Chemistry Commons^™

The Structure Of A Lactobacillus Helveticus Chlorogenic Acid Esterase And The Dynamics Of Its Insertion Domain Provide Insights Into Substrate Binding, Kellie K. Omori, Charles T. Drucker, Tracie L. S. Okumura, Nathaniel B. Carl, Brianna T. Dinn, Destiny Ly, Kylie N. Sacapano, Allie Tajii, Cedric P. Owens

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Chlorogenic acid esterases (ChlEs) are a useful class of enzymes that hydrolyze chlorogenic acid (CGA) into caffeic and quinic acid. ChlEs can break down CGA in foods to improve their sensory properties and release caffeic acid in the digestive system to improve the absorption of bioactive compounds. This work presents the structure, molecular dynamics, and biochemical characterization of a ChlE from Lactobacillus helveticus (Lh). Molecular dynamics simulations suggest that substrate access to the active site of LhChlE is modulated by two hairpin loops above the active site. Docking simulations and mutational analysis suggest that two residues within …

Poly(Propylene Glycol)-Based Non-Isocyanate Polyurethane Ionenes: Thermal, Morphological And Conductive Properties, Jordan C. Pierce, George M. Timmermann, Creston Singer, David Salas-De La Cruz, Kevin Miller

Faculty & Staff Research and Creative Activity

The synthesis and characterization of a series of polyurethane ionenes using a non-isocyanate approach is disclosed. Imidazole-capped, urethane-containing prepolymers are prepared by first reacting carbonyl diimidazole (CDI) with several poly(propylene glycol) (PPG) diols with variable molecular weight, followed by subsequent reaction with 3-aminopropylimidazole (API). Polymerization with 1,4-dibromomethylbenzene followed by anion exchange resulted in the desired polyurethane ionenes bearing the [NTf2] counteranion as a series of viscous liquids. NMR and FTIR spectroscopy are used to characterize the intermediates and final ionenes, including molecular weight determination by end-group analysis. A single glass transition temperature (Tg), as determined by differential scanning …

Multiple Structural And Functional Annotations Based In-Silico Characterization Of Q9brx8 Protein, Eiman Zahid, Muhammad Farhan Sarwar

Karbala International Journal of Modern Science

Numerous proteins found in humans are poorly understood because there is a dearth of experimental evidence. Hypothetical proteins (HPs) or uncharacterized proteins are the terms used to describe these proteins. In this work, one of these proteins, Q9BRX8, is investigated using in-silico or bioinformatics tools to reveal its significant properties. In this regard, NCBI for the sequence retrieval, ProtParam tool for analysis of physiochemical properties, SOPMA for secondary structure prediction, SWISS-Model for homology modelling, STRING for protein-protein interaction and HDOCK for protein-protein docking analysis among other tools, were incorporated. The physiochemical characteristics indicated that Q9BRX8, which has an instability score …

Investigations On Copper Assisted Oxidative Transformations For The Construction Of Diverse C-C/C-N(O) Bonds, Prasanna Kumari S

Theses and Dissertations

Copper catalyzed C-C, C-N/C-O bond formation reactions are a prominent tool to access diverse biologically relevant molecules. Herein, we present the copper- catalyzed diverse C-C/C-N(O) bond forming reactions. In Chapter-I (introduction), we briefly discussed the various copper mediated organic transformations with appropriate examples.

In Chapter II, we report a one-pot methodology for the vicinal aminoalkylation of naphthoquinone through a direct C(sp2)-H functionalization reaction. Through this method, readily available planar naphthoquinone substrates were transformed into three-dimensional molecular scaffolds through the formation of one C(sp2)-C(sp2) and two C(sp2)-N bonds. The indole fused nitrogen heterocyclic products were obtained in good yields. Apart from …

Development Of Bioactive Peptidomimetics, Lei Wang

USF Tampa Graduate Theses and Dissertations

In the past two decades, a lot of different peptidomimetics, such as β-peptides, oligoureas, azapeptides, peptoids, aromatic oligoamides, and others, have been developed. These peptidomimetics with distinctive scaffolds have shown potential in protein surface recognition and mimicry, PPI regulation, catalysis, etc. Moreover, these bioactive peptidomimetics demonstrate much better bioavailability and biostability than the bioactive peptides. To expand the application of peptidomimetics, our group have developed a new sequence-specific peptidomimetics- γ-AApeptide, which is derived from chiral γ-PNA. It shows excellent advantages including highly resistant to various proteolytical degradations and has the potential to increase chemodiversity. γ-AApeptide also exhibits remarkable biomedical applications, …

Mechanistic Insights Into Electrocatalytic Carbon−Bromine Bond Cleavage In Polybrominated Phenols, Eric C.R. Mckenzie, Seyyedamirhossein Hosseini, Mayank Tanwar, Matthew Neurock, Shelley D. Minteer, Stephen C. Jacobson

Chemistry Faculty Research & Creative Works

Carbon−halogen bond cleavage has been studied extensively for many years as a simple electrosynthesis step in the formation of more complex natural products. Reduction of halogenated phenols has received less attention, in part, due to the lowered faradaic efficiency resulting from the competing hydrogen evolution reaction. Herein, we report the electroreduction of a series of brominated phenols through a homogeneous electrocatalytic (EC′) mechanism. Beginning with the structurally simple 2-bromophenol, we use foot-of-the-wave analysis to determine optimal catalysts. Nickel (II) salen requires the lowest overpotential for C−Br reduction and was used across all substrates. Chronoamperometric studies and density functional theory calculations …

Dipole Effects In The Angular Distributions Of Photoelectron Spectroscopy, C. Annie Hart

Arts & Sciences Graduate Student Theses and Dissertations

Comparing experimental photoelectron angular distributions to theoretical predictions for direct detachment is a valuable tool for indicating more complex detachment pathways, such as those which access temporary anion states. This is exemplified by resonance mediated detachment from NiO2−. The presence of forbidden transitions and deviations in photoelectron angular distribution and relative transition intensities indicate a resonance, which is further supported with multireference calculations. In detachment processes that produce a neutral molecule with a permanent dipole, the quality of angular distribution predictions suffer by treating the outgoing electron as a free particle. To improve upon this issue, angular distribution prediction methods …

Strengthening Brain Research In Africa, Abdullahi Tunde Aborode, Nike Jesutofunmi Idowu, Samuel Tundealao, Joseph Jaiyeola, Ogunware Adedayo Emmanuel

Department of Chemistry: Faculty Publications

This paper explores the emerging field of neuroscience in Africa, considering the unique genetic diversity, sociocultural determinants, and health inequalities in the continent. It presents numerous brain research initiatives, such as ABDRN, AMARI, APCDR, and H3Africa, aimed at understanding genetic and environmental factors influencing brain disorders in Africa. Despite numerous challenges like the brain drain phenomenon, inadequate infrastructure, and scarce research expertise, significant progress has been achieved. The paper proposes solutions, including international collaboration, capacity-building efforts, and policies to promote neuroscience research, to enhance the understanding of brain function and address brain-related health issues within the African context.

Development Of Antiviral Peptidomimetics, Songyi Xue

USF Tampa Graduate Theses and Dissertations

Protein-protein interactions (PPIs) are essential for biological processes and are associated with a number of diseases, including cancer, infectious diseases, and neurodegenerative diseases. As a result, modulation of PPIs has been recognized as one of the most promising strategies to develop the novel drugs. Peptide modulators always exhibit higher specificity and affinities with targets than small compounds or monoclonal antibodies, but their broad medicinal effectiveness is constrained by their poor bioavailability and biostability. Peptidomimetics, which have been developed to mimic the structure as well as function of bioactive peptides and proteins, have shown excellent potential in protein surface mimicry and …

Streamlined Synthesis Of Potential Dual-Emissive Fluorescent Silicon Quantum Dots (Siqds) For Cell Imaging, Di Sun, Steven Wu, Jeremy P. Martin, Kirati Tayutivutikul, Guodong Du, Colin Combs, Diane Darland, Julia Zhao

Biology Faculty Publications

One of the current challenges of working with nanomaterials in bioapplications is having a tool that is biocompatible (non-toxic) and produces stable, intense fluorescence for bioimaging. To address these challenges, we have developed a streamlined and one-pot synthetic route for silicon-based quantum dots (SiQDs) using a hydrothermal method. Part of our unique approach for designing the SiQDs was to incorporate (3-aminopropyl) triethoxysilane (APTES), which is an amphipathic molecule with hydroxyl and amine functional groups available for modification. In order to reduce the toxicity of APTES, we chose glucose as a reducing agent for the reaction. The resulting SiQDs produced potent, …

In Vitro Antioxidant, Anti-Inflammatory, And Photoprotective Activities Of Aqueous Extract Of The Endemic Plant Hammada Scoparia L. From Algeria, Benine Chaima, Djahra Ali Boutlelis, Laiche Ammar Touhami, Tlili Hajer, Tliba Ali, Ben Arfa Abdelkarim, Najjaa Hanen

Karbala International Journal of Modern Science

This study aimed to analyze the chemical profile and evaluate the biological activities of the aqueous extract of H. Scoparia, an endemic plant found in Southeastern Algeria. The aqueous extract was subjected to phytochemical screening, RP-HPLC, and FT-IR analysis. The anti-inflammatory activity was examined using the protein denaturation method, and the photoprotective activity was evaluated using UV-Visible spectrophotometry. The antioxidant activity was assessed using ABTS, DPPH, and FRAP assays. The study found the presence of various secondary metabolites such as polyphenols, tannins, and saponins. This study suggests that H. Scoparia extract has the potential as a natural source of bio-actives …

B/Lv Laboratory Accessibility Technology Adapted For Neurodiverse Chemistry Students, Christin B. Monroe

Journal of Science Education for Students with Disabilities

Text-to-speech technology is a common accommodation available for students with disabilities. Despite the ubiquitous nature of text-to-speech, this technology has not been explored in laboratory settings for neurodiverse college students. This study explores the adaptability of laboratory accessible text-to-speech technology (originally developed for blind/low vision (B/LV) students) for neurodiverse students. Students were asked to provide general feedback about the usability and effectiveness of the technology using Likert surveys. The students also answered open-ended questions about how the technology could be adapted to be more neurodiverse friendly. Overall, more than 50% of the students found the technology useful but had specific …

Equine In Vivo Metabolite Profiling Of The Selective Androgen Receptor Modulator Lgd-3303 For Doping Control, Malin Nilsson Broberg, Heather Knych, Ulf Bondesson, Curt Pettersson, Börje Tidstedt, Scott Stanley, Mario Thevis, Mikael Hedeland

UK CARES Faculty Publications

LGD-3303 is a Selective Androgen Receptor Modulator (SARM) that is prohibited in both equine and human sports due to its anabolic properties. The aim of this study was to investigate the equine in vivo metabolite profile of LGD-3303 and identify drug metabolites that can be suitable as new and improved analytical targets for equine doping control. This was performed by an oral administration of 0.05 mg⋅kg 1 LGD-3303 to horses, where blood and urine samples were collected up to 96 h after administration. The in vivo samples consisting of plasma, urine and hydrolyzed urine were analyzed utilizing ultra-high performance liquid …

Syntheses And Characterization Of Photoactive Ruthenium And Iron Polypyridyl Complexes, Rajani Thapa Magar

Chemistry and Chemical Biology ETDs

Within this dissertation, two distinct classes of metal complexes have been discussed that bear significance in the field of solar energy conversion, photo redox catalysis and memory devices. The first class of the metal complexes is a series of photochromic Ruthenium polypyridyl N-heterocyclic carbene tethered sulfoxide complexes that are reported to undergo unusually slow isomerization from S-bonded to O-bonded and unusually fast thermal reversion from O-bonded to S-bonded configuration. The role of NHC in the excited state dynamics of these complexes have been discussed in detail in Chapter 3.

For the first time in two decades, structural information of the …

Comparative Efficacy Of Systemic And Combination Fungicides For The Control Of Alternaria Leaf Spot Of Cabbage, Patience U. Ishieze, Chinedu F. Amuji, Kevin I. Ugwuoke, Paul K. Baiyeri, Michael O. Eze

Chemistry Faculty Research & Creative Works

Alternaria leaf spot of cabbage, caused by the Alternaria brassicicola, affects leaves of cabbages and often results in head rots causing severe decline in yield. in this work, the effects of systemic and combination fungicides on A. brassicicola mycelia growth in vitro and disease severity in field trials were investigated. the results of in vitro evaluation revealed that both fungicides significantly inhibited (p < 0.05) the growth of A. brassicicola under in vitro conditions. However, metal Axyl-M 6% was less effective with 100 μg/mL having only 30 ± 3.5% inhibition. on the other hand, 100 μg/mL of mancozeb 63% + carbendazim 12% had 94 ± 3.5% growth inhibition of A. brassicicola, respectively, under the same conditions. Dose-response analysis of the efficacy of the two fungicides showed that the LC50 of metal Axyl-M 6% and mancozeb 63% + carbendazim 12% were 125.52 ppm and 57.22 ppm, respectively, indicating the superiority of combination fungicide over systemic fungicide alone. Field studies showed that while manure type significantly impacted on biomass production (p < 0.001), it did not significantly affect disease severity. on the other hand, the frequency of fungicide application impacted on disease severity, with biweekly application leading to a significant reduction in disease severity after 10 weeks.

Development Of An Enhanced Hybrid Bi-Catalytic Electrode Containing Bimetallic Composite Catalyst And Immobilized Enzyme For Complete Glucose Electrooxidation, Jefferson Honorio Franco, João Victor Bonaldo, Rodrigo Garcia Da Silva, Shelley D. Minteer, Adalgisa R. De Andrade

Chemistry Faculty Research & Creative Works

We describe an enzymatic fuel cell (EFC) that can electrooxidize glucose completely. the EFC contains the hybrid Ni@Pt-CNT/OxOx bioanode, composed of a bimetallic composite catalyst (Ni@Pt-CNT) and the enzyme oxalate oxidase (OxOx), which can cleave carbon-carbon bonds. Ni@Pt-CNT/OxOx displayed 3-fold higher catalytic activity in the presence than in the absence of glucose (1.3 and 0.4 mA cm−2, respectively), indicating that Ni@Pt-CNT and OxOx acted synergistically. Electrochemical impedance spectroscopy showed that Ni@Pt-CNT/OxOx had higher charge transfer resistance and double layer capacitance than Ni@Pt-CNT. Long-term bulk electrolysis (18 h) revealed that the EFC operating with Ni@Pt-CNT/OxOx presented better current density and stability …

Alkaline Pretreatment And Air Mixing For Improvement Of Methane Production From Anaerobic Co-Digestion Of Poultry Litter With Wheat Straw, Yuanhang Zhan, Jun Zhu, Yiting Xiao, Leland C. Schrader

Biological and Agricultural Engineering Faculty Publications and Presentations

Alkaline pretreatment (AL) and air mixing (air) both have the potential to improve anaerobic co-digestion (Co-AD) of poultry litter with wheat straw for methane production. In this study, the effects of the combination of AL (pH 12 for 12 h) and air mixing (12 mL·d⁻¹) on the Co-AD process were investigated. The substrate hydrolysis was enhanced by AL, with soluble chemical oxygen demand increased by 4.59 times and volatile fatty acids increased by 5.04 times. The cumulative methane yield in the group of Co-AD by AL integrated with air (Co-(AL + air)), being 287 mL·(g VS_added) …

Reproducibly Defining Electrode Area Of Carbon Paper Electrodes Via Machine Cutting And High-Throughput Waxing, Rokas Gerulskis, Shelley D. Minteer

Chemistry Faculty Research & Creative Works

Carbon paper is one of the most common carbon electrode materials employed in electrochemical research due to its low cost, disposability, and controllable dimensions and scaling. Carbon paper is usually hand cut, and a variety of strategies are used to define electrode area. This procedure is tedious, imprecise, and inaccurate, yielding coefficients of variation in peak current output as high as 20%. Imprecision in hand-preparation translates directly to poor reproducibility in electrochemical data leading to challenges in directly comparing data across research groups and research fields. This work introduces an inexpensive and precise method to automatically cut and rapidly wax …

Straight Out-Of-The-Tube: Analysis And Conservation Of George Mathieu’S Pour Une Aliénation Définitive Du Logos, Christy H. Mccutchen

Art Conservation Master's Projects

Pour une aliénation définitive du logos (96.5 cm × 195.6 cm, Buffalo AKG Art Museum, Acc.1971:7), painted in 1955 by French artist Georges Mathieu (1921-2012) is an iconic example of Lyrical Abstraction. Mathieu launched this European counterpart to Abstract Expressionism in the post-war upheaval of 1947. His unorthodox methods present a unique combination of aesthetic concerns and intrinsic material instability. Mathieu’s technique involved squeezing oil paints out-of-the-tube directly onto his canvas with rapid and spontaneous calligraphic motions. The primary condition issue for Pour une aliénation définitive du logos was the failing adhesion between this thickly applied paint and the primed …

Optimizing Mn-Al Permanent Magnet Performance Through Control Of The Phase Transformation, Ternary Element Addition, And Advanced Processing, Thomas R. Keller

Dartmouth College Ph.D Dissertations

The growing need for electrical power in machines and vehicles brings with it a growing need for critical materials. The current high-performance permanent magnets (PMs) based on rare-earth (RE) elements Nd and Sm cannot escape the problem of raw material cost, geographic scarcity in the earth’s crust, and lack of circular global supply chains. This poses a problem of industrial ecology: can PMs be made from inexpensive, more abundant materials while still meeting sufficient performance criteria? PMs based on the magnetic τ phase of Mn-Al offer a possible alternative to REPMs. However, years of innovation have not yet achieved real-world …

Guar-Based Injectable Hydrogel For Drug Delivery And In Vitro Bone Cell Growth, Humandra Poudel, Ambar R. Rangumagar, Pooja Singh, Adeolu Oluremi, Nawab Ali, Fumiya Watanabe, Joseph Batta-Mpouma, Jin-Woo Kim, Ahona Ghosh, Anindya Ghosh

Chemistry & Biochemistry Faculty Publications and Presentations

Injectable hydrogels offer numerous advantages in various areas, which include tissue engineering and drug delivery because of their unique properties such as tunability, excellent carrier properties, and biocompatibility. These hydrogels can be administered with minimal invasiveness. In this study, we synthesized an injectable hydrogel by rehydrating lyophilized mixtures of guar adamantane (Guar-ADI) and poly-β-cyclodextrin (p-βCD) in a solution of phosphate-buffered saline (PBS) maintained at pH 7.4. The hydrogel was formed via host-guest interaction between modified guar (Guar-ADI), obtained by reacting guar gum with 1-adamantyl isocyanate (ADI) and p-βCD. Comprehensive characterization of all synthesized materials, including the hydrogel, was performed using …

Development Of Dibenzofuran Linkers And Phenazine-Based Redox-Responsive Foldamers, Ruth Son

Arts & Sciences Graduate Student Theses and Dissertations

Our group has demonstrated the feasibility of utilizing phenazine-1,6-dicarboxamides as redox-responsive molecular switches: changes in the oxidation state of the phenazine core forces the secondary amide arms to rotate between the doubly folded form when oxidized and the unfolded form when reduced to its dihydrophenazine form. To construct phenazine-based oligomers, we have developed dibenzofuran linkers that can easily be decorated with different solubilizing groups and incorporated into the foldamer backbone. In our initial attempts, we used xanthene linkers. However, problems with limited solubility and preference for cyclization prompted us to consider an alternative cisoid linker with a wider bite angle. …

Upgraded Carbon Ores To Products, University Of North Dakota. Energy And Environmental Research Center

EERC Brochures and Fact Sheets

Fact sheet on the Energy & Environmental Research Center project to develop domestic battery materials from upgraded carbon ores. Includes information on upgraded carbon ores to products (UCOP) technology and a timeline for development.

Singlet Oxygen-Mediated Conformational Flexibility, Antioxidant, And Isomerization Studies In Chemistry And Biochemistry, Oliver Turque

Dissertations, Theses, and Capstone Projects

Three chapters are included in this dissertation, each of which describes non-oxidative reactions, with peroxy intermediates formed between singlet oxygen (¹O₂) and substrate. (1) Novel discoveries related to the intermediate formed by ¹O₂ and dimethyl disulfane are explored. (2) A new mechanism is proposed, wherein the dihedral angle CS–SC (θ) determines the pro- or antioxidant activity of an organic disulfide. (3) A review of ¹O₂'s ability to facilitate the geometric isomerization of alkenes and polyenes is presented in Chapter 3.

Chapter 1 investigates the role of singlet oxygen potentially …

Disordered Protein Aggregates Are Linked To Changes In The Histone Post-Translational Modification Landscape In Disease And Non-Disease Models, Samantha Cobos

Dissertations, Theses, and Capstone Projects

Proper protein folding is a delicate balance that is crucial for normal biological function. In mammals, protein misfolding and aggregation leads to loss of function of the original protein while in many cases being associated with neurodegenerative diseases, eventually leading to death of the organism. In yeast however, the aggregated prion state is associated with positive cellular outcomes, and cells can switch between the [PRION+] and [prion-] states. Understanding the factors that lead to changes in prion state conformation in yeast could lead to novel insight into the conditions controlling misfolding by neurodegenerative proteinopathies. We believe that by studying the …

Synthesis And Characterization Of Polymer-Based Complex Nanomaterials, Prashun G. Roy

Dissertations, Theses, and Capstone Projects

The original research work in this dissertation is about the use of polymers in two significantly important areas. One involves creating mesoporous silica materials with various morphologies using a mixed Pluronic surfactant system made up of two poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) surfactants, one of which contains long hydrophilic (PEO) blocks and the other has a significantly higher proportion of hydrophobic PPO . In addition, a glucose responsive core-shell type microgel was also developed for shifting the glucose responsive volume phase transition by using polymeric nanomaterials.

Chapter 1 of the dissertation discussed some historical background of synthesis and uses of …

Kinetics Of Photochemical And Mechanochemical Organic Reactions On Surface, Yerzhan Zholdassov

Dissertations, Theses, and Capstone Projects

Solvents used in traditional chemical processes account for a large percentage of reaction mass and waste and can pose significant environmental and health risks. The environmentally friendly nature of mechanochemistry, in addition to other benefits, makes it a promising approach for sustainable chemistry over traditional solvent-based methods. However, it is still not a widely adopted method for performing chemical reactions on an industrial scale. This is partially due to the significant challenge associated with understanding the reaction kinetics under mechanochemical conditions. Many variations of scanning probe lithography (SPL) techniques are able to manipulate the organic molecules with precise control over …

Electrochemical Resistive-Pulse Sensing In Biological Systems, Rui Jia

Dissertations, Theses, and Capstone Projects

Electrochemical resistive-pulse (ERP) sensing with conductive carbon nanopipettes (CNPs) is a powerful technique for detecting single nanoscopic entities, such as single liposomes and biological vesicles, enabling qualitative and quantitative analysis of the redox molecules contained in such entities. ERP experiments were first carried out in biological system by inserting a conductive carbon nanopipette into a macrophage cell to sample single vesicles and measuring reactive oxygen and nitrogen species (ROS/RNS) contained inside them.

Besides sensing intracellular vesicles in macrophage cells, we applied this technique to direct detect single extracellular vesicles (EVs) released from a specific cell, and analysis of reactive oxygen …

Construction And Performance Optimization Of Bioconjugated Nanosensors For Early Detection Of Breast Cancer And Pro-Inflammatory Diseases, Pooja Gaikwad

Dissertations, Theses, and Capstone Projects

In recent years, nanosensors have emerged as a tool with strong potential in medical diagnostics. Single-walled carbon nanotube (SWCNT) based optical nanosensors have notably garnered interest due to the unique characteristics of their near-infrared fluorescence emission, including tissue transparency, photostability, and various chiralities with discrete absorption and fluorescence emission bands. Additionally, the optoelectronic properties of SWCNT are sensitive to the surrounding environment, which makes them suitable for in vitro and in vivo biosensing. Single-stranded (ss) DNA-wrapped SWCNTs have been reported as optical nanosensors for cancers and metabolic diseases. Breast cancer and cardiovascular diseases are the most common causes of death …

The Development Of Novel Radioscandium And Hydroxypyridinonate Based Radiopharmaceuticals, Michael Phipps

Dissertations, Theses, and Capstone Projects

The use of radiometals in radiopharmaceutical development has drastically increased over the last decade, owed in part to the diverse chemistry and emission characteristics of the radiometals, which allow chemists to create a toolbox of agents to better tailor patient care. Challenges with the use of radiometals include the selection of the metal and the development of optimized chelators to cover the diverse chemistry of the metals which make up the majority of the periodic table. Scandium is the first transition metal and has multiple radioisotopes whose emission characteristics have potential application in medicine. 3,4,3-LI(1,2-HOPO) is a chelator whose denticity, …