Assignment of individual structures from intermetalloid nickel gallium cluster ensembles.

Poorly selective mixed-metal cluster synthesis and separation yield reaction solutions of inseparable intermetalloid cluster mixtures, which are often discarded. High-resolution mass spectrometry, however, can provide precise compositional data of such product mixtures. Structure assignments can be achieved by advanced computational screening and consideration of the complete structural space. Here, we experimentally verify structure and composition of a whole cluster ensemble by combining a set of spectroscopic techniques. Our study case are the very similar nickel/gallium clusters of M12, M13 and M14 core composition Ni6+xGa6+y (x + y ≤ 2). The rationalization of structure, bonding and reactivity is built upon the organometallic superatom cluster [Ni6Ga6](Cp*)6 = [Ga6](NiCp*)6 (1; Cp* = C5Me5). The structural conclusions are validated by reactivity tests using carbon monoxide, which selectively binds to Ni sites, whereas (triisopropylsilyl)acetylene selectively binds to Ga sites.

Development of a New Affinity Gold Polymer Membrane with Immobilized Protein A.

New and highly selective stationary phases for affinity membrane chromatography have the potential to significantly enhance the efficiency and specificity of therapeutic protein purification by reduced mass transfer limitations. This work developed and compared different immobilization strategies for recombinant Protein A ligands to a gold-sputtered polymer membrane for antibody separation in terms of functionalization and immobilization success, protein load, and stability. Successful, functionalization was validated via X-ray photoelectron spectroscopy (XPS). Here, a recombinant Protein A ligand was coupled by N-hydroxysuccinimide (NHS)/N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) chemistry to carboxy-functionalized, gold-sputtered membranes. We achieved a binding capacity of up to 104 ± 17 mg of the protein ligand per gram of the gold-sputtered membrane. The developed membranes were able to successfully capture and release the monoclonal antibody (mAb) Trastuzumab, as well as antibodies from fresh frozen human blood plasma in both static and dynamic setups. Therefore, they demonstrated successful functionalization and immobilization strategies. The antibody load was tested using bicinchoninic acid (BCA), ultraviolet-visible spectroscopy (UV-vis) measurements, and sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). The outcome is a fully functional affinity membrane that can be implemented in a variety of different antibody purification processes, eliminating the need for creating individualized strategies for modifying the surface to suit different substrates or conditions.

Exceptional ultrafast nonlinear optical response of functionalized silicon nanosheets.

The present work reports on the ultrafast saturable absorption (SA), optical limiting (OL), and the nonlinear refractive response of hydride-terminated silicon nanosheets (SiNS-H) differently functionalized with styrene and tert-butyl methacrylate (tBuMA), namely, SiNS-styrene and SiNS-tBuMA, using 50 fs, 400 nm and 70 fs, 800 nm laser pulses. SiNS-styrene and SiNS-tBuMA exhibit dramatically enhanced nonlinear optical (NLO) responses compared to SiNS-H, with their absorptive nonlinearity strongly dependent on the laser excitation wavelength. More specifically, the studied functionalized SiNSs reveal strong SA behavior under 400 nm laser excitation, with NLO absorption coefficients, saturable intensities, and modulation depths comparable to various two-dimensional (2D) materials, known to exhibit strong SA, such as graphene, black phosphorous (BP), some transition metal dichalcogenides (TMDs), and some MXenes. On the other hand, under 800 nm laser excitation, SiNS-styrene and SiNS-tBuMA show highly efficient OL performance with OL onset values of about 0.0045 and 0.0065 J cm-2, respectively, which are significantly lower than those of other 2D nanostructures. In addition, it is shown that both SiNS samples have great potential in already existing Si-based optoelectronic devices for optical-switching applications since they exhibit very strong NLO refraction comparable to that of bulk Si. The results of the present work demonstrate that the chemical functionalization of SiNSs provides a highly efficient strategy for the preparation of 2D Si-based nanostructures with enhanced NLO response in view of several optoelectronic and photonic applications, such as OL, SA, and all-optical switching.

Thermomechanical Stress Analysis of Hydrated Vital Gluten with Large Amplitude Oscillatory Shear Rheology.

Vital gluten is increasingly researched as a non-food product for biodegradable materials. During processing, the protein network is confronted with increased thermal and mechanical stress, altering the network characteristics. With the prospect of using the protein for materials beyond food, it is important to understand the mechanical properties at various processing temperatures. To achieve this, the study investigates hydrated vital gluten under thermomechanical stress based on large amplitude oscillatory shear (LAOS) rheology. LAOS rheology was conducted at increasing shear strains (0.01-100%), various frequencies (5-20 rad/s) and temperatures of 25, 45, 55, 65, 70 and 85 °C. With elevating temperatures up to 55 °C, the linear viscoelastic moduli decrease, indicating material softening. Then, protein polymerization and the formation of new cross-links due to thermal denaturation cause more network connectivity, resulting in significantly higher elastic moduli. Beyond the linear viscoelastic regime, the strain-stiffening ratio rises disproportionately. This effect becomes even more evident at higher temperatures. Lacking a viscous contribution, the highly elastic but also stiff network shows less mechanical resilience. Additionally, at these elevated temperatures, structural changes during the protein's denaturation and network shrinkage due to water evaporation could be visualized with confocal laser scanning microscopy (CLSM).

Versatile procedure for the correction of non-isochromatism in XPEEM spectroscopic imaging.

Non-isochromatism in X-ray PhotoEmission Electron Microscopy (XPEEM) may result in unwanted artifacts especially when working with large field of views. The lack of isochromatism of XPEEM images may result from multiple factors, for instance the energy dispersion of the X-rays on the sample or the effect of one or more dispersive elements in the electron optics of the microscope, or the combination of both. In practice, the photon energy or the electron kinetic energy may vary across the image, complicating image interpretation and analysis. The effect becomes severe when imaging at low magnification upon irradiation with high energy photons. Such imaging demands for a large X-ray illuminating spot size usually achieved by opening the exit slit of the X-ray monochromator while reducing the monochromaticity of the irradiating light. However, we show that the effect is linear and can be fully removed. A versatile correction procedure is presented which leads to true monochromatic photoelectron images at improved signal-to-noise ratio. XPEEM data recorded at the nanospectroscopy beamline of the Elettra synchrotron radiation facility illustrate the working principle of the procedure. Also, reciprocal space XPEEM data such as angle-resolved photoelectron spectroscopy (ARPES) momentum plots suffer from linear energy dispersion artifacts which can be corrected in a similar way. Representative data acquired from graphene synthesized on copper by chemical vapor deposition prove the benefits of the correction procedure.

Exploiting Cooperative Catalysis for the On-Surface Synthesis of Linear Heteroaromatic Polymers via Selective C-H Activation.

Regiospecific C-H activation is a promising approach to achieve extended polymers with tailored structures. While a recent on-surface synthetic approach has enabled regioselective homocoupling of heteroaromatic molecules, only small oligomers have been achieved. Herein, selective C-H activation for dehydrogenative C-C couplings of hexaazatriphenylene by Scholl reaction is reported for the first time. By combining low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM), we revealed the formation of one-dimensional polymers with a double-chain structure. The details of the growth process are rationalized by density functional theory (DFT) calculations, pointing out a cooperative catalytic action of Na and Ag adatoms in steering the C-H selectivity for the polymerization.

Nanometallurgy in solution: organometallic synthesis of intermetallic Pd-Ga colloids and their activity in semi-hydrogenation catalysis.

Nanoparticles (NPs) of Pd1--xGax (x = 0.67, 0.5, 0.33), stabilized in non-aqueous colloidal solution, were obtained via an organometallic approach under mild conditions using [Pd2(dvds)3] and GaCp* as all-hydrocarbon ligated metal-precursor compounds (dvds = 1,1,3,3-tetramethyl-1,3-divinyl-disiloxane; Cp* = η5-C5Me5; Me = CH3). The reaction of the two precursors involves the formation of a library of molecular clusters [PdnGamCp*y(dvds)z], as shown by liquid injection field desorption ionization mass spectrometry (LIFDI-MS). Full characterization of the catalytic system (HR-TEM, EDX, DLS, PXRD, XPS, NMR, IR, Raman) confirmed the formation of ultra-small, spherical NPs with narrow size distributions ranging from 1.2 ± 0.2 nm to 2.1 ± 0.4 nm (depending on the Pd : Ga ratio). The catalytic performance of the Pd1--xGax NPs in the semi-hydrogenation of terminal and internal alkynes and the influence of the gallium content on product selectivity were investigated. The highest activities (65%) and selectivities (81%) are achieved using colloids with a "stoichiometric" Pd/Ga ratio of 1 : 1 at 0 °C and 2.0 bar H2 pressure. While lower Ga ratios lead to an increase in activity, higher Ga contents increase the olefin selectivity but are detrimental to the activity.

Thermally induced gluten modification observed with rheology and spectroscopies.

The protein vital gluten is mainly used for food while interest for non-food applications, like biodegradable materials, increases. In general, the structure and functionality of proteins is highly dependent on thermal treatments during production or modification. This study presents conformational changes and corresponding rheological effects of vital wheat gluten depending on temperature. Dry samples analyzed by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FTIR) and thermalgravimetric analysis coupled with mass spectrometry (TGA-MS) show surface compositions and conformational changes from 25 to 250 °C. Above 170 °C, XPS reveals a decreased N content at the surface while FTIR band characteristics for ß-sheets prove structural changes. At 250 °C, protein denaturation accompanied by a significant mass loss due to dehydration and decarbonylation reactions is observed. Oscillatory measurements of optimally hydrated vital gluten describing network properties of the material show two structural changes along a temperature ramp from 25 to 90 °C: at 56-64 °C, the temperature necessary to trigger structural changes increases with the ratio of gliadin to total protein mass, determined by reversed-phase high performance liquid chromatography (RP-HPLC). At a temperature of 79-81 °C, complete protein denaturation occurs. FTIR confirms the denaturation process by showing band shifts with both temperature steps.

Silicon Nanosheets versus Graphene Nanosheets: A Comparison of Their Nonlinear Optical Response.

Silicene, the silicon analogue of graphene, represents a new class of two-dimensional (2D) materials, which shares some of the outstanding physical properties of graphene. Furthermore, it has the advantage of being compatible with the current Si-based technology. However, this 2D material is not stable and is quite prone to oxidation. The hydride-terminated silicene, called silicane, is a more stable form of 2D silicon, if functionalized via, for example, the hydrosilylation reaction. In this work, the third-order nonlinear optical (NLO) properties of two functionalized silicanes, namely hydride-terminated silicon nanosheets (SiNS-H) and 1-dodecene-functionalized silicon nanosheets (SiNS-dodecene), are accessed and compared to those of single-layer graphene, under 35 ps, 532 and 1064 nm excitation. The present results show that the functionalized silicanes exhibit comparable and even higher NLO response than that of single-layer graphene, making them strong competitors of graphene and very interesting candidates for future photonic and optoelectronic applications.

Generation and Stabilization of Small Platinum Clusters Pt12±x Inside a Metal-Organic Framework.

The generation and matrix stabilization of ligand-free, small platinum nanoclusters (NCs) Pt12±x is presented. The metal-organic framework-template approach is based on encapsulating CO-ligated, atom-precise Pt9 Chini clusters [{Pt3(CO)6}3]2- into the zeolitic imidazolate framework ZIF-8. The selective formation of the air-stable inclusion compound [NBu4]2[{Pt3(CO)6}4]@ZIF-8 of defined atomicity Pt12 and with Pt loadings of 1-20 wt % was monitored by UV/vis and IR spectroscopy and was confirmed by high-resolution transmission electron microscopy (HR-TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), and powder X-ray diffraction (PXRD). Thermally induced decarbonylation at 200 °C yields the composite material Ptn@ZIF-8 with a cluster atomicity n close to 12, irrespective of the Pt loading. The PtNCs retain their size even during annealing at 300 °C for 24 h and during catalytic hydrogenation of 1-hexene at 25 °C in the liquid phase. The Ptn@ZIF-8 material can conveniently be used for storing small PtNCs and their further processing. Removal of the protective ZIF-8 matrix under acidic conditions and transfer of the PtNCs to carbon substrates yields defined aggregation to small Pt nanoparticles (1.14 ± 0.35 nm, HR-TEM), which have previously shown exceptional performance in the electrocatalytic oxygen reduction reaction (ORR).

Mixed precious-group metal-organic frameworks: a case study of the HKUST-1 analogue [RuxRh3-x(BTC)2].

This work presents the first full series of mixed precious-group metal-organic frameworks (MPG-MOFs) using ruthenium and rhodium. The obtained crystalline, highly porous and thermally robust materials were characterized by means of powder X-ray diffraction, N2/CO2 sorption isotherms, thermogravimetry, spectroscopy methods (IR, Raman, UV/VIS-, NMR and XPS) and as well by high resolution transmission electron microscopy (HR-TEM) with elemental mapping (HAADF-EDS). Additionally, the assignment of spectroscopic data is supported by computational (time dependent)-density functional theory methods. The materials turned out to consist of homogeneously dispersed Ru2 and Rh2 paddlewheel units being linked by benzenetricarboxylate (BTC) to yield a framework that is isoreticular to [Cu3(BTC)2] (HKUST-1, Hong Kong University of Science and Technology). However, acetate (OAc) is incorporated as an intrinsic component which compensates for missing BTC-linker defects and some Cl is coordinated to the Ru centre at an apical position. The exact empirical formula of the MPG-MOFs is derived as [RuxRh3-x(BTC)2-a(OAc)b(Cl)c].

Optimizing the Size of Platinum Nanoparticles for Enhanced Mass Activity in the Electrochemical Oxygen Reduction Reaction.

High oxygen reduction (ORR) activity has been for many years considered as the key to many energy applications. Herein, by combining theory and experiment we prepare Pt nanoparticles with optimal size for the efficient ORR in proton-exchange-membrane fuel cells. Optimal nanoparticle sizes are predicted near 1, 2, and 3 nm by computational screening. To corroborate our computational results, we have addressed the challenge of approximately 1 nm sized Pt nanoparticle synthesis with a metal-organic framework (MOF) template approach. The electrocatalyst was characterized by HR-TEM, XPS, and its ORR activity was measured using a rotating disk electrode setup. The observed mass activities (0.87±0.14 A mgPt -1 ) are close to the computational prediction (0.99 A mgPt -1 ). We report the highest to date mass activity among pure Pt catalysts for the ORR within similar size range. The specific and mass activities are twice as high as the Tanaka commercial Pt/C catalysis.

Observation of a novel double layer surface oxide phase on Ni3Al(111) at low temperature.

The Ni3Al(111) surface was characterized during oxidation within the temperature range of 690-800 K by in situ scanning tunneling microscopy (STM), low energy electron diffraction (LEED) and auger electron spectroscopy (AES). Within this temperature range oxygen dosing always leads to the formation of a surface aluminum oxide layer while Ni atoms remain in their metallic state. The temperature however, affects the kinetics and the structure of the grown oxides. Above 790 K the known (√67 × âˆš67)R12.2° double layer oxide grows, which consists of two Al-O layers. Oxygen dosing at the lower temperature of 740 ± 10 K leads to a single layer oxide with only one Al-O plane. The lattice mismatch of the aligned oxygen and substrate lattices induce a (7 × 7) moiré pattern of this surface phase. Surprisingly, when lowering the sample temperature below 720 K during oxygen exposure, again a bilayer oxide grows on the Ni3Al(111) surface. The formation of this bilayer oxide starts with the growth of the single layer oxide that is subsequently covered by a second Al-O layer. At temperatures close to 720 K, the 2nd layer is ordered and a diffraction pattern is observed indicating a (4√3 × 4√3)R30° unit cell with regard to the oxygen lattice of the surface oxide. A structure model is presented that relates this so far unknown double layer oxide to the building principle of α-Al2O3. The respective growth kinetics and the availability of Al atoms dictate whether the single or the low temperature double layer oxide is formed. The related mass transport on the surface can be observed using in situ STM which allows the qualitative discussion of the growth kinetics. When lowering the oxide growth temperature below 700 K, the 2nd oxide layer is still formed ontop of the single layer oxide but in a disordered state so that the LEED pattern of the single layer oxide with a (7 × 7) moiré unit cell is again observed. This accounts for the confusing fact that the (7 × 7) moiré LEED pattern may indicate either the formation of a single or a low temperature double layer oxide.