Digital Commons Network^™

Programmable Diagnostic Devices Made From Paper And Tape, Andres W. Martinez, Scott T. Phillips, Zhihong Nie, Chao-Min Cheng, Emanuel Carrilho, Benjamin J. Wiley, George M. Whitesides

Chemistry and Biochemistry

This paper describes three-dimensional microfluidic paper-based analytical devices (3-D μPADs) that can be programmed (postfabrication) by the user to generate multiple patterns of flow through them. These devices are programmed by pressing single-use ‘on’ buttons, using a stylus or a ballpoint pen. Pressing a button closes a small space (gap) between two vertically aligned microfluidic channels, and allows fluids to wick from one channel to the other. These devices are simple to fabricate, and are made entirely out of paper and double-sided adhesive tape. Programmable devices expand the capabilities of μPADs and provide a simple method for controlling the movement …

Millimeter-Scale Contact Printing Of Aqueous Solutions Using A Stamp Made Out Of Paper And Tape, Chao-Min Cheng, Aaron D. Mazzeo, Jinlong Gong, Andres W. Martinez, Scott T. Phillips, Nina Jain, George M. Whitesides

Chemistry and Biochemistry

This communication describes a simple method for printing aqueous solutions with millimeter-scale patterns on a variety of substrates using an easily fabricated, paper-based microfluidic device (a paper-based ―stamp‖) as a contact printing device. The device is made from inexpensive materials, and it is easily assembled by hand; this method is thus accessible to a wide range of laboratories and budgets. A single device was used to print over 2500 spots in less than three minutes at a density of 16 spots per square centimetre. This method provides a new tool to pattern biochemicals—reagents, antigens, proteins, and DNA—on planar substrates. The …

Statistical Analysis Of Visible Absorption Spectra And Mass Spectra Obtained From Dyed Textile Fibers, Katie Margaret White

Electronic Theses and Dissertations

The National Academy of Sciences recently published a report which calls for improvements to the field of forensic science. Their report criticized many forensic disciplines for failure to establish rigorously-tested methods of comparison, and encouraged more research in these areas to establish limitations and assess error rates. This study applies chemometric and statistical methods to current and developing analytical techniques in fiber analysis. In addition to analysis of commercially available dyed textile fibers, two pairs of dyes are selected based for custom fabric dyeing on the similarities of their absorbance spectra and dye molecular structures. Visible absorption spectra for all …

Localized Surface Plasmon Resonance Enhanced Magneto-Optical Activity In Core-Shell Fe-Ag Nanoparticles, L. Wang, K. Yang, C. Clavero, A. J. Nelson, K. J. Carroll, E. E. Carpenter, R. A. Lukaszew

Chemistry Publications

Metallic nanoparticles (NPs) are suitable platforms for miniaturized biosensing based on their optical and magneto-opticalproperties. It is possible to enhance the sensitivity of specific kinds of NPs by exploiting their optical and magneto-opticalproperties under suitable external magnetic field modulation. Here, the magneto-opticalproperties of Fe–Ag core-shell ferromagnet-noble metal NPs have been investigated as a function of the incident light frequency. For Fe–Ag NPs with a concentration ratio around 25:75, an optical absorption band centered at 3 eV due to localized surface plasmon resonance (LSPR) excitation is observed. A strong enhancement of the Faraday rotation is also observed, greatly exceeding the value …

Spectrally Tunable Magnetic Nanoparticles Designed For Distribution/Recollection Applications, Nicholas B. Mcdowall, James R. Wilkins, Kyler J. Carroll, Jarrod D. Edwards, Jean D. Nelson, Everett E. Carpenter, Garry P. Glaspell

Chemistry Publications

The comprehensive goal of this research is the synthesis and characterization of nanomaterials that are spectrally tunable in terms of their electromagnetic signal, are robust, magnetic (allowing their piloted movement), and have the potential to be functionalized for the detection of CBRNE threats. Various chemical methods were utilized for synthesis of magnetic (iron) and luminescent rare earth (RE) components, and their mixtures. Effects of integrating an iron core into RE luminescent lattices (excited by UV, emit in the VIS) were investigated. The determination of the optimum balances between magnetic and luminescent components such that the magnetism was maximized while maintaining …

Sampling The Conformation Of Protein Surface Residues For Flexible Protein Docking, Patricia Francis-Lyon, S Gu, J Hass, N Amenta, P Koehl

Nursing and Health Professions Faculty Research and Publications

Background: The problem of determining the physical conformation of a protein dimer, given the structures of the two interacting proteins in their unbound state, is a difficult one. The location of the docking interface is determined largely by geometric complementarity, but finding complementary geometry is complicated by the flexibility of the backbone and side-chains of both proteins. We seek to generate candidates for docking that approximate the bound state well, even in cases where there is backbone and/or side-chain difference from unbound to bound states.

Results: We divide the surfaces of each protein into local patches and describe the effect …

Trace Gas And Particle Emissions From Domestic And Industrial Biofuel Use And Garbage Burning In Central Mexico, Ted J. Christian, Robert Yokelson, B. Cardenas, L. T. Molina, G. Engling, S. C. Hsu

Chemistry and Biochemistry Faculty Publications

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl(-), NO(3)(-), and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Global biofuel use has been estimated at over 2600 Tg/y. With several simple case studies we show that cooking fires can be a major, or the major, source of several gases and fine particles in developing countries. Insulated cook stoves with chimneys were earlier shown to reduce …

Laboratory Measurements Of Trace Gas Emissions From Biomass Burning Of Fuel Types From The Southeastern And Southwestern United States, I. R. Burling, Robert J. Yokelson, David W. T. Griffith, T. J. Johnson, P. Veres, J. M. Roberts, C. Warneke, S. P. Urbanski, J. Reardon, D. R. Weise, Wei Min Hao, J. De Gouw

Chemistry and Biochemistry Faculty Publications

Vegetation commonly managed by prescribed burning was collected from five southeastern and southwestern US military bases and burned under controlled conditions at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The smoke emissions were measured with a large suite of state-of-the-art instrumentation including an open-path Fourier transform infrared (OP-FTIR) spectrometer for measurement of gas-phase species. The OP-FTIR detected and quantified 19 gas-phase species in these fires: CO2, CO, CH4, C2H2, C2H4, C3H6, HCHO, HCOOH, CH3OH, CH3COOH, furan, H2O, NO, NO2, HONO, NH3, HCN, HCl, and SO2. Emission factors for these species are presented for each vegetation type burned. …

Evolution Of Trace Gases And Particles Emitted By A Chaparral Fire In California, S. K. Akagi, J. S. Craven, J. W. Taylor, G. R. Mcmeeking, Robert J. Yokelson, I. R. Burling, S. P. Urbanski, C. E. Wold, J. H. Seinfeld, H. Coe, M. J. Alvarado, D. R. Weise

Chemistry and Biochemistry Faculty Publications

Biomass burning (BB) is a major global source of trace gases and particles. Accurately representing the production and evolution of these emissions is an important goal for atmospheric chemical transport models. We measured a suite of gases and aerosols emitted from an 81 hectare prescribed fire in chaparral fuels on the central coast of California, US on 17 November 2009. We also measured physical and chemical changes that occurred in the isolated down-wind plume in the first similar to 4 h after emission. The measurements were carried out onboard a Twin Otter aircraft outfitted with an airborne Fourier transform infrared …

Design, Synthesis And Characterization Of Oriented Glyco-Affinity Macroligands For Glyco-Capturing, Glycomics And Glycoproteomics Applications, Srinivas Chalagalla

ETD Archive

Cell surface carbohydrates existing as parts of glycoproteins, glycolipids, and other conjugates present the first information about cell to the outside world and are intimately involved in various biological events such as intercellular communication, and molecular and cellular targeting. However, mechanisms of most processes at the molecular level are still unclear. Therefore, it is very important to develop carbohydrate-specific binding molecules for rapid, efficient, sensitive purification and accurate analysis of complex carbohydrate structures as well as their functions. Furthermore, carbohydrate-specific binding molecules can be expected to be used in medical diagnostic applications for carbohydrate biomarkers. In this thesis study, oriented …

Dna Mutation/Methylation Screening Method For Colon Cancer Screening, Wei Meng

ETD Archive

Cancer is a result of unregulated cell growth. For all types of cancer currently studied, the transition from a healthy cell to a malignant tumor cell is a step-by-step process which requires mutation in at least several oncogenes and tumor suppressor genes together. Another cancer early event is DNA methylation. Cancer-related DNA methylation focuses on promoter hypermethylation of the certain genes. The DNA mutation and methylation profile can serve as biomarkers for diagnosing early stage of cancer. Colorectal cancer is the third most common cancer type in the United States and has been well studied. The essential mechanism of cancer …

Molecular Basis Of The Role Of Kindlin 2 In Cell Adhesion, Hettiarachchige Dhanuja Deepamalee Perera

ETD Archive

Kindlins are a novel family of cytoskeleton proteins that plays an important role in the activation of heterodimeric integrin transmembrane receptors. These receptors play a vital role in cell adhesion, cell migration and other cellular processes. The Kindlin protein family consists of three homologous proteins, Kindlin 1, 2 and 3 with differential tissue distribution and varying expression levels in human. Mutations of Kindlin 1 protein are clinically linked to Kindler Syndrome. Kindlin 2 knockdown studies have shown embryonic lethality in mouse, but no diseases have been clinically testified. Kindlin 3 mutations are associated with bleeding disorders, e.g. LADIII. Talin is …

Human Prostate Cancer Cell Apoptosis Induced By Interferon-Y And Double-Stranded Rna And Studies On The Biological Roles Of Transmembrane And Coiled-Coil Domains 1, Haiyan Tan

ETD Archive

No abstract provided.

Study Of Drug Delivery Behavior Through Biomembranes Using Thermal And Bioanalytical Techniques, Hareesha Reddy Venumuddala

ETD Archive

This Master of Science thesis encompasses two projects in chemical pharmaceuticals. The first is a study of excipients and the added new information collected beyond Thermal Gravimetric Analysis and Differential Scanning Calorimetry from Dielectric Analysis. These new properties enhance our global knowledge of excipients by thermal analytical methods. Excipients, the inactive ingredients in formulated drugs, aid different functions of the active pharmacy ingredient, the drugs. Low temperature transitions, by DEA including melting of frozen solvents, e.g. water, are more definitive than observed by low temperature DSC. Millions of dollars are expended annually on pharmaceutical testing to qualify excipients for fully …

Temporal And Spatial Variations In Freshwater 14C Reservoir Effects: Lake Mývatn, Northern Iceland, Philippa L. Ascough, G. T. Cook, M. J. Church, E. Dunbar, Á. Einarsson, Thomas H. Mcgovern, A. J. Dugmore, Sophia Perdikaris, H. Hastie, A. Friðriksson, H. Gestsdóttir

School of Global Integrative Studies: Faculty Publications

Lake Mývatn is an interior highland lake in northern Iceland that forms a unique ecosystem of international scientific importance and is surrounded by a landscape rich in archaeological and paleoenvironmental sites. A significant freshwater reservoir effect (FRE) has been identified in carbon from the lake at some Viking (about AD 870–1000) archaeological sites in the wider region (Mývatnssveit). Previous accelerator mass spectrometry (AMS) measurements indicated this FRE was about 1500–1900 ¹⁴C yr. Here, we present the results of a study using stable isotope and ¹⁴C measurements to quantify the Mývatn FRE for both the Viking and modern periods. …

Transition Metal-Mediated Higher-Order Cycloaddition Reactions: Application To The Total Synthesis Of Complex Natural Products, Bilal Abou Aleiwi

Wayne State University Dissertations

ABSTRACT

TRANSITION METAL-MEDIATED HIGHER-ORDER CYCLOADDITION REACTIONS: APPLICATION TO THE TOTAL SYNTHESIS OF COMPLEX NATURAL PRODUCTS

by

BILAL ABOU ALEIWI

October 2010

Advisor: Dr. James H. Rigby

Major: Chemistry (Organic)

Degree: Doctor of Philosophy

Chromium (0)-mediated [6ð + 2ð] and [6ð + 2ð + 2ð] cycloaddition reactions between cyclic trienes and alkynes is reported. The development, investigation and the application of these reactions in the total synthesis of complex ring systems and natural products is described. Two natural products, namely, ∆ 9(12) -Capnellene and Echinopines A and B were targeted.

An investigation led to the successful development of a methodology to …

Development And Applications Of Thioacids In Peptide Chemistry And Exploration Of Methods Toward The Stereochemical Elucidation And Synthesis Of Virgineone, Kasinath Sana

Wayne State University Dissertations

ABSTRACT

DEVELOPMENT AND APPLICATIONS OF THIOACIDS IN PEPTIDE CHEMISTRY AND EXPLORATION OF METHODS TOWARD THE STEREOCHEMICAL ELUCIDATION AND SYNTHESIS OF VIRGINEONE

by

KASINATH SANA

December 2010

Advisor: David Crich

Major: Chemistry

Degree: Doctor of Philosophy

This dissertation describes investigations toward the development of methods for the synthesis of peptidyl thioacids and thioesters, with particular emphasis on applications in peptide chemistry, and the exploration of methods toward the assignment of the relative and absolute configuration of virgineone and its total synthesis.

The first part of chapter one introduces the general characteristics and reactivity of thioacids, and describes their potential for application …

Synthetic Levers Enabling Control Of Phase, Size And Morphology In Transition Metal Phosphide Nanoparticles (Fe, Ni), Elayaraja Muthuswamy

Wayne State University Dissertations

ABSTRACT

SYNTHETIC LEVERS ENABLING CONTROL OF PHASE, SIZE AND MORPHOLOGY IN TRANSITION METAL PHOSPHIDE NANOPARTICLES (FE, NI)

by

ELAYARAJA MUTHUSWAMY

May 2011

Advisor:Dr. Stephanie L. Brock

Major: Chemistry

Degree: Doctor of Philosophy

This dissertation study focuses on (1) development of a synthetic strategy to control phase in nanoscale iron phosphides; (2) extension of the developed phase control strategy to the nanoscale nickel phosphide system with simultaneous control on size and morphology and (3) illustration of the enhanced reactivity of nanoscale oxide systems.

A synthetic strategy to control phase in nanoscale iron phosphides was developed to prepare phase-pure samples of …

Dechalcogenative Allylic Selenosulfide And Disulfide Rearrangements For Cysteine Modification And Glycoligation, Venkataraman Subramanian

Wayne State University Dissertations

This thesis describes investigations directed at the development of methods for the selenosulfide and disulfide rearrangements for the permanent functionalization of thiols, and in particular of cysteine and carbohydrate based thiols. Emphasis is placed on the newly invented silver mediated allylic desulfurative rearrangement for the primary modification of thiols and the synthesis of complex oligosaccharide mimics.

Chapter one introduces the concept of chemoselective ligations for the modification of macromolecules like carbohydrates and proteins. It overviews the native and non-native ligation techniques for their modification of such entities with a attention focusing on thiol based ligation techniques. The later part of …

Metal Chalcogenide Nanocrystal Assembly: From Synthesis To Applications, Qinghong Yao

Wayne State University Dissertations

This dissertation study is focused on (1) the application of an oxidation-induced sol-gel assembly method to formation of CdTe aerogels; (2) extension of existing aerogel compositions and properties by an alternative synthetic approach: cation-exchange reactions; and (3) probing the functionality of CdSe aerogels as optical sensors of Lewis base analytes.

Highly porous CdTe aerogels were successfully synthesized by sol-gel assembly of CdTe nanocrystals with thiolate or nonthiolate (phosphine oxide) ligated surfaces by treatment with tetranitromethane. Both phosphine oxide-capped and the thiolate-capped aerogels exhibit similar structure, morphology and porosimetry properties, suggesting that precursor ligation does not have a no major effect …

Routes To Acylated Sydnones Utilizing Microwave Chemistry, Amber C. Rumple

Browse all Theses and Dissertations

In the present work, microwave chemistry was utilized to improve and optimize two methods for the acylation of sydnones. Whereas before, 4-acyl-3-arylsydnones could be synthesized by the use of Friedel-Crafts reactions utilizing either Montmorillonite K-10 or bismuth(III) triflate/lithium perchlorate as catalysts in moderate to good yields after long reaction times, with the introduction of microwave chemistry 4-acyl-3-arylsydnones can be synthesized in good to excellent yields in much shorter times. A previous method using Montmorillonite K-10 allowed for a variety of 4-acetyl-3-arylsydnones to be synthesized thermally in moderate to good yields after at least 24 hours. This method was extended in …

Fabrication And Characterization Of Gel-Type Solar Cells Sensitized By Green-Synthesized Zinc Sulfide Quantum Dots, Adam Alman

Undergraduate Honors Theses

Three different types of fully integrated ZnS quantum dot-TiO₂ nanoparticle gels were used to create films for usage in photovoltaic cells. The films were annealed onto TEC-8 F:SnO₂ conductive glass electrode and the cell was completed by adding a polyolsolvated I/I₃ redox couple to the film and capping the cell with a counter electrode constructed of graphite-coated TEC-8 glass. Electrical output of the cells under a 360 W halogen light source and a natural or simulated (1000 W xenon arc lamp) sunlight source were estimated by multi-meter. The highest absolute energy conversion efficiency seen was from an …

Characterization Of Phytochemicals Isolated From Plants Of The Pacific Northwest And Western United States For Combating Fungal Multidrug Resistance, John David Schreiber

Undergraduate Honors Theses

Fungal multidrug resistance is an emerging problem for those suffering from fungal infections, and for those seeking to discover or produce novel fungicidal drugs. Plants native to the Pacific Northwest as well as in the Olympic national rainforest were collected and screened for phytochemicals which exhibit direct antifungal activity toward Candida and Saccharomyces spp. as well as those that inhibit fungal ABC transporters that are, in large part, responsible for the development of multidrug resistance. Dalea formosa (Fabaceae), a plant native to the American Southwest, was also screened for phytochemicals of medicinal interest. The methanolic extract of aerial portions of …

Toward A General Approach For Rna-Templated Hierarchical Assembly Of Split-Proteins, Jennifer L. Furman, Ahmed H. Badran, Oluyomi Ajulo, Jason R. Porter, Cliff I. Stains, David J. Segal, Indraneel Ghosh

Cliff Stains Publications

The ability to conditionally turn on a signal or induce a function in the presence of a user-defined RNA target has potential applications in medicine and synthetic biology. Although sequence-specific pumilio repeat proteins can target a limited set of ss- RNA sequences, there are no general methods for targeting ssRNA with designed proteins. As a first step toward RNA recognition, we utilized the RNA binding domain of argonaute, implicated in RNA interference, for specifically targeting generic 2-nucleotide, 3′ overhangs of any dsRNA. We tested the reassembly of a split-luciferase enzyme guided by argonaute-mediated recognition of newly generated nucleotide overhangs when …

Inhibition Of Nonsense-Mediated Mrna Decay By Antisense Morpholino Oligonucleotides Restores Functional Expression Of Herg Nonsense And Frameshift Mutations In Long-Qt Syndrome, Qiuming Gong, Matthew R. Stump, Zhengfeng Zhou

Faculty Publications - Department of Biological & Molecular Science

Mutations in the human ether-a-go-go-related gene (hERG) cause long-QT syndrome type 2 (LQT2). We previously described a homozygous LQT2 nonsense mutation Q1070X in which the mutant mRNA is degraded by nonsense-mediated mRNA decay (NMD) leading to a severe clinical phenotype. The degradation of the Q1070X transcript precludes the expression of truncated but functional mutant channels. In the present study, we tested the hypothesis that inhibition of NMD can restore functional expression of LQT2 mutations that are targeted by NMD. We showed that inhibition of NMD by RNA interference-mediated knockdown of UPF1 increased Q1070X mutant channel protein expression and hERG current …

Mutational Studies Uncover Non-Native Structure In The Dimeric Kinetic Intermediate Of The H2a–H2b Heterodimer, Matthew R. Stump, Lisa M. Gloss

Faculty Publications - Department of Biological & Molecular Science

The folding pathway of the histone H2A–H2B heterodimer minimally includes an on-pathway, dimeric, burst-phase intermediate, I2. The partially folded H2A and H2B monomers populated at equilibrium were characterized as potential monomeric kinetic intermediates. Folding kinetics were compared for initiation from isolated, folded monomers and the heterodimer unfolded in 4 M urea. The observed rates were virtually identical above 0.4Murea, exhibiting a log-linear relationship on the final denaturant concentration. Below ∼0.4 M urea (concentrations inaccessible from the 4-M urea unfolded state), a rollover in the rates was observed; this suggests that a component of the I2 ensemble contains non-native structure that …

Estrogen Analysis By Liquid Chromatography - Mass Spectrometry, Hien P. Nguyen

Chemistry & Biochemistry Dissertations - Archive

Estrogens are well known as female hormones associated with both health and disease. Although they have been reported as potential carcinogens, their use as therapy in the treatment of neurodegeneration has recently received a great deal of attention. The main goal of this work was to advance estrogen analysis using liquid chromatography - mass spectrometry (LC-MS) and associated techniques in order to support pre-clinical and clinical research on the neuroprotective effects of estrogens. Native estrogen analyses were performed in different types of biological samples, including human cerebrospinal fluid (CSF), horse serum, phosphate buffered saline - bovine serum albumin (PBS-BSA), mouse …

Total Synthesis Of Cyclooroidin And Studies Towards Some Oroidin Dimers, Sabuj Mukherjee

Chemistry & Biochemistry Dissertations - Archive

This dissertation consists of two parts. The first part describes the synthesis of northern fragment of nagelamide R and the enantioselective total synthesis of cyclooroidin. The oroidin family of marine natural products is a growing group of marine sponge-derived alkaloids which contain 2-aminoimidazole and pyrrolecarboxamide fragments as their signature features. The structural complexity, and in many cases interesting biological profiles, of these compounds has rendered several of these natural products as targets of interest. In the context of nagelamide R, the key transformation involves the intramolecular cyclization of a pyrrolecarboxamide via the carbonyl oxygen leading to the formation of oxazoline, …

Elucidation Of The Structure And Recognition Properties Of Antimony(Iii)-Tartrate Using Electrospray Ionization Mass Spectrometry, Aruna B. Wijeratne

Chemistry & Biochemistry Dissertations - Archive

Chirality of molecules is a major topic in the design, discovery and development of new drugs. Currently, analytical chemistry research divisions are challenged to find new methods to screen enantiospecific molecular recognition properties of potential chiral drug candidates with targeted biological molecules in a time-sensitive environment. Recently, mass spectrometry (MS) has received significant attention for its use in studying molecular recognition systems. Electrospray ionization mass spectrometry (ESI-MS) has received the most attention for the investigation of stereochemical association phenomena, due to its capacity to transfer solution phase chiral interactions into the gas phase for analysis in single-stage mass spectra. ESI-MS …

Application Of Pd-Catalyzed Reactions In The Total Synthesis Of Oroidin-Derived Alkaloids, Manojkumar R. Bhandari

Chemistry & Biochemistry Dissertations - Archive

The oroidin family of marine natural products is a growing group of sponge-derived alkaloids which contain 2-aminoimidazole and pyrrolecarboxamide fragments as their signature features. Due to their structural diversity and biological activity, many groups are interested in the total synthesis of these natural products. It has been proposed that many of the alkaloids in this family are produced in nature simply by dimerization and/or cyclization of the simplest member, oroidin. In this dissertation we have attempted to explore these biosynthetic relationships to complete the total synthesis of several oridin-derived natural products. This dissertation consists of two parts. The first part …