Chemistry Commons^™

Using Chemical Speciation Modelling To Discuss Variations In Patch Test Reactions To Different Aluminium And Chromium Salts, Saman Nikpour, Yolanda S. Hedberg

Chemistry Publications

Background: Allergic contact dermatitis to metals is diagnosed by applying a metal salt in a patch test. The bioavailability of the metal salt might depend on the choice of metal salt, the concentration, sweat composition, and pH.

Objectives: The main purpose of this study was to apply chemical speciation modelling, which is based on experimentally derived input data and calculates the concentrations of chemical forms (species) in solutions, to reproduce and discuss clinical patch test results of aluminium and chromium.

Methods: Joint Expert Speciation System (JESS), Hydra/Medusa, and Visual Minteq were employed to study the bioavailable fraction and chemical form …

Keap1 Cancer Mutants: A Large-Scale Molecular Dynamics Study Of Protein Stability., Carter J Wilson, Megan Chang, Mikko Karttunen, Wing-Yiu Choy

Chemistry Publications

We have performed 280 μs of unbiased molecular dynamics (MD) simulations to investigate the effects of 12 different cancer mutations on Kelch-like ECH-associated protein 1 (KEAP1) (G333C, G350S, G364C, G379D, R413L, R415G, A427V, G430C, R470C, R470H, R470S and G476R), one of the frequently mutated proteins in lung cancer. The aim was to provide structural insight into the effects of these mutants, including a new class of ANCHOR (additionally NRF2-complexed hypomorph) mutant variants. Our work provides additional insight into the structural dynamics of mutants that could not be analyzed experimentally, painting a more complete picture of their mutagenic effects. Notably, blade-wise …

Patch Testing With Aluminium Finn Chambers Could Give False-Positive Reactions In Patients With Contact Allergy To Aluminium, Lisbeth Rosholm Comstedt, Jakob Dahlin, Magnus Bruze, Yolanda S. Hedberg, Mihály Matura, Cecilia Svedman

Chemistry Publications

Background

Earlier laboratory studies have shown that sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride trigger the release of aluminium (Al) from Finn Chambers (FC).

Objectives

To investigate whether aluminium realease from FC could influence the diagnostic outcome of patch testing with FC.

Method

A retrospective analysis of patch test results from 2010 to 2019 was performed. A two-sided Fisher's exact test was used to calculate any overrepresentation of contact allergy to Al among patients with positive reactions to sodium tetrachloropalladate, Myroxylon pereirae, caine mix II, and palladium chloride.

Results

A total of 5446 patients had been tested …

Mobile Protons Limit The Stability Of Salt Bridges In The Gas Phase: Implications For The Structures Of Electrosprayed Protein Ions., Lars Konermann, Elnaz Aliyari, Justin H Lee

Chemistry Publications

Electrosprayed protein ions can retain native-like conformations. The intramolecular contacts that stabilize these compact gas-phase structures remain poorly understood. Recent work has uncovered abundant salt bridges in electrosprayed proteins. Salt bridges are zwitterionic BH⁺/A^- contacts. The low dielectric constant in the vacuum strengthens electrostatic interactions, suggesting that salt bridges could be a key contributor to the retention of compact protein structures. A problem with this assertion is that H⁺ are mobile, such that H⁺ transfer can convert salt bridges into neutral B⁰/HA⁰ contacts. This possible salt bridge annihilation puts into question the …

A Divergent Strategy For The Synthesis Of Redox-Active Verdazyl Radical Polymers, Francois Magnan, Jasveer S. Dhindsa, Michael Anghel, Paul Bazylweski, Giovanni Fanchini, Joe Gilroy

Chemistry Publications

Stable radical polymers have attracted significant attention due to their use as magnetic materials, (co)catalysts in organic synthesis, and as functional components of organic electronics including batteries and memory devices. Despite their importance, a relatively narrow range of synthetic strategies exist for their production. The most common examples involve the transition-metal catalyzed polymerization of radical-containing monomers or the sequential polymerization of monomers containing radical precursors and their post-polymerization conversion to radicals. Post-polymerization installation of stable radicals is not commonly reported. Copper-assisted azide-alkyne cycloaddition (CuAAC) chemistry has seen limited use in this regard, but only for the production of p-conjugated and …

Polyesters Based On Aspartic Acid And Poly(Ethylene Glycol): Functional Polymers For Hydrogel Preparation, Trent N. Gordon, Anna Kornmuller, Yashveer Soni, Lauren E. Flynn, Elizabeth R. Gillies

Chemistry Publications

Hydrogels are commonly used as scaffolds for the preparation of three-dimensional tissue constructs and for the encapsulation and delivery of cells in regenerative medicine. Polyesters are an attractive class of polymers for hydrogel preparation. However, most polyesters have hydrophobic backbones and lack pendent groups that can be chemically functionalized. We describe here the development of water-soluble polyesters based on aspartic acid and poly(ethylene glycol) (PEG) (600 or 1500 g/mol), having pendent reactive amines. The reactivity of these amines with methacrylic anhydride, maleic anhydride, and itaconic anhydride was explored for the introduction of crosslinkable groups. The resulting methacrylamide-functionalized polymers were successfully …

Detection Of Gold Cysteine Thiolate Complexes On Gold Nanoparticles With Time-Of-Flight Secondary Ion Mass Spectrometry, Yolanda Hedberg, Jonas Hedberg, Valentin Romanovski, Elena Romanovskaia, Heng-Yong Nie

Chemistry Publications

Gold (Au) nanoparticles (NPs) are widely used in nanomedical applications as a carrier for molecules designed for different functionalities. Previous findings suggested that biological molecules, including amino acids, could contribute to the dissolution of Au NPs in physiological environments and that this phenomenon was size-dependent. We, therefore, investigated the interactions of L-cysteine with 5-nm Au NPs by means of time-of-flight secondary ion mass spectrometry (ToF-SIMS). This was achieved by loading Au NPs on a clean aluminum (Al) foil and immersing it in an aqueous solution containing L-cysteine. Upon rinsing off the excessive cysteine molecules, ToF-SIMS confirmed the formation of gold …

Polymer Particles For The Intra-Articular Delivery Of Drugs To Treat Osteoarthritis, Xueli Mei, Ian J. Villamagna, Tony Nguyen, Frank Beier, C. Thomas Appleton, Elizabeth R. Gillies

Chemistry Publications

Osteoarthritis (OA) is a leading cause of chronic disability. It is a progressive disease, involving pathological changes to the entire joint, resulting in joint pain, stiffness, swelling, and loss of mobility. There is currently no disease-modifying pharmaceutical treatment for OA, and the treatments that do exist suffer from significant side effects. An increasing understanding of the molecular pathways involved in OA is leading to many potential drug targets. However, both current and new therapies can benefit from a targeted approach that delivers drugs selectively to joints at therapeutic concentrations, while limiting systemic exposure to the drugs. Delivery systems including hydrogels, …

Ph-Sensitive Chitosan Nanoparticles For Salivary Protein Delivery, Yi Zhu, Lina M. Marin, Yizhi Xiao, Elizabeth R. Gillies, Walter L. Siqueira

Chemistry Publications

Salivary proteins such as histatins (HTNs) have demonstrated critical biological functions directly related to tooth homeostasis and prevention of dental caries. However, HTNs are susceptible to the high proteolytic activities in the oral environment. Therefore, pH-sensitive chitosan nanoparti-cles (CNs) have been proposed as potential carriers to protect proteins from enzymatic degradation at physiological salivary pH. Four different types of chitosan polymers were investigated and the optimal formulation had good batch to batch reproducibility, with an average hydrodynamic diame-ter of 144 ± 6 nm, a polydispersity index of 0.15 ± 0.04, and a zeta potential of 18 ± 4 mV at …

Imaging Of Neurotransmitters And Small Molecules In Brain Tissues Using Laser Desorption/Ionization Mass Spectrometry Assisted With Zinc Oxide Nanoparticles., Chaochao Chen, Steven R Laviolette, Shawn N Whitehead, Justin B Renaud, Ken K-C Yeung

Chemistry Publications

Inorganic nanostructured materials such as silicon, carbon, metals, and metal oxides have been explored as matrices of low-background signals to assist the laser desorption/ionization (LDI) mass spectrometric (MS) analysis of small molecules, but their applications for imaging of small molecules in biological tissues remain limited in the literature. Titanium dioxide is one of the known nanoparticles (NP) that can effectively assist LDI MS imaging of low molecular weight molecules (LMWM). TiO₂ NP is commercially available as dispersions, which can be applied using a chemical solution sprayer. However, aggregation of NP can occur in the dispersions and the aggregated NP …

Three-Color Plasmon-Mediated Reduction Of Diazonium Salts Over Metasurfaces., Denis A B Therien, Danielle M Mcrae, Claire Mangeney, Nordin Félidj, François Lagugné-Labarthet

Chemistry Publications

Surface plasmon-mediated chemical reactions are of great interest for a variety of applications ranging from micro- and nanoscale device fabrication to chemical reactions of societal interest for hydrogen production or carbon reduction. In this work, a crosshair-like nanostructure is investigated due to its ability to induce local enhancement of the local electromagnetic field at three distinct wavelengths corresponding to three plasmon resonances. The structures are irradiated in the presence of a solution containing diazonium salts at wavelengths that match the resonance positions at 532 nm, 632.8 nm, and 800 nm. The resulting grafting shows polarization and wavelength-dependent growth patterns at …

Welding Fume Nanoparticles From Solid And Flux-Cored Wires: Solubility, Toxicity, And Role Of Fluorides, Yolanda S. Hedberg, Z. Wei, S. Mccarrick, V. Romanovski, J. Theodore, E. M. Westin, R. Wagner, K.-A. Persson, H. L. Karlsson, I. Odnevall Wallinder

Chemistry Publications

Welding fume particles are hazardous. Their toxicity likely depends on their composition and reactivity. This study aimed at exploring the role of sodium or other fluorides (NaF), which are intentionally added to flux-cored wire electrodes for stainless steel welding, on the solubility (in phosphate buffered saline) and toxicity of the generated welding fume particles. A multi-analytical particle characterization approach along with in-vitro cell assays was undertaken. The release of Cr(VI) and Mn from the particles was tested as a function of fluoride solution concentration. The welding fume particles containing NaF released significantly higher amounts of Cr(VI) compared with solid wire …

Sulfolane-Induced Supercharging Of Electrosprayed Salt Clusters: An Experimental/Computational Perspective., Leanne M Martin, Lars Konermann

Chemistry Publications

It is well-known that supercharging agents (SCAs) such as sulfolane enhance the electrospray ionization (ESI) charge states of proteins, although the mechanistic origins of this effect remain contentious. Only very few studies have explored SCA effects on analytes other than proteins or peptides. This work examines how sulfolane affects electrosprayed NaI salt clusters. Such alkali metal halide clusters have played a key role for earlier ESI mechanistic studies, making them interesting targets for supercharging investigations. ESI of aqueous NaI solutions predominantly generated singly charged [Na_nI_(n-1)]⁺ clusters. The addition of sulfolane resulted in abundant …

Experimental And Computational Observations Of Immunogenic Cobalt Porphyrin Lipid Bilayers: Nanodomain-Enhanced Antigen Association., Jasmin Federizon, Conrard Giresse Tetsassi Feugmo, Wei-Chiao Huang, Xuedan He, Kazutoyo Miura, Aida Razi, Joaquin Ortega, Mikko Karttunen, Jonathan F Lovell

Chemistry Publications

Cobalt porphyrin phospholipid (CoPoP) can incorporate within bilayers to enable non-covalent surface-display of antigens on liposomes by mixing with proteins bearing a polyhistidine tag (his-tag); however, the mechanisms for how this occurs are poorly understood. These were investigated using the his-tagged model antigen Pfs25, a protein antigen candidate for malaria transmission-blocking vaccines. Pfs25 was found to associate with the small molecule aquocobalamin, a form of vitamin B12 and a cobalt-containing corrin macrocycle, but without particle formation, enabling comparative assessment. Relative to CoPoP liposomes, binding and serum stability studies indicated a weaker association of Pfs25 to aquocobalamin or cobalt nitrilotriacetic acid …

Single-Beam Inscription Of Plasmon-Induced Surface Gratings, Denis Ab Therien, Nina M. Culum, Danielle M. Mcrae, Leila Mazaheri, Francois Lagugne-Labarthet

Chemistry Publications

The formation of gratings on gold nanoprisms arrays by plasmon-mediated reduction of a diazonium salt is investigated. Nanosphere lithography (NSL) is used to produce large surfaces of gold nanoprisms that are effective at reducing diazonium salts by producing hot electrons through excitation of localized surface plasmon resonances (LSPRs). Using single beam irradiation, we report here on the formation of periodic structures formed from the diazonium salts and that follow the NSL structures. On plasmonically active nanoprism substrates, the electric field enhancement promotes chemical reduction and hence modifies the grafting direction and grating properties of the ripples. The nanoprisms act as …

Probing The Effects Of Heterogeneous Oxidative Modifications On The Stability Of Cytochrome, Victor Yin, Lars Konermann

Chemistry Publications

Covalent modifications by reactive oxygen species can modulate the function and stability of proteins. Thermal unfolding experiments in solution are a standard tool for probing oxidation-induced stability changes. Complementary to such solution investigations, the stability of electrosprayed protein ions can be assessed in the gas phase by collision-induced unfolding (CIU) and ion-mobility spectrometry. A question that remains to be explored is whether oxidation-induced stability alterations in solution are mirrored by the CIU behavior of gaseous protein ions. Here, we address this question using chloramine-T-oxidized cytochrome c (CT-cyt c) as a model system. CT-cyt c comprises various proteoforms that have …

Interrogating The Quaternary Structure Of Noncanonical Hemoglobin Complexes By Electrospray Mass Spectrometry And Collision-Induced Dissociation., Alexander I M Sever, Victor Yin, Lars Konermann

Chemistry Publications

Various activation methods are available for the fragmentation of gaseous protein complexes produced by electrospray ionization (ESI). Such experiments can potentially yield insights into quaternary structure. Collision-induced dissociation (CID) is the most widely used fragmentation technique. Unfortunately, CID of protein complexes is dominated by the ejection of highly charged monomers, a process that does not yield any structural insights. Using hemoglobin (Hb) as a model system, this work examines under what conditions CID generates structurally informative subcomplexes. Native ESI mainly produced tetrameric Hb ions. In addition, "noncanonical" hexameric and octameric complexes were observed. CID of all these species [(αβ)_{2 …}

Reversible Electrowetting Transitions On Superhydrophobic Surfaces, D. Vanzo, A. Luzar, D. Bratko

Chemistry Publications

Electric field applied across the interface has been shown to enable transitions from Cassie to Wenzel state on superhydrophobic surfaces with miniature corrugations. Molecular Dynamics (MD) simulations manifest the possibility of reversible cycling between the two states when narrow surface wells support spontaneous expulsion of water in the absence of the field. With approximately 1 nm sized wells between the surface asperities, response times to changes of electric field are of O(0.1) ns, allowing up to GHz frequency of the cycle. Because of orientation preferences of interfacial water in contact with the solid, the phenomenon depends on the polarity of …

A Strongly Lewis-Acidic And Fluorescent Borenium Cation Supported By A Tridentate Formazanate Ligand, Benjamin D. Katzman, Ryan R. Maar, Daniela Cappello, Madeleine O. Sattler, Paul D. Boyle, Viktor N. Staroverov, Joe B. Gilroy

Chemistry Publications

Lewis acids are highly sought after for their applications in sensing, small-molecule activation, and catalysis. When combined with π-conjugated molecular frameworks, Lewis acids with unique optoelectronic properties can be realized. Here, we use a tridentate formazanate ligand to create a planar, redox-active, fluorescent, and strongly Lewis-acidic borenium cation. We also demonstrate that this compound can act as a colourimetric probe for reactivity.

Corrosion Failure Of Titanium Tubes Of A Heat Exchanger For The Heating Of Dissolving Lye, Valentin Romanovski, Yolanda S. Hedberg, Andrei Paspelau, Vitali Frantskevich, James J. Noël, Elena Romanovskaia

Chemistry Publications

Corrosion of titanium heat exchangers in the processing of sylvinite ore is undesirable from economic, safety, and process sustainability perspectives. Triggered by an industrial case, we investigated the extent of corrosion during simulated contact with sylvinite ore (in dissolving lye) in relevant conditions. Detailed characterization of the failed tubes and corrosion products was carried out to understand the mechanism of failure. Corrosion of titanium (Grade 2) tubes was investigated at room temperature, 60, 70, 80, and 90 °C. After electrochemical and surface morphology analysis, we found that pitting corrosion of the titanium tube material sharply increased above 80 °C in …

Strained Alkyne Polymers Capable Of Spaac Via Ring-Opening Metathesis Polymerization, Rajeshwar Vasdev, Wilson Luo, Kyle Classen, Michael Anghel, Samantha Novoa, Mark S. Workentin, Joe B. Gilroy

Chemistry Publications

The incorporation of strained alkynes into polymers is generally achieved by employing step-growth polymerization methods or post-polymerization reactions. Here, we demonstrate that cyclopropenone-masked strained alkynes are tolerant to chain-growth ring-opening metathesis polymerization, and that, upon post-polymerization photochemical demasking with loss of CO, the strained alkyne group appended to each repeating unit can be used to prepare functional (e.g., fluorescent or redox-active) polymers from a common polymer backbone. We support our claims about polymer transformations throughout the manuscript through the inclusion of a complete set of model reactions and characterization data for analogous molecular species. The findings of this …

Band-Gap Tuning In Acceptor-Donor-Acceptor Boron Difluoride Formazanates, Francis L. Buguis, Michael Anghel, Joe B. Gilroy, Jasveer S. Dhindsa

Chemistry Publications

π-Conjugated molecules with acceptor-donor-acceptor (A-D-A) electronic structures are an important class of materials due to their tunable optoelectronic properties and applications in, for example, organic light-emitting diodes, nonlinear optical devices, and organic solar cells. The frontier molecular orbital energies, and thus band gaps, of these materials can be tuned by varying the donor and acceptor traits and π-electron counts of the structural components. Herein, we report the synthesis and characterization of a series of A-D-A compounds consisting of BF₂ formazanates as electron acceptors bridged by a variety of π-conjugated donors. The results, which are supported by DFT calculations, demonstrate …

Metal Bioaccessibility In Synthetic Bodyfluids–A Way To Considerpositive And Negative Alloying Effects In Hazard Assessments, Yolanda S. Hedberg, Xuying Wang, James J. Noël, Inger Odnevall Wallinder

Chemistry Publications

Hazard classification of metal alloys is today generally based on their bulk content, an approach that seldom reflects the extent of metal release for a given environment. Such information can instead be achieved via bioelution testing under simulated physiological conditions. The use of bioelution data instead of bulk contents would hence refine the current hazard classification of alloys and enable grouping. Bioelution data have been generated for nickel (Ni) and cobalt (Co) released from several stainless steel grades, one low-alloyed steel, and Ni and Co metals in synthetic sweat, saliva and gastric fluid, for exposure periods from 2 to 168 …

New Weldable 316l Stainless Flux-Cored Wires With Reduced Cr(Vi) Fume Emissions Part 2 – Round Robin Creating Fume Emission Data Sheets, Yolanda Hedberg

Chemistry Publications

Welding fumes have been found to be carcinogenic and stainless steel welders may be at higher risk due to increased formation of hexavalent chromium (Cr(VI)). The slag-shielded methods, identified to generate most airborne particles and Cr(VI), would potentially be most harmful. With ever-stricter limits set to protect workers, measures to minimize human exposure become crucial. Austenitic stainless steel flux-cored wires of 316L type have been developed with the aim to reduce the toxicity of the welding fume without compromised usability. Collected particles were compared with fumes formed using solid, metal-cored and standard flux-cored wires. In Part 1, the new wires …

New Weldable 316l Stainless Flux-Cored Wires With Reduced Cr(Vi) Fume Emissions Part 1 – Health Aspects Of Particle Composition And Release Of Metals, Yolanda Hedberg

Chemistry Publications

Welding fumes have been found to be carcinogenic and stainless steel welders may be at higher risk due to increased formation of hexavalent chromium (Cr(VI)). The slag-shielded methods, identified to generate most airborne particles and Cr(VI), would potentially be most harmful. With ever-stricter limits set to protect workers, measures to minimize human exposure become crucial. Austenitic stainless steel flux-cored wires of 316L type have been developed with the aim to reduce the toxicity of the welding fume without compromised usability. Collected particles were compared with fumes formed using solid, metal-cored and standard flux-cored wires. The size, morphology and composition were …

A Boron Difluoride Hydrazone (Bodihy) Polymer Exhibits Aggregation-Induced Emission, Alexander E. R. Watson, Joe Gilroy, Daniela Cappello

Chemistry Publications

Polymers that exhibit aggregation-induced emission (AIE) find use, for example, as cell-imaging agents and as fluorometric sensors due to their unique optical properties. However, the structural diversity of AIE-active polymers has not necessarily advanced at the same rate as their applications. In this work, ring-opening metathesis polymerization is used to synthesize the first example of a polymer (M_n = 61,600 g mol^‒1, Đ = 1.32) containing boron difluoride hydrazone (BODIHY) heterocycles in its repeating unit. The BODIHY monomer and polymer described absorb and emit in the visible region in solution (λ_abs = 428 and 429 nm, …

Unspecified Verticality Of Franck-Condon Transitions, Absorption And Emission Spectra Of Cyanine Dyes, And A Classically Inspired Approximation, Joseph D. Alia, Joseph A. Flack

Chemistry Publications

The computed vertical energy, Ev,a/f, from the equilibrium geometry of the initial electronic state is frequently considered as representative of the experimental excitation/emission energy, Eabs/fl = hc/λmax. Application of the quantum mechanical version of the Franck–Condon principle does not involve precise specification of nuclear positions before, after, or during an electronic transition. Moreover, the duration of an electronic transition is not experimentally accessible in spectra with resolved vibrational structure. It is shown that computed vibronic spectra based on TDDFT methods and application of quantum mechanical FC analysis predict Eabs = hc/λmax …

Cationic Boron Formazanate Dyes, Benjamin D. Katzman, Paul D. Boyle, Viktor N. Staroverov, Joe Gilroy, Ryan R. Maar

Chemistry Publications

Incorporation of cationic boron atoms into molecular frameworks is an established strategy for creating chemical species with unusual bonding and reactivity but is rarely thought of as a way of enhancing molecular optoelectronic properties. Using boron formazanate dyes as examples, we demonstrate that the wavelengths, intensities, and type of the first electronic transitions in BN heterocycles can be modulated by varying the charge, coordination number, and supporting ligands at the cationic boron atom. UV‐vis absorption spectroscopy measurements and density‐functional (DFT) calculations show that these modulations are caused by changes in the geometry and extent of π‐conjugation of the boron formazanate …

Near-Infrared Boron Difluoride Formazanate Dyes, Francis L. Buguis, Ryan R. Maar, Viktor N. Staroverov, Joe Gilroy

Chemistry Publications

Near-infrared (NIR) dyes are sought after for their utility in light harvesting, bioimaging, and light-mediated therapies. Since long-wavelength photoluminescence typically involves extensive p-conjugated systems of double bonds and aromatic rings, it is often assumed that NIR dyes have to be large molecules that require complex syntheses. We challenge this assumption by demonstrating that facile incorporation of tertiary amine groups into readily available 3-cyanoformazans affords efficient production of relatively simple NIR-active BF₂ formazanate dyes (λ_abs = 691−760 nm, λ_PL = 834−904 nm in toluene). Cyclic voltammetry experiments on these compounds reveal multiple reversible redox waves linked to the …

Delineating Heme-Mediated Versus Direct Protein Oxidation In Peroxidase-Activated Cytochrome, Victor Yin, Derek Holzscherer, Lars Konermann

Chemistry Publications

Oxidation of key residues in cytochrome c (cyt c) by chloramine T (CT) converts the protein from an electron transporter to a peroxidase. This peroxidase-activated state represents an important model system for exploring the early steps of apoptosis. CT-induced transformations include oxidation of the distal heme ligand Met80 (MetO, +16 Da) and carbonylation (LysCHO, -1 Da) in the range of Lys53/55/72/73. Remarkably, the 15 remaining Lys residues in cyt c are not susceptible to carbonylation. The cause of this unusual selectivity is unknown. Here we applied top-down mass spectrometry (MS) to examine whether CT-induced oxidation is catalyzed by heme. …