Physical Sciences and Mathematics Commons^™

Structural Dynamics Of A Thermally Stressed Monoclonal Antibody Characterized By Temperature-Dependent H/D Exchange Mass Spectrometry., Nastaran N Tajoddin, Lars Konermann

Chemistry Publications

Differential scanning calorimetry (DSC) is a standard tool for probing the resilience of monoclonal antibodies (mAbs) and other protein therapeutics against thermal degradation. Unfortunately, DSC usually only provides insights into global unfolding, although sequential steps are sometimes discernible for multidomain proteins. Temperature-dependent hydrogen/deuterium exchange (HDX) mass spectrometry (MS) has the potential to probe heat-induced events at a much greater level of detail. We recently proposed a strategy to deconvolute temperature-dependent HDX data into contributions from local dynamics, global unfolding/refolding, as well as chemical labeling. However, that strategy was validated only for a small protein (Tajoddin, N. N.; Konermann, L.

Ultrasound Regulated Flexible Protein Materials: Fabrication, Structure And Physical-Biological Properties., Bowen Cai, Hanling Gu, Fang Wang, Kyle Printon, Zhenggui Gu, Xiao Hu

Faculty Scholarship for the College of Science & Mathematics

Ultrasound can be used in the biomaterial field due to its high efficiency, easy operation, no chemical treatment, repeatability and high level of control. In this work, we demonstrated that ultrasound is able to quickly regulate protein structure at the solution assembly stage to obtain the designed properties of protein-based materials. Silk fibroin proteins dissolved in a formic acid-CaCl solution system were treated in an ultrasound with varying times and powers. By altering these variables, the silks physical properties and structures can be fine-tuned and the results were investigated with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron …

Thermodynamics Of Ligand Binding And Global Structural Stability Of Human Serum Albumin, Matthew Walter Eskew

Dissertations and Theses

Protein structure is integral to its function. For the past 70 years differential scanning calorimetry has been used to measure protein structural stability. More recently it has been used to study macromolecular interactions. Interactions between proteins and ligands can manifest on differential scanning calorimetry melting curves or thermograms. Utilizing differential scanning calorimetry thermograms to detect or diagnose diseases has been a major goal in disease diagnostics. However, correlating specific ligand-protein interactions, as manifested in a thermogram, with a disease-specific plasma thermogram, has proven elusive.

Modified human serum albumin was utilized to develop a process to capture and retrieve ligands from …

Charged Particle Identification Using Calorimetry And Tracking At The Belle Ii Experiment, Joseph T. Nunziata, Atanu Pathak, Swagato Banerjee

Undergraduate Arts and Research Showcase

Particle identification (PID) is a critical procedure carried out in high energy physics experiments in search of new physics. When particles of matter (i.e., an electron) and antimatter (i.e., a positron) collide, new types of particles may form given certain conditions. Such particles may be classified as hadrons--which feel the strong nuclear force--and leptons--which do not. Identifying particles at the Belle II experiment is done by combining the measurement of energy deposited in the calorimeter with the measurement of track momentum in the tracker. In a tau lepton ($\tau$) decay sample, particles such as electrons, muons, and pions may be …

Cdse Quantum Dot Surface Chemistry Thermodynamics Via Isothermal Titration Calorimetry: An Emphasis On The Fundamentals, Megan Y. Gee

Theses and Dissertations

For several decades, the study and development of colloidal semiconductor nanocrystals, or quantum dots (QD), has become a rich field heralding improved integration into applications ranging from photovoltaics and photocatalysis to biomedical imaging and drug delivery. CdxSey is the most extensively studied QD system, however numerous compositional details still confound the nanocrystal field. Although CdSe QDs with native ligand coatings can show high fluorescence quantum yield and may be suitable for some applications, often times these original ligand layers are comprised of long aliphatic chains that preclude incorporation into biological matrices or severely impede charge transfer – depending on the …

Diagnostic Platform For Current Health Status Monitoring, Albert S. Benight, Megan M. Koslen, Matthew W. Eskew

Student Research Symposium

Our approach is based on physical measurements of blood plasma and exploits the plethora of information contained in the human plasma proteome, as a reporter of human health status. The assay involves collection and analysis ofthermograms of plasma from human blood measured by differential scanning calorimetry (DSC).

Plasma thermograms arise from the temperature-induced denaturation profile of proteins within blood plasma measured by DSC. This insightful measurement thereby provides a snapshot of the current state of the human plasma proteome which directly informs on overall systemic health. Such measurements have been shown to be highly accurate and sensitive indicators of health …

Identification Of The Hadronic Interaction Layer In A Highly Granular Calorimeter By Multivariate Techniques, Burak Bi̇lki̇

Turkish Journal of Physics

Calorimetry in future and upgrade collider detectors has a clear overall trend towards high granularity, both laterally and longitudinally. This trend is a requirement for the full exploitation of particle flow algorithms, which reconstruct individual particles using the subdetector that provides the best resolution for this specific particle. The increased level of detail in the event topologies due to higher segmentation of the calorimeter provides additional handles for several calorimetric measurements, such as the identification of the hadronic interaction layer, which is not possible for calorimeters with traditional tower geometry. Here, the power of using multivariate statistical techniques in the …

Calorimetry And Body Composition Research In Broilers And Broiler Breeders, Justina Victoria Caldas Cueva

Graduate Theses and Dissertations

Indirect calorimetry to study heat production (HP) and dual energy X-ray absorptiometry (DEXA) for body composition (BC) are powerful techniques to study the dynamics of energy and protein utilization in poultry. The first two chapters present the BC (dry matter, lean, protein, and fat, bone mineral, calcium and phosphorus) of modern broilers from 1 – 60 d of age analyzed by chemical analysis and DEXA. DEXA has been validated for precision, standardized for position, and equations and validations developed for chickens under two different feeding levels. These equations are unique to the machine and software in use. Research in broilers …

Methods Of Analysis For Fermentation Science Products Using Various Analytical Techniques, Casey Jay Howdieshell

Online Theses and Dissertations

Fermentation science, the study of microorganisms as they digest food sources to produce usable products for consumption, has been around since the dawn of modern civilization. Historically, the fermentation process has been utilized for the production of alcoholic beverages. More recently, however, the production of bioethanol and biodiesel as a fuel source alternative to classical fossil fuels has gained increased popularity. As with any synthetic process, derivations and optimizations for ideal production are needed. As such, analytical techniques must be implemented to ensure quality control and pinnacle efficiency. This body of work describes analytical techniques providing key qualitative and quantitative …

Bcl-2 Promoter Sequence G-Quadruplex Interactions With Three Planar And Non-Planar Cationic Porphyrins: Tmpyp4, Tmpyp3, And Tmpyp2., Vu H. Le, Narayana Nagesh, Edwin A. Lewis

College of Arts and Sciences Publications and Scholarship

The interactions of three related cationic porphyrins, TMPyP4, TMPyP3 and TMPyP2, with a WT 39-mer Bcl-2 promoter sequence G-quadruplex were studied using Circular Dichroism, ESI mass spectrometry, Isothermal Titration Calorimetry, and Fluorescence spectroscopy. The planar cationic porphyrin TMPyP4 (5, 10, 15, 20-meso-tetra (N-methyl-4-pyridyl) porphine) is shown to bind to a WT Bcl-2 G-quadruplex via two different binding modes, an end binding mode and a weaker mode attributed to intercalation. The related non-planar ligands, TMPyP3 and TMPyP2, are shown to bind to the Bcl-2 G-quadruplex by a single mode. ESI mass spectrometry experiments confirmed that the saturation stoichiometry is 4:1 for …

Characterization Of Pharmaceutical Materials By Thermal And Analytical Methods, Manik Pavan Kumar Maheswaram

ETD Archive

No abstract provided.

Novel Thermal Analytical Techniques To Characterize Drugs And Drug Delivery, Lakshmi Swetha Kaza

ETD Archive

This thesis encompasses three significant projects. The study includes the characterization and evaluation of the properties of a commercial contraceptive transdermal patch, Ortho Evra® by Dielectric Analysis and Differential Scanning Calorimetry (DSC). This study helps in monitoring the mobility of the drug and transport properties by Isothermal and Scanning Dielectric Analysis as a function of temperature and frequency. The drugs in this product are norelgestromin and ethinyl estradiol. DSC was used to detect any crystalline character of the drugs by their fusion properties. Having no melting endotherm and detecting a glass transition temperature suggested that the drugs in the patches …

Introduction To Pharmaceutical Thermal Analysis: A Teaching Tool, Shravan Singh Thakur

ETD Archive

Significant Thermal Analysis-physical chemical data needs to be acquired by the new analyst whether an entry level chemist or a new function for the experienced pharmaceutical scientist. This teaching tool describes the introductory use of Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Thermomechanical Analysis (TMA) for characterizing pharmaceuticals. Optimum Experimental conditions for DSC, TGA and TMA will focus on collecting the best results and interpretations. Does the sample contain volatiles? Evaporation creates endothermic peaks, 2 water or solvent can lower the glass transition temperature (Tg) by up to 100°C and affect the crystallization temperature on cooling. The decomposition temperature …

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 …

Enthalpies Of Mixing Of Water And Alkoxyethanols, John Enriquez

Open Access Theses & Dissertations

Alkoxyethanols [C_mH_2m+1·(OC₂H₄)·OH] (conveniently abbreviated to C_mE₁) are a subgroup of the alkyl poly(ethylene glycol) mono-ethers. They are small relatives of a large number of non-ionic detergents. The thermodynamic properties of their mixing in water have been shown to be good sources of information about the interactions of both hydrophilic and hydrophobic groups with water. Theses alkoxyethanols, or glycol ethers, are the ether derivatives of ethylene glycol where one hydroxyl functional group is substituted for an alkoxy functional group. Our group has already published results for aqueous excess properties …

Cholesterol Levels And Activity Of Membrane Bound Proteins: Characterization By Thermal And Electrochemical Methods, Noufissa Zanati, Michael Ellen Mathews, Perera N. Indika, John J. Moran, Jean A. Boutros, Alan T. Riga, Mekki Bayachou

Chemistry Faculty Publications

The long-term goal of this investigation is to study the effects of increased cholesterol levels on the molecular activity of membrane-bound enzymes such as nitric oxide synthase, that are critical in the functioning of the cardiovascular system. In this particular investigation, we used differential scanning calorimetry (DSC) and dielectric thermal analysis (DETA) to study the effect of added cholesterol on melting/recrystallization and dielectric behavior, respectively, of phosphatidylcholine (PC) bilayered thin films. We also used electrochemical methods to investigate the effect of added cholesterol on the redox behavior of the oxygenase domain of nitric oxide synthase as a probe embedded in …

Dynamics Of Pipa-D₇ On Silica Surface, Piyawan Krisanangkura, Frank D. Blum

Chemistry Faculty Research & Creative Works

Molecular motion of polymer chains is an important determinant in understanding the physical properties of polymeric materials. Glass transition temperature (Tg) is a physical property of polymers, which is of primary interest. The study of the dynamics of polymer segments assists in understanding the dependence of Tg on polymer structure.1 For decades, studies have addressed the molecular motion in various polymers. Some of them have probed the dynamics of polymer backbones.2,3 the properties of a polymer at an interface may change because of the type of polymer, the substrate, or other variables. The side chain of a polymer can also …

Optical Absorption, Depolarization, And Scatter Of Epitaxial Single-Crystal Chemical-Vapor-Deposited Diamond At 1.064 Μm, Giorgio Turri, Ying Chen, Michael Bass

Publications

No abstract provided.

Optical Properties Of Epitaxial Single-Crystal Chemical-Vapor-Deposited Diamond, Giorgio Turri, Ying Chen, Michael Bass, David Orchard, James E. Butler

Publications

Epitaxial single-crystal chemical-vapor-deposited diamond was obtained from Element Six Ltd. (Ascot, UK) and from Apollo Diamond (Boston, MA). Both companies provided 5 x 5 mm squares with thicknesses ranging from 0.5 to 1.5 mm. In addition, Element Six provided 10-mm-diameter disks with a thickness of 1.0 mm. The absorptance of all specimens at 1064 nm was measured by laser calorimetry, with good agreement between independent measurements at the University of Central Florida and at QinetiQ (Malvern, UK). Depolarization at 1064 nm and ultraviolet absorption properties are also reported.

Structure And Phase Transitions Of The 6, 6-Cyclopropane Isomer Of C_ {61} H_ {2}, M. R. Stetzer, Paul A. Heiney, Peter W. Stephens, R. E. Dinnebier, Q. Zhu, Andrew R. Mcghie, Robert M. Strongin, B. M. Brandt, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

We have used x-ray powder diffraction and differential scanning calorimetry to study the crystalline structures and thermal behavior of the 6,6-cyclopropane isomer of C₆₁H₂. At room temperature, the C₆₁H₂ cyclopropane molecules, like those of the 6,5-annulene isomer and C₆₀O epoxide, are orientationally disordered and crystallize on a face-centered-cubic lattice such that their methylene groups are statistically disordered among the octahedral voids. Unlike 6,5−C₆₁H₂ and C₆₀O, the low-temperature structure is not Pa3¯, but rather a low-symmetry orthorhombic lattice in which a≈b

Structure And Phase Transition Of The 6,5-Annulene Isomer Of C_{61}H_{2}, Andrea N. Lommen, Paul A. Heiney, Gavin B. M. Vaughan, Peter W. Stephens, Dengfa Liu, Dayin Li, Allan L. Smith, Andrew R. Mcghie, Robert M. Strongin, Laurent Brard, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

We have used differential scanning calorimetry and x-ray diffraction to study the crystalline phases of the 6,5-annulene isomer of C₆₁H₂. At 308 K the methylenated fullerenes are orientationally disordered in a face-centered cubic lattice with lattice parameter 14.19±0.02 Å. Below Tc=290 K the symmetry is lowered to Pa3¯, a simple-cubic structure. At 20 K the lattice parameter is 14.06±0.02 Å, with substantial statistical disorder remaining. The transition temperature in C₆₁H₂ is slightly higher than in C₆₀O and higher still than in C₆₀, but the three compounds exhibit orientationally …

Orientational Phase Transition In Na_{X}C_{60} (1, T. Yildirim, J. E. Fischer, A. B. Harris, Peter W. Stephens, Dengfa Liu, Laurent Brard, Robert M. Strongin, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

X-ray diffraction and calorimetry data on cubic Na_xC₆₀(1<x60, e.g., T_m(x=1.3)=325 K. The ordered phases are the same as in pure C₆₀: simple cubic, space group Pa3¯, but the orientations in the disordered phase are more restricted. We explain how Na stabilizes the ordered phase to rather high T, while K and Rb do not, in terms of Coulomb interactions between C₆₀ molecules and and Na ions which we calculate from the local charge density of C₆₀.

Existence Of High-Order Superlattices In Orientationally Ordered C_{60}, J. E. Fischer, D. E. Luzzi, K. Kniaź, A. R. Mcghie, D. A. Ricketts-Foot, W. R. Romanow, Gavin B. M. Vaughan, Dayin Li, Allan L. Smith, Robert M. Strongin, M. A. Cichy, Laurent Bard, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

We correlate the presence or absence of high-order modulated structures in solid C₆₀ with the differential scanning calorimetry signature of the orientational ordering transition and other diagnostic data. We have searched for, but not observed, the 2a face-centered cubic structure recently observed in low-temperature electron and single-crystal x-ray diffraction. We conclude that the intrinsic ground state is the previously reported simple cubic structure [space groupPa3¯, a(14 K)=14.06 Å], and that other structures may be stabilized by defects or impurities.

Unusual Thermal Stability Of A Site-Ordered Mc60 Rocksalt Structure (M=K, Rb, Or Cs), Q. Zhu, O. Zhou, J. E. Fischer, Andrew R. Mcghie, W. R. Romanow, Robert M. Strongin, M. A. Cichy, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

X-ray diffraction and differential scanning calorimetry of M_xC₆₀, with x∼1 and M=K, Rb, or Cs, reveal an unusual T-dependent phase sequence. A low-symmetry ground state is found, while the high-T limit is an ordered rocksalt structure in which only the octahedral sites are occupied. The unusual high-T stability of this ordered phase is attributed to the entropy of molecular orientational disorder and/or thermal disorder of the alkali-metal ions within the octahedral sites. Unique to K_xC₆₀ with x≥1.4, we find at intermediate temperatures an fcc site-disordered lattice gas …

I. An Isothermal Titration Microcalorimeter. Ii. Importance Of Micronutrients In Nutrition. Iii. Zinc Bibliography, John Willard Gardner

Theses and Dissertations

I. An isothermal titration microcalorimeter having a colume of 4 ml and capable of temerature control to ±2 x 10-5°C is described. Major components include a constant temperature water bath controlled to ±3 x 10-4°C, a platinum reation vessel, and an isothermal control circuit consisting of constant Peltier thermoelectric cooling and variable Joule heating controlled by a thermistor in an AC Wheatstone bridge circuit. The calorimeter was tested by measuring the heat of ionization of water and was found to produce data accurate to ± 0.1% where small samples are used such as in the investigation of many biological systems.

|Ni.|Pa Calorimetric Study Of The Heat Of Ionization Of Water At 10 And 40°C, And,|Nii.|Pa Calorimetric Determination Of The Heat Of Reaction Of Tris (Hydroxymethyl) Aminomethane (Tham) With Hydrochloric Acid In Aqueous Solution At 10, 25, And 40°C, Griffith Lyn Kimball

Theses and Dissertations

The heat of neutralization, ΔH_-N, of perchloric acid with sodium hydroxide has been determined at 10 and 40° in a low ionic strength, μ, region using a nonisothermal, constant-temperature-environment solution calorimeter. Correction of the data to infinite dilution by extrapolation of a plot of ΔH_-N vs μ^0.5 gives values at zero ionic strength for the heat of ionization of water of 14.216 and 12.695 kcal/mole, respectively, at 10 and 40° . The data are correlated with those of earlier workers to give an equation allowing the calculation of the heat of ionization of water at zero ionic strength over the …

A Calorimetric Study Of Metal Ion Cyclic Polyether Interaction :|Bi. Cation Binding Properties Of Macrocyclic Polyethers In Aqueous Solution As A Function Of Temperature ; Ii. Effect Of Solvent Dielectric Constant On The Binding Properties Of Cyclic Polyethers For Na[Superscript +] And K[Superscript +], Dennis Pershing Nelson

Theses and Dissertations

The complexation properties of the two isomers of the cyclic polyether dicyclohexyl-18-crown-6 are examined in aqueous solution for a series of metal ions at various reaction temperatures. The results are discussed in terms of size relationships and salvation characteristics of both polyether and metal ions. ΔCp° values are determined from the temperature dependence of the ΔH° values. A discussion of the errors involved in the determination of ΔH° from the temperature dependence of log K values is also included. Comparisons are made between the results of this study and those of a similar study by H. K. Frensdorff, E. I. …

Thermodynamics Of Proton Ionization In Aqueous Solution I. A Precision Thermometric Titration Calorimeter ; Ii. Entropy Titration : A Calorimetric Method For Equilibrium Constant Determinations ; Iii. H And S Values For Carboxylic Acid Proton Ionization At 25c ; Iv. Site Of Proton Ionization From Adenosine, Lee D. Hansen

Theses and Dissertations

The design, construction, and calibration of a precision thermometric titration calorimeter is described. This calorimeter was tested by determining the enthalpy change for ionization of water. The result, 13.34 ±0.03 kcal/mole (standard deviation), is in exact agreement with the best literature values. This standard deviation indicates that, using this calorimeter, ΔH values can be determined with an accuracy of ±0.0.5 kcal/mole. A calorimetric procedure has been developed for the, simultaneous determination of the equilibrium constant, the enthalpy change, and the entropy change for a chemical reaction from a single titration (Entropy Titration). This procedure has been tested by determining pK, …

A Calorimetric Study Of Metal Amino Acid Complexes In Aqueous Solution. I. The Copper (Ii) Glycine System. Ii. The Nickel (Ii) Glycine, Alanine And Phenylalanine Systems, Wilbur Orme Greenhalgh

Theses and Dissertations

Calorimeter values were obtained for the standard enthalpy change for the following reactions at 10,25, and 40 degrees C.: 1. The dissaciation of the amino acid, glycine, in the zwitterion form (HA) to give the basic form (A-) and a proton. 2. The reactions of copper (II) ion with glycine to form the Cu gly+ and Cu (gly)2 complexes. 3. The reactions of nickel (II) ion with glycine and alanine to form Ni gly+, Ni (gly)2, Ni al+, and Ni (al)2 complexes. For calorimetric enthalpy calculations, the initial and final concentrations of all species in the calorimeter must be known; …

Thermodynamics Of I) Metal Cyanide Coordination, Ii) Water Formation, And Iii) Metal Halide Coordination, John Dewey Hale

Theses and Dissertations

ΔH values for the formation of Ni(CN)4(aq)= have been determined calorimetrically at 25° using a simple calorimeter and a thermometric titration procedure at high and low ionic strengths, respectively. Extrapolation of these ΔH values to infinite dilution resulted in a ΔH° value of -42.7 kcal./mole. Combination of ΔH° and ΔF° values gives a ΔS° value of -5.5 e.u. for Ni(CN)4(aq)= formation. A value of +70 e.u. is calculated for the ionic entropy of Ni(CN)4(aq)=. A preliminary investigation of the Zn(CN)4(aq)= system indicated the existence of zinc cyanide complexes other than Zn(CN)4= and allowed calculation of an approximate ΔH° value of …