Chemistry Commons^™

Sensitive And Accurate Determination Of Oil-Soluble And Water-Soluble Organosulfur Compounds In Garlic Matrix Using Reversed Phase-High Performance Liquid Chromatography, Ümmügülsüm Polat Korkunç, Buse Tuğba Zaman, Sezgi̇n Bakirdere, Emine Karakuş

Turkish Journal of Chemistry

Garlic is in the family Liliaceae and has many different constituents such as organic sulfur compounds, amino acids, carbohydrates, minerals, and vitamins. In this work, a simple, sensitive, and accurate analytical method was developed for the determination of selected organosulfur compounds (OSCs) in garlic bulbs using reversed phase-high performance liquid chromatography (RP-HPLC). Oil-soluble and water-soluble OSCs were extracted from the garlic samples via acetonitrile and deionized water, respectively. The OSCs were separated on a Phenomenex C18 (250 mm, 4 mm, 5mm) column and the monitoring was performed with a UV detector at 220 nm. An isocratic mobile phase comprising of …

Phosphorus And Nitrogen-Containing Soybean Oil Polyols: Effect On The Mechanical Properties And Flame Retardancy Of Polyurethane Foam, Deni̇z Öztaşkin, Lütfullah Yusuf Yi̇vli̇k, İlayda Acaroğlu Degitz, Tarik Eren

Turkish Journal of Chemistry

In recent years, there has been an increasing interest in producing new materials that use renewable resources and halogen-free flame retardants with nonleaching properties. This research focuses on designing and synthesizing phosphorus-nitrogen-based biopolyols for use in polyurethane (PU) foam production. Polyol (ESBO-DYM) with dual functionalities, renewability, and nonflammability is synthesized through the epoxy ring-opening reaction of epoxidized soybean oil with phosphorus and nitrogen-containing tetraol products (DYM). The mechanical and flame retardant properties of PU foams with the addition of an ESBO-DYM were investigated. Increasing the amount of phosphorus in the PU foams increased the thermal stability properties. Using 100% ESBO-DYM …

Improving The Water Solubility Of Cannabidiol Using A Peptide Carrier, Melek Parlak Khalily

Turkish Journal of Chemistry

Cannabidiol (CBD), nonpsychotropic cannabinoid found in Cannabis sativa, is a very promising drug candidate offering many differential effects such as sedative, antiinflammatory, antioxidant, and neuroprotective properties. Nevertheless, the therapeutic use of CBD is hindered by its lack of water solubility and relatively low bioavailability. Various carriers have been used to address the solubility issues of CBD and other highly lipophilic drugs so far. However, self-assembled peptide nanostructures as carrier have not been used to improve the water solubility of CBD yet. In this study, a self-assembling peptide micelle was demonstrated to be an effective vehicle for encapsulation of CBD and …

Computational Drug Repurposing Effort For Identifying Novel Hits For The Treatment Of Diseases Such As Endometriosis, Uterine Fibroids, And Prostate Cancer, Ahmet Buğra Ortaakarsu, Hi̇lal Medetali̇beyoğlu

Turkish Journal of Chemistry

This research aimed to identify potential drug compounds from the ZINC15 molecule database that could effectively treat GnRH1R-related diseases. The study utilized molecular docking and molecular dynamics methods to achieve this goal, which is crucial in drug repurposing research. The virtual screening process involved analyzing known drug compounds using molecular docking. Additionally, molecular dynamics simulations and MM-GBSA were employed to evaluate the stability of the complexes and determine the interactions between the compounds and protein structure. As a result, this study provides significant insights for treating diseases such as endometriosis, uterine fibroids, and prostate cancer related to GnRH1R. The study …

Hummers’ Method-Assisted Liquid-Phase Exfoliation Enables The Fabrication Of Few-Layer Borophene From Bulk Boron, Mehmet Semih Bingöl, Mehmet Yilmaz, Ahmet Emre Kasapoğlu

Turkish Journal of Chemistry

The fabrication of few-layer borophene (BP) from bulk boron (b-B) is of great importance and still a scientific challenge due to the complex structure and crystallinity of b-B. Herein, we propose a novel technique to prepare a few-layer BP on a large scale with a large lateral size in a well-controlled manner. For this, we employed the Hummers’ method-assisted liquid-phase exfoliation. In the first step, the chemical exfoliation of the b-B as a precursor was performed by the modified Hummers’ method. After chemical exfoliation, mechanical delamination was employed by using an immersion sonicator. Finally, BP sheets were collected with dimensions …

Supramolecular Solvent-Based-Vortex-Assisted-Dispersive Liquid Liquid Microextraction Of Sudan Black B In Food Samples Prior To Spectrophotometric Detection, Fi̇gen Erek, Mustafa Tüzen

Turkish Journal of Chemistry

A new, simple and rapid spectrophotometric method was developed for determination of Sudan Black B in food products by supramolecular solvent-based-vortex-assisted-dispersive liquid liquid microextraction (SUPRAS-VA-DLLME). Extraction solvent type, volume of solvent, pH, volume of THF, centrifugation time, vortex time, and sample volume were investigated as optimization parameters of the developed method. Under the optimum conditions, limit of detection and limit of quantification, preconcentration factor and enhancement factor of the developed method were calculated to be 9.01 µg L–1, 29.73 µg L–1, 20, and 55, respectively. The developed microextraction method was successfully applied to food samples for the determination of Sudan …

Evaluation Of P(Hema-Co-Nipam) Hydrogels For Removal Of Methylene Blue From Aqueous Solution:Isotherm, Kinetic, And Thermodynamic Studies, Hayri̇ye Mi̇ne Antep, Müni̇re Nalan Demi̇r, Cevher Gündoğdu Hizliateş, Si̇mge Öztürk, Eli̇f Esen

Turkish Journal of Chemistry

In this study, a novel adsorbent material, poly (2-hydroxyethyl methacrylate-co-N-isopropyl acrylamide) (p(HEMA-co-NIPAM) hydrogel, was synthesized for the purpose of removing methylene blue (MB) from aqueous media. The synthesis of hydrogel was carefully conducted, and its properties were thoroughly examined using techniques such as Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The adsorption experiments conducted revealed a remarkable affinity of p(HEMA-co-NIPAM) hydrogel towards MB. The highest adsorption was observed when 0.05 g of the adsorbent were utilized, with optimal conditions at a pH of 6.0 and a temperature of 15 °C. This underscores the importance of …

Investigation Of Benzoic Acid And Sorbic Acid Concentrations In Tomato Paste, Pepper Paste, Ketchup, Mayonnaise, And Barbeque Sauce Samples By Headspace Gas Chromatography-Mass Spectrometry, Orhan Destanoğlu

Turkish Journal of Chemistry

In this study, it was aimed at investigating benzoic acid (BA) and sorbic acid (SoA) concentrations in tomato paste, pepper paste, ketchup, mayonnaise, and barbeque sauce samples by a validated static headspace gas chromatography–mass spectrometry (GC-MS) method. Salicylic acid (SalA) was used as internal standard and the measurements were conducted in the wide linear concentration ranges of BA and SoA which were 2.5–5000 and 12.5–5000, respectively. The limit of detections (LODs) were determined to be 1.5 and 4.5 mg/kg while the limit of quantifications (LOQs) were 2.5 and 12.5 mg/kg for BA and SoA, respectively. The average recovery% values of …

Construction Of Hyperbranched Imprinted Nanomaterials For Selective Adsorption Of Cadmium (Ii), Sheng Nan Hu, Xinyu Zhang, Ming Guo, Shengchun Wu, Wenjun Lu

Turkish Journal of Chemistry

A hyperbranched ion-imprinted polymer (IIP) material containing multiple selective adsorption sites was synthesized using halloysite nanotubes, methyl acrylate, and ethylenediamine in the presence of a template ion [i.e. Cd (II) heavy metal]. The successful preparation of the Cd-IIP composition was confirmed by FT-IR, XRD, TEM, TGA, and elemental analysis. The polymers exhibited good adsorption of Cd (II) with a maximum adsorption capacity of 64.37 mg·g–1. The imprinting factor (α) for Cd (II) was 2.62 and the selection factor (β) was 1.78, indicating a specific adsorption of Cd (II) ion. The selection coefficients of Cd-IIP for Cd (II)/Pb (II), Cd (II)/Cu …

Transdermal Delivery System To Release Phthalocyanine Photosensitizers For The Potential Treatment Of Skin Cancer With Pdt, Meryem Çamur Demi̇r, Fatma Kurşun Baysak, Caner Yahya Boyar, Ali̇han Toksoy, Fati̇h Algi

Turkish Journal of Chemistry

This research aims to examine the transdermal release of water-soluble indium and zinc metallo phthalocyanine (InPc and ZnPc) compounds from the poly(vinyl alcohol) (PVA) membrane and the cytotoxicity effect of these Pcs on normal mouse fibroblasts (L929 fibroblast) and human melanoma (SK-MEL-30) cells. For this purpose, the effects of temperature, pH, drug concentration and membrane thickness on transdermal release were investigated in order to obtain the optimum transdermal release profile by preparing PVA membranes with different thicknesses and crosslinked by heat treatment. Optimum drug release was found to be 85.36% using 6 µm thick PVA membrane at 37 ± 0.5 …

Graphene Aerogels: Part 2 - Derived From Commercial Graphene And Chemically Reduced Graphene Oxide Via Supercritical Carbon Dioxide Drying, Meryem Samanci, Ayşe Bayrakçeken

Turkish Journal of Chemistry

Graphene aerogels (GAs), the most important class of carbonaceous aerogels, have attracted attention of many researchers due to their superior physical and chemical properties. In this study, commercial graphene (GR) and chemically reduced graphene oxide (RGO) were used as graphene-based precursor materials, unlike graphene oxide (GO), which is widely used in the literature in GA synthesis. GAs were synthesized using the sol-gel technique and dried with supercritical carbon dioxide (SCCO2). In addition, graphene-based materials were used in different ratios and their distribution in the aerogel matrix and its effect on surface properties were investigated. In addition, the synthesized GAs were …

Performance Test Of Zn-Astaxanthin Complex-Sensitized Solar Cell: Effect Of Light Intensity On Open-Circuit Voltage And Short-Circuit Current Values, Septiani Septiani, Winda Rahmalia, Thamrin Usman

Turkish Journal of Chemistry

The sensitizer is one of the most essential dye-sensitized solar cell (DSSC) components. In the present research, a Zn-astaxanthin complex was investigated as a sensitizer, compared to pure astaxanthin. The complex with a 1:1 mole ratio between astaxanthin and Zn2+ was synthesized in a reflux reactor at 37–60 °C. The product was analyzed using Proton Nuclear Resonance (1H-NMR), which indicates the presence of chelate formation between Zn2+ with two atoms of oxygen on the terminal cyclohexane ring of astaxanthin. The interaction of sensitizers (astaxanthin and Zn-astaxanthin) on the photoelectrode surface in this study was analyzed using a Fourier Transform Infra-Red …

Preparation Of Cholesterol-Imprinted Polymer For Selective Adsorption Of Cholesterol From Gastrointestinal Mimicking Solution, Veyi̇s Karakoç, Erol Erçağ

Turkish Journal of Chemistry

The purpose of this study is to synthesize a highly selective adsorbent to remove cholesterol, one of the most important causes of cardiovascular diseases, from the intestinal mimic solution (IMS). For this purpose, cholesterol imprinted polymers were synthesized by suspension polymerization method using the molecular imprinting technique. In the first step, the functional monomer MATyr with hydrophobic character was synthesized. Then, the cholesterol-MATyr monomer precomplex was formed and the polymerization process was carried out by adding cross-linkers with the comonomer HEMA. The synthesized polymer poly(2-hydroxyethyl methacrylate-N-methacryloyl-(L)-tyrosine methylester) poly(HEMA–MATyr) was characterized by FTIR and SEM. The cholesterol adsorbing behavior of the …

Graphene Aerogels: Part 1 - Derived From Graphene Oxide And Thermally Reduced Graphene Oxide Via Supercritical Carbon Dioxide Drying, Meryem Samanci, Ayşe Bayrakçeken

Turkish Journal of Chemistry

Graphene aerogels have become promising materials in many areas of industry, especially in energy applications due to their superior physical and electrochemical properties. Generally, graphene oxide (GO)-derived aerogels (A) are synthesized by using the hydrothermal method. In this study, both GO and reduced graphene oxide (RGO)-derived aerogels were synthesized by using the sol-gel method coupled with the supercritical carbon dioxide (SCCO2) drying process. It aims to examine the changes in the structure of the final aerogel by changing the amount (0.25–0.5–1% wt.) and type of graphene-based precursor materials used in the synthesis. Physical characterizations of graphene aerogels were conducted using …

Why Your Clothes Could Be Killing You: The Detection Of Bpa In Clothing Using Fluorescence Spectrophotometry, Bella Bevel

Scholars Day Conference

Bisphenol-A, better known as BPA, is a carcinogenic compound found in many plastic-containing products due to its ability to add rigidity and strength to the plastic. However, BPA has been found in a wide variety of products not traditionally thought of as “plastic” including feminine hygiene products, printer receipts, and even clothing. Clothing containing a polyester/spandex blend, common in athletic wear, contains BPA, whereas traditional cotton clothing does not. Using flourospectroscopy, the presence of BPA in these types of clothing was confirmed, as well as measured over time. Strips of clothing containing polyester and spandex blends were submerged in a …

The Mental Health And Developmental Effects Of Bisphenol-A, Maryann Rettig

Scholars Day Conference

My directed study focuses on the mental health and developmental effects of bisphenol-A (BPA) on individuals in close contact with the chemical product. BPA is an organic chemical produced in large quantities that is used in the production of many polycarbonate plastics, feminine hygiene products, and epoxy resins that coat some metal food cans. Because of it being everywhere, BPA often leaches dermally and orally into the human body. The physical effects of BPA have been known and observed for years. However, its mental health effects specifically are not as commonly known. Therefore, in my directed study I would be …

Vt-Nmr Analysis Of Rotation-Inversion Of N-(4-Hydroxybutyl)-N-(2,2,2-Trifluoroethyl) Tert-Butyl Carbamate: Utilizing The −Ch2cf3 Appendage As A Reporter On E/Z-Isomerization, Brian Jameson, Rainer Glaser

Chemistry Faculty Research & Creative Works

The rotational barrier about the CN carbamate bond of N-(4-hydroxybutyl)-N-(2,2,2-trifluoroethyl) tert-butyl carbamate 1 was determined by variable temperature (VT) 13C and 19F NMR spectroscopy. The −CH2CF3 appendage reports on rotational isomerism and allows for the observation of separate signals for the E- and Z-ensembles at low temperature. The activation barrier for E/Z-isomerization was quantified using Eyring-Polanyi theory which requires the measurements of the maximum difference in Larmor frequency Δνmax and the convergence temperature Tc. Both Δνmax and Tc were interpolated by analyzing sigmoidal functions fitted to data describing signal separation and the quality of the superposition of the E- and …

Enhancing The Antibiotic Properties Of Meropenem With Hydrophobic Ion-Pairing, Krishna Paul, Bidhan Barua, Lark Perez

STEM Student Research Symposium Posters

Antibiotic Resistance is one of the most urgent global threat to humankind. Most antibiotics are hydrophilic in nature while proteins and peptides are lipophilic. Enhancing lipophilicity of the antibiotic by HIP can increase solubility of the drugs in human and improve antibacterial effect as well. We hypothesized that formation of a hydrophobic drug complex would change the physical properties of the antibiotic and enhance its antimicrobial activity.

Identifying V. Cholerae's Autoinducer To Manipulate Its Quorum Sensing, Jason X. Tran, Daniel Palacio, Lark Perez

STEM Student Research Symposium Posters

• Vibrio cholerae is a gram-negative anaerobic bacteria that inhabits brackish or saltwater areas.

• Causative agent of cholera, which results in acute diarrhea and dehydration.

• Uses quorum sensing, a cell density dependent method of communicating with other bacteria and regulating its entire lifecycle of infection. (gene expression of functions such as biofilm formation, virulence, and more)

• Vibrio cholerae determines bacterial population based on the secretion of several signaling molecules called an autoinducer from others of their kind.

• Upon adequate accumulation, they can deactivate their virulence and begin to leave their host’s body to continue infecting other …

Myoglobin Unfolding And Protein Stability With Tmg, Eustratios R. Kossis, Dimitra N. Kossis, Kristen Rass, Taha Shahbaz, Gregory A. Caputo, Timothy Vaden

STEM Student Research Symposium Posters

Myoglobin, a widely studied protein in biophysics, is a small, helical, and highly soluble protein that has been investigated for decades. Its heme prosthetic group facilitates easy analysis of its folding state through absorbance spectroscopy. Ionic liquids (ILs), particularly room-temperature ionic liquids or molten salts, have gained significant attention in the past 15- 20 years for their potential use in electrochemical devices. Recently, their biocompatibility has become a focal point in research, given that certain IL species can either stabilize or destabilize biomolecular structures. This study employs absorbance and fluorescence spectroscopy to examine how amino acid-based ILs, specifically tetramethyl guanidine …

Thermal Destabilization Of Azurin By Fatty Acid Ionic Liquids, Brandon Burrell, Austin K. Clark, Achismita Dutta, Esha Prajapati, Sierra Cottle, Andrew Ogungimi, Justin Burrell, Timothy D. Vaden

STEM Student Research Symposium Posters

Azurin is a mixed-structure redox protein involved in bacterial denitrification. Previous studies have shown that azurin is destabilized by imidazolium chloride ionic liquids (ImCl ILs) that can form micelles in aqueous solution, likely by micellar encapsulation. In these ImCl ILs the micelles form from the imidazolium cations. A relatively new class of ionic liquids is fatty acid ionic liquids (FAILs), in which the anion is a fatty acid. In FAILs micelles can form from the fatty acid anions. This presentation presents the results of a thermal unfolding study of azurin in the presence of FAILs in solution. The FAILs tetramethylguanidinium …

Characterization Of Lysozyme Stability In The Presence Of Lonic Liquids, Madison Scott, Ramzy T.M. Malak, Daniel Obeid, Chun Wu, Timothy Vaden, Gregory A. Caputo

STEM Student Research Symposium Posters

Hen egg white lysozyme (Lyz) has been a well studied model system in biophysical investigations for decades. The protein is a small, primarily helical, highly soluble protein that is both commercially available and easily accessible. lonic liquids (ILs), often referred to as room-temperature ionic liquids or molten salts, have garnered great interest in the last 15-20 years as potential components of electrochemical devices or applications. More recently, the biocompatibility of these molecules has developed an increased interest in the field, especially considering that some IL species can stabilize biomolecular structures while other ILs strongly destabilize 3D structures. In this study, …

Molybdenum Alkylidyne Complexes With Phenoxide Ligands For Alkyne Metathesis, Marvin L. Stewart Jr

LSU Doctoral Dissertations

Abstract

Alkyne metathesis is a powerful synthetic tool, which provides easy access to complex organic molecules in a single-step. It is a dynamic covalent reaction that scrambles alkynes, carbon-carbon triple bonds (C≡C). Molybdenum- or tungsten-alkylidyne (Mo≡C, W≡C) complexes are typically used as catalyst to cleave and reform alkyne bonds. Our goal has been to gain a deeper understanding of the intrinsic differences between functional ligands by the development of novel phenoxide ligands.

In chapter 2 we explore the detailed synthesis of novel phenoxide podand ligands in an effort to identify their mo-alkylidyne complexes. We were able to synthesize a variety …

Predictors Of Student Success In College-Level General Chemistry, Elijah J. Engler, Clarice Ak Kelleher

Binghamton University Undergraduate Journal

Success in college-level general chemistry is important because it is a required course for many different STEM majors and student success in early STEM classes correlates with retention of students in STEM. Identifying factors associated with success and failure can give educators a better understanding of the warning signs to look out for in struggling students. This paper compares factors and behaviors with final grades in general chemistry courses at Binghamton University, including adjectives selected from a word bank (“valued,” “supported,” etc.), resources used, and opinion on group work as it relates to learning. Correlations were found between student adjective …

One-Pot Synthesis Green Zinc Oxide Nanoparticles Immobilized On Activated Carbon Derived From Pineapple Peel For Adsorption Of Pb(Ii), Vienna Saraswaty, Evyka Setya Aji, Ardi Ardiansyah, Ayu Hanifah, Nathania Puspitasari, Shella Permatasari Santoso, Sandy Budi Hartono, Chandra Risdian, Elsy Rahimi Chaldun, Henry Setiyanto

Karbala International Journal of Modern Science

The current study introduces a one-pot technique for synthesizing an environmentally benign and cheap composite adsorbent, namely ZnO-PPAC, for the adsorption of Pb(II). The designated adsorbent was prepared by incorporating green synthesized zinc oxide (ZnO) nanoparticles on activated carbon-derived from pineapple peel. The prepared adsorbents were characterized using XRD, SEM, EDS, FTIR, and BET techniques. The XRD pattern verifies that the ZnO was successfully synthesized and immobilized onto the PPAC in a one pot synthesis system. The surface areas of ZnOPPAC and PPAC adsorbents were 13.62 m2/g and 961.96 m2/g, respectively. The FTIR evaluation of the ZnO-PPAC adsorbent revealed several …

Modern Approaches To Treating Hospital Acquired Infections: An Overview Of Current Treatments Using Antibiotics And New Therapies Centered Around Photo-Activated Porphyrins, Meghan Johns

Senior Honors Theses

Annually, hospital-acquired infections (HAIs) affect hundreds of thousands of people in the U.S. and impose a great economic burden. The current problem is further exacerbated due to the failure of traditional treatment strategies considering the rise in antimicrobial resistance rates. Besides the fact that antimicrobial resistances complicates clinical treatment strategies, patients are also more vulnerable to secondary infections and complications from prolonged antibiotic use. As a result, research investigating novel treatment strategies for bacterial infections has recently increased. A strategy using porphyrin-based compounds is showing promise. Porphyrins and their derivatives have exhibited bactericidal effects against Gram-positive bacteria by the destruction …

Ruthenium Metal Complex Interaction With Dna Of Tumor Cells, Danielle N. Baca

Research & Creative Achievement Day

In this project, computational chemistry was used to dock variations of (p-Cymene)Ru(curcuminato)chloro (Ru-cur) in DNA strands to find the best affinity for potential anti-cancer drugs. The Ru-cur complex has been chosen as the metal anticancer complex because it is not very toxic, selective for cancer cells, and has ligand exchange kinetics similar to those of platinum. First the geometry of the Ru-cur complex was optimized via a quantum mechanical method. The GAMESS program was used for this portion. Once the geometry of the complex was optimized, docking programs were explored to find the best docking poses and binding energies for …

Allylic Rearrangement In Nbs Bromination Reactions, Devann J. Harris, Bryanna L. Wichner

Research & Creative Achievement Day

The allylic bromination of alkenes using N-bromosuccinimide (NBS) is a useful and selective substitution reaction, in which bromine radicals abstract hydrogen from the alkene to form a resonance-stabilized radical intermediate. However, allylic rearrangement can be a consequence of the intermediate's two resonance structures. Some literature sources imply that NBS bromination gives only one major product from asymmetrical alkenes, e.g., 2-hexene and 2-heptene, even when they should form equally stable but non-equivalent resonance contributors. In this research, bromination of trans-2-hexene was performed using cyclohexane as the solvent, and the products were analyzed using GC-MS to determine if only one product, 4-bromo-2-hexene, …

Investigating Chemotherapeutic Resistance In Glioblastoma Multiforme A, Katrina M. Yaeger

Research & Creative Achievement Day

Glioblastoma (GBM) multiforme A is a highly variable, grade four cancer that affects the glial tissues of the brain and spinal cord. Cancer cells, including GBM, have purine metabolism markers that make them distinguishable for biochemical research, marked through the rate limiting step in the conversion of inosine monophosphate (IMP) to guanosine triphosphate (GTP), catalyzed by inosine monophosphate dehydrogenase (IMPDH). Cell cultures for both 3T3 cells, used to study normal cell cycles, and GBM cells were grown and replicated, until sufficient cells existed to extract the desired proteins. These proteins were then run through a gel electrophoresis apparatus, followed by …

Analysis Of Rabies Neutralizing Antibody Titers In The Feline Population Of Winona County, Olivia M. Hendrickson, Jensen K. Christensen

Research & Creative Achievement Day

Canine rabies vaccination, vital for both animal and human health, is well studied and understood. In contrast, our understanding of feline rabies vaccinations, particularly with those that have a compromised immune status, is much less comprehensive. The purpose of this project is to enhance our current knowledge of feline vaccination states through a surveillance study on the feline rabies antibody titer in Winona County's cat population. Specifically, we seek to explore the relationship between an individual feline's immune status and their active anti-rabies antibody titer. To achieve this, we conducted a bicinchoninic acid (BCA) protein assay to determine the total …