Borosilicate glass is an important material used in various industries due to its chemical durability, such as for the immobilization of high-level nuclear waste. However, it is susceptible to ...aqueous corrosion, recognizable by the formation of surface alteration layers (SALs). Here, we report in situ fluid-cell Raman spectroscopic experiments providing real-time insights into reaction and transport processes during the aqueous corrosion of a borosilicate glass. The formation of a several-micrometre-thick water-rich zone between the SAL and the glass, interpreted as an interface solution, is detected, as well as pH gradients at the glass surface and within the SAL. By replacing the solution with a deuterated solution, it is observed that water transport through the SAL is not rate-limiting. The data support an interface-coupled dissolution-reprecipitation process for SAL formation. Fluid-cell Raman spectroscopic experiments open up new avenues for studying solid-water reactions, with the ability to in situ trace specific sub-processes in real time by using stable isotopes.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Looking for magnetic clues
Thin films of the neodymium nickelate NdNiO
2
doped with strontium have recently been found to be superconducting. This materials class bears structural and electronic ...similarities to the famed cuprate superconductors, but how far the analogy goes remains unclear. Lu
et al.
used resonant inelastic x-ray scattering to look for magnetism, which exists in the cuprates, in Nd
1-x
Sr
x
NiO
2
films (see the Perspective by Benckiser). The authors observed magnetic modes in the undoped compound that had a doping evolution consistent with the behavior of a doped Mott insulator.
Science
, abd7726, this issue p.
213
; see also abi6855, p.
157
Resonant inelastic x-ray scattering is used to probe the magnetic excitations in Nd
1−
x
Sr
x
NiO
2
films.
The discovery of superconductivity in infinite-layer nickelates brings us tantalizingly close to a material class that mirrors the cuprate superconductors. We measured the magnetic excitations in these nickelates using resonant inelastic x-ray scattering at the Ni
L
3
-edge. Undoped NdNiO
2
possesses a branch of dispersive excitations with a bandwidth of approximately 200 milli–electron volts, which is reminiscent of the spin wave of strongly coupled, antiferromagnetically aligned spins on a square lattice. The substantial damping of these modes indicates the importance of coupling to rare-earth itinerant electrons. Upon doping, the spectral weight and energy decrease slightly, whereas the modes become overdamped. Our results highlight the role of Mottness in infinite-layer nickelates.
Ultrafast materials science promises optical control of physical properties of solids. Continuous-wave circularly polarized laser driving was predicted to induce a light-matter coupled state with an ...energy gap and a quantum Hall effect, coined Floquet topological insulator. Whereas the envisioned Floquet topological insulator requires high-frequency pumping to obtain well-separated Floquet bands, a follow-up question regards the creation of Floquet-like states in graphene with realistic low-frequency laser pulses. Here we predict that short optical pulses attainable in experiments can lead to local spectral gaps and novel pseudospin textures in graphene. Pump-probe photoemission spectroscopy can track these states by measuring sizeable energy gaps and Floquet band formation on femtosecond time scales. Analysing band crossings and pseudospin textures near the Dirac points, we identify new states with optically induced nontrivial changes of sublattice mixing that leads to Berry curvature corrections of electrical transport and magnetization.
The search continues for nickel oxide-based materials with electronic properties similar to cuprate high-temperature superconductors
. The recent discovery of superconductivity in the doped ...infinite-layer nickelate NdNiO
(refs.
) has strengthened these efforts. Here, we use X-ray spectroscopy and density functional theory to show that the electronic structure of LaNiO
and NdNiO
, while similar to the cuprates, includes significant distinctions. Unlike cuprates, the rare-earth spacer layer in the infinite-layer nickelate supports a weakly interacting three-dimensional 5d metallic state, which hybridizes with a quasi-two-dimensional, strongly correlated state with Formula: see text symmetry in the NiO
layers. Thus, the infinite-layer nickelate can be regarded as a sibling of the rare-earth intermetallics
, which are well known for heavy fermion behaviour, where the NiO
correlated layers play an analogous role to the 4f states in rare-earth heavy fermion compounds. This Kondo- or Anderson-lattice-like 'oxide-intermetallic' replaces the Mott insulator as the reference state from which superconductivity emerges upon doping.
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FZAB, GEOZS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
Selective oxy‐functionalization of nonactivated C‐H bonds is a long‐standing “dream reaction” of organic synthesis for which chemical methodology is not well developed. Mono‐oxygenase enzymes are ...promising catalysts for such oxy‐functionalization to establish. Limitation on their applicability arises from low reaction output. Here, we showed an integrated approach of process engineering to the intensification of the cytochrome P450 BM3‐catalyzed hydroxylation of dodecanoic acid (C12:0). Using P450 BM3 together with glucose dehydrogenase for regeneration of nicotinamide adenine dinucleotide phosphate (NADPH), we compared soluble and co‐immobilized enzymes in O2‐gassed and pH‐controlled conversions at high final substrate concentrations (≥40mM). We identified the main engineering parameters of process output (i.e., O2 supply; mixing correlated with immobilized enzyme stability; foam control correlated with product isolation; substrate solubilization) and succeeded in disentangling their complex interrelationship for systematic process optimization. Running the reaction at O2‐limited conditions at up to 500‐ml scale (10% dimethyl sulfoxide; silicone antifoam), we developed a substrate feeding strategy based on O2 feedback control. Thus, we achieved high reaction rates of 1.86g·L−1·hr−1 and near complete conversion (≥90%) of 80mM (16g/L) C12:0 with good selectivity (≤5% overoxidation). We showed that “uncoupled reaction” of the P450 BM3 (~95% utilization of NADPH and O2 not leading to hydroxylation) with the C12:0 hydroxylated product limited the process efficiency at high product concentration. Hydroxylated product (~7g; ≥92% purity) was recovered from 500ml reaction in 82% yield using ethyl‐acetate extraction. Collectively, these results demonstrate key engineering parameters for the biocatalytic oxy‐functionalization and show their integration into a coherent strategy for process intensification.
Cytochrome P450‐catalyzed oxy‐functionalization reactions of fatty acid substrates represent a class of synthetically important bio‐transformations. Here, the authors identified key engineering parameters for the hydroxylation of dodecanoic acid by soluble and immobilized forms of cytochrome P450 BM3 and demonstrated their integration into a coherent strategy for process intensification. Metrics of process performance (as shown in the figure) revealed a highly efficient enzymatic hydroxylation. Reaction scale up to 500 ml enabled production of gram amounts of purified product.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Convolutional neural networks (CNNs) have become the dominant neural network architecture for solving many state-of-the-art (SOA) visual processing tasks. Even though graphical processing units are ...most often used in training and deploying CNNs, their power efficiency is less than 10 GOp/s/W for single-frame runtime inference. We propose a flexible and efficient CNN accelerator architecture called NullHop that implements SOA CNNs useful for low-power and low-latency application scenarios. NullHop exploits the sparsity of neuron activations in CNNs to accelerate the computation and reduce memory requirements. The flexible architecture allows high utilization of available computing resources across kernel sizes ranging from <inline-formula> <tex-math notation="LaTeX">1\times 1 </tex-math></inline-formula> to <inline-formula> <tex-math notation="LaTeX">7\times 7 </tex-math></inline-formula>. NullHop can process up to 128 input and 128 output feature maps per layer in a single pass. We implemented the proposed architecture on a Xilinx Zynq field-programmable gate array (FPGA) platform and presented the results showing how our implementation reduces external memory transfers and compute time in five different CNNs ranging from small ones up to the widely known large VGG16 and VGG19 CNNs. Postsynthesis simulations using Mentor Modelsim in a 28-nm process with a clock frequency of 500 MHz show that the VGG19 network achieves over 450 GOp/s. By exploiting sparsity, NullHop achieves an efficiency of 368%, maintains over 98% utilization of the multiply-accumulate units, and achieves a power efficiency of over 3 TOp/s/W in a core area of 6.3 mm 2 . As further proof of NullHop's usability, we interfaced its FPGA implementation with a neuromorphic event camera for real-time interactive demonstrations.
Chemical Synthesis of Glycosaminoglycans Mende, Marco; Bednarek, Christin; Wawryszyn, Mirella ...
Chemical reviews,
07/2016, Volume:
116, Issue:
14
Journal Article
Peer reviewed
Glycosaminoglycans (GAGs) as one major part of the glycocalyx are involved in many essential biological cell processes, as well as in many courses of diseases. Because of the potential therapeutic ...application of GAG polymers, fragments, and also derivatives toward different diseases (e.g., heparin derivatives against Alzheimer’s disease), there is a continual growing demand for new chemical syntheses, which suffice the high claim to stereoselectivity and chemoselectivity. This Review summarizes the progress of chemical syntheses of GAGs over the last 10 years. For each class of the glycosaminoglycanshyaluronan (HA), heparan sulfate/heparin (HS/HP), chondroitin/dermatan sulfate (CS/DS), and keratan sulfate (KS)mainly novel glycosylation strategies, elongation sequences, and protecting group patterns are discussed, but also (semi)automated syntheses, enzymatic approaches, and functionalizations of synthesized or isolated GAGs are considered.
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IJS, KILJ, NUK, PNG, UL, UM
High-temperature copper oxide superconductors consist of stacked CuO
planes, with electronic band structures and magnetic excitations that are primarily two-dimensional
, but with superconducting ...coherence that is three-dimensional. This dichotomy highlights the importance of out-of-plane charge dynamics, which has been found to be incoherent in the normal state
within the limited range of momenta accessible by optics. Here we use resonant inelastic X-ray scattering to explore the charge dynamics across all three dimensions of the Brillouin zone. Polarization analysis of recently discovered collective excitations (modes) in electron-doped copper oxides
reveals their charge origin, that is, without mixing with magnetic components
. The excitations disperse along both the in-plane and out-of-plane directions, revealing its three-dimensional nature. The periodicity of the out-of-plane dispersion corresponds to the distance between neighbouring CuO
planes rather than to the crystallographic c-axis lattice constant, suggesting that the interplane Coulomb interaction is responsible for the coherent out-of-plane charge dynamics. The observed properties are hallmarks of the long-sought 'acoustic plasmon', which is a branch of distinct charge collective modes predicted for layered systems
and argued to play a substantial part in mediating high-temperature superconductivity
.
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KISLJ, NUK, SBMB, UL, UM, UPUK
Electron-boson coupling plays a key role in superconductivity for many systems. However, in copper-based high-critical temperature (
) superconductors, its relation to superconductivity remains ...controversial despite strong spectroscopic fingerprints. In this study, we used angle-resolved photoemission spectroscopy to find a pronounced correlation between the superconducting gap and the bosonic coupling strength near the Brillouin zone boundary in Bi
Sr
CaCu
O
The bosonic coupling strength rapidly increases from the overdoped Fermi liquid regime to the optimally doped strange metal, concomitant with the quadrupled superconducting gap and the doubled gap-to-
ratio across the pseudogap boundary. This synchronized lattice and electronic response suggests that the effects of electronic interaction and the electron-phonon coupling (EPC) reinforce each other in a positive-feedback loop upon entering the strange-metal regime, which in turn drives a stronger superconductivity.
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