bluuebunny/crossref_metadata_2025_split huggingface dataset:
Covalent Scrambling in Porous Polyarylthioethers through a Stepwise SNAr for Tunable Bandgap and Porosity
Authors: Kim Doyun , Nguyen Thien S. , Lee Hyejeong , Bayarkhuu Bolormaa , Rozyyev Vepa , Byun Jeehye , Li Sheng , Yavuz Cafer T. 
Published: April 2023

AbstractPorous poly(aryl thioether)s offer stability and electronic tunability by robust sulfur‐aryl conjugated architecture, but synthetic access is hindered due to limited control over the nucleophilic nature of sulfides and the air sensitivity of aromatic thiols. Here, we report a simple, one‐pot, inexpensive, regioselective synthesis of highly porous poly(aryl thioether)s through polycondensation of perfluoroaromatic compounds with sodium sulfide. The unprecedented temperature‐dependent para‐directing formation of thioether linkages leads to a stepwise transition of the polymer extension into a network, thereby allowing fine control of the porosity and optical band gaps. The obtained porous organic polymers with ultra‐microporosity (<1 nm) and sulfur as the surface functional groups show size‐dependent separation of organic micropollutants and selective removal of mercury ions from water. Our findings offer easy access to poly(aryl thioether)s with accessible sulfur functionalities and higher complexity, which will help in realizing advanced synthetic designs in applications such as adsorption, (photo)catalysis, and (opto)electronics.
Cobalt‐Catalyzed Efficient Convergent Asymmetric Hydrogenation of E/Z‐Enamides
Authors: Chen Tiantian , Zou Yashi , Hu Yanhua , Zhang Zhenfeng , Wei Hao , Wei Liangming , Zhang Wanbin 
Published: April 2023

AbstractUsing the diphosphine‐cobalt‐zinc catalytic system, an efficient asymmetric hydrogenation of internal simple enamides has been realized. In particular, the Ph‐BPE ligand can achieve convergent asymmetric hydrogenation of E/Z‐substrates. High yields and excellent enantioselectivities were obtained for both acyclic and cyclic enamides bearing α‐alkyl‐β‐aryl, α‐aryl‐β‐aryl, and α‐aryl‐β‐alkyl substituents. Hydrogenated products can be applied for the synthesis of useful chiral drugs such as Arfromoterol, Rotigotine, and Norsertraline. In addition, reasonable catalytic mechanism and stereocontrol mode are proposed based on DFT calculations.
Synthesis of Cleavable Polymers via Oxidation of Thioether Moieties and Thiol Click Reactions: A Click‐Declick Strategy
Authors: Wang Lun , Liu Li , Zhao Hanying 
Published: April 2023

AbstractIn the past decades click chemistries including thiol chemistries have found wide applications in the synthesis of well‐defined polymers. In this research, a click‐declick strategy based on the oxidation of heteroaromatic thioethers and the substitution reactions between the oxidized groups and thiols, is proposed for the synthesis of the cleavable polymers. In proof‐of‐concept experiments, block copolymers (BCPs) and star‐like polymers are synthesized by thiol‐phenylsulfone substitution reactions, and heteroaromatic thioethers are produced at the junction points of the BCP chains or on the crosslinking sites of the star‐like polymer. The thioethers can be oxidized to heteroaromatic sulfoxides or sulfones, depending on the oxidization condition. It is demonstrated that both sulfoxides or sulfones can have base catalyzed nucleophilic substitution reactions with thiols, leading to the cleavage of the polymers.
Tube‐based batch model predictive control for polystyrene polymerization reaction process
Authors: Zhou Chengyu , Jia Li , Zhou Yang 
Published: April 2023

AbstractThis paper focuses on product quality control issue of polystyrene polymerization reaction process. A novel tube‐based batch model predictive control (BMPC) strategy based on a data‐driven model is presented, which is inspired by the tube‐based robust model predictive control (MPC) strategy. First, the dynamic behavior of the polystyrene polymerization reaction process is captured with high accuracy by establishing a just‐in‐time learning (JITL) model. Then, the built JITL model is regarded as the nominal system, and a BMPC is designed on the basis of JITL model to obtain the nominal trajectory, which is an integrated control system framework composed of iterative learning control (ILC) and MPC. Meanwhile, another auxiliary MPC (AMPC) is designed to minimize the deviation between the actual trajectory and the nominal trajectory, and the actual tracking errors are limited to the tube invariant set centered on the nominal errors to restrain the performance deterioration of the control system caused by the modeling errors. Finally, the effectiveness of the proposed tube‐based BMPC method is verified by simulating an industrial batch polystyrene polymerization reaction process. The results indicate that the presented control algorithm not only enhances the tracking performance of the system but also provides a more robust system stability than existing methods. This paper provides a new solution to improve the product quality of polystyrene polymerization reaction process.
Theoretical and Experimental Studies on Material Gain for Wide Polar InGaN Quantum Well‐Mechanism Leading to Electric Field Screening and Lasing
Authors: Gładysiewicz Marta , Kudrawiec Robert , Muzioł Grzegorz , Turski Henryk , Skierbiszewski Czesław 
Published: April 2023

AbstractThe width of polar InGaN quantum wells (QWs) is usually limited to a few nanometers to ensure a sufficient overlap between the wave functions of the ground electron and hole state. This paper presents the results of material gain measurements for thin (2.6 nm), wide (10.4 nm), and extremely wide (25 nm) InGaN QWs. The comparison of experimental data with theoretical predictions allows for correlation of the current density with the carrier concentration, which contributes to the positive material gain, and determination of the coefficients in the standard ABC model. It is shown that the mechanism in wide and narrow polar QWs that leads to electric field screening and lasing is different. For wide QWs, the optical transitions between excited states become dominant in the gain spectrum. The reason for such a gain mechanism is the built‐in electric field, which must first be screened. The ground electron and hole states play a very important role in the screening; however, their contribution to the material gain and lasing in wide QWs is very weak.
In situ Synthesis of Gel Polymer Electrolytes for Lithium Batteries
Authors: Cheng Xiangran , Jiang Yi , Lu Chenhao , Li Jiaxin , Qu Jiahe , Wang Bingjie , Peng Huisheng 
Published: April 2023

AbstractGel polymer electrolytes (GPEs) are considered as a promising solution to replace organic liquid electrolytes for safer lithium (Li) batteries due to their high ionic conductivity comparable to liquid electrolytes, no risk of leakage, and high flexibility. However, poor interfacial contact between electrodes and GPEs leads to high interfacial impedance and unsatisfactory electrochemical performance. The emerging in situ synthesized GPEs can fully infiltrate into porous electrodes and form intimate interfaces, improving interfacial contact and electrochemical performance. This perspective covers recent advances of in situ GPEs in design, synthesis, and applications in lithium (Li) batteries. Polyester and polyether‐based GPEs are mainly discussed followed by a brief introduction of GPEs with other polymer matrices, such as poly(ionic liquid)s, cyanoethyl polyvinyl alcohol, poly(vinyl acetal) and single‐ion conductors. Then, the recent progress in Li batteries using in situ GPEs are summarized, including Li‐ion battery, Li‐metal battery, Li‐sulfur battery, and Li‐air battery. Finally, the remaining challenges and future perspectives of in situ GPEs are discussed. We hope this perspective can offer guidance for in situ synthesis of GPEs and facilitate their applications in high‐performance Li batteries.
PI‐RADS 3 score: A retrospective experience of clinically significant prostate cancer detection
Authors: Camacho Andrés , Salah Fatima , Bay Camden P. , Waring Jonathan , Umeton Renato , Hirsch Michelle S. , Cole Alexander P. , Kibel Adam S. , Loda Massimo , Tempany Clare M. , Fennessy Fiona M. 
Published: April 2023

AbstractRationale and objectivesThe study aims to propose an optimal workflow in patients with a PI‐RADS 3 (PR‐3) assessment category (AC) through determining the timing and type of pathology interrogation used for the detection of clinically significant prostate cancer (csPCa) in these men based upon a 5‐year retrospective review in a large academic medical center.Materials and methodsThis United States Health Insurance Probability and Accountability Act (HIPAA)‐compliant, institutional review board‐approved retrospective study included men without prior csPCa diagnosis who received PR‐3 AC on magnetic resonance (MR) imaging (MRI). Subsequent incidence and time to csPCa diagnosis and number/type of prostate interventions was recorded. Categorical data were compared using Fisher's exact test and continuous data using ANOVA omnibus F‐test.ResultsOur cohort of 3238 men identified 332 who received PR‐3 as their highest AC on MRI, 240 (72.3%) of whom had pathology follow‐up within 5 years. csPCa was detected in 76/240 (32%) and non‐csPCa in 109/240 (45%) within 9.0 ± 10.6 months. Using a non‐targeted trans‐rectal ultrasound biopsy as the initial approach (n = 55), another diagnostic procedure was required to diagnose csPCa in 42/55 (76.4%) of men, compared with 3/21(14.3%) men with an initial MR targeted‐biopsy approach (n = 21); (p < 0.0001). Those with csPCa had higher median serum prostate‐specific antigen (PSA) and PSA density, and lower median prostate volume (p < 0.003) compared with non‐csPCa/no PCa.ConclusionMost patients with PR‐3 AC underwent prostate pathology exams within 5 years, 32% of whom were found to have csPCa within 1 year of MRI, most often with a higher PSA density and a prior non‐csPCa diagnosis. Addition of a targeted biopsy approach initially reduced the need for a second biopsy to reach a for csPCa diagnosis. Thus, a combination of systematic and targeted biopsy is advised in men with PR‐3 and a co‐existing abnormal PSA and PSA density.
Quorum sensing‐based metabolic engineering of the precursor supply in Streptomyces coelicolor to improve heterologous production of neoaureothin
Authors: Kim Do‐Kyung , Gu Boncheol , Kim Duck Gyun , Oh Min‐Kyu 
Published: April 2023

AbstractStreptomyces are important industrial bacteria that produce pharmaceutically valuable polyketides. However, mass production on an industrial scale is limited by low productivity, which can be overcome through metabolic engineering and the synthetic biology of the host strain. Recently, the introduction of an auto‐inducible expression system depending on microbial physiological state has been suggested as an important tool for the industrial‐scale production of polyketides. In this study, titer improvement by enhancing the pool of CoA‐derived precursors required for polyketide production was driven in a quorum sensing (QS)‐dependent manner. A self‐sustaining and inducer‐independent regulatory system, named the QS‐based metabolic engineering of precursor pool (QMP) system, was constructed, wherein the expression of genes involved in precursor biosynthesis was regulated by the QS‐responsive promoter, scbAp. The QMP system was applied for neoaureothin production in a heterologous host, Streptomyces coelicolor M1152, and productivity increased by up to 4‐fold. In particular, the engineered hyperproducers produced high levels of neoaureothin without adversely affecting cell growth. Overall, this study showed that self‐regulated metabolic engineering mediated by QS has the potential to engineer strains for polyketide titer improvement.
CircPTPRA promotes the progression of pancreatic ductal adenocarcinoma via the miR‐140‐5p/LMNB1 axis
Authors: Fu Wen , Wang Xianxing , Xiang Jifeng , Chen Shengkai , Xia Renpei , Xie Fuming , Chi Bojing , Qin Fanbo , Li Zhuo , Mou Li , Xie Chuanming , Wang Huaizhi 
Published: April 2023

AbstractBackgroundGrowing evidences suggest that circular RNAs (circRNAs) are important factors in cancer progression. Nevertheless, the role of circRNAs in the progression of pancreatic ductal adenocarcinoma (PDAC) remains unclear.MethodsCircPTPRA was identified based on our previous circRNA array data analysis. Wound healing, transwell, and EdU assays were performed to investigate the effect of circPTPRA on the migration, invasion, and proliferation of PDAC cells in vitro. RNA pull‐down, fluorescence in situ hybridization (FISH), RNA immunoprecipitation (RIP), and dual‐luciferase reporter assays were conducted to verify the binding of circPTPRA with miR‐140‐5p. Subcutaneous xenograft model was constructed for in vivo experiment.ResultsCircPTPRA was significantly upregulated in PDAC tissues and cells compared to normal controls. Moreover, circPTPRA overexpression was positively correlated with lymph node invasion and worse prognosis in PDAC patients. In addition, overexpression of circPTPRA promoted PDAC migration, invasion, proliferation, and epithelial‐mesenchymal transition (EMT) in vitro and in vivo. Mechanistically, circPTPRA upregulates LaminB1 (LMNB1) expression by sponging miR‐140‐5p and ultimately promotes the progression of PDAC.ConclusionsThis study revealed that circPTPRA plays an important role in the progression of PDAC by sponging miR‐140‐5p. It can be explored as a potential prognostic marker and therapeutic target for PDAC.
ALK+ ALCL in the setting of adalimumab‐related hidradenitis suppurativa
Authors: Craig Alexander , Wen Kwun Wah 
Published: April 2023

AbstractThis ALK‐positive anaplastic large cell lymphoma (ALCL) case highlights the importance of considering ALCL in the setting of iatrogenic immunosuppression in hidradenitis suppurativa patients. Diagnosis of ALCL can be challenging in situations with very low viability/cellularity, negative CD3 and/or other T‐cell markers, and immunosuppression.
Highly Efficient Catalysts for CO2 Fixation using Guanidinium‐Functionalized Zr‐MOFs
Authors: Masoom Nataj Seyedeh Molood , Kaliaguine Serge , Fontaine Frédéric‐Georges 
Published: April 2023

AbstractAn effective approach for tuning CO2 adsorption, activation and transformations of various epoxides in CO2 fixation reactions is introducing functional groups into the pores of metal‐organic frameworks (MOFs) through ligand modification. Herein, a novel ionic ligand, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene‐biphenyl‐4,4′‐dicarboxylic acid (H2BPDC−[TBD]+Br−), was synthesized to construct derivatives of the cationic guanidinium‐containing Zr‐MOF (UiO67‐[TBD]+Br−) with free bromide ions, as multifunctional heterogeneous catalysts. The materials were characterized comprehensively by multiple techniques such as PXRD, FTIR, TGA, SEM, EDS, 1H NMR, 13C NMR, mass spectrometry (MS), elemental analysis, as well as N2 and CO2 adsorption measurements. The synthesized UiO67‐[TBD]+Br− exhibits an efficient heterogeneous catalytic performance in the CO2 fixation reaction with epoxides, with high yield and selectivity, under mild conditions (0.1 MPa CO2, 80 °C, without co‐catalyst and solvent). In addition, these catalysts display good thermal stability, recyclability and could be reused at least five times without a significant decrease in their catalytic performance.
Versatile Diazomethane Sulfonamide for Expedited Exploration of Azole‐Based Carbonic Anhydrase Inhibitors via [3+2] Cycloaddition
Authors: Krivovicheva Vasilisa , Bubyrev Andrey , Kalinin Stanislav , Dar'in Dmitry , Gureev Maxim , Burianova Valeria , Vullo Daniella , Krasavin Mikhail , Supuran Claudiu T. 
Published: April 2023

AbstractA newly introduced diazo reagent, 1‐diazo‐N,N‐bis(4‐methoxybenzyl)methanesulfonamide, enables access to a range of azole‐based primary sulfonamides via [3+2] cycloaddition followed by protecting group removal. Such compounds are representative of the sulfonamide chemical space highly relevant but hitherto not investigated in the context of inhibition of therapeutically relevant isoforms of carbonic anhydrase enzyme. Using this reagent, three sets of primary sulfonamides based on pyrazole, 1,2,3‐triazole and tetrazole cores were synthesized and profiled for inhibition of tumor‐associated hCA IX and XII isoforms as well as abundant cytosolic hCA I and II isoforms. Using virtual library design and docking prioritization tool of the Schrödinger suite, one of the promising leads was evolved into a dual hCA IX/XII inhibitor with excellent selectivity over off‐target hCA I and II. The new synthetic strategy to access azole‐based primary sulfonamides will support the discovery of novel, isoform‐selective inhibitors of carbonic anhydrase within the poorly explored azole chemical space.
Dose‐escalation trial of combination dabrafenib, trametinib, and AT13387 in patients with BRAF‐mutant solid tumors
Authors: Mooradian Meghan J. , Cleary James M. , Giobbie‐Hurder Anita , Darville Lancia N. F. , Parikh Aparna , Buchbinder Elizabeth I. , Cohen Justine V. , Lawrence Donald P. , Shapiro Geoffrey I. , Keer Harold , Chen Helen X. , Ivy Susan Percy , Smalley Keiran S. M. , Koomen John M. , Sullivan Ryan J. 
Published: April 2023

AbstractBackgroundCombination BRAF and MEK inhibitor therapy is an active regimen in patients who have BRAF V600E‐mutated tumors; however, the clinical efficacy of this therapy is limited by resistance. Preclinically, the addition of heat shock protein 90 (HSP90) inhibition improves the efficacy of BRAF inhibitor therapy in both BRAF inhibitor–sensitive and BRAF inhibitor–resistant mutant cell lines.MethodsCancer Therapy Evaluation Program study 9557 (ClinicalTrials.gov identifier NCT02097225) is a phase 1 study that was designed to assess the safety and efficacy of the small‐molecule HSP90 inhibitor, AT13387, in combination with dabrafenib and trametinib in BRAF V600E/K–mutant solid tumors. Correlative analyses evaluated the expression of HSP90 client proteins and chaperones.ResultsTwenty‐two patients with metastatic, BRAF V600E–mutant solid tumors were enrolled using a 3 + 3 design at four dose levels, and 21 patients were evaluable for efficacy assessment. The most common tumor type was colorectal cancer (N = 12). Dose‐limiting toxicities occurred in one patient at dose level 3 and in one patient at dose level 4; specifically, myelosuppression and fatigue, respectively. The maximum tolerated dose was oral dabafenib 150 mg twice daily, oral trametinib 2 mg once daily, and intravenous AT13387 260 mg/m2 on days 1, 8, and 15. The best response was a partial response in two patients and stable disease in eight patients, with an overall response rate of 9.5% (90% exact confidence interval [CI], 2%–27%), a disease control rate of 47.6% (90% CI, 29%–67%), and a median overall survival of 5.1 months (90% CI, 3.4–7.6 months). There were no consistent proteomic changes associated with response or resistance, although responders did have reductions in BRAF expression, and epidermal growth factor receptor downregulation using HSP90 inhibition was observed in one patient who had colorectal cancer.ConclusionsHSP90 inhibition combined with BRAF/MEK inhibition was safe and produced evidence of modest disease control in a heavily pretreated population. Additional translational work may identify tumor types and resistance mechanisms that are most sensitive to this approach.
Temperature Ramp Strategy for Regulating Oxygen Vacancies in NiCo2O4 Nanoneedles Towards Enhanced Electrocatalytic Water Splitting
Authors: Rashid Bushra , Mala Kanchan , Ali Mubashir , Rafiq Umer , Quereshi Mehroosa , Ahmad Parvaz , Dar Mudasir , Wahid Malik 
Published: April 2023

AbstractOxide‐based systems often suffer from higher overpotentials compared to transition metal sulfides and phosphides for the electrochemical hydrogen evolution reaction (HER). Interestingly, the generation of oxygen vacancy/defect has been seen as the strategy for further activating transition metal oxides (NiCo2O4 as a model system) for an electrochemical water‐splitting process. Herein, we employ the temperature ramp strategy (ambient air calcination) for the generation of oxygen vacancies in NiCo2O4 (NCO) towards the tuning of electrocatalytic enhancements. The NiCo2O4 synthesized at temperature ramp rates of 2 °C/min (NCO‐2), 5 °C/min (NCO‐5), and 10 °C/ min (NCO‐10) depicts contrasting structural features and varying Ni : Co : O surface composition. The decrease in the crystallite size and converse trend in the particle strain were observed from NCO‐2 to NCO‐10. Interestingly, the surface Ni : Co : O ratios of 1 : 0.78 : 3.6, 1 : 0.81 : 3.3, and 1 : 0.69 : 2.8 for NCO‐2, NCO‐5, and NCO‐10, respectively, were observed. The reduced relative oxygen ratio in the latter implies the generation of an ample amount of oxygen vacancy defects. HER performance depicts a consistent trend with enhanced oxygen defect concentration with the overpotential requirement of 700, 647, and 597 mV for NCO‐2, NCO‐5, and NCO‐10, respectively, for the generation of a cathodic current of 25 mA cm−2. The same trend in an electrocatalytic enhancement is observed for other cathodic currents.
Formate Over‐Oxidation Limits Industrialization of Glycerol Oxidation Paired with Carbon Dioxide Reduction to Formate
Authors: van den Bosch Bart , Rawls Brian , Brands Maria B. , Koopman Christel , Phillips Matthew F. , Figueiredo Marta C. , Gruter Gert‐Jan M. 
Published: April 2023

AbstractElectrocatalytic CO2 reduction processes are generally coupled with the oxidation of water. Process economics can greatly improve by replacing the water oxidation with a more valuable oxidation reaction, a process called paired electrolysis. Here we report the feasibility of pairing CO2 reduction with the oxidation of glycerol on Ni3S2/NF anodes to produce formate at both anode and cathode. Initially we optimized the oxidation of glycerol to maximize the Faraday efficiency to formate by using design of experiments. In flow cell electrolysis, excellent selectivity (up to 90 % Faraday efficiency) was achieved at high current density (150 mA/cm2 of geometric surface area). Then we successfully paired the reduction of CO2 with the oxidation of glycerol. A prerequisite for industrial application is to obtain reaction mixtures with a high concentration of formate to enable efficient downstream separation. We show that the anodic process is limited in formate concentration, as Faraday efficiency to formate greatly decreases when operating at 2.5 M formate (∼10 w%) in the reaction mixture due to over‐oxidation of formate. We identify this as a major bottleneck for the industrial feasibility of this paired electrolysis process.
Electrochemically Activated Expanded Graphite with Tailor‐Made Pores for Magnesium–Organocation Hybrid Batteries
Authors: Mohanty Sangram Keshari , Cao Lei , Choi Byeong Kil , Ryu Ji Heon , Park Jin Kyoon , Yoo Hyun Deog 
Published: April 2023

AbstractPersisting limitations of lithium‐ion batteries (LIBs) in terms of safety, energy and power density, natural resources, and the price call for expeditious research to develop the “beyond Li‐ion” technologies. In this regard, magnesium–organocation hybrid batteries (MOHB) hold the potential to address the above issues associated with LIBs by utilizing abundant and inexpensive elements of magnesium and carbon for the anode and cathode, respectively. Moreover, magnesium metal anode is highly energy‐dense yet less susceptible to the dendrite formation, enabling safer operation compared to lithium metal anodes. In this study, we targeted to increase the capacity and rate capability of porous carbon cathode of MOHB by generating tailor‐made pores, which were provided by the interlayer accommodation of solvated organic cations with controlled sizes during the electrochemical activation of expanded graphite. Our electrochemically activated expanded graphite can be used as an efficient cathode in MOHB with enhanced kinetics, specific capacitance, and cycle life.