bluuebunny/crossref_metadata_2025_split huggingface dataset:
Substrate‐ and Catalyst‐Controlled C−H Bond Activation/Annulation for Construction of Pyrido[2,3,4‐de]quinazolinones and Indolo[1,2‐c]quinazolinones
Authors: Hou Xinjiao , Wang Run , Zhou Jianhui , Li Yuan , Li Jiyuan , Liu Hong , Wang Dechuan , Zhou Yu 
Published: November 2023

AbstractA substrate and catalyst‐controlled synthetic strategy was employed to construct two distinct types of fused polycyclic heterocycles, namely pyrido[2,3,4‐de]quinazolinones and indolo[1,2‐c]quinazolinones. The most notable advantage of this method is its ability to rapidly generate two different polycyclic scaffolds via a simple C−H activation and subsequent cyclization cascade pathway. Specifically, sulfoxonium ylides played a crucial role in both transformations, serving as a two‐carbon synthon and a one‐carbon synthon, to independently construct the two fused polycyclic scaffolds through [4+2] and [4+1] annulation pathways, respectively.
Catalyst‐Free, Air‐Mediated C(sp2)−H Alkylation of Cyclic Aldimines with Alkylboronic Acids
Authors: Zhang Jie , Li Xiaolan , Liao Lieqiang , Liu Haidong , Luo Haiqing 
Published: November 2023

AbstractThe air mediated radical alkylation of cyclic aldimines via autoxidation of alkylboronic acids has been realized under mild reaction conditions. By simply heating cyclic aldimines with alkylboronic acid using air as sole oxidant, this protocol provides a catalyst‐free access to a variety of alkylated cyclic aldimines with 21–91% yields. Preliminary mechanistic studies suggest that a radical pathway might be involved in the reaction.
Universal and Energy‐Efficient Approach to Synthesize Pt‐Rare Earth Metal Alloys for Proton Exchange Membrane Fuel Cell
Authors: Jiang Nannan , Huang Bing , Wang Minghao , Chen Yumo , Yu Qiangmin , Guan Lunhui 
Published: November 2023

AbstractTraditional synthesis methods of platinum‐rare earth metal (Pt‐RE) alloys usually involve harsh conditions and high energy consumption because of the low standard reduction potentials and high oxophilicity of RE metals. In this work, a one‐step strategy is developed by rapid Joule thermal‐shock (RJTS) to synthesize Pt‐RE alloys within tens of seconds. The method can not only realize the regulation of alloy size, but also a universal method for the preparation of a family of Pt‐RE alloys (RE = Ce, La, Gd, Sm, Tb, Y). In addition, the energy consumption of the Pt‐RE alloy preparation is only 0.052 kW h, which is 2–3 orders of magnitude lower than other reported methods. This method allows individual Pt‐RE alloy to be embedded in the carbon substrate, endowing the alloy catalyst excellent durability for oxygen reduction reaction (ORR). The performance of alloy catalyst shows negligible decay after 20k accelerated durability testing (ADT) cycles. This strategy offers a new route to synthesize noble/non‐noble metal alloys with diversified applications besides ORR.
Evolutionary Spread of Distinct O‐methyltransferases Guides the Discovery of Unique Isoaspartate‐Containing Peptides, Pamtides
Authors: Lee Hyunbin , Park Sho Hee , Kim Jiyoon , Lee Jaehak , Koh Min Sun , Lee Jung Ho , Kim Seokhee 
Published: November 2023

AbstractRibosomally synthesized and post‐translationally modified peptides (RiPPs) are a structurally diverse class of natural products with a distinct biosynthetic logic, the enzymatic modification of genetically encoded precursor peptides. Although their structural and biosynthetic diversity remains largely underexplored, the identification of novel subclasses with unique structural motifs and biosynthetic pathways is challenging. Here, it is reported that peptide/protein L‐aspartyl O‐methyltransferases (PAMTs) present in several RiPP subclasses are highly homologous. Importantly, it is discovered that the apparent evolutionary transmission of the PAMT gene to unrelated RiPP subclasses can serve as a basis to identify a novel RiPP subclass. Biochemical and structural analyses suggest that homologous PAMTs convert aspartate to isoaspartate via aspartyl‐O‐methyl ester and aspartimide intermediates, and often require cyclic or hairpin‐like structures for modification. By conducting homology‐based bioinformatic analysis of PAMTs, over 2,800 biosynthetic gene clusters (BGCs) are identified for known RiPP subclasses in which PAMTs install a secondary modification, and over 1,500 BGCs where PAMTs function as a primary modification enzyme, thereby defining a new RiPP subclass, named pamtides. The results suggest that the genome mining of proteins with secondary biosynthetic roles can be an effective strategy for discovering novel biosynthetic pathways of RiPPs through the principle of “guilt by association”.
Serum NY‐ESO‐1 and p53 antibodies as useful tumor markers in gastric cancer
Authors: Kawada Junji , Saito Takuro , Kurokawa Yukinori , Kawabata Ryohei , Takeno Atsushi , Takeoka Tomohira , Nose Yohei , Wada Hisashi , Eguchi Hidetoshi , Doki Yuichiro ,   Osaka University Clinical Research Group for Gastroenterological Study
Published: November 2023

AbstractPurposeThe NY‐ESO‐1 antigen is highly immunogenic and often spontaneously induces an immune response in patients with cancer. We conducted a large‐scale multicenter cohort study to investigate the utility of serum NY‐ESO‐1 and p53 antibodies as predictive markers for the postoperative recurrence of gastric cancer. Here, we examined the usefulness of pre‐treatment NY‐ESO‐1 and p53 antibodies as tumor markers for the diagnosis of gastric cancer in combination with carcinoembryonic antigen (CEA) and carbohydrate antigen 19‐9 (CA19‐9).MethodsA total of 1031 patients with cT3‐4 gastric cancer were enrolled in the study. NY‐ESO‐1 and p53 antibodies were assessed prior to treatment. The positivity of NY‐ESO‐1 and p53 antibodies, CEA, and CA19‐9 was evaluated before treatment.ResultsSerum NY‐ESO‐1 and p53 antibodies were positive in 12.6% and 18.1% of the patients, respectively. Positive NY‐ESO‐1 antibody response was correlated with male gender, higher cStage, and upper tumor location. However, a positive p53 antibody response was not associated with tumor factors. The combination of NY‐ESO‐1 or p53 antibody response with CEA and CA19‐9, or the 4‐factors, was positive in 45.1%, 49.6%, and 53.8% of patients, respectively. Moreover, the 4‐factor combination was able to detect >60% of cStage III‐IV diseases, which was 14% higher than that with the combination of CEA and CA19‐9.ConclusionThe combination of NY‐ESO‐1 and p53 antibody responses to CEA and CA19‐9 increases the diagnostic accuracy of gastric cancer. Serum NY‐ESO‐1 and p53 antibodies may be useful tumor markers for gastric cancer.
Synchronous Elimination of Excess Photoinstable PbI2 and Interfacial Band Mismatch for Efficient and Stable Perovskite Solar Cells
Authors: He Jiacheng , Sheng Wangping , Yang Jia , Zhong Yang , Cai Qianqian , Liu Yikun , Guo Zhao , Tan Licheng , Chen Yiwang 
Published: November 2023

AbstractEliminating the undesired photoinstability of excess lead iodide (PbI2) in the perovskite film and reducing the energy mismatch between the perovskite layer and heterogeneous interfaces are urgent issues to be addressed in the preparation of perovskite solar cells (PVSCs) by two‐step sequential deposition method. Here, the 1‐ethyl‐3‐methylimidazolium tetrafluoroborate (EMIMBF4) is employed to convert superfluous PbI2 to more robust 1D EMIMPbI3 which can withstand lattice strain, while forming an interfacial dipole layer at the SnO2/perovskite interface to reconfigure the interfacial energy band structure and accelerate the charge extraction. Consequently, the unencapsulated PVSCs device attains a champion efficiency of 24.28 % with one of the highest open‐circuit voltage (1.19 V). Moreover, the unencapsulated devices showcase significantly improved thermal stability, enhanced environmental stability and remarkable operational stability accompanied by 85 % of primitive efficiency retained over 1500 h at maximum power point tracking under continuous illumination.
Bent π‐Conjugation within a Macrocycle: Asymmetric Total Syntheses of Spirohexenolides A and B
Authors: Guo Lian‐Dong , Wu Yanting , Xu Xin , Lin Zhenyang , Tong Rongbiao 
Published: November 2023

AbstractMacrocycles with bent π‐conjugation motif are extremely rare in nature and synthetically daunting and anticancer haouamines and spirohexenolides were representative of such rare natural products with synthetically challenging bent π‐conjugation within a macrocycle. While the total synthesis of haouamines has been elegantly achieved, spirohexenolides remains an unmet synthetic challenge due to the highly strained bent 1,3,5‐triene conjugation within C15 macrocycle. Inspired by the chemical synthesis of cycloparaphenylenes (CPPs) and haouamines, herein we devise a synthetic strategy to overcome the highly strained bent 1,3,5‐triene conjugation within the macrocycle and achieve the first, asymmetric total synthesis of spirohexenolides A (>20 mg) and B (>50 mg). Our synthesis features strategic design of ring‐closing metathesis (RCM) macrocyclization followed by double dehydration to achieve the C15 macrocycle with the deformed nonplanar 1,3,5‐triene conjugation. In addition, we have developed a new enantioselective construction of highly functionalized spirotetronate fragment (northeast moiety) through RCM and Ireland–Claisen rearrangement. Our in vitro bioassay studies reveal that both spirohexenolides are cytotoxic against a panel of human cancer cells with IC50 1.2–13.3 μM and spirohexenolide A is consistently more potent (up to 3 times) than spirohexenolide B, suggesting the importance of alcohol for their bioactivity and for medicinal chemistry development.
Pd8 Nanocluster with Nonmetal‐to‐Metal‐ Ring Coordination and Promising Photothermal Conversion Efficiency
Authors: You Qing , Jiang Xue‐Lian , Fan Wentao , Cui Yun‐Shu , Zhao Yan , Zhuang Shengli , Gu Wanmiao , Liao Lingwen , Xu Cong‐Qiao , Li Jun , Wu Zhikun 
Published: November 2023

AbstractConstructing ambient‐stable, single‐atom‐layered metal‐based materials with atomic precision and understanding their underlying stability mechanisms are challenging. Here, stable single‐atom‐layered nanoclusters of Pd were synthesized and precisely characterized through electrospray ionization mass spectrometry and single‐crystal X‐ray crystallography. A pseudo‐pentalene‐like Pd8 unit was found in the nanocluster, interacting with two syn PPh units through nonmetal‐to‐metal ‐ring coordination. The unexpected coordination, which is distinctly different from the typical organoring‐to‐metal coordination in half‐sandwich‐type organometallic compounds, contributes to the ambient stability of the as‐obtained single‐atom‐layered nanocluster as revealed through theoretical and experimental analyses. Furthermore, quantum chemical calculations revealed dominant electron transition along the horizontal x‐direction of the Pd8 plane, indicating high photothermal conversion efficiency (PCE) of the nanocluster, which was verified by the experimental PCE of 73.3 %. Therefore, this study unveils the birth of a novel type of compound and the finding of the unusual nonmetal‐to‐metal ‐ring coordination and has important implications for future syntheses, structures, properties, and structure–property correlations of single‐atom‐layered metal‐based materials.
Regiodivergent Carbonylation of Alkenes: Selective Palladium‐Catalyzed Synthesis of Linear and Branched Selenoesters
Authors: Cao Zhusong , Wang Qiang , Neumann Helfried , Beller Matthias 
Published: November 2023

AbstractAn unprecedented regiodivergent palladium‐catalyzed carbonylation of aromatic alkenes has been developed. Utilizing commercially available Pd(CH3CN)2Cl2 in the presence of 1,1′‐ferrocenediyl‐bis(tert‐butyl(pyridin‐2‐yl)phosphine) ligand L8 diverse selenoesters are obtained in a straightforward manner. Key to success for the control of the regioselectivity of the carbonylation step is the concentration of the acidic co‐catalyst. This general protocol features wide functional group compatibility and good regioselectivity. Mechanistic studies suggest that the presence of stoichiometric amounts of acid changes the properties and coordination mode of the ligand leading to reversed regioselectivity.
Main‐chain Macromolecular Hydrazone Photoswitches
Authors: Thai Linh Duy , Fanelli Julian , Munaweera Rangika , O'Mara Megan L. , Barner‐Kowollik Christopher , Mutlu Hatice 
Published: November 2023

AbstractHydrazones—consisting of a dynamic imine bond and an acidic NH proton—have recently emerged as versatile photoswitches underpinned by their ability to form thermally bistable isomers, (Z) and (E), respectively. Herein, we introduce two photoresponsive homopolymers containing structurally different hydrazones as main‐chain repeating units, synthesized via head‐to‐tail Acyclic Diene METathesis (ADMET) polymerization. Their key difference lies in the hydrazone design, specifically the location of the aliphatic arm connecting the rotor of the hydrazone photoswitch to the aliphatic polymer backbone. Critically, we demonstrate that their main photoresponsive property, i.e., their hydrodynamic volume, changes in opposite directions upon photoisomerization (λ=410 nm) in dilute solution. Further, the polymers—independent of the design of the individual hydrazone monomer—feature a photoswitchable glass transition temperature (Tg) by close to 10 °C. The herein established design strategy allows to photochemically manipulate macromolecular properties by simple structural changes.
Chemically decomposable imine‐based thermoset using oxidized sugar
Authors: Jeong Jisu , Goh Munju 
Published: November 2023

AbstractIncreasing environmental concerns have driven the pursuit of sustainable alternatives to petrochemical‐based plastics in polymer chemistry. In this study, we demonstrated a method by which sugar, the most chemically produced biomass, can be used as a thermosetting resin. The sucrose was successfully oxidized, synthesized, and then incorporated into a resin. Sodium periodate (NaIO4) was used to convert sucrose into chemical raw materials. The resulting polymer, prepared via the imine reaction, exhibited a glass transition temperature Tg of 96°C, as determined by differential scanning calorimetry. Additionally, the thermosetting resin exhibited a tensile strength of 7 MPa, a modulus of 515 MPa, and a Tg of 100°C. We obtained reaction rate constants of 0.7 × 10−3 h−1 and 3.2 × 10−1 h−1 using THF and citric acid solutions, respectively. Furthermore, we reused the resin from the decomposed organic matter and confirmed that the resynthesized overall, our findings suggest the potential for green recycling by converting commonly used sugars into nature‐derived raw materials, leading to the development of eco‐friendly polymer synthesis.
Sulfurization of Electrode Material: A Promising Window for Supercapacitor Technology
Authors: Khan Junaid , Shakeel Noshaba , Alam Shahid , Alam Faiz , Dahshan Alaa 
Published: November 2023

AbstractSupercapacitors have emerged as a promising energy storage technology with attributes like high power and tuneable energy density along with splined cyclic potential. Their performance is heavily driven by the employed electrode materials that still crave high charge storage and rate capabilities as well as virile conductivity. Among numerous applied strategies to patch the corresponding quandary, sulfurization has garnered significant attention as an effective method for improving the electrochemical depiction of electrode materials. This review article presents a comprehensive analysis of the sulfurization process applied to the electrode with the aim of providing profound overview of the latest developments, the impact of sulfur incorporation on electrode properties, and the resulting performance enhancement in supercapacitors. It explores the influence of sulfidation on the morphological, structural, and compositional aspects of electrode materials, highlighting the modification of surface area, pore size distribution, crystal structure, and the formation of active sites. The discussions on the improved specific capacitance, enhanced rate capability, prolonged cycle life, and upgraded energy density achieved are accumulated. Additionally, the review explores the challenges and limitations associated with sulfurization and strategies to mitigate trials for future directions of research and developments.
Pax‐8: Molecular biology, pathophysiology, and potential pathogenesis
Authors: Zhou Qinyi , Li Heng , Cheng Yaqiong , Ma Xiaofeng , Tang Shilin , Tang Chaoke 
Published: November 2023

AbstractTranscription factors, as the convergence points of multiple signaling pathways in eukaryotic cells, are closely involved in disease development. Pax‐8, an important transcription factor belonging to the Pax family, exerts a crucial influence on the regulation of gene expression required for both physiological conditions and pathological processes. Pax‐8 contributes to the pathogenesis of many human diseases, ranging from cardiovascular disease to many cancers, and therefore, it can be imagined that Pax‐8 holds great therapeutic potential. In this review, we summarize the structure, distribution, function, and regulatory mechanisms of Pax‐8 to provide a new research direction for Pax‐8.
On‐line targeted metabolomics for real‐time monitoring of relevant compounds in fermentation processes
Authors: Cortada‐Garcia Joan , Haggarty Jennifer , Weidt Stefan , Daly Rónán , Arnold S. Alison , Burgess Karl 
Published: November 2023

AbstractFermentation monitoring is a powerful tool for bioprocess development and optimization. On‐line metabolomics is a technology that is starting to gain attention as a bioprocess monitoring tool, allowing the direct measurement of many compounds in the fermentation broth at a very high time resolution. In this work, targeted on‐line metabolomics was used to monitor 40 metabolites of interest during three Escherichia coli succinate production fermentation experiments every 5 min with a triple quadrupole mass spectrometer. This allowed capturing high‐time resolution biological data that can provide critical information for process optimization. For nine of these metabolites, simple univariate regression models were used to model compound concentration from their on‐line mass spectrometry peak area. These on‐line metabolomics univariate models performed comparably to vibrational spectroscopy multivariate partial least squares regressions models reported in the literature, which typically are much more complex and time consuming to build. In conclusion, this work shows how on‐line metabolomics can be used to directly monitor many bioprocess compounds of interest and obtain rich biological and bioprocess data.
Pushing the boundaries of phosphorylase cascade reaction for cellobiose production II: Model‐based multiobjective optimization
Authors: Sigg Alexander , Klimacek Mario , Nidetzky Bernd 
Published: November 2023

AbstractThe inherent complexity of coupled biocatalytic reactions presents a major challenge for process development with one‐pot multienzyme cascade transformations. Kinetic models are powerful engineering tools to guide the optimization of cascade reactions towards a performance suitable for scale up to an actual production. Here, we report kinetic model‐based window of operation analysis for cellobiose production (≥100 g/L) from sucrose and glucose by indirect transglycosylation via glucose 1‐phosphate as intermediate. The two‐step cascade transformation is catalyzed by sucrose and cellobiose phosphorylase in the presence of substoichiometric amounts of phosphate (≤27 mol% of substrate). Kinetic modeling was instrumental to uncover the hidden effect of bulk microviscosity due to high sugar concentrations on decreasing the rate of cellobiose phosphorylase specifically. The mechanistic‐empirical hybrid model thus developed gives a comprehensive description of the cascade reaction at industrially relevant substrate conditions. Model simulations serve to unravel opposed relationships between efficient utilization of the enzymes and maximized concentration (or yield) of the product within a given process time, in dependence of the initial concentrations of substrate and phosphate used. Optimum balance of these competing key metrics of process performance is suggested from the model‐calculated window of operation and is verified experimentally. The evidence shown highlights the important use of kinetic modeling for the characterization and optimization of cascade reactions in ways that appear to be inaccessible to purely data‐driven approaches.
Advances in the role of circulating tumor cell heterogeneity in metastatic small cell lung cancer
Authors: Wang Qunxia , Tan Li‐Ming 
Published: November 2023

AbstractSmall cell lung cancer (SCLC), a highly aggressive malignancy, is rapidly at an extensive stage once diagnosed and is one of the leading causes of death from malignancy. In the past decade, the treatment of SCLC has largely remained unchanged, and chemotherapy remains the cornerstone of SCLC treatment. The therapeutic value of adding immune checkpoint inhibitors to chemotherapy for SCLC is low, and only a few SCLC patients have shown a response to immune checkpoint inhibitors. Circulating tumor cells (CTCs) are tumor cells shed from solid tumor masses into the peripheral circulation and are key to tumor metastasis. Single‐cell sequencing has revealed that the genetic profiles of individual CTCs are highly heterogeneous and contribute to the poor outcome and prognosis of SCLC patients. Theoretically, phenotypic analysis of CTCs may be able to predict the diagnostic significance of new potential targets for metastatic tumors. In this paper, we will discuss in depth the heterogeneity of CTCs in SCLC and the value of CTCs for the diagnosis and prognosis of SCLC and as relevant tumor markers in metastatic SCLC.
Radiotranscriptomics identified new mRNAs and miRNA markers for distinguishing prostate cancer from benign prostatic hyperplasia
Authors: Yang Qian , Li Qiuyang , Li Nan , Wang Dingyi , Niu Shaoxi , Tang Peng , Xiao Jing , Zhao Jiahang , Wang Pei , Luo Yukun , Tang Jie 
Published: November 2023

AbstractThe present study investigated ultrasound (US) phenotypes reflecting prostate cancer (PCa)‐related genetic mutations. Herein, integration of radiotranscriptomic data, US and contrast‐enhanced ultrasound (CEUS) radiomic images, and RNA sequencing was performed with the aim of significantly improving the accuracy of PCa prognosis. We performed radiotranscriptomic analysis of clinical, imaging, and two genomic (mRNA and microRNA expression) datasets from 48 and 22 men with PCa and benign prostatic hyperplasia (BPH), respectively. Twenty‐three US texture features and four microvascular perfusion features were associated with various patterns of 52 differentially expressed genes related to PCa (p < 0.05); 17 overexpressed genes were associated with two key texture features. Twelve overexpressed genes were identified using microvascular perfusion features. Furthermore, mRNA and miRNA biomarkers could be used to distinguish between PCa and BPH. Compared with RNA sequencing, B‐mode and CEUS features reflected genomic alterations associated with hormone receptor status, angiogenesis, and prognosis in patients with PCa. These findings indicate the potential of US to assess biomarker levels in patients with PCa.