bluuebunny/crossref_metadata_2025_split huggingface dataset:
A DNA–Azobenzene Nanopump Fueled by Upconversion Luminescence for Controllable Intracellular Drug Release
Authors: Zhang Yue , Zhang Yue , Song Guobin , He Yuling , Zhang Xiaobo , Liu Ying , Ju Huangxian 
Published: October 2019

AbstractStimulus‐responsive drug release possesses considerable significance in cancer therapy. This work reports an upconversion‐luminescence‐fueled DNA–azobenzene nanopump for rapid and efficient drug release. The nanopump is constructed by assembling the azobenzene‐functionalized DNA strands on upconversion nanoparticles (UCNPs). Doxorubicin (DOX) is loaded in the nanopump by intercalation in the DNA helix. Under NIR light, the UCNPs emit both UV and visible photons to fuel the continuous photoisomerization of azo, which acts as an impeller pump to trigger cyclic DNA hybridization and dehybridization for controllable DOX release. In a relatively short period, this system demonstrates 86.7 % DOX release. By assembling HIV‐1 TAT peptide and hyaluronic acid on the system, targeting of the cancer‐cell nucleus is achieved for perinuclear aggregation of DOX and enhanced anticancer therapy. This highly effective drug delivery nanopump could contribute to chemotherapy development.
Regioselektive oxidative Arylierung von Fluorophenolen
Authors: Yu Congjun , Patureau Frederic W. 
Published: October 2019

AbstractEine metallfreie und hochregioselektive oxidative Arylierung von Fluorophenolen wird gezeigt. Die relative Position der Fluoridabgangsgruppe (also ortho oder para) kontrolliert das 1,2 oder 1,4 Substitutionsmuster des Chinons, was diese Reaktion zu einem vielseitigen und allgemeinen Konzept für diese oxidative defluorierende Arylierung macht.
Loading Photochromic Molecules into a Luminescent Metal–Organic Framework for Information Anticounterfeiting
Authors: Li Zhiqiang , Wang Guannan , Ye Yingxiang , Li Bin , Li Huanrong , Chen Banglin 
Published: October 2019

AbstractStimuli‐responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly in materials with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible information anticounterfeiting by loading a photoswitchable diarylethene derivative into a lanthanide metal–organic framework (MOF). Light triggers the open‐ and closed‐form isomerization of the diarylethene unit, which respectively regulates the inactivation and activation of the photochromic FRET process between the diarylethene acceptor and lanthanide donor, resulting in reversible luminescence on–off switching of the lanthanide emitting center in the MOF host. This photoresponsive host–guest system allows for reversible multiple information pattern visible/invisible transformation by simply alternating the exposure to UV and visible light.
Construction of Covalent‐Organic Frameworks (COFs) from Amorphous Covalent Organic Polymers via Linkage Replacement
Authors: Zhai Yufeng , Liu Guiyan , Jin Fenchun , Zhang Yingying , Gong Xuefang , Miao Zhuang , Li Jinheng , Zhang Mengyao , Cui Yumeng , Zhang Lingyan , Liu Yu , Zhang Huixin , Zhao Yanli , Zeng Yongfei 
Published: October 2019

AbstractCovalent‐organic frameworks (COFs) as porous crystalline materials show promising potential applications. However, developing facile strategies for the construction of COFs directly from amorphous covalent organic polymers (COPs) is still a great challenge. To this end, we report a novel approach for easy preparation of COFs from amorphous COPs through the linkage replacement under different types of reactions. Four COFs with high crystallinity and porosity were constructed via the linkage substitution of polyimide‐linked COPs to imine‐linked COFs as well as imine‐linked COPs to polyimide‐linked COFs. The realization of the linkage substitution would significantly expand the research scope of COFs.
Regioselective Oxidative Arylation of Fluorophenols
Authors: Yu Congjun , Patureau Frederic W. 
Published: October 2019

AbstractA metal free and highly regioselective oxidative arylation reaction of fluorophenols is described. The relative position of the fluoride leaving group (i.e., ortho or para) controls the 1,2 or 1,4 nature of the arylated quinone product, lending versatility and generality to this oxidative, defluorinative, arylation concept.
RAFT‐Mediated Polymerization‐Induced Self‐Assembly
Authors: D'Agosto Franck , Rieger Jutta , Lansalot Muriel 
Published: October 2019

AbstractAfter a brief history that positions polymerization‐induced self‐assembly (PISA) in the field of polymer chemistry, this Review will cover the fundamentals of the PISA mechanism. Furthermore, this Review will also give an overview of some of the features and limitations of RAFT‐mediated PISA in terms of the choice of the components involved, the nature of the nanoobjects that can be obtained and how the syntheses can be controlled, as well as some potential applications.
Mechanism and Selectivity of the Oxidative Ring Contraction of Cyclic α‐Formyl Ketones
Authors: Xu Li‐Ping , Hou Xu‐Dong , Wang Hui , Zhou Jing‐Bo , Ma Jie , Zhuo Shuping , Wang Qian 
Published: October 2019

AbstractThe oxidative contraction of α‐formal ketone to form continuous all carbon chiral centers promoted by H2O2 is widely used in natural product total synthesis. Typically, using this transformation, chiral cyclic ketones are obtained as the major products and ring‐opening products as the minor products. Herein, DFT calculations have been used to investigate the detailed reaction mechanism and chemoselectivity. In addition, with the widely accepted mechanism of H2O2‐promoted transformation, our systematic investigation with various explicit‐solvent‐model calculations for the first time shows that H2O and H2O2 are comparable at catalyzing the rate‐determining step of this reaction, which emphasis the importance of solvent effect in such transformations. It is found that both the less ring‐constrain and a later transition state in an exothermic reaction account for the origin why the reaction favors ring‐contraction pathway rather than ring‐opening one. By a comprehensive analysis for the substituted groups, it has been disclosed that the steric effects of the substituted groups on R2 and R3 contribute to the selectivity with larger steric hindrance favoring the chiral cyclic products. Moreover, the electronic effects on R1 but not R3 affect the selectivity with electron‐donating groups leading to the cyclic products. Based on our calculations, some predictions for higher selectivity have been made.
Coupon Procedures for Evaluating Lead and Copper Solubility
Authors: Cornwell David A. , Wagner Jacob R. 
Published: October 2019

Key TakeawaysCoupons have been used to evaluate corrosion in pipes since before the Lead and Copper Rule was enacted; there's a new way to conduct coupon studies.Tests using coupon protocol can provide reproduceable data quickly and cost‐effectively.Coupon studies have their limitations, but when used and interpreted correctly, they're useful in multivariable analysis.
The PFAS Problem: How Regulators Are Responding and What It Means for Drinking Water
Authors: Stewart Andrew , Morales Marshall , Zaleski Joseph 
Published: October 2019

Key TakeawaysWater system operators need to understand evolving initiatives and enforcement risks related to PFAS.Some steps the US Environmental Protection Agency might take to remediate PFAS contamination could have wide‐ranging consequences for public water delivery and treatment systems.Utilities can help themselves by keeping their compliance programs robust and building goodwill within their communities and with regulators at all levels.
Application of the Clean Water Act to Groundwater Is Anathema to the Water Industry: An Unfolding Tale
Authors: Hoch Steven L. 
Published: October 2019

Key TakeawaysAmendments to the Clean Water Act (CWA) and the definition of “waters of the United States” have evolved over time.US courts have differed on whether the CWA regulates groundwater discharges.Water projects could become too costly, too burdensome, and subject to delays if the Supreme Court decides that the CWA regulates groundwater.
Kinetic model for effects of simulated flue gas onto growth profiles of Chlorella sp. AE10 and Chlorella sp. Cv
Authors: Cheng Dujia , Li Xuyang , Yuan Yizhong , Zhao Quanyu 
Published: October 2019

AbstractMicroalgae are potential candidate for biofuel production as alternative one for fossil fuels. CO2 in flue gas is available carbon source to support microalgae growth. In this study, the effects of different concentrations of the simulated flue gas onto algal growth and photosynthetic activity were evaluated for both Chlorella sp. AE10 and Chlorella sp. Cv. The growth profiles were correlated by a simple kinetic model. It was indicated that the simulated flue gas led to low pH and the photosynthetic activity was partially destroyed. Chlorella sp. Cv can tolerate full simulated flue gas, 10% CO2 + 200 ppm NOx + 100 ppm SOx. The pH in medium maintained at 6 and the photosynthetic activity was more than 0.6 at the first 6 days. If the concentration of NOx was more 100 ppm and that of SOx was more than 50 ppm, the pH was declined to 4 at day 2 or 3 for Chlorella sp. AE10. At the same time, the related photosynthetic activities of Chlorella sp. AE10 were less than 0.4, which was not suitable for algal growth. It was shown that Chlorella sp. Cv could be used for CO2 fixation from the simulated flue gas.
Influence of the Formation Current Density on the Transport Properties of Galvanostatically Formed Model‐Type Solid Electrolyte Interphases
Authors: Kranz Sebastian , Kranz Tobias , Graubner Tim , Yusim Yuriy , Hellweg Lukas , Roling Bernhard 
Published: October 2019

AbstractDuring the production of commercial lithium‐ion batteries, the solid electrolyte interphase (SEI) on the graphite particles of the negative electrode is typically formed through galvanostatic protocols with low current densities. Consequently, SEI formation is a time‐consuming and rather expensive production step. In order to better understand the influence of the formation current density on the transport of ions and molecules across the SEI, we formed model‐type SEIs on planar glassy carbon electrodes under galvanostatic control. In accordance with the expectations from electrochemical nucleation and growth theory, we find that the transport of both ions and molecule becomes slower with increasing formation current density. However, it is remarkable that the ion transport is slowed down more strongly than the molecule transport. We show that at high formation current densities of about −71 μA cm−2, our model‐type SEIs clearly exceed the area‐specific resistance tolerable in commercial lithium‐ion cells.
Validation of the multiple sclerosis diagnosis in the Norwegian Patient Registry
Authors: Benjaminsen Espen , Myhr Kjell‐Morten , Grytten Nina , Alstadhaug Karl Bjørnar 
Published: October 2019

AbstractBackgroundHealth registries may yield important data for epidemiological studies. However, in order to be a valuable source for information, the registered data have to be correct.ObjectivesThe aim of the study was to validate data from the Norwegian Patient Registry (NPR) regarding multiple sclerosis (MS).Materials and MethodsWe obtained data on individuals residing in Nordland County and registered with a MS diagnosis in the NPR or in local hospital records. The NPR data included a unique 11‐digit personal identity number that made it possible to identify the individuals medical records. For each individual registered with MS in the NPR, the hospital record was scrutinized in order to confirm or rule out the diagnosis.ResultsIn Nordland County, 657 individuals had MS 1 January 2017. Of these, 637 were recorded with a correct diagnosis of MS in the NPR, while 59 were recorded incorrectly. Incorrect registration was due to a diagnosis that did not fulfill the diagnostic criteria, later investigation had ruled out MS or it was an error in the diagnostic code registration process. Twenty individuals were not registered with MS in the NPR. These were patients who received their diagnosis before data in the NPR were person identifiable (before 2008), and who later had no MS‐registered contact with public specialist healthcare services. The sensitivity is 0.97, and the positive predictive value is 0.92.ConclusionData from the NPR gave a good estimate of the occurrence of MS, but nearly one in 10 registered diagnoses was not correct.
Myeloid sarcoma manifesting as generalized lymphadenopathy in a patient with myelofibrosis
Authors: Trennepohl Christopher , Sorah Jonathan , Eulitt Patrick , Galeotti Jonathan , Zeidner Joshua F. , Montgomery Nathan D. , Coombs Catherine C. 
Published: October 2019

AbstractImmunophenotyping is critical to the diagnosis of MS, as it can be difficult to differentiate from other diagnoses including lymphoma using conventional light microscopy.
Carbon‐based perovskite solar cells: From single‐junction to modules
Authors: He Rui , Huang Xiaozhou , Chee Mason , Hao Feng , Dong Pei 
Published: October 2019

AbstractPerovskite solar cells (PSCs) have attracted more and more attention in the scientific community due to their high performance and simple fabrication process. In the past few years, emerging technologies have made manufacturing large‐scale PSC modules possible. However, stability and fabrication issues still limit the modularization and commercialization of PSCs. Carbon materials have been widely used in PSCs to overcome these challenges due to their excellent optical, electrical, and mechanical properties. In addition, the hydrophobic properties of certain carbon materials are highly effective at protecting the perovskite film from moisture and improving the stability of PSCs. All these superior properties have made carbon one of the most promising materials to fabricate future high‐performance PSC modules with long service lifetimes. In this review, recent developments of carbon‐based materials in different layers of single‐junction PSCs will first be discussed, with an emphasis on functionalities related to PSCs’ stability and modularization. Then, current improvements and future discussions in the manufacturing of monolithic PSC modules will be reviewed in detail.
Phosphahelicenes with (Thio)Phosphinic Acid and Ester Functions by the Oxidative Photocyclisation Approach
Authors: Febvay Julie , Demmer Charles S. , Retailleau Pascal , Crassous Jeanne , Abella Laura , Autschbach Jochen , Voituriez Arnaud , Marinetti Angela 
Published: October 2019

AbstractPhosphahelicenes with thiophosphinic acid and ester functions have been obtained by the oxidative photocyclisation of olefins bearing both a benzophenanthrene and a benzophosphole unit. When the method has been extended to olefins bearing a partially saturated benzophospholene unit, a divergent regioselectivity of the photocyclisation step has been observed, leading to new helicenes in which the phosphorus function is located on the external rim of the helical backbone. The observed regioselectivity correlates well with the free‐valence numbers of the atoms involved in the photocyclisation reaction (DFT calculations).
Solid‐State Emission from Mono‐ and Bichromophoric Boron Dipyrromethene (BODIPY) Derivatives and Comparison with Fluid Solution
Authors: Bozdemir Özgür Altan , Al‐Sharif Hatun H. T. , McFarlane William , Waddell Paul G. , Benniston Andrew C. , Harriman Anthony 
Published: October 2019

AbstractThe syntheses and crystal structures of sterically crowded mono‐ and bichromophoric BODIPY‐based dyes are reported. The “monomeric” compound is weakly fluorescent in the liquid phase due to fast internal conversion associated with rotation of aryl rings at the boron atom. The side‐by‐side “dimer” exhibits weak excitonic coupling between the dipyrrin units and is much more emissive in fluid solution. Solid samples of both molecular entities are strongly fluorescent under near‐UV illumination. Thus, the mono‐chromophore exhibits dual fluorescence from what appears to be a mixture of crystalline and possibly amorphous (or interfacial regions) distributions. The bi‐chromophore packs in the crystal as pairs of chromophores with each unit being provided by a different molecule. This leads to excitonic splitting and the formation of a strong H‐band in the absorption spectrum. Fluorescence occurs from the corresponding J‐species and also from what appears to be an aggregated state associated with interfacial areas. Both bulk and interface‐bound states show relatively long‐lived fluorescence while the crystal structures indicate the likelihood for fast electronic energy migration between molecules.
Silver‐Mediated Homochiral and Heterochiral α‐dC/β‐dC Base Pairs: Synthesis of α‐dC through Glycosylation and Impact of Consecutive, Isolated, and Multiple Metal Ion Pairs on DNA Stability
Authors: Chai Yingying , Leonard Peter , Guo Xiurong , Seela Frank 
Published: October 2019

AbstractIsolated and consecutive heterochiral α‐dC– base pairs have been incorporated into 12‐mer oligonucleotide duplexes at various positions, thereby replacing Watson–Crick pairs. To this end, a new synthesis of the α‐d anomer of dC has been developed, and oligonucleotides containing α‐dC residues have been synthesized. Silver‐mediated base pairs were formed upon the addition of silver ions. Furthermore, we have established that heterochiral α‐dC–dC base pairs can approach the stability of a Watson–Crick pair, whereas homochiral dC–dC pairs are significantly less stable. A positional change of the silver‐mediated base pairs affects the duplex stability and reveals the nearest‐neighbor influence. When the number of silver ions was equivalent to the number of duplex base pairs (12), non‐melting silver‐rich complexes were formed. Structural changes have been supported by circular dichroism (CD) spectra, which showed that the B‐DNA structure was maintained whilst the silver ion concentration was low. At high silver ion concentration, silver‐rich complexes displaying different CD spectra were formed.
Synthesis of Chiral Tertiary α,α‐Difluoromethyl Carbinols by Cu‐Catalyzed Asymmetric Propargylation
Authors: Guo Peihua , Zhang Rui , Wang Xiaoming , Wang Zheng , Ding Kuiling 
Published: October 2019

AbstractChiral α,α‐difluoromethyl carbinols are recurring structural motifs in many therapeutic agents. Despite the indubitable interest in the catalytic asymmetric synthesis of such compounds, this research field still remains largely underexplored. Herein, an efficient approach to a range of chiral homopropargylic α,α‐difluoromethyl carbinols has been developed, through a Cu‐catalyzed enantioselective propargylation of α,α‐difluoroketones with (pinacolato)allenylboron. In the presence of a cuprous complex, generated in situ from CuCl and a spiroketal‐based diphosphine (SKP) ligand, a variety of aryl‐, heteroaryl‐, alkyl‐, alkynyl, alkenyl, or benzyloxycarbonyl‐substituted α,α‐difluoromethyl carbinols were obtained in 75–99 % yields with 84–98 % ee values. The catalytic system was further investigated using a combined dynamic NMR spectroscopic, X‐ray crystallographic, and non‐linear effect studies. The origin of the enantioselectivity was rationalized based on DFT calculations. Finally, several efficient transformations were showcased to highlight the utilities of the protocol in synthesis of complex compounds bearing an α,α‐difluoromethyl carbinol moiety.
Four Methods to Estimate Minimum Miscibility Pressure of CO2‐Oil Based on Machine Learning
Authors: Li Ding , Li Xiangliang , Zhang Yinghua , Sun Lixin , Yuan Shiling 
Published: October 2019

Summary of main observation and conclusionCO2 flooding accounts for a considerable proportion in gas flooding. Using CO2 as a gas displacement agent is benefit for enhanced oil recovery (EOR), and the alleviation of the greenhouse effect by the permanent storage of CO2 in the crust. Minimum miscibility pressure (MMP) of CO2‐oil is a key factor affecting EOR, which determines the yield and economic benefit of crude oil recovery. Therefore, it is of great importance to use fast, accurate and cheap prediction methods for MMP estimation. In the present study, to evaluate the reliability of four recently developed prediction models based on machine learning (i.e., neural network analysis (NNA), genetic function approximation (GFA), multiple linear regression (MLR), partial least squares (PLS)), 136 sets of data are selected for calculation via outlier analysis from 147 sets of data. Afterwards, we compared the four models with existing prediction models from the literature. The analysis of correlation coefficients and multiple error functions shows that the four models can solve the MMP prediction problem well, and the model using intelligent algorithm has a higher prediction accuracy than the simple linear model. Besides, intelligent methods based on similarity algorithm have little difference from each other. Finally, a sensitivity analysis was conducted.
High neutrophil‐to‐lymphocyte ratio (NLR) is associated with treatment failure and death in patients who have melanoma treated with PD‐1 inhibitor monotherapy
Authors: Bartlett Edmund K. , Flynn Jessica R. , Panageas Katherine S. , Ferraro Richard A. , Sta.Cruz Jessica M. , Postow Michael A. , Coit Daniel G. , Ariyan Charlotte E. 
Published: October 2019

BackgroundAn elevated neutrophil‐to‐lymphocyte ratio (NLR) is associated with poor survival in patients with cancer, including those who receive immunotherapies. The authors sought to investigate NLR as a biomarker of treatment outcomes in patients with melanoma who were treated with PD‐1 inhibition.MethodsPatients undergoing initial treatment with PD‐1 inhibitor monotherapy for stage IV melanoma at a single center from 2012 to 2015 were included. Clinical characteristics and the NLR at baseline and before subsequent treatment cycles were collected. The time to treatment failure (TTF) and overall survival (OS) were evaluated using Kaplan‐Meier and landmark analyses.ResultsAmong 224 study patients, 63 (28%) had a baseline NLR ≥5. The baseline NLR was significantly associated with Eastern Cooperative Oncology Group performance status and the number of involved metastatic sites. With a median follow‐up of 39 months in survivors, a baseline NLR ≥5 was independently associated with shorter OS (hazard ratio, 2.0; 95% CI, 1.3‐2.9) and TTF (hazard ratio, 1.7; 95% CI, 1.2‐2.4). An NLR increase ≥30% during the first 2 cycles of treatment was associated with worse OS (median, 47 vs 13.5 months; P < .001) and a trend toward shorter TTF (12.8 vs 5.9 months; P = .05). A combined baseline NLR ≥5 and an NLR increase ≥30% identified a small cohort with markedly shortened OS (median, 5.8 months) and TTF (median, 1.8 months).ConclusionsElevated baseline NLR and an increased NLR early during treatment are prognostic for TTF and OS in patients who have melanoma treated with PD‐1 inhibitor monotherapy. Combined, these biomarkers can widely risk‐stratify patients for treatment failure and survival.