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Articles 1 - 30 of 40
Full-Text Articles in Physical Sciences and Mathematics
Development Of Single-Crystalline And 3d-Printable Porous Organic Materials, Mingshi Zhang
Development Of Single-Crystalline And 3d-Printable Porous Organic Materials, Mingshi Zhang
Dartmouth College Ph.D Dissertations
Porous organic materials with designable structures, large surface areas, low densities, and unique electronic and optical properties have found widespread applications in adsorption, separation, energy storage, and catalysis. However, the majority of organic porous materials are synthesized as fluffy powders, which poses two fundamental challenges for them. Firstly, they lack a single-crystal structure at the microscopic scale, making it difficult to study the specific pore size, shape, and potential substrate binding sites at the atomic level and further establish the structure-property relationship. Secondly, they lack the general processing method and macroscopic shape design, making it difficult to manufacture suitable components …
Rhodium-Catalyzed Asymmetric Synthesis Of P-P And P-C Bonds, Sarah T. Chachula
Rhodium-Catalyzed Asymmetric Synthesis Of P-P And P-C Bonds, Sarah T. Chachula
Dartmouth College Ph.D Dissertations
Chapter 1: Synthesis, Structure, Dynamics, and Enantioface-Selective η3-Benzyl Coordination in the Chiral Rhodium Complexes Rh(diphos*)(η3-CH2Ph) Abstract: The rhodium benzyl complexes Rh(diphos*)(η3-CH2Ph) (1-14, diphos* = chiral bis(phosphine)) were prepared either by treatment of Rh(COD)(η3-CH2Ph) (15, COD = 1,5-cyclooctadiene) with diphos*, or from the reaction of [Rh(diphos*)(Cl)]2 (16- 20) with PhCH2MgCl. For C2-symmetric diphos*, observation of one set of NMR signals for complexes 1-12 suggested that the two diastereomers in which different 3-benzyl enantiofaces were coordinated to rhodium interconverted rapidly on the NMR time scale via suprafacial shifts; observation of five inequivalent aryl 1H NMR signals showed that antarafacial shifts were slow …
Synthetic, Catalytic, And Mechanistic Studies Of Supermesityl Phosphiranes And Phosphines, Ryan M. Tipker
Synthetic, Catalytic, And Mechanistic Studies Of Supermesityl Phosphiranes And Phosphines, Ryan M. Tipker
Dartmouth College Ph.D Dissertations
Methylation of P-stereogenic phosphiranes Mes*PCH2CH(R) (Mes* = 2,4,6-(t-Bu)3C6H2, R = Me, Ph) with MeOTf gave P-stereogenic phosphiranium cations; [Mes*P(Me)CH2CH(Ph)][OTf] underwent syn-anti isomerization via P-epimerization. Mechanistic studies suggested ring opening gave a hyperconjugation-stabilized carbocation in which pyramidal inversion at P was promoted by s-interaction with the pendant cation. Attempted phosphirane protonation with HOTf resulted in ring opening and C-H activation of an o-t-Bu group to give phospholanium cations. Treatment of [Mes*P(Me)CH2CH(Ph)][OTf] with LiPPh2 gave bis(phosphino)ethanes. Copper- catalyzed P-alkylation of the secondary phosphine PHPh(Mes*) with benzyl bromides gave P-stereogenic tertiary phosphines with a supermesityl substituent.
Metallacycle-Mediated Cross-Coupling As An Enabling Tool For Studies In Carbocycle Synthesis And Functionalization, Adam Barry Millham
Metallacycle-Mediated Cross-Coupling As An Enabling Tool For Studies In Carbocycle Synthesis And Functionalization, Adam Barry Millham
Dartmouth College Ph.D Dissertations
Natural products, specifically complex, carbocyclic natural products, have served as the inspiration for novel methods development for decades. Over that time, metallacycle-mediated cross-coupling has arisen as a powerful means for the synthesis of fused carbocycles. This work details three methods for the synthesis and functionalization of carbocyclic motifs that have been enabled by Ti-mediated cross-coupling reactions. The first of these studies include a complementary method to the Pauson–Khand reaction for the synthesis of highly substituted cyclopentenones via Ti-mediated alkyne–β-ketoester coupling. The second project, a modern approach to steroidal tetracycles, will be discussed that features: (1) an alkoxide-directed metallacycle-mediated [2+2+2] annulation …
Development Of Novel Nucleophile-Intercepted Beckmann Fragmentations And Progress Toward The Total Synthesis Of 2(S)-Cathafoline, Evan M. Dunkley
Development Of Novel Nucleophile-Intercepted Beckmann Fragmentations And Progress Toward The Total Synthesis Of 2(S)-Cathafoline, Evan M. Dunkley
Dartmouth College Master’s Theses
This thesis is comprised of two chapters, the first being the discovery of a novel nucleophile-intercepted Beckmann fragmentation of [2.2.1] indoline systems that resulted in highly stereo- and regioselective reactions. Chapter one details the exploration of this reaction as well as its relevant background information detailing its significance. Chapter two describes the application of the novel nucleophile-intercepted Beckmann fragmentation in the context of a total synthesis of akuammilline alkaloid 2(S)-cathafoline. While the target natural product was never synthesized, unpredicted reactivity resulted in interesting discoveries worthy of discussion.
Efforts Towards The Asymmetric De Novo Synthesis Of Lanostanes And Euphanes, Htoo Tint Wai
Efforts Towards The Asymmetric De Novo Synthesis Of Lanostanes And Euphanes, Htoo Tint Wai
Dartmouth College Ph.D Dissertations
Tetracyclic triterpenoids are ubiquitous in nature and biology, with members displaying a wide range of medically relevant properties and occupying rather distinct regions of chemical space. Members of this large class include well-known steroid hormones and sterols as well as structurally interesting subclasses such as lanostanes and euphanes, among others. Comprised of the tetracyclic skeleton with three stereodefined quaternary centers at ring-junction positions, lanostanes and euphanes present synthetic challenges that are different from those encountered in efforts targeting the structurally less complex steroid hormones. Lanostanes, in particular, stand as a historically important class of compounds as significant attention has been …
Converting Hydrazone-Based Photoswitches Into Functional Materials, Sirun Yang
Converting Hydrazone-Based Photoswitches Into Functional Materials, Sirun Yang
Dartmouth College Ph.D Dissertations
The development of new classes of molecular switches with enhanced performance and brand-new functionalities enables practitioners to push the frontiers of adaptive materials. In the realm of photoswitches, the bistability of hydrazones (i.e., molecules that incorporate the C=N-NH functional group) allows for the kinetic trapping of polymer and supramolecular assemblies resulting in multistate actuation and emergent phenomena that are not tractable with other photoswitches. This property has transformed hydrazone photoswitches into powerful tools that can be used in understanding fundamental molecular interactions and how to apply them in modulating the physicochemical properties of materials.
Progressing from disordered to …
Cysteine Metallochemistry And Metal Binding: Quantification Of The Thermodynamic Foundations Of Cellular Homeostasis, Matthew R. Mehlenbacher
Cysteine Metallochemistry And Metal Binding: Quantification Of The Thermodynamic Foundations Of Cellular Homeostasis, Matthew R. Mehlenbacher
Dartmouth College Ph.D Dissertations
Metals are required for life. Many metalloproteins contain cysteine in their metal-binding site (MBS) and cysteines are unique in that they are reactive, and strongly bind certain metals, which aid in metal selectivity and specificity. Using isothermal titration calorimetry (ITC), the thermodynamic foundation for metal binding, cellular protection, and transcriptional regulation, which all utilize cysteines in their MBS, are quantified.
In bacteria there are metalloprotein pathways that actively uptake mercury, which are regulated by the metalloregulatory protein MerR. MerR de-represses the transcription of these mer proteins in a metal-dependent manner. Using ITC, the thermodynamic foundation of the negative allosteric coupling …
Solution And Solid-State Emission Toggling Of A Photochromic Hydrazone, Baihao Shao, Massimo Baroncini, Laura Bussotti, Mariangela Di Donato, Alberto Credi, Ivan Aprahamian
Solution And Solid-State Emission Toggling Of A Photochromic Hydrazone, Baihao Shao, Massimo Baroncini, Laura Bussotti, Mariangela Di Donato, Alberto Credi, Ivan Aprahamian
Dartmouth Scholarship
The proliferation of light-activated switches in recent years has enabled their use in a broad range of applications encompassing an array of research fields and disciplines. All current systems, however, have limitations (e.g., from complicated synthesis to incompatibility in biologically relevant media and lack of switching in the solid-state) that can stifle their real-life application. Here we report on a system that packs most, if not all, the desired, targeted and sought-after traits from photochromic compounds (bistability, switching in various media ranging from serum to solid-state, while exhibiting ON/OFF fluorescence emission switching, and two-photon assisted near-infrared light toggling) in an …
Faculty Spotlight: Gordon Gribble, Samuel R. Reed
Faculty Spotlight: Gordon Gribble, Samuel R. Reed
Dartmouth Undergraduate Journal of Science
Professor Gordon Gribble received his B.S. from U.C. Berkeley and his Ph.D. from the University of Oregon. He has been at Dartmouth for the past 49 years, and in that time he has taught chemistry to a great number of students. His research in the field of organic chemistry features indole and triterpenoid synthesis, and has yielded a wide range of medications.
Annual Variation In Event-Scale Precipitation Δ 2 H At Barrow, Ak, Reflects Vapor Source Region, Annie Putman, Xiahong Feng, Leslie Sonder, Eric Posmentier
Annual Variation In Event-Scale Precipitation Δ 2 H At Barrow, Ak, Reflects Vapor Source Region, Annie Putman, Xiahong Feng, Leslie Sonder, Eric Posmentier
Dartmouth Scholarship
In this study, precipitation isotopic variations at Barrow, AK, USA, are linked to conditions at the moisture source region, along the transport path, and at the precipita- tion site. Seventy precipitation events between January 2009 and March 2013 were analyzed for δ2H and deuterium ex- cess. For each precipitation event, vapor source regions were identified with the hybrid single-particle Lagrangian inte- grated trajectory (HYSPLIT) air parcel tracking program in back-cast mode. The results show that the vapor source re- gion migrated annually, with the most distal (proximal) and southerly (northerly) vapor source regions occurring during the winter (summer). This may …
Fluorocarbene, Fluoroolefin, And Fluorocarbyne Complexes Of Rh, Christopher Pell, Yanjun Zhu, Rafael Huacuja, David Herbert, Russell Hughes, Oleg Ozerov
Fluorocarbene, Fluoroolefin, And Fluorocarbyne Complexes Of Rh, Christopher Pell, Yanjun Zhu, Rafael Huacuja, David Herbert, Russell Hughes, Oleg Ozerov
Dartmouth Scholarship
The manuscript reports the synthesis, characterization, and analysis of electronic structure in a series of complexes of small perfluorocarbon ligands with the (PNP)Rh fragment (where PNP is a diarylamido/bis(phosphine) pincer ligand). Reactions of (PNP)Rh(TBE) as the source of (PNP)Rh with CHF3 and C2HF5 produced perfluoroalkylidene complexes (PNP)RhCF2 and (PNP)RhC(F)(CF3). (PNP)RhCF2 could also be obtained via the reaction of (PNP)Rh(TBE) with Me3SiCF3/CsF, with an admixture of (PNP) Rh(C2F4), where TBE = tert-butylethylene. Abstraction of fluoride from these neutral (PNP)RhCxFy complexes was successful, although only abstraction from (PNP)Rh]CF2 allowed unambiguous identification of the Rh product, [(PNP)Rh CF] +. DFT computational studies allowed …
Vapor Deposited Cr-Doped Zns Thin Films: Towards Optically Pumped Mid-Infrared Waveguide Lasers, Eric A. Karhu, Charles R. Ildstad, Stefano Poggio, Vedran Furtula, Nikolai Tolstik, Irina T. Sorokina, Joseph J. Belbruno, Ursula J. Gibson
Vapor Deposited Cr-Doped Zns Thin Films: Towards Optically Pumped Mid-Infrared Waveguide Lasers, Eric A. Karhu, Charles R. Ildstad, Stefano Poggio, Vedran Furtula, Nikolai Tolstik, Irina T. Sorokina, Joseph J. Belbruno, Ursula J. Gibson
Dartmouth Scholarship
Compact, affordable mid-IR lasers require the development of gain materials in waveguide form. We report on the high vacuum deposition of Cr:ZnS films with concentration ranging from 1018-1020 dopants/cm3 . At low concentrations, films display well-isolated absorption associated with substitutional Cr2+ ions in the lattice. Spatial modulation of the dopant concentration suppresses the absorption associated with this substitution. Lateral crystallite sizes less than 30 nm are associated with the lowest substrate temperatures (<50 °C) used during deposition, and waveguide losses as low as 8dB/cm are observed. These materials are promising candidates as gain media for fabrication of waveguide mid-IR lasers.
Synthesis, Crystal Structures, And Dft Calculations Of Three New Cyano(Phenylsulfonyl)Indoles And A Key Synthetic Precursor Compound, William Montgomery, Justin Lopchuk, Gordon Gribble, Jerry Jasinski
Synthesis, Crystal Structures, And Dft Calculations Of Three New Cyano(Phenylsulfonyl)Indoles And A Key Synthetic Precursor Compound, William Montgomery, Justin Lopchuk, Gordon Gribble, Jerry Jasinski
Dartmouth Scholarship
Three cyano-1-(phenylsulfonyl)indole derivatives, 3-cyano-1-(phenylsulfonyl) indole, (I), 2-cyano-1-(phenylsulfonyl)indole, (II), and 2,3-dicyano-1-(phenylsulfonyl) indole, (III), and a key synthetic precursor 1-(phenylsulfonyl)-1-(1,1-dimethylethyl) indole-3-carboxamide, (IV), have been synthesized and their structures determined by single crystal X-ray crystallography. (I), C15H10N2O2S, is orthorhombic with space group P 212121 and cell constants: a = 4.9459(3) Å, b = 10.5401(7) Å, c = 25.0813(14) Å, V = 1307.50(14) Å3 and Z = 4. (II), C15H10N2O2S, …
Biological Activity Of Recently Discovered Halogenated Marine Natural Products, Gordon Gribble
Biological Activity Of Recently Discovered Halogenated Marine Natural Products, Gordon Gribble
Dartmouth Scholarship
This review presents the biological activity—antibacterial, antifungal, anti-parasitic, antiviral, antitumor, antiinflammatory, antioxidant, and enzymatic activity—of halogenated marine natural products discovered in the past five years. Newly discovered examples that do not report biological activity are not included.
(3+2)-Cycloaddition Reactions Of Oxyallyl Cations, Jimmy Wu, Hui Li
(3+2)-Cycloaddition Reactions Of Oxyallyl Cations, Jimmy Wu, Hui Li
Dartmouth Scholarship
The (3+2)-cycloaddition reaction involving oxyallyl cations has proven to be a versatile and efficient approach for the construction of five-membered carbo- and heterocycles, which are prevalent frameworks in natural products and pharmaceuticals. The following article will provide a brief summary of recent disclosures on this process featuring chemo-, regio- and diastereoselective oxyallyl cycloadditions with both electron-rich and electron-deficient 2π partners.
Regulating Signal Enhancement With Coordination-Coupled Deprotonation Of A Hydrazone Switch, Justin T. Foy, Debdas Ray, Ivan Aprahamian
Regulating Signal Enhancement With Coordination-Coupled Deprotonation Of A Hydrazone Switch, Justin T. Foy, Debdas Ray, Ivan Aprahamian
Dartmouth Scholarship
Proton relay plays an important role in many biocatalytic pathways. In order to mimic such processes in the context of molecular switches, we developed coordination-coupled deprotonation (CCD) driven signaling and signal enhancement sequences. This was accomplished by using the zinc(ii)-initiated CCD of a hydrazone switch to instigate an acid catalyzed imine bond hydrolysis that separates a quencher from a fluorophore thus leading to emission amplification. Because CCD is a reversible process, we were able to show that the catalysis can be regulated and turned “on” and “off” using a metalation/demetalation cycle.
Methyl 1-Benzyl-5-Methyl-2,4-Diphenyl-1h-Pyrrole-3-Carboxyl-Ate, Justin M. Lopchuk, Gordon W. Gribble, Jerry P. Jasinski
Methyl 1-Benzyl-5-Methyl-2,4-Diphenyl-1h-Pyrrole-3-Carboxyl-Ate, Justin M. Lopchuk, Gordon W. Gribble, Jerry P. Jasinski
Dartmouth Scholarship
In the title compound, C26H23NO2, the dihedral angles between the pyrrole ring and the two phenyl rings are 58.1 (6) and 71.5 (5)°. The mean planes of the 5-methylbenzene ring and the carboxyl group are twisted by 89.5 (3) and 22.1 (9)°, respectively, from the pyrrole ring. In the crystal, weak C—H⋯O interactions lead to supramolecular layers in the ab plane.
Gene And Protein Sequence Optimization For High-Level Production Of Fully Active And Aglycosylated Lysostaphin In Pichia Pastoris, Hongliang Zhao, Kristina Blazanovic, Yoonjoo Choi, Chris Bailey-Kellogg, Karl E. Griswold
Gene And Protein Sequence Optimization For High-Level Production Of Fully Active And Aglycosylated Lysostaphin In Pichia Pastoris, Hongliang Zhao, Kristina Blazanovic, Yoonjoo Choi, Chris Bailey-Kellogg, Karl E. Griswold
Dartmouth Scholarship
Lysostaphin represents a promising therapeutic agent for the treatment of staphylococcal infections, in particular those of methicillin-resistant Staphylococcus aureus (MRSA). However, conventional expression systems for the enzyme suffer from various limitations, and there remains a need for an efficient and cost-effective production process to facilitate clinical translation and the development of nonmedical applications. While Pichia pastoris is widely used for high-level production of recombinant proteins, there are two major barriers to the production of lysostaphin in this industrially relevant host: lack of expression from the wild-type lysostaphin gene and aberrant glycosylation of the wild-type protein sequence. The first barrier can …
The Importance Of The Rotor In Hydrazone-Based Molecular Switches, Xin Su, Timo Lessing, Ivan Aprahamian
The Importance Of The Rotor In Hydrazone-Based Molecular Switches, Xin Su, Timo Lessing, Ivan Aprahamian
Dartmouth Scholarship
The pH-activated E/Z isomerization of a series of hydrazone-based systems having different functional groups as part of the rotor (R = COMe, CN, Me, H), was studied. The switching efficiency of these systems was compared to that of a hydrazone-based molecular switch (R = COOEt) whose E/Z isomerization is fully reversible. It was found that the nature of the R group is critical for efficient switching to occur; the R group should be a moderate H-bond acceptor in order to (i) provide enough driving force for the rotor to move upon protonation, and (ii) stabilize the obtained Z configuration, to …
Variability Of Black Carbon Deposition To The East Antarctic Plateau, 1800-2000 Ad, M. M. Bisiaux, R. Edwards, J. R. Mcconnell, M. R. Albert
Variability Of Black Carbon Deposition To The East Antarctic Plateau, 1800-2000 Ad, M. M. Bisiaux, R. Edwards, J. R. Mcconnell, M. R. Albert
Dartmouth Scholarship
Refractory black carbon aerosols (rBC) from biomass burning and fossil fuel combustion are deposited to the Antarctic ice sheet and preserve a history of emissions and long-range transport from low- and mid-latitudes. Antarctic ice core rBC records may thus provide information with respect to past combustion aerosol emissions and atmospheric circulation. Here, we present six East Antarctic ice core records of rBC concentrations and fluxes covering the last two centuries with approximately annual resolution (cal. yr. 1800 to 2000). The ice cores were drilled in disparate regions of the high East Antarctic ice sheet, at different elevations and net snow …
3,3-Dimethyl-1,2,3,4-TetraHydroCycloPenta[B]Indole-1,2-Dione (Bruceolline E), Jason A. Jordon, Jeanese C. Badenock, Gordon W. Gribble, Jerry P. Jasinski, James A. Golen
3,3-Dimethyl-1,2,3,4-TetraHydroCycloPenta[B]Indole-1,2-Dione (Bruceolline E), Jason A. Jordon, Jeanese C. Badenock, Gordon W. Gribble, Jerry P. Jasinski, James A. Golen
Dartmouth Scholarship
The title compound, C13H11NO2, crystallizes with two molecules in the asymmetric unit. The crystal packing is stabilized by N—H⋯O hydrogen bonds, which link the molecules into chains along [10], and weak C—H⋯O interactions.
4-PhenylSulfonYl-2-(P-TolylSulfonYl)-1h,8h-Pyrrolo[2,3-B]Indole, Jeanese C. Badenock, Jason A. Jordan, Erin T. Pelkey, Gordon W. Gribble, Jerry P. Jasinski
4-PhenylSulfonYl-2-(P-TolylSulfonYl)-1h,8h-Pyrrolo[2,3-B]Indole, Jeanese C. Badenock, Jason A. Jordan, Erin T. Pelkey, Gordon W. Gribble, Jerry P. Jasinski
Dartmouth Scholarship
The title compound, C23H18N2O4S2, contains a pyrrolo group fused onto the plane of an indole ring with phenylsulfonyl and p-toluenesulfonyl groups bonded to the indole and pyrrolo rings. The angles between the mean planes of the pyrrolo- indole ring and the phenylsulfonyl and p-toluenesulfonyl rings are 73.7 (6) and 80.6 (0), respectively. The dihedral angle between the mean planes of the two benzene rings is 78.7 (4). In the crystal, both classical N—H O and non-classical C— H O intermolecular hydrogen-bonding interactions are observed, as well as weak – interactions [centroid–centroid distances = 3.6258 (8) and 3.9298 (8) …
An Improved Synthesis Of A Ring-C Precursor To Cobyric Acid, Hui Wang, Peter A. Jacobi
An Improved Synthesis Of A Ring-C Precursor To Cobyric Acid, Hui Wang, Peter A. Jacobi
Dartmouth Scholarship
Alkyne acid 10 was prepared in enantioselective fashion from allylic ester derivative (R)-18 via an E-selective Ireland-Claisen rearrangement followed by Si-assisted elimination of HBr. The present route offers significant advantages in terms of both scalability and overall yield compared to that previously described. Alkyne acid 10 is an attractive ring-C precursor for an ongoing synthesis of cobyric acid.
1, 2-Bis (Phenylsulfonyl)-1h-Indole As An Acceptor Of Organocuprate Nucleophiles, David C. Qian, Philip E. Alford, Tara L. S. Kishbaugh, Sean T. Jones, Gordon W. Gribble
1, 2-Bis (Phenylsulfonyl)-1h-Indole As An Acceptor Of Organocuprate Nucleophiles, David C. Qian, Philip E. Alford, Tara L. S. Kishbaugh, Sean T. Jones, Gordon W. Gribble
Dartmouth Scholarship
1,2-Bis(phenylsulfonyl)-1H-indole is a novel example of an electron-deficient indole that undergoes nucleophilic attack at C-3. Though a variety of other organometallic nucleophiles fail to engender nucleophilic substitution, organocuprates produce 3-substituted 2-(phenylsulfonyl)-1H-indoles. These reactions contribute to the growing number of examples of nucleophilic addition to the indole core.
Synthetic Studies In Phytochrome Chemistry, Peter A. Jacobi, Imad Odeh, Subhas Buddhu, Guolin Cai, Sundaramoorthi Rajeswari, Douglas Fry, Wanjun Zheng, Robert W. Desimone, Jiasheng Guo, Lisa D. Coutts, Sheila I. Hauck, Sam H. Leung, Indranath Ghosh, Douglas Pippin
Synthetic Studies In Phytochrome Chemistry, Peter A. Jacobi, Imad Odeh, Subhas Buddhu, Guolin Cai, Sundaramoorthi Rajeswari, Douglas Fry, Wanjun Zheng, Robert W. Desimone, Jiasheng Guo, Lisa D. Coutts, Sheila I. Hauck, Sam H. Leung, Indranath Ghosh, Douglas Pippin
Dartmouth Scholarship
An account is given of the author’s several approaches to the synthesis of the parent chromophore of phytochrome (1), a protein-bound linear tetrapyrrole derivative that controls photomorphogenesis in higher plants. These studies culminated in enantioselective syntheses of both (2R)- and (2S)-phytochromobilin (4), as well as several 13C-labeled derivatives designed to probe the site of Z,E-isomerization during photoexcitation. When reacted in vitro, synthetic 2R-4 and recombinant-derived phytochrome apoprotein N-C produced a protein-bound chromophore with identical difference spectra to naturally occurring 1.
Crystal Structure Of The Gtpase Domain Of Rat Dynamin 1, Thomas F. Reubold, Susanne Eschenburg, Andreas Becker, Marilyn Leonard, Sandra L. Schmid, Richard B. Vallee, F. Jon Kull, Dietmar J. Manstein
Crystal Structure Of The Gtpase Domain Of Rat Dynamin 1, Thomas F. Reubold, Susanne Eschenburg, Andreas Becker, Marilyn Leonard, Sandra L. Schmid, Richard B. Vallee, F. Jon Kull, Dietmar J. Manstein
Dartmouth Scholarship
Here, we present the 1.9-A crystal structure of the nucleotide-free GTPase domain of dynamin 1 from Rattus norvegicus. The structure corresponds to an extended form of the canonical GTPase fold observed in Ras proteins. Both nucleotide-binding switch motifs are well resolved, adopting conformations that closely resemble a GTP-bound state not previously observed for nucleotide-free GTPases. Two highly conserved arginines, Arg-66 and Arg-67, greatly restrict the mobility of switch I and are ideally positioned to relay information about the nucleotide state to other parts of the protein. Our results support a model in which switch I residue Arg-59 gates GTP binding …
Probabilistic Disease Classification Of Expression-Dependent Proteomic Data From Mass Spectrometry Of Human Serum, Ryan H. Lilien, Hany Farid, Bruce R. Donald
Probabilistic Disease Classification Of Expression-Dependent Proteomic Data From Mass Spectrometry Of Human Serum, Ryan H. Lilien, Hany Farid, Bruce R. Donald
Dartmouth Scholarship
We have developed an algorithm called Q5 for probabilistic classification of healthy vs. disease whole serum samples using mass spectrometry. The algorithm employs Principal Components Analysis (PCA) followed by Linear Discriminant Analysis (LDA) on whole spectrum Surface-Enhanced Laser Desorption/Ionization Time of Flight (SELDI-TOF) Mass Spectrometry (MS) data, and is demonstrated on four real datasets from complete, complex SELDI spectra of human blood serum.
Q5 is a closed-form, exact solution to the problem of classification of complete mass spectra of a complex protein mixture. Q5 employs a novel probabilistic classification algorithm built upon a dimension-reduced linear discriminant analysis. Our solution is …
Regulation And Localization Of Endogenous Human Tristetraprolin, Anna-Marie Fairhurst, John E. Connolly, Katharine A Hintz, Nicolas J Goulding
Regulation And Localization Of Endogenous Human Tristetraprolin, Anna-Marie Fairhurst, John E. Connolly, Katharine A Hintz, Nicolas J Goulding
Dartmouth Scholarship
Tumor necrosis factor (TNF) has been implicated in the development and pathogenicity of infectious diseases and autoimmune disorders, such as septic shock and arthritis. The zinc-finger protein tristetraprolin (TTP) has been identified as a major regulator of TNF biosynthesis. To define its intracellular location and examine its regulation of TNF, a quantitive intracellular staining assay specific for TTP was developed. We establish for the first time that in peripheral blood leukocytes, express
Synthesis Of Novel [3, 2-B] Indole Fused Oleanolic Acids As Potential Inhibitors Of Cell Proliferation, Heather J. Finlay, Tadashi Honda, Gordon W. Gribble
Synthesis Of Novel [3, 2-B] Indole Fused Oleanolic Acids As Potential Inhibitors Of Cell Proliferation, Heather J. Finlay, Tadashi Honda, Gordon W. Gribble
Dartmouth Scholarship
Seven new indole-fused oleanolic acid derivatives were synthesized from oleanolic acid for their ability to inhibit cell proliferation in NRP. 152 cells.