Excited-State Charge Distribution of a Donor-π-Acceptor Zn Porphyrin Probed by N K-Edge Transient Absorption Spectroscopy.

Zinc porphyrin solar cell dyes with donor-π-acceptor architectures combine light absorber (π), electron-donor, and electron-acceptor moieties inside a single molecule with atomic precision. The donor-π-acceptor design promotes the separation of charge carriers following optical excitation. Here, we probe the excited-state electronic structure within such molecules by combining time-resolved X-ray absorption spectroscopy at the N K-edge with first-principles time-dependent density functional theory (TD-DFT) calculations. Customized Zn porphyrins with strong-donor triphenylamine groups or weak-donor tri-tert-butylbenzene groups were synthesized. Energetically well-separated N K-edge absorption features simultaneously probe the excited-state electronic structure from the perspectives of the macrocycle and triphenylamine N atoms. New absorption transitions between the macrocycle N atoms and the excited-state HOMO vacancy are observed, and the triphenylamine associated absorption feature blue-shifts, consistent with partial oxidation of the donor groups in the excited state.

On the orbital anisotropy in hematite nanorod-based photoanodes.

The orbital anisotropy of hematite (α-Fe2O3) nanorod arrays, an engineered structure commonly investigated for applications in solar water oxidation photoanodes, is probed using polarization-dependent soft X-ray absorption spectroscopy at the O K-edge and at the Fe L2,3-edge. Thereby the unoccupied states of α-Fe2O3 are examined. In the lowest energy region these are found to be strongly-hybridized Fe 3d (a1g) orbitals and O(2-) ligand 2p orbitals, oriented along the c-axis. For [110]-oriented α-Fe2O3 nanocrystals the observed direction of strong hybridization is parallel to the substrate surface (perpendicular to the direction of electron conduction and light propagation in operating electrodes). The Fe L3-edge line shape and aspects of polarization dependence can be reproduced by crystal field atomic multiplet calculations of 2p-to-3d transitions for Fe(3+) in the D3d point group symmetry of metal ions in the corundum structure. Both the O K-edge and Fe L3-edge spectra possess features that may be related to the high density of surface atoms in this nanoscale system. They are associated with partial coordination and therefore reduced symmetry compared to that for Fe(3+) in bulk crystals.

In situ metallization of patterned polymer brushes created by molecular transfer print and fill.

A chemical pattern consisting of end-grafted polystyrene brushes (20 nm lines on a 40 nm pitch) on the native oxide of silicon wafers was defined by molecular transfer printing from assembled block co-polymer films. End-grafted hydroxyl-terminated poly(2-vinyl pyridine) brushes were selectively deposited in the interspatial regions. The poly(2-vinyl pyridine) regions selectively sequester acidic HAuCl4 from solution and form arrays of small Au nanoparticles upon exposure to oxygen plasma within the confines of the macromolecular brush layer. This print and fill process to pattern polymer brushes is a generalizable strategy to create functional chemical surface patterns.

Influence of molecular ordering on electrical and friction properties of ω-(trans-4-stilbene)alkylthiol self-assembled monolayers on Au(111).

The electrical and friction properties of ω-(trans-4-stilbene)alkylthiol self-assembled monolayers (SAMs) on Au(111) were investigated using atomic force microscopy (AFM) and near edge X-ray absorption fine structure spectroscopy (NEXAFS). The sample surface was uniformly covered with a molecular film consisting of very small grains. Well-ordered and flat monolayer islands were formed after the sample was heated in nitrogen at 120 °C for 1 h. While lattice resolved AFM images revealed a crystalline phase in the islands, the area between islands showed no order. The islands exhibit substantial reduction (50%) in friction, supporting the existence of good ordering. NEXAFS measurements revealed an average upright molecular orientation in the film, both before and after heating, with a narrower tilt-angle distribution for the heated fim. Conductance-AFM measurements revealed a 2 orders of magnitude higher conductivity on the ordered islands than on the disordered phase. We propose that the conductance enhancement is a result of a better π-π stacking between the trans-stilbene molecular units as a result of improved ordering in islands.

Quantum confinement, surface roughness, and the conduction band structure of ultrathin silicon membranes.

We report direct measurements of changes in the conduction-band structure of ultrathin silicon nanomembranes with quantum confinement. Confinement lifts the 6-fold-degeneracy of the bulk-silicon conduction-band minimum (CBM), Delta, and two inequivalent sub-band ladders, Delta(2) and Delta(4), form. We show that even very small surface roughness smears the nominally steplike features in the density of states (DOS) due to these sub-bands. We obtain the energy splitting between Delta(2) and Delta(4) and their shift with respect to the bulk value directly from the 2p(3/2)-->Delta transition in X-ray absorption. The measured dependence of the sub-band splitting and the shift of their weighted average on degree of confinement is in excellent agreement with theory, for both Si(001) and Si(110).

Polymeric brushes as functional templates for immobilizing ribonuclease A: study of binding kinetics and activity.

The ability to immobilize proteins with high binding capacities on surfaces while maintaining their activity is critical for protein microarrays and other biotechnological applications. We employed poly(acrylic acid) (PAA) brushes as templates to immobilize ribonuclease A (RNase A), which is commonly used to remove RNA from plasmid DNA preparations. The brushes are grown by surface-anchored atom-transfer radical polymerization (ATRP) initiators. RNase A was immobilized by both covalent esterification and a high binding capacity metal-ion complexation method to PAA brushes. The polymer brushes immobilized 30 times more enzyme compared to self-assembled monolayers. As the thickness of the brush increases, the surface density of the RNase A increases monotonically. The immobilization was investigated by ellipsometry, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). The activity of the immobilized RNase A was determined using UV absorbance. As much as 11.0 microg/cm(2) of RNase A was bound to PAA brushes by metal-ion complexation compared to 5.8 microg/cm(2) by covalent immobilization which is 30 and 16 times the estimated mass bound in a monolayer. The calculated diffusion coefficient D was 0.63 x 10(-14) cm(2)/s for metal-ion complexation and 0.71 x 10(-14) cm(2)/s for covalent immobilization. Similar values of D indicate that the binding kinetics is similar, but the thermodynamic equilibrium coverage varies with the binding chemistry. Immobilization kinetics and thermodynamics were characterized by ellipsometry for both methods. A maximum relative activity of 0.70-0.80 was reached between five and nine monolayers of the immobilized enzyme. However, the relative activity for covalent immobilization was greater than that of metal-ion complexation. Covalent esterification resulted in similar temperature dependence as free enzyme, whereas metal-ion complexation showed no temperature dependence indicating a significant change in conformation.