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- ItemApplication of molecular SERS nanosensors: where we stand and where we are headed towards?(Berlin ; Heidelberg : Springer, 2020) Jahn I.J.; Mühlig A.; Cialla-May D.Molecular specific and highly sensitive detection is the driving force of the surface-enhanced Raman spectroscopy (SERS) community. The technique opens the window to the undisturbed monitoring of cellular processes in situ or to the quantification of small molecular species that do not deliver Raman signals. The smart design of molecular SERS nanosensors makes it possible to indirectly but specifically detect, e.g. reactive oxygen species, carbon monoxide or potentially toxic metal ions. Detection schemes evolved over the years from simple metallic colloidal nanoparticles functionalized with sensing molecules that show uncontrolled aggregation to complex nanostructures with magnetic properties making the analysis of complex environmental samples possible. The present article gives the readership an overview of the present research advancements in the field of molecular SERS sensors, highlighting future trends. © 2020, The Author(s).
- ItemVariations of the aerosol chemical composition during Asian dust storm at Dushanbe, Tajikistan(Les Ulis : EDP Sciences, 2019) Fomba, Khanneh Wadinga; Müller, Konrad; Hofer, Julian; Makhmudov, Abduvosit N.; Althausen, Dietrich; Nazarov, Bahron I.; Abdullaev, Sabur F.; Herrmann, HartmutAerosol chemical composition was characterized during the Central Asian Dust Experiment (CADEX) at Dushanbe (Tajikistan). Aerosol samples were collected during a period of 2 months from March to May 2015 using a high volume DIGITEL DHA-80 sampler on quartz fiber filters. The filters were analyzed for their ionic, trace metals as well as organic and elemental carbon (OC/EC) content. The aerosol mass showed strong variation with mass concentration ranging from 18 μg/m3 to 110 μg/m3. The mineral dust concentrations varied between 0.9 μg/m3 and 88 μg/m3. Days of high aerosol mass loadings were dominated by mineral dust, which made up to about 80% of the aerosol mass while organic matter and inorganic ions made up about 70% of the aerosol mass during days of low aerosol mass loadings. The mineral dust composition showed different trace metal signatures in comparison to Saharan dust with higher Ca content and Ca/Fe ratios twice as high as that observed in Saharan dust. Strong influence of anthropogenic activities was observed in the trace metal concentrations with Zn and Pb concentrations ranging from 7 to 197 ng/m3 and 2 to 20 ng/m3, respectively. Mineral dust and anthropogenic activities relating to traffic, combustion as well as metallurgical industrial emissions are identified as the sources of the aerosol during this period. © 2019 The Authors, published by EDP Sciences.
- ItemExpansion of the (BB)Ru metallacycle with coinage metal cations: Formation of B-M-Ru-B (M = Cu, Ag, Au) dimetalacyclodiboryls(Cambridge : Royal Society of Chemistry, 2018) Eleazer, B.J.; Smith, M.D.; Popov, A.A.; Peryshkov, D.V.In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium-boron bonds on a surface of icosahedral boron clusters. M(i) cations (M = Cu, Ag, and Au) insert into B-Ru bonds of the (BB)-carboryne complex of ruthenium with the formation of four-membered B-M-Ru-B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B-M⋯Ru interactions that are isolobal to B-H⋯Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B-Au and Au-Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu-B (2.029(2) Å) and Ag-B (2.182(3) Å) bonds and the shortest Au-B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu(i) and Au(i) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M-B bonds.
- ItemMetallofullerene photoswitches driven by photoinduced fullerene-to-metal electron transfer(Cambridge : RSC, 2021) Zalibera, Michal; Ziegs, Frank; Schiemenz, Sandra; Dubrovin, Vasilii; Lubitz, Wolfgang; Savitsky, Anton; Deng, Shihu H.M.; Wang, Xue-Bin; Advoshenko, Stanislav M.; Popov, Alexey A.We report on the discovery and detailed exploration of the unconventional photo-switching mechanism in metallofullerenes, in which the energy of the photon absorbed by the carbon cage π-system is transformed to mechanical motion of the endohedral cluster accompanied by accumulation of spin density on the metal atoms. Comprehensive photophysical and electron paramagnetic resonance (EPR) studies augmented by theoretical modelling are performed to address the phenomenon of the light-induced photo-switching and triplet state spin dynamics in a series of YxSc3−xN@C80 (x = 0–3) nitride clusterfullerenes. Variable temperature and time-resolved photoluminescence studies revealed a strong dependence of their photophysical properties on the number of Sc atoms in the cluster. All molecules in the series exhibit temperature-dependent luminescence assigned to the near-infrared thermally-activated delayed fluorescence (TADF) and phosphorescence. The emission wavelengths and Stokes shift increase systematically with the number of Sc atoms in the endohedral cluster, whereas the triplet state lifetime and S1–T1 gap decrease in this row. For Sc3N@C80, we also applied photoelectron spectroscopy to obtain the triplet state energy as well as the electron affinity. Spin distribution and dynamics in the triplet states are then studied by light-induced pulsed EPR and ENDOR spectroscopies. The spin–lattice relaxation times and triplet state lifetimes are determined from the temporal evolution of the electron spin echo after the laser pulse. Well resolved ENDOR spectra of triplets with a rich structure caused by the hyperfine and quadrupolar interactions with 14N, 45Sc, and 89Y nuclear spins are obtained. The systematic increase of the metal contribution to the triplet spin density from Y3N to Sc3N found in the ENDOR study points to a substantial fullerene-to-metal charge transfer in the excited state. These experimental results are rationalized with the help of ground-state and time-dependent DFT calculations, which revealed a substantial variation of the endohedral cluster position in the photoexcited states driven by the predisposition of Sc atoms to maximize their spin population.
- ItemDesign of a core-shell catalyst : an effective strategy for suppressing side reactions in syngas for direct selective conversion to light olefins(Cambridge : RSC, 2020) Tan, Li; Wang, Fan; Zhang, Peipe; Suzuki, Yuichi; Wu, Yingquan; Chen, Jiangang; Yang, Guohui; Tsubaki, NoritatsuAn elegant catalyst is designedviathe encapsulation of metallic oxide Zn-Cr inside of zeolite SAPO34 as a core-shell structure (Zn-Cr@SAPO) to realize the coupling of methanol-synthesis and methanol-to-olefin reactions. It can not only break through the limitation of the Anderson-Schulz-Flory distribution but can also overcome the disadvantages of physical mixture catalysts, such as excessive CO2formation. The confinement effect, hierarchical structure and extremely short distance between the two active components result in the Zn-Cr@SAPO capsule catalyst having better mass transfer and diffusion with a boosted synergistic effect. Due to the difference between the adsorption energies of the Zn-Cr metallic oxide/SAPO zeolite physical mixture and capsule catalysts, the produced water and light olefins are easily removed from the Zn-Cr@SAPO capsule catalyst after formation, suppressing the side reactions. The light olefin space time yield (STY) of the capsule catalyst is more than twice that of the typical physical mixture catalyst. The designed capsule catalyst has superior potential for scale-up in industrial applications while simultaneously extending the capabilities of hybrid catalysts for other tandem catalysis reactions through this strategy. © The Royal Society of Chemistry 2020.
- ItemPerforming DNA nanotechnology operations on a zebrafish(Cambridge : RSC, 2018) Yang, Jian; Meng, Zhuojun; Liu, Qing; Shimada, Yasuhito; Olsthoorn, René C. L.; Spaink, Herman P.; Herrmann, Andreas; Kros, AlexanderNanoscale engineering of surfaces is becoming an indispensable technique to modify membranes and, thus cellular behaviour. Here, such membrane engineering related was explored on the surface of a living animal using DNA nanotechnology. We demonstrate the immobilization of oligonucleotides functionalized with a membrane anchor on 2 day old zebrafish. The protruding single-stranded DNA on the skin of zebrafish served as a handle for complementary DNAs, which allowed the attachment of small molecule cargo, liposomes and dynamic relabeling by DNA hybridization protocols. Robust anchoring of the oligonucleotides was proven as DNA-based amplification processes were successfully performed on the outer membrane of the zebrafish enabling the multiplication of surface functionalities from a single DNA-anchoring unit and the dramatic improvement of fluorescent labeling of these animals. As zebrafish are becoming an alternative to animal models in drug development, toxicology and nanoparticles characterization, we believe the platform presented here allows amalgamation of DNA nanotechnology tools with live animals and this opens up yet unexplored avenues like efficient bio-barcoding as well as in vivo tracking. © The Royal Society of Chemistry.
- ItemModified powder-in-tube technique based on the consolidation processing of powder materials for fabricating specialty optical fibers(Basel : MDPI AG, 2014) Auguste, J.-L.; Humbert, G.; Leparmentier, S.; Kudinova, M.; Martin, P.-O.; Delaizir, G.; Schuster, K.; Litzkendorf, D.The objective of this paper is to demonstrate the interest of a consolidation process associated with the powder-in-tube technique in order to fabricate a long length of specialty optical fibers. This so-called Modified Powder-in-Tube (MPIT) process is very flexible and paves the way to multimaterial optical fiber fabrications with different core and cladding glassy materials. Another feature of this technique lies in the sintering of the preform under reducing or oxidizing atmosphere. The fabrication of such optical fibers implies different constraints that we have to deal with, namely chemical species diffusion or mechanical stress due to the mismatches between thermal expansion coefficients and working temperatures of the fiber materials. This paper focuses on preliminary results obtained with a lanthano-aluminosilicate glass used as the core material for the fabrication of all-glass fibers or specialty Photonic Crystal Fibers (PCFs). To complete the panel of original microstructures now available by the MPIT technique, we also present several optical fibers in which metallic particles or microwires are included into a silica-based matrix.
- ItemProcessing metallic glasses by selective laser melting(Amsterdam [u.a.] : Elsevier, 2013) Pauly, S.; Löber, L.; Petters, R.; Stoica, M.; Scudino, S.; Kühn, U.; Eckert, J.Metallic glasses and their descendants, the so-called bulk metallic glasses (BMGs), can be regarded as frozen liquids with a high resistance to crystallization. The lack of a conventional structure turns them into a material exhibiting near-theoretical strength, low Young's modulus and large elasticity. These unique mechanical properties can be only obtained when the metallic melts are rapidly cooled to bypass the nucleation and growth of crystals. Most of the commonly known and used processing routes, such as casting, melt spinning or gas atomization, have intrinsic limitations regarding the complexity and dimensions of the geometries. Here, it is shown that selective laser melting (SLM), which is usually used to process conventional metallic alloys and polymers, can be applied to implement complex geometries and components from an Fe-base metallic glass. This approach is in principle viable for a large variety of metallic alloys and paves the way for the novel synthesis of materials and the development of parts with advanced functional and structural properties without limitations in size and intricacy.
- ItemThe Contrasting Character of Early and Late Transition Metal Fluorides as Hydrogen Bond Acceptors(Washington, DC : ACS Publications, 2015) Smith, Dan A.; Beweries, Torsten; Blasius, Clemens; Jasim, Naseralla; Nazir, Ruqia; Nazir, Sadia; Robertson, Craig C.; Whitwood, Adrian C.; Hunter, Christopher A.; Brammer, Lee; Perutz, Robin N.The association constants and enthalpies for the binding of hydrogen bond donors to group 10 transition metal complexes featuring a single fluoride ligand (trans-[Ni(F)(2-C5NF4)(PR3)2], R = Et 1a, Cy 1b, trans-[Pd(F)(4-C5NF4)(PCy3)2] 2, trans-[Pt(F){2-C5NF2H(CF3)}(PCy3)2] 3 and of group 4 difluorides (Cp2MF2, M = Ti 4a, Zr 5a, Hf 6a; Cp*2MF2, M = Ti 4b, Zr 5b, Hf 6b) are reported. These measurements allow placement of these fluoride ligands on the scales of organic H-bond acceptor strength. The H-bond acceptor capability β (Hunter scale) for the group 10 metal fluorides is far greater (1a 12.1, 1b 9.7, 2 11.6, 3 11.0) than that for group 4 metal fluorides (4a 5.8, 5a 4.7, 6a 4.7, 4b 6.9, 5b 5.6, 6b 5.4), demonstrating that the group 10 fluorides are comparable to the strongest organic H-bond acceptors, such as Me3NO, whereas group 4 fluorides fall in the same range as N-bases aniline through pyridine. Additionally, the measurement of the binding enthalpy of 4-fluorophenol to 1a in carbon tetrachloride (−23.5 ± 0.3 kJ mol–1) interlocks our study with Laurence’s scale of H-bond basicity of organic molecules. The much greater polarity of group 10 metal fluorides than that of the group 4 metal fluorides is consistent with the importance of pπ–dπ bonding in the latter. The polarity of the group 10 metal fluorides indicates their potential as building blocks for hydrogen-bonded assemblies. The synthesis of trans-[Ni(F){2-C5NF3(NH2)}(PEt3)2], which exhibits an extended chain structure assembled by hydrogen bonds between the amine and metal-fluoride groups, confirms this hypothesis.
- Item(BB)-Carboryne Complex of Ruthenium: Synthesis by Double B-H Activation at a Single Metal Center(Washington, DC : ACS Publications, 2016) Eleazer, Bennett J.; Smith, Mark D.; Popov, Alexey A.; Peryshkov, Dmitry V.The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)2 (POBBOP = 1,7-OP(i-Pr)2-2,6-dehydro-m-carborane) was synthesized by double B-H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B-Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne-carboranyl transformations reported herein represent a new mode of cooperative metal-ligand reactivity of boron-based complexes.