Gd-HOPO Based High Relaxivity MRI Contrast Agents (open access)

Gd-HOPO Based High Relaxivity MRI Contrast Agents

Tris-bidentate HOPO-based ligands developed in our laboratory were designed to complement the coordination preferences of Gd{sup 3+}, especially its oxophilicity. The HOPO ligands provide a hexadentate coordination environment for Gd{sup 3+} in which all he donor atoms are oxygen. Because Gd{sup 3+} favors eight or nine coordination, this design provides two to three open sites for inner-sphere water molecules. These water molecules rapidly exchange with bulk solution, hence affecting the relaxation rates of bulk water olecules. The parameters affecting the efficiency of these contrast agents have been tuned to improve contrast while still maintaining a high thermodynamic stability for Gd{sup 3+} binding. The Gd- HOPO-based contrast agents surpass current commercially available agents ecause of a higher number of inner-sphere water molecules, rapid exchange of inner-sphere water molecules via an associative mechanism, and a long electronic relaxation time. The contrast enhancement provided by these agents is at least twice that of commercial contrast gents, which are based on polyaminocarboxylate ligands.
Date: November 6, 2008
Creator: Datta, Ankona & Raymond, Kenneth
Object Type: Article
System: The UNT Digital Library
QCD Corrections in Transversely Polarized Scattering (open access)

QCD Corrections in Transversely Polarized Scattering

We discuss two recent calculations of higher-order QeD corrections to scattering of transversely polarized hadrons. A basic concept underlying much of the theoretical description of high-energy hadronic scattering is the factorization theorem, which states that large momentum-transfer reactions may be factorized into long-distance pieces that contain information on the structure of the nucleon in terms of its parton densities, and parts that are short-distance and describe the hard interactions of the partons. Two crucial points are that on the one hand the long-distance contributions are universal, i.e., they are the same in any inelastic reaction under consideration, and that on the other hand the short-distance pieces depend only on the large scales related to the large momentum transfer in the overall reaction and, therefore, may be evaluated using QCD perturbation theory. The lowest order for the latter can generally only serve to give a rough description of the reaction under study. It merely captures the main features, but does not usually provide a quantitative understanding. The first-order ('next-to-leading order' (NLO)) corrections are generally indispensable in order to arrive at a firmer theoretical prediction for hadronic cross sections, and in some cases even an all-order resummation of large perturbative corrections is …
Date: October 6, 2008
Creator: Vogelsang, W.
Object Type: Article
System: The UNT Digital Library
LARG at chromosome 11q23 has functional characteristics of a tumor suppressor in human breast cancer (open access)

LARG at chromosome 11q23 has functional characteristics of a tumor suppressor in human breast cancer

Deletion of 11q23-q24 is frequent in a diverse variety of malignancies, including breast and colorectal carcinoma, implicating the presence of a tumor suppressor gene at that chromosomal region. We show here that LARG, from 11q23, has functional characteristics of a tumor suppressor. We examined a 6-Mb region on 11q23 by high-resolution deletion mapping, utilizing both loss of heterozygosity (LOH) analysis and microarray comparative genomic hybridization (CGH). LARG (also called ARHGEF12), identified from the analyzed region, was underexpressed in 34% of primary breast carcinomas and 80% of breast cancer cell lines including the MCF-7 line. Multiplex ligation-dependent probe amplification on 30 primary breast cancers and six breast cancer cell lines showed that LARG had the highest frequency of deletion compared to the BCSC-1 and TSLC1 genes, two known candidate tumor suppressor genes from 11q. In vitro analysis of breast cancer cell lines that underexpress LARG showed that LARG could be reactivated by trichostatin A, a histone deacetylase inhibitor, but not by 5-Aza-2{prime}-deoxycytidine, a demethylating agent. Bisulfite sequencing and quantitative high-throughput analysis of DNA methylation confirmed the lack of CpG island methylation in LARG in breast cancer. Restoration of LARG expression in MCF-7 cells by stable transfection resulted in reduced proliferation and …
Date: May 6, 2008
Creator: Ong, Danny C.T.; Rudduck, Christina; Chin, Koei; Kuo, Wen-Lin; Lie, Daniel K.H.; Chua, Constance L.M. et al.
Object Type: Article
System: The UNT Digital Library
Characterization and Monitoring Data for Evaluating Constructed Emergent Sandbar Habitat in the Missouri River Mainstem (open access)

Characterization and Monitoring Data for Evaluating Constructed Emergent Sandbar Habitat in the Missouri River Mainstem

Emergent sandbar habitat (ESH) in the Missouri River Mainstem System is a critical habitat element for several federally listed bird species: the endangered interior least tern (Sterna antillarum) and the threatened Northern Great Plains piping plover (Charadrius melodus). The Army Corps of Engineers (Corps) provides the primary operational management of the Missouri River and is responsible under the Endangered Species Act (ESA) to take actions within its authorities to conserve listed species. To comply with the 2000 USFWS BiOp and the 2003 amended USFWS BiOp, the Corps has created habitats below Gavins Point Dam using mechanical means. Initial monitoring indicates that constructed sandbars provide suitable habitat features for nesting and foraging least terns and piping plovers. Terns and plovers are using constructed sandbars and successfully reproducing at or above levels stipulated in the BiOp. However, whether such positive impacts will persist cannot yet be adequately assessed at this time.
Date: November 6, 2008
Creator: Duberstein, Corey A. & Downs, Janelle L.
Object Type: Report
System: The UNT Digital Library
RHIC Polarized proton performance in run-8 (open access)

RHIC Polarized proton performance in run-8

During Run-8, the Relativistic Heavy Ion Collider (RHIC) provided collisions of spin-polarized proton beams at two interaction regions. Physics data were taken with vertical orientation of the beam polarization, which in the 'Yellow' RHIC ring was significantly lower than in previous years. We present recent developments and improvements as well as the luminosity and polarization performance achieved during Run-8, and we discuss possible causes of the not as high as previously achieved polarization performance of the 'Yellow' ring.
Date: October 6, 2008
Creator: Montag, C.; Bai, M.; MacKay, W. W.; Roser, T.; Abreu, N.; Ahrens, L. et al.
Object Type: Article
System: The UNT Digital Library
The Future of High Energy Polarized Proton Beams (open access)

The Future of High Energy Polarized Proton Beams

None
Date: October 6, 2008
Creator: Roser, T.
Object Type: Article
System: The UNT Digital Library
An integrative genomic and proteomic analysis of PIK3CA, PTEN and AKT mutations in breast cancer (open access)

An integrative genomic and proteomic analysis of PIK3CA, PTEN and AKT mutations in breast cancer

Phosphatidylinositol-3-kinase (PI3K)/AKT pathway aberrations are common in cancer. By applying mass spectroscopy-based sequencing and reverse phase protein arrays to 547 human breast cancers and 41 cell lines, we determined the subtype specificity and signaling effects of PIK3CA, AKT and PTEN mutations, and the effects of PIK3CA mutations on responsiveness to PI3K inhibition in-vitro and on outcome after adjuvant tamoxifen. PIK3CA mutations were more common in hormone receptor positive (33.8%) and HER2-positive (24.6%) than in basal-like tumors (8.3%). AKT1 (1.4%) and PTEN (2.3%) mutations were restricted to hormone receptor-positive cancers with PTEN protein levels also being significantly lower in hormone receptor-positive cancers. Unlike AKT1 mutations, PIK3CA (39%) and PTEN (20%) mutations were more common in cell lines than tumors, suggesting a selection for these but not AKT1 mutations during adaptation to culture. PIK3CA mutations did not have a significant impact on outcome in 166 hormone receptor-positive breast cancer patients after adjuvant tamoxifen. PIK3CA mutations, in comparison with PTEN loss and AKT1 mutations, were associated with significantly less and indeed inconsistent activation of AKT and of downstream PI3K/AKT signaling in tumors and cell lines, and PTEN loss and PIK3CA mutation were frequently concordant, suggesting different contributions to pathophysiology. PTEN loss but not …
Date: May 6, 2008
Creator: Stemke-Hale, Katherine; Gonzalez-Angulo, Ana Maria; Lluch, Ana; Neve, Richard M.; Kuo, Wen-Lin; Davies, Michael et al.
Object Type: Article
System: The UNT Digital Library
Selection and Implementation of a Replacement Cutting Tool Selection Application (open access)

Selection and Implementation of a Replacement Cutting Tool Selection Application

A new commercial cutting tool software package replaced an internally created legacy system. This report describes the issues that surfaced during the migration and installation of the commercial package and the solutions employed. The primary issues discussed are restructuring the data between two drastically different database schemas and the creation of individual component graphics.
Date: October 6, 2008
Creator: Rice, Gordon
Object Type: Report
System: The UNT Digital Library
Spin resonance strength calculations (open access)

Spin resonance strength calculations

In calculating the strengths of depolarizing resonances it may be convenient to reformulate the equations of spin motion in a coordinate system based on the actual trajectory of the particle, as introduced by Kondratenko, rather than the conventional one based on a reference orbit. It is shown that resonance strengths calculated by the conventional and the revised formalisms are identical. Resonances induced by radiofrequency dipoles or solenoids are also treated; with rf dipoles it is essential to consider not only the direct effect of the dipole but also the contribution from oscillations induced by it.
Date: October 6, 2008
Creator: Courant, E. D.
Object Type: Article
System: The UNT Digital Library
System Design and the Safety Basis (open access)

System Design and the Safety Basis

The objective of this paper is to present the Bechtel Jacobs Company, LLC (BJC) Lessons Learned for system design as it relates to safety basis documentation. BJC has had to reconcile incomplete or outdated system description information with current facility safety basis for a number of situations in recent months. This paper has relevance in multiple topical areas including documented safety analysis, decontamination & decommissioning (D&D), safety basis (SB) implementation, safety and design integration, potential inadequacy of the safety analysis (PISA), technical safety requirements (TSR), and unreviewed safety questions. BJC learned that nuclear safety compliance relies on adequate and well documented system design information. A number of PIS As and TSR violations occurred due to inadequate or erroneous system design information. As a corrective action, BJC assessed the occurrences caused by systems design-safety basis interface problems. Safety systems reviewed included the Molten Salt Reactor Experiment (MSRE) Fluorination System, K-1065 fire alarm system, and the K-25 Radiation Criticality Accident Alarm System. The conclusion was that an inadequate knowledge of system design could result in continuous non-compliance issues relating to nuclear safety. This was especially true with older facilities that lacked current as-built drawings coupled with the loss of 'historical knowledge' as …
Date: May 6, 2008
Creator: Ellingson, Darrel
Object Type: Article
System: The UNT Digital Library
Mini-conference on Angular Momentum Transport in Laboratory and Nature (open access)

Mini-conference on Angular Momentum Transport in Laboratory and Nature

This paper provides a concise summary of the current status of the research and future perspectives discussed in the Mini-Conference on Angular Momentum Transport in Laboratory and Nature. This Mini-conference, sponsored by the Topical Group on Plasma Astrophysics, was held as part of the American Physical Society's Division of Plasma Physics 2007 Annual Meeting (November 12{16, 2007). This Mini-conference covers a wide range of phenomena happening in fluids and plasmas, either in laboratory or in nature. The purpose of this paper is not to comprehensively review these phenomena, but to provide a starting point for interested readers to refer to related research in areas other than their own.
Date: May 6, 2008
Creator: Hantao Ji, Philipp Kronberg, Stewart C. Prager, and Dmitri A. Uzdensky
Object Type: Report
System: The UNT Digital Library
Decreased expression of RNA interference machinery, Dicer and Drosha, is associated with poor outcome in ovarian cancer patients (open access)

Decreased expression of RNA interference machinery, Dicer and Drosha, is associated with poor outcome in ovarian cancer patients

The clinical and functional significance of RNA interference (RNAi) machinery, Dicer and Drosha, in ovarian cancer is not known and was examined. Dicer and Drosha expression was measured in ovarian cancer cell lines (n=8) and invasive epithelial ovarian cancer specimens (n=111) and correlated with clinical outcome. Validation was performed with previously published cohorts of ovarian, breast, and lung cancer patients. Anti-Galectin-3 siRNA and shRNA transfections were used for in vitro functional studies. Dicer and Drosha mRNA and protein levels were decreased in 37% to 63% of ovarian cancer cell lines and in 60% and 51% of human ovarian cancer specimens, respectively. Low Dicer was significantly associated with advanced tumor stage (p=0.007), and low Drosha with suboptimal surgical cytoreduction (p=0.02). Tumors with both high Dicer and Drosha were associated with increased median patient survival (>11 years vs. 2.66 years for other groups; p<0.001). In multivariate analysis, high Dicer (HR=0.48; p=0.02), high-grade histology (HR=2.46; p=0.03), and poor chemoresponse (HR=3.95; p<0.001) were identified as independent predictors of disease-specific survival. Findings of poor clinical outcome with low Dicer expression were validated in separate cohorts of cancer patients. Galectin-3 silencing with siRNA transfection was superior to shRNA in cell lines with low Dicer (78-95% vs. …
Date: May 6, 2008
Creator: Merritt, William M.; Lin, Yvonne G.; Han, Liz Y.; Kamat, Aparna A.; Spannuth, Whitney A.; Schmandt, Rosemarie et al.
Object Type: Article
System: The UNT Digital Library
Predicting Efficient Antenna Ligands for Tb(III) Emission (open access)

Predicting Efficient Antenna Ligands for Tb(III) Emission

A series of highly luminescent Tb(III) complexes of para-substituted 2-hydroxyisophthalamide ligands (5LI-IAM-X) has been prepared (X = H, CH{sub 3}, (C=O)NHCH{sub 3}, SO{sub 3}{sup -}, NO{sub 2}, OCH{sub 3}, F, Cl, Br) to probe the effect of substituting the isophthalamide ring on ligand and Tb(III) emission in order to establish a method for predicting the effects of chromophore modification on Tb(III) luminescence. The energies of the ligand singlet and triplet excited states are found to increase linearly with the {pi}-withdrawing ability of the substituent. The experimental results are supported by time-dependent density functional theory (TD-DFT) calculations performed on model systems, which predict ligand singlet and triplet energies within {approx}5% of the experimental values. The quantum yield ({Phi}) values of the Tb(III) complex increases with the triplet energy of the ligand, which is in part due to the decreased non-radiative deactivation caused by thermal repopulation of the triplet. Together, the experimental and theoretical results serve as a predictive tool that can be used to guide the synthesis of ligands used to sensitize lanthanide luminescence.
Date: October 6, 2008
Creator: Samuel, Amanda P.S.; Xu, Jide & Raymond, Kenneth
Object Type: Article
System: The UNT Digital Library
Photoproduction at RHIC and the LHC (open access)

Photoproduction at RHIC and the LHC

The strong electromagnetic fields carried by relativistic highly charged ions make heavy-ion colliders attractive places to study photonuclear interactions and two-photon interactions. At RHIC, three experiments have studied coherent photoproduction of {rho}{sup 0}, 4{pi}, J/{psi}, e{sup +}e{sup -} pairs, and e{sup +}e{sup -} pairs where the electron is bound to one of the incident nuclei. These results show that photoproduction studies are possible, and demonstrate some of the unique possibilities due to the symmetric final states and the ion targets. The LHC will reach photon-nucleon energies many times higher than at HERA; these collisions can be used to measure the gluon distributions in nuclei at very low Bjorken-x, where shadowing and gluon saturation may become important; LHC {gamma}{gamma} collisions may also be attractive places to search for some types of new physics. ATLAS, CMS and ALICE are all planning to study photoproduction. After introducing the principles of photoproduction at hadron colliders, I will review recent results from RHIC on meson and e{sup +}e{sup -} production, and then discuss prospects for studies at the LHC.
Date: October 6, 2008
Creator: Klein, Spencer
Object Type: Article
System: The UNT Digital Library
Using CO2 Lidar for Standoff Detection of a Perfluorocarbon Tracer in Air (open access)

Using CO2 Lidar for Standoff Detection of a Perfluorocarbon Tracer in Air

The Tag, Track and Location System Program (TTL) is investigating the use of PFTs as tracers for tagging and tracking items of interest or fallen soldiers. In order for the tagging and tracking to be valuable there must be a location system that can detect the PFTs. This report details the development of an infrared lidar platform for standoff detection of PFTs released into the air from a tagged object or person. Furthering work performed using a table top lidar system in an indoor environment; a mobile mini lidar platform was assembled using an existing Raman lidar platform, a grating tunable CO{sub 2} IR laser, Judson HgCdTe detector and miscellaneous folding optics and electronics. The lidar achieved {approx}200 ppb-m sensitivity in laboratory and indoor testing and was then successfully demonstrated at an outdoor test. The lidar system was able to detect PFTs released into a vehicle from a distance of 100 meters. In its final, fully optimized configuration the lidar was capable of repeatedly detecting PFTs in the air released from tagged vehicles. Responses were immediate and clear. This report details the results of a proof-of-concept demonstration for standoff detection of a perfluorocarbon tracer (PFT) using infrared lidar. The project …
Date: February 6, 2008
Creator: Heiser,J.H.; Smith, S. & Sedlacek, A.
Object Type: Report
System: The UNT Digital Library
Java Metadata Facility (open access)

Java Metadata Facility

The Java Metadata Facility is introduced by Java Specification Request (JSR) 175 [1], and incorporated into the Java language specification [2] in version 1.5 of the language. The specification allows annotations on Java program elements: classes, interfaces, methods, and fields. Annotations give programmers a uniform way to add metadata to program elements that can be used by code checkers, code generators, or other compile-time or runtime components. Annotations are defined by annotation types. These are defined the same way as interfaces, but with the symbol {at} preceding the interface keyword. There are additional restrictions on defining annotation types: (1) They cannot be generic; (2) They cannot extend other annotation types or interfaces; (3) Methods cannot have any parameters; (4) Methods cannot have type parameters; (5) Methods cannot throw exceptions; and (6) The return type of methods of an annotation type must be a primitive, a String, a Class, an annotation type, or an array, where the type of the array is restricted to one of the four allowed types. See [2] for additional restrictions and syntax. The methods of an annotation type define the elements that may be used to parameterize the annotation in code. Annotation types may have default …
Date: March 6, 2008
Creator: Buttler, D. J.
Object Type: Article
System: The UNT Digital Library
Fluxnet Synthesis Dataset Collaboration Infrastructure (open access)

Fluxnet Synthesis Dataset Collaboration Infrastructure

The Fluxnet synthesis dataset originally compiled for the La Thuile workshop contained approximately 600 site years. Since the workshop, several additional site years have been added and the dataset now contains over 920 site years from over 240 sites. A data refresh update is expected to increase those numbers in the next few months. The ancillary data describing the sites continues to evolve as well. There are on the order of 120 site contacts and 60proposals have been approved to use thedata. These proposals involve around 120 researchers. The size and complexity of the dataset and collaboration has led to a new approach to providing access to the data and collaboration support and the support team attended the workshop and worked closely with the attendees and the Fluxnet project office to define the requirements for the support infrastructure. As a result of this effort, a new website (http://www.fluxdata.org) has been created to provide access to the Fluxnet synthesis dataset. This new web site is based on a scientific data server which enables browsing of the data on-line, data download, and version tracking. We leverage database and data analysis tools such as OLAP data cubes and web reports to enable browser …
Date: February 6, 2008
Creator: Agarwal, Deborah A.; Humphrey, Marty; van Ingen, Catharine; Beekwilder, Norm; Goode, Monte; Jackson, Keith et al.
Object Type: Report
System: The UNT Digital Library
Idaho Watershed Habitat Restoration Lemhi, Final Annual Report FY2007. (open access)

Idaho Watershed Habitat Restoration Lemhi, Final Annual Report FY2007.

None
Date: November 6, 2008
Creator: Branbury, Allen
Object Type: Report
System: The UNT Digital Library
Efficient Route to Highly Water-Soluble Aromatic Cyclic Hydroxamic Acid Ligands (open access)

Efficient Route to Highly Water-Soluble Aromatic Cyclic Hydroxamic Acid Ligands

2-Hydroxyisoquinolin-1-one (1,2-HOIQO) is a new member of the important class of aromatic cyclic hydroxamic acid ligands which are widely used in metal sequestering applications and metal chelating therapy. The first general approach for the introduction of substituents at the aromatic ring of the chelating moiety is presented. As a useful derivative, the highly water-soluble sulfonic acid has been synthesized by an efficient route that allows general access to 1,2-HOQIO 3-carboxlic acid amides, which are the most relevant for applications.
Date: February 6, 2008
Creator: Seitz, Michael & Raymond, Kenneth N.
Object Type: Article
System: The UNT Digital Library
Tough, bio-inspired hybrid materials (open access)

Tough, bio-inspired hybrid materials

The notion of mimicking natural structures in the synthesis of new structural materials has generated enormous interest but has yielded few practical advances. Natural composites achieve strength and toughness through complex hierarchical designs extremely difficult to replicate synthetically. Here we emulate Nature's toughening mechanisms through the combination of two ordinary compounds, aluminum oxide and polymethylmethacrylate, into ice-templated structures whose toughness can be over 300 times (in energy terms) that of their constituents. The final product is a bulk hybrid ceramic material whose high yield strength and fracture toughness ({approx}200 MPa and {approx}30 MPa{radical}m) provide specific properties comparable to aluminum alloys. These model materials can be used to identify the key microstructural features that should guide the synthesis of bio-inspired ceramic-based composites with unique strength and toughness.
Date: October 6, 2008
Creator: Munch, Etienne; Launey, Maximimilan E.; Alsem, Daan H.; Saiz, Eduardo; Tomsia, Antoni P. & Ritchie, Robert O.
Object Type: Article
System: The UNT Digital Library
Spectral Asymmetry Due to Magnetic Coordinates (open access)

Spectral Asymmetry Due to Magnetic Coordinates

The use of magnetic coordinates is ubiquitous in toroidal plasma physics, but the distortion in Fourier spectra produced by these coordinates is not well known. A spatial symmetry of the field is not always represented by a symmetry in the Fourier spectrum when magnetic coordinates are used because of the distortion of the toroidal angle. The practical importance of spectral distortion is illustrated with a tokamak example.
Date: May 6, 2008
Creator: Jong-kyu Park,, Allen H. Boozer, and Jonathan E. Menard
Object Type: Report
System: The UNT Digital Library
Dworshak Kokanee Population and Entrainment Assessment 2005-2006 Annual Report. (open access)

Dworshak Kokanee Population and Entrainment Assessment 2005-2006 Annual Report.

During this contract, we continued testing underwater strobe lights to determine their effectiveness at repelling kokanee Oncorhynchus nerka away from Dworshak Dam. We tested one set of nine strobe lights flashing at a rate of 360 flashes/min in front of turbine 3 while operating at higher discharges than previously tested. The density and distribution of fish, (thought to be mostly kokanee), were monitored with a split-beam echo sounder. We then compared fish counts and densities during nights when the lights were flashing to counts and densities during adjacent nights without the lights on. On five nights between January 31 and February 28, 2006, when no lights were present, fish counts near turbine 3 averaged eight fish and densities averaged 91 fish/ha. When strobe lights were turned on during five adjacent nights during the same period, mean counts dropped to four fish and densities dropped to 35 fish/ha. The decline in counts (49%) was not statistically significant (p = 0.182), but decline in densities (62%) was significant (p = 0.049). There appeared to be no tendency for fish to habituate to the lights during the night. Test results indicated that strobe lights were able to reduce fish densities by at least …
Date: November 6, 2008
Creator: Stark, Eric J.
Object Type: Report
System: The UNT Digital Library
Berkeley Program Offers New Option for Financing Residential PV Systems (open access)

Berkeley Program Offers New Option for Financing Residential PV Systems

Readily accessible credit has often been cited as a necessary ingredient to open up the market for residential photovoltaic (PV) systems. Though financing does not reduce the high up-front cost of PV, by spreading that cost over some portion of the system's life, financing can certainly make PV systems more affordable. As a result, a number of states have, in the past, set up special residential loan programs targeting the installation of renewable energy systems and/or energy-efficiency improvements and often featuring low interest rates, longer terms and no-hassle application requirements. Historically, these loan programs have had mixed success (particularly for PV), for a variety of reasons, including a historical lack of homeowner interest in PV, a lack of program awareness, a reduced appeal in a low-interest-rate environment, and a tendency for early PV adopters to be wealthy and not in need of financing. Some of these barriers have begun to fade. Most notably, homeowner interest in PV has grown in some states, particularly those that offer solar rebates. The passage of the Energy Policy Act of 2005 (EPAct 2005), however, introduced one additional roadblock to the success of low-interest PV loan programs: a residential solar investment tax credit (ITC), subject …
Date: July 6, 2008
Creator: Bolinger, Mark A.
Object Type: Article
System: The UNT Digital Library
Evolution of the Surface Science of Catalysis from Single Crystals to Metal Nanoparticles under Pressure (open access)

Evolution of the Surface Science of Catalysis from Single Crystals to Metal Nanoparticles under Pressure

Vacuum studies of metal single crystal surfaces using electron and molecular beam scattering revealed that the surface atoms relocate when the surface is clean (reconstruction) and when it is covered by adsorbates (adsorbate induced restructuring). It was also discovered that atomic steps and other low coordination surface sites are active for breaking chemical bonds (H-H, O=O, C-H, C=O and C-C) with high reaction probability. Investigations at high reactant pressures using sum frequency generation (SFG)--vibrational spectroscopy and high pressure scanning tunneling microscopy (HPSTM) revealed bond breaking at low reaction probability sites on the adsorbate-covered metal surface, and the need for adsorbate mobility for continued turnover. Since most catalysts (heterogeneous, enzyme and homogeneous) are nanoparticles, colloid synthesis methods were developed to produce monodispersed metal nanoparticles in the 1-10 nm range and controlled shapes to use them as new model catalyst systems in two-dimensional thin film form or deposited in mesoporous three-dimensional oxides. Studies of reaction selectivity in multipath reactions (hydrogenation of benzene, cyclohexene and crotonaldehyde) showed that reaction selectivity depends on both nanoparticle size and shape. The oxide-metal nanoparticle interface was found to be an important catalytic site because of the hot electron flow induced by exothermic reactions like carbon monoxide oxidation.
Date: March 6, 2008
Creator: Somorjai, Gabor A. & Park, Jeong Y.
Object Type: Article
System: The UNT Digital Library