Digital Commons Network^™

Tribocorrosion And Metal Release From Austenitic Stainless Steels 304 And 201 In Simulated Cassava Food Contact, Robert Addai, Temitope E. Olowoyo, Thalia E. Standish, Jeffrey Daniel Henderson, Ubong Eduok, Yolanda Hedberg

Chemistry Publications

Cassava is the third most significant calorie source in the tropics. Its processing has changed from traditional methods to stainless steel processing machines. This study investigated the influence of cassava on metal release from two common stainless steels, ASTM 304 and 201, with and without friction, and on tribocorrosion (multianalytically) of 304. Cassava was relatively corrosive and hindered repassivation of the surface oxide of stainless steel, but it also acted as a lubricant against mechanical friction. The combined action of friction and cassava caused a significant increase in iron, chromium, nickel, and manganese release from the stainless steels (30–35- fold …

A Bio-Tribocorrosion Comparison Between Additively Manufactured And Forged Ti6al4v Parts, Sina Matin, Sahar Toorandaz, Saman Nikpour, Hamidreza Abdolvand, Eshan Toyserkani, Yolanda S. Hedberg

Chemistry Publications

Ti6Al4V has been used widely as a biomedical alloy and is increasingly manufactured by additive manufacturing due to customized shapes. As implant material, it is frequently exposed to both friction and corrosive environments. This study investigates the effect of the fabrication process (laser powder bed fusion and forging) on the tribocorrosion behavior of Ti6Al4V in various environments including diluted hydrochloric acid to simulate the acidic environment in a crevice (HCl), phosphate-buffered saline (pH 7.3) with 10 g/L bovine serum albumin (PBS+BSA), and PBS+BSA with 30 mM H2O2. While the presence of BSA hindered the repassivation (reforming of the protective passive …

Corrosion Of Implant Materials In The Human Body, Maedeh Barzmehri

Corrosion Research

This paper extensively examines the complex problem of implant corrosion occurring within the human body. The corrosion of implants gives rise to substantial challenges, encompassing compromised implant durability, patient safety concerns, and potential adverse impacts on the long-term functionality of the medical device. The study's primary objectives include offering a concise overview of the various corrosion mechanisms that impact a range of implant materials and outlining health complications linked to the byproducts of implant corrosion. Furthermore, it delves into a cost analysis specific to hip or knee revision arthroplasty, which has become a prevalent scenario in implant failure cases on …

Corrosion Case Study On Pipeline, Kangze Ren

Corrosion Research

The Kashagan pipeline leaks were likely caused by sulfur stress corrosion cracking, a combined corrosion mechanism developed by the presence of high pressure, the high level of hydrogen sulfide(the main "ingredient" of sour gas), and poor metallurgical choice. Improper welding and poor metallurgical examination were blamed for causing the leaking issue. The purpose of the current review is to raise the alarm about the inappropriate corrosion management of Kashagan oil production and its societal and environmental consequences.

The Impact Of Lead Corrosion Relating To The Contamination Of Drinking Water In Canada And In Indigenous Communities., Jessie A. Mcdonald

Corrosion Research

No abstract provided.

The Impact Of Lead Corrosion Relating To The Contamination Of Drinking Water In Canada And In Indigenous Communities., Jessie A. Mcdonald

Corrosion Research

No abstract provided.

Synergistic Effect Of Nanoclay And Barium Sulfate Fillers On The Corrosion Resistance Of Polyester Powder Coatings, Jinbao Huang, Marshall Shuai Yang, Chengqian Xian, James Joseph Noel, Yolanda S. Hedberg, Jian Chen, Ubong Eduok, Ivan Barker, Jeffrey Daniel Henderson, Haiping Zhang, Liqin Wang, Hui Zhang, Jesse Zhu

Chemistry Publications

No abstract provided.

Study On The Self-Repairing Effect Of Nanoclay In Powder Coatings For Corrosion Protection, Marshall S. Yang, Jinbao Huang, Hui Zhhang, James Noel, Yolanda S. Hedberg, Jian Chen, Ubong Eduok, Ivan Barker, Jeffrey D. Henderson, Chengqian Xian, Haiping Zhang, Jesse Zhu

Chemistry Publications

Powder coatings are a promising, solvent-free alternative to traditional liquid coatings due to the superior corrosion protection they provide. This study investigates the effects of incorporating montmorillonite-based nanoclay additives with different particle sizes into polyester/triglycidyl isocyanurate (polyester/TGIC) powder coatings. The objective is to enhance the corrosion-protective function of the coatings while addressing the limitations of commonly employed epoxy-based coating systems that exhibit inferior UV resistance. The anti-corrosive and surface qualities of the coatings were evaluated via neutral salt spray tests, electrochemical measurements, and surface analytical techniques. Results show that the nanoclay with a larger particle size of 18.38 µm (D50, …

Skin Permeation Studies Of Chromium Species - Evaluation Of A Reconstructed Human Epidermis Model., L Hagvall, M Munem, M Hoang Philipsen, M Dowlatshahi Pour, Yolanda S. Hedberg, P Malmberg

Chemistry Publications

A reconstructed human epidermis (RHE) model, the EpiDerm, was investigated and compared to human skin ex vivo regarding tissue penetration and distribution of two chromium species, relevant in both occupational and general exposure in the population. Imaging mass spectrometry was used in analysis of the sectioned tissue. The RHE model gave similar results compared to human skin ex vivo for skin penetration of Cr

Investigating The Structure Of The Oxide On Ni-Cr-Mo Alloys While Presenting A Method For Analysis Of Complex Oxides Using Quases, Adam M. Morgan, Jeffrey D. Henderson, Brad A. Kobe, Mark Biesinger, James J. Noel

Chemistry Publications

X-ray photoelectron spectroscopy (XPS) is a technique that is widely used to studythin oxide films because of its extremely high surface sensitivity. Utilizing theQUASES (Quantitative Analysis of Surfaces by Electron Spectroscopy) software pack-age developed by Sven Tougaard (University of Southern Denmark), a user canobtain additional information that is not extracted in conventional XPS analysis, spe-cifically the composition as a function of depth. Presented here is the QUASES analy-sis of four Ni-Cr-Mo alloys performed while testing various inelastic mean free path(IMFP) determination methods in the context of providing a framework for the analy-sis of complex oxides in QUASES. Ni-Cr-Mo alloys are …

In Vitro Corrosion And Biocompatibility Behavior Of Cocrmo Alloy Manufactured By Laser Powder Bed Fusion Parallel And Perpendicular To The Build Direction, Masoud Atapour, Saber Sanaei, Zheng Wei, Mohammadali Sheikholeslam, Jeffrey D. Henderson, Ubong Eduok, Yara K. Hosein, David W. Holdsworth, Yolanda S. Hedberg, Hamid Reza Ghorbani

Chemistry Publications

Biomedical cobalt-chromium-molybdenum alloys (CoCrMo) are frequently used for orthopedic implant and dental materials exposed to mechanical stressors, such as wear and cyclic load. Due to the high demand for customizable implant shapes, these alloys are increasingly manufactured by additive manufacturing methods such as laser powder bed fusion (LPBF). LPBF results in different microstructures and surface roughness as a function of the building direction. This study investigated the corrosion resistance, bioactivity, biocompatibility, and microstructure of LPBF CoCrMo (low carbon content, heat-treated) in the XY (perpendicular) and XZ (parallel) plane of the building direction for as-printed (as-received) and abraded surfaces. A distinct …

Reconstruction Of Exchange–Correlation Potentials From Their Matrix Representations, Yan Oueis, Viktor N. Staroverov

Chemistry Publications

Within a basis set of one-electron functions that form linearly independent products (LIPs), it is always possible to construct a unique local (multiplicative) real-space potential that is precisely equivalent to an arbitrary given operator. Although standard basis sets of quantum chemistry rarely form LIPs in a numerical sense, occupied and low-lying virtual canonical Kohn–Sham orbitals often do so, at least for small atoms and molecules. Using these principles, we construct atomic and molecular exchange–correlation potentials from their matrix representations in LIP basis sets of occupied canonical Kohn–Sham orbitals. The reconstructions are found to imitate the original potentials in a consistent …

The Ability Of Sweat And Buffer Solutions To Reduce Hexavalent Chromium Of Relevance For Leather Extraction, Alexandra Wright, Lila Laundry-Mottiar, Yolanda Hedberg

Chemistry Publications

The European Union restricted the amount of hexavalent chromium (Cr(VI)) in leather in 2015, but skin allergy cases due to Cr-tanned leather are not declining. Standardized extraction methods have been criticized to both over- and underestimate the expected amount of bioavailable Cr(VI) in leather. This study aims to evaluate the ability of four extraction solutions to reduce or preserve Cr(VI): artificial sweat solutions (ASWs) of pH 4.7, 6.5, and 8.0, and phosphate buffer (PB) of pH 8.0. This was investigated by incubating each solution with added Cr(VI) as a function of time, and then measuring the recovered Cr(VI). All solutions, …

Noninteracting V-Representable Subspaces Of Orbitals In The Kohn–Sham Method, Viktor N. Staroverov

Chemistry Publications

The notion of noninteracting v-representability is extended from electron densities to finite-dimensional linear subspaces of orbitals. Unlike electron densities, orbital subspaces can be tested for noninteracting v-representability using a transparent necessary condition: the subspace must be invariant under the action of some one-electron Kohn–Sham Hamiltonian. This condition allows one to determine in principle, and sometimes in practice, whether a given one-electron basis set can represent an N-electron density within the Kohn–Sham method and to find the corresponding Kohn–Sham effective potential v if it exists. If the occupied Kohn–Sham orbitals form linearly independent products, then their subspace is …

Grotthuss Molecular Dynamics Simulations For Modeling Proton Hopping In Electrosprayed Water Droplets., Lars Konermann, Scott Kim

Chemistry Publications

Excess protons in water exhibit unique transport properties because they can rapidly hop along H-bonded water wires. Considerable progress has been made in unraveling this Grotthuss diffusion mechanism using quantum mechanical-based computational techniques. Unfortunately, high computational cost tends to restrict those techniques to small systems and short times. Molecular dynamics (MD) simulations can be applied to much larger systems and longer time windows. However, standard MD methods do not permit the dissociation/formation of covalent bonds, such that Grotthuss diffusion cannot be captured. Here, we bridge this gap by combining atomistic MD simulations (using Gromacs and TIP4P/2005 water) with proton hopping. …

Self-Immolative Polyplexes For Dna Delivery, Quinton E. A. Sirianni, Tianduo Wang, Aneta Borecki, Zhengyu Deng, Elizabeth R. Gillies, John A. Ronald

Chemistry Publications

Nucleic acids have immense potential for the treatment and prevention of a wide range of diseases, but delivery vehicles are needed to assist with their entry into cells. Polycations can reversibly complex with nucleic acids via ionic interactions to form polyplexes and transport them into cells, but they are still hindered by the need to balance cytotoxicity and delivery effectiveness. In this work, we describe a new self-immolative polyglyoxylamide (PGAm) platform designed to address these challenges by complexing nucleic acids viamultivalent interactions in the polymeric form and releasing them upon depolymerization. Nine PGAms were synthesized and characterized, with different …

Electrochemical Estimations Of The Gold Nanoparticle Size Effect On Cysteine-Gold Oxidation,, E. Romanovskaia, P. Slovenský, M. Kalantarian, L. Laundry-Mottiar, V. Romanovski, M. Halama, M. Auinger, Yolanda S. Hedberg

Chemistry Publications

Gold nanoparticles are interesting for nanobiomedical applications, such as for drug delivery and as diagnostic imaging contrast agents. However, their stability and reactivity in-vivo are influenced by their surface properties and size. Here, we investigate the electrochemical oxidation of differently sized citrate-coated gold nanoparticles in the presence and absence of L-cysteine, a thiol-containing amino acid with high binding affinity to gold. We found that smaller sized (5, 10 nm) gold nanoparticles were significantly more susceptible to electrochemical L-cysteine interactions and/or L-cysteine-facilitated gold oxidation than larger (20, 50 nm) sized gold nanoparticles, both for the same mass and nominal surface area, …

Mechanism Of Thermal Protein Aggregation: Experiments And Molecular Dynamics Simulations On The High-Temperature Behavior Of Myoglobin., Yuen Ki Ng, Nastaran N Tajoddin, Pablo M Scrosati, Lars Konermann

Chemistry Publications

Proteins that encounter unfavorable solvent conditions are prone to aggregation, a phenomenon that remains poorly understood. This work focuses on myoglobin (Mb) as a model protein. Upon heating, Mb produces amorphous aggregates. Thermal unfolding experiments at low concentration (where aggregation is negligible), along with centrifugation assays, imply that Mb aggregation proceeds via globally unfolded conformers. This contrasts studies on other proteins that emphasized the role of partially folded structures as aggregate precursors. Molecular dynamics (MD) simulations were performed to gain insights into the mechanism by which heat-unfolded Mb molecules associate with one another. A prerequisite for these simulations was the …

Metal Release From A Biomedical Cocrmo Alloy In Mixed Protein Solutions Under Static And Sliding Conditions: Effects Of Protein Aggregation And Metal Precipitation, Zheng Wei, Valentine Romanovski, Luimar Filho, Cecilia Persson, Yolanda S. Hedberg

Chemistry Publications

Biomedical materials made of cobalt-chromium-molybdenum (CoCrMo) alloys are commonly used in artificial prostheses and dental implants, which are exposed to friction and load. The release of Co, Cr, and Mo from these surfaces is governed by physical and chemical processes. The extent of measured metal release from biomedical CoCrMo alloys into mixed protein solutions may be influenced by protein aggregation and metal precipitation effects. Metal release from, and the surface composition of, a CoCrMo alloy was investigated in physiological relevant solutions (phosphate buffered saline, PBS, with varying concentrations of fibrinogen from bovine plasma and/or bovine serum albumin) at pH 7.3 …

Characterization Of Ovarian Cancer-Derived Extracellular Vesicles By Surface-Enhanced Raman Spectroscopy., Nina M. Culum, Tyler T. Cooper, Gilles A. Lajoie, Thamara Dayarathna, Stephen H. Pasternak, Jiahui Liu, Yangxin Fu, Francois Lagugne-Labarthet, Lynne Marie Postovit

Chemistry Publications

Ovarian cancer is the most lethal gynecological malignancy, owing to the fact that most cases are diagnosed at a late stage. To improve prognosis and reduce mortality, we must develop methods for the early diagnosis of ovarian cancer. A step towards early and non-invasive cancer diagnosis is through the utilization of extracellular vesicles (EVs), which are nanoscale, membrane-bound vesicles that contain proteins and genetic material reflective of their parent cell. Thus, EVs secreted by cancer cells can be thought of as cancer biomarkers. In this paper, we present gold nanohole arrays for the capture of ovarian cancer (OvCa)-derived EVs and …

Using Covalent Modifications To Distinguish Protein Electrospray Mechanisms: Charged Residue Model (Crm) Vs. Chain Ejection Model (Cem), Lars Konermann, Douglas J. D. Pimlott

Chemistry Publications

Different mechanisms have been proposed for the formation of gaseous protein ions during electrospray ionization (ESI). In the charged residue model (CRM) ions are produced upon nanodroplet evaporation to dryness. This mechanism is thought to dominate in native ESI, where proteins retain compact conformations, with charge states close to the Rayleigh charge of protein-sized aqueous droplets. Much higher charge states are generated from proteins that are unfolded in solution. The chain ejection model (CEM) has been proposed for ESI under such denaturing conditions. In the CEM proteins are gradually expelled, while mobile H⁺ equilibrate between the droplet and its …

Post-Polymerization ‘Click’ End-Capping Of Polyglyoxylate Self-Immolative Polymers, Peter G. Maschmeyer, Xiaoli Liang, Allison Hung, Oksana Ahmadzai, Annmaree L. Kenny, Yuan C. Luong, Timothy N. Forder, Haoxiang Zeng, Elizabeth R. Gillies, Derrick A. Roberts

Chemistry Publications

No abstract provided.

Self-Immolative Dendron Hydrogels, Karanpreet Gill, Xueli Mei, Elizabeth Gillies

Chemistry Publications

Smart hydrogels are of great interest in areas such as drug delivery and sensing. Dendrimer-based hydrogels can exhibit tunable properties due to their structural precision. We prepared hydrogels from self-immolative dendrons. Controlled hydrogel degradation in response to light was demonstrated and the hydrogel properties as a function of dendron generation were compared.

Pressure-Induced Polymorphic Transformations Of Ethylenediamine Bisborane, Rongfeng Guan, Pan Wang, Yang Song, Viktor N. Staroverov

Chemistry Publications

Pressure-induced phase transitions of crystalline ethylenediamine bisborane (EDAB), a prospective hydrogen storage material, are investigated using vibrational spectroscopy, X-ray diffraction, evolutionary crystal structure prediction, and density functional theory. The results indicate that EDAB undergoes two transitions in the 0–17 GPa pressure range: the first one is near 1 GPa, from the orthorhombic ambient-pressure Pbca structure (phase I) to a monoclinic structure of P21/c symmetry (phase II); the second is near 7 GPa, from phase II to another P21/c structure (phase III). The latter coexists with phase II and remains the most stable form of EDAB up …

Systematic And Collaborative Approach To Problem Solving Using X-Ray Photoelectron Spectroscopy, Neal Fairley, Vincent Fernandez, Mireille Richard-Plouet, Catherine Guillot-Deudon, John Walton, Emily Smith, Delphine Flahaut, Mark Greiner, Mark Biesinger, Sven Tougaard, David Morgan, Jonas Baltrusaitis

Chemistry Publications

The methodology presented within this work is a result of years of interactions between many junior and senior X-ray Photoelectron Spectroscopy (XPS) users operating within the CasaXPS spectral processing and interpretation program framework. In particular, discussions arising from a series of workshops have been a significant source for developing the overall XPS data processing concept and are the motivation for creating this work. These workshops organized by the Institut des Matériaux Jean Rouxel (IMN), Nantes gather both experienced and novice users of XPS for a week of discourse in conceptual experiment design and the resulting data processing. However, the framework …

Skin Permeation Of Nickel, Cobalt And Chromium Salts In Ex Vivo Human Skin, Visualized Using Mass Spectrometry Imaging, Lina Hagvall, Masoumeh Dowlatshahi Pour, Jiabao Feng, Moshtak Karma, Yolanda Hedberg, Per Malmberg

Chemistry Publications

Skin permeation and distribution of three of the most common skin sensitizers was investigated using a previ-ously developed animal-free exposure method combined with imaging mass spectrometry. Nickel, cobalt, and chromium (III) salts were dissolved in a buffer and exposed to human skin ex vivo, to be analyzed using time of flight secondary ion mass spectrometry (ToF-SIMS). Our findings demonstrate that metal haptens mainly accumulated in the stratum corneum, however all three metal sensitizers could also be detected in the epidermis. Cobalt and chromium (III) species penetrated into the epidermis to a larger extent than nickel species. The degree of penetration …

Extending Nanoscale Patterning With Multipolar Surface Plasmon Resonances., Issam Kherbouche, Danielle Macrae, Théo Geronimi Jourdain, François Lagugné-Labarthet, Azedine Lamouri, Alexandre Chevillot Biraud, Claire Mangeney, Nordin Félidj

Chemistry Publications

Plasmonic excitation of metallic nanoparticles can trigger chemical reactions at the nanoscale. Such optical effects can also be employed to selectively and locally graft photopolymer layers at the nanostructure surface, and, when combined with a surface functionalization agent, new pathways can be explored to modify the surface of a plasmonic nanoparticle. Among these approaches, diazonium salt chemistry is seen as an attractive strategy due to the high photoinduced reactivity of these salts. In this work, we demonstrate that it is possible to trigger the site-selective grafting of aryl films derived from diazonium salts on distinct nano-localized area of single gold …

Analytical Survey Of Tattoo Inks—A Chemical And Legal Perspective With Focus On Sensitizing Substances, Xuying Wang, Leila Josefsson, Silvia Meschnark, Marie-Louise Lind, Åsa Emmer, Walter Goessler, Yolanda S. Hedberg

Chemistry Publications

Background

Tattoo inks have been reported to elicit allergic contact dermatitis.

Objectives

To investigate the labels and the contents of metals and pigments in tattoo inks, considering restrictions within the European Union.

Methods

Seventy-three tattoo inks currently available on the market, either bought or donated (already used), were investigated for trace metals and pigments by inductively coupled plasma mass spectrometry and by matrix-assisted laser desorption/ionization time of flight tandem mass spectrometry.

Results

Ninety-three percent of the bought tattoo inks violated European, legal requirements on labeling. Fifty percent of the tattoo inks declared at least one pigment ingredient incorrectly. Sixty-one percent …

Effects Of Amino Acid Side-Chain Length And Chemical Structure On Anionic Polyglutamic And Polyaspartic Acid Cellulose-Based Polyelectrolyte Brushes., Dmitry Tolmachev, George Mamistvalov, Natalia Lukasheva, Sergey Larin, Mikko Karttunen

Chemistry Publications

We used atomistic molecular dynamics (MD) simulations to study polyelectrolyte brushes based on anionic α,L-glutamic acid and α,L-aspartic acid grafted on cellulose in the presence of divalent CaCl₂ salt at different concentrations. The motivation is to search for ways to control properties such as sorption capacity and the structural response of the brush to multivalent salts. For this detailed understanding of the role of side-chain length, the chemical structure and their interplay are required. It was found that in the case of glutamic acid oligomers, the longer side chains facilitate attractive interactions with the cellulose surface, which forces the …

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 …