bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phosphino‐Phosphination Reactions: Frustrated Lewis Pair Reactivity of Phosphino‐Phosphonium Cations with Alkynes
Authors: Kim Hyehwang , Qu Zheng‐wang , Grimme Stefan , Al‐Zuhaika Nahil , Stephan Douglas W. 
Published: September 2023

AbstractThe phosphino‐phosphonium cations of the form [R3PPR′2]+ are labile and provide access to the constituent Lewis acidic and Lewis basic fragments. This permits frustrated Lewis pair‐type addition reactions to alkynes, affording unprecedented phosphino‐phosphination reactions and giving cations of the form [cis‐R3PCHC(R′′)PR′2]+. This reactivity is further adapted to prepare several examples of a rare class of dissymmetric cis‐olefin‐linked bidentate phosphines.
Counter‐Anions Rendered Weak‐Interactions Perturb the Stability of Tyrosinase‐Mimicked Peroxo‐Dicopper(II) Active Site: Unraveling Computational Indicators
Authors: Arora Sumangla , Gupta Puneet 
Published: September 2023

AbstractIt has been observed in literature that the stability of tyrosinase‐mimicked μ‐η2:η2‐peroxo‐dicopper(II) (P) can be perturbed in presence of counter‐anions (CAs) such as PhCO2−, CF3SO3−, TsO− and SbF6−. In this work, we unravel computational indicators using density functional theory to screen and study the stability of P in experimentally‐reported cases. These indicators are Gibbs energies, geometrical parameters such as distances and angles, independent gradient model based on Hirshfeld partition (IGMH) generated data, orbitals’ overlap, and distortion‐interaction (DI) energies. Our DFT computed Gibbs energies indicate that P is stable in case of PhCO2− and TsO−. CF3SO3− allows P and its isoelectronic species bis‐μ‐oxo‐dicopper (O) to coexist. SbF6− shows that O is in excess. Our indicators reveal that the stability of P in case of PhCO2− and TsO− is due to the better placing of P and its CA, thus leading to better interactions and overlap of orbitals. Other indicator displays that the plane of Cu2O2 core in P is more bend in PhCO2− and TsO− cases as compared to the plane in the other two cases. In addition, the IGMH‐based indicator displays higher values in the case of PhCO2− and TsO− than the other CAs.
Review on carbon dots: Synthesis and application in biology field
Authors: Li Xueting , Yu Lidong , He Mingyue , Chen Ce , Yu Zewen , Jiang Shanshan , Wang Yi , Li Li , Li Bingsheng , Wang Guixue , Shen Aidong , Fan Jianglin 
Published: September 2023

AbstractAs a multifunctional fluorescent nanomaterial, carbon dots (CDs) not only have small size, stable chemical properties, excellent photoluminescence characteristics, but also exhibit good biocompatibility and low toxicity. It has attracted considerable attention in the field of nanotechnology and biological science. CDs contain abundant functional groups on the surface, which not only retain part of the properties of raw materials, but also may have new photoelectric, catalytic, biomedical, and other functions. In this review, we systematically summarize the synthesis methods, modifications, optical properties, and main biological functions of CDs in recent years. The application of functionalized modified CDs in biological detection, biological imaging, photodynamic therapy, photothermal therapy, targeted therapy, drug delivery, gene delivery, protein delivery, and other biomedical fields is introduced. The latest progress of CDs with its own biomedical function in antioxidant, anti‐pathogen, and disease treatment is summarized. Finally, we discuss some problems in the practical application of CDs and look forward to the future development trend of self‐functional CDs combined with surface modification to achieve multimodal treatment of diseases.
Genipa americana L.: A New Phytochemical for White Hair Coloring
Authors: Machado Andréa V. , Menezes Luana R. O. , Santana Adilson A. M. , Marques Maria N. , de Lima Adriana K. , Cano Amanda , Severino Patrícia , Souto Eliana B. , Cardoso Juliana C. 
Published: September 2023

AbstractThis work describes a new hair dyeing methodology using a chemical reaction between geniposide, an iridoid glycoside extracted from the fruit of Genipa americana (geniposide extract, GE) and the amine group of hair keratin. The influence of reaction conditions (pH, temperature, and extract concentration) on the staining of hair fibers, color development, fiber morphology, and mechanical hair properties of black and white human hair samples, was evaluated before and after GE dyeing treatment. Eye contact safety of GE was also studied using HET‐CAM. The treatment of white hair fibers using GE at 20 mg mL−1, temperature of 80 °C and pH 5.5 presented the greatest color change (ΔE=54.0). The higher pH influence was observed at pH 10.0 on white hair tresses (ΔE=6.8), using an GE concentration of 20 mg mL−1 and room temperature (25 °C). Treated samples showed marked changes on mechanical and morphological properties. The HET‐CAM did not show any change, thus demonstrating that using GE is safe. In conclusion, the temperature and concentration of the extract were the variables that mostly influenced the color and hair damage. A new approach for hair dyeing was established where iridoids may potentially be useful as a natural hair dyeing.
Structurally Diverse Sesquiterpenoids with NO Production and α‐Glucosidase Inhibitory Activities from the Fruits of Schisandra chinensis
Authors: Sun Ping , Pan Yin‐Bo , Ma Ren‐Fen , Zhao Xue‐Chun , Wang Yin‐Yin , Miao Lei , Zhang Hua 
Published: September 2023

AbstractChemical fractionation of the AcOEt partition, generated from the EtOH extract of the fruits of Schisandra chinensis, afforded a series of sesquiterpenyl constituents including two new cadinanes, a new eudesmane, two new widdranes (a handling artefact and a new natural product), a new bisabolane and two new natural cuparane enantiomers, along with 15 known structurally related analogs. Structures of the new compounds were unambiguously characterized by interpretation of detailed spectroscopic data including ESI‐MS and 1D/2D NMR, with their absolute configurations being established by electronic circular dichroism (ECD) calculation and induced ECD experiment. The inhibitory effects of all the isolates against α‐glucosidase and lipopolysaccharide (LPS) induced nitric oxide (NO) production in murine RAW264.7 macrophages, as well as their antibacterial and cytotoxic potential, were evaluated, with selective compounds showing moderate α‐glucosidase and NO inhibitory activity. Notably, canangaterpene III exhibited the most significant NO inhibitory effect with an IC50 value of 31.50±1.49 μM.
Hemodynamics after TAVR matter
Authors: Herrmann Howard C. 
Published: September 2023

Key Points
Adverse hemodynamics after transcatheter aortic valve replacement (TAVR) are more common in patients with a small aortic annulus (SAA) and affect clinical outcomes.
In this observational study of 628 patients with a very SAA, 89% of whom were women, severe prothesis patient mismatch (PPM) was associated with an up to fivefold increase in 1‐year mortality.
As younger and more active patients are treated with TAVR, it will be important to consider strategies including prosthesis choice as well as surgical root enlargement to avoid severe PPM.
Abdominal pseudocyst complicating ventriculoperitoneal shunt: A rare indication for ventriculopleural shunt conversion
Authors: Shrestha Nishan , Gautam Naveen , Shrestha Merina 
Published: September 2023

Key Clinical MessageAbdominal pseudocyst is a rare complication of ventriculoperitoneal (VP) shunt placement. Ventriculopleural shunt (VPL) can be an effective treatment option for the recurrent complications of VP shunt failure.AbstractAbdominal pseudocyst (APC) is a rare complication of ventriculoperitoneal (VP) shunt placement for the treatment of congenital hydrocephalus. This case report presents a two‐and‐a‐half‐year‐old male child who underwent VP shunt placement for aqueductal stenosis‐related hydrocephalus. The patient subsequently developed recurrent shunt failure and an APC, which was managed initially by surgical excision of the cyst and repositioning of the catheter. However, shunt failure recurred. The patient underwent ventriculopleural (VPL) shunt conversion as a more viable option for recurrent blockage. Postoperatively, the patient developed respiratory distress with massive pleural effusion, which was treated with chest tube insertion. This case highlights the complexity of managing congenital hydrocephalus and its rare complication, APC. Prompt recognition and appropriate management of APC can lead to improved outcomes and minimize the need for invasive procedures. VPL shunt conversion can be considered an alternative treatment option when other treatments have failed. Further research is needed to establish guidelines for the management of APC and determine the long‐term effectiveness of VPL shunting.
Relapsing anemia associated with parvovirus B19 infection in a kidney transplant recipient: A case report and review of the literature
Authors: Yaghoubi Fatemeh , Dalil Davood , Tavakoli Farnaz , Hosseini Seyyed Mohammad 
Published: September 2023

Key clinical messagePB19 infection should be considered an uncommon cause of posttransplant anemia in renal transplant recipients, particularly those whose anemia is not associated with common etiologies. IVIG treatment and reduced immunosuppression could be beneficial.AbstractParvovirus B19‐associated relapsing anemia is rare in kidney transplant recipients. Herein, we report a case of relapsed anemia due to parvovirus B19 infection in a 53‐year‐old woman 18 months after kidney transplantation. The patient presented with palpitations, shortness of breath, dizziness, weakness, and lethargy. Early laboratory findings showed a WBC count of 6.000/μL, RBC count of 1.89/μL, hemoglobin (Hb) 3.5 g/dL, hematocrit (Hct) 15%, platelet count 266.000/μL, MCV 89, reticulocyte count 0.8%, and serum iron 221 μg/dL. Upon further evaluation, the RT‐PCR test for BK polyomavirus and cytomegalovirus (CMV) was negative, while the parvovirus B19 RT‐PCR was positive. The patient was treated with blood transfusion and IVIG 25 g daily for 5 days. Two months after discharge, the patient presented, complaining of palpitation, shortness of breath, and dizziness, with RBC 2.7/μL, Hb 6.5 g/dL, Hct 25%, and MCV 85. Again, the CMV RT‐PCR was negative, while the parvovirus B19 RT‐PCR was positive. Tacrolimus and mycophenolic acid were stopped, and IVIG 25 g daily for 5 days was administered. Consequently, her Hb level increased to 9 g/dL, and the patient was discharged with prednisolone 5 mg daily and cyclosporine 50 mg daily instead of tacrolimus. Viral infection, particularly PB19 infection, should be considered in the differential diagnosis of posttransplantation anemia in KTRs. IVIG treatment and modification of immunosuppressive medications are suggested standard therapies for such patients. The function of transplanted kidneys should be carefully monitored during treatment.
From a Batch to a Continuous Supported Ionic Liquid Phase (SILP) Process: Anhydrous Synthesis of Oxymethylene Dimethyl Ethers
Authors: Billion Andreas , Vogel Andreas , Schulte Jonas , Scherer Harald , Krossing Ingo 
Published: September 2023

AbstractOxymethylene dimethyl ethers (OMEn; CH3(−OCH2)n−OCH3) are promising sustainable synthetic fuels when produced from CO2 and green H2. The synthesis pathway presented here overcomes synthetic problems and includes the reaction of dimethoxymethane (OME1) with molecular gaseous formaldehyde in a novel continuous, anhydrous reaction setup. An initially performed wide batch‐catalyst screening highlighted the salts M[NTf2]x with M=Cu+, Co2+ and Mg2+ as especially interesting catalysts (NTf2=N(SO2CF3)2). Supported ionic liquid phase (SILP)‐catalysts were prepared on this basis and demonstrated the successful synthesis of OMEn in a continuous process. The SILP‐catalysts immobilized in the IL EMIM[BF4] showed a fast and strong deactivation, but those with the IL EMIM[NTf2] showed excellent catalytic performance and stable results in continuous operations exceeding 19 h. The influence of the weight hourly space velocity (WHSV), the reaction temperature as well as the storage conditions of the catalysts (inert vs non‐inert) were investigated. 90 °C was identified as ideal reaction temperature. High feed‐gas flows (WHSV=15.8 h−1) are preferable in terms of product selectivity SOME2‐5>90 mol‐ % with an OME1 conversion XOME1=5.10 mol‐ % at the same time. We also demonstrated that the catalysts can be stored in air for 50 days without loss of activity. The SILP‐catalysts were analyzed by NMR and IR spectroscopy. Furthermore, the thermodynamics of the reaction mechanism of some selected catalysts was calculated by DFT theory to this reaction.
Manganese‐catalyzed Dehydrogenation of Amido Alcohols with Liberation of Hydrogen for the Synthesis of Oxazoles
Authors: Leinert Max , Irrgang Torsten , Kempe Rhett 
Published: September 2023

AbstractSyntheses of important classes of (heterocyclic) compounds, the sustainable generation of hydrogen, and the use of abundantly available metals are highly desirable. We introduce here a catalytic oxazole synthesis. Our reaction is a regio selective, one‐pot reaction and starts from esters and amino alcohols. Both are abundantly and diversely available and inexpensive starting materials. Hydrogen is liberated during the reaction and a molecular earth‐abundant metal catalyst, a Mn(I) compound, mediates the reaction most effectively ‐ and more efficiently than Ir and Ru catalysts. None of the oxazole derivatives synthesized, except the screening substrate and an active ingredient of a drug (an application), have been reported in literature yet.
Water‐Abundant Electrolytes: Towards Safer and Greener Aqueous Zinc‐Metal Batteries
Authors: Qian Long , Yao Rui , Yang Cheng 
Published: September 2023

AbstractAqueous Zn metal batteries have been regarded as promising candidates as an alternative to Li‐ion batteries in large‐scale energy storage systems due to their low‐cost, safe and environmentally benign advantages. However, because of the introduction of solvent water, several problems, for example dendrites, parasite reactions, hydrogen evolution, and so on, are brought into aqueous Zn metal batteries. Regrettably, when trying to solve these problems, most efforts have taken the form of adding a large amount of non‐aqueous components, which are usually harmful to the environment and not conducive to greener and safer aqueous batteries. In this Concept, we will introduce several electrolyte systems and mainly focus on how to build a water‐abundant electrolyte with fewer non‐aqueous components. This work will review the literature and offer instructive guidance for environmentally benign Zn metal batteries.
The Origin of Delayed Polymorphism in Molecular Crystals Under Mechanochemical Conditions
Authors: Linberg Kevin , Szymoniak Paulina , Schönhals Andreas , Emmerling Franziska , Michalchuk Adam A. L. 
Published: September 2023

AbstractWe show that mechanochemically driven polymorphic transformations can require extremely long induction periods, which can be tuned from hours to days by changing ball milling energy. The robust design and interpretation of ball milling experiments must account for this unexpected kinetics that arises from energetic phenomena unique to the solid state. Detailed thermal analysis, combined with DFT simulations, indicates that these marked induction periods are associated with processes of mechanical activation. Correspondingly, we show that the pre‐activation of reagents can also lead to marked changes in the length of induction periods. Our findings demonstrate a new dimension for exerting control over polymorphic transformations in organic crystals. We expect mechanical activation to have a much broader implication across organic solid‐state mechanochemistry.
Surface Modification Functionalized Carbon Dots
Authors: Wang Haolin , Ai Lin , Song Ziqi , Nie Mingjun , Xiao Jiping , Li Guoping , Lu Siyu 
Published: September 2023

AbstractCarbon dots (CDs) smaller than 10 nm constitute a new type of fluorescent carbon‐based nanomaterial. They have attracted much attention owing to their unique structures and excellent photoelectric properties. Primitive CDs usually comprise carbon and oxygen and are synthesized in one step from various natural products or synthetic organic compounds, usually via microwave or hydrothermal methods. However, the uniformity of surface functional groups often make CDs lack the diversity of active sites required for specific applications. Therefore, the functionalization of CDs by specific groups is a powerful strategy for improving their photophysical and photochemical properties. This paper reviews surface modification strategies to overcome these shortcomings. Functionalizing CDs using covalent or non‐covalent modification can give them unique properties and broaden their applicability.
Impact of Hard Magnetic Nanocrystals on the Properties of Hardened Cement Paste
Authors: Kißling Patrick A. , Mahlbacher Markus , Wesemann Christoph , Mundstock Alexander , Lübkemann-Warwas Franziska , Klimke Stephen , Renz Franz , Lohaus Ludger , Haist Michael , Bigall Nadja C. 
Published: September 2023

AbstractIn this work, nano‐sized hard magnetic gallium‐substituted iron oxide crystals, wherein gallium is used to stabilize the metastable epsilon iron oxide phase, were added to cement‐water suspensions at different ratios, which were subsequently hydrated for at least 28 days. It is shown that higher contents of such nanocrystals in the hardened cement paste introduce a magnetic moment, whereas the mechanical properties remain unchanged compared to non‐blended hardened cement paste for a wide concentration range.
Necroptosis‐related regulatory pattern and scoring system for predicting therapeutic efficacy and prognosis in ovarian cancer
Authors: Lai Huiling , Guo Yunyun , Wu Linxiang , Yusufu Aligu , Zhong Qiyu , Liao Zhouzhou , Ma Jianyu , Shi Wen , Yang Guofen , Chen Shuqin 
Published: September 2023

AbstractBackgroundOvarian cancer is difficult to treat and is, therefore, associated with a high fatality rate. Although targeted therapy and immunotherapy have been successfully used clinically to improve the diagnosis and treatment of ovarian cancer, most tumors become drug resistant, and patients experience relapse, meaning that the overall survival rate remains low.AimsThere is currently a lack of effective biomarkers for predicting the prognosis and/or outcomes of patients with ovarian cancer. Therefore, we used published transcriptomic data derived from a large ovarian cancer sample set to establish a molecular subtyping model of the core genes involved in necroptosis in ovarian cancer.Methods and ResultsClustering analysis and differential gene expression analyses were performed to establish the genomic subtypes related to necroptosis and to explore the patterns of regulatory gene expression related to necroptosis in ovarian cancer. A necroptosis scoring system (NSS) was established using principal component analysis according to different regulatory patterns of necroptosis. In addition, this study revealed important biological processes with essential roles in the regulation of ovarian tumorigenesis, including external encapsulating structure organization, leukocyte migration, oxidative phosphorylation, and focal adhesion. Patients with high NSS scores had unique immunophenotypes, such as more abundant M2 macrophages, monocytes, CD4+ memory T cells, and regulatory T cells. Immune checkpoint CD274 had a greater expression in patients with high NSS values.ConclusionThis NSS could be used as an independent predictor of prognosis to determine the sensitivity of ovarian cancer to various small‐molecule inhibitors, immune checkpoint inhibitors, and platinum‐based chemotherapy drugs.
Inferring chromosomal instability from copy number aberrations as a measure of chromosomal instability across human cancers
Authors: Taluri Sasha , Oza Vishal H. , Soelter Tabea M. , Fisher Jennifer L. , Lasseigne Brittany N. 
Published: September 2023

AbstractBackgroundCancer is a complex disease that is the second leading cause of death in the United States. Despite research efforts, the ability to manage cancer and select optimal therapeutic responses for each patient remains elusive. Chromosomal instability (CIN) is primarily a product of segregation errors wherein one or many chromosomes, in part or whole, vary in number. CIN is an enabling characteristic of cancer, contributes to tumor‐cell heterogeneity, and plays a crucial role in the multistep tumorigenesis process, especially in tumor growth and initiation and in response to treatment.AimsMultiple studies have reported different metrics for analyzing copy number aberrations as surrogates of CIN from DNA copy number variation data. However, these metrics differ in how they are calculated with respect to the type of variation, the magnitude of change, and the inclusion of breakpoints. Here we compared metrics capturing CIN as either numerical aberrations, structural aberrations, or a combination of the two across 33 cancer data sets from The Cancer Genome Atlas (TCGA).Methods and ResultsUsing CIN inferred by methods in the CINmetrics R package, we evaluated how six copy number CIN surrogates compared across TCGA cohorts by assessing each across tumor types, as well as how they associate with tumor stage, metastasis, and nodal involvement, and with respect to patient sex.ConclusionsWe found that the tumor type impacts how well any two given CIN metrics correlate. While we also identified overlap between metrics regarding their association with clinical characteristics and patient sex, there was not complete agreement between metrics. We identified several cases where only one CIN metric was significantly associated with a clinical characteristic or patient sex for a given tumor type. Therefore, caution should be used when describing CIN based on a given metric or comparing it to other studies.
Effects of Charged Surfactants on Interfacial Water Structure and Macroscopic Properties of the Air‐Water Interface
Authors: Nguyen Thao T. P. , Raji Foad , Nguyen Cuong V. , Nguyen Ngoc N. , Nguyen Anh V. 
Published: September 2023

AbstractSurfactants are used to control the macroscopic properties of the air‐water interface. However, the link between the surfactant molecular structure and the macroscopic properties remains unclear. Using sum‐frequency generation spectroscopy and molecular dynamics simulations, two ionic surfactants (dodecyl trimethylammonium bromide, DTAB, and sodium dodecyl sulphate, SDS) with the same carbon chain lengths and charge magnitude (but different signs) of head groups interact and reorient interfacial water molecules differently. DTAB forms a thicker but sparser interfacial layer than SDS. It is due to the deep penetration into the adsorption zone of Br− counterions compared to smaller Na+ ones, and also due to the flip‐flop orientation of water molecules. SDS alters two distinctive interfacial water layers into a layer where H+ points to the air, forming strong hydrogen bonding with the sulphate headgroup. In contrast, only weaker dipole‐dipole interactions with the DTAB headgroup are formed as they reorient water molecules with H+ point down to the aqueous phase. Hence, with more molecules adsorbed at the interface, SDS builds up a higher interfacial pressure than DTAB, producing lower surface tension and higher foam stability at a similar bulk concentration. Our findings offer improved knowledge for understanding various processes in the industry and nature.