bluuebunny/crossref_metadata_2025_split huggingface dataset:
Chemotherapy Mediated by Biomimetic Polymeric Nanoparticles Potentiates Enhanced Tumor Immunotherapy via Amplification of Endoplasmic Reticulum Stress and Mitochondrial Dysfunction
Authors: Guo Yunqi , Fan Yu , Wang Zhiqiang , Li Gaoming , Zhan Mengsi , Gong Junli , Majoral Jean‐Pierre , Shi Xiangyang , Shen Mingwu 
Published: September 2022

AbstractConstruction of multifunctional nanoplatforms to elevate chemotherapeutic efficacy and induce long‐term antitumor immunity still remains to be an extreme challenge. Herein, the design of an advanced redox‐responsive nanomedicine formulation based on phosphorus dendrimer–copper(II) complexes (1G3‐Cu)‐ and toyocamycin (Toy)‐loaded polymeric nanoparticles (GCT NPs) coated with cancer cell membranes (CM) are reported. The designed GCT@CM NPs with a size of 210 nm are stable under physiological conditions but are rapidly dissociated in the reductive tumor microenvironment to deplete glutathione and release drugs. The co‐loading of 1G3‐Cu and Toy within the NPs causes significant tumor cell apoptosis and immunogenic cell death through 1G3‐Cu‐induced mitochondrial dysfunction and Toy‐mediated amplification of endoplasmic reticulum stress, respectively, thus effectively suppressing tumor growth, promoting dendritic cell maturation, and increasing tumor‐infiltrating cytotoxic T lymphocytes. Likewise, the coated CM and the loaded 1G3‐Cu render the GCT@CM NPs with homotypic targeting and T1‐weighted magnetic resonance imaging of tumors, respectively. With the assistance of programmed cell death ligand 1 antibody, the GCT@CM NP‐mediated chemotherapy can significantly potentiate tumor immunotherapy for effective inhibition of tumor recurrence and metastasis. The developed GCT@CM NPs hold a great potential for chemotherapy‐potentiated immunotherapy of different tumor types through different mechanisms or synergies.
Chinese agriculture in the age of high‐speed rail: Effects on agricultural value added and food output
Authors: Gao Yanyan , Wang Xinping 
Published: September 2022

AbstractAlthough evidence shows that roads and conventional railways promote rural development, little is known about the impact of high‐speed rail (HSR) on agricultural output. To bridge this gap, this study explores how the establishment of HSR affects agricultural production. The causal effect was identified by constructing panel data mainly for Chinese counties between 2001 and 2017 using a difference‐in‐differences (DID) framework. The empirical results, after controlling for county‐specific linear trends, reveal that an HSR connection contributes to increasing agricultural value added and food output by approximately 4% and 6%, respectively. Moreover, the effects are mainly driven by increased productivity and adjustments to grain production and economic crops rather than the increased use of observed inputs. These results provide fresh evidence on the effect of transportation improvements on agricultural economies and highlight the need to control nonparallel trends when using the DID method to disentangle the effect. [EconLit Citations: O18, Q13, L92].
Palladium‐Catalyzed Alkenyl C−H Bonds Benzoxylation of Benzofurans by Perester
Authors: He Li , Xu Yongjun 
Published: September 2022

AbstractA palladium‐catalyzed intermolecular oxidative C−O bond formation for alkenyl C−H benzoxylation of benzofurans has been developed. This catalytic process utilizes perester as both the benzoxylate reagent and the oxidant to form the products in good to excellent yields under room temperature. A plausible mechanism was proposed based on the experimental data and mechanistic studies. It is noteworthy that this transformation performs well when using water as the only solvent.
Lewis Acid Catalyzed [3+3] Annulation/Aldol Condensation in Water: One Pot Synthesis of (E,E)‐4,6‐Bis(styryl)‐Pyrimidines
Authors: Singh Bal Dev , Pandey Jyoti , Khanam Huda , Singh Sameer 
Published: September 2022

AbstractAn efficient and facile one pot synthesis of (E,E)‐4,6‐bis(styryl)‐pyrimidines has been developed. It involves one pot two step reactions in environmentally benign solvent water, where first step involves pyrimidine ring formation from acetylacetone and urea via [3+3] annulation, followed by aldol condensation with differently substituted aromatic aldehyde to give desired (E,E)‐4,6‐bis(styryl)‐pyrimidines in moderate to good yields.
Nickel‐Hydride‐Catalyzed Diastereo‐ and Enantioselective Hydroalkylation of Cyclopropenes
Authors: Huang Qingqin , Chen Ya , Zhou Xueting , Dai Lei , Lu Yixin 
Published: September 2022

AbstractCyclopropanes are structural motifs that are widely present in natural products and bioactive molecules, and they are also tremendously useful building blocks in synthetic organic chemistry. Asymmetric synthesis of cyclopropane derivatives has been an intensively researched area over the years, but efficient asymmetric preparation of alkylcyclopropane scaffolds remains a challenging topic. Herein, we report a nickel‐hydride‐catalyzed enantioselective and diastereoselective hydroalkylation of cyclopropenes for facile synthesis of chiral alkylcyclopropane motifs. The reported method is efficient and versatile, taking place under mild reaction conditions, and having broad applicability and excellent functional group tolerance.
Efficient Photocatalytic Hydrogen and Oxygen Evolution by Side‐Group Engineered Benzodiimidazole Oligomers with Strong Built‐in Electric Fields and Short‐Range Crystallinity
Authors: Xu Jingyi , Li Wenlu , Liu Weixu , Jing Jianfang , Zhang Kunfeng , Liu Liping , Yang Jun , Zhu Enwei , Li Junshan , Zhu Yongfa 
Published: September 2022

AbstractThe insufficient charge separation and sluggish exciton transport severely limit the utilization of polymeric photocatalysts. To resolve the above issues, we incorporate bountiful carboxyl substituents within a novel benzodiimidazole oligomer and assemble it into a crystalline semiconductor. The photocatalyst is polar, hydrophilic, short‐range crystalline, and capable of both hydrogen and oxygen evolution. The introduction of carboxyl side‐groups adds asymmetry to the local structure and increases the built‐in electric field. Further, accelerated carrier transfer is enabled via the short‐range crystallinity. The superior hydrogen and oxygen production rates of 18.63 and 2.87 mmol g−1 h−1represent one of the best performances ever reported among dual‐functional polymeric photocatalysts. Our work initiates studies on high‐performance oligomer photocatalysts, opening a new frontier to produce solar fuel.
Bioinspired Total Synthesis of Pyritide A2 through Pyridine Ring Synthesis
Authors: Hooper Annie R. , Oštrek Andraž , Milian‐Lopez Ana , Sarlah David 
Published: September 2022

AbstractPyritides belong to the ribosomally synthesized and post‐translationally modified peptide class of natural products that were recently genome‐predicted and are structurally defined by unique pyridine‐containing macrocycles. Inspired by their biosynthesis, proceeding through peptide modification and cycloaddition to form the heterocyclic core, we report the chemical synthesis of pyritide A2 involving pyridine ring synthesis from an amino acid precursor through aza‐Diels–Alder reaction. This strategy permitted the preparation of the decorated pyridine core with an appended amino acid residue in two steps from a commercially available arginine derivative and secured pyritide A2 in ten steps. Moreover, the synthetic logic enables efficient preparation of different pyridine subunits associated with pyritides, allowing rapid and convergent access to this new class of natural products and analogues thereof.
Biosynthesis of the Plant‐Produced Toxin Strychnine Elucidated
Authors: Kandy Sanath K. , Chekan Jonathan R. 
Published: September 2022

AbstractWhile natural products isolated from plants have historically been an important source of bioactive molecules, elucidating their biosynthetic pathways has remained a challenging process. Strychnine is the one such compound known for its neurotoxicity and use as a rodent pesticide. Considerable interest has been shown in the synthesis of strychnine for many decades, yet little was known about its biosynthesis. A recent report from the O'Connor lab has solved this long‐standing puzzle using modern transcriptomics and transient expression approaches to uncover each enzyme responsible for the production of strychnine along with an unexpected final non‐enzymatic step.
Perfectly Isotactic Polypropylene upon In Situ Activation of Ultrarigid meso Hafnocenes
Authors: Stieglitz Lucas , Lenz Tim M. , Saurwein Andreas , Rieger Bernhard 
Published: September 2022

AbstractFor more than 40 years, the synthesis of C2‐symmetric indenyl‐based racemic metallocenes for the isoselective polymerization of propylene relied on a tedious separation of the produced rac and meso isomers. Status quo, latter are considered wasteful as they produce atactic polypropylene (aPP) rather than isotactic polypropylene (iPP) if activated with methylaluminoxane (MAO). Unexpectedly, the in situ activation of meso hafnocene I yielded perfectly isotactic polypropylene. We verified an isomerization of the meso compound to the corresponding racemic one upon triisobutylaluminum (TIBA) addition via nuclear magnetic resonance (NMR) spectroscopy and established an easy and convenient polymerization protocol, enabling productivities comparable to pure rac‐I if applied to pure meso‐I or a mixture of both isomers. With this established isomerization protocol, the potential yield of iPP was enhanced by more than 400 %. This protocol was also shown to be applicable to other meso hafnocenes and some initial mechanistic insights were received.
Narrowband Emissive TADF Conjugated Polymers towards Highly Efficient Solution‐Processible OLEDs
Authors: Wang Tao , Zou Yang , Huang Zhongyan , Li Nengquan , Miao Jingsheng , Yang Chuluo 
Published: September 2022

AbstractThermally activated delayed fluorescence (TADF) conjugated polymers usually show broad emission spectra due to the large structure relaxation, which is not desirable for high‐quality organic light‐emitting diode (OLED) displays. Herein, through attaching multiple resonance (MR) induced emitting moiety as pendant onto the polycarbazole backbone, TADF conjugated polymers with narrowband emission are demonstrated. The obtained conjugated polymers exhibit typical TADF characteristics with narrowband emission with full‐width at half‐maximums (FWHMs) of 33–43 nm. The solution‐processed devices employing these polymers as emissive layers realize excellent performances with maximum external quantum efficiency (EQE) of 17.5 %, emission peak at 496 nm and FWHM of 34 nm.
Strategies in synthetic design and structure–activity relationship studies of novel heterocyclic scaffolds as aldose reductase‐2 inhibitors
Authors: Yahya Shaikh , Haider Kashif , Pathak Ankita , Choudhary Akram , Hooda Pooja , Shafeeq Mohd , Shahar Yar Mohammad 
Published: September 2022

AbstractHeterocyclic scaffolds of natural as well as synthetic origin provide almost all categories of drugs exhibiting a wide range of pharmacological activities, such as antibiotics, antidiabetic and anticancer agents, and so on. Under normal homeostasis, aldose reductase 2 (ALR2) regulates vital metabolic functions; however, in pathological conditions like diabetes, ALR2 is unable to function and leads to secondary diabetic complications. ALR2 inhibitors are a novel target for the treatment of retinopathy (cataract) influenced by diabetes. Epalrestat (stat), an ALR2 inhibitor, is the only drug candidate that was approved in the last four decades; the other drugs from the stat class were retracted after clinical trial studies due to untoward iatrogenic effects. The present study summarizes the recent development (2014 and onwards) of this pharmacologically active ALR2 heterocyclic scaffold and illustrates the rationale behind the design, structure–activity relationships, and biological studies performed on these molecules. The aim of the current review is to pave a straight path for medicinal chemists and chemical biologists, and, in general, to the drug discovery scientists to facilitate the synthesis and development of novel ALR2 inhibitors that may serve as lead molecules for the treatment of diseases related to the ALR2 enzyme.
Risk factors and prognostic factors for pulmonary large cell neuroendocrine carcinoma with brain metastasis
Authors: Chen Xiaoyun , Huang Yedong , Chen Fangrong , She Hui , Chen Xiangqi 
Published: September 2022

AbstractBackgroundAs the studies regarding the brain metastasis (BM) of pulmonary large cell neuroendocrine carcinoma (LCNEC) are insufficient, the present research aims to describe the risk factors and prognostic factors that are related to cancer‐specific survival (CSS) for LCNEC patients with BM.MethodsThe data of LCNEC patients between January 2010 and October 2018 were obtained from the SEER database. Binary logistic regression analyses were utilized to screen the possible risk factors related to BM. Prognostic factors for LCNEC patients with BM were indentified by Cox regression analyses. Moreover, a nomogram was established to predict the 6‐, 12‐, and 18‐month CSS rates. The concordance index (C‐index), receiver operating characteristic (ROC) curves and calibration curves were utilized to assess the discrimination and reliability of the model. Clinical decision curves (DCAs) were used to evaluate the clinical benefits and utility of our model.ResultsTotally, 1875 patients were enrolled, with 294 (15.7%) of them having BM at diagnosis. Multivariate logistic regression analyses revealed that patients with age < 65 (odds ratio, OR = 1.564) and N2 staging (OR = 1.775) had a greater chance of developing BM. Age (≥ 65 vs. < 65: hazard ratio, HR = 1.409), T staging (T1 vs. T0: HR = 4.580; T2 vs. T0: HR = 6.008; T3 vs. T0: HR = 7.065; T4 vs. T0: HR = 6.821), N staging (N2 vs. N0: HR = 1.592; N3 vs. N0: HR = 1.654), liver metastasis (HR = 1.410), primary site surgery (HR = 0.581) and chemotherapy (HR = 0.452) were independent prognostic factors for LCNEC patients with BM. A nomogram prediction model was constructed by incorporating these factors. Using the C‐index, calibration curves, ROC curves, and DCAs, we found that the clinical prediction model performed well.ConclusionWe described the risk factors and prognostic factors that were associated with CSS for LCNEC patients with BM. The related nomogram was established and validated to help clinicians formulate more rational and effective treatment strategies.
Solid‐Liquid Mass Transfer of an Array of Separated Parallel Corrugated Plates
Authors: Elsobki Amira M. , Fouad Yasmine O. , Zewail Taghreed M. , Zaatout Ahmed A. , El-Ashtoukhy Elsayed Z. , Abdel-Aziz Mohamed H. , Sedahmed Gomaa H. 
Published: September 2022

AbstractA vertical array of corrugated copper plates was tested for its ability to conduct diffusion‐controlled liquid‐solid reactions. The mass transfer coefficient was investigated in terms of solution velocity, physical parameters of the solution, equivalent diameter of the channel, and array height. It was found that the mass transfer coefficient increases with increasing solution velocity and channel equivalent diameter while decreasing with increasing array height. Compared with flow through flat plates under the same conditions, flow across corrugated‐plate channels enhanced the mass transfer rate by a factor of 2–2.72. Dimensionless analysis was used to correlate the mass transfer data. The present work finds wide practical applications in enhancing mass transfer in many processes, such as membrane separation processes, electrochemical processes, heterogeneous liquid‐solid catalytic and photocatalytic reactions, and biochemical reactors in which enzymes or microorganisms are immobilized on such corrugated surfaces.
Photochemically Enhanced Emission by Introducing Rational Photoactive Subunits into an Aggregation‐Induced Emission Luminogen
Authors: Zhu Qiaozhi , Zhu Yuqing , Liu Weidong , Ping Xinni , Cai Xuting , Zuo Jiaqi , Qian Zhaosheng , Feng Hui 
Published: September 2022

AbstractHerein, we propose a rational design strategy by introducing photoactive thienyl and pyridyl groups into an AIE‐active tetraarylethene skeleton to achieve highly efficient photochemistry‐activated fluorescence enhancement from dominantly photo‐physical aggregation‐induced emission behavior, and prove that such photoactivated fluorescence enhancement is perfectly suited for superstable photocontrollable dual‐mode patterning applications in both solution and solid matrix. It is found that the photoactivated fluorescence of designed AIEgen is attributed to the irreversible cyclized‐dehydrogenation reaction under UV irradiation, and the oxidation product has a brighter fluorescence in both solution and solid states owning to its rigid and planar structure. The overall transformation rate of the AIEgen from its opened form to dehydrogenated form is up to nearly 100 % in a short period of UV irradiation, and the fast transformation and the stable product of this photochemical reaction guarantees super stability of photocontrolled patterning, which can be applied in photoactivated dual‐mode patterning and advanced anti‐counterfeiting.
Pnictogen‐Bridged Diphenyl Sulfones as Photoinduced Pnictogen Bond Forming Emission Motifs
Authors: Fujii Toshiki , Kusukawa Takahiro , Imoto Hiroaki , Naka Kensuke 
Published: September 2022

AbstractIn this study, pnictogen (Pn)‐bridged diphenyl sulfones were synthesized as motifs for photoinduced dynamic rearrangement. The newly synthesized sulfones exhibited dual fluorescence at 298 K. Density functional theory calculations revealed that the longer‐wavelength fluorescence was derived from the geometries after structural relaxation through photo‐driven pnictogen bond formation between the O atom lone pair of the sulfonyl moiety and the antibonding orbital of the Pn−C bond. This is the first report on emission dynamics driven by pnictogen bond formation upon photoexcitation.
Single‐Metal‐Encapsulated Double‐Cage [Pt@Sn17]4−: An Exception from Group 14 Endohedral Clusters
Authors: Xu Hong‐Lei , Studvick Chad , Liu Chao , Xue Yuan , Popov Ivan A. , Sun Zhong‐Ming 
Published: September 2022

AbstractGroup 14 endohedral clusters containing a metal center inside usually possess a single cage topological structure, but here an unexpected single‐metal‐filled double‐cage cluster, [Pt@Sn17]4− (1 a) is reported. It can be seen as a combination of the more extended Pt‐filled [Pt@Sn9] cage and hollow [Sn9] cage sharing a central Sn atom, which is offset from the central position. This double‐cage species represents the largest group 14 intermetalloid cluster encapsulating a single transition metal atom. DFT calculations show that the capsule‐like architecture of [Sn17]4−, similar to that found in [Pt2@Sn17]4−, is unstable if filled with a single Pt atom and collapses to the title cluster 1 a upon geometry optimization. Deviation of the central Sn atom occurs due to the vibronic coupling as a consequence of pseudo‐Jahn‐Teller distortion leading to the bent Cs‐symmetrical structure, in contrast to the more symmetrical D2d cage previously reported in [Ni2@Sn17]4−.
Long‐Term, Single‐Molecule Imaging of Proteins in Live Cells with Photoregulated Fluxional Fluorophores
Authors: Eördögh Ádám , Martin Annabell , Rivera‐Fuentes Pablo 
Published: September 2022

AbstractSingle‐molecule localization microscopy (SMLM) can reveal nanometric details of biological samples, but its high phototoxicity hampers long‐term imaging in live specimens. A significant part of this phototoxicity stems from repeated irradiations that are necessary for controlled switching of fluorophores to maintain the sparse labeling of the sample. Lower phototoxicity can be obtained using fluorophores that blink spontaneously, but controlling the density of single‐molecule emitters is challenging. We recently developed photoregulated fluxional fluorophores (PFFs) that combine the benefits of spontaneously blinking dyes with photocontrol of emitter density. These dyes, however, were limited to imaging acidic organelles in live cells. Herein, we report a systematic study of PFFs that culminates in probes that are functional at physiological pH and operate at longer wavelengths than their predecessors. Moreover, these probes are compatible with HaloTag labeling, thus enabling timelapse, single‐molecule imaging of specific protein targets for exceptionally long times.
Potential‐Dependent Pt(111)/Water Interface: Tackling the Challenge of a Consistent Treatment of Electrochemical Interfaces**
Authors: Braunwarth Laura , Jung Christoph , Jacob Timo 
Published: September 2022

AbstractThe interface between an electrode and an electrolyte is where electrochemical processes take place for countless technologically important applications. Despite its high relevance and intense efforts to elucidate it, a description of the interfacial structure and, in particular, the dynamics of the electric double layer at the atomic level is still lacking. Here we present reactive force‐field molecular dynamics simulations of electrified Pt(111)/water interfaces, shedding light on the orientation of water molecules in the vicinity of the Pt(111) surface, taking into account the influence of potential, adsorbates, and ions simultaneously. We obtain a shift in the preferred orientation of water in the surface oxidation potential region, which breaks with the previously proclaimed strict correlation to the free charge density. Moreover, the characterization is complemented by course of the entropy and the intermolecular ordering in the interfacial region complements the characterization. Our work contributes to the ongoing process of understanding electric double layers and, in particular, the structure of the electrified Pt(111)/water interface, and aims to provide insights into the electrochemical processes occurring there.
Monitoring the Light‐induced Isomerisation of the Prototypical Polycyclic Aromatic Hydrocarbons C10H8+ through Ion‐Molecule Reactions
Authors: Jacovella Ugo , Rossi Corentin , Romanzin Claire , Alcaraz Christian , Thissen Roland 
Published: September 2022

AbstractStructural rearrangements in ions are essential for understanding the composition and evolution of energetic and chemically active environments. This study explores the interconversion routes for simple polycyclic aromatic hydrocarbons, namely naphthalene and azulene radical cations (C10H8+), by combining mass spectrometry and vacuum ultraviolet tunable synchrotron radiation through the chemical monitoring technique. Products of ion‐molecule reactions are used to probe C10H8+ structures that are formed as a function of their internal energies. Isomerisation from azulene radical cation towards naphthalene radical cation in a timescale faster than 80 μs was monitored, whereas no reverse isomerisation was observed in the same time window. When energising C10H8+ with more than 6 eV, the reactivity of C10H8+ unveils the formation of a new isomeric group with a contrasted reactivity compared with naphthalene and azulene cations. We tentatively assigned these structures to phenylvinylacetylene cations.