Design Principles for Two-Dimensional Molecular Aggregates Using Kasha's Model: Tunable Photophysics in Near and Short-Wave Infrared

Technologies which utilize near-infrared (700 – 1000 nm) and short-wave infrared (1000 – 2000 nm) electromagnetic radiation have applications in deep-tissue imaging, telecommunications and satellite telemetry due to low scattering and decreased background signal in this spectral region. It is therefore necessary to develop materials that absorb light efficiently beyond 1000 nm. Transition dipole moment coupling (e.g. J-aggregation) allows for redshifted excitonic states and provides a pathway to highly absorptive electronic states in the infrared. We present aggregates of two cyanine dyes whose absorption peaks redshift dramatically upon aggregation in water from ~800 nm to 1000 nm and 1050 nm respectively with sheet-like morphologies and high molar absorptivities (e ~ 105 M-1cm-1). We use Frenkel exciton theory to extend Kasha’s model for J and H aggregation and describe the excitonic states of 2-dimensional aggregates whose slip is controlled by steric hindrance in the assembled structure. A consequence of the increased dimensionality is the phenomenon of an intermediate “I-aggregate”, one which redshifts yet displays spectral signatures of band-edge dark states akin to an H-aggregate. We distinguish between H-, I- and J-aggregates by showing the relative position of the bright (absorptive) state within the density of states using temperature dependent spectroscopy. I-aggregates hold potential for applications as charge injection moieties for semiconductors and donors for energy transfer in NIR and SWIR. Our results can be used to better design chromophores with predictable and tunable aggregation with new photophysical properties

Afterglow Properties of Silica-Capped Sr 2 MgSi 2 O 7 :Eu,Dy Nanoparticles Prepared by Laser Ablation in Ethanol

Abstract The effect of silica-capping on the afterglow property of Sr 2 MgSi 2 O 7 :Eu,Dy nanoparticles was investigated. Sr 2 MgSi 2 O 7 :Eu,Dy nanoparticles were prepared by laser ablation in liquid. Afterglow nanoparticles were capped with silica using Stöber method. A dense silica capping layer was achieved after 4 hours of reaction. Silica-capping of the afterglow nanoparticles improved the particles' afterglow property, which was degraded by nanosizing. Decay curves indicated that initial values of afterglow intensity were increased with silica-capping capacity. Moreover, silica-capping decreased the decay curve constant γ, which was related to trap parameters. The decrease in the value of γ resulted in the reduction in the slope of decay curve, and thus the improvement of the afterglow property. We concluded that capping nanoparticles with silica improved the particles' afterglow property by the passivation of surface defects and the prevention of energy transfer to water molecules

A Surface Energy Transfer Nanoruler for Measuring Binding Site Distances on Live Cell Surfaces

Measuring distances at molecular length scales in living systems is a significant challenge. Methods like Forster resonance energy transfer (FRET) have limitations due to short detection distances and strict oriental ions. Recently, surface energy transfer (SET) has been used in bulk solutions; however, it cannot be applied to living systems. Here, we have developed an SET nanoruler, using aptamer-gold nanoparticle conjugates with different diameters, to monitor the distance between binding sites of a receptor on living cells. The nanoruler can measure separation distances well beyond the detection limit of FRET. Thus, for the firs: time, we have developed an effective SET nanoruler for live cells with long distance, easy construction, fast detection, and low background. This is also the first time that the distance between the aptamer and antibody binding sites in the membrane protein PTK7 was measured accurately. The SET nanoruler represents the next leap forward to monitor structural components within living cell membranes.Chinese Government ; Academic Women Madelyn Lockhart Dissertation Fellowship ; NIH ; NSF ; National Basic Research Program of China [2007CB935603, 2010CB732402]; [2009ZX10004-312

Catalytically active gold on ordered titania supports

Almost two decades have passed since supported An nanoparticles were found to be active for CO oxidation. This discovery inspired extensive research addressing the origin of the unique properties of supported Au nanoparticles, the design and synthesis of potentially technical An catalysts, and the extension of An catalysis to other reactions. This tutorial review summarises the current understanding of the origin of the unique properties of titania-supported ALL catalysts for carbon monoxide oxidation. The key issues of catalysis by nanostructured An, effects of oxide support and active site/structure, especially those provided from model studies are discussed in detail. The successful synthesis of a highly catalytically active gold bilayer may lead to the design and synthesis of practically active Au nanofilm catalysts.Department of Energy ; Office of Basic Energy ; Division of Chemical Sciences ; Robert A. Welch Foundatio

Promotional Effects of Au in Pd-Au Catalysts for Vinyl Acetate Synthesis

Silica Supported Pd-Au bimetallic catalysts are highly selective for the acetoxylation of ethylene to vinyl acetate (VA). In this study we have used model catalysts consisting of planer surfaces and supported nanoparticles to investigate the promotional effects of Au in Pd-Au bimetallic catalysts. Low energy ion scattering spectroscopy, low energy electron diffraction, X-ray photoelectron spectroscopy, infrared reflection adsorption spectroscopy, and temperature-programmed desorption et al, were used to characterize the model systems. The catalytic performance for acetoxylation of ethylene to VA was examined for these model surfaces. In this paper, We summarize the Current understanding of the promotional effects of Au in Pd-Au bimetallic catalysts for VA synthesis. The key results are that An atoms break contiguous Pd atom ensembles at the surface into isolated Pd monomers. The absence of contiguous Pd sites significantly reduces the formation of combustion by-products and Suppresses the poison effects of CO, thus enhancing the VA formation selectivity and activity.Department of Energy, Office of Basic Energy, Division of Chemical Science ; Robert A. Welch Foundatio

INFLUENCE OF LINEAR ALKYLBENZENE SULFONATE (LAS) AS ORGANIC COSOLVENT ON LEACHING BEHAVIOR OF PCDD/FS FROM FLY-ASH AND SOIL

The leaching of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) was measured in soil and standard fly ash column eluted with pure water and linear alkylbenzene sulfonate (LAS)- water. The data obtained were used to evaluate the leachability of PCDD/Fs from waste dump like incineration residual slag and fly ash deposition. The leaching rate was shown to be increased significantly by using LAS water. The leachate contents of PCDD/Fs were above their known water solubility. Concentration of PCDD/Fs in the leachates as well as the relative leaching (calculated on the fly ash content) increased with increasing chlorinating degree and decreasing water solubility. LAS above the critical micelle concentration (CMC) probably enhances PCDD/Fs solubility

Cutaneous lupus erythematosus after treatment with paclitaxel and bevacizumab for metastatic breast cancer: a case report

Abstract Introduction The monoclonal anti-vascular endothelial growth factor antibody bevacizumab is increasingly used in the treatment of several malignant tumors. The usual side effects of this drug are hypertension and proteinuria. Paclitaxel is widely used in the treatment of breast cancer and head and neck carcinomas. Neither of these two drugs typically causes skin disorders. Paclitaxel-related cutaneous lupus erythematosus has been described before, but in earlier cases patients had a history of autoimmune disease. Case presentation We report a case of a 65-year-old Caucasian woman who presented with cutaneous lupus erythematosus after receiving paclitaxel-bevacizumab combination treatment as first-line therapy for metastatic breast cancer. Her cutaneous symptoms and increased serum anti-SSA and anti-SSB antibodies disappeared shortly after the discontinuation of therapy. Conclusion We conclude that cutaneous lupus erythematosus can also be seen in patients without earlier anamnesis of autoimmune disorders and that, furthermore, bevacizumab might cause atypical cutaneous side effects.</p

Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces

Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F+H2 yields HF+H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces

Sulfur K-Edge XAS and DFT Calculations on [Fe4S4]2+Clusters: Effects of H-bonding and Structural Distortion on Covalency and SpinTopology

Sulfur K-edge X-ray absorption spectroscopy of a hydrogen-bonded elongated [Fe{sub 4}S{sub 4}]{sup 2+} cube is reported. The data show that this synthetic cube is less covalent than a normal compressed cube with no hydrogen bonding. DFT calculations reveal that the observed difference in electronic structure has significant contributions from both the cluster distortion and from hydrogen bonding. The elongated and compressed Fe{sub 4}S{sub 4} structures are found to have different spin topologies (i.e., orientation of the delocalized Fe{sub 2}S{sub 2} subclusters which are antiferromagnetically coupled to each other). It is suggested that the H-bonding interaction with the counterion does not contribute to the cluster elongation. A magneto-structural correlation is developed for the Fe{sub 4}S{sub 4} cube that is used to identify the redoxactive Fe{sub 2}S{sub 2} subclusters in active sites of HiPIP and ferredoxin proteins involving these clusters

Modification and Measurement of the Adjustable Permanent Magnet Quadrupole for the Final Focus in a Linear Collider

An adjustable permanent magnet quadrupole has been developed for the final focus (FF) in a linear collider. Recent activities include a newly fabricated inner ring to demonstrate the strongest field gradient at a smaller bore diameter of 15mm and a magnetic field measurement system with a new rotating coil. The prospects of the R&amp;D will be discussed