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At least 361 records · Page 20

Dynamics of Charge States of Relativistic Gold Ion Beams Passing through Cu and Au Foils in the NICA Project

In order to study the properties of dense baryonic matter, an accelerator complex is under development at the Joint Institute for Nuclear Research (Dubna, Russia) within the new NICA project. The NICA project assumes the use of accelerated ion beams ranging from protons to gold ions with relativistic energies up to 4.5 GeV/nucleon. To design experiments, it is necessary to have information on the efficiency of the yield of bare gold nuclei formed at the passage of a gold ion beam with energies of about several hundreds of MeV per nucleon through a foil of a specialized stripping station at the output of the booster of the accelerator. In this work, the optimal conditions (material and thickness of the foil and the energy of the ion) for the formation of fractions of bare gold nuclei with a probability of 80–90% have been determined by calculating electron loss and capture cross sections, as well as the dynamics of charge states of gold ions colliding with copper and gold foils at energies of 400 and 600 MeV/nucleon,.

74 ATOMIC AND MOLECULAR PHYSICS↗

Syntheses, crystal structures, and properties of four complexes based on polycarboxylate and imidazole ligands

Four metal–organic coordination polymers [Zn(HL)(H{sub 2}O)]·4H{sub 2}O (1), [Zn(HL)(L{sub 1})]·4H{sub 2}O (2), [Cu(HL)(H{sub 2}O)]·3H{sub 2}O (3) and [Cu(HL)(L{sub 1})]·5H{sub 2}O (4) were synthesized by reactions of the corresponding metal(II) salts with semirigid polycarboxylate ligand (5-((4-carboxypiperidin-1-yl)methyl)isophthalic acid hydrochloride, H{sub 3}L·HCl) or auxiliary ligand (1,4-di(1H-imidazol-4-yl)benzene, L{sub 1}). The structures of the compounds were characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction. The use of auxiliary ligand L{sub 1} has great influence on the structures of two pairs of complexes 1, 2 and 3, 4. Complex 1 is a uninodal 3-connected rare 2-fold interpenetrating ZnSc net with a Point (Schlafli) symbol of (10{sup 3}) while 2 is a one-dimensional (1D) ladder structure. Compound 3 features a two-dimensional (2D) honeycomb network with typical 6{sup 3}-hcb topology, while 4 is 2D network with (4, 4) sql topology based on binuclear Cu{sup II} subunits. The non-covalent bonding interactions such as hydrogen bonds, π···π stacking and C–H···π exist in complexes 1–4, which contributes to stabilize crystal structure and extend the low-dimensional entities into high-dimensional frameworks. And the photoluminescent property of 1 and 2 and gas sorption property of 4 have been investigated. - Graphical abstract: Four new coordination polymers have been obtained and their photoluminescent and gas sorption properties have also been investigated. - Highlights: • Two pairs of Zn{sup II}/ Cu{sup II} compounds have been synthesized. • Auxiliary ligand-controlled assembly of the complexes is reported. • The luminescent properties of complexes 1–2 were investigated. • The gas sorption property of 4 has been investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NO Coupling at Copper to cis -Hyponitrite: N 2 O Formation via Protonation and H-Atom Transfer

Copper nitrite reductases (CuNIRs) convert NO 2 – to NO as well as NO to N 2 O under high NO flux at a mononuclear type 2 Cu center. While model complexes illustrate N–N coupling from NO that results in symmetric trans-hyponitrite [Cu II ]– ONNO–[Cu II ] complexes, in this work we report NO assembly at a single Cu site in the presence of an external reductant Cp* 2 M (M = Co, Fe) to give the first copper cis-hyponitrites [Cp* 2 M]{[Cu II ](κ 2 - O 2 N 2 )[Cu I ]}. Importantly, the κ 1 –N-bound [Cu I ] fragment may be easily removed by the addition of mild Lewis bases such as CNAr or pyridine to form the spectroscopically similar anion {[Cu II ](κ 2 -O 2 N 2 )} – . The addition of electrophiles such as H + to these anionic copper(II) cis-hyponitrites leads to N 2 O generation with the formation of the dicopper(II)-bis-μ-hydroxide [Cu II ] 2 (μ- OH) 2 . One-electron oxidation of the {[Cu II ](κ 2 -O 2 N 2 )} – core turns on H-atom transfer reactivity, enabling the oxidation of 9,10- dihydroanthracene to anthracene with concomitant formation of N 2 O and [Cu II ] 2 (μ-OH) 2 . These studies illustrate both the reductive coupling of NO at a single copper center and a way to harness the strong oxidizing power of nitric oxide via the neutral cis- hyponitrite [Cu](κ 2 -O 2 N 2 ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

L-edge sum rule analysis on 3d transition metal sites: from d 10 to d 0 and towards application to extremely dilute metallo-enzymes

According to L-edge sum rules, the number of 3d vacancies at a transition metal site is directly proportional to the integrated intensity of the L-edge X-ray absorption spectrum (XAS) for the corresponding metal complex. In this study, the numbers of 3d holes are characterized quantitatively or semi-quantitatively for a series of manganese (Mn) and nickel (Ni) complexes, including the electron configurations 3d 10 → 3d 0 . In addition, extremely dilute (<0.1% wt/wt) Ni enzymes were examined by two different approaches: (1) by using a high resolution superconducting tunnel junction X-ray detector to obtain XAS spectra with a very high signal-to-noise ratio, especially in the non-variant edge jump region; and (2) by adding an inert tracer to the sample that provides a prominent spectral feature to replace the weak edge jump for intensity normalization. In this publication, we present for the first time: (1) L-edge sum rule analysis for a series of Mn and Ni complexes that include electron configurations from an open shell 3d0 to a closed shell 3d 10 ; (2) a systematic analysis on the uncertainties, especially on that from the edge jump, which was missing in all previous reports; (3) a clearly-resolved edge jump between pre-L 3 and post-L 2 regions from an extremely dilute sample; (4) an evaluation of an alternative normalization standard for L-edge sum rule analysis. XAS from two copper (Cu) proteins measured using a conventional semiconductor X-ray detector are also repeated as bridges between Ni complexes and dilute Ni enzymes. The differences between measuring 1% Cu enzymes and measuring <0.1% Ni enzymes are compared and discussed. As a result, this study extends L-edge sum rule analysis to virtually any 3d metal complex and any dilute biological samples that contain 3d metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-current field-assisted assembly of copper nanoparticles for current collectors

Current collectors are essential features of batteries and many other electronic devices being responsible for efficient charge transport to active electrode materials. Three-dimensional (3D), high surface area current collectors considerably improve the performance of cathodes and anodes in batteries, but their technological implementation is impeded by the complexity of their preparation, which needs to be simple, fast, and energy efficient. In this paper we demonstrate that field-stimulated assembly of ~3 nm copper nanoparticles (NPs) enables the preparation of porous Cu NP films. The use of NP dispersions enables 30× reduction of the deposition current for making functional 3D coatings. In addition to high surface area, lattice-to-lattice connectivity in the self-assembly of NPs in 3D structures enables fast charge transport. The mesoscale dimensions of out-of-plane features and the spacing between them in Cu films made by field-stimulated self-assembly of NPs provides promising morphology for current collection in lithium ion batteries (LIBs). Half-cell electrochemical models based on self-assembled films show improved specific capacity, total capacity, and cycling performance compared to traditional flat and other 3D current collectors. While integration of active electrode material into the 3D topography of the current collector needs to be improved, this study indicates that self-assembled NP films represent a viable manufacturing approach for 3D electrodes.

36 MATERIALS SCIENCE↗

Adsorption Behavior of Organic Molecules: A Study of Benzotriazole on Cu(111) with Spectroscopic and Theoretical Methods

The adsorption of organic molecules on solid substrates is important to applications in fields such as catalysis, photovoltaics, corrosion inhibition, adhesion, and sensors. The molecular level description of the surface–molecule interaction and of the adsorption structures in these complex systems is crucial to understand their properties and function. Here, we present an investigation of one such system, benzotriazole (BTAH) on single-crystal Cu(111) in vacuum conditions. BTAH is the most widely used corrosion inhibitor for copper and thus a molecule of great industrial relevance. We show that the co-application of a wide range of spectroscopic techniques with theoretical methods provides unique insight in the description of the atomistic details of the adsorbed structures. Specifically, spectroscopic photoemission, absorption, and standing wave experiments combined with ab initio computational modeling allowed us to identify that benzotriazole forms overlayers of intact BTAH when deposited at low temperature, and it dissociates into BTA and H at room temperature and above. The dissociated molecule then forms complex structures of mixed chains and dimers of BTA bound to copper adatoms. Our work also reveals that copper adatoms at low concentrations, such as the theoretically predicted superstructures, cannot be resolved by means of current X-ray photoelectron spectroscopy as the modeled Cu 2p spectra are practically indistinguishable from those for a Cu surface without adatoms. Overall this study significantly deepens understanding of BTAH on Cu, a system studied for more than 50 years, and it highlights the benefits of combining spectroscopic and computational methods to obtain a complete picture of a complex adsorption system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper-containing ceramic precursor synthesis: Solid-state transformations and materials technology

Three copper systems with relevance to materials technology are discussed. In the first, a CuS precursor, Cu4S1O (4-methylpyridine)(sub 4)- (4-MePy), was prepared by three routes: reaction of Cu2S, reaction of CuBr-SMe2, and oxidation of copper powder with excess sulfur in 4-methylpyridine by sulfur. In the second, copper powder was found to react with excess thiourea (H2NC(S)NH2) in 4-methylpyridine to produce thiocyanate (NCS(-)) complexes. Three isolated and characterized compounds are: Cu(NCS)(4-MePy)(sub 2), a polymer, (4-MePy-H)(Cu(NCS)(sub 3)(4-MePy)(sub 2)), a salt, and t-Cu(NCS)(sub 2)(4-MePy)(sub 4). Finally, an attempt to produce a mixed-metal sulfide precursor of Cu and Ga in N-methylimidazole (N-MeIm) resulted in the synthesis of a Cu-containing polymer, Cu(SO4)(N-MeIm). The structures are presented; the chemistry will be briefly discussed in the context of preparation and processing of copper-containing materials for aerospace applications.

Hepp, Aloysius F.↗

Structural-Phase Features of Low-Stability Pre-Transitional States of BCC-Alloys with Complexes of Planar Defects (Antiphase Boundaries)

Using the Monte Carlo method, the influence of the complexes of antiphase boundaries (APBs) (a pair of shear APBs and a pair of thermal APBs) on the low-stability, pre-transitional states of BCC-alloys is considered by the example of a conventional copper alloy CuZn and an intermetallic compound NiAl. It is shown that in the region of low-stability structural-phase states the energy of formation of a complex of thermal APBs is higher than that of shear APBs. The contribution of APBs into disordering is appreciable up to the structural-phase transition temperature. The most significant factor in terms of the long-range order is the formation of the defect itself; the differences in the APB type or the plane of their occurrence do not so much affect the longrange order behavior with the temperature variation. The type of APBs however appreciably affects the structural-energy characteristics of the system at the temperatures below the phase transformation temperature. Logically, a system with structural defects is less ordered than a defect-free system. The presence of a defect favors the onset of disordering at lower temperatures: it starts at lower temperatures in the case of thermal APBs (TAPBs) compared to shear APBs (TAPBs). In a BCC-system with a complex of TAPBs the first signs of disordering invariably appear near the phase boundary in the neighborhood of large atoms (Zn–Zn in the CuZn alloy or Al–Al in the NiAl intermetallide). In the alloy with a complex of shear APBs the distortion of ordering at low temperatures is observed in the regions where the boundaries cross. The presence of antiphase boundaries affects the alloy stability under heating. It is shown that disordering is accompanied by smearing of the boundaries and their faceting. It follows from a comparative analysis of the peculiarities of disordering in the BCC-system under study (classical alloy CuZn and intermetallide NiAl) under conditions of higher temperatures in the region of low-stability, pre-transitional states that the order – disorder phase transition in the CuZn alloy takes place as a result of disordering of the system, while in the intermetallide NiAl the change of long-range order results from the structural-phase transition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Evaluating the structural complexity of isomeric bile acids with ion mobility spectrometry

Bile acids (BAs) play an integral role in digestion through the absorption of nutrients, emulsification of fats and fat-soluble vitamins, and maintenance of cholesterol levels. Metabolic disruption, diabetes, colorectal cancer, and numerous other diseases have been linked with BA disruption, making improved BA analyses essential. To date, most BA measurements are performed using liquid chromatography separations in conjunction with mass spectrometry measurements (LC-MS). However, 10–40 min LC gradients are often used for BA analyses and these may not even be sufficient for distinguishing all the important isomers present in the human body. Ion mobility spectrometry (IMS) is a promising tool for BA evaluations due to its ability to quickly separate isomeric molecules with subtle structural differences. In this study, we utilized drift tube IMS (DTIMS) coupled with MS to characterize 56 different unlabeled BA standards and 16 deuterated versions. In the DTIMS-MS analyses of 12 isomer groups, BAs with smaller m/z values were easily separated in either their deprotonated or sodiated forms (or both). However, as the BAs grew in m/z value, they became more difficult to separate with two isomer groups being inseparable. Metal ions such as copper and zinc were then added to the overlapping BAs, and due to different binding sites, the resulting complexes were separable. Thus, the rapid structural measurements possible with DTIMS-MS show great potential for BAs measurements with and without prior LC separations.

Zheng, Xueyun↗

Paramagnetic Cu{sup II} complexes with 1-(hetarylmethyl)silatranes

The structures of paramagnetic complexes CuCl{sub 2}•L with L = HetCH{sub 2}Si(OCH{sub 2}CH{sub 2}){sub 3}N [Het = pyrrol-1-yl (1), indol-1-yl (2), carbazol-9-yl (3), imidazole-1-yl (4), 3,5-dimethylpyrazol-1-yl (5), 1,2,4-triazol-1-yl (6), benzimidazol-1-yl (7), and 1,2,3-benzotriazol-1-yl (8)] were studied by the ESR and quantum chemical methods in terms of the density functional theory (DFT) approximation. The difference in structures of complexes CuCl{sub 2}•1—CuCl{sub 2}•8 is mainly determined by the nature of the five-membered heterocycle. The ESR spectra at room temperature are typical of the mononuclear complexes of Cu{sup II} of axial symmetry with various types of distortions. In complexes CuCl{sub 2}•1—CuCl{sub 2}•3, narrow symmetric signals of zero-valent copper are recorded. These signals remain in the spectra for at least six months, which can characterize them as efficient stabilizing matrices of nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Importance of Pipe Deposits to Lead and Copper Rule Compliance

When Madison, Wis., exceeded the lead action level in 1992, residential and off-line tests suggested that lead release into the water was more complex than a lead solubility mechanism. Scale analyses (color and texture as well as mineralogical and elemental composition) of five excavated lead service lines (LSLs) revealed that accumulation of manganese (and iron) onto pipe walls had implications for lead corrosion by providing a high-capacity sink for lead. Manganese that accumulated from source well water onto pipe scales (up to 10% by weight of scale composition) served to capture and eventually transport lead to consumer taps. In addition, manganese sometimes obstructed the predominance of an insoluble (and thus potentially protective) plattnerite [Pb(IV) solid] scale layer. Full LSL replacement in Madison achieved Lead and Copper Rule compliance and a major reduction in lead contamination and exposure, supplemented by unidirectional flushing of water mains and manganese control in the source well water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An Activity-Based Sensing Approach to Monitor Nanomaterial-Promoted Changes in Labile Metal Pools in Living Systems

Metal-based nanoparticles are a promising class of materials for diagnosis and treatment of cancer and other diseases. However, mechanisms of action of these nanomedicines remain insufficiently understood due in large part to our limited understanding of the dynamic equilibria between solid metal nanoparticles and labile metal ions generated from these nanoparticles within complex biological milieus. Here, we apply activitybased sensing to directly identify and investigate the fate of labile copper pools with metal and oxidation state-specificity generated by anticancer copper nanomedicines. We found that treatment of cells with copper-releasing nanoparticles alter labile Cu(I)/Cu(II) ratios through an increase in labile Cu(II), while overall labile copper levels decrease. Labile copper release triggers compensatory responses in two major antioxidant pathways, glutathione (GSH) and nuclear factor erythroid 2-related factor 2 (NRF2), as well as in metal homeostasis to limit copper availability via regulation of copper export (ATP7B) and copper import (CTR1) proteins. These findings establish the value of activity-based sensing as a generalizable approach for labile metal imaging to help decipher molecular mechanisms of bioactive metal nanoparticles and guide the development of more effective nanomedicine diagnostics and therapies to target metal-dependent disease vulnerabilities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trans-Bis(acetato-o)bis(4-methylpyridine-N)copper(II)

The structure of trans-bis(acetato-O)bis(4-methyl- pyridine-N)copper(II), (Cu(C2H302)(sub 2)(C6H7N)(sub 2)), re- ported herein, represents a monomeric parent acetate complex with a distorted square-planar arrangement of acetate and 4-methylpyridine ligands around the Cu atom with the following distances and angles: Cu-N = 2.027 (4) and Cu-O1 = 1.950 (3) A; O1-Cu-N = 89.1 (2) and O1 -Cu-N' = 90.9 (2)deg. The Cu atom resides on a center of inversion. The most important dihedral angles are the angle between the 4-methylpyridine plane and the acetate plane (O1, O2, C21 and C22), 78.2 deg and the angle between the 4-methylpyridine ring and the coordination plane (Cu, N, O1), 31.6 deg.

Jedrzejas, Marek J.↗

Cell‐free protein synthesis enables high yielding synthesis of an active multicopper oxidase

Abstract Multicopper oxidases (MCOs) are broadly distributed in all kingdoms of life and perform a variety of important oxidative reactions. These enzymes have potential biotechnological applications; however, the applications are impeded by low expression yields in traditional recombinant hosts, solubility issues, and poor copper cofactor assembly. As an alternative to traditional recombinant protein expression, we show the ability to use cell‐free protein synthesis (CFPS) to produce complex MCO proteins with high soluble titers. Specifically, we report the production of MCOs in an Escherichia coli ‐based cell‐free transcription‐translation system. Total yields as high as 1.2 mg mL −1 were observed after a 20‐h batch reaction. More than 95% of the protein was soluble and activity was obtained by simple post‐CFPS addition of copper ions in the form of CuSO 4 . Scale‐up reactions were achieved from 15 to 100 µL without a decrease in productivity and solubility. CFPS titers were higher than in vivo expression titers and more soluble, avoiding the formation of inclusion bodies. Our work extends the utility of the cell‐free platform to the production of active proteins containing copper cofactors and demonstrates a simple method for producing MCOs.

Li, Jian↗

Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{sup 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties. - Highlights: • Reaction variables affecting Mo(W)/S/Cu cluster-based CPs is firstly explored. • Replacing central metal atom had a pronounced effect on W/S/Cu cluster-based CPs. • Photocatalytic activities of Mo(W)/S/Cu cluster-based CPs are firstly investigated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper migration and surface oxidation of CuxBi2Se3 in ambient pressure environments

Abstract Chemical modifications such as intercalation can be used to modify surface properties or to further functionalize the surface states of topological insulators (TIs). Using ambient pressure x-ray photoelectron spectroscopy, we report copper migration in C u x B i 2 S e 3 , which occurs on a timescale of hours to days after initial surface cleaving. The increase in near-surface copper proceeds along with the oxidation of the sample surface and large changes in the selenium content. These complex changes are further modeled with core-level spectroscopy simulations, which suggest a composition gradient near the surface which develops with oxygen exposure. Our results shed light on a new phenomenon that must be considered for intercalated TIs—and intercalated materials in general—that surface chemical composition can change when specimens are exposed to ambient conditions.

36 MATERIALS SCIENCE↗

Chromatographic and Spectroscopic Study of the Interaction between Polysulfides and Copper Sulfides

To mitigate the “polysulfide shuttle” in lithium–sulfur batteries, different hosting materials that can interact with the polysulfide species physically or chemically have been widely investigated. Copper sulfides as one type of material are believed to have strong chemical interactions with the polysulfide species to consequently influence the performances of Li–S batteries. In this work, high-performance liquid chromatography (HPLC), electrospray ionization mass spectrometry (ESI/MS), scanning electron microscopy with energy-dispersive X-ray spectrometry (SEM-EDS), and inductively coupled plasma optical emission spectroscopy (ICP-OES) were used to systematically investigate the interactions between ether-based polysulfide solutions and copper sulfides (as well as silver sulfide). Furthermore, based on chromatographic and spectroscopic results, the interactions between polysulfides and Cu 2 S can be classified into two types of reactions: one is the redox reaction with the formation of CuS, while another is the complexation reaction with the formation of soluble LiCuS n (n ≥ 4). Contrarily, Ag 2 S (and CuS) shows no interactions with polysulfides. Accordingly, the cycling behaviors of Li–S batteries with copper sulfides as hosting materials or with copper as additives were explained reasonably.

25 ENERGY STORAGE↗

Electric field effects in graphene/LaAlO{sub 3}/SrTiO{sub 3} heterostructures and nanostructures

We report the development and characterization of graphene/LaAlO{sub 3}/SrTiO{sub 3} heterostructures. Complex-oxide heterostructures are created by pulsed laser deposition and are integrated with graphene using both mechanical exfoliation and transfer from chemical-vapor deposition on ultraflat copper substrates. Nanoscale control of the metal-insulator transition at the LaAlO{sub 3}/SrTiO{sub 3} interface, achieved using conductive atomic force microscope lithography, is demonstrated to be possible through the graphene layer. LaAlO{sub 3}/SrTiO{sub 3}-based electric field effects using a graphene top gate are also demonstrated. The ability to create functional field-effect devices provides the potential of graphene-complex-oxide heterostructures for scientific and technological advancement.

36 MATERIALS SCIENCE↗