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An orthogonal, charge-density-versus-net-charge, surface-chemical gradient, composed of ternary mixed self-assembled monolayers, has been prepared from three hydrophilic components: positively chargeable amine-terminated, negatively chargeable carboxylic-acid-terminated, and hydroxyl-terminated alkanethiols, with the latter bearing a slight negative charge in electrolytes. The chemical composition and its distribution have been monitored by X-ray photoelectron spectroscopy. The adsorption behavior of negatively charged SiO(2) nanoparticles and positively charged amine-modified SiO(2) nanoparticles has been studied. Additionally, negatively charged proteins (bovine serum albumin and fibrinogen) and positively charged proteins (lysozyme) were adsorbed on the gradients. Negatively charged nanoparticles and proteins adsorb mainly in the positively charged region and vice versa, illustrating that the adsorption behavior is mainly influenced by electrostatic interactions, and showing the potential of the gradient for sorting applications. Despite literature reports to the contrary, no area was found that was completely resistant to protein adsorption.

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An orthogonal surface-chemical gradient composed of self-assembled monolayers on gold has been prepared by successive, controlled immersions in orthogonal directions into dilute solutions of dodecanethiol and perfluorododecanethiol. The resulting two-component orthogonal gradient in surface coverage was backfilled with 11-mercaptoundecanol, leading to a two-directional, three-component surface-chemical gradient. Water and hexadecane show distinctly different wetting behaviors on the gradient surface because of the differences in the hydrophobic and oleophobic natures of the three different constituents. These results are correlated with the chemical composition maps of the surface obtained by X-ray photoelectron spectroscopy. The homogeneity and the ordering of the self-assembled monolayer were investigated by dynamic water contact angle measurements and polarization-modulation infrared reflection-absorption spectroscopy.

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We describe a novel platform on which to study carbohydrate-protein interactions based on ruthenium(II) glycodendrimers as optical and electrochemical probes. Using the prototypical concanavalin A (ConA)-mannose lectin-carbohydrate interaction as an example, oligosaccharide concentrations were electrochemically monitored. The displacement of the Ru(II) complex from lectin-functionalized gold surfaces was repeatedly regenerated. This new platform presents a method to monitor many different complex sugars in parallel.

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Low-temperature absorption spectra of single crystals of Tm2+-doped CsCaCl3, CsCaBr3, and CsCaI3 in the spectral range from 8700 to 47000 cm-1 are presented. Weak sharp-line 4f-4f absorptions around 8800 cm-1 are essentially independent of the nature of the halide. More-intense broad absorptions cover the region between 12000 and 47000 cm-1. They are assigned to 4f-5d excitations and interpreted in terms of a simple qualitative picture taking into account the most important interactions. As a result of two counterbalancing effects, the onsets of the 4f-5d spectra are almost coincident in the three materials: The blue-shift of about 3000 cm-1 between chloride and iodide resulting from the decreasing crystal field splitting of 5d is roughly balanced by the red-shift resulting from the reduced energy gap between the average energy of the 4f13 and the 4f125d1 electron configurations. The absorption helps the understanding of the most unusual light emission properties of these materials.

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Absorption, light emission, and upconversion properties of Tm2+-doped CsCaI3 and RbCaI3 single crystals are presented and compared. Both compounds show multiple emissions after excitation at 21834 cm(-1) between 10 and 300 K. Besides sharp 4f-4f transitions around 8800 cm(-1), five and three broad 4f-5d emission bands are observed at higher energies in CsCaI3:Tm2+ and RbCaI3:Tm2+, respectively. The 4f-5d transitions are very sensitive to the crystalline environment: the onset of the 4f-5d excitations is red-shifted by about 1000 cm(-1) in RbCaI3:Tm2+ compared to CsCaI3:Tm2+. In addition, a broadening of bands is observed in the former compound. These differences are attributed to the structural changes that occur when the alkali metal is changed from Cs to Rb in these crystal lattices. An increased energy splitting of the multiplets and a red shift of the barycenter of the (4f)12(5d)1 electron configuration in RbCaI3:Tm2+ is the result. This affects not only the color of the visible emission, which turns from green in CsCaI3:Tm2+ to yellow in RbCaI3:Tm2+, but also the excited state dynamics. As a consequence, the dominant upconversion processes are different in the two compounds. Thus, the two title compounds nicely illustrate the influence of the structural environment on the optical spectroscopic properties of Tm2+.

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Tm2+ doped in CsCaI3 displays unusual optical properties that are characterized by the existence of two metastable 4f-5d excited states in the near-infrared and visible spectral region, respectively. For the first time, a photon upconversion process based on sequential absorption of light by 4f-5d states is reported. The large absorption cross-section of the involved transitions allows highly efficient pumping in the NIR. An efficiency of 11% for the green upconversion luminescence is reached at 10 K, and the upconversion luminescence remains visible by eye up to room temperature. The energy positions of the relevant 4f-5d states and thus the photophysical and light emission properties can be tuned by chemical variation, such as placing the Tm2+ ion into the isostructural CsCaBr3 and CsCaCl3 lattices.

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The light-emission and photophysical properties of CsCaCl3:Tm2+ (1.04%), CsCaBr3:Tm2+ (0.48%), and CsCaI3:Tm2+ (0.76%) are presented. We find that Tm2+ is a multiple emitter under 21,834 cm-1 laser excitation at low temperatures in all three compounds. Several distinct types of emission are observed and characterized: sharp and long-lived 4f-4f emission in the infrared (IR) and up to four broad and fast decaying emission bands in the near-IR and visible, originating from the 4f-5d states of Tm2+. The optical spectroscopic properties of the samples are compared, and we find that the measured differences in the relative intensities and the shifts in the position of the emissions can be related to the chemical influence on the absorption and emission properties of Tm2+. Thus, it nicely illustrates the principle of chemical variation on the optical spectroscopic properties. An investigation of the temperature dependence of the luminescence yields important information about the dynamics of the excited states. The interplay and competition between radiative and nonradiative pathways is explained and modeled using a single configurational coordinate approach.

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A high quantum yield and an enhanced photostability was found for a europium(III) tetrakis(2-thenoyltrifluoroacetonate) complex after dissolving the complex in a weakly-coordinating imidazolium ionic liquid.