc. Application of a cell-based, high-throughput chemical screen led to the identification of Src family kinase (SFK) inhibitors as chemical replacements for retroviral Sox2 delivery. These compounds are used to study the mechanisms underlying direct reprogramming and may ultimately help to bring iPS cell technology one step closer to clinical application.National Institutes of Health (U.S.) (Grant HD 045022)National Institutes of Health (U.S.) (Grant 5 R37A084198
Pd-Catalyzed Synthesis of Ar-SCF3 Compounds under Mild Conditions

Good to excellent yields of aryl trifluoromethyl sulfides, which are an important class of compounds in both the pharmaceutical and agrochemical areas, can be achieved under mild conditions by the Pd-catalyzed reaction of aryl bromides with a trifluoromethylthiolate nucleophile (see scheme).National Institutes of Health (U.S.) (GM-58160)American Society for Engineering Education. National Defense Science and Engineering Graduate Fellowship (32 CFR 168a)National Science Foundation (U.S.) (CHE-980861
Cryogenic magnetocaloric effect in a ferromagnetic molecular dimer

El pdf del artículo es la versión post-print.Molecoolers: An unprecedentedly large cryogenic magnetocaloric effect is observed in gadolinium acetate tetrahydrate (see picture, Gd pink, O red, C gray). The change in its magnetic entropy is ascribed to the high magnetic density combined with dominant ferromagnetism. For the first time in a molecular complex, direct measurements of the magnetocaloric effect corroborate indirect estimates based on heat capacity and magnetization.This work was supported by the Spanish MICINN through grants MAT2009-13977-C03, MAT2007-61621 and CSD2007-00010.Peer Reviewe
Developing synthetic approaches with non-innocent metalloligands: Easy access to Ir I/Pd 0 and Ir I/Pd 0/Ir I cores

Guilty as charged is the verdict for anionic Ir complex [Ir(bpa-2 H)(cod)] - in its reactions with Pd II compounds. The net transfer of two electrons from the Ir complex to Pd allows easy preparation of di- and trinuclear Ï€-imine-coordinated Pd 0 compounds such as [{Ir(PyCH 2NCHPy)(cod)} 2Pd] (see picture; C white, Ir red, N blue, Pd yellow). bpa-2 H: doubly deprotonated form of N,N-bis(2-picolyl)amine (bpa); cod: 1,5-cyclooctadiene. Â© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.The generous financial support from MICINN/FEDER (Project CTQ2008-03860) and Gobierno de Aragón (GA, Project: PI 155/08) is gratefully acknowledged. L.A. and P.R. thank MICINN/FEDER for a fellowship and a post-doctoral contract, respectively.Peer Reviewe
Copper-Catalyzed Trifluoromethylation of Unactivated Olefins

Activating the inactive: A copper-catalyzed allylic trifluoromethylation of unactivated terminal olefins proceeds under mild conditions to produce linear allylic trifluoromethylated products with high E/Z selectivity (see scheme). The reaction can be applied to a range of substrates bearing numerous functional groups. Furthermore, the reaction is scalable and amenable to a benchtop setup.National Institutes of Health (U.S.) (GM46059)National Institutes of Health (U.S.) (Postdoctoral Fellowship F32GM093532)National Science Foundation (U.S.) (Grant ACHE-9808061)National Science Foundation (U.S.) (Grant DBI-9729592)National Institutes of Health (U.S.) (Grant 1S10RR13886-01
Fluorescent Nanorods and Nanospheres for Real-Time In Vivo Probing of Nanoparticle Shape-Dependent Tumor Penetration

Shape dependent: Fluorescent quantum-dot-based nanospheres and nanorods with identical hydrodynamic size and surface properties but different aspect ratios were developed for real-time in vivo tumor imaging. The nanorods exhibited superior transport and distribution into mammary tumors in vivo versus nanospheres of similar plasma half-life.National Cancer Institute (U.S.) (Grant Number R01-CA126642)MIT-Harvard Center for Cancer Nanotechnology Excellence (1U54-CA119349)Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (CHE-980806)Massachusetts Institute of Technology. Dept. of Chemistry Instrumentation Facility (DBI-9729592)ISN (W911NF-07-D-0004
Direct access to parent amido complexes of rhodium and iridium through N-H activation of ammonia

Simplicity! A direct entry to amido rhodium and iridium complexes was easily achieved by reaction of gaseous ammonia with alkoxo-bridged precursors under very mild conditions. This new approach allowed the high-yield access for the first time to elusive [Rh-NH 2] complexes. Copyright Â© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Financial support from CONSOLIDER INGENIO-2010 program under the projects MULTICAT (CSD2009-00050) and Factoría de Cristalización (CSD2006-0015). P.G.O. acknowledges financial support from the CSIC “JAE-Doc” program.Peer Reviewe
Designing Excited States: Theory-Guided Access to Efficient Photosensitizers for Photodynamic Action

Cataloged from PDF version of article.The in silico design of tetraradical S 1 states was validated experimentally through synthesis, followed by characterization including phosphorescence measurements, use of trap molecules, and cell culture studies, leading to a series of orthogonal dimers of Bodipy chromophores with remarkable singlet oxygen efficiencies (see picture). A new path for the rational development of efficient photosensitizers is thus revealed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Combined Oxypalladation/C-H Functionalization: Palladium(II)-Catalyzed Intramolecular Oxidative Oxyarylation of Hydroxyalkenes

An efficient protocol has been developed for the intramolecular oxidative oxyarylation using a Pd[superscript II]-catalyzed tandem oxypalladation/C-H functionalization strategy. This methodology allows rapid access to tetrahydro-2H-indeno-[2,1-b]furan frameworks from simple hydroxyalkenes. The reactivity of this process is orthogonal to that of Pd[superscript 0]-catalyzed transformations, enabling the divergent modification of a single molecule.National Institutes of Health (U.S.) (GM46059)National Institutes of Health (U.S.) (Grant 1S10RR13886-01)National Science Foundation (U.S.) (CHE-0946721
Iron(II)-Catalyzed Trifluoromethylation of Potassium Vinyltrifluoroborates

Exchanging BF[subscript 3] by CF[subscript 3]: The title reaction proceeds under exceedingly mild reaction conditions and provides 2-arylvinyl- and 2-heteroarylvinyl-substituted substrates with E/Z selectivities of more than 95:5. Experimental observations suggest that the reaction does not proceed through a transmetalation of the RBF[subscript 3]K species to the iron catalyst.National Institutes of Health (U.S.) (Grant GM46059)National Institutes of Health (U.S.) (Postdoctoral Fellowship F32M093532)National Science Foundation (U.S.) (Grant CHE-9808061)National Science Foundation (U.S.) (Grant DBI-9729592)National Institutes of Health (U.S.) (Grant 1S10RR13886-01
The importance of being exchanged: [Gd III 4M II 8(OH) 8(L) 8(O 2CR) 8] 4+ clusters for magnetic refrigeration

El pdf del artículo es la versión post-print.-- et al.Playing it cool: Almost all of the constituent parts of the complex [Ln III 4M II 8(OH) 8(L) 8(O 2CR) 8]X 4, namely the lanthanide ions Ln 3+, the transition-metal ions M 2+, the bridging ligand L, the carboxylates, and the counterions X can be exchanged, thus allowing a thorough understanding of the individual contributions to the magnetocaloric effect. Example in picture: Gd purple, Cu green, O red, N blue. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.E.K.B. wishes to thank the EPSRC for funding. M.E. acknowledges contracts MAT2009-13977-C03 and CSD2007-00010. S.P. thanks the Danish Natural Science Research Council for a Sapere Aude Fellowship (10-081659).Peer Reviewe
A Concise and Versatile Double-Cyclization Strategy for the Highly Stereoselective Synthesis and Arylative Dimerization of Aspidosperma Alkaloids

Building cycles: A strategy for the concise, stereoselective synthesis of aspidosperma alkaloids and related structures via a common putative diiminium ion intermediate is reported. The approach enables the dimerization of aspidosperma-type structures at the sterically hindered C2 position. The intermediate is prepared in one step from the shown lactam through an electrophilic double-cyclization cascade (see scheme; Tf=trifluoromethanesulfonyl).National Institute of General Medical Sciences (U.S.) (GM074825