bluuebunny/crossref_metadata_2025 huggingface dataset:
The Essential Role of Water Molecules in the Reaction Mechanism of Protein O‐Fucosyltransferase 2
Authors: Sanz‐Martínez Ignacio , García‐García Ana , Tejero Tomás , Hurtado‐Guerrero Ramón , Merino Pedro
Published: October 2022

Protein O‐fucosyltransferase 2 (PoFUT2) is an inverting glycosyltransferase (GT) that fucosylates thrombospondin repeats (TSRs) from group 1 and 2. PoFUT2 recognizes a large and diverse number of TSRs through a dynamic network of water‐mediated interactions. By X‐ray structural studies of C. elegans PoFUT2 complexed to a TSR of group 2, we demonstrate that this GT recognizes similarly the 3D structure of TSRs from both groups 1 and 2. Its active site is highly exposed to the solvent, suggesting that water molecules might also play an essential role in the fucosylation mechanism. We applied QM/MM methods using human PoFUT2 as a model, and found that HsPoFUT2 follows a classical SN2 reaction mechanism in which water molecules contribute to a great extent in facilitating the release of the leaving pyrophosphate unit, causing the H transfer from the acceptor nucleophile (Thr/Ser) to the catalytic base, which is the last event in the reaction. This demonstrates the importance of water molecules not only in recognition of the ligands but also in catalysis.
A Flexible Hydrogen‐Bonded Organic Framework Constructed from a Tetrabenzaldehyde with a Carbazole N−H Binding Site for the Highly Selective Recognition and Separation of Acetone
Authors: Chen Liangji , Yuan Zhen , Zhang Hao , Ye Yingxiang , Yang Yisi , Xiang Fahui , Cai Kaicong , Xiang Shengchang , Chen Banglin , Zhang Zhangjing
Published: October 2022

Rational design of hydrogen‐bonded organic frameworks (HOFs) with multiple functionalities is highly sought after but challenging. Herein, we report a multifunctional HOF (HOF‐FJU‐2) built from 4,4′,4′′,4′′′‐(9H‐carbazole‐1,3,6,8‐tetrayl)tetrabenzaldehyde molecule with tetrabenzaldeyde for their H bonding interactions and carbazole N−H site for its specific recognition of small molecules. The Lewis acid N−H sites allowHOF‐FJU‐2facilely separate acetone from its mixture with another solvent like methanol with smaller pKavalue. The donor (D)‐π‐acceptor (A) aromatic nature of the organic building molecule endows this HOF with solvent dependent luminescent/chromic properties, so the column acetone/methanol separation onHOF‐FJU‐2can be readily visualized.
Alkyl Formates as Transfer Hydroalkylation Reagents and Their Use in the Catalytic Conversion of Imines to Alkylamines**
Authors: Crochet Etienne , Anthore‐Dalion Lucile , Cantat Thibault
Published: October 2022

Easily accessible via a simple esterification of alcohols with formic acid, alkyl formates are used as a novel class of transfer hydroalkylation reagents, CO2 acting as a traceless linker. As a proof‐of‐concept, their reactivity in the transfer hydroalkylation of imines is investigated, using a ruthenium‐based catalyst and LiI as promoter to cleave the C−O σ‐bond of the formate scaffold. Providing tertiary amines, the reaction displays a divergent regioselectivity compared to previously reported transfer hydroalkylation strategies.
Correlation between Electrolyte Chemistry and Solid Electrolyte Interphase for Reversible Ca Metal Anodes
Authors: Hou Zhen , Zhou Rui , Yao Yunduo , Min Zhiwen , Lu Ziheng , Zhu Ye , Tarascon Jean‐Marie , Zhang Biao
Published: October 2022

The development of rechargeable Ca metal batteries (RCMBs) is hindered by the Ca2+ passivating solid electrolyte interphases (SEIs). The cation solvation structure dictated by electrolyte chemistry plays a critical role in the SEIs properties. While a relatively weak cation‐solvent binding is preferred in Li metal anodes to promote anion‐derived SEIs, we demonstrate an enhanced Ca deposition/stripping reversibility under a strong cation‐solvent interaction, which is materialized in strongly‐solvating solvent and highly‐dissociated salt combinations. Such electrolyte formulations benefit the formation of solvent‐occupied solvation structure and minimize the anion reduction, resulting in organic‐rich/CaF2‐poor SEIs for reversible Ca metal anodes. Furthermore, RCMBs paired with an organic cathode using the optimized electrolytes are demonstrated as a proof‐of‐concept. Our work reveals the paradigm shift in SEIs design for Ca metal anodes, opening up new opportunities for emerging RCMBs.
“A whole new perspective on how the body fits together”—An evaluation of a cadaver laboratory experience for high school students
Authors: Cale Andrew S. , Byram Jessica N. , Organ Jason M. , Schmalz Naomi A.
Published: October 2022

The Center for Anatomy and Physiology Education has hosted interactive human cadaver laboratory tours for local high schools (ages 14–18) and undergraduate university students since 2014 to expose students to healthcare careers. Students receive information on the history of body donation and healthcare careers and observe human anatomy on prosections and with isolated organs. The goal of this study was to evaluate students' perceptions of the anatomy laboratory tours and their impact on students' interests in healthcare careers. Students completed pre‐ and post‐tour questionnaires. Responses were analyzed using thematic analysis and linguistic inquiry. Of the 261 students who completed pre‐tour questionnaires, 204 (78%) completed the post‐tour questionnaire. Before the tour, students anticipated learning about human anatomy and expected to only see but not touch a cadaver. Most students expressed excitement and/or nervousness. A few students viewed the laboratory tour as an opportunity to test if they could see themselves in a healthcare career. After the tour, most students indicated that the tour either met or exceeded their expectations. Students found the laboratory tour to be educational and interesting and were surprised by the opportunity to interact with the donor. Numerous students expressed an increased interest in healthcare careers after the tour. Overall, students perceived the tour as an engaging experience that improved their anatomical knowledge and reinforced/increased their interest in healthcare careers. Academic institutions can positively impact local students by implementing an anatomy tour, sharing access to their in‐house human cadaver laboratory, and recruiting instructors to share their anatomy expertise.
Metal free, one pot 1,6‐Conjugate Addition of Diol on para‐Quinone Methide followed by ipso cyclization: An Approach to Spiro 1,4‐Dioxane cyclohexadienone Derivatives
Authors: Gaikwad Ramesh A. , Kamble Sumit B. , Waghmode Suresh B.
Published: October 2022

A novel one‐pot transition metal‐free and Brönsted acid mediated 1,6‐conjugate addition of bisnuleophilic diol on biselectrophilc para‐quinone methide followed by ipso cyclization assisted by NBS has been developed under mild reaction conditions, offers a new approach to synthesize spiro 1,4‐dioxane cyclohexadienone derivatives. This strategy features broad substrate scope of p‐QMs with high functional group tolerance and good yields of spirocyclic scaffolds (60–92 %). N‐Bromo succinimide an important role in an ipso spirocyclization with high efficiency.
An enhanced adaptive Kalman filtering for linear systems with inaccurate noise statistics
Authors: Fu Hongpo , Cheng Yongmei
Published: October 2022

This paper investigates the simultaneous state and noise covariance estimation for linear systems with inaccurate noise statistics. An enhanced adaptive Kalman filtering (EAKF) based on dynamic recursive nominal covariance estimation (DNRCE) and modified variational Bayesian (VB) inference is presented. The EAKF realizes the concurrently estimation of state and noise covariance matrices by introducing a nominal parameter in the traditional recursive covariance estimation and designing a new adaptive forgotten factor for the dynamic model of the estimated information propagation. The simulation of a target tracking example shows that, compared with the existing filters, the proposed filter has good adaptive performance for inaccurate and time‐varying noise covariance matrices.
Bayesian Parameterization of Continuum Battery Models from Featurized Electrochemical Measurements Considering Noise**
Authors: Kuhn Yannick , Wolf Hannes , Latz Arnulf , Horstmann Birger
Published: October 2022

Physico‐chemical continuum battery models are typically parameterized by manual fits, relying on the individual expertise of researchers. In this article, we introduce a computer algorithm that directly utilizes the experience of battery researchers to extract information from experimental data reproducibly. We extend Bayesian Optimization (BOLFI) with Expectation Propagation (EP) to create a black‐box optimizer suited for modular continuum battery models. Standard approaches compare the experimental data in its raw entirety to the model simulations. By dividing the data into physics‐based features, our data‐driven approach uses orders of magnitude less simulations. For validation, we process full‐cell GITT measurements to characterize the diffusivities of both electrodes non‐destructively. Our algorithm enables experimentators and theoreticians to investigate, verify, and record their insights. We intend this algorithm to be a tool for the accessible evaluation of experimental databases.
School age educational outcomes of infants born with congenital diaphragmatic hernia
Authors: Walden Alyssa R. , Nembhard Wendy N. , Akmyradov Chary , Goudie Anthony , ElHassan Nahed O.
Published: October 2022

Background

To compare academic proficiency among children with congenital diaphragmatic hernia (CDH) versus controls and identify predictors of academic performance among children with CDH.

Methods

Infants born with CDH in Arkansas, 2000–2005, were identified from the Arkansas Reproductive Health Monitoring System. For each case, two controls were selected from birth certificate data and matched for hospital and month of birth, sex, and race/ethnicity. Data on re‐hospitalization within the first 5 years and payer data were collected from the Arkansas Hospital Inpatient Discharge database. Surviving cases and controls were linked to the Arkansas Department of Education database. Primary outcomes were odds of proficiency on fourth grade literacy and mathematics achievement tests. Multivariable logistic regression models evaluated the association between study characteristics and academic proficiency.

Results

The final study cohort included 25 surviving CDH cases and 31 controls who were linked to their education data. After adjusting for differences in characteristics (5‐min Apgar score and associated congenital anomalies) between cases and controls, there were no statistically significant differences in literacy (72% vs. 84%, p = .93) or mathematics (64% vs. 81%, p = .98) test proficiency between the two groups. In multivariable analyses, among CDH cases, oxygen at discharge and Medicaid payer/longer hospital stay were associated with worse fourth grade literacy and mathematics proficiency, respectively.

Conclusions

Oxygen at discharge, Medicaid payer, and longer hospital stay were associated with lower academic performance among CDH cases.
Gamifying structural analysis assessments for first‐year architecture engineering students
Authors: Micheal Amany G. B.
Published: October 2022

The structural analysis module is a challenge for both teachers and students. The module content is usually presented to students in the form of a set of equations when solved, the structure of internal forces is obtained. Usually, the assignments adopted in such modules are paper‐based exams. Such a strategy may assess the capacity of the students to employ different sets of equations to solve a problem. However, this is not enough for a vivid educational atmosphere. Transforming these equations into a digital simulation is the best solution for the education process. Digitalization is more appealing to nowadays students and it gives the teacher a wide spectrum of discussions without the hindrance of calculations time. It is also a mitigation for the online teaching process during the Covid‐19 pandemic. This paper presents a digital simulation of different structures using a simple tool that enables students to visualize the simultaneous interaction between geometry, loading, boundary conditions, and internal forces. Furthermore, transforming this tool into an offline mobile app helps both the teacher and the student to gamify the investigation of any structure.
Utility of BerEp4/calretinin and desmin/epithelial membrane antigen (EMA) dual immunocytochemical staining in effusion cytology
Authors: Hjerpe Anders , Demir Enes , Abd‐Own Sulaf , Dobra Katalin
Published: October 2022

Background

Pleural mesothelioma (PM) is typically diagnosed late during the disease. Earlier detection can increase the chance of effective therapy. Recurrent pleural effusions are the earliest symptoms displaying an array of cytomorphological changes from reactive atypia to malignancy. Diagnosis is possible on effusion cytology by applying molecular and immunocytochemical markers, the main difficulty being when to suspect PM and to differentiate PM from metastatic adenocarcinoma and reactive mesothelial proliferations.

Methods

We evaluated the diagnostic performance of two immunocytochemical dual stains (BerEp4/Calretinin and Desmin/Epithelial Membrane Antigen (EMA)) on 149 ethanol‐fixed cytospin preparation as an initial step to solve the mentioned diagnostic difficulty. The immunocytochemical reactivity pattern was evaluated by two independent investigators. The final diagnosis corresponded to PM (n = 20), metastatic adenocarcinoma (n = 83), and mesotheliosis (n = 46) in these cases.

Results

Calretinin had 99% specificity and 98% sensitivity for indicating a mesothelial phenotype, while BerEp4 distinguished the adenocarcinoma cases with 98% specificity and 99% sensitivity. EMA displayed 96% specificity and 99% sensitivity in malignant cases, while Desmin without EMA present showed 99% specificity and 96% sensitivity for indicating benign mesothelial proliferation.

Conclusions

Interpretation of the four immunoreactions is improved when performed as dual stains. The dual staining is a useful tool in the initial handling of atypical effusions and guides the subsequent choice of antibody panels for more detailed subclassification of malignant effusions.
The feasibility and effects of a pharmacological treatment algorithm for cancer patients with terminal dyspnea: A multicenter cohort study
Authors: Mori Masanori , Yamaguchi Takashi , Suzuki Kozue , Matsuda Yoshinobu , Matsunuma Ryo , Watanabe Hiroaki , Ikari Tomoo , Matsumoto Yoshihisa , Imai Kengo , Yokomichi Naosuke , Miwa Satoru , Yamauchi Toshihiro , Okamoto Soichiro , Inoue Satoshi , Inoue Akira , Morita Tatsuya , Satomi Eriko ,   the Japanese Dyspnea Relief Investigators
Published: October 2022

Background

How clinicians treat patients with terminal dyspnea widely varies, which could hamper quality care. We visualized comprehensive pharmacological treatment delivered by palliative care physicians.

Aim

To examine adherence to a comprehensive pharmacological treatment algorithm for patients with terminal dyspnea, and to explore its outcomes during 48 h.

Design

A multicenter cohort study at five sites (February 2020 to June 2021).

Setting/Participants

We prospectively enrolled consecutive patients with advanced cancer, Eastern Cooperative Oncology Group performance status 3–4, and moderate/severe dyspnea. Participating palliative care physicians initiated algorithm‐based treatment. The primary outcome was the proportion of adherence to the treatment algorithm over 24 h (predefined goal, 70%). We evaluated the adherence, goal achievement, and dyspnea level with a numerical rating scale (NRS), as well as adverse events over 48 h.

Results

All 108 patients received algorithm‐based pharmacological treatment. Among 96 and 87 patients who were alive at 24 and 48 h, respectively, 96 (100%; 95% confidence interval [CI] = 96%–100%) and 82 (94%; 95%CI = 87%–98%) continued to receive the algorithm treatment, respectively, and 66 (69%; 95%CI = 59%–77%) and 64 (74%; 95%CI = 63%–82%) achieved the treatment goals, respectively. Using a complete case analysis with paired t‐tests, mean dyspnea NRS scores significantly reduced from 7.3 (standard error, 0.2) at the baseline to 4.9 (0.3) at 24 h (n = 72; p < 0.001), and 7.2 (0.3) at the baseline to 4.6 (0.4) at 48 h (n = 55; p < 0.001). Most adverse events were mild to moderate.

Conclusions

The comprehensive pharmacological treatment algorithm was feasible, and the study data supports its preliminary efficacy and safety. The use of this algorithm may help clinicians improve care for patients with terminal dyspnea.
Observation is an important leadership skill
Authors: Hodges Dawn Z.
Published: October 2022

A few months ago, my siblings and I agreed it was necessary to place my mother in a skilled nursing facility. It's something you swear you'll never do, but at 91, with congestive heart failure and progressing vascular dementia, it was the best decision for everyone.
Development of venetoclax performance using its new derivatives on BCL‐2 protein inhibition
Authors: Najafi Vahideh , Yoosefian Mehdi , Hassani Zahra
Published: October 2022

Cancer cells are resistant to apoptosis and this is one of the most obvious symptoms of cancer in humans. One of the most exciting strategies for treating cancer is to design regulators that increase cell death and stop cell growth. Members of the BCL‐2 family of proteins play an important role in the regulation of apoptosis. In this study, an attempt was made to improve the performance of one of the anticancer drugs by designing new analogs of venetoclax (VNT). For this purpose, molecular docking studies were performed to determine the best binding state of VNT and its newly designed derivatives at the protein‐binding site to estimate the binding energy. The best analog in terms of free energy was VNT‐12 with the lowest energy (−12.15 kcal/mol). Finally, to investigate the inhibitory effect of the compounds on BCL‐2 protein, molecular dynamics simulation was used, and by performing the relevant analyses during the simulation, it was observed that the newly designed ligand had better performance in inhibiting BCL‐2 protein compared to VNT.
Regulation of radiation‐induced liver damage by modulation of SIRT‐1 activity: In vivo rat model
Authors: El‐Sheikh Marwa M. , Abdel‐Naby Doaa H. , El‐Hazek Rania M. , El‐Ghazaly Mona A.
Published: October 2022

Silent information regulator 1 (SIRT‐1), a nicotinamide adenine dinucleotide‐dependent deacetylase, was found to regulate cell apoptosis, inflammation, and oxidative stress response in living organisms. Therefore, the role of SIRT‐1 in regulating forkhead box O/poly ADP‐ribose polymerase‐1 (FOXO‐1/PARP‐1) signaling could provide the necessary validation for developing new pharmacological targets for the promotion or inhibition of SIRT‐1 activity toward radiation sensitivity. In the present study, the SIRT‐1 signaling pathway is being investigated to study the possible modulatory effect of resveratrol (RSV, SIRT‐1 activator) versus nicotinamide (NAM, SIRT‐1 inhibitor) in case of liver damage induced by whole‐body gamma irradiation. Rats were exposed to 6 Gy gamma radiation after being pretreated with either RSV (10 mg/kg/day) or NAM (100 mg/kg/day) for 5 days, and subsequent examining hepatic morphological changes and apoptotic markers were assessed. The expression of SIRT‐1, FOXO‐1, and cleaved PARP‐1 in the liver was analyzed. RSV improved radiation‐induced apoptosis, mitochondrial dysfunction, and inflammation signified by low expression of caspase‐3, lactate dehydrogenase, complex‐I activity, myeloperoxidase, and total nitric oxide content. RSV increased the expression of SIRT‐1, whereas cleaved PARP‐1 and FOXO‐1 were suppressed. These protective effects were suppressed by inhibition of SIRT‐1 activity using NAM. These findings suggest that RSV can attenuate radiation‐induced hepatic injury by reducing apoptosis and inflammation via SIRT‐1 activity modulation.
Fluvoxamine prompts the antitumor immune effect via inhibiting the PD‐L1 expression on mice‐burdened colon tumor
Authors: Wei Pengkun , Jia Huijie , Li Ruipeng , Zhang Congli , Guo Shuoshuo , Wei Sujiao , Sun Ke , Cheng Sichang , Cui Tongquan , Huang Juan , Guo Sheng , Guo Jing , Yang Zishan , Zhong Jiateng , Lu Chengbiao , Feng Zhiwei , Zhao Tiesuo
Published: October 2022

A colon tumor, one of the digestive tract malignant tumors, is harmful to human health. A potential new treatment still deserves attention. The development of a new drug needs more resources, including time and expense. Therefore, the old drug with new targets has become a current research hotspot. Fluvoxamine, as an antidepressant, could play an effect on inhibiting 5‐hydroxytryptamine reuptake. In the present research, the antitumor effects and possible mechanisms of fluvoxamine are validated. The results showed that fluvoxamine significantly suppressed the migration and proliferation of tumor cells, and increased the apoptosis in vitro. Additionally, fluvoxamine significantly delays tumor development, and prompts the apoptosis in tumor tissues of mice‐burdened colon tumors in vivo. The tumor suppression might be related with that fluvoxamine inhibits the expression of phosphorylated signal transducer and activator of transcription 3, matrix metalloproteinase 2, and cleaved‐caspase 3. Importantly, fluvoxamine significantly reduces the expression level of programmed cell death ligand 1. This could be a possible reason that treatment with fluvoxamine drives the infiltration of T lymphocytes and M1‐type macrophages in tumor tissues. Taken together, this research suggests that fluvoxamine might be a promising drug to treat colon cancer by inhibiting the proliferation and migration, inducing apoptosis, and even increasing the immune response of antitumor.
Multiple asymptomatic papules following breast cancer treatment
Authors: Chaima Kouki , Khadija Sellami , Emna Bahloul , Emna Mnif , Soumaya Graja , Nadine Kammoun , Naourez Gouiaa , Tahya Boudawara , Hamida Turki
Published: October 2022

Acquired lymphangiectasia (AL) represents superficial lymphatic dilatation caused by different processes. It is a consequence of lymphatic damage by an external cause; leading to obstruction of local lymphatic drainage.1 We report a case of AL of the breast in a 45‐year‐old woman mimicking warts.
Chitosan‐Silica as a Cheap Carrier and Green Soft Ligand for Improved Ru‐catalyzed Hydroformylation
Authors: Escobar‐Bedia Francisco Javier , Martin‐Diaconescu Vlad , Simonelli Laura , Sabater Maria J. , Concepción Patricia
Published: October 2022

Dodecacarbonyltriruthenium Ru3(CO)12 has been immobilized onto a biopolymer (chitosan) supported on SiO2 (Ch@SiO2) to give Ru−Ch@SiO2. Ch@SiO2 behaves as a soft, recoverable and bulky ligand allowing the stabilization of released Ru active species and preventing its irreversible reduction to Ru0. Under these conditions very high activity (TOF= 1086 h−1; TON=2749) and regioselectivity (n:iso=92 : 8) are obtained, surpassing that of the homogeneous Ru3(CO)12 counterpart.

Spectroscopic studies have shown that Ru3(CO)12 transforms into a mononuclear Run+ (n=2,3) di o try carbonyl species by interacting with the amido/amino groups of the biopolymer, being released into the reaction media whilst stabilized by the chitosan functional groups.

The herein 0.5 Ru‐Ch@SiO2 catalyst can operate be operated under a semi‐continuous mode for at least 14 h without deactivation, representing providing a starting point in the search for a green catalyst with definitive industrial application in hydroformylations. In particular in the search for a heterogeneous catalyst away from the use of phosphines and their known drawbacks (i. e. tedious synthesis, facile oxidation of phosphor center, ..) as well as expensive Rh as active site.
Water‐Triggered Chemical Transformation of Perovskite Nanocrystals
Authors: Das Avik , Debnath Tushar
Published: October 2022

Recently emerged lead‐halide perovskite nanocrystals (PNCs) are promising optoelectronic material due to their easy solution processability, wide range of color tunability, as well as very high photoluminescence quantum yield. Despite their significant success in lab‐scale optoelectronic applications, the long‐term stability becomes the main issue, hindering them towards commercialization. The highly ionic nature of such lead‐halide structure makes them extremely unstable in water and air. But a very few groups have taken the advantage of such nature of the crystal structure for water‐triggered chemical transformation towards shape, composition, and morphology controlled stable and bright PNCs, which are otherwise difficult to obtain by typical direct approach. Furthermore, using polymer as an encapsulating layer for the PNCs, water‐soluble stable PNCs have been prepared. In this review, the recent progress on the water–hexane interface chemistry towards chemical transformation to produce several PNCs is described. Such method not only ensure to yield several shape‐controlled perovskites nanocrystals, but also formation of perovskites in aqueous phase that show promising application towards bio‐imaging.
Cobalt Cyclopentadienyl‐Phosphine Dinitrogen Complexes
Authors: Wang Gao‐Xiang , Yan Xuechao , Yin Jianhao , Yin Zhu‐Bao , Wei Junnian , Xi Zhenfeng
Published: October 2022

By applying the potassium salts of cyclopentadienyl‐phosphine ligands LK to CoCl2, the corresponding cobalt chlorides (1, LCoIICl) were prepared. By reducing complexes 1 with KHBEt3 under a N2 atmosphere, bridging end‐on complexes, LCoI−N2−CoIL (2 a and 2 b), were successfully obtained. 15N2‐labeled [15N2]‐2 a was prepared under 15N2/14N2 exchange in THF solution. LCoI−N2−CoIL complex 2 a could react with P4 molecules to release N2 and generate a Co−P4−Co moiety 4. Further reduction of complex 2 b led to cleavage of a P−C bond in the cyclopentadienyl‐phosphine ligand to provide novel μ‐PCy2‐bridged Co0−N2 complex 5. DFT calculations confirmed the experimental observations.
Stimulus‐Responsive Lanthanide MOF Materials Encapsulated with Viologen Derivatives: Characterization, Photophysical Properties and Sensing on Nitrophenols
Authors: Li Hui‐Shu , Xing Shang‐Hua , Xiao Yao , Wang Chen , Guan Qing‐Lin , Bai Feng‐Ying , Xing Yong‐Heng , Xu Fen
Published: October 2022

Viologens (1,1’‐disubstituted 4,4’‐bipyridyls) possessing electron‐deficient properties and redox activity are a class of suitable chromophores to assemble metal–organic hybrid photochromic materials. Thus, viologen‐functionalized metal–organic frameworks (MOFs) have attracted much attention for their photochromic properties; however, the syntheses of lanthanide‐viologen hybrid crystalline photochromic materials still face many challenges. For example, the structures and properties of the final products are difficult to predict and are limited by molecular configurations. In this work, host‐guest composite‐material Ln‐NH2BDC‐pbpy MOFs were constructed by encapsulating viologen derivative pbpyCl2. The pbpy2+ moieties are uniformly embed by their π‐π conjugation in the pores of the 3D structure by electrostatic interactions. Due to the encapsulation of the chromophore pbpy2+ moieties, Ln‐NH2BDC‐pbpy MOFs have reversible photochromic properties: they can change color after irradiation and can return to the original color after being protected from light or heating. Interestingly, the fluorescence intensity decreases with illumination time and recovers in the dark. As a result, Ln‐NH2BDC‐pbpy MOFs show both photochromic and photomodulated fluorescence. Based on the outstanding fluorescence performance of the Ln‐NH2BDC‐pbpy MOFs, they also show a wonderful effect for detecting nitrophenols, especially TNP.
Coordination of Pnictogenylboranes Towards Tl(I) Salts and a Tl‐ Mediated P−P Coupling
Authors: Szlosek Robert , Ackermann Matthias T. , Marquardt Christian , Seidl Michael , Timoshkin Alexey Y. , Scheer Manfred
Published: October 2022

The coordination chemistry of only Lewis‐base (LB)‐stabilized pnictogenylboranes EH2BH2⋅NMe3 (E=P, As) towards Tl(I) salts has been studied. The reaction of Tl[BArCl] (BArCl=[B(3,5‐C6H3Cl2)4]−) with the corresponding pnictogenylborane results in the formation of [Tl(EH2BH2⋅NMe3)][BArCl] (1 a: E=P; 1 b: E=As). Whereas the Tl ion in 1 a/b is monocoordinated, the exchange of the weakly coordinating anion (WCA) in the Tl(I) salt leads to the formation of a trigonal pyramidal coordination mode at the Tl atom by coordination of three equivalents of EH2BH2 ⋅ NMe3 in [Tl(EH2BH2 ⋅ NMe3)3][WCA] (2 a: E=P, WCA=TEFCl; 2 b: E=As, WCA=TEF) (TEF=[Al{OC(CF3)3}4]−, TEFCl=[Al{(OC(CF3)2(CCl3)}4]−). Furthermore, by using two equivalents of PH2BH2⋅NMe3, a Tl(I)‐mediated P−P coupling takes place in CH2Cl2 as solvent resulting in [Me3N⋅BH2PH2PHBH2⋅NMe3][WCA] (WCA=TEF, 3 a; BArCl, 3 b; TEFCl, 3 c). In contrast, for the arsenic derivatives 1 b and 2 b, no coupling reaction is observed. The underlying chemical processes are elucidated by quantum chemical computations.
Overclocking Nitronyl Nitroxide Gold Derivatives in Cross‐Coupling Reactions
Authors: Zayakin Igor , Tretyakov Evgeny , Akyeva Anna , Syroeshkin Mikhail , Burykina Julia , Dmitrenok Andrey , Korlyukov Alexander , Nasyrova Darina , Bagryanskaya Irina , Stass Dmitri , Ananikov Valentine
Published: October 2022

Nitronyl nitroxides are functional building blocks in cutting‐edge research fields, such as the design of molecular magnets, the development of redox and photoswitchable molecular systems and the creation of redox‐active components for organic and hybrid batteries. The key importance of the nitronyl nitroxide function is to translate molecular‐level‐optimized structures into nano‐scale devices and new technologies. In spite of great importance, efficient and versatile synthetic approaches to these compounds still represent a challenge. Particularly, methods for the direct introduction of a nitronyl nitroxide moiety into aromatic systems possess many limitations. Here, we report gold derivatives of nitronyl nitroxide that can enter Pd(0)‐catalysed cross‐coupling reactions with various aryl bromides, affording the corresponding functionalized nitronyl nitroxides. Based on the high thermal stability and enhanced reactivity in catalytic transformation, a new reagent is suggested for the synthesis of radical systems via a universal cross‐coupling approach.
A novel modified long short term memory architecture for automatic liver disease prediction from patient records
Authors: Antony Asir Daniel V. , Ramaraj Ravi
Published: October 2022

The liver is the second largest organ in the human body after the skin and liver disease mainly impacts the liver's functionality by properly separating the nutrients and waste into the digestive system and also causes scarring (cirrhosis) as time passes. The scarring over time affects the healthy liver tissue and also affects its proper functioning and if left untreated for a prolonged period it can also result in severe complications such as liver failure or liver cancer. The patients can be prevented from the severe complications if the disease is detected at an earlier stage and the existing research for liver disease prediction mainly encouraged the usage of intelligent machine learning‐based techniques. However, these techniques have several complexities such as low accuracy, overfitting, higher training time, poor feature extraction capabilities and so on. To overcome these problems, we present modified long short term emory (MLSTM) architecture for chronic liver disease prediction. The proposed methodology has three stages: information enhancement, feature extraction, and classification. The modified generative adversarial network uses an autoencoder system for sample augmentation which helps to enrich the diversity present in both the normal and abnormal classes. The outlier information is eliminated via the criminal search algorithm which captures the differences and correlation associated with multiple samples. The fast independent component analysis algorithm and enhanced whale optimization algorithm are used for feature extraction. This step mainly identifies the crucial features for liver disease prediction and leaves out the irrelevant and duplicate features thus enhancing the convergence, computational time, and prediction accuracy. The MLSTM architecture is used to classify the samples present in the liver disease datasets into normal and abnormal (liver disease) classes. The proposed methodology offers improved performance in terms of accuracy, recall, means square error, and F‐measure. The results show that the proposed methodology will be efficient for doctors to diagnose liver disease in the earlier stage.
A real‐time privacy‐preserving scheme based on grouping queries for continuous location‐based services
Authors: Liu Haoyu , Zhang Shiwen , Li Mengling , Liang Wei , Arthur Sandor Voundi Koe
Published: October 2022

With the advancement of global positioning systems and communication technologies, location‐based services (LBS) have become widely used. However, user location privacy is vulnerable during service exchange, and location‐related queries may result in serious privacy disclosure issues. In this article, considering that attackers may make use of auxiliary information to track a mobile user, we propose a real‐time privacy‐preserving scheme based on the grouping of queries in continuous LBS. In this scheme, we first design the probability density functions to select virtual locations. Then, we group these virtual locations and the query location of the user into several queries. Simultaneously, we send these grouping queries to the LBS server. Following the steps outlined above, grouping queries can be used to conceal the true query. Moreover, the results of security analyses and performance evaluations show that the proposed scheme is effective and secure.
Photoactive Covalent Organic Frameworks for Catalyzing Organic Reactions
Authors: Yang Liting , Wang Jialin , Zhao Kun , Fang Zhe , Qiao Huijie , Zhai Lipeng , Mi Liwei
Published: October 2022

Because of their large surface areas, long‐range order, π‐π stacking interactions and hierarchically integrated building blocks, covalent organic frameworks (COFs) have attracted increasing attention. Recently, COFs have been regarded as promising heterogeneous photocatalysts, owing to their remarkable light‐harvesting and energy transition capabilities. The research progress of COFs in photocatalytic organic synthesis is summarized, such as preparation of imines through the oxidation of amines, selective oxidation of sulfides, oxidative hydroxylation of arylboronic acids, C−H bond activation, cyclization, asymmetric organic synthesis and so on. Finally, a perspective of the present challenges of photoactive COFs in organic transformations is given.
Fostering Innovation and Global Competitiveness in the 2023 Farm Bill
Authors: Owen Rachel K.
Published: October 2022

With the 2018 farm bill set to expire next year, stakeholder groups—like CCAs and members of the American Society of Agronomy (ASA), Crop Science Society of America (CSSA), and Soil Science Society of America (SSSA)—are working to develop their recommendations to put forward to Congress. During this time, it is critical that our Societies engage in the discussion and make sure that Congress is aware of the effects that farm bill programs have on the scientific community. To do this, a Farm Bill Task Force, made up of CCAs and members from all three Societies, has been established to assist the Science Policy Office staff in developing our policy and research recommendations.
Biodiversity conservation adaptation to climate change: Protecting the actors or the stage
Authors: Zhu Gengping , Giam Xingli , Armsworth Paul R. , Cho Seong‐Hoon , Papeş Monica
Published: October 2022

To be able to protect biodiversity in coming decades, conservation strategies need to consider what sites will be important for species not just today but also in the future. Different methods have been proposed to identify places that will be important for species in the future. Two of the most frequently used methods, ecological niche modeling and climate resilience, have distinct aims. The former focuses on identifying the suitable environmental conditions for species, thus protecting the “actor,” namely, the species, whereas the latter seeks to safeguard the “stage,” or the landscape in which species occur. We used the two methods to identify climate refugia for 258 forest vertebrates under short‐ and long‐term climatic changes in a biodiversity hotspot, the Appalachian ecoregion of the United States. We also evaluated the spatial congruence of the two approaches for a possible conservation application, that of protecting 30% of the Appalachian region, in line with recent national and international policy recommendations. We detected weak positive correlations between resilience scores and baseline vertebrate richness, estimated with ecological niche models for historical (baseline) climatic conditions. The correlations were stronger for amphibians and mammals than for birds and reptiles. Under climate change scenarios, the correlations between estimated vertebrate richness and resilience were also weakly positive; a positive correlation was detected only for amphibians. Locations with estimated future gain of suitable climatic conditions for vertebrates showed low correlation with resilience. Overall, our results indicate that climate resilience and ecological niche modeling approaches capture different characteristics of projected distributional changes of Appalachian vertebrates. A climate resilience (the stage) approach could be more effective in safeguarding species with low dispersal abilities, whereas an ecological niche modeling (the actor) approach could be more suitable for species with long‐distance dispersal capacity because they may be more broadly impacted by climate and less sensitive to geophysical features captured by a climate resilience approach.
What's behind your eosinophilic myocarditis? A case of Churg–Strauss syndrome diagnosed during acute heart failure
Authors: Amelotti Nicola , Mapelli Massimo , Guglielmo Marco , Pires Maria Inês Fiuza Branco , Campodonico Jeness , Majocchi Benedetta , Ribatti Valentina , Vettor Giulia , Baggiano Andrea , Catto Valentina , Basso Cristina , Pontone Gianluca , Agostoni Piergiuseppe
Published: October 2022

Eosinophilic granulomatosis with polyangiitis (EGPA) is a rare multisystem disorder; cardiac involvement may include eosinophilic myocarditis. A 67‐year‐old woman presented with 1‐week history of dyspnoea and orthopnoea. She had a history of adult‐onset asthma and peripheral eosinophilia. The investigations showed T‐wave inversion on lateral leads, peripheral eosinophilia, elevated troponin and BNP values, and severe biventricular systolic dysfunction with diffuse hypokinesia and apical akinesia. Computed tomography excluded coronary disease and showed bilateral basal ground‐glass opacities, air‐space consolidation, and bilateral reticular‐nodular pattern. Cardiac magnetic resonance findings were compatible with active myocardial inflammation. An endomyocardial biopsy (EMB) confirmed the diagnosis of eosinophilic myocarditis, and a therapy with oral corticosteroids and heart failure medications was started.
Effects of a one‐time application of controlled‐release nitrogen fertilizer on quality and yield of rice
Authors: Dong Xu , Ying Zhu , Haibin Zhu , Qun Hu , Guodong Liu , Haiyan Wei , Hongcheng Zhang
Published: October 2022

Limited information is available on the influence of a one‐time application of controlled‐release nitrogen fertilizer (CRNF) in improving both yield and quality of rice. In this study, two rice cultivars, Jia58 (J58) and Jia67(J67), were used to study the effects of six combinations of short‐acting (40–60‐day release periods) and a long‐acting (80–120‐day release periods) CRNF. The six combinations were as follows: A1, 40‐day + 80‐day CRNFs; A2, 40‐day + 100‐day CRNFs; A3, 40‐day + 120‐day CRNFs; B1, 60‐day + 80‐day CRNFs; B2, 60‐day + 100‐day CRNFs; and B3, 60‐day + 120‐day CRNFs. Each combination of CRNFs was mixed with common urea (CU) to apply as basal fertilizer to rice crops to assess grain yield and quality. In addition, CU without CRNFs was applied as the control (CK). The results showed that the release of nitrogen from A2 and B2 were most matched with nitrogen accumulation by rice resulting in a higher yield (B2 treatment) or the same yield (A2 treatment) as CK. The average yield of 2 years of J58 in B2 was 7.38% higher than that of the CK. Similarly, the average yield of J67 in B2 was 6.46% higher than CK for both years. Milling quality, appearance quality, milled rice starch content, and taste value of rice in CRNF treatments were significantly higher than CK. In contrast, protein, gliadin, and glutenin contents and hardness of rice in the CRNF treatments were lower than CK. The higher protein content of rice in the CK resulted in higher gelatinization temperature and harder rice, which may explain why the eating and cooking qualities of rice in the CK were lower than those of rice in the CRNF treatment. These results demonstrate that the A2 and B2 treatments can produce improvements in both yield and quality of rice.
Extensions of the Lee–Carter model to project the data‐driven rotation of age‐specific mortality decline and forecast coherent mortality rates
Authors: Liu Cuixia , Shi Yanlin
Published: October 2022

Accurate forecasts and analyses of mortality rates are essential to many operational practices, such as the designing of pension schemes. Recent studies have focused on the age coherent forecasts, such that long‐term predictions will not diverge infinitely among ages. Although intuitively and biologically reasonable, this age coherence property is lost when the seminal Lee–Carter (LC) model and almost all its existing extensions are employed. Those include the famous Li–Lee (LL) model, which is argued to produce coherent forecasts of mortality rates across populations, but not ages. In this paper, we progressively explore two effective frameworks with three extensions, by applying the LL specification to the single‐population model (LC‐S) and by introducing time‐dependent age patterns of mortality declines in the forecasting steps with fixed (LC‐VF) and variant (LC‐V) intercepts when modeling those patterns. In particular, the recommended LC‐V model is motivated from the intermediate LC‐S and LC‐VF and resolves all remaining issues of both models. Also, the final LC‐V model is easy to implement, incorporates the dynamic and rotating age‐specific patterns of mortality decline, provides age‐coherent forecasts of mortality rates in the long run, and is straightforwardly extensible to multi‐population cases. Using a large sample of 15 countries, we show that the LC‐V model and its multipopulation counterpart can consistently improve the forecasting accuracy of the competing LC, LL and other extensions in both single‐population and multipopulation scenarios. Long‐term analyses up to 2100 further demonstrate the existence of age coherence when forecasting with the proposed LC‐V model.
X‐Ray Crystallographic Studies of Quasi‐Racemates for Absolute Configuration Determinations
Authors: Wu Xingxing , Malinčík Juraj , Prescimone Alessandro , Sparr Christof
Published: October 2022

The determination of the absolute configuration of chiral molecular entities by means of X‐ray crystallography is overall of central importance in stereochemistry. However, the growth of enantiopure single crystals often represents an unsurmountable and frustrating hurdle. Quasi‐racemic crystals of biomacromolecules, for which the absolute configuration is predetermined by the chiral monomers, allowed the X‐ray crystallographic analysis of systems that are difficult to crystallize as pure enantiomers, with aims other than the determination of the absolute structure. Taking advantage of the greater propensity of quasi‐racemic mixtures to co‐crystallize compared to growing enantiomerically pure crystals of a single compound, we herein describe the use of X‐ray crystallography of quasi‐racemates for the absolute configuration determination. We expect that this approach is particularly useful to establish the sense of selectivity in the development of stereoselective methods by simplified crystallizations, while confirming the consistent selectivity with a second molecular structure within the same measurement.
Adding a Chemical Biology Twist to CRISPR Screening
Authors: Huang Shiying , Baskin Jeremy M.
Published: October 2022

In less than a decade, CRISPR screening has revolutionized forward genetics and cell and molecular biology. Advances in screening technologies, including sgRNA libraries, Cas9‐expressing cell lines, and streamlined sequencing pipelines, have democratized pooled CRISPR screens at genome‐wide scale. Initially, many such screens were survival‐based, identifying essential genes in physiological or perturbed processes. With the application of new chemical biology tools to CRISPR screening, the phenotypic space is no longer limited to live/dead selection or screening for levels of conventional fluorescent protein reporters. Further, the resolution has been increased from cell populations to single cells or even the subcellular level. We highlight advances in pooled CRISPR screening, powered by chemical biology, that have expanded phenotypic space, resolution, scope, and scalability as well as strengthened the CRISPR/Cas enzyme toolkit to enable biological hypothesis generation and discovery.
Interleukin‐11/gp130 upregulates MMP‐13 expression and cell migration in OSCC by activating PI3K/Akt and AP‐1 signaling
Authors: Wu Chia‐Yu , Liu Ju‐Fang , Tsai Hsiao‐Chi , Tzeng Huey‐En , Hsieh Tsung‐Han , Wang Ming , Lin Yu‐Feng , Lu Chien‐Chi , Lien Ming‐Yu , Tang Chih‐Hsin
Published: October 2022

Oral squamous cell carcinoma (OSCC) is an extremely common head and neck cancer with a poor 5‐year survival rate, especially in cases of metastatic disease. Interleukin (IL)‐11 reportedly promotes cell growth and the epithelial–mesenchymal transition process in metastasis. However, the molecular mechanisms of IL‐11 in OSCC metastasis are unclear. This study found that IL‐11 upregulates matrix metalloproteinase 13 (MMP‐13) expression in OSCC via the IL‐11 receptor alpha subunit/glycoprotein 130 receptors that activate phosphatidyl‐inositol 3‐kinase, Ak strain transforming, and activator protein 1 signaling, which subsequently enhance MMP‐13‐induced tumor metastasis. TIMER2.0 analysis revealed a positive correlation between MMP‐13 and IL‐11 levels (r = 0.454). Moreover, a strong positive association was observed between higher levels of IL‐11 expression in OSCC tissue (p < 0.01), lymph node metastasis (p = 0.0154), and clinical disease stage (p = 0.0337). IL‐11 knockdown suppressed the migration of OSCC cells (p < 0.05). The evidence indicates that IL‐11 can serve as a new molecular therapeutic target in OSCC metastasis.