bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Platinum(II)‐Based Molecular Cage with Aggregation‐Induced Emission for Enzymatic Photocyclization of Alkynylaniline
Authors: Wei Zhong , Jing Xu , Yang Yang , Yuan Jiayou , Liu Mingxu , He Cheng , Duan Chunying 
Published: November 2022

AbstractEnzymes facilitate chemical conversions through the collective activity of aggregated components, but the marriage of aggregation‐induced emission (AIE) with molecular containers to emulate enzymatic conversion remains challenging. Herein, we report a new approach to construct a PtII‐based octahedral cage with AIE characteristics for the photocyclization of alkynylaniline by restricting the rotation of the pendant phenyl rings peripheral to the PtII corner. With the presence of water, the C−H⋅⋅⋅π interactions involving the triphenylphosphine fragments resulted in aggregation of the molecular cages into spherical particles and significantly enhanced the PtII‐based luminescence. The kinetically inert Pt‐NP chelator, with highly differentiated redox potentials in the ground and excited states, and the efficient coordination activation of the platinum corner facilitated excellent catalysis of the photocyclization of alkynylaniline. The enzymatic kinetics and the advantages of binding and activating substrates in an aqueous medium provide a new avenue to develop mimics for efficient photosynthesis.
Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence
Authors: Meng Xianghe , Zhang Xingyu , Liu Qingxiong , Zhou Zhengyang , Jiang Xingxing , Wang Yonggang , Lin Zheshuai , Xia Mingjun 
Published: November 2022

AbstractNonlinear optical (NLO) crystal, which simultaneously exhibits strong second‐harmonic‐generation (SHG) response and desired optical anisotropy, is a core optical material accessible to the modern optoelectronics. Accompanied by strong SHG effect in a NLO crystal, a contradictory problem of overlarge birefringence is ignored, leading to low frequency doubling efficiency and poor beam quality. Herein, a series of rare earth cyanurates RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) were successfully characterized by 3D electron diffraction technique. Based on a “three birds with one stone” strategy, they enable the simultaneous fulfillment of strong SHG responses (2.5–4.2× KH2PO4), short UV cutoff (ca. 220 nm) and applicable birefringence (ca. 0.15 at 800 nm) by the introduction of rare earth coordination control of π‐conjugated (C3N3O3)3− anions. These findings provide high‐performance short‐wavelength NLO materials and highlight the exploration of cyanurates as a new research area.
Oxidation and Reduction Pathways in the Knowles Hydroamination via a Photoredox‐Catalyzed Radical Reaction**
Authors: Harabuchi Yu , Hayashi Hiroki , Takano Hideaki , Mita Tsuyoshi , Maeda Satoshi 
Published: November 2022

AbstractSystematic reaction path exploration revealed the entire mechanism of Knowles's light‐promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non‐radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non‐adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield.
Controlling Selectivity in Shuttle Hetero‐difunctionalization Reactions: Electrochemical Transfer Halo‐thiolation of Alkynes
Authors: Dong Xichang , Klein Martin , Waldvogel Siegfried R. , Morandi Bill 
Published: November 2022

AbstractShuttle hetero‐difunctionalization reaction, in which two chemically distinct functional groups are transferred between two molecules, has long been an unmet goal due to the daunting challenges in controlling the chemo‐, regio‐, and stereoselectivity. Herein, we disclose an electrochemistry enabled shuttle reaction (e‐shuttle) to selectively transfer one RS− and one X− group between β‐halosulfides and unsaturated hydrocarbons via a consecutive paired electrolysis mechanism. The preferential anodic oxidation of one anion over the other, which is controlled by their distinct redox potentials, plays a pivotal role in controlling the high chemoselectivity of the process. This easily scalable methodology enables the construction of a myriad of densely functionalized β‐halo alkenyl sulfides in unprecedented chemo‐, regio‐, and stereoselectivity using benign surrogates, e.g., 2‐bromoethyl sulfide, avoiding the handling of corrosive and oxidative RS–Br reagents. In a broader context, these results open up new strategies for selective shuttle difunctionalization reactions.
Dithiol‐Activated Bioorthogonal Chemistry for Endoplasmic Reticulum‐Targeted Synergistic Chemophototherapy
Authors: Sun Jian , Zhang Xiaoran , Wang Xia , Peng Jinlei , Song Gang , Di Yufei , Feng Fude , Wang Shu 
Published: November 2022

AbstractThe controlled intracellular release of nitrite is still an unmet challenge due to the lack of bio‐friendly donors, and the antitumor effect of nitrite is limited by its physiologically inert activity. Herein, we designed benzothiadiazole‐based organic nitrite donors that are stable against bio‐relevant species but selectively respond to dithiol species through SNAr/intramolecular cyclization tandem reactions in the aqueous media. The bioorthogonal system was established to target the endoplasmic reticulum (ER) of liver cancer HepG2 cells. The nitrite and nonivamide were coupled to induce elevation of intracellular levels of calcium ions as well as reactive oxygen/nitrogen species, which resulted in ER stress and mitochondrial dysfunction. We demonstrated that a combination of photoactivation and “click to release” strategy could enhance antitumor effect in cellular level and show good potential for cancer precision therapy.
Selecting Better Biocatalysts by Complementing Recoded Bacteria**
Authors: Rubini Rudy , Jansen Suzanne C. , Beekhuis Houdijn , Rozeboom Henriëtte J. , Mayer Clemens 
Published: November 2022

AbstractIn vivo selections are powerful tools for the directed evolution of enzymes. However, the need to link enzymatic activity to cellular survival makes selections for enzymes that do not fulfill a metabolic function challenging. Here, we present an in vivo selection strategy that leverages recoded organisms addicted to non‐canonical amino acids (ncAAs) to evolve biocatalysts that can provide these building blocks from synthetic precursors. We exemplify our platform by engineering carbamoylases that display catalytic efficiencies more than five orders of magnitude higher than those observed for the wild‐type enzyme for ncAA‐precursors. As growth rates of bacteria under selective conditions correlate with enzymatic activities, we were able to elicit improved variants from populations by performing serial passaging. By requiring minimal human intervention and no specialized equipment, we surmise that our strategy will become a versatile tool for the in vivo directed evolution of diverse biocatalysts.
Tunable Electrochemical Peptide Modifications: Unlocking New Levels of Orthogonality for Side‐Chain Functionalization
Authors: Karipal Padinjare Veedu Dhanya , Connal Luke A. , Malins Lara R. 
Published: November 2022

AbstractElectrochemical transformations provide enticing opportunities for programmable, residue‐specific peptide modifications. Herein, we harness the potential of amidic side‐chains as underutilized handles for late‐stage modification through the development of an electroauxiliary‐assisted oxidation of glutamine residues within unprotected peptides. Glutamine building blocks bearing electroactive side‐chain N,S‐acetals are incorporated into peptides using standard Fmoc‐SPPS. Anodic oxidation of the electroauxiliary in the presence of diverse alcohol nucleophiles enables the installation of high‐value N,O‐acetal functionalities. Proof‐of‐principle for an electrochemical peptide stapling protocol, as well as the functionalization of dynorphin B, an endogenous opioid peptide, demonstrates the applicability of the method to intricate peptide systems. Finally, the site‐selective and tunable electrochemical modification of a peptide bearing two discretely oxidizable sites is achieved.
Discovery of new cinnamic derivatives as anti‐inflammatory agents for treating acute lung injury in mice
Authors: Chen Pengqin , Xu Zhengwei , Wang Xiemin , He Jie , Yang Jun , Wang Jun , Chattipakorn Nipon , Wu Di , Tang Qidong , Liang Guang , Chen Ting 
Published: November 2022

AbstractThe blockade of the overexpression of pro‐inflammatory cytokines by anti‐inflammatory natural products has been proven therapeutically beneficial in the treatment of acute lung injury (ALI). Given the fact that cinnamic acid has been proven to have significant anti‐inflammatory activity, we selected it as a promising lead compound to develop more effective analogs in treating ALI. Learning from the symmetric structure of curcumin, 32 new symmetric cinnamic derivatives were designed, synthesized, and evaluated for their anti‐inflammatory activity. Among them, 6h not only displayed a remarkable inhibitory activity in vitro (85.9% and 65.7% for IL‐6 and TNF‐α, respectively) without cytotoxicity but also possessed chemical structure stability. Furthermore, an in vivo study in mice revealed that the administration of 6h significantly attenuated lipopolysaccharide‐induced ALI, providing new lead structures for the development of anti‐inflammatory drugs for the treatment of ALI.
Graphic medicine meets human anatomy: The potential role of comics in raising whole body donation awareness in Italy and beyond. A pilot study
Authors: De Stefano Alessia , Rusciano Isabella , Moretti Veronica , Scavarda Alice , Green Michael J. , Wall Shelley , Ratti Stefano 
Published: November 2022

AbstractCadaver dissection has always played a fundamental role in medical education. However, especially in Italy, the topic of body donation has remained partially unknown for years. The current study analyses graphic medicine as a new possible communication tool, evaluating and reflecting, with second‐year students enrolled in the International School of Medicine and Surgery at the University of Bologna, about its potentialities for body donation awareness‐raising in both the scientific community and the general population. For the first time in an Italian University, two graphic medicine workshops were organized focusing on human anatomy and body donation. Seminars were positively evaluated by students using a four items Likert‐scale question: mean 3.54 (± SD 0.73) for the Likert question about the experiences of the workshops; 3.88 (± 0.33) for the Likert question regarding the use of graphic medicine in body donation awareness campaigns among the general population; 3.59 (± 0.65) for the Likert question regarding the use of graphic medicine in body donation awareness campaigns among the scientific community. Furthermore, the open‐ended questions included in the anonymous questionnaire were analyzed using the constructivist grounded qualitative analysis, whence various themes emerged. Finally, five graphic medicine projects about body donation were created by students, proving their interest in testing this method to promote body donation, focusing the attention on different communicative aspects. Considering the results of this pilot study, the co‐creative collaborative use of graphic medicine could be evaluated as an additional strategy to increase body donation awareness‐raising in Italy and beyond, especially in the non‐experts' community.
Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity
Authors: Ullah Khan Munir , Ullah Khan Safir , Cao Xiaohan , Usman Muhammad , Yue Xinchen , Ghaffar Abdul , Hassan Muhammad , Zhang Chengjian , Zhang Xinghong 
Published: November 2022

AbstractThis study demonstrates the superiority of a stable and well‐defined heterogeneous cobalt hexacyanocobaltate (Co3[Co(CN)6]2), a typical cobalt Prussian Blue Analogue (CoCo‐PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number‐average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0–3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen‐sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo‐PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS.
Sorting of cargo in the tubular endosomal network
Authors: Solinger Jachen A. , Spang Anne 
Published: November 2022

AbstractIntercellular communication is an essential process in all multicellular organisms. During this process, molecules secreted by one cell will bind to a receptor on the cognate cell leading to the subsequent uptake of the receptor‐ligand complex. Once inside, the cell then determines the fate of the receptor‐ligand complex and any other proteins that were endocytosed together. Approximately 80% of endocytosed material is recycled back to the plasma membrane either directly or indirectly via the Golgi apparatus and the remaining 20% is delivered to the lysosome for degradation. Although most pathways have been identified, we still lack understanding on how specificity in sorting of recycling cargos into different pathways is achieved, and how the cell reaches high accuracy of these processes in the absence of clear sorting signals in the bulk of the client proteins. In this review, we will summarize our current understanding of the mechanism behind recycling cargo sorting and propose a model of differential affinities between cargo and cargo receptors/adaptors with regards to iterative sorting in endosomes.
Machine learning with in silico analysis markedly improves survival prediction modeling in colon cancer patients
Authors: Lee Choong‐Jae , Baek Bin , Cho Sang Hee , Jang Tae‐Young , Jeon So‐El , Lee Sunjae , Lee Hyunju , Nam Jeong‐Seok 
Published: November 2022

AbstractBackgroundPredicting the survival of cancer patients provides prognostic information and therapeutic guidance. However, improved prediction models are needed for use in diagnosis and treatment.ObjectiveThis study aimed to identify genomic prognostic biomarkers related to colon cancer (CC) based on computational data and to develop survival prediction models.MethodsWe performed machine‐learning (ML) analysis to screen pathogenic survival‐related driver genes related to patient prognosis by integrating copy number variation and gene expression data. Moreover, in silico system analysis was performed to clinically assess data from ML analysis, and we identified RABGAP1L, MYH9, and DRD4 as candidate genes. These three genes and tumor stages were used to generate survival prediction models. Moreover, the genes were validated by experimental and clinical analyses, and the theranostic application of the survival prediction models was assessed.ResultsRABGAP1L, MYH9, and DRD4 were identified as survival‐related candidate genes by ML and in silico system analysis. The survival prediction model using the expression of the three genes showed higher predictive performance when applied to predict the prognosis of CC patients. A series of functional analyses revealed that each knockdown of three genes reduced the protumor activity of CC cells. In particular, validation with an independent cohort of CC patients confirmed that the coexpression of MYH9 and DRD4 gene expression reflected poorer clinical outcomes in terms of overall survival and disease‐free survival.ConclusionsOur survival prediction approach will contribute to providing information on patients and developing a therapeutic strategy for CC patients.
The Chromatin Regulator HMGA1a Undergoes Phase Separation in the Nucleus**
Authors: Zhu Hongjia , Narita Masako , Joseph Jerelle A. , Krainer Georg , Arter William E. , Olan Ioana , Saar Kadi L. , Ermann Niklas , Espinosa Jorge R. , Shen Yi , Kuri Masami Ando , Qi Runzhang , Welsh Timothy J. , Collepardo‐Guevara Rosana , Narita Masashi , Knowles Tuomas P. J. 
Published: November 2022

AbstractThe protein high mobility group A1 (HMGA1) is an important regulator of chromatin organization and function. However, the mechanisms by which it exerts its biological function are not fully understood. Here, we report that the HMGA isoform, HMGA1a, nucleates into foci that display liquid‐like properties in the nucleus, and that the protein readily undergoes phase separation to form liquid condensates in vitro. By bringing together machine‐leaning modelling, cellular and biophysical experiments and multiscale simulations, we demonstrate that phase separation of HMGA1a is promoted by protein‐DNA interactions, and has the potential to be modulated by post‐transcriptional effects such as phosphorylation. We further show that the intrinsically disordered C‐terminal tail of HMGA1a significantly contributes to its phase separation through electrostatic interactions via AT hooks 2 and 3. Our work sheds light on HMGA1 phase separation as an emergent biophysical factor in regulating chromatin structure.
Structure‐Dependent Electrical Conductance of DNA Origami Nanowires
Authors: Marrs Jonathan , Lu Qinyi , Pan Victor , Ke Yonggang , Hihath Joshua 
Published: November 2022

AbstractExploring the structural and electrical properties of DNA origami nanowires is an important endeavor for the advancement of DNA nanotechnology and DNA nanoelectronics. Highly conductive DNA origami nanowires are a desirable target for creating low‐cost self‐assembled nanoelectronic devices and circuits. In this work, the structure‐dependent electrical conductance of DNA origami nanowires is investigated. A silicon nitride (Si3N4) on silicon semiconductor chip with gold electrodes was used for collecting electrical conductance measurements of DNA origami nanowires, which are found to be an order of magnitude less electrically resistive on Si3N4 substrates treated with a monolayer of hexamethyldisilazane (HMDS) (∼1013 ohms) than on native Si3N4 substrates without HMDS (∼1014 ohms). Atomic force microscopy (AFM) measurements of the height of DNA origami nanowires on mica and Si3N4 substrates reveal that DNA origami nanowires are ∼1.6 nm taller on HMDS‐treated substrates than on the untreated ones indicating that the DNA origami nanowires undergo increased structural deformation when deposited onto untreated substrates, causing a decrease in electrical conductivity. This study highlights the importance of understanding and controlling the interface conditions that affect the structure of DNA and thereby affect the electrical conductance of DNA origami nanowires.
Recent advances in cold atmospheric plasma (CAP) for breast cancer therapy
Authors: Chupradit Supat , Widjaja Gunawan , Radhi Majeed Basman , Kuznetsova Maria , Ansari Mohammad Javed , Suksatan Wanich , Turki Jalil Abduladheem , Ghazi Esfahani Bahar 
Published: November 2022

AbstractThe serious problems of conventional breast cancer therapy strategies such as drug resistance, severe side effects, and lack of selectivity prompted the development of various cold atmospheric plasma (CAP) devices. Due to its advanced technology, CAP can produce a unique environment rich in reactive oxygen and nitrogen species (RONS), photons, charged ions, and an electric field, making it a promising revolutionary platform for cancer therapy. Despite substantial technological successes, CAP‐based therapeutic systems are encounter with distinct limitations, including low control of the generated RONS, poor knowledge about its anticancer mechanisms, and challenges concerning designing, manufacturing, clinical translation, and commercialization, which must be resolved. The latest developments in CAP‐based therapeutic systems for breast cancer treatment are discussed in this review. More significantly, the integration of CAP‐based medicine approaches with other breast cancer therapies, including chemo‐ and nanotherapy is thoroughly addressed.
Black liver in a patient with Wilson's disease
Authors: Jiang Wei , Zeng Qingmin , Liu Chang‐Hai , Wu Dongbo , Tang Hong 
Published: November 2022

AbstractWilson's disease is an autosomal recessive inherited disease with congenital copper metabolism disorder, characterized by decreased ceruloplasmin and increased urine copper, which can involve multiple organs. This case was complicated by iron overload, which is of great value in differentiating hereditary hemochromatism.
Diagnosis and management of rabies encephalitis in two patients in northwest Africa: A case series
Authors: Boushab Boushab Mohamed , Ahmed Benane Hacen , Ould Baba Sidi El‐Wafi , Basco Leonardo K. 
Published: November 2022

AbstractIn persons bitten by a stray dog, prompt administration of post‐exposure rabies vaccination, anti‐rabies immunoglobulin, and wound care can save lives. However, rabies is often fatal once the patient develops signs and symptoms. Here, we describe two fatal cases of rabies following a long delay after dog bites.
Urinary liver‐type fatty acid‐binding protein: A hemodynamic index during extracorporeal membrane oxygenation
Authors: Ichibayashi Ryo , Yamamoto Saki , Nakamichi Yoshimi , Masuyama Yuka , Serizawa Hibiki , Watanabe Masayuki , Yabe Takayuki , Honda Mitsuru 
Published: November 2022

AbstractWe discuss a case in which urinary L‐FABP measurements were used to manage a 46‐year‐old male patient receiving V‐A ECMO support. His mean blood pressure was ≥75 mmHg for the first 24 h after the initiation of V‐A ECMO, and he experienced a rapid decrease in urinary L‐FABP levels.
Monitored anesthesia care with remimazolam for gynecological day surgeries: Case reports
Authors: Choi So Ron , Kim Tae Hyung , Eom Deuk Won , Jung Ji Wook , Park Sang Yoong 
Published: November 2022

AbstractRemimazolam is a newly approved benzodiazepine characterized by rapid onset, predictable maintenance, fast recovery, and availability of a reversal agent. We describe four cases of patients who received monitored anesthesia care with remimazolam for gynecological day surgery.