Physical Sciences and Mathematics Commons^™

Novel Mips-Parabens Based Spe Stationary Phases Characterization And Application, Angela Tartaglia, Abuzar Kbir, Songhul Ulusoy, Halil Ibrahim Ulusoy, Giuseppe Maria Merone, Fabio Savini, Cristian D'Ovidio, Ugo De Grazia, Serena Gabrielli, Fabio Maroni, Pantaleone Bruni, Fausto Croce, Dora Melucci, Kenneth G. Furton, Marcello Locatelli

Department of Chemistry and Biochemistry

In this work, the synthesis, characterization, and application of novel parabens imprinted polymers as highly selective solid-phase extraction (SPE) sorbents have been reported. The imprinted polymers were created using sol–gel molecular imprinting process. All the seven parabens were considered herein in order to check the phase selectivity. By means of a validated HPLC-photodiode array detector (PDA) method all seven parabens were resolved in a single chromatographic run of 25 min. These SPE sorbents, in-house packed in SPE empty cartridges, were first characterized in terms of extraction capability, breakthrough volume, retention volume, hold-up volume, number of theoretical plates, and retention factor. …

Molecular Mass Growth Through Ring Expansion In Polycyclic Aromatic Hydrocarbons Via Radical–Radical Reactions, Long Zhao, Ralf I. Kaiser, Wenchao Lu, Bo Xu, Musahid Ahmed, Alexander N. Morozov, Alexander Mebel, A. Hasan Howlader, Stanislaw F. Wnuk

Department of Chemistry and Biochemistry

Polycyclic aromatic hydrocarbons (PAHs) represent key molecular building blocks leading to carbonaceous nanoparticles identified in combustion systems and extraterrestrial environments. However, the understanding of their formation and growth in these high temperature environments has remained elusive. We present a mechanism through laboratory experiments and computations revealing how the prototype PAH—naphthalene—can be efficiently formed via a rapid 1-indenyl radical—methyl radical reaction. This versatile route converts five- to six-membered rings and provides a detailed view of high temperature mass growth processes that can eventually lead to graphene-type PAHs and two-dimensional nanostructures providing a radical new view about the transformations of carbon in …

A Randomized Cross-Over Trial Comparing The Effect Of Intramuscular Versus Intranasal Naloxone Reversal Of Intravenous Fentanyl On Odor Detection In Working Dogs, Jennifer L. Essler, Paige G. Smith, Danielle Berger, Elizabeth Gregorio, M. Ross Pennington, Amanda Mcguire, Kenneth G. Furton, Cynthia M. Otto

Department of Chemistry and Biochemistry

Fentanyl is a potent opioid used clinically as a pain medication and anesthetic but has recently seen a sharp rise as an illicit street drug. The potency of fentanyl means mucous membrane exposure to a small amount of the drug can expose first responders, including working canines, to accidental overdose. Naloxone, a fast-acting opioid antagonist administered intranasally (IN) or intramuscularly (IM) is currently carried by emergency personnel in the case of accidental exposure in both humans and canines. Despite the fact that law enforcement relies heavily on the olfactory abilities of canine officers, the effects of fentanyl exposure and subsequent …

Frailty, Cognitive Decline, Neurodegenerative Diseases And Nutrition Interventions, Maria Elena Gomez-Gomez, Sara C. Zapico

Department of Chemistry and Biochemistry

Currently the human population is aging faster. This leads to higher dependency rates and the transformation of health and social care to adapt to this aged population. Among the changes developed by this population is frailty. It is defined as a clinically detectable syndrome, related to the aging of multiple physiological systems, which prompts a situation of vulnerability. The etiology of frailty seems to be multifactorial and its pathophysiology is influenced by the interaction of numerous factors. Morley et al. propose four main mechanisms triggering the frailty: atherosclerosis, sarcopenia, cognitive deterioration and malnutrition, with their respective metabolic alterations. Malnutrition is …

Uv And Visible Light-Driven Production Of Hydroxyl Radicals By Reduced Forms Of N, F, And P Codoped Titanium Dioxide, A. M. Abdullah, Miguel A. Gracia-Pinilla, Suresh C. Pillai, Kevin E. O'Shea

Department of Chemistry and Biochemistry

The photocatalytic activities of reduced titanium dioxide (TiO₂) materials have been investigated by measuring their ability to produce hydroxyl radicals under UV and visible light irradiation. Degussa P25 TiO₂ was doped with nitrogen (N), fluorine (F), and/or phosphorus (P) and then subjected to surface modification employing a thermo-physicochemical process in the presence of reducing agent sodium borohydride (NaBH₄). The reduced TiO₂ materials were characterized by a number of X-ray, spectroscopic and imaging methods. Surface doping of TiO₂ was employed to modulate the band gap energies into the visible wavelength region for better overlap …

Uv And Visible Light-Driven Production Of Hydroxyl Radicals By Reduced Forms Of N, F, And P Codoped Titanium Dioxide, A. M. Abdullah, Miguel A. Gracia-Pinella, Suresh C. Pillai, Kevin E. O'Shea

Department of Chemistry and Biochemistry

The photocatalytic activities of reduced titanium dioxide (TiO₂) materials have been investigated by measuring their ability to produce hydroxyl radicals under UV and visible light irradiation. Degussa P25 TiO₂ was doped with nitrogen (N), fluorine (F), and/or phosphorus (P) and then subjected to surface modification employing a thermo-physicochemical process in the presence of reducing agent sodium borohydride (NaBH₄). The reduced TiO₂ materials were characterized by a number of X-ray, spectroscopic and imaging methods. Surface doping of TiO₂ was employed to modulate the band gap energies into the visible wavelength region for better overlap …

Label-Free, Visual Detection Of Small Molecules Using Highly Target-Responsive Multimodule Split Aptamer Constructs, Yingping Luo, Haixiang Yu, Obtin Alkhamis, Yingzhu Liu, Xinhui Lou, Boyang Yu, Yi Xiao

Department of Chemistry and Biochemistry

Colorimetric aptamer-based sensors offer a simple means of on-site or point-of-care analyte detection. However, these sensors are largely incapable of achieving naked-eye detection, because of the poor performance of the target-recognition and signal-reporting elements employed. To address this problem, we report a generalizable strategy for engineering novel multimodule split DNA constructs termed "CBSAzymes" that utilize a cooperative binding split aptamer (CBSA) as a highly target-responsive bioreceptor and a new, highly active split DNAzyme as an efficient signal reporter. CBSAzymes consist of two fragments that remain separate in the absence of target, but effectively assemble in the presence of the target …

5′,8-Cyclopurine Lesions In Dna Damage: Chemical, Analytical, Biological, And Diagnostic Significance, Chryssostomos Chatgilialoglu, Carla Ferreri, Nicholas E. Geacintov, Marios G. Krokidis, Yuan Liu, Annalisa Masi, Vladimir Shafirovich, Michael A. Terzidis, Pawlos S. Tsegay

Department of Chemistry and Biochemistry

Purine 5′,8-cyclo-2′-deoxynucleosides (cPu) are tandem-type lesions observed among the DNA purine modifications and identified in mammalian cellular DNA in vivo. These lesions can be present in two diasteroisomeric forms, 5′R and 5′S, for each 2′-deoxyadenosine and 2′-deoxyguanosine moiety. They are generated exclusively by hydroxyl radical attack to 2′-deoxyribose units generating C5′ radicals, followed by cyclization with the C8 position of the purine base. This review describes the main recent achievements in the preparation of the cPu molecular library for analytical and DNA synthesis applications for the studies of the enzymatic recognition and repair mechanisms, their impact on transcription and genetic …

Oil Hydrocarbon Degradation By Caspian Sea Microbial Communities, John I. Miller, Stephen Techtmann, Julian Fortney, Nagissa Mahmoudi, Dominique Joyner, Jiang Liu, Scott Olesen, Eric Alm, Adolfo Fernandez, Piero Gardinali, Nargiz Garajayeva, Faig S. Askerov, Terry C. Hazen

Department of Chemistry and Biochemistry

The Caspian Sea, which is the largest landlocked body of water on the planet, receives substantial annual hydrocarbon input from anthropogenic sources (e.g., industry, agriculture, oil exploration, and extraction) and natural sources (e.g., mud volcanoes and oil seeps). The Caspian Sea also receives substantial amounts of runoff from agricultural and municipal sources, containing nutrients that have caused eutrophication and subsequent hypoxia in the deep, cold waters. The effect of decreasing oxygen saturation and cold temperatures on oil hydrocarbon biodegradation by a microbial community is not well characterized. The purpose of this study was to investigate the effect of oxic and …

Oil Hydrocarbon Degradation By Caspian Sea Microbial Communities, John I. Miller, Stephen Techtmann, Julian Fortney, Nagissa Mahmoudi, Dominique Joyner, Jiang Liu, Scott Olesen, Eric Alm, Adolfo Fernandez, Piero Gardinali, Nargiz Garajayeva, Faig S. Askerov, Terry C. Hazen

Department of Chemistry and Biochemistry

The Caspian Sea, which is the largest landlocked body of water on the planet, receives substantial annual hydrocarbon input from anthropogenic sources (e.g., industry, agriculture, oil exploration, and extraction) and natural sources (e.g., mud volcanoes and oil seeps). The Caspian Sea also receives substantial amounts of runoff from agricultural and municipal sources, containing nutrients that have caused eutrophication and subsequent hypoxia in the deep, cold waters. The effect of decreasing oxygen saturation and cold temperatures on oil hydrocarbon biodegradation by a microbial community is not well characterized. The purpose of this study was to investigate the effect of oxic and …

Amyz1: A Novel Α-Amylase From Marine Bacterium Pontibacillus Sp. Zy With High Activity Toward Raw Starches, Wei Fang, Saisai Xue, Pengjun Deng, Xuecheng Zhang, Xiaotang Wang, Yazhong Xiao, Zemin Fang

Department of Chemistry and Biochemistry

No abstract provided.

Amyz1: A Novel Α-Amylase From Marine Bacterium Pontibacillus Sp. Zy With High Activity Toward Raw Starches, Wei Fang, Saisai Xue, Pengjun Deng, Xuecheng Zhang, Xiaotang Wang, Yazhong Xiao, Zemin Fang

Department of Chemistry and Biochemistry

Background

Starch is an inexpensive and renewable raw material for numerous industrial applications. However, most starch-based products are not cost-efficient due to high-energy input needed in traditional enzymatic starch conversion processes. Therefore, α-amylase with high efficiency to directly hydrolyze high concentration raw starches at a relatively lower temperature will have a profound impact on the efficient application of starch.

Results

A novel raw starch digesting α-amylase (named AmyZ1) was screened and cloned from a deep-sea bacterium Pontibacillus sp. ZY. Phylogenetic analysis showed that AmyZ1 was a member of subfamily 5 of glycoside hydrolase family 13. When expressed in Escherichia coli …

Gas Phase Synthesis Of [4]-Helicene, Long Zhao, Ralf I. Kaiser, Bo Xu, Utuq Ablikim, Wenchao Lu, Musahid Ahmed, Mikhail M. Evseev, Eugene K. Bashkirov, Valeriy N. Azyazov, Marsel V. Zagidullin, Alexander N. Morozov, A. Hasan Howlader, Stanislaw F. Wnuk, Alexander M. Mebel, Dharati Joshi, Gregory Veber, Felix R. Fischer

Department of Chemistry and Biochemistry

A synthetic route to racemic helicenes via a vinylacetylene mediated gas phase chemistry involving elementary reactions with aryl radicals is presented. In contrast to traditional synthetic routes involving solution chemistry and ionic reaction intermediates, the gas phase synthesis involves a targeted ring annulation involving free radical intermediates. Exploiting the simplest helicene as a benchmark, we show that the gas phase reaction of the 4-phenanthrenyl radical ([C14H9]•) with vinylacetylene (C4H4) yields [4]-helicene (C18H12) along with atomic hydrogen via a low-barrier mechanism through a resonance-stabilized free radical intermediate (C18H13). This pathway may represent a versatile mechanism to build up even more complex …

The Ability Of Narcotic Detection Canines To Detect Illegal Synthetic Cathinones (Bath Salts), Vanquilla Shellman Francis, Howard K. Holness, Kenneth G. Furton

Department of Chemistry and Biochemistry

Twelve certified narcotic detection canines were tested for their ability to detect confiscated illegal synthetic cathinones (bath salts). These canine teams were randomly assigned to two different groups and each group imprinted on one of two types of bath salts, ethylone and alpha-pyrrolidinovalerophenone (α-PVP), over the period of 1 month; while simultaneously documenting the imprinting procedure. The newly imprinted canines were validated by field testing and found to not only detect the imprinted bath salt to which they were trained, but they were able to detect other bath salts. The imprinting procedure and results are the first scientifically validated studies …

In Vitro Isolation Of Class-Specific Oligonucleotide-Based Small-Molecule Receptors, Weijuan Yang, Haixiang Yu, Obtin Alkhamis, Yingzhu Liu, Juan Canoura, Fengfu Fu, Yi Xiao

Department of Chemistry and Biochemistry

Class-specific bioreceptors are highly desirable for recognizing structurally similar small molecules, but the generation of such affinity elements has proven challenging. We here develop a novel ‘parallel-and-serial’ selection strategy for isolating class-specific oligonucleotide-based receptors (aptamers) in vitro. This strategy first entails parallel selection to selectively enrich cross-reactive binding sequences, followed by serial selection that enriches aptamers binding to a designated target family. As a demonstration, we isolate a class-specific DNA aptamer against a family of designer drugs known as synthetic cathinones. The aptamer binds to 12 diverse synthetic cathinones with nanomolar affinity and does not respond to 11 structurally …

Rapid Monitoring Of Organochlorine Pesticide Residues In Various Fruit Juices And Water Samples Using Fabric Phase Sorptive Extraction And Gas Chromatography-Mass Spectrometry, Ramandeep Kaur, Ripneel Kaur, Susheela Rani, Ashok Kumar Malik, Abuzar Kbir, Kenneth G. Furton, Victoria F. Samanidou

Department of Chemistry and Biochemistry

Fabric phase sorptive extraction, an innovative integration of solid phase extraction and solid phase microextraction principles, has been combined with gas chromatography-mass spectrometry for the rapid extraction and determination of nineteen organochlorine pesticides in various fruit juices and water samples. FPSE consolidates the advanced features of sol-gel derived extraction sorbents with the rich surface chemistry of cellulose fabric substrate, which could extract the target analytes directly from the complex sample matrices, substantially simplifying the sample preparation operation. Important FPSE parameters, including sorbent chemistry, extraction time, stirring speed, type and volume of back-extraction solvent, and back-extraction time have been optimized. Calibration …

A Donor-Chromophore-Catalyst Assembly For Solar Co2 Reduction, Degao Wang, Ying Wang, Matthew D. Brady, Matthew V. Sheridan, Benjamin D. Sherman, Byron H. Farnum, Yanming Liu, Seth L. Marquard, Gerald J. Meyer, Christopher J. Dares

Department of Chemistry and Biochemistry

We describe here the preparation and characterization of a photocathode assembly for CO2 reduction to CO in 0.1 M LiClO4 acetonitrile. The assembly was formed on 1.0 μm thick mesoporous films of NiO using a layer-by-layer procedure based on Zr(IV)–phosphonate bridging units. The structure of the Zr(IV) bridged assembly, abbreviated as NiO|-DA-RuCP22+-Re(I), where DA is the dianiline-based electron donor (N,N,N′,N′-((CH2)3PO3H2)4-4,4′-dianiline), RuCP2+ is the light absorber [Ru((4,4′-(PO3H2CH2)2-2,2′-bipyridine)(2,2′-bipyridine))2]2+, and Re(I) is the CO2 reduction catalyst, ReI((4,4′-PO3H2CH2)2-2,2′-bipyridine)(CO)3Cl. Visible light excitation of the assembly in CO2 saturated solution resulted in CO2 reduction to CO. A steady-state …

Recommendations For Reporting Ion Mobility Mass Spectrometry Measurements, Valerie Gabelica, Alexandre A. Shvartsburg, Carlos Afonso, Perdita Barran, Justin L.P. Benesch, Christian Bleiholder, Michael T. Bowers, Aivett Bolbao, Matthew F. Bush, J. Larry Campbell, Iain D.G. Campuzano, Tim Causon, Brian H. Clowers, Colin S. Creaser, Edwin De Pauw, Johann Far, Francisco Fernandez-Lima, John C. Fjeldsted, Kevin Giles, Michael Groessl, Christopher J. Hogen Jr., Stephan Hann, Hugh I. Kim, Ruwan T. Kurulugama, Jody C. May, John A. Mclean, Kevin Pagel, Keith Richardson, Mark E. Ridgeway, Frederic Rosu, Frank Sobott, Konstantinos Thalassinos, Stephen J. Valentine, Thomas Wyttenbach

Department of Chemistry and Biochemistry

Here we present a guide to ion mobility mass spectrometry experiments, which covers both linear and nonlinear methods: what is measured, how the measurements are done, and how to report the results, including the uncertainties of mobility and collision cross section values. The guide aims to clarify some possibly confusing concepts, and the reporting recommendations should help researchers, authors and reviewers to contribute comprehensive reports, so that the ion mobility data can be reused more confidently. Starting from the concept of the definition of the measurand, we emphasize that (i) mobility values (K0) depend intrinsically on ion structure, …