bluuebunny/crossref_metadata_2025 huggingface dataset:
Transcriptome-wide and expression analysis of the NAC gene family in pepino (Solanum muricatum) during drought stress
Authors: Yang Shipeng , Zhu Haodong , Huang Liping , Zhang Guangnan , Wang Lihui , Jiang Xiaoting , Zhong Qiwen
Published: March 2021

Solanum muricatum(Pepino) is an increasingly popular solanaceous crop and is tolerant of drought conditions. In this study, 71 NAC transcription factor family genes ofS. muricatumwere selected to provide a theoretical basis for subsequent in-depth study of their regulatory roles in the response to biological and abiotic stresses, and were subjected to whole-genome analysis. The NAC sequences obtained by transcriptome sequencing were subjected to bioinformatics prediction and analysis. Three concentration gradient drought stresses were applied to the plants, and the target gene sequences were analyzed by qPCR to determine their expression under drought stress. The results showed that theS. muricatumNAC family contains 71 genes, 47 of which have conserved domains. The protein sequence length, molecular weight, hydrophilicity, aliphatic index and isoelectric point of these transcription factors were predicted and analyzed. Phylogenetic analysis showed that theS. muricatumNAC gene family is divided into seven subfamilies. Some NAC genes ofS. muricatumare closely related to the NAC genes of Solanaceae crops such as tomato, pepper and potato. The seedlings ofS. muricatumwere grown under different gradients of drought stress conditions and qPCR was used to analyze the NAC expression in roots, stems, leaves and flowers. The results showed that 13 genes did not respond to drought stress while 58 NAC genes ofS. muricatumthat responded to drought stress had obvious tissue expression specificity. The overall expression levels in the root were found to be high. The number of genes at extremely significant expression levels was very large, with significant polarization. Seven NAC genes with significant responses were selected to analyze their expression trend in the different drought stress gradients. It was found that genes with the same expression trend also had the same or part of the same conserved domain. Seven SmNACs that may play an important role in drought stress were selected for NAC amino acid sequence alignment ofSolanaceaecrops. Four had strong similarity to other Solanaceae NAC amino acid sequences, and SmNAC has high homology with theSolanum pennellii. The NAC transcription factor family genes ofS. muricatumshowed strong structural conservation. Under drought stress, the expression of NAC transcription factor family genes ofS. muricatumchanged significantly, which actively responded to and participated in the regulation process of drought stress, thereby laying foundations for subsequent in-depth research of the specific functions of NAC transcription factor family genes ofS. muricatum.
Study of Gas-solid-solid Three-phase Flow in Non-Powered Separator
Authors: Huang Weiyi , Shi Jinfa , Yang Jie , Ma Junxu
Published: March 2021

The non-powered separator is one of the key equipment in the dry sand production line, which is responsible for the separation of coarse and fine materials. In this paper, based on the turbulence Standard  Model, the air sand powder three-phase fluid model is simplified to gas-solid-solid three-phase flow, and the 3D model of the non-powered separator was built. The process of sand powder separation was simulated by using Fluent software. It is found that the larger the air volume control valve blade angle is, the more sand is removed, and the blade angle can be adjusted in the range of 15° to 60° according to the actual needs in industrial production.
Echocardiographic Evaluation of Patients with Chronic Obstructive Pulmonary Disease
Authors: Goudar Shishirakumar A. , Patil Virendra Chandrashekhar
Published: March 2021

There is an overlap of risk factors between heart disease and COPD like cigarette smoking, sedentary lifestyle and old age. The economic burden of COPD is also very high. It is now proven that the only strategy which can reduce COPD incidence is cessation of smoking. The Aim of the present research is to study the Two-dimensional transthoracic Echocardiography (TTE) findings in patients with chronic obstructive pulmonary disease (COPD).The method is that all the enrolled patients were subjected to chest radiography, pulmonary function test, Two-dimensional transthoracic echocardiogram and Doppler study, according to the standard protocol. The findings in our study are consistent with previous studies about the COPD. Total 111(60.7%) of the patients had echocardiographic evidence of pulmonary hypertension and 83(45.4%) of the patients in this study had evidence of cor pulmonale.  We found significant difference between the duration of smoking and severity of the disease based on FEV1 values (p= 0.005). A significant moderate inverse correlation existed between pack years of smoking and FEV1 scores. (r= - 0.379, P < 0.001).
Colistimethate Sodium Dosing and Nephrotoxicity among in-Patients at Tertiary Care Hospital Karachi, Pakistan
Authors: Arif Javeria Mohammad , Baig Mirza Tasawer , Shahid Uzma , Huma Ambreen , Sheikh Samina , Jabeen Aisha , Pirzada Quratul Ain , Shaikh Saba , Rawat Arva , Kadir Abdul , Kashif Muhammad
Published: March 2021

Introduction: Colistimethate sodium (CMS) is a polymyxin group of antibiotics which were throw out for many years, due to their potential adverse reaction neurotoxicity and nephrotoxicity. The different guidelines were reported regarding CMS dosing some based on Creatinine clearance (CrCl) and some on weight and CrCl. There are many discrepancies in the prevalence of nephrotoxicity that has been reported which included various definitions of acute renal injury and many CMS doses used in a variety of literature. In EMA guideline they suggested the dose as 9 MIU which is equivalent to 300 mg of CBA given as a maintenance dose with normal renal function patients.  In FDA standard dosing of CMS remains 5 mg/kg CBA per day used and also dose is dependent on patient weight. The aim of this study was to evaluate the dosing criteria of colistimethate sodium associated with nephrotoxicity.

Methodology: A prospective observational study was conducted in private sector tertiary care hospital in Karachi, Pakistan, for duration of six months from July 2020 to December 2020. Sample size was comprised of 157 patients, calculated at 35% prevalence, 95% Confidence Interval and 7% margin of error. Patient included were ≥ 18 years of age, who have received intravenous CMS therapy for greater than 48 hours. Patients having an acute kidney injury or on dialysis (at start of therapy) were excluded. Loading dose and daily dose of CMS was calculated by using actual body weight and Creatinine clearance (CrCl). Cockcroft and Gault equation was used to estimate CrCl before and after the therapy. Nephrotoxicity was assessed by using the RIFLE criteria. SPSS-20 was used for frequency distribution and percentage calculation to show categorical variable.

Results: Among 157 enrolled patients, 101 (64.3%) were male and 56(35.7%) were female (Table 1). Table 2. represents that 68(43.3%) patients were admitted in intensive care unit (ICU) and 89(56.7%) were in medicinal ward; 22.9% patients were in between the age range 60-70 years (Table 3). Among all patients 63(40.1%) patients were at risk of nephrotoxicity, 27(17.2%) patients were developing injury and 14(8.9%) patients were diagnosed to kidney failure and 53(33.8%) patients were found not to developed nephrotoxicity (Table 4). Table 5 exhibits that 48.4% of the patients were receiving dose of CMS using EMA guideline while 51.6% patients were receiving dose of CMS 2.5-5 mgCBA/kg/day according to FDA. Nephrotoxicity was high among FDA regimen (44.5%).

Conclusion: It was concluded that CMS dosing criteria have a significant impact on nephrotoxicity. Close monitoring of renal function, particularly the first week of CMS therapy should be considered to evaluate the renal toxicity of CMS.
Assessment of the Infections and Use of Antibiotics in Pregnancy among the Pregnant Women Reported at Gynae Opd Civil Hospital Khairpur Mirs Pakistan
Authors: Pathan Nusrat Fozia , Ramejo Bushra , Khuhro Bushra Noor , Jamali Anwar Ali , Shaikh Farheen , Ain Qurat Ul , Ahmer Arslan
Published: March 2021

Introduction: Pregnancy presents uncommon issues regarding anti-infection treatment. A significant concern is the conceivable teratogenic or harmful impact on the fetus.

Objectives: The objectives of this study are to assess the infections and use of antibiotics in pregnancy among the pregnant women reported at Gynae OPD Civil Hospital Khairpur Mirs Pakistan.

Methodology: This was an observational cross-section study conducted at Gynae OPD Civil Hospital Khairpur Mirs Pakistan from July 2020 to January 2021. A total of 400 sample size was calculated by using Slovin’s Formula. Data were collected by purposive sampling technique. Finally, collected data were analyzed by using a statistical package for social science (SPSS) software version 24. 

Results: Results reported commonly prescribed antibiotics during the pregnancy in which Phenoxymethylpenicillin was most commonly prescribed i.e. 31% and it was indicated for Maxillary sinusitis 40% and Acute tonsillitis 74%. The infections which were diagnosed during pregnancy among which vaginal candidiasis was high 117 (29.2%). Common antibiotics duration of treatment was observed in which penicillin frequency for 8-10 days was high 39 (9.7%). Common prescribed antibiotic dosages during pregnancy were observed in which the frequency of penicillin's recommended dose was high at 80 (20%). Antibiotics timing during pregnancy was observed in which Metronidazole+Tinidazole were mostly used during II trimester.

Conclusion: The antibiotics use in Khairpur Mirs is very high. The dosage regiment should be properly monitored, according to the pharmacokinetic data of particular antibiotics during the pregnancy.
Coffee pulp accelerates early tropical forest succession on old fields
Authors: Cole Rebecca J. , Zahawi Rakan A.
Published: March 2021

Applying nutrient‐rich agricultural by‐products, such as fruit peels and pulp, to degraded land has been proposed as a strategy to overcome a number of barriers to tropical forest recovery. While such linkages between agroindustry and restoration represent win–win scenarios, practical applications remain largely unexplored. In this case study, we tested coffee pulp as an amendment to catalyze forest succession on post‐agricultural land in southern Costa Rica.

A 0.5‐m‐deep layer of coffee pulp was deposited across a 35 × 40‐m area and an adjacent similar‐sized control plot (no coffee pulp addition) was delineated. Over 2 years, we measured changes in soil nutrients, ground cover, understory vegetation, tree establishment and canopy cover across both coffee pulp and control treatments.

Our results show that soil carbon, nitrogen, and phosphorous were substantially elevated in the coffee pulp compared to control treatment after 2 years. Coffee pulp addition significantly altered the ground cover characteristics, eliminating pasture grasses, facilitating establishment of herbaceous plants and increasing the percent area covered by leaf litter.

Early‐successional trees and shrubs established quickly in the coffee pulp treatment, reaching 30‐fold greater mean basal area and 20‐fold greater woody stem density (>1‐cm‐dbh) compared to the control treatment. Structural metrics showed fourfold greater mean canopy height in the coffee pulp compared to control treatment. Canopy height >5 m was ∼40% in the coffee pulp but was negligible (<3%) in the control treatment.

Our study highlights the significant potential for using agricultural waste, such as coffee pulp, to jump start forest succession on degraded tropical lands and encourages further research to optimize linkages between agroindustry and restoration.
Teratogenic and Neurotoxic Effects of n-Butanol on Zebrafish Development
Authors: Köktürk Mine , Çomaklı Selim , Özkaraca Mustafa , Alak Gonca , Atamanalp Muhammed
Published: March 2021

In recent years, n-butanol, a type of alcohol, has been widely used from the chemical industry to the food industry. In this study, toxic effects of n-butanol's different concentrations (10, 50, 250, 500, 750, 1,000, and 1,250 mg/L) in Zebrafish Danio rerio embryos and larvae were investigated. For this purpose, Zebrafish embryos were exposed to n-butanol in acute semistatic applications. Teratogenic effects such as cardiac edema, scoliosis, lordosis, head development abnormality, yolk sac edema, and tail abnormality were determined at different time intervals (24, 48, 72, 96, and 120 h). Additionally, histopathological abnormalities such as vacuole formation in brain tissue and necrosis in liver tissue were observed at high doses (500, 750, and 1,000 mg/L) in all treatment groups at 96 h. It was determined that heart rate decreased at 48, 72, and 96 h due to an increase in concentration. In addition, alcohol-induced eye size reduction (microphthalmia) and single eye formation (cyclopia) are also among the effects observed in our research findings. In conclusion, n-butanol has been observed to cause intense neurotoxic, teratogenic, and cardiotoxic effects in Zebrafish embryos and larvae.
Variation in thyroid volumes due to differences in the measured length or area of the cross‐sectional plane: A validation study of the ellipsoid approximation method using CT images
Authors: Fujita Naotoshi , Kato Katsuhiko , Abe Shinji , Naganawa Shinji
Published: March 2021

Purpose

This study examined the variation in the thyroid volume determined by the ellipsoid approximation method due to differences in the measured length or area of the cross‐sectional plane of CT images.

Methods

Forty‐five patients with Graves' disease were included in this retrospective study. We designated the three‐dimensional thyroid volumes extracted manually (VCT) as the reference data and calculated five approximate volumes for comparison: (a) the mean volume of 8100 different thyroid volumes depending on the diameter of the cross‐sectional plane at the midpoint of the major axis, (Vellipsoid,mean); (b) the volume using the maximum diameter and its orthogonal diameter, (Vellipsoid,maxlength); (c) the maximum (Vellipsoid,maxvolume); (d) minimum (Vellipsoid,minvolume) of the 8100 thyroid volumes; and (e) the volume determined with an equivalent circle diameter, (Vellipsoid,Heywood).

Results

Thyroid volumes obtained via the ellipsoid approximation method varied depending on the diameter of the cross‐sectional plane and included a mean error of approximately 20%, while the concordance correlation coefficient (CCC) differed for each approximate volume. Among these volumes, Vellipsoid,mean and Vellipsoid,Heywood were in good agreement with VCT, according to single regression analyses and the resultant CCC values, with mean errors of 0.1% and 10.4%, respectively.

Conclusion

While Vellipsoid,Heywood approximated thyroid volumes with vastly reduced errors, we recommend utilizing three‐dimensional thyroid volumetry if measurement accuracy is required.
A method for quantitative evaluations of scanning‐proton dose distributions
Authors: Allred Bryce C. , Shan Jie , Robertson Daniel G. , DeWees Todd A. , Shen Jiajian , Liu Wei , Stoker Joshua B.
Published: March 2021

Purpose

Patient‐Specific Quality Assurance (PSQA) measurement analysis depends on generating metrics representative of calculation and measurement agreement. Considering the heightened capability of discrete spot scanning protons to modulate individual dose voxels, a dose plane comparison approach that maintained all of the capabilities of the well‐established γ test, but that also provided a more intuitive error parameterization, was desired.

Methods

Analysis was performed for 300 dose planes compared by searching all calculated points within a fixed radius around each measured pixel to determine the dose deviation. Dose plane agreement is reported as the dose difference minimum (DDM) within an empirically established search radius: ΔDmin(r). This per‐pixel metric is aggregated into a histogram binned by dose deviation. Search‐radius criteria were based on a weighted‐beamlet 3σ spatial deviation from imaging isocenter. Equipment setup error was mitigated during analysis using tracked image registration, ensuring beamlet deviations to be the dominant source of spatial error. The percentage of comparison points with <3% dose difference determined pass rate.

Results

The mean beamlet radial deviation was 0.38mm from x‐ray isocenter, with a standard deviation of 0.19mm, such that 99.9% of relevant pencil beams were within 1 mm of nominal. The dose‐plane comparison data showed no change in passing rate between a 3%/1mm ΔDmin(r) analysis (97.6 +/‐ 3.6%) and a 3%/2mm γ test (97.7 +/‐ 3.2%).

Conclusions

PSQA dose‐comparison agreements corresponding to a search radius outside of machine performance limits are likely false positives. However, the elliptical shape of the γ test is too dose‐restrictive with a spatial‐error threshold set at 1 mm. This work introduces a cylindrical search shape, proposed herein as more relevant to plan quality, as part of the new DDM planar‐dose comparison algorithm. DDM accepts all pixels within a given dose threshold inside the search radius, and carries forward plan‐quality metrics in a straightforward manner for evaluation.
Effects of variable‐width jaw motion on beam characteristics for Radixact Synchrony®
Authors: Ferris William S. , Culberson Wesley S. , Smilowitz Jennifer B. , Bayouth John E.
Published: March 2021

Purpose

Radixact Synchrony corrects for target motion during treatment by adjusting the jaw and MLC positions in real time. As the jaws move off axis, Synchrony attempts to adjust for a loss in output due to the un‐flattened 6 MV beam by increasing the jaw aperture width. The purpose of this work was to assess the impact of the variable‐width aperture on delivered dose using measurements and simulations.

Methods

Longitudinal beam profile measurements were acquired using an Edge diode with static gantry. Jaw‐offset peak, width, and integral factors were calculated for profiles with the jaws in the extreme positions using both variable‐width (Synchrony) and fixed‐width apertures. Treatment plans with target motion and compensation were compared to planned doses to study the impact of the variable aperture on volumetric dose.

Results

The jaw offset peak factor (JOPF) for the Synchrony jaw settings were 0.964 and 0.983 for the 1.0‐ and 2.5‐cm jaw settings, respectively. These values decreased to 0.925 and 0.982 for the fixed‐width settings, indicating that the peak value of the profile would decrease by 7.5% compared to centered if the aperture width was held constant. The IMRT dose distributions reveal similar results, where gamma pass rates are above tolerance for the Synchrony jaw settings but fall significantly for the fixed‐width 1‐cm jaws.

Conclusions

The variable‐width behavior of Synchrony jaws provides a larger output correction for the 1‐cm jaw setting. Without the variable‐aperture correction, plans with the 1‐cm jaw setting would underdose the target if the jaws spend a significant amount of time in the extreme positions. This work investigated the change in delivered dose with jaws in the extreme positions, therefore overall changes in dose due to offset jaws are expected to be less for composite treatment deliveries.
Decreased Levels of STAT1 and Interferon‐γ–Induced STAT1 Phosphorylation in Rheumatoid Arthritis CD4 and CD8 T Cells
Authors: Sharma Vishal , Pope Brandon J. , Santiago Nathan V. , Boland Molly T. , Sun Dongmei , Reynolds Richard J. , Szalai Alexander J. , Bridges S. Louis , Raman Chander
Published: March 2021

Objective

We investigated whether a previously reported association of IFNGR expression with rheumatoid arthritis (RA) and its radiographic severity reflects differences in proximal interferon‐γ (IFN‐γ) signaling in T cells from patients with RA compared with healthy controls (HC).

Methods

Using phosphoflow cytometry, we compared IFN‐γ–stimulated signal transducer and activator of transcription 1 (STAT1) activation in CD4+ and CD8+ T‐cell populations from patients with RA and HC.

Results

Compared with controls, patients with RA had a higher proportion of CD4+ T cells, associated with expansion of the CD4+ effector memory subset. Several CD4+ T‐cell types exhibited reduced IFN‐γ–induced phosphoSTAT1Y701 (pSTAT1Y701) in patients with RA compared with HC. Engaging the T‐cell receptor (TCR) complex on CD4+ T cells during IFN‐γ stimulation abrogated the reduction in STAT1 activation in patients with RA but had no effect in HC. The phosphorylation of STAT1S727 was similar in CD4+ T cells from patients with RA and HC. In contrast to CD4+ T cells, IFN‐γ–induced pSTAT1Y701 levels in CD8+ T cells were equivalent or higher in patients with RA compared with HC. Total STAT1 levels (phosphorylated + unphosphorylated) were lower in CD4+ and CD8+ T cells from patients with RA compared with HC.

Conclusion

We report diminished IFN‐γ–induced pSTAT1Y701 levels in CD4+ T cells in patients with RA, which were restored by TCR engagement. There were lower levels of total STAT1 in patients with RA compared with HC, but this likely does not explain diminished IFN‐γ–induced pSTAT1Y701 levels in CD4+ T cells because activation in CD8+ T cells was higher or equivalent to that seen in HC. The enhanced IFNGR expression in patients with RA reported previously may reflect a compensatory mechanism to overcome deficiency in IFN‐γ responsiveness.
Recurrent ganglioneuroma in PTPN11‐associated Noonan syndrome: A case report and literature review
Authors: Morales‐Rosado Joel A. , Singh Herchran , Olson Rory J. , Larsen Brandon T. , Hager Megan M. , Klee Eric W. , Dhamija Radhika
Published: March 2021

Noonan syndrome (NS) is an autosomal dominant condition with variable expressivity most commonly due to a germline pathogenic variant in PTPN11, which encodes the protein tyrosine phosphatase SHP‐2. Gain‐of‐function variants in PTPN11 are known to promote oncogenic behavior in affected tissues. We report the clinical description of a young adult male presenting with relapsing ganglioneuromas, dysmorphic features, cardiac abnormalities, and multiple lentigines, strongly suspicious for NS. Solid tumor testing identified the recurrent pathogenic c.922G>A (p.Asn308Asp) in PTPN11. Proband and parental blood sampling testing confirmed c.922G>A as a de novo germline alteration. Comprehensive literature review of solid tumors specifically associated to PTPN11, indicates that this is the first documentation of ganglioneuroma and its clinical recurrence after resection in conjunction with a genetically confirmed NS diagnosis. The findings in our patient further extend the list of neuroblastic and neural crest‐derived neoplasms associated with this condition.
Entdeckung und Biosynthese eines strukturdynamischen antibakteriellen Diterpenoids
Authors: Zhu Chenxi , Xu Baofu , Adpressa Donovon A. , Rudolf Jeffrey D. , Loesgen Sandra
Published: March 2021

Ein neues bicyclisches Diterpenoid, Benditerpensäure, wurde aus einem im Erdreich vorkommenden Streptomyceten‐Stamm (CL12‐4) isoliert. Wir sequenzierten das Bakteriengenom, identifizierten den verantwortlichen Biosynthesegencluster, verifizierten die Funktion der Terpensynthase und produzierten heterolog das Diterpenoid‐Grundgerüst. Vergleichende Bioinformatik zeigte, dass dieser Streptomyceten‐Stamm phylogenetisch einzigartig ist und neun Terpensynthasen besitzt. Die absoluten Konfigurationen der neuen trans‐fusionierten Bicyclo[8.4.0]tetradecane wurden durch umfangreiche spektroskopische Analysen erreicht, einschließlich Moshers Analyse, NMR‐basierter Kopplungsanalyse, sowie DFT Berechnungen auf Basis von experimentellen NMR Parametern. Interessanterweise liegt Benditerpensäure in Lösung in zwei Ringkonformationen vor. Die Rotationsbarriere beträgt ca. 16 kcal mol−1. Die Diterpenoide zeigen mäßige antibakterielle Aktivität gegen Gram‐positive Bakterien, einschließlich Methicillin‐resistenten und multiresistenten Staphylococcus aureus. Hier präsentieren wir die erste Isolierung eines bakteriellen Eunicellan‐Diterpenoids und die Identifizierung der Diterpensynthase und des Biosynthesegenclusters, der für den Aufbau des bakteriellen Eunicellan‐Gerüsts verantwortlich ist.
Stabilization of the Elusive 9‐Carbene‐9‐Borafluorene Monoanion
Authors: Wentz Kelsie E. , Molino Andrew , Weisflog Sarah L. , Kaur Aishvaryadeep , Dickie Diane A. , Wilson David J. D. , Gilliard Robert J.
Published: March 2021

Two‐electron reduction of carbene‐supported 9‐bromo‐9‐borafluorenes with excess KC8, Na, or Li‐naphthalenide affords six N‐heterocyclic carbene (NHC)‐ or cyclic(alkyl)(amino) carbene (CAAC)‐stabilized borafluorene anions (3–8)‐the first isolated and structurally authenticated examples of the elusive 9‐carbene‐9‐borafluorene monoanion. The electronic structure, bonding, and aromaticity of the boracyclic anions were comprehensively investigated via computational studies. Compounds 5 and 8 react with metal halides via salt elimination to give new B‐E (E=Au, Se, Ge)‐containing materials (9–12). Upon reaction with diketones, the carbene ligand cleanly dissociates from 5 or 8 to yield new B‐O containing spirocycles (13–14) that cannot be easily obtained using “normal” valent borafluorene compounds. Collectively, these results support the notion that carbene‐stabilized monoanionic borafluorenes may serve as a new platform for the one‐step construction of higher‐value boracyclic materials.
Explore the effects of Shidan granules on chronic atrophic gastritis using LC–MS based plasma metabolomics study
Authors: Xi Zhaohong , Wang Min , Xia Junquan , Li Hui , Hua Yongzhi , Xu Tingting , An Zhentao , Tian Yaozhou
Published: March 2021

Shidan granule (SDG), a traditional Chinese medicine in‐hospital preparation, has been demonstrated to exert good effects on chronic atrophic gastritis (CAG) in clinics. However, the underlying mechanism of SDG against CAG is still unclear. This study utilized an untargeted plasma metabolomics approach to explore the potential mechanism of SDG in CAG rats using LC–MS and pattern recognition analysis. The results indicated that SDG could effectively improve the biochemical indexes and pathology features of CAG rats. Nineteen potential biomarkers (variable importance in projection > 1 and P < 0.05) contributing to CAG progress were identified. After SDG intervention, 17 biomarkers were obviously restored to normal levels. Further metabolic pathway analysis showed that aspartate and glutamate metabolism, arachidonic acid metabolism, arginine and proline metabolism, and TCA cycle were the most related pathways for SDG treatment. Based on these findings, the main mechanisms of SDG against CAG might be attributed to the regulatory effects of energy balance, inflammatory suppression, and improvement in disturbed amino acid and lipid metabolism. This study provided information for the mechanism research of SDG against CAG and would promote its clinical application.
Disparities in male versus female oncologic outcomes following bladder preservation: A population‐based cohort study
Authors: Ballas Leslie K. , Navarro Stephanie , Luo Chunqiao , Fossum Croix C. , Farias Albert , Daneshmand Siamak , Groshen Susan
Published: March 2021

Introduction

In surgical series of muscle‐invasive bladder cancer (MIBC), women have higher recurrence rates, disease progression, and mortality following radical cystectomy than men. Similar reports of oncologic differences between men and women following trimodality therapy (TMT) are rare. Our hypothesis was that there would be no difference in overall survival (OS) between sexes receiving TMT.

Methods

We queried the National Cancer Database (NCDB) for patients diagnosed with clinical stage T2‐T4aN0 M0 MIBC between 2004–2016. We considered patients to have received TMT if they received 55 Gy in 20 fractions or 59.4–70.2 Gy of radiotherapy with concurrent chemotherapy following a transurethral resection of bladder tumor (TURBT). We used multivariable Cox proportional hazard models to determine whether sex was associated with risk of mortality. In addition to OS, we calculated relative survival (RS) to adjust for the fact that females generally survive longer than males.

Results

Of the patients, 1960 underwent TMT and had survival data. Less than one quarter were female. In the first year following treatment, women had worse OS and RS than men (p = 0.093 and p = 0.030, respectively). However, overall and relative survival differences between sexes were not statistically significantly different in Years 2 and later. Unlike with OS, the RS between sexes remained significant at 9 years; in multivariable analysis based on RS, women were 43% more likely to die than men (p < 0.001).

Conclusions

Women had a higher initial risk of death than men in the first year following TMT. However, long‐term survival between sexes was similar. TMT is an important treatment option in both men and women seeking bladder preservation.
Lantana camara Essential Oils from Vietnam: Chemical Composition, Molluscicidal, and Mosquito Larvicidal Activity
Authors: Huy Hung Nguyen , Ngoc Dai Do , Satyal Prabodh , Thi Huong Le , Thi Chinh Bui , Quang Hung Dinh , Anh Tai Thieu , Setzer William N.
Published: March 2021

Lantana camara is a troublesome invasive plant introduced to many tropical regions, including Southeast Asia. However, the plant does hold promise as a source of essential oils that may be explored for potential use. Fresh water snails such as Pomacea canaliculata, Gyraulus convexiusculus, and Tarebia granifera can be problematic agricultural pests as well as hosts for parasitic worms. Aedes and Culex mosquitoes are notorious vectors of numerous viral pathogens. Control of these vectors is of utmost importance. In this work, the essential oil compositions, molluscicidal, and mosquito larvicidal activities of four collections of L. camara from north‐central Vietnam have been investigated. The sesquiterpene‐rich L. camara essential oils showed wide variation in their compositions, not only compared to essential oils from other geographical locations (at least six possible chemotypes), but also between the four samples from Vietnam. L. camara essential oils showed molluscicidal activities comparable to the positive control, tea saponin, as well as other botanical agents. The median lethal concentrations (LC50) against the snails were 23.6–40.2 μg/mL (P. canaliculata), 7.9–29.6 μg/mL (G. convexiusculus), and 15.0–29.6 μg/mL (T. granifera). The essential oils showed good mosquito larvicidal activities with 24‐h LC50 values of 15.1–29.0 μg/mL, 26.4–53.8 μg/mL, and 20.8–59.3 μg/mL against Ae. aegypti, Ae. albopictus, and Cx. quinquefasciatus, respectively. The essential oils were more toxic to snails and mosquito larvae than they were to the non‐target water bug, Diplonychus rusticus (24‐h LC50=103.7–162.5 μg/mL). Sesquiterpene components of the essential oils may be acting as acetylcholinesterase (AChE) inhibitors. These results suggest that the invasive plant, L. camara, may be a renewable botanical pesticidal agent.
A case report of idiopathic Hemophagocytic lymphohistiocytosis in an immunocompetent adult
Authors: Rabadão Tiago , Naia Leonor , Ferreira Filipa , Teixeira Mariana , Aveiro Marcelo , Eulálio Margarida , Silva Fernando
Published: March 2021

Hemophagocytic lymphohistiocytosis poses a diagnostic dilemma due to the absence of specific clinical and laboratory findings, especially in adults. Despite greater recognition of the disease, secondary idiopathic forms are still reported.
Ileocecal and hepatic tuberculosis mimicking a metastatic cecal malignancy: Case report
Authors: Ben Ismail Imen , Rebii Saber , Ben Chaabane Hamadi , Hakim Zenaidi , Zoghlami Ayoub
Published: March 2021

We wish to highlight that on encountering a suspicious hepatic and a colonic lesion, the possibility of TB should also be kept in mind apart from the obvious possibility of metastasis of a colonic cancer especially in an endemic country like Tunisia.
Porous FeO(OH) Dispersed on Mg‐Al Hydrotalcite Surface for One‐Pot Synthesis of Quinoline Derivatives
Authors: Motokura Ken , Ozawa Nao , Sato Risako , Manaka Yuichi , Chun Wang‐Jae
Published: March 2021

The use of ubiquities elements such as iron instead of expensive precious metals as catalysts is one goal toward realizing environmentally benign synthetic chemistry. Here, we report that porous FeO(OH) dispersed on Mg−Al hydrotalcite acts as a bifunctional heterogeneous catalyst in the one‐pot synthesis of 2‐substituted quinoline derivatives through dehydrogenative oxidation‐cyclization reactions. The catalyst was prepared by a simple grafting method using FeCl3 and Mg−Al hydrotalcite. The prepared porous FeO(OH) possesses a higher surface area than those previously reported for α‐FeO(OH) particles. The one‐pot quinoline synthesis proceeded effectively under non‐noble‐metal catalysis in air without requiring additional homogeneous bases or solvents.
Sulfur‐Induced Growth of Coordination Polymer Derived‐Straight Carbon Nanotubes on Carbon Nanofiber Network for Zn‐Air Batteries
Authors: Wang Xian , Du Yujing , Chai Lulu , Ding Junyang , Zhong Li , Miao Ting‐Ting , Hu Yue , Qian Jinjie , Huang Shaoming
Published: March 2021

Low‐cost heteroatom‐doped carbon nanomaterials have been widely studied for efficient oxygen reduction reaction and energy storage and conversion in metal‐air batteries. A Masson pine twigs‐like 3‐dimensional network construction of carbon nanofibers (CNFs) with abundant straight long Co, N, and S‐doped carbon nanotubes (CNTs) is developed by thermal treatment of Co‐based polymer coated onto polyacrylonitrile nanofiber network together with thiourea at 900 °C, denoted as CNFT‐Co9S8‐900. It is interesting to note that the introduction of a high concentration of sulfur does not lead to the complete toxicity of catalysts, but promotes the axial growth to selectively form straight CNTs instead of curly bamboo‐like CNTs. The highly graphitized in‐situ grown Co, N, S‐doped CNTs and the 3‐dimensional N‐doped CNF network provide both active catalytic sites and highly conductive paths, which are beneficial for oxygen reduction reaction (ORR). Thus, the optimal CNFT‐Co9S8‐900 performs the excellent ORR catalytic activity with a half‐wave potential of 0.84 V and a diffusion‐limited current density of 5.49 mA cm−2. Furthermore, the CNFT‐Co9S8‐900‐based Zn‐air devices also possess a high power density of 136.9 mW cm−2 better than commercial Pt/C.
Photoinduced Electron vs. Concerted Proton Electron Transfer Pathways in SnIV (l‐Tryptophanato)2 Porphyrin Conjugates
Authors: Natali Mirco , Amati Agnese , Demitri Nicola , Iengo Elisabetta
Published: March 2021

Aromatic amino acids such as l‐tyrosine and l‐tryptophan are deployed in natural systems to mediate electron transfer (ET) reactions. While tyrosine oxidation is always coupled to deprotonation (proton‐coupled electron‐transfer, PCET), both ET‐only and PCET pathways can occur in the case of the tryptophan residue. In the present work, two novel conjugates 1 and 2, based on a SnIV tetraphenylporphyrin and SnIV octaethylporphyrin, respectively, as the chromophore/electron acceptor and l‐tryptophan as electron/proton donor, have been prepared and thoroughly characterized by a combination of different techniques including single crystal X‐ray analysis. The photophysical investigation of 1 and 2 in CH2Cl2 in the presence of pyrrolidine as a base shows that different quenching mechanisms are operating upon visible‐light excitation of the porphyrin component, namely photoinduced electron transfer and concerted proton electron transfer (CPET), depending on the chromophore identity and spin multiplicity of the excited state. The results are compared with those previously described for metal‐mediated analogues featuring SnIV porphyrin chromophores and l‐tyrosine as the redox active amino acid and well illustrate the peculiar role of l‐tryptophan with respect to PCET.
Synthesis and Properties of Partially Saturated Fluorenyl‐Derived [n]Helicenes Featuring an Overcrowded Alkene
Authors: Pallova Lenka , Gauthier Etienne S. , Abella Laura , Jean Marion , Vanthuyne Nicolas , Dorcet Vincent , Vendier Laure , Autschbach Jochen , Crassous Jeanne , Bastin Stéphanie , César Vincent
Published: March 2021

The straightforward, multigram‐scale synthesis of the partially saturated H6‐fluoreno[n]helicenes (n=5 or 7) featuring a central, overcrowded alkene is described. The key cyclization step was based on an intramolecular McMurry reaction from the corresponding 1,5‐diketones. Chiral stationary phase HPLC analysis and isomer separation indicate that each helicenic compound is constituted of three diastereoisomers at room temperature, i. e. the configurationally stable (R,R,P)/(S,S,M) pair of enantiomers and an apparently achiral compound resulting from the rapid interconversion between the (R,S,P) and (S,R,M) enantiomers. The partially saturated H6‐fluoreno[n]helicenes are oxidatively aromatized to give an efficient access to the corresponding fluoreno[n]helicenes. The chiroptical properties (vibrational and electronic circular dichroism) of the chiral, enantiopure compounds have been measured and analyzed by quantum‐chemical calculations, confirming their helicoidal nature.
Synthesis, Structure, and Chiroptical Properties of Indolo‐ and Pyridopyrrolo‐Carbazole‐Based C2‐Symmetric Azahelicenes
Authors: Taniguchi Taisei , Nishii Yuji , Mori Tadashi , Nakayama Ken‐ichi , Miura Masahiro
Published: March 2021

Treatment of 11,12‐bis(1,1’‐biphenyl‐3‐yl or 6‐phenylpyridin‐2‐yl)‐substituted 11,12‐dihydro‐indolo[2,3‐a]carbazole with an oxidizing system of Pd(II)/Ag(I) induced effective double dehydrogenative cyclization to afford the corresponding π‐extended azahelicenes. The optical resolutions were readily achieved by a preparative chiral HPLC. It was found that the pyridopyrrolo‐carbazole‐based azahelicene that contains four nitrogen atoms exhibits ca. 6 times larger dissymmetry factors both in circularly dichroism (CD) and circularly polarized luminescence (CPL), |gCD| and |gCPL| values being 1.1×10−2 and 4.4×10−3, respectively, as compared with the parent indolocarbazole‐based azahelicene. Theoretical calculations at the RI‐CC2 level were employed to rationalize the observed enhanced chiroptical responses. The (chir)optical properties of the former helicene was further tuned by a protonation leading to remarkable red‐shift with a considerable enhancement of the |gCPL| value.
A Novel M8L6 Cubic Cage That Binds Tetrapyridyl Porphyrins: Cage and Solvent Effects in Cobalt‐Porphyrin‐Catalyzed Cyclopropanation Reactions
Authors: Mouarrawis Valentinos , Bobylev Eduard O. , de Bruin Bas , Reek Joost N. H.
Published: March 2021

Confinement of a catalyst can have a significant impact on catalytic performance and can lead to otherwise difficult to achieve catalyst properties. Herein, we report the design and synthesis of a novel caged catalyst system Co−G@Fe8(Zn−L ⋅ 1)6, which is soluble in both polar and apolar solvents without the necessity of any post‐functionalization. This is a rare example of a metal‐coordination cage able to bind catalytically active porphyrins that is soluble in solvents spanning a wide variety of polarity. This system was used to investigate the combined effects of the solvent and the cage on the catalytic performance in the cobalt catalyzed cyclopropanation of styrene, which involves radical intermediates. Kinetic studies show that DMF has a protective influence on the catalyst, slowing down deactivation of both [Co(TPP)] and Co−G@Fe8(Zn−L ⋅ 1)6, leading to higher TONs in this solvent. Moreover, DFT studies on the [Co(TPP)] catalyst show that the rate determining energy barrier of this radical‐type transformation is not influenced by the coordination of DMF. As such, the increased TONs obtained experimentally stem from the stabilizing effect of DMF and are not due to an intrinsic higher activity caused by axial ligand binding to the cobalt center ([Co(TPP)(L)]). Remarkably, encapsulation of Co−G led to a three times more active catalyst than [Co(TPP)] (TOFini) and a substantially increased TON compared to both [Co(TPP)] and free Co−G. The increased local concentration of the substrates in the hydrophobic cage compared to the bulk explains the observed higher catalytic activities.
Chemical Bonding in Silicon Carbonyl Complexes
Authors: Sergeieva Tetiana , Mandal Debdeep , Andrada Diego M.
Published: March 2021

Although silylene‐carbonyl complexes are known for decades, only recently isolable examples have been accomplished. In this work, the bonding situation is re‐evaluated to explain the origins of their remarkable stability within the Kohn‐Sham molecular orbital theory framework. It is shown that the chemical bond can be understood as CO interaction with the silylene via a donor‐acceptor interaction: a σ‐donation from the σCO into the empty p‐orbital of silicon, and a π‐back donation from the sp2 lone pair of silicon into the π*CO antibonding orbitals. Notably, it was established that the driving force behind the surprisingly stable Si−CO compounds, however, is another π‐back donation from a perpendicular bonding R−Si σ‐orbital into the π*CO antibonding orbitals. Consequently, the pyramidalization of the central silicon atom cannot be associated with the strength of the π‐back donation, in sharp contrast to the established chemical bonding model. Considering this additional bonding interaction not only shed light on the bonding situation, but is also an indispensable key for broadening the scope of silylene‐carbonyl chemistry.
Lewis Acid‐Catalyzed Diels‐Alder Reactions: Reactivity Trends across the Periodic Table
Authors: Vermeeren Pascal , Tiezza Marco Dalla , van Dongen Michelle , Fernández Israel , Bickelhaupt F. Matthias , Hamlin Trevor A.
Published: March 2021

The catalytic effect of various weakly interacting Lewis acids (LAs) across the periodic table, based on hydrogen (Group 1), pnictogen (Group 15), chalcogen (Group 16), and halogen (Group 17) bonds, on the Diels‐Alder cycloaddition reaction between 1,3‐butadiene and methyl acrylate was studied quantum chemically by using relativistic density functional theory. Weakly interacting LAs accelerate the Diels‐Alder reaction by lowering the reaction barrier up to 3 kcal mol−1 compared to the uncatalyzed reaction. The reaction barriers systematically increase from halogen<hydrogen<chalcogen<pnictogen‐bonded LAs, i. e., the latter have the least catalytic effect. Our detailed activation strain and Kohn‐Sham molecular orbital analyses reveal that these LAs lower the Diels‐Alder reaction barrier by increasing the asynchronicity of the reaction to relieve the otherwise destabilizing Pauli repulsion between the closed‐shell filled π‐orbitals of diene and dienophile. Notably, the reactivity can be further enhanced on going from a Period 3 to a Period 5 LA, as these species amplify the asynchronicity of the Diels‐Alder reaction due to a stronger binding to the dienophile. These findings again demonstrate the generality of the Pauli repulsion‐lowering catalysis concept.
Intertwined Analytical, Experimental and Theoretical Studies on the Formation and Structure of a Copper Dienolate
Authors: Lecachey Baptiste , Palais Laetitia , de Courcy Benoît , Bouauli Samira , Durandetti Muriel , Oulyadi Hassan , Harisson‐Marchand Anne , Maddaluno Jacques , Gérard Hélène , Vrancken Emmanuel , Campagne Jean‐Marc
Published: March 2021

The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate catalytic species. Finally, we showed that that the copper catalyst promote the E/Z s‐cis/s‐trans equilibration of the silyl dienolate precursor through a copper dienolate intermediate. All of these results unveil some peculiarities of the catalytic and asymmetric vinylogous Mukaiyama reaction.
Supramolecular Coordination Cages Based on N‐Heterocyclic Carbene‐Gold(I) Ligands and Their Precursors: Self‐Assembly, Structural Transformation and Guest‐Binding Properties
Authors: Shi Wen‐Jie , Liu Dan , Li Xin , Bai Sha , Wang Yao‐Yu , Han Ying‐Feng
Published: March 2021

The incorporation of functional groups into the cavity of discrete supramolecular coordination cages (SCCs) will bring unique functions and applications. Here, three dicarboxylate ligands (H2L1Cl, H2L2Cl and H2L3Cl) containing N‐heterocyclic carbene (NHC) precursors as linkers were introduced to construct SCCs by combining with two C3‐symmertic (CpZr)3(μ3‐O)(μ2‐OH)3 clusters as three‐connect vertices, resulted in a series of rugby‐like V2E3 (V=vertex, E=edge) type homoleptic cages (SCC‐1, SCC‐2 and SCC‐3). However, V4E6‐type tetrahedral cages (SCC‐4 and SCC‐5), incorporating six Au‐NHC moieties, were obtained when the corresponding NHC‐gold(I) functionalized ligands (H2L1Au, H2L2Au) were applied. For the first time, we present a trackable CpZr‐involved cage to cage conversion to generate a heteroleptic V2E3 cage (SCC‐6) from two homoleptic cages (SCC‐2 and SCC‐5) with different geometries of V2E3 and V4E6. The heteroleptic assembly SCC‐6 can also be formed upon a subcomponent displacement strategy. The structural transformation and reassembly processes were detected and monitored by 1H NMR spectroscopy and electrospray‐ionization mass spectrometry. The formation of heteroleptic assembly was further supported by single crystal X‐ray diffraction analysis. Moreover, homoleptic cage SCC‐2 possesses a trigonal bipyramidal cationic cavity allowing the encapsulation of a series of sulfonate anionic guests.
Scaling Up DNA Origami Lattice Assembly
Authors: Xin Yang , Shen Boxuan , Kostiainen Mauri A. , Grundmeier Guido , Castro Mario , Linko Veikko , Keller Adrian
Published: March 2021

The surface‐assisted hierarchical assembly of DNA origami nanostructures is a promising route to fabricate regular nanoscale lattices. In this work, the scalability of this approach is explored and the formation of a homogeneous polycrystalline DNA origami lattice at the mica‐electrolyte interface over a total surface area of 18.75 cm2is demonstrated. The topological analysis of more than 50 individual AFM images recorded at random locations over the sample surface showed only minuscule and random variations in the quality and order of the assembled lattice. The analysis of more than 450 fluorescence microscopy images of a quantum dot‐decorated DNA origami lattice further revealed a very homogeneous surface coverage over cm2areas with only minor boundary effects at the substrate edges. At total DNA costs of € 0.12 per cm2, this large‐scale nanopatterning technique holds great promise for the fabrication of functional surfaces.
Reductive Rearrangement of a 1‐Phospha‐2‐azanorbornene
Authors: Wonneberger Peter , König Nils , Sárosi Menyhárt B. , Hey‐Hawkins Evamarie
Published: March 2021

The reduction of the 1‐phospha‐2‐azanorbornene derivate endo‐1 with lithium aluminium hydride leads to an unprecedented 1‐phosphabicyclo[3.2.1]octa‐2,5‐diene, while a phospholide anion is formed with lithium. The latter can be protonated resulting in formation of an unusual 2H‐phosphole dimer. Furthermore, 3H‐phospholes, previously assumed to have no synthetic relevance as intermediates, were proposed to act as dienophile in the dimerisation of 3,4‐dimethyl‐1‐phenylphosphole at elevated temperatures based on theoretical calculations.