Physical Sciences and Mathematics Commons^™

Electrophilic Oligodeoxynucleotide Synthesis Using Dm-Dmoc For Amino Protection, Shahien Shahsavari, Dhananjani N. A. M. Eriyagama, Bhaskar Halami, Vagarshak Begoyan, Marina Tanasova, Jinsen Chen, Shiyue Fang

Department of Chemistry Publications

Solid-phase synthesis of electrophilic oligodeoxynucleotides (ODNs) was achieved using dimethyl-Dmoc (dM-Dmoc) as amino protecting group. Due to the high steric hindrance of the 2-(propan-2-ylidene)-1,3-dithiane side product from deprotection, the use of excess nucleophilic scavengers such as aniline to prevent Michael addition of the side product to the deprotected ODN during ODN cleavage and deprotection was no longer needed. The improved technology was demonstrated by the synthesis and characterization of five ODNs including three modified ones. The modified ODNs contained the electrophilic groups ethyl ester, α-chloroamide, and thioester. Using the technology, the sensitive groups can be installed at any location within …

A Redox Conjugated Polymer-Based All-Solid-State Reference Electrode, Ke Qu, Mingxi Fang, Shuwei Zhang, Haiying Liu, Xiangqun Zeng

Department of Chemistry Publications

This work reports the design, synthesis, and characterization of a novel redox-active conjugated polyaniline containing quinone moiety as a solid state reference electrode. The union of electro-active quinone with π-conjugated polyaniline was created by the first chemical synthesis of para-dimethoxybenzene-functionalized aniline as a monomer using a palladium-mediated coupling. The successful polymerization of the as-prepared monomer was accomplished without acid additives. Its post-polymerization modification with strong Lewis acid boron tribromide furnished unique poly (aniline quinone/hydroquinone) with desired properties for all-solid-state reference electrode (RE) applications. The electrochemical responses from the conjugated polyaniline backbone in this unique polymer have been “suppressed” by the …

A Near-Infrared Fluorescent Probe Based On A Fret Rhodamine Donor Linked To A Cyanine Acceptor For Sensitive Detection Of Intracellular Ph Alternations, Yibin Zhang, Jianheng Bi, Shuai Xia, Wafa Mazi, Shulin Wan, Logan Mikesell, Rudy Luck, Haiying Liu

Department of Chemistry Publications

A fluorescence resonance energy transfer (FRET)-based near-infrared fluorescent probe (B⁺) for double-checked sensitive detection of intracellular pH changes has been synthesized by binding a near-infrared rhodamine donor to a near-infrared cyanine acceptor through robust C-N bonds via a nucleophilic substitution reaction. To demonstrate the double-checked advantages of probe B⁺, a near-infrared probe (A) was also prepared by modification of a near-infrared rhodamine dye with ethylenediamine to produce a closed spirolactam residue. Under basic conditions, probe B⁺ shows only weak fluorescence from the cyanine acceptor while probe A displays nonfluorescence due to retention of the closed …

Molecular And Physical Characteristics Of Aerosol At A Remote Free Troposphere Site: Implications For Atmospheric Aging, Simeon Schum, Bo Zhang, Katja Džepina, Paolo Fialho, Claudio Mazzoleni, Lynn Mazzoleni

Department of Chemistry Publications

Aerosol properties are transformed by atmospheric processes during long-range transport and play a key role in the Earth's radiative balance. To understand the molecular and physical characteristics of free tropospheric aerosol, we studied samples collected at the Pico Mountain Observatory in the North Atlantic. The observatory is located in the marine free troposphere at 2225m above sea level, on Pico Island in the Azores archipelago. The site is ideal for the study of long-range-transported free tropospheric aerosol with minimal local influence. Three aerosol samples with elevated organic carbon concentrations were selected for detailed analysis. FLEXPART retroplumes indicated that two of …

Molecular Insights On Aging And Aqueous-Phase Processing From Ambient Biomass Burning Emissions-Influenced Po Valley Fog And Aerosol, Matthew Brege, Marco Paglione, Stefania Gilardoni, Maria Cristina Facchini, Lynn Mazzoleni

Department of Chemistry Publications

To study the influence of regional biomass burning emissions and secondary processes, ambient samples of fog and aerosol were collected in the Po Valley (Italy) during the 2013 Supersito field campaign. After the extent of fresh vs. aged biomass burning influence was estimated from proton nuclear magnetic resonance (¹H NMR) and high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), two samples of fog water and two samples of PM1 aerosol were selected for ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) analysis. Molecular compositions indicated that the water-soluble organic matter was largely non-polymeric without clearly repeating units. The …

Light Absorption By Polar And Non-Polar Aerosol Compounds From Laboratory Biomass Combustion, Deep Sengupta, Vera Samburova, Chiranjiva Bhattarai, Elena Kirillova, Lynn Mazzoleni, Michealene Iaukea-Lum, Adam Watts, Audrey Khlystov

Department of Chemistry Publications

Fresh and atmospherically aged biomass-burning (BB) aerosol mass is mostly comprised of strongly light-absorbing black carbon (BC) and of organic carbon (OC) with its light-absorbing fraction – brown carbon (BrC). There is a lack of data on the physical and chemical properties of atmospheric BB aerosols, leading to high uncertainties in estimates of the BB impact on air quality and climate, especially for BrC. The polarity of chemical compounds influences their fate in the atmosphere including wet/dry deposition and chemical and physical processing. So far, most of the attention has been given to the water-soluble (polar) fraction of BrC, while …

Ultrahigh Resolution Ft-Icr Ms Data For Biomass Burning Emissions-Influenced Fog And Aerosol From The Po Valley, Matthew Brege, Lynn Mazzoleni

Department of Chemistry Publications

This dataset and the methods used to obtain it were described in "Molecular insights on aging and aqueous phase processing from ambient biomass burning emissions-influenced Po Valley fog and aerosol” submitted to Atmospheric Chemistry and Physics in March of 2018. Briefly, two samples of ambient fog water and two samples of ambient aerosol collected in the Po Valley (Italy) during the 2013 Supersito field campaign were analyzed using negative mode electrospray ionization Fourier transform ion cyclotron mass spectrometry (FT-ICR MS). The extent of “fresh” vs. “aged” biomass burning influence was estimated prior to FT-ICR MS analysis using proton nuclear magnetic …

Ultrahigh Resolution Ft-Icr Ms Data Of Long-Range Transported Free Tropospheric Aerosol Collected At The Pico Mountain Observatory In The Azores, Simeon K. Schum, Lynn Mazzoleni

Department of Chemistry Publications

This dataset and the methods used to obtain it were described in “Molecular and physical characteristics of aerosol at a remote marine free troposphere site: Implications for atmospheric aging” submitted to Atmospheric Chemistry and Physics in February 2018. Briefly, three long-range transported organic aerosol samples were analyzed using negative mode electrospray ionization Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) with a mass resolving power of 400,000 (defined at m/z 400). FLEXPART retroplume simulations indicated that two of the samples (PMO-1 & PMO-3) were influenced by North American wildfire emissions transported in the free troposphere and one (PMO-2) by North …

Ice Cloud Formation Potential By Free Tropospheric Particles From Long-Range Transport Over The Northern Atlantic Ocean, Swarup China, Peter A. Alpert, B. Zhang, Simeon Schum, Katja Dzepina, Kendra Wright, R. Chris Owen, Paulo Fialho, Lynn Mazzoleni, Claudio Mazzoleni, Daniel A. Knopf

Department of Chemistry Publications

Long-range transported free tropospheric particles can play a significant role on heterogeneous ice nucleation. Using optical and electron microscopy we examine the physicochemical characteristics of ice nucleating particles (INPs). Particles were collected on substrates from the free troposphere at the remote Pico Mountain Observatory in the Azores Islands, after long-range transport and aging over the Atlantic Ocean. We investigate four specific events to study the ice formation potential by the collected particles with different ages and transport patterns. We use single-particle analysis, as well as bulk analysis to characterize particle populations. Both analyses show substantial differences in particle composition between …

Ten-Year Chemical Signatures Associated With Long-Range Transport Observed In The Free Troposphere Over The Central North Atlantic, B. Zhang, R. C. Owen, Judith Perlinger, D. Helmig, M. Val Martín, L. Kramer, Lynn Mazzoleni, C. Mazzoleni

Department of Chemistry Publications

Ten-year observations of trace gases at Pico Mountain Observatory (PMO), a free troposphere site in the central North Atlantic, were classified by transport patterns using the Lagrangian particle dispersion model, FLEXPART. The classification enabled identifying trace gas mixing ratios associated with background air and long- range transport of continental emissions, which were defined as chemical signatures. Comparison between the chemical signatures revealed the impacts of natural and anthropogenic sources, as well as chemical and physical processes during long transport, on air composition in the remote North Atlantic. Transport of North American anthropogenic emissions (NA-Anthro) and summertime wildfire plumes (Fire) significantly …

Hygroscopic Growth Of Water Soluble Organic Carbon Isolated From Atmospheric Aerosol Collected At Us National Parks And Storm Peak Laboratory, Nathan F. Taylor, Don R. Collins, Douglas H. Lowenthal, Ian B. Mccubbin, A. Gannet Hallar, Vera Samburova, Barbara Zielinska, Naresh Kumar, Lynn Mazzoleni

Department of Chemistry Publications

Due to the atmospheric abundance and chemical complexity of water soluble organic carbon (WSOC), its contribution to the hydration behavior of atmospheric aerosol is both significant and difficult to assess. For the present study, the hygroscopicity and CCN activity of isolated atmospheric WSOC particulate matter was measured without the compounding effects of common, soluble inorganic aerosol constituents. WSOC was extracted with high purity water from daily high-volume PM_2.5 filter samples and separated from water soluble inorganic constituents using solid-phase extraction. The WSOC filter extracts were concentrated and combined to provide sufficient mass for continuous generation of the WSOC-only aerosol …

Data Representing Two Separate Lc-Ms Methods For Detection And Quantification Of Water-Soluble And Fat-Soluble Vitamins In Tears And Blood Serum, Maryam Khaksari, Lynn Mazzoleni, Chunhai Ruan, Robert T. Kennedy, Adrienne Minerick

Department of Chemistry Publications

Tears serve as a viable diagnostic fluid with advantages including less invasive sample to collect and less complex to prepare for analysis. Several water-soluble and fat-soluble vitamins were detected and quantified in human tears and compared with blood serum levels. Samples from 15 family pairs, each pair consisting of a four-month-old infant and one parent were analyzed; vitamin concentrations were compared between tears and blood serum for individual subjects, between infants and parents, and against self-reported dietary intakes. Water-soluble vitamins B₁, B₂, B₃ (nicotinamide), B₅, B₉ and fat-soluble vitamin E (α-tocopherol) were …

Tropospheric Ozone Assessment Report: Database And Metrics Data Of Global Surface Ozone Observations, Martin G. Schultz, Sabine Schroder, Oleg Lyapina, Owen Cooper, Ian Galbally, Irina Petropavlovskikh, Lynn Mazzoleni, Et Al.

Department of Chemistry Publications

In support of the first Tropospheric Ozone Assessment Report (TOAR) a relational database of global surface ozone observations has been developed and populated with hourly measurement data and enhanced metadata. A comprehensive suite of ozone data products including standard statistics, health and vegetation impact metrics, and trend information, are made available through a common data portal and a web interface. These data form the basis of the TOAR analyses focusing on human health, vegetation, and climate relevant ozone issues, which are part of this special feature.

Cooperation among many data centers and individual researchers worldwide made it possible to build …

The Morphology Of Atmospheric Aerosol And Some Implications, Claudio Mazzoleni, Swarup China, Barbara Scarnato, Noopur Sharma, Janarjan Bhandari, Lynn Mazzoleni, Paulo Fialho, Cristina Facchini, Stefano Decesari, Stefania Gilardoni, Nicola Zanca

Department of Chemistry Publications

The morphology of individual atmospheric particles, including their mixing state, shape and internal structure, can have important atmospheric implications. Understanding the mechanisms leading to specific morphologies, the role of morphology in different atmospheric processes, and accounting for these details in models present considerable challenges. Several approaches are currently underway to make progress toward the resolution of these difficulties; for example, development and deployment of improved single particle analytical and observational tools, use of accurate electromagnetic models to quantitatively predict the interactions of solar radiation with single complex particles, and particle resolved models. In this presentation we will present single particle …

Bodipy-Based Fluorescent Probes For Sensing Protein Surface-Hydrophobicity, Nethaniah Dorh, Shilei Zhu, Kamal B. Dhungana, Ranjit Pati, Fen-Tair Luo, Haiying Liu, Ashutosh Tiwari

Department of Chemistry Publications

Mapping surface hydrophobic interactions in proteins is key to understanding molecular recognition, biological functions, and is central to many protein misfolding diseases. Herein, we report synthesis and application of new BODIPY-based hydrophobic sensors (HPsensors) that are stable and highly fluorescent for pH values ranging from 7.0 to 9.0. Surface hydrophobic measurements of proteins (BSA, apomyoglobin, and myoglobin) by these HPsensors display much stronger signal compared to 8-anilino-1-naphthalene sulfonic acid (ANS), a commonly used hydrophobic probe; HPsensors show a 10- to 60-fold increase in signal strength for the BSA protein with affinity in the nanomolar range. This suggests that these HPsensors …

Climatology And Atmospheric Chemistry Of The Non-Methane Hydrocarbons Ethane And Propane Over The North Atlantic, Detlev Helmig, Mauricio Muñoz, Jacques Hueber, Claudio Mazzoleni, Lynn Mazzoleni, Richard C. Owen, Maria Val-Martin, Paulo Fialho, Christian Plass-Duelmer, Paul I. Palmer, Alastair C. Lewis, Gabriele Pfister

Department of Chemistry Publications

A record spanning ten years of non-methane hydrocarbon (NMHC) data from the Pico Mountain Observatory (PMO), Pico Island, Azores, Portugal, was analyzed for seasonal NMHC behavior, atmospheric processing, and trends, focusing on ethane and propane. The location of this site in the central North Atlantic, at an elevation of 2225 m asl, allows these data to be used to investigate the background conditions and pollution transport events occurring in the lower free North Atlantic troposphere. The quantity ln([propane]/[ethane]) was used as an indicator of both photochemical processing and a marker for the occurrence of pollution transport events detected at the …

Molecular Characterization Of Free Tropospheric Aerosol Collected At The Pico Mountain Observatory: A Case Study With A Long-Range Transported Biomass Burning Plume, K. Dzepina, C. Mazzoleni, Paulo Fialho, Swarup China, B. Zhang, R. C. Owen, D. Helmig, D. Helmig, S. Kumar, Judith Perlinger, L. Kramer, M. P. Dziobak, M. T. Ampadu, S. Olsen, D. J. Wuebbles, Lynn Mazzoleni

Department of Chemistry Publications

Free tropospheric aerosol was sampled at the Pico Mountain Observatory located at 2225 m above mean sea level on Pico Island of the Azores archipelago in the North Atlantic. The observatory is located ~ 3900 km east and downwind of North America, which enables studies of free tropospheric air transported over long distances. Aerosol samples collected on filters from June to October 2012 were analyzed to characterize organic carbon, elemental carbon, and inorganic ions. The average ambient concentration of aerosol was 0.9 ± 0.7 μg m−3. On average, organic aerosol components represent the largest mass fraction of the total measured …

Facile Electrochemical Synthesis Of Antimicrobial Tio2 Nanotube Arrays, Yu Zhao, Qi Xing, Jagadeesh Janjanam, Kun He, Fei Long, Ke-Bin Low, Ashutosh Tiwari, Feng Zhao, Reza Shahbazian-Yassar, Tolou Shokuhfar

Department of Chemistry Publications

Infection-related complications have been a critical issue for the application of titanium orthopedic implants. The use of Ag nanoparticles offers a potential approach to incorporate antimicrobial properties into the titanium implants. In this work, a novel and simple method was developed for synthesis of Ag (II) oxide deposited TiO₂ nanotubes (TiNTs) using electrochemical anodization followed by Ag electroplating processes in the same electrolyte. The quantities of AgO nanoparticles deposited in TiNT were controlled by selecting different electroplating times and voltages. It was shown that AgO nanoparticles were crystalline and distributed throughout the length of the nanotubes. Inductively coupled plasma …

Atmospheric Organic Matter In Clouds: Exact Masses And Molecular Formula Identification Using Ultrahigh-Resolution Ft-Icr Mass Spectrometry, Y. Zhao, A. G. Hallar, Lynn Mazzoleni

Department of Chemistry Publications

Clouds alter the composition of atmospheric aerosol by acting as a medium for interactions between gas- and particulate-phase substances. To determine the cloud water atmospheric organic matter (AOM) composition and study the cloud processing of aerosols, two samples of supercooled clouds were collected at the Storm Peak Laboratory near Steamboat Springs, Colorado (3220 m a.s.l.). Approximately 3000 molecular formulas were assigned to ultrahigh-resolution mass spectra of the samples after using a reversed-phase extraction procedure to isolate the AOM components from the cloud water. Nitrogen-containing compounds (CHNO compounds), sulfur-containing compounds (CHOS and CHNOS compounds) and other oxygen-containing compounds (CHO compounds) with …

Inhibition Of Fast Axonal Transport By Pathogenic Sod1 Involves Activation Of P38 Map Kinase, Gerardo Morfini, Daryl Bosco, Hannah Brown, Rodolfo Gatto, Agnieszka Kaminska, Yuyu Song, Ashutosh Tiwari, Et. Al.

Department of Chemistry Publications

Dying-back degeneration of motor neuron axons represents an established feature of familial amyotrophic lateral sclerosis (FALS) associated with superoxide dismutase 1 (SOD1) mutations, but axon-autonomous effects of pathogenic SOD1 remained undefined. Characteristics of motor neurons affected in FALS include abnormal kinase activation, aberrant neurofilament phosphorylation, and fast axonal transport (FAT) deficits, but functional relationships among these pathogenic events were unclear. Experiments in isolated squid axoplasm reveal that FALS-related SOD1 mutant polypeptides inhibit FAT through a mechanism involving a p38 mitogen activated protein kinase pathway. Mutant SOD1 activated neuronal p38 in mouse spinal cord, neuroblastoma cells and squid axoplasm. Active p38 …

Hygroscopic Growth And Ccn Activity Of Hulis From Different Environments, Thomas B. Kristensen, Heike Wex, Bettina Nekat, Jacob K. Nøjgaard, Dominik Van Pinxteren, Douglas H. Lowenthal, Lynn Mazzoleni, Katrin Dieckmann, Christian Bender Koch, Thomas F. Mentel, Hartmut Herrmann, A. Gannet Hallar

Department of Chemistry Publications

[1] Humic-like substances (HULIS) constitute a significant fraction of aerosol particles in different environments. Studies of the role of HULIS in hygroscopic growth and cloud condensation nuclei (CCN) activity of aerosol particles are scarce, and results differ significantly. In this work the hygroscopic growth and CCN activity of water extracts (WE) and HULIS extracted from particulate matter (PM) collected at a polluted urban site (Copenhagen, Denmark), a rural site (Melpitz, Germany) and the remote site Storm Peak Laboratory (Colorado, USA) were investigated. Measurements of inorganic ions, elemental carbon, organic carbon and water soluble organic carbon (WSOC) within the PM confirmed …

High Molecular Weight Soa Formation During Limonene Ozonolysis: Insights From Ultrahigh-Resolution Ft-Icr Mass Spectrometry Characterization, Shuvashish Kundu, Rebeka Fisseha, Annie L. Putman, Thom A. Rahn, Lynn Mazzoleni

Department of Chemistry Publications

The detailed molecular composition of laboratory generated limonene ozonolysis secondary organic aerosol (SOA) was studied using ultrahigh-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Approximately 1200 molecular formulas were identified in the SOA over the mass range of 140 to 850 Da. Four characteristic groups of high relative abundance species were observed; they indicate an array of accretion products that retain a large fraction of the limonene skeleton. The identified molecular formulas of each of the groups are related to one another by CH2, O and CH2O homologous series. The CH2 and O homologous series of the low molecular …