CO adsorption on the calcite(10.4) surface: a combined experimental and theoretical study.

Detailed information on structural, chemical, and physical properties of natural cleaved (10.4) calcite surfaces was obtained by a combined atomic force microscopy (AFM) and infrared (IR) study using CO as a probe molecule under ultrahigh vacuum (UHV) conditions. The structural quality of the surfaces was determined using non-contact AFM (NC-AFM), which also allowed assigning the adsorption site of CO molecules. Vibrational frequencies of adsorbed CO species were determined by polarization-resolved infrared reflection absorption spectroscopy (IRRAS). At low exposures, adsorption of CO on the freshly cleaved (10.4) calcite surface at a temperature of 62 K led to the occurrence of a single C-O vibrational band located at 2175.8 cm-1, blue-shifted with respect to the gas phase value. For larger exposures, a slight, coverage-induced redshift was observed, leading to a frequency of 2173.4 cm-1 for a full monolayer. The width of the vibrational bands is extremely small, providing strong evidence that the cleaved calcite surface is well-defined with only one CO adsorption site. A quantitative analysis of the IRRA spectra recorded at different surface temperatures revealed a CO binding energy of -0.31 eV. NC-AFM data acquired at 5 K for sub-monolayer CO coverage reveal single molecules imaged as depressions at the position of the protruding surface features, in agreement with the IRRAS results. Since there are no previous experimental data of this type, the interpretation of the results was aided by employing density functional theory calculations to determine adsorption geometries, binding energies, and vibrational frequencies of carbon monoxide on the (10.4) calcite surface. It was found that the preferred geometry of CO on this surface is adsorption on top of calcium in a slightly tilted orientation. With increased coverage, the binding energy shows a small decrease, revealing the presence of repulsive adsorbate-adsorbate interactions.

Nanomolar Synthesis in Droplet Microarrays with UV-Triggered On-Chip Cell Screening.

Miniaturization and parallelization of combinatorial organic synthesis is important to accelerate the process of drug discovery while reducing the consumption of reagents and solvents. This work presents a miniaturized platform for on-chip solid-phase combinatorial library synthesis with UV-triggered on-chip cell screening. The platform is based on a nanoporous polymer coating on a glass slide, which is modified via photolithography to yield arrays of hydrophilic (HL) spots surrounded by superhydrophobic (SH) surface. The combination of HL spots and SH background enables confinement of nanoliter droplets, functioning as miniaturized reactors for the solid-phase synthesis. The polymer serves as support for nanomolar solid-phase synthesis, while a photocleavable linker enables the release of the synthesized compounds into the droplets containing live cells. A 588 compound library of bisamides is synthesized via a four-component Ugi reaction on the chip and products are detected via stamping of the droplet array onto a conductive substrate and subsequent matrix-assisted laser desorption ionization mass spectrometry. The light-induced cleavage shows high flexibility in screening conditions by spatial, temporal, and quantitative control.

Chemical Reactivity of Supported ZnO Clusters: Undercoordinated Zinc and Oxygen Atoms as Active Sites.

The growth of ZnO clusters supported by ZnO-bilayers on Ag(111) and the interaction of these oxide nanostructures with water have been studied by a multi-technique approach combining temperature-dependent infrared reflection absorption spectroscopy (IRRAS), grazing-emission X-ray photoelectron spectroscopy, and density functional theory calculations. Our results reveal that the ZnO bilayers exhibiting graphite-like structure are chemically inactive for water dissociation, whereas small ZnO clusters formed on top of these well-defined, yet chemically passive supports show extremely high reactivity - water is dissociated without an apparent activation barrier. Systematic isotopic substitution experiments using H2 16 O/D2 16 O/D2 18 O allow identification of various types of acidic hydroxyl groups. We demonstrate that a reliable characterization of these OH-species is possible via co-adsorption of CO, which leads to a red shift of the OD frequency due to the weak interaction via hydrogen bonding. The theoretical results provide atomic-level insight into the surface structure and chemical activity of the supported ZnO clusters and allow identification of the presence of under-coordinated Zn and O atoms at the edges and corners of the ZnO clusters as the active sites for H2 O dissociation.

Nanoscale-Specific Reaction in a Precursor Film: Mixing Sodium Carbonate, Calcium Chloride, and an Organic Thiol to Produce Crystals of Calcium sulfate.

The ultrathin precursor film surrounding droplets of liquid on a solid surface is used here as a confined reaction medium in order to drive a reaction that would not occur in bulk fluid. Sodium carbonate and calcium chloride mixed together in the presence of the organic thiol dithiothreitol (DTT) produced crystals of gypsum, or calcium sulfate, instead of the otherwise expected calcium carbonate. The possible sources of sulfate in the system are contaminants in the DTT or the oxidation product of the DTT sulfhydryl. The amount of gypsum produced implies that contaminants do not account for the total sulfate present in the system, suggesting that the DTT could be oxidized. The reaction quotient may be skewed in favor of this unexpected reaction by a combination of efficient removal of sulfate by precipitation and the concentration of DTT at the leading edge of the precursor film through the coffee-ring effect during a brief drying step.

Magnetic Properties and Mössbauer Spectroscopy of Fe3O4/CoFe2O4 Nanorods.

Fe3O4/CoFe2O4 nanorods were obtained via a simple seed-mediated synthesis. Nanorods were used as seeds to grow CoFe2O4 by thermal codecomposition of the cobalt(II) and iron(III) acetylacetonate precursors. The growth process was monitored by electron microscopy (SEM, TEM), and the resulting nanorods were characterized by powder X-ray diffraction analysis and IR and Raman spectroscopy. Magnetometry and AC susceptometry studies revealed a distribution of Néel relaxation times with an average blocking temperature of 140 K and a high-field magnetization of 42 Am2/kg. Complementarily recorded 57Fe-Mössbauer spectra were consistent with the Fe3O4/CoFe2O4 spinel structure and exhibited considerable signs of spin frustration, which was correlated to the internal and surface structure of the nanorods.

Interplay of Electronic and Steric Effects to Yield Low-Temperature CO Oxidation at Metal Single Sites in Defect-Engineered HKUST-1.

In contrast to catalytically active metal single atoms deposited on oxide nanoparticles, the crystalline nature of metal-organic frameworks (MOFs) allows for a thorough characterization of reaction mechanisms. Using defect-free HKUST-1 MOF thin films, we demonstrate that Cu+ /Cu2+ dimer defects, created in a controlled fashion by reducing the pristine Cu2+ /Cu2+ pairs of the intact framework, account for the high catalytic activity in low-temperature CO oxidation. Combining advanced IR spectroscopy and density functional theory we propose a new reaction mechanism where the key intermediate is an uncharged O2 species, weakly bound to Cu+ /Cu2+ . Our results reveal a complex interplay between electronic and steric effects at defect sites in MOFs and provide important guidelines for tailoring and exploiting the catalytic activity of single metal atom sites.

Inverse Vulcanization of Styrylethyltrimethoxysilane-Coated Surfaces, Particles, and Crosslinked Materials.

Sulfur as a side product of natural gas and oil refining is an underused resource. Converting landfilled sulfur waste into materials merges the ecological imperative of resource efficiency with economic considerations. A strategy to convert sulfur into polymeric materials is the inverse vulcanization reaction of sulfur with alkenes. However, the materials formed are of limited applicability, because they need to be cured at high temperatures (>130 °C) for many hours. Herein, we report the reaction of elemental sulfur with styrylethyltrimethoxysilane. Marrying the inverse vulcanization and silane chemistry yielded high sulfur content polysilanes, which could be cured via room temperature polycondensation to obtain coated surfaces, particles, and crosslinked materials. The polycondensation was triggered by hydrolysis of poly(sulfur-r-styrylethyltrimethoxysilane) (poly(Sn -r-StyTMS) under mild conditions (HCl, pH 4). For the first time, an inverse vulcanization polymer could be conveniently coated and mildly cured via post-polycondensation. Silica microparticles coated with the high sulfur content polymer could improve their Hg2+ ion remediation capability.

Biopebble Containers: DNA-Directed Surface Assembly of Mesoporous Silica Nanoparticles for Cell Studies.

The development of methods for colloidal self-assembly on solid surfaces is important for many applications in biomedical sciences. Toward this goal, described is a versatile class of mesoporous silica nanoparticles (MSN) that contain on their surface various types of DNA molecules to enable their self-assembly into micropatterned surface architectures useful for cell studies. Monodisperse dye-doped MSN are synthesized by biphase stratification and functionalized with an aptamer oligonucleotide that serves as gatekeeper for the triggered release of encapsulated molecular cargo, such as fluorescent dye rhodamine B or the anticancer drug doxorubicin. One or two additional types of oligonucleotides are installed on the MSN surface to enable DNA-directed immobilization on solid substrates bearing patterns of complementary capture oligonucleotides. It is demonstrated that this strategy can be used for efficient self-assembly of microstructured surface architectures, which not only promote the adhesion and guidance of cells but also are capable of affecting the fate of adhered cells through triggered release of their cargo. It is believed that this approach is useful for diverse applications in tissue engineering and nanobio sciences.

Monitoring Reactions on Solid Phases with Raman Spectroscopy.

The benefits of Raman spectroscopy were shown for the on-bead monitoring of diverse reactions. Raman spectroscopy was used for the development of new procedures on established linker systems, the real-time observation of several reactions on solid phases and the estimation of the reaction time for a new cleavage strategy. Selected conversions on solid phases, such as the on-bead conversion of functional groups and the attachment of novel building blocks, were demonstrated. Raman spectra were obtained after isolation and purification of the solid supports, but they were also measured directly in the reaction vessels. Even the detection of Raman-active functional groups in swollen polymer resins and in reaction mixtures was demonstrated, and allows real-time observation of the progress of diverse reactions on solid supports.

Surface Faceting and Reconstruction of Ceria Nanoparticles.

The surface atomic arrangement of metal oxides determines their physical and chemical properties, and the ability to control and optimize structural parameters is of crucial importance for many applications, in particular in heterogeneous catalysis and photocatalysis. Whereas the structures of macroscopic single crystals can be determined with established methods, for nanoparticles (NPs), this is a challenging task. Herein, we describe the use of CO as a probe molecule to determine the structure of the surfaces exposed by rod-shaped ceria NPs. After calibrating the CO stretching frequencies using results obtained for different ceria single-crystal surfaces, we found that the rod-shaped NPs actually restructure and expose {111} nanofacets. This finding has important consequences for understanding the controversial surface chemistry of these catalytically highly active ceria NPs and paves the way for the predictive, rational design of catalytic materials at the nanoscale.

Rendering Photoreactivity to Ceria: The Role of Defects.

The photoreactivity of ceria, a photochemically inert oxide with a large band gap, can be increased to competitive values by introducing defects. This previously unexplained phenomenon has been investigated by monitoring the UV-induced decomposition of N2 O on well-defined single crystals of ceria by using infrared reflection-absorption spectroscopy (IRRAS). The IRRAS data, in conjunction with theory, provide direct evidence that reducing the ceria(110) surface yields high photoreactivity. No such effects are seen on the (111) surface. The low-temperature photodecomposition of N2 O occurs at surface O vacancies on the (110) surface, where the electron-rich cerium cations with a significantly lowered coordination number cause a local lowering of the huge band gap (ca. 6 eV). The quantum efficiency of strongly reduced ceria(110) surfaces in the photodecomposition of N2 O amounts to 0.03 %, and is thus comparable to that reported for the photooxidation of CO on rutile TiO2 (110).

O2 Activation on Ceria Catalysts-The Importance of Substrate Crystallographic Orientation.

An atomic-level understanding of dioxygen activation on metal oxides remains one of the major challenges in heterogeneous catalysis. By performing a thorough surface-science study of all three low-index single-crystal surfaces of ceria, probably the most important redox catalysts, we provide a direct spectroscopic characterization of reactive dioxygen species at defect sites on the reduced ceria (110) and (100) surfaces. Surprisingly, neither of these superoxo and peroxo species was found on ceria (111), the thermodynamically most stable surface of this oxide. Applying density functional theory, we could relate these apparently inconsistent findings to a sub-surface diffusion of O vacancies on (111) substrates, but not on the less-closely packed surfaces. These observations resolve a long standing debate concerning the location of O vacancies on ceria surfaces and the activation of O2 on ceria powders.

Novel Prodrug of Doxorubicin Modified by Stearoylspermine Encapsulated into PEG-Chitosan-Stabilized Liposomes.

Here, we report a new modification of doxorubicin based on an amphiphilic stearoylspermine anchor, enabling loading into liposomal membranes. Doxorubicin is coupled with stearoylspermine through an acid-labile hydrazone linker to ensure the release of the drug in the acidic interstitium of tumors. Using ATR-FTIR spectroscopy (Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy), the mechanism of interaction of doxorubicin with the anionic liposomal membrane was studied: incorporation of stearoyl chains leads to an increase in local microfluidity, and the amino groups of spermine interact with the phosphate groups of lipids. To stabilize liposomes against aggregation, we applied the copolymer PEG-chitosan as a coating: complex formation leads to charge neutralization, and the liposomes grow in size. According to MTT tests and confocal microscopy for cell lines A459 and Caco-2, PEG-chitosan-coated liposomes are as effective as neutral liposomes but are much more stable.

Electrochromic switching of monolithic Prussian blue thin film devices.

Monolithic, crystalline and highly oriented coordination network compound (CNC) Prussian blue (PB) thin films have been deposited though different routes on conductive substrates. Characterization of the monolithic thin films reveals a long-term stability, even after many redox cycles the crystallinity as well as the high orientation remain intact during the electrochromic switching process.

A photolithographic approach to spatially resolved cross-linked nanolayers.

The preparation of cross-linked nanosheets with 1-2 nm thickness and predefined shape was achieved by lithographic immobilization of trimethacryloyl thioalkanoates onto the surface of Si wafers, which were functionalized with 2-(phenacylthio)acetamido groups via a photoinduced reaction. Subsequent cross-linking via free radical polymerization as well as a phototriggered Diels-Alder reaction under mild conditions on the surface led to the desired nanosheets. Electrospray ionization mass spectrometry (ESI-MS), X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), as well as infrared reflection-absorption spectroscopy (IRRAS) confirmed the success of individual surface-modification and cross-linking reactions. The thickness and lateral size of the cross-linked structures were determined by atomic force microscopy (AFM) for samples prepared on Si wafers functionalized with a self-assembled monolayer of 1H,1H,2H,2H-perfluorodecyl groups bearing circular pores obtained via a polymer blend lithographic approach, which led to the cross-linking reactions occurring in circular nanoareas (diameter of 50-640 nm) yielding an average thickness of 1.2 nm (radical cross-linking), 1.8 nm (radical cross-linking in the presence of 2,2,2-trifluoroethyl methacrylate as a comonomer), and 1.1 nm (photochemical cross-linking) of the nanosheets.

On the self-assembly of TiOx into 1D NP network nanostructures.

Here, we report for the first time a 'ligand free' method of designing 1D TiOx supramolecular network materials, which starts from Ti bare metal powder. Each TiOx oxidation step has been carefully investigated with different analytical techniques, including high resolution transmission electron microscopy/high resolution scanning electron microscopy (HRTEM/HRSEM), x-ray photoelectron spectroscopy (XPS), Raman spectroscopy and superconducting quantum interference device (SQUID) measurements. The self-assembly of TiOx nanoparticles (NPs) into 1D supramolecular nanoparticle networks is induced by the formation of mixed valent Ti(II,III) species. The synthesis starts with etching a bare Ti surface, followed by a continuous oxidation of TiOx clusters and NPs, and it finally ends with the self-assembly into rigid 1D NPs chains. Today, such self-assembled 1D NP TiOx network materials are bridging the gap between the nanoscale and the macroscopic material world and will further provide interesting research opportunities.

Oriented circular dichroism analysis of chiral surface-anchored metal-organic frameworks grown by liquid-phase epitaxy and upon loading with chiral guest compounds.

Oriented circular dichroism (OCD) is explored and successfully applied to investigate chiral surface-anchored metal-organic frameworks (SURMOFs) based on camphoric acid (D- and Lcam) with the composition [Cu2(Dcam)(2x)(Lcam)(2-2x)(dabco)]n (dabco = 1,4-diazabicyclo-[2.2.2]-octane). The three-dimensional chiral SURMOFs with high-quality orientation were grown on quartz glass plates by using a layer-by-layer liquid-phase epitaxy method. The growth orientation, as determined by X-ray diffraction (XRD), could be switched between the [001] and [110] direction by using either OH- or COOH-terminated substrates. These SURMOFs were characterized by using OCD, which confirmed the ratio as well as the orientation of the enantiomeric linker molecules. Theoretical computations demonstrate that the OCD band intensities of the enantiopure [Cu2(Dcam)2(dabco)]n grown in different orientations are a direct result of the anisotropic nature of the chiral SURMOFs. Finally, the enantiopure [Cu2(Dcam)2(dabco)]n and [Cu2(Lcam)2(dabco)]n SURMOFs were loaded with the two chiral forms of ethyl lactate [(+)-ethyl-D-lactate and (-)-ethyl-L-lactate)]. An enantioselective enrichment of >60 % was observed by OCD when the chiral host scaffold was loaded from the racemic mixture.

Interaction of human plasma proteins with thin gelatin-based hydrogel films: a QCM-D and ToF-SIMS study.

In the fields of surgery and regenerative medicine, it is crucial to understand the interactions of proteins with the biomaterials used as implants. Protein adsorption directly influences cell-material interactions in vivo and, as a result, regulates, for example, cell adhesion on the surface of the implant. Therefore, the development of suitable analytical techniques together with well-defined model systems allowing for the detection, characterization, and quantification of protein adsorbates is essential. In this study, a protocol for the deposition of highly stable, thin gelatin-based films on various substrates has been developed. The hydrogel films were characterized morphologically and chemically. Due to the obtained low thickness of the hydrogel layer, this setup allowed for a quantitative study on the interaction of human proteins (albumin and fibrinogen) with the hydrogel by Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D). This technique enables the determination of adsorbant mass and changes in the shear modulus of the hydrogel layer upon adsorption of human proteins. Furthermore, Secondary Ion Mass Spectrometry and principal component analysis was applied to monitor the changed composition of the topmost adsorbate layer. This approach opens interesting perspectives for a sensitive screening of viscoelastic biomaterials that could be used for regenerative medicine.

Chemical activity of oxygen vacancies on ceria: a combined experimental and theoretical study on CeO2(111).

The chemical activity of oxygen vacancies on well-defined, single-crystal CeO2(111)-surfaces is investigated using CO as a probe molecule. Since no previous measurements are available, the assignment of the CO ν1 stretch frequency as determined by IR-spectroscopy for the stoichiometric and defective surfaces are aided by ab initio electronic structure calculations using density functional theory (DFT).

Resemblance of electrospun collagen nanofibers to their native structure.

Electrospinning is a promising method to mimic the native structure of the extracellular matrix. Collagen is the material of choice, since it is a natural fibrous structural protein. It is an open question how much the spinning process preserves or alters the native structure of collagen. There are conflicting results in the literature, mainly due to the different solvent systems in use and due to the fact that gelatin is employed as a reference state for the completely unfolded state of collagen in calculations. Here we used circular dichroism (CD) and Fourier-transform infrared spectroscopy (FTIR) to investigate the structure of regenerated collagen samples and scanning electron microscopy (SEM) and transmission electron microscopy (TEM) to illuminate the electrospun nanofibers. Collagen is mostly composed of folded and unfolded structures with different ratios, depending on the applied temperature. Therefore, CD spectra were acquired as a temperature series during thermal denaturation of native calf skin collagen type I and used as a reference basis to extract the degree of collagen folding in the regenerated electrospun samples. We discussed three different approaches to determine the folded fraction of collagen, based on CD spectra of collagen from 185 to 260 nm, since it would not be sufficient to obtain simply the fraction of folded structure θ from the ellipticity at a single wavelength of 221.5 nm. We demonstrated that collagen almost completely unfolded in fluorinated solvents and partially preserved its folded structure θ in HAc/EtOH. However, during the spinning process it refolded and the PP-II fraction increased. Nevertheless, it did not exceed 42% as deduced from the different secondary structure evaluation methods, discussed here. PP-II fractions in electrospun collagen nanofibers were almost same, being independent from the initial solvent systems which were used to solubilize the collagen for electrospinning process.