bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nutrient balancing in a fruit‐specialist primate, the black‐and‐white ruffed lemur (Varecia variegata)
Authors: Beeby Nina , Rothman Jessica M. , Baden Andrea L. 
Published: March 2023

AbstractAnimals' foraging behavior and dietary choices are, in part, driven by their ultimate function: to meet nutritional demands. However, depending on their degree of dietary specialization and the availability and distribution of food resources in their environment, species may utilize different nutritional strategies. With shifting plant phenology, increasing unpredictability of fruiting, and declining food quality in response to anthropogenic climate change, existing nutritional constraints may become exacerbated. Such changes are especially concerning for Madagascar's endemic fruit specialists given the nutrient‐limitation of the island's landscapes. In this study, we examined the nutritional strategy of one such fruit‐specialist primate, the black‐and‐white ruffed lemur (Varecia variegata), over a 12‐month period (January to December 2018) in Ranomafana National Park, Madagascar. We hypothesized that Varecia would balance nonprotein energy (NPE) to protein (AP) at a high ratio similar to other frugivorous primates, and that they would prioritize protein intake given their high degree of frugivory. We found that Varecia balance NPE:AP at a ratio of 11:1, higher than in any other primate studied to date; however, diets shifted such that nutrient balancing varied seasonally (12.6:1 abundant–9.6:1 lean). Varecia meet NRC suggested recommendations of 5–8% of calories from protein, despite having a diet mostly comprising fruits. However, seasonal shifts in NPE intakes result in significant energy shortfalls during fruit‐lean seasons. Flowers provide an important source of NPE during these periods, with flower consumption best predicting lipid intake, suggesting this species' ability to shift resource use. Nevertheless, achieving adequate and balanced nutrient intakes may become precarious in the face of increasing unpredictability in plant phenology and other environmental stochasticities resulting from climate change.
Turning the Inert Element Zinc into an Active Single‐Atom Catalyst for Efficient Fenton‐Like Chemistry
Authors: Zhao Zhiyu , Tan Haobin , Zhang Peng , Liang Xiaoying , Li Tong , Gao Yaowen , Hu Chun 
Published: March 2023

AbstractAmongst various Fenton‐like single‐atom catalysts (SACs), the zinc (Zn)‐related SACs have been barely reported due to the fully occupied 3d10configuration of Zn2+being inactive for the Fenton‐like reaction. Herein, the inert element Zn is turned into an active single‐atom catalyst (SA−Zn−NC) for Fenton‐like chemistry by forming an atomic Zn−N4coordination structure. The SA−Zn−NC shows admirable Fenton‐like activity in organic pollutant remediation, including self‐oxidation and catalytic degradation by superoxide radical (O2⋅−) and singlet oxygen (1O2). Experimental and theoretical results unveiled that the single‐atomic Zn−N4site with electron acquisition can transfer electrons donated by electron‐rich pollutants and low‐concentration PMS toward dissolved oxygen (DO) to actuate DO reduction into O2⋅−and successive conversion into1O2. This work inspires an exploration of efficient and stable Fenton‐like SACs for sustainable and resource‐saving environmental applications.
Influence of Potassium Metal‐Support Interactions on Dendrite Growth
Authors: Liu Pengcheng , Yen Dean , Vishnugopi Bairav S. , Kankanallu Varun R. , Gürsoy Doğa , Ge Mingyuan , Watt John , Mukherjee Partha P. , Chen‐Wiegart Yu‐chen Karen , Mitlin David 
Published: March 2023

AbstractCombined synchrotron X‐ray nanotomography imaging, cryogenic electron microscopy (cryo‐EM) and modeling elucidate how potassium (K) metal‐support energetics influence electrodeposit microstructure. Three model supports are employed: O‐functionalized carbon cloth (potassiophilic, fully‐wetted), non‐functionalized cloth and Cu foil (potassiophobic, nonwetted). Nanotomography and focused ion beam (cryo‐FIB) cross‐sections yield complementary three‐dimensional (3D) maps of cycled electrodeposits. Electrodeposit on potassiophobic support is a triphasic sponge, with fibrous dendrites covered by solid electrolyte interphase (SEI) and interspersed with nanopores (sub‐10 nm to 100 nm scale). Lage cracks and voids are also a key feature. On potassiophilic support, the deposit is dense and pore‐free, with uniform surface and SEI morphology. Mesoscale modeling captures the critical role of substrate‐metal interaction on K metal film nucleation and growth, as well as the associated stress state.
Simple and Versatile Nitrooxylation: Noncyclic Hypervalent Iodine Nitrooxylating Reagent
Authors: Cheng Xuan , Yin Quan , Jiang Yu‐Xuan , Jiang Ling‐Feng , Li Si‐Yuan , Cheng Yi‐Fei , Sun Xin‐Chang , Peng Lujun , Zhong Cheng , Deng Qing‐Hai 
Published: March 2023

AbstractOrganic nitrates are broadly applied as pharmaceuticals (acting as efficient nitric oxide donor), energetic materials, building blocks in organic synthesis, etc. However, practical and direct methods to access organic nitrates efficiently are still rare, mainly due to the lack of powerful nitrooxylating reagents. Herein, we report bench‐stable and highly reactive noncyclic hypervalent iodine nitrooxylating reagents, oxybis(aryl‐λ3‐iodanediyl) dinitrates (OAIDNs, 2), which are prepared just by using aryliodine diacetate and HNO3. The reagents are used to achieve a mild and operationally simple protocol to access diverse organic nitrates. By employing of 2, zinc‐catalyzed regioselective nitrooxylation of cyclopropyl silyl ethers is realized efficiently to access the corresponding β‐nitrooxy ketones with high functional‐group tolerance. Moreover, a series of direct and catalyst‐free nitrooxylations of enolizable C−H bonds are carried out smoothly to afford the desired organic nitrates within minutes by just mixing the substrates with 2 in dichloromethane.
Turning the Inert Element Zinc into an Active Single‐Atom Catalyst for Efficient Fenton‐Like Chemistry
Authors: Zhao Zhiyu , Tan Haobin , Zhang Peng , Liang Xiaoying , Li Tong , Gao Yaowen , Hu Chun 
Published: March 2023

AbstractAmongst various Fenton‐like single‐atom catalysts (SACs), the zinc (Zn)‐related SACs have been barely reported due to the fully occupied 3d10 configuration of Zn2+ being inactive for the Fenton‐like reaction. Herein, the inert element Zn is turned into an active single‐atom catalyst (SA−Zn−NC) for Fenton‐like chemistry by forming an atomic Zn−N4 coordination structure. The SA−Zn−NC shows admirable Fenton‐like activity in organic pollutant remediation, including self‐oxidation and catalytic degradation by superoxide radical (O2⋅−) and singlet oxygen (1O2). Experimental and theoretical results unveiled that the single‐atomic Zn−N4 site with electron acquisition can transfer electrons donated by electron‐rich pollutants and low‐concentration PMS toward dissolved oxygen (DO) to actuate DO reduction into O2⋅− and successive conversion into 1O2. This work inspires an exploration of efficient and stable Fenton‐like SACs for sustainable and resource‐saving environmental applications.
Twelve‐component pharmacokinetic study of rat plasma after oral administration of You‐Gui‐Wan in osteoporosis rats with kidney‐yin deficiency and kidney‐yang deficiency
Authors: Wang Yahong , Zhang Jianhua , Wang Ling , Yin Hua 
Published: March 2023

AbstractYou‐Gui‐Wan is a widely used traditional Chinese medicine preparation for the treatment of osteoporosis with kidney‐yang deficiency, and is composed of both yang‐invigorating and kidney‐tonifying herbs, and yin‐nourishing and kidney essence‐replenishing herbs. Considering that the pharmacokinetics of drugs might differ in different pathological conditions, it is necessary to study the pharmacokinetic characteristics of You‐Gui‐Wan under different osteoporotic conditions. In this study, the pharmacokinetic behaviors of You‐Gui‐Wan in osteoporosis rats with kidney‐yin and kidney‐yang deficiency were compared. The results showed that the absorption, metabolism, and disposition of You‐Gui‐Wan varied widely in animals with different types of osteoporosis. The active components belonging to the yang‐invigorating herbs, such as aconitine, hypaconitine, mesaconitine, benzoylaconine, benzoylhypacoitine, benzoylmesaconine, chlorogenic acid and pinoresinol diglucoside, had a higher uptake and slower elimination in osteoporosis rats with kidney‐yang deficiency, which corresponds to the opinion that You‐Gui‐Wan is used to treat kidney‐yang deficiency syndrome, and indicates the scientific nature of Bian‐Zheng‐Lun‐Zhi.
Mapping the Chemical Space of Active‐Site Targeted Covalent Ligands for Protein Tyrosine Phosphatases**
Authors: Hong Suk ho , Xi Sarah Y. , Johns Andrew C. , Tang Lauren C. , Li Allyson , Hum Madeleine N. , Chartier Cassandra A. , Jovanovic Marko , Shah Neel H. 
Published: March 2023

AbstractProtein tyrosine phosphatases (PTPs) are an important class of enzymes that modulate essential cellular processes through protein dephosphorylation and are dysregulated in various disease states. There is demand for new compounds that target the active sites of these enzymes, for use as chemical tools to dissect their biological roles or as leads for the development of new therapeutics. In this study, we explore an array of electrophiles and fragment scaffolds to investigate the required chemical parameters for covalent inhibition of tyrosine phosphatases. Our analysis juxtaposes the intrinsic electrophilicity of these compounds with their potency against several classical PTPs, revealing chemotypes that inhibit tyrosine phosphatases while minimizing excessive, potentially non‐specific reactivity. We also assess sequence divergence at key residues in PTPs to explain their differential susceptibility to covalent inhibition. We anticipate that our study will inspire new strategies to develop covalent probes and inhibitors for tyrosine phosphatases.
Thiophene‐Based Ligands: Design, Synthesis and Their Utilization for Optical Assignment of Polymorphic‐Disease‐Associated Protein Aggregates
Authors: Björk Linnea , Klingstedt Therése , Nilsson K. Peter R. 
Published: March 2023

AbstractThe development of ligands for detecting protein aggregates is of great interest, as these aggregated proteinaceous species are the pathological hallmarks of several devastating diseases, including Alzheimer's disease. In this regard, thiophene‐based ligands have emerged as powerful tools for fluorescent assessment of these pathological entities. The intrinsic conformationally sensitive photophysical properties of poly‐ and oligothiophenes have allowed optical assignment of disease‐associated protein aggregates in tissue sections, as well as real‐time in vivo imaging of protein deposits. Herein, we recount the chemical evolution of different generations of thiophene‐based ligands, and exemplify their use for the optical distinction of polymorphic protein aggregates. Furthermore, the chemical determinants for achieving a superior fluorescent thiophene‐based ligand, as well as the next generation of thiophene‐based ligands targeting distinct aggregated species are described. Finally, the directions for future research into the chemical design of thiophene‐based ligands that can aid in resolving the scientific challenges around protein aggregation diseases are discussed.
Cusp overlap technique for self‐expanding valves: Refining technique defining outcomes
Authors: Seth Ashok , Chopra Manik 
Published: March 2023

Key Points
Cusp overlap (COV) technique for Transcatheter Aortic Valve Implantation (TAVI) with self‐expanding valves (SEV) has been proposed to enable accurate and high placement of valves to decrease permanent pacemaker implantation (PPI).
Metanalysis of published experience with COV technique confirms decrease in PPI rates without compromising on safety.
COV technique could be considered the technique of choice for implantation of SEV.
Clinical and MRI findings of a suspected cortical malformation presented as a giant cerebral pseudomass in a German Shepherd dog
Authors: Bongers Jos Jacqueline , Gutierrez‐Quintana Rodrigo , Hammond Gawain , José‐López Roberto 
Published: March 2023

AbstractA 5‐month‐old German Shepherd dog was presented with cluster seizures. MR imaging showed a large irregular pseudomass in the central region of the cranial cavity, compatible with a malformation of cortical development. Despite the extensive changes, the patient was neurologically normal interictally 1 year following diagnosis.
Baker's cyst with extra‐ and intra‐articular synovial chondromatosis of knee: A case report
Authors: Khadka Sushant Kumar , Chaudhary Aashutosh , Acharya Suyash , Maharjan Sagar , Shrestha Rohit 
Published: March 2023

AbstractSynovial chondromatosis is a rare benign condition characterized by chondral proliferation from synovium forming loose bodies which can occur extra‐articularly and intra‐articularly. Surgical removal remains the mainstay of treatment for synovial chondromatosis. Due to the risk of recurrence, every case must be followed up with an MRI.
Experimental and ab initio Investigation on the Effect of CO and CO2 during Hydrodeoxygenation of m‐Cresol over Co/SBA‐15
Authors: Teles Camila A. , Gueddida Saber , Deplazes Roger , Ciotonea Carmen , Canilho Nadia , Lebègue Sébastien , Dhainaut Jérémy , Badawi Michael , Richard Frédéric , Royer Sébastien 
Published: March 2023

AbstractThe hydrodeoxygenation (HDO) is a fundamental step in the production of biofuels from lignin, and the catalyst type and reaction conditions can play an important role. In this work, Co nanoparticles finely dispersed in the porosity of SBA‐15 stand out a high selectivity toward deoxygenated products (63 % of methylcyclohexenes and 16 % of methylcyclohexane) in the HDO of m‐cresol (30 bar of pressure, temperature of 350 °C). The effect of co‐feeding CO and CO2, which can be present in the pyrolysis gas after transformation of carboxylic acids, was investigated. An unexpected positive effect on the stability of the catalyst was observed when CO2 was added in the feed stream. On the contrary, the presence of CO led to a strong decrease of the m‐cresol conversion. These experimental findings are supported by DFT calculations which show that the m‐cresol is much more strongly adsorbed than CO2 at the Co@SiO2 interface while the interaction energy of CO is close to the one of m‐cresol.
Fine Tuning the Properties of Stapled Peptides by Stereogenic α‐Amino Acid Bridges
Authors: Wang Qian , Wang Fengzhang , Li Rui , Wang Pushu , Yuan Ruixin , Liu Dangliang , Liu Yuan , Luan Yi , Wang Chu , Dong Suwei 
Published: March 2023

AbstractPeptide stapling represents a versatile strategy to generate peptide derivatives with stable helical structures. While a wide range of skeletons have been investigated for cyclizing the side chains of peptides, the stereochemical outcomes from the linkers remain to be better understood. In this study, we incorporated α‐amino acids (α‐AAs) as bridges to construct side chain‐stapled analogs of an interleukin‐17A‐binding peptide (HAP) and evaluated the impacts of the staples on the peptide's properties. While all AA‐derived peptidyl staples drastically increase the enzymatic stability of HAP, our results indicate that compared to the D‐amino acid bridges, the L‐AA‐based staples may generate more significant impacts in increasing the helicity and enhancing the interleukin‐17A(IL‐17A)‐binding affinity of the modified peptide. Using Rosetta modelling and molecular dynamics (MD) simulations, we demonstrate that the chirality (L/D) possessed within the AAs substantially influences the conformation of stapled HAP peptides, providing either stabilizing or destabilizing effects. Based on the computational model, a modification of the stapled HAP leads to the discovery of a peptide with further enhanced helicity, enzymatic stability and IL‐17A‐inhibiting ability. This systematic study reveals that chiral AAs can serve as modulatory linkers for optimizing the structures and properties of stapled peptides.
Oxymethylene Ether (OME) Fuel Catalyst Screening Using In Situ NMR Spectroscopy
Authors: Endres Patrick , Schuett Timo , Kimmig Julian , Zechel Stefan , Hager Martin D. , Geitner Robert , Schubert Ulrich S. 
Published: March 2023

AbstractOnline NMR measurements are introduced in the current study as a new analytical setup for investigation of the oxymethylene dimethyl ether (OME) synthesis. For the validation of the setup, the newly established method is compared with state‐of‐the‐art gas chromatographic analysis. Afterwards, the influence of different parameters, such as temperature, catalyst concentration and catalyst type on the OME fuel formation based on trioxane and dimethoxymethane is investigated. As catalysts, AmberlystTM 15 (A15) and trifluoromethanesulfonic acid (TfOH) are utilized. A kinetic model is applied to describe the reaction in more detail. Based on these results, the activation energy (A15: 48.0 kJ mol−1 and TfOH: 72.3 kJ mol−1) and the order in catalyst (A15: 1.1 and TfOH: 1.3) are calculated and discussed.
Insight into the Effect of Stabilizers on Anticancer and Antibacterial Activity of AgBiS2 Nanomaterial
Authors: Joseph Anju , Khatun Sajmina , Sai Hemanth Kumar Dasari , Rengan Aravind K. , Muralidharan Krishnamurthi 
Published: March 2023

AbstractThe near‐infrared (NIR) light‐absorbing AgBiS2 nanoparticles can be excited by single‐wavelength light, which is the primary characteristic of a photo responsive platform. Chemical synthesis of nanomaterials inevitably requires long‐chain organic surfactants or polymers to stabilize them in the nano regime. These stabilizing molecules barricade the interaction of nanomaterials with biological cells. We have produced stabilizer‐free (sf‐AgBiS2) and polymer‐coated (PEG‐AgBiS2) nanoparticles; and assessed their NIR mediated anticancer and antibacterial activity to evaluate the effect of stabilizers. sf‐AgBiS2 showed better antibacterial activity against Gram‐positive Staphylococcus aureus (S. aureus) and displayed excellent cytotoxicity against HeLa cells and live 3‐D tumour spheroids compared to PEG‐AgBiS2 both in presence and absence of NIR radiation. The photothermal therapy (PTT) results illustrated the tumour ablation ability of sf‐AgBiS2, which converted light into heat effectively up to 53.3 °C under NIR irradiation. This work demonstrates the importance of synthesizing stabilizer‐free nanoparticles to produce safe and highly active PTT agents.
Nature‐Inspired Chemistry of Complex Alkaloids: Combining Targeted Molecular Networking Approach and Semisynthetic Strategy to Access Rare Communesins in a Marine‐Derived Penicillium expansum
Authors: Hoang Thi Phuong Thuy , Roullier Catherine , Evanno Laurent , Kerzaon Isabelle , Gentil Emmanuel , Robiou du Pont Thibaut , Nazih El‐Hassane , Pouchus Yves François , Bertrand Samuel , Poupon Erwan , Grovel Olivier 
Published: March 2023

AbstractCommunesins are rare alkaloids isolated from fungi of the genus Penicillium. In this work, the extract of a marine‐derived Penicillium expansum strain was studied using targeted molecular networking approach allowing to detect 65 communesins including 55 new ones. A fragmentation pattern for dimethylvinyl communesins was established and a script was implemented allowing to predict the structure and map all communesins in a global molecular network. A semisynthetic strategy was carried out to obtain some minor congeners from the two isolated communesins A and B. Nine communesins were then synthetised: two of them were already described as produced by the studied strain; four are new natural products which occurrence in the extracts was confirmed; three are new semi‐synthetic analogues never described so far. These communesins were evaluated for their cytotoxicity on two human cancer cell lines KB and MCF‐7 leading to a preliminary study of their structure‐activity relationships.
Copper (I) Chloride‐Catalyzed Photoredox Synthesis of Multifunctionalized Compounds at Room Temperature and Their Antifungal Activities
Authors: Charpe Vaibhav Pramod , Ragupathi Ayyakkannu , Sagadevan Arunachalam , Ho Yeu‐Shiuan , Cheng Mu‐Jeng , Hwang Kuo Chu 
Published: March 2023

AbstractA simple visible‐light‐induced CuCl‐catalyzed synthesis was developed for highly functionalized carbon‐centered compounds (α‐alk/aryloxy‐α‐diaryl/alkylaryl‐acetaldehydes/ketones) at room temperature using benzoquinone, alkyl/aryl alcohol, and alkyl/aryl terminal/internal alkynes. Late‐stage functionalized compounds show good antifungal activities, especially againstCandida kruseifungal strain, in in vitro experiments (the Broth microdilution method). Moreover, toxicity tests (zebrafish egg model experiments) indicated that these compounds had negligible cytotoxicity. The green chemistry metrics (E‐factor value is 7.3) and eco‐scale (eco‐scale value is 58.8) evaluations show that the method is simple, mild, highly efficient, eco‐friendly, and environmentally feasible.
Graphene Oxide‐BODIPY Conjugates as Highly Fluorescent Materials
Authors: Reina Giacomo , Beneventi Giovanni Mariano , Kaur Ramandeep , Biagiotti Giacomo , Cadranel Alejandro , Ménard‐Moyon Cécilia , Nishina Yuta , Richichi Barbara , Guldi Dirk M. , Bianco Alberto 
Published: March 2023

AbstractCovalent functionalization of graphene oxide (GO) with boron dipyrromethenes (BODIPYs) was achieved through a facile synthesis, affording two different GO‐BODIPY conjugates where the main difference lies in the nature of the spacer and the type of bonds between the two components. The use of a long but flexible spacer afforded strong electronic GO‐BODIPY interactions in the ground state. This drastically altered the light absorption of the BODIPY structure and impeded its selective excitation. In contrast, the utilisation of a short, but rigid spacer based on boronic esters resulted in a perpendicular geometry of the phenyl boronic acid BODIPY (PBA‐BODIPY) with respect to the GO plane, which enables only minor electronic GO‐BODIPY interactions in the ground state. In this case, selective excitation of PBA‐BODIPY was easily achieved, allowing to investigate the excited state interactions. A quantitative ultrafast energy transfer from PBA‐BODIPY to GO was observed. Furthermore, due to the reversible dynamic nature of the covalent GO‐PBA‐BODIPY linkage, some PBA‐BODIPY is free in solution and, hence, not quenched from GO. This resulted in a weak, but detectable fluorescence from the PBA‐BODIPY that will allow to exploit GO‐PBA‐BODIPY for slow release and imaging purposes.
The Role of Anionic Ligands on Photoreactivity in Mo(VI) Dioxo Complexes of the Form MoO2X2(NN)**
Authors: Fosshat Saeed , Fronczek Frank R. , Chambers Matthew B. 
Published: March 2023

AbstractThe photoreactivity of d0 metal dioxo complexes in activating C−H bonds has been recently studied.[1–3] We have previously reported that MoO2Cl2(bpy‐tBu) is an effective platform for light initiated C−H activation with unique product selectivity for the overall functionalization.[1] Herein we expand on these studies and report the synthesis and photoreactivity of several new Mo(VI) dioxo complexes with the general formula MoO2(X)2(NN); where X=F−, Cl−, Br−, CH3−, PhO−, tBuO− and NN=2,2’‐bipyridine (bpy) or 4,4′‐tert‐butyl‐2,2’bipyridine (bpy‐tBu). Among these compounds, MoO2Cl2(bpy‐tBu) and MoO2Br2(bpy‐tBu) are able to participate in bimolecular photoreactivity with several substrates containing C−H bonds of various types such as allyls, benzyls, aldehydes (RCHO) and alkanes. MoO2(CH3)2bpy and MoO2(PhO)2bpy do not participate in bimolecular photoreactions and instead they undergo photodecompositions. Computational studies indicate that the nature of the HOMO and LUMO is critical in supporting photoreactivity, with access to an LMCT (bpy→Mo) being necessary for tractable hydrocarbon functionalization.