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BACKGROUND: Taxanes are effective chemotherapy drugs for breast cancer care, but adverse effects pose a significant challenge in cancer treatment. Taxane-induced fluid retention and lower-extremity edema are two of the important dose-limiting toxicity and result in decreased quality of life (QoL). However, there is no standard of care to alleviate the symptoms. We conducted a clinical study to assess the efficacy of short-term aroma lymphatic tressage therapy (ALTT) in reducing taxane-induced edema in breast cancer patients. METHODS: In this phase 2 clinical trial, patients with edema of CTCAE grade 2 or higher were enrolled and conducted 8 sessions of ALTT. The primary endpoint was to determine the proportion of patients with a reduction in lower extremity circumference of 3% or more before and 6 weeks after starting ALTT. The change in QoL was assessed as the secondary endpoint using QoL questionnaires. RESULTS: A total of 37 breast cancer patients completed the protocol and were analyzed. The median sum of the 3-point circumference (thigh, calf, and ankle) was 230.8 cm (IQR 218-243) in the baseline and 220.2 cm (IQR 212-236) at the end of the study. The average decrease of circumference was 3.8%. About, 23 patients (62%) experienced a circumference decrease of 3% or more. An improvement in every scale of FACT-TAXANE and EORTC-QLQ-C30 was observed when comparing questionnaire results before and at the end of the intervention (P < 0.0001). CONCLUSION: Eight sessions of ALTT over 4 weeks were effective in reducing lower-extremity edema and resulted in improvement of QoL in patients with breast cancer.
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Layered BC3, a metastable phase within the binary boron-carbon system that is composed of graphite-like sheets with hexagonally symmetric C6B6 units, has never been successfully crystallized. Instead, poorly-crystalline BC3-like materials with significant stacking disorder have been isolated, based on the co-pyrolysis of a boron trihalide precursor with benzene at around 800 °C. The halide leaving group (-X) is a significant driving force of these reactions, but the subsequent evolution of gaseous HX species at such high temperatures hampers their scaling up and also prohibits their further use in the presence of hard-casting templates such as ordered silicates. Herein, we report a novel halide-free synthesis route to turbostratic BC3 with long-range in-plane ordering, as evidenced by multi-wavelength Raman spectroscopy. Judicious pairing of the two molecular precursors is crucial to achieving B-C bond formation and preventing phase-segregation into the thermodynamically favored products. A simple computational method used herein to evaluate the compatibility of bottom-up molecular precursors can be generalized to guide the future synthesis of other metastable materials beyond the boron-carbon system.
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In multicopper oxidases (MCOs), the type 1 (T1) Cu accepts electrons from the substrate and transfers these to the trinuclear Cu cluster (TNC) where O2 is reduced to H2O. The T1 potential in MCOs varies from 340 to 780 mV, a range not explained by the existing literature. This study focused on the â¼350 mV difference in potential of the T1 center in Fet3p and Trametes versicolor laccase (TvL) that have the same 2His1Cys ligand set. A range of spectroscopies performed on the oxidized and reduced T1 sites in these MCOs shows that they have equivalent geometric and electronic structures. However, the two His ligands of the T1 Cu in Fet3p are H-bonded to carboxylate residues, while in TvL they are H-bonded to noncharged groups. Electron spin echo envelope modulation spectroscopy shows that there are significant differences in the second-sphere H-bonding interactions in the two T1 centers. Redox titrations on type 2-depleted derivatives of Fet3p and its D409A and E185A variants reveal that the two carboxylates (D409 and E185) lower the T1 potential by 110 and 255-285 mV, respectively. Density functional theory calculations uncouple the effects of the charge of the carboxylates and their difference in H-bonding interactions with the His ligands on the T1 potential, indicating 90-150 mV for anionic charge and â¼100 mV for a strong H-bond. Finally, this study provides an explanation for the generally low potentials of metallooxidases relative to the wide range of potentials of the organic oxidases in terms of different oxidized states of their TNCs involved in catalytic turnover.
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Ceruloplasmina , Histidina , Ceruloplasmina/química , Ligantes , Cobre/química , Trametes , Eletricidade Estática , Lacase/metabolismoRESUMO
The oxygen evolution reaction (OER) is a critical step for sustainable fuel production through electrochemistry process. Maximizing active sites of nanocatalyst with enhanced intrinsic activity, especially the activation of lattice oxygen, is gradually recognized as the primary incentive. Since the surface reconfiguration to oxyhydroxide is unavoidable for oxygen-activated transition metal oxides, developing a surface termination like oxyhydroxide in oxides is highly desirable. In this work, we demonstrate an unusual surface termination of (111)-facet Co3O4 nanosheet that is exclusively containing edge-sharing octahedral Co3+ similar to CoOOH that can perform at approximately 40 times higher current density at 1.63 V (vs RHE) than commercial RuO2. It is found that this surface termination has an oxidized oxygen state in contrast to standard Co-O systems, which can serve as active site independently, breaking the scaling relationship limit. This work forwards the applications of oxide electrocatalysts in the energy conversion field by surface termination engineering.
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Purpose@#The purpose of this study was to construct the education applying the Havruta method for nursing students and to investigate the effects on self-directed learning ability, critical thinking, and learning commitment. @*Methods@#A nonequivalent control group pre-posttest design was used. The participants were 63 nursing students (experimental group, n=31; control group, n=32) at two universities. The experimental group received education applying the Havruta method for five weeks. The study was conducted from September 1 to November 30, 2022. The data were analyzed using IBM SPSS 27.0 for an χ2 test, Fisher’s exact test, independent t-test, and Mann–Whitney U-test. @*Results@#The experimental group had a significant increase in self-directed learning ability (z=-2.13, p=.033). However, there was no significant difference in critical thinking competency (t=0.64, p=.524) and learning commitment (t=0.04, p=.969) between the two groups. @*Conclusion@#The Havruta method is an effective nursing education tool for self-directed learning ability. The result of this study could be a guide for nursing professors in designing and implementing educational programs that apply the Havruta method. In the future, research that applies the Havruta method and evaluates its effectiveness in nursing education programs should be continued.
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Objective@#The objective of this study was to investigate job stress, depression, insomnia, and fatigue of coronavirus disease 2019 (COVID-19) medical staff and analyze the differences according to their general characteristics. @*Methods@#The study enrolled 98 workers at emergency medical institutions with COVID-19 treatment facilities located in Gangwon Province. An online survey was used to protect personal information. Data were analyzed using the statistical program SPSS version 28. The differences in job stress, depression, insomnia, and fatigue of COVID-19 medical staff were verified by t-test and analysis of variance. @*Results@#Analyzing job stress revealed that the average of the lowest relationship conflict stress for each sub-factor was 2.22, the average stress for job demand was the highest at 3.78, and the average whole job stress was 3.04. Contrarily, the average for depression was 1.69, insomnia 2.96, and fatigue 3.07. No statistically significant differences were observed for job stress, depression, insomnia, and fatigue when considering the type of workplace, gender, and occupation of COVID-19 medical staff. However, statistically significant differences were obtained in some variables including age, family members, working period, COVID-19 confirmed, and COVID-19-related education experience. @*Conclusion@#In this study, differences in job-related stress, depression, insomnia, and fatigue were confirmed considering the general characteristics of COVID-19 medical staff. In particular, the results of this study are significant since the difference in perceived stress in performing COVID-19 tasks was identified through empirical analysis by considering sub-factors of job stress.
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5-Hydroxymethylfurfural (HMF) has aroused considerable interest over the past years as an important biomass-derived platform molecule, yielding various value-added products. The conventional HMF conversion requires noble metal catalysts and harsh operating conditions. On the other hand, the electrocatalytic conversion of HMF has been considered as an environmentally benign alternative. However, its practical application is limited by low overall energy efficiency and incomplete conversion. Paired electrolysis and highly efficient electrocatalysts are two viable strategies to address these limitations. Herein, an overview of coupled electrocatalytic HMF hydrogenation or hydrogen evolution reaction (HER) with HMF oxidation as well as the associated electrocatalysts are reviewed and discussed. In this mini-review, a brief introduction of electrocatalytic HMF upgrading is given, followed by the recent advances and challenges of paired electrolysis with an emphasis on the integration HMF electrohydrogenation with HMF electrooxidation. Finally, a perspective for a future sustainable biomass upgrading community based on electrocatalysis is proposed.
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The key to increasing the energy density of lithium-ion batteries is to incorporate high contents of extractable Li into the cathode. Unfortunately, this triggers formidable challenges including structural instability and irreversible chemistry under operation. Here, we report a new kind of ultra-high Li compound: Li4+x MoO5 Fx (1≤x≤3) for cathode with an unprecedented level of electrochemically active Li (>3â Li+ per formula), delivering a reversible capacity up to 438â mAh g-1 . Unlike other reported Li-rich cathodes, Li4+x MoO5 Fx presents distinguished structure stability to immunize against irreversible behaviors. Through spectroscopic and electrochemical techniques, we find an anionic redox-dominated charge compensation with negligible oxygen release and voltage decay. Our theoretical analysis reveals a "reductive effect" of high-level fluorination stabilizes the anionic redox by reducing the oxygen ions in pure-Li conditions, enabling a facile, reversible, and high Li-portion cycling.
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The results of quantum chemical and molecular dynamics calculations reveal that polyanionic gallium-based cages accelerate cyclization reactions of pentadienyl alcohols as a result of substrate cage interactions, preferential binding of reactive conformations of substrate/H3O+ pairs, and increased substrate basicity. However, the increase in basicity dominates. Experimental structure-activity relationship studies in which the metal vertices and overall charge of the cage are varied confirm the model derived via calculations.
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Biomimética , Simulação de Dinâmica Molecular , Aceleração , Ciclização , Conformação MolecularRESUMO
Reduced dithiolene ligands are bound to high valent Mo centers in the active site of the oxotransferase family of enzymes. Related model complexes have been studied with great insight by Prof. Holm and his colleagues. This study focuses on the other limit of dithiolene chemistry: an investigation of the 2-electron oxidized dithiolene bound to low-valent late transition metal (TM) ions (ZnII, CuI, and CuII). The bonding descriptions of the oxidized dithiolene [N,N-dimethyl piperazine 2,3-dithione (Me2Dt0)] complexes are probed using S K-edge X-ray absorption spectroscopy (XAS) and the results are correlated to density functional theory (DFT) calculations. These experimentally supported calculations are then extended to explain the different geometric structures of the three complexes. The ZnII(Me2Dt0)2 complex has only ligand-ligand repulsion so it is stabilized at the D2d symmetry limit. The CuI(Me2Dt0)2 complex has additional weak backbonding thus distorts somewhat from D2d toward D2h symmetry. The CuII(Me2Dt0)2 complex has a strong σ donor bond that leads to both a large Jahn-Teller stabilization to D2h and an additional covalent contribution to the geometry. The combined strong stabilization results in the square planar, D2h structure. This study quantifies the competition between the ligand-ligand repulsion and the change in electronic structures in determining the final geometric structures of the oxidized dithiolene complexes, and provides quantitative insights into the Jahn-Teller stabilization energy and its origin.
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Zinco , Ligantes , Modelos Moleculares , Oxirredução , Espectroscopia por Absorção de Raios XRESUMO
Nanoscale zerovalent iron (nZVI) is considered as a highly efficient material for sequestrating arsenite, but the origin of its high efficacy as well as the chemical transformations of arsenite during reaction is not well understood. Here, we report an in situ X-ray absorption spectroscopy (XAS) study to investigate the complex mechanism of nZVI reaction with arsenite under anaerobic conditions at the time scale from seconds to days. The time-resolved XAS analysis revealed a gradual oxidation of AsIII to AsV in the course of minutes to hours in both the solid and liquid phase for the high (above 0.5 g/L) nZVI dose system. When the reaction time increased up to 60 days, AsV became the dominant species. The quick-scanning extended X-ray absorption fine structure (QEAXFS) was introduced to discover the transient intermediate at the highly reactive stage, and a small red-shift in As K-edge absorption edge was observed. The QEAXFS combined with density functional theory (DFT) calculation suggested that the red-shift is likely due to the electron donation in a Fe-O-As complex and possible active sites of As sequestrations include Fe(OH)4 and 4-Fe cluster. This is the first time that the transient reaction intermediate was identified in the As-nZVI sequestration system at the fast-reacting early stage. This study also demonstrated usefulness of in situ monitoring techniques in environmental water research.
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ArsenitosRESUMO
The reversibility of the redox processes plays a crucial role in the electrochemical performance of lithium-excess cation-disordered rocksalt (DRX) cathodes. Here, we report a comprehensive analysis of the redox reactions in a representative Ni-based DRX cathode. The aim of this work is to elucidate the roles of multiple cations and anions in the charge compensation mechanism that is ultimately linked to the electrochemical performance of Ni-based DRX cathode. The low-voltage reduction reaction results in the low energy efficiency and strong voltage hysteresis. Our data reveal that the Mo migration between octahedral and tetrahedral sites enhances the O reduction potential, thus offering a potential strategy to improve energy efficiency. This work highlights the important role that the high-valence transition metal plays in the redox chemistry and provides useful insights into the potential pathway to further address the challenges in Ni-based DRX systems.
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High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging class of solid solutions composed of a large number of species. These materials offer the benefit of large compositional flexibility and can be used in a wide variety of applications, including thermoelectrics, catalysts, superionic conductors and battery electrodes. We show here that the HE concept can lead to very substantial improvements in performance in battery cathodes. Among lithium-ion cathodes, cation-disordered rocksalt (DRX)-type materials are an ideal platform within which to design HE materials because of their demonstrated chemical flexibility. By comparing a group of DRX cathodes containing two, four or six transition metal (TM) species, we show that short-range order systematically decreases, whereas energy density and rate capability systematically increase, as more TM cation species are mixed together, despite the total metal content remaining fixed. A DRX cathode with six TM species achieves 307 mAh g-1 (955 Wh kg-1) at a low rate (20 mA g-1), and retains more than 170 mAh g-1 when cycling at a high rate of 2,000 mA g-1. To facilitate further design in this HE DRX space, we also present a compatibility analysis of 23 different TM ions, and successfully synthesize a phase-pure HE DRX compound containing 12 TM species as a proof of concept.
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Although the crystal structures for many inorganic compounds are readily available, researchers are still working hard to understand the relations between the structures and chemical properties of solutions because most of the chemical reactions take place in solutions. A huge amount of effort has been put toward modeling the ion solvation structure from the perspectives of both experiments and theories. In this study, the solvation structures of Ca2+ ions in aqueous and alcoholic solutions at different concentrations were carefully evaluated by Ca K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. Density functional theory (DFT) calculations were also performed to correlate the results with the experimental data and then further extended to other similar systems. It was found that the number of coordinating solvent molecules decreases with increasing Ca2+ concentration and increasing solvent molecule sizes. From the EXAFS data, it was observed that the first solvation shell of Ca2+ splits into two Ca-O distances in a methanol solution and the counter ion Cl- might also be within the first shell at high concentrations. For the first time, the effects of solvents with different polarities and sizes on the ion solvation environment were systematically evaluated.
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The solvation shell structures of Ca2+ in aqueous and organic solutions probed by calcium L-edge soft X-ray absorption spectroscopy (XAS) and DFT/MD simulations show the coordination number of Ca2+ to be negatively correlated with the electrolyte concentration and the steric hindrance of the solvent molecule. In this work, the calcium L-edge soft XAS demonstrates its sensitivity to the surrounding chemical environment. Additionally, the total electron yield (TEY) mode is surface sensitive because the electron penetration depth is limited to a few nanometers. Thus this study shows its implications for future battery studies, especially for probing the electrolyte/electrode interface for electrochemical reactions under in situ/operando conditions.
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NikR is a nickel-responsive metalloregulator protein that controls the level of Ni2+ ions in living cells. Previous studies have shown that NikR can bind a series of first-row transition metal ions but binds to DNA with high affinity only as a Ni2+ complex. To understand this metal selectivity, S K-edge X-ray absorption spectroscopy of NikR bound to different metal ions was used to evaluate the different electronic structures. The experimental results are coupled with density functional theory calculations on relevant models. This study shows that both the Zeff of the metal ion and the donor nature of the ligands determine the electronic structure of the metal site. This impacts the geometric structure of the metal site and thus the conformation of the protein. This contribution of electronic structure to geometric structure can be extended to other metal selective metalloregulators.
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Domínio Catalítico , Proteínas de Escherichia coli/metabolismo , Escherichia coli/metabolismo , Proteínas Repressoras/metabolismo , Proteínas de Escherichia coli/química , Modelos Moleculares , Níquel , Conformação Proteica , Proteínas Repressoras/química , Espectroscopia por Absorção de Raios XRESUMO
OBJECTIVE: Black sticky rice with giant embryo (BSRGE) contains high GABA content and affects alcohol-related indices among social drinkers, and alcohol intake and anxiety-related behavior of mice. However, it is unknown whether the intake of BSRGE affects GABAergic activity of brain directly. The purpose of this study is to elucidate the effect of oral administration of BSRGE on brain GABA concentrations compared with commercially available GABA compound and regular feeds. METHODS: Twenty-one male C57BL/6 mice were assigned to BSRGE, a regular feed (AIN-76) lacking GABA, and a regular feed containing GABA compound. After feeding freely for 48 h, the cortex and striatum were separated from the brain. An enzyme-linked immunosorbent assay was conducted to measure GABA and glutamate concentrations in mouse brain. RESULTS: The GABA concentration of the BSRGE group was higher than that of regular feed and GABA compound group (p<0.001). However, the GABA compound group showed no significant difference from the regular feed group (p=0.50). CONCLUSION: Intake of BSRGE containing high GABA content increased GABA concentrations in mouse brain compared with regular feed unlike GABA compound. The results of this study constitute an important basis for further investigations into the clinical applications of BSRGE.
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Animais , Humanos , Masculino , Camundongos , Administração Oral , Encéfalo , Estruturas Embrionárias , Ensaio de Imunoadsorção Enzimática , Ácido gama-Aminobutírico , Ácido GlutâmicoRESUMO
S K-edge X-ray absorption spectroscopy (XAS) was used to study the [Fe4S4] clusters in the DNA repair glycosylases EndoIII and MutY to evaluate the effects of DNA binding and solvation on Fe-S bond covalencies (i.e., the amount of S 3p character mixed into the Fe 3d valence orbitals). Increased covalencies in both iron-thiolate and iron-sulfide bonds would stabilize the oxidized state of the [Fe4S4] clusters. The results are compared to those on previously studied [Fe4S4] model complexes, ferredoxin (Fd), and to new data on high-potential iron-sulfur protein (HiPIP). A limited decrease in covalency is observed upon removal of solvent water from EndoIII and MutY, opposite to the significant increase observed for Fd, where the [Fe4S4] cluster is solvent exposed. Importantly, in EndoIII and MutY, a large increase in covalency is observed upon DNA binding, which is due to the effect of its negative charge on the iron-sulfur bonds. In EndoIII, this change in covalency can be quantified and makes a significant contribution to the observed decrease in reduction potential found experimentally in DNA repair proteins, enabling their HiPIP-like redox behavior.
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DNA Glicosilases/metabolismo , DNA/metabolismo , Desoxirribonuclease (Dímero de Pirimidina)/metabolismo , Proteínas de Escherichia coli/metabolismo , Escherichia coli/enzimologia , Geobacillus stearothermophilus/enzimologia , Bactérias/química , Bactérias/enzimologia , Bactérias/metabolismo , Proteínas de Bactérias/química , Proteínas de Bactérias/metabolismo , Sítios de Ligação , DNA Glicosilases/química , Desoxirribonuclease (Dímero de Pirimidina)/química , Escherichia coli/química , Escherichia coli/metabolismo , Proteínas de Escherichia coli/química , Geobacillus stearothermophilus/química , Geobacillus stearothermophilus/metabolismo , Proteínas Ferro-Enxofre/química , Proteínas Ferro-Enxofre/metabolismo , Modelos Moleculares , Complexo de Proteínas do Centro de Reação Fotossintética/química , Complexo de Proteínas do Centro de Reação Fotossintética/metabolismo , Ligação Proteica , Espectroscopia por Absorção de Raios X/métodosRESUMO
PURPOSE: The purpose of this study was to construct and test a structural equation model on resilience of breast cancer patients receiving chemotherapy. METHODS: Participants were 204 patients with breast cancer who received chemotherapy treatment. They participated in a structured interview, which included social support, depression, symptom experience, self-efficacy, hope, resilience, and infection prevention behaviors. Data were analyzed using SPSS/WIN 20.0 and AMOS 18.0. RESULTS: Lower depression (γ=-.33, p=.020) and symptom experience (γ=-.31, p=.012) and higher self-efficacy (γ=.32, p=.005) and hope (γ=.48, p=.016) were influenced by higher social support. Greater resilience was influenced by lower symptom experience (β=-.18, p=.016), higher self-efficacy (β=.49, p=.023), and higher hope (β=.46, p=.012), and these predictors explained 66.7% of variance in resilience. Greater resilience (β=.54, p=.009) made an impact on greater infection prevention behaviors. Resilience mediated the relations of symptom experience (β=-.10 p=.013), self-efficacy (β=.27, p=.006) and hope (β=.25, p=.009) with infection prevention behaviors. These predictors explained 24.9% of variance in infection prevention behaviors. CONCLUSION: The findings of the study suggest that breast cancer patientsw ith greater resilience who are receiving chemotherapy participate in increased infection prevention behaviors. Further research should be conducted to seek intervention strategies that improve breast cancer patients' resilience.
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Humanos , Neoplasias da Mama , Mama , Depressão , Tratamento Farmacológico , Esperança , Controle de Infecções , Resiliência PsicológicaRESUMO
Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two complexes [Mo(IV)O(bdt)2](2-) and [Mo(VI)O2(bdt)2](2-) (bdt = benzene-1,2-dithiolate(2-)) that relate to the reduced and oxidized forms of sulfite oxidase (SO). These are compared with those of previously studied dimethyl sulfoxide reductase (DMSOr) models. DFT calculations supported by the data are extended to evaluate the reaction coordinate for oxo transfer to a phosphite ester substrate. Three possible transition states are found with the one at lowest energy, stabilized by a P-S interaction, in good agreement with experimental kinetics data. Comparison of both oxo transfer reactions shows that in DMSOr, where the oxo is transferred from the substrate to the metal ion, the oxo transfer induces electron transfer, while in SO, where the oxo transfer is from the metal site to the substrate, the electron transfer initiates oxo transfer. This difference in reactivity is related to the difference in frontier molecular orbitals (FMO) of the metal-oxo and substrate-oxo bonds. Finally, these experimentally related calculations are extended to oxo transfer by sulfite oxidase. The presence of only one dithiolene at the enzyme active site selectively activates the equatorial oxo for transfer, and allows facile structural reorganization during turnover.