bluuebunny/crossref_metadata_2025 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

Animals' 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

Amongst 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

Combined 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

Organic 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

Amongst 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

You‐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

Protein 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

The 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

A 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

Synovial 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

The 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

Peptide 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

Online 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

The 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

Communesins 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

A 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

Covalent 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

The 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.
Insight into the Evolution Track for the Metathesis of Alkenes within Hierarchical Zeolite‐Based Catalysts
Authors: Wei Ning , Wang Lizhuo , Yang Wenjie , Zhang Dazhi , Jia Zhenghao , Liu Wei , Zhang Weiping , Zang Jiazhong , Huang Shengjun , Huang Jun
Published: March 2023

The usage of hierarchical MFI zeolite enables a boost of the catalytic performance of Mo‐based catalysts for the olefin‐metathesis reaction. The harvest of active catalysts roots in a segmental evolution track between hierarchical zeolite and Al2O3slices for the fabrication of active sites. The working evolution track requires the indispensable engagements from intracrystalline mesoporous surface, Al2O3slices, and zeolitic Brønsted acid sites. The infilling of disaggregated Al2O3slices into the intracrystalline mesopores triggers the creation of localized intrazeolite−Al2O3interfaces, which enables the subsequent migration and trapping of surface molybdates into the micropores. The insulation of intrazeolite−Al2O3interface or shielding of zeolitic Brønsted acid sites leads to the break of the evolution track. Our findings disclose the hidden functionality of mesoporosity as intrazeolite interface boundary for the fabrication of active sites and supply a new strategy for the rational design of zeolite catalysts.
Structure‐Property Relationships in a New Family of Photoactive Diimine‐Diphosphine Copper(I) Complexes
Authors: Beaudelot Jérôme , Evano Gwilherm , Moucheron Cécile
Published: March 2023

A new family of heteroleptic diimine‐diphosphine copper(I) complexes is reported, with six new complexes compared to benchmark [Cu(bcp)(DPEPhos)]PF6. These new complexes are based on 1,4,5,8‐tetraazaphenanthrene (TAP) ligands with representative electronic properties as well as substitution patterns and DPEPhos and XantPhos as diphosphine ligands. Their photophysical and electrochemical properties were investigated and correlated with the number and position of substituents on the TAP ligands. Stern‐Volmer studies using Hünig's base as reductive quencher demonstrated the influence of the complex photoreduction potential and of the excited state lifetime on the photoreactivity. This study refines the structure‐property relationship profile for heteroleptic copper(I) complexes and confirms that such profiles are of high interest to design new copper complexes as optimized photoredox catalysts.
Real‐Time Monitoring of Dynamic Chemical Processes in Microbial Metabolism with Optical Sensors
Authors: Chen Na , Cheng Di , He Tianpei , Yuan Quan
Published: March 2023

Monitoring microbial metabolism is vital for revealing the mechanism of disease related to microbial metabolism and providing guidance for biomanufacturing processes optimization. However, it remains a grand challenge to offer real‐time insights into microbial metabolism owing to the complex and dynamic process. In this paper, the recent advances and prospects of optical biosensors including the organic, genetic coding and inorganic optical biosensors are briefly described for real‐time monitoring of dynamic microbial metabolism. This paper points out that challenges remain in microbial heterogeneity. We believe that this work will inspire the application of developing new methods for single cell real‐time analysis.
Trying to outRun‐DIC in KMT2Ar AML: It's tricky
Authors: Venugopal Sangeetha , Taylor Justin
Published: March 2023

In this issue of Cancer, Nguyen and colleagues describe high risk of disseminated intravascular coagulation (DIC) in patients with KMT2Ar acute myeloid leukemia (AML) compared with matched controls in a retrospective single‐institution analysis. The authors of this editorial put this study into perspective of other AML subtypes at high risk of DIC and bleeding.
Models of Affective Illness: Chronic Mild Stress in the Rat
Authors: Papp Mariusz , Willner Paul
Published: March 2023

This article describes a chronic mild stress (CMS) model for predicting antidepressant response and investigating mechanisms of antidepressant action in rats. Following exposure to a variety of mild stressors for several weeks, the rats’ behavior is modified in several ways that parallel symptoms of depression. Among these is a substantial reduction in consumption of a 1% sucrose solution, which models the cardinal symptom of major depression, anhedonia. Our standard procedure employs a battery of behavioral tests, comprising weekly assessment of sucrose intake and, at the end of treatment, the elevated plus‐maze and novel object recognition tests to assess the anxiogenic and dyscognitive effects of CMS. Chronic administration of antidepressant drugs reverses the decreased sucrose intake and other behavioral changes in these subjects. Also effective are second‐generation antipsychotics. The CMS model can be employed in discovery programs to identify anti‐anhedonic drugs (e.g., antidepressants and antipsychotics) that act more quickly than existing agents. While most antidepressants require 3 to 5 weeks to normalize behavior, some treatments provide a faster onset of action. For example, the CMS‐induced deficits can be reversed by acute or sub‐chronic application of treatments that act rapidly in depressed patients, such as deep brain stimulation (DBS), ketamine, and scopolamine, as well as several compounds that have yet to be tested in humans but have fast‐onset antidepressant‐like effects in animals, such as the 5‐HT‐1A biased agonists NLX‐101 and GLYX‐13. Application of the CMS model in Wistar‐Kyoto (WKY) rats causes similar behavioral changes to those seen in Wistars, but these are not reversed by antidepressant treatment. However, WKY rats respond to DBS and ketamine, which are effective in patients who are antidepressant non‐responders, establishing CMS in WKY rats as a model of treatment‐resistant depression. © 2023 The Authors. Current Protocols published by Wiley Periodicals LLC.

Basic Protocol: Induction of chronic mild stress in rats as a model of depression and treatment‐resistant depression
Cytology of micropapillary mucinous carcinoma: A case report of a clinically and genetically distinct breast carcinoma variant
Authors: Pradeep Immanuel , Nigam Jitendra Singh , Rathod Gunvanti , Parmeshwar Tushar Mohanlal
Published: March 2023

Micropapillary mucinous carcinoma (MPMC) is an uncommon histopathological variant of breast cancer accounting for approximately one‐fifth of all mucinous breast carcinomas. In contrast to pure mucinous carcinoma, MPMC tends to affect younger women and is associated with decreased progression‐free survival, higher nuclear grade, lymphovascular invasion, lymph node metastasis, and positive HER2 status. Typically MPMC histology shows micropapillary architecture with “hobnailing” of cells and reverse polarity. Very few publications document the cytomorphological findings of MPMC. We report a case of MPMC that was suspected in fine needle aspiration cytology (FNAC) and confirmed at histopathology.
Multiscale phenological niches of seed fall in diverse Amazonian plant communities
Authors: Pak Damie , Swamy Varun , Alvarez‐Loayza Patricia , Cornejo‐Valverde Fernando , Queenborough Simon A. , Metz Margaret R. , Terborgh John , Valencia Renato , Wright S. Joseph , Garwood Nancy C. , Lasky Jesse R.
Published: March 2023

Phenology has long been hypothesized as an avenue for niche partitioning or interspecific facilitation, both promoting species coexistence. Tropical plant communities exhibit striking diversity in reproductive phenology, but many are also noted for large synchronous reproductive events. Here we study whether the phenology of seed fall in such communities is nonrandom, the temporal scales of phenological patterns, and ecological factors that drive reproductive phenology. We applied multivariate wavelet analysis to test for phenological synchrony versus compensatory dynamics (i.e., antisynchronous patterns where one species' decline is compensated by the rise of another) among species and across temporal scales. We used data from long‐term seed rain monitoring of hyperdiverse plant communities in the western Amazon. We found significant synchronous whole‐community phenology at multiple timescales, consistent with shared environmental responses or positive interactions among species. We also observed both compensatory and synchronous phenology within groups of species (confamilials) likely to share traits and seed dispersal mechanisms. Wind‐dispersed species exhibited significant synchrony at ~6‐month scales, suggesting these species might share phenological niches to match the seasonality of wind. Our results suggest that community phenology is shaped by shared environmental responses but that the diversity of tropical plant phenology may partly result from temporal niche partitioning. The scale‐specificity and time‐localized nature of community phenology patterns highlights the importance of multiple and shifting drivers of phenology.
Serum angiotensin‐converting enzyme levels indicating early sarcoidosis diagnosis and immunosuppressive therapy efficacy
Authors: Kawai Hideki , Naruse Hiroyuki , Sarai Masayoshi , Kato Yasuchika , Sato Yoshihiro , Takahashi Hiroshi , Ishii Junnichi , Ito Hiroyasu , Morimoto Shin‐ichiro , Izawa Hideo
Published: March 2023

Aims

This study aimed to determine the new cut‐off value of serum angiotensin‐converting enzyme (ACE) levels for detecting patients with sarcoidosis and to examine the change in ACE levels after the initiation of immunosuppressive therapy.

Methods and results

We retrospectively examined patients in whom serum ACE levels were measured for suspected sarcoidosis between 2009 and 2020 in our institution. For patients diagnosed with sarcoidosis, changes in ACE levels were also observed. Of the 3781 patients (51.1% men, 60.1 ± 17.0 years old), 477 were excluded for taking ACE inhibitors and/or immunosuppression agents or those with any diseases affecting serum ACE levels. In 3304 patients including 215 with sarcoidosis, serum ACE levels were 19.6 IU/L [interquartile range, 15.1–31.5] in patients with sarcoidosis and 10.7 [8.4–16.5] in those without sarcoidosis (P < 0.01), and the best cut‐off value was 14.7 IU/L with 0.865 of the area under the curves. Compared with the current ACE cut‐off of 21.4, the sensitivity improved from 42.3 to 78.1 at the new cut‐off, although specificity slightly decreased from 98.6 to 81.7. The ACE level significantly decreased more in those with immunosuppression therapy than in those without it (P for interaction <0.01), although it decreased in both groups (P < 0.01).

Conclusions

Because the sensitivity for detecting sarcoidosis is comparatively low at the current standard value, further examinations are needed for patients suspected of sarcoidosis with relatively high ACE levels in the normal range. In patients with sarcoidosis, ACE levels decreased after the initiation of immunosuppression therapy.
Ideologically‐based contact avoidance during a pandemic: Blunt or selective distancing from ‘others’?
Authors: Hodson Gordon , Meleady Rose
Published: March 2023

This project sought to understand when ideology is relevant (or not) to predicting contact avoidance of ‘others’ during the COVID‐19 pandemic. Right‐leaning ideologies (political conservatism, right‐wing authoritarianism, social dominance orientation) were not expected to predict greater contact avoidance per se, but rather exhibit selective avoidance of outgroup (vs. ingroup) members. White British participated in one exploratory (Study 1 N = 364) and two pre‐registered (Study 2 N = 431, Study 3 N = 700) studies. As expected, right‐leaning ideologies were significantly stronger predictors of greater preferred personal distance and contact discomfort regarding foreign outgroups (vs. British ingroup) in Studies 1 and 3 (partially supported in Study 2). Ideology rarely predicted ingroup reactions. This Ideology × Target pattern was itself not moderated by the perceived COVID‐19 threat. Pre‐pandemic theorizing that heightened behavioural immune system responses are associated with heightened right‐leaning ideologies appear insufficient for use in actual pandemic contexts, especially when highly politicized.
Evaluation of the accuracy of hTERT gene aberrant methylation using electrochemical hybridization assay and liquid‐based cytology in screening for oral squamous cell carcinoma
Authors: Haraguchi Kazuya , Sato Shinobu , Habu Manabu , Yada Naomi , Hayakawa Mana , Sasaguri Masaaki , Yoshioka Izumi , Tominaga Kazuhiro , Takenaka Shigeori
Published: March 2023

In order to improve the survival rate of oral squamous cell carcinoma (OSCC) patients, a reliable diagnostic method for early OSCC detection is required that is minimally invasive, less burdensome to the patient, and has high sensitivity and specificity. Therefore, we performed the detection of abnormal methylation at three locations in the hTERT promoter region of oral exfoliated cells by employing the ferrocenylnaphthalene diimide (FND)‐based electrochemical hybridization assay (FND‐EHA) using three types of DNA probe‐immobilized electrodes. We also performed liquid cytology using oral exfoliated cells and compared these obtained data to evaluate whether FND‐ EHA can be used as an OSCC screening system. The results showed a good correlation between this method and conventional OSCC screening, and cytology. In addition, FND‐EHA was also able to determine samples that had been ambiguously determined by liquid cytology. This indicates that FND‐EHA may be useful as an OSCC screening system.
Next‐generation liquid biopsy instruments: Challenges and opportunities
Authors: Zhu Shu , Fang Yaohui , Guo Kefan , Ni Zhonghua , Xiang Nan
Published: March 2023

Conventional cancer diagnosis needs to excise diseased tissue from the patient's body for biopsy, causing severe injury to patients. Liquid biopsy (LB), with the superior advantage of minimal invasiveness, has shown its ability to cancer diagnosis in real‐time and has been developing promising diagnostic instruments. However, until today, the developed instrument still cannot be an alternative to tissue biopsy in the majority of research and clinical settings. In this paper, we first summarize the challenges and limitations suffered by the existing LB instrument. Then, the opportunities and future progression of the next‐generation instrument are discussed in detail. In all, we hope that the future LB instrument can be eventually integrated into the clinical workflow and serve as a validated and reliable tool for cancer diagnosis.
Catalytic activity of glucose oxidase after dielectrophoretic immobilization on nanoelectrodes
Authors: Prüfer Mareike , Stanke Sandra , Bier Frank F. , Hölzel Ralph
Published: March 2023

Dielectrophoresis (DEP) is an AC electrokinetic effect that is proven to be effective for the immobilization of not only cells, but also of macromolecules, for example, antibodies and enzyme molecules. In our previous work, we have already demonstrated the high catalytic activity of immobilized horseradish peroxidase after DEP. To evaluate the suitability of the immobilization method for sensing or research in general, we want to test it for other enzymes, too. In this study, glucose oxidase (GOX) from Aspergillus niger was immobilized on TiN nanoelectrode arrays by DEP. Fluorescence microscopy showed the intrinsic fluorescence of the immobilized enzymes flavin cofactor on the electrodes. The catalytic activity of immobilized GOX was detectable, but a fraction of less than 1.3% of the maximum activity that was expected for a full monolayer of immobilized enzymes on all electrodes was stable for multiple measurement cycles. Therefore, the effect of DEP immobilization on the catalytic activity strongly depends on the used enzyme.
Implementation of ubiquitous chromatin opening elements as artificial integration sites for CRISPR/Cas9‐mediated knock‐in in mammalian cells
Authors: Kim Seul Mi , Lee Jaejin , Lee Jae Seong
Published: March 2023

CRISPR/Cas9‐mediated targeted gene integration (TI) has been used to generate recombinant mammalian cell lines with predictable transgene expression. Identifying genomic hot spots that render high and stable transgene expression and knock‐in (KI) efficiency is critical for fully implementing TI‐mediated cell line development (CLD); however, such identification is cumbersome. In this study, we developed an artificial KI construct that can be used as a hot spot at different genomic loci. The ubiquitous chromatin opening element (UCOE) was employed because of its ability to open chromatin and enable stable and site‐independent transgene expression. UCOE KI cassettes were randomly integrated into CHO‐K1 and HEK293T cells, followed by TI of enhanced green fluorescent protein (EGFP) onto the artificial UCOE KI site. The CHO‐K1 random pool harboring 5′2.2A2UCOE‐CMV displayed a significant increase in EGFP expression level and KI efficiency compared with that of the control without UCOE. In addition, 5′2.2A2UCOE‐CMV showed improved Cas9 accessibility in the HEK293T genome, leading to an increase in indel frequency and homology‐independent KI. Overall, this assessment revealed the potential of UCOE KI constructs as artificial integration sites in streamlining the screening of high‐production targeted integrants by mitigating the selection of genomic hot spots.
Surgical factors affecting regionally metastatic cutaneous squamous cell carcinoma to the parotid gland
Authors: Rao Vishwanatha M. , Feng Allen L. , Deschler Daniel G. , Kaufman Howard L. , Lin Derrick T. , Miller David , Richmon Jeremy D. , Shalhout Sophia Z. , Varvares Mark A. , Emerick Kevin S.
Published: March 2023

Background

Understanding the impact of surgical treatment on regionally metastatic cutaneous squamous cell carcinoma (cSCC).

Methods

Retrospective series of 145 patients undergoing parotidectomy and neck dissection for regionally metastatic cSCC to the parotid. Overall survival (OS), disease‐specific survival (DSS), and disease‐free survival (DFS) analyzed over 3 years. Multivariate analysis was completed using Cox proportional hazard models.

Results

OS was 74.5%, DSS was 85.5% and DFS was 64.8%. On multivariate analysis, immune status (HR = 3.225[OS], 5.119[DSS], 2.071[DFS]) and lymphovascular invasion (HR = 2.380[OS], 5.237[DSS], 2.595[DFS]) were predictive for OS, DSS, and DFS. Margin status (HR = 2.296[OS], 2.499[DSS]) and ≥18 resected nodes (HR = 0.242[OS], 0.255[DSS]) were predictive of OS and DSS, while adjuvant therapy was predictive of DSS (p = 0.018).

Conclusions

Immunosuppression and lymphovascular invasion portended worse outcomes in patients with metastatic cSCC to the parotid. Microscopically positive margins and <18 nodes resected are associated with worse OS and DSS, while patients receiving adjuvant therapy had improved DSS.
Ligation of the ethmoid arteries in superselective intra‐arterial infusion of cisplatin for advanced maxillary sinus cancer fed by the ophthalmic artery
Authors: Tamagawa Kotaro , Shinomiya Hirotaka , Okada Takuya , Tatehara Shun , Teshima Masanori , Sasaki Ryohei , Nibu Ken‐ichi
Published: March 2023

Background

Superselective cisplatin (CDDP) infusion via the external carotid artery system and concomitant radiotherapy (RADPLAT) provides favorable oncological and functional outcomes in patients with maxillary sinus cancer. However, targeted lesions are occasionally fed by the branch of the internal carotid artery.

Methods

In RADPLAT for maxillary sinus cancer partly fed by the ophthalmic artery, the ethmoid arteries were ligated in two patients without medial orbital wall involvement. In four patients with that, CDDP was administered via the ophthalmic artery.

Results

A complete response was obtained in all six patients. Locoregional recurrence was not observed in any cases. However, visual acuity was lost in four patients who received the ophthalmic artery infusion.

Conclusions

Ligation of the ethmoid arteries is recommended in RADPLAT for maxillary sinus cancer with lesions fed by the ophthalmic artery. CDDP administered via the ophthalmic artery may be considered if a patient accepts the possibility of visual loss.
Bayesian sample size planning for developmental studies
Authors: Visser Ingmar , Kucharský Šimon , Levelt Claartje , Stefan Angelika M. , Wagenmakers Eric‐Jan , Oakes Lisa
Published: March 2023

Running developmental experiments, particularly with infants, is often time‐consuming and intensive, and the recruitment of participants is hard and expensive. Thus, an important goal for developmental researchers is to optimize sampling plans such that neither too many nor too few participants are tested given the hypothesis of interest. One approach that enables such optimization is the use of Bayesian sequential designs. The use of such sequential designs allows data collection to be terminated as soon as the evidence is deemed sufficiently strong, without compromising the interpretability of the test outcome. In this tutorial, we illustrate how to plan a Bayesian sequential testing design prior to data collection by the method of Bayes factor design analysis—the Bayesian equivalent of power analysis—and discuss the relevance of this for developmental psychologists. The tutorial provides a step‐by‐step guide to perform such analyses, and the methods are illustrated using commonly used statistics in a typical infant‐looking time paradigm such that researchers can easily adapt these methods for their studies.

Highlights

Bayesian Sequential Testing can be used to optimize sample sizes and save on data collection.

Bayes Factor Design Analysis can be used to analyze a sequential testing study prior to data collection.

Step‐by‐step guide for performing Bayes Sequential Testing and Bayes Factor Design Analysis.
Seed lost to perineum from hydrogel spacer after brachytherapy for prostate cancer
Authors: Nakiri Makoto , Ueda Kosuke , Hoshino Ryuji , Ogasawara Naoyuki , Kurose Hirofumi , Nishihara Kiyoaki , Muraki Koichiro , Hattori Chikayuki , Ogo Etsuyo , Igawa Tsukasa
Published: March 2023

Introduction

We describe a rare case of brachytherapy for prostate cancer in which a seed was lost from the perineum after a hydrogel injection.

Case presentation

A 71‐year‐old Japanese man was diagnosed with localized high‐risk prostate cancer. Trimodality therapy with I‐125 brachytherapy was selected, and combined androgen blockade therapy was initiated. Brachytherapy and hydrogel injection were performed 7 months after combined androgen blockade initiation; 6 months later, the patient visited our hospital with complaints of redness and bleeding in the perineum. Serous effusion and loss of a seed on the right side of the perineal anus were observed. Pelvic magnetic resonance imaging showed a tunnel like discharge of hydrogel from the dorsal prostate to the perineum. The fistula was incised, the seed was removed, and drainage was performed.

Conclusion

Appropriate diagnosis and treatment with careful follow‐up are required in patients at high risk of infection after brachytherapy with hydrogel injection.
Optimal 3D trajectory design for UAV‐assisted cellular communications in the post‐disaster scenarios
Authors: GC Deepak , Politis Christos
Published: March 2023

Unmanned aerial vehicle (UAV) assisted wireless communication has been recently proposed as an effective solution to provide wireless connectivity to ground users which can improve the network coverage area and spectral efficiency. In this paper, we consider the post‐disaster network scenario where users are isolated from the network infrastructure. We investigate the best positioning of the UAV in terms of the optimal trajectory as well as UAV vertical location to cover as many ground users as possible to improve the spectral efficiency. When the trajectory is optimized, the optimal transmit power within the available power budget is then obtained. The simulation results demonstrate that the proposed UAV‐enabled wireless communication technique improves the overall spectral and energy efficiency.