bluuebunny/crossref_metadata_2025 huggingface dataset:
Depth‐Dependent Post‐Treatment for Reducing Voltage Loss in Printable Mesoscopic Perovskite Solar Cells
Authors: Xiao Xufeng , Zhang Wenhao , Liu Jiale , Du Jiankang , Qiu Cheng , Meng Ranjun , Mei Anyi , Han Hongwei , Hu Yue
Published: January 2023

The printable mesoscopic perovskite solar cells consisting of a double layer of metal oxides covered by a porous carbon film have attracted attention due to their industrialization advantages. However, the tens‐of‐micrometer thickness of the triple scaffold leads to a challenge for perovskite to crystallize and for the charge carriers to separate and travel to the electrode, which limits the open circuit voltage (VOC) of such devices. In this work, a depth‐dependent post‐treatment strategy is demonstrated to synergistically passivate defects and tune interfacial energy band alignment. Two thiophene derivatives, namely 3‐chlorothiophene (3‐CT) and 3‐thiophene ethylenediamine (3‐TEA), are selected for the post‐treatment. Energy‐dispersive X‐ray spectroscopy proves that 3‐CT is uniformly distributed throughout the triple scaffold and effectively passivates the defects of the bulky perovskite, while 3‐TEA reacts rapidly with the loose perovskite in the carbon layer to form 2D perovskite, forming a type II energy band alignment at the perovskite/carbon interface. As a result, the defect‐assisted recombination is suppressed and the interfacial energy band is regulated, increasing theVOCto 1012 mV. The PCE of the devices is enhanced from 16.26% to 18.49%. This depth‐dependent post‐treatment strategy takes advantage of the unique structure and provides a new insight for reducing the voltage loss.
Metallic 4D Printing of Laser Stimulation
Authors: Wu Wenzheng , Zhou Yiming , Liu Qingping , Ren Luquan , Chen Fan , Fuh Jerry Ying Hsi , Zheng Aodu , Li Xuechao , Zhao Ji , Li Guiwei
Published: January 2023

4D printing of metallic shape‐morphing systems can be applied in many fields, including aerospace, smart manufacturing, naval equipment, and biomedical engineering. The existing forming materials for metallic 4D printing are still very limited except shape memory alloys. Herein, a 4D printing method to endow non‐shape‐memory metallic materials with active properties is presented, which could overcome the shape‐forming limitation of traditional material processing technologies. The thermal stress spatial control of 316L stainless steel forming parts is achieved by programming the processing parameters during a laser powder bed fusion (LPBF) process. The printed parts can realize the shape changing of selected areas during or after forming process owing to stress release generated. It is demonstrated that complex metallic shape‐morphing structures can be manufactured by this method. The principles of printing parameters programmed and thermal stress pre‐set are also applicable to other thermoforming materials and additive manufacturing processes, which can expand not only the materials used for 4D printing but also the applications of 4D printing technologies.
Synergistic Structure and Iron‐Vacancy Engineering Realizing High Initial Coulombic Efficiency and Kinetically Accelerated Lithium Storage in Lithium Iron Oxide
Authors: Wu Naiteng , Shen Jinke , Yong Kai , Chen Chengqian , Li Jian , Xie Yi , Guo Donglei , Liu Guilong , Li Jin , Cao Ang , Liu Xianming , Mi Hongyu , Wu Hao
Published: January 2023

Transition metal oxides with high capacity still confront the challenges of low initial coulombic efficiency (ICE, generally <70%) and inferior cyclic stability for practical lithium‐storage. Herein, a hollow slender carambola‐like Li0.43FeO1.51 with Fe vacancies is proposed by a facile reaction of Fe3+‐containing metal–organic frameworks with Li2CO3. Synthesis experiments combined with synchrotron‐radiation X‐ray measurements identify that the hollow structure is caused by Li2CO3 erosion, while the formation of Fe vacancies is resulted from insufficient lithiation process with reduced Li2CO3 dosage. The optimized lithium iron oxides exhibit remarkably improved ICE (from 68.24% to 86.78%), high‐rate performance (357 mAh g−1 at 5 A g−1), and superior cycling stability (884 mAh g−1 after 500 cycles at 0.5 A g−1). Paring with LiFePO4 cathodes, the full‐cells achieve extraordinary cyclic stability with 99.3% retention after 100 cycles. The improved electrochemical performances can be attributed to the synergy of structural characteristics and Fe vacancy engineering. The unique hollow structure alleviates the volume expansion of Li0.43FeO1.51, while the in situ generated Fe vacancies are powerful for modulating electronic structure with boosted Li+ transport rate and catalyze more Li2O decomposition to react with Fe in the first charge process, hence enhancing the ICE of lithium iron oxide anode materials.
Van der Waals Heterostructures With Built‐In Mie Resonances For Polarization‐Sensitive Photodetection
Authors: Yan Jiahao , Yang Xinzhu , Liu Xinyue , Du Chun , Qin Fei , Yang Mengmeng , Zheng Zhaoqiang , Li Jingbo
Published: January 2023

Few‐layer transition metal dichalcogenides (TMDs) and their combination as van der Waals heterostructures provide a promising platform for high‐performance optoelectronic devices. However, the ultrathin thickness of TMD flakes limits efficient light trapping and absorption, which triggers the hybrid construction with optical resonant cavities for enhanced light absorption. The optical structure enriched photodetectors can also be wavelength‐ and polarization‐sensitive but require complicated fabrication. Herein, a new‐type TMD‐based photodetector embedded with nanoslits is proposed to enhance light trapping. Taking ReS2 as an example, strong anisotropic Mie‐type optical responses arising from the intrinsic in‐plane anisotropy and nanoslit‐enhanced anisotropy are discovered. Owing to the nanoslit‐enhanced optical resonances and band engineering, excellent photodetection performances are demonstrated with high responsivity of 27 A W−1 and short rise/decay times of 3.7/3.7 ms. More importantly, through controlling the angle between the nanoslit orientation and the polarization direction to excite different resonant modes, polarization‐sensitive photodetectors with anisotropy ratios from 5.9 to 12.6 can be achieved, representing one of the most polarization‐sensitive TMD‐based photodetectors. The depth and orientation of nanoslits are demonstrated crucial for optimizing the anisotropy ratio. The findings bring an effective scheme to construct high‐performance and polarization‐sensitive photodetectors.
Grain Boundary‐Rich Copper Nanocatalysts Generated from Metal‐Organic Framework Nanoparticles for CO2‐to‐C2+ Electroconversion
Authors: Kim Sungjoo , Shin Dongwoo , Park Jonghyeok , Jung Jong‐Yeong , Song Hyunjoon
Published: January 2023

Due to severe contemporary energy issues, generating C2+ products from electrochemical carbon dioxide reduction reactions (eCO2RRs) gains much interest. It is known that the catalyst morphology and active surface structures are critical for product distributions and current densities. Herein, a synthetic protocol of nanoparticle morphology on copper metal‐organic frameworks (n‐Cu MOFs) is developed by adjusting growth kinetics with termination ligands. Nanoscale copper oxide aggregates composed of small particulates are yielded via calcining the Cu‐MOF nanoparticles at a specific temperature. The resulting nanosized MOF‐derived catalyst (n‐MDC) exhibits Faradaic efficiencies toward ethylene and C2+ products of 63% and 81% at −1.01 V versus reversible hydrogen electrode (RHE) in neutral electrolytes. The catalyst also shows prolonged stability for up to 10 h. A partial current density toward C2+ products is significantly boosted to −255 mA cm−2 in an alkaline flow cell system. Comprehensive analyses reveal that the nanoparticle morphology of pristine Cu MOFs induces homogeneous decomposition of organic frameworks at a lower calcination temperature. It leads to evolving grain boundaries in a high density and preventing severe agglomeration of copper domains, the primary factors for improving eCO2RR activity toward C2+ production.
Complement‐driven hemolytic uremic syndrome
Authors: Leon Juliette , LeStang Marie‐Bénédicte , Sberro‐Soussan Rebecca , Servais Aude , Anglicheau Dany , Frémeaux‐Bacchi Véronique , Zuber Julien
Published: January 2023

Overactivation of the complement alternative pathway drives the pathogenesis of primary atypical hemolytic uremic syndrome (aHUS). Genetically‐determined or acquired dysregulation of the complement is frequently identified in patients with aHUS, pregnancy‐related hemolytic uremic syndrome (HUS), and severe hypertension‐associated HUS. In contrast, it is still unclear whether self‐limited complement activation, which frequently occurs in other forms of HUS, provides key mechanistic clues or results from endothelial damage. Development of novel biomarkers is underway to firmly establish complement‐driven pathogenesis. C5 blockade therapy has revolutionized the management of aHUS patients, resulting in a halving of the subpopulation under chronic dialysis over the course of a few years. On the other hand, the efficacy of C5 blockade in secondary forms of HUS, as assessed by small and uncontrolled case series, is less compelling and should be investigated through properly designed prospective clinical trials. The increased risk of meningococcal infection, related to C5 inhibition, must be rigorously addressed with suitable prophylaxis. Treatment duration should be determined based on an individualized benefit/risk assessment.
A Forward Vision for Chemodynamic Therapy: Issues and Opportunities
Authors: Zhao Peiran , Li Huiyan , Bu Wenbo
Published: January 2023

Since the insight to fuse Fenton chemistry and nanomedicine into cancer therapy, great signs of progress have been made in the field of chemodynamic therapy (CDT). However, the exact mechanism of CDT is obscured by the unique tumor chemical environment and inevitable nanoparticle‐cell interactions, thus impeding further development. In this Scientific Perspective, the significance of CDT is clarified, the complex mechanism is deconstructed into primitive chemical and biological interactions, and the mechanism research directions based on the chemical kinetics and biological signaling pathways are discussed in detail. Moreover, beneficial outlooks are presented to enlighten the evolution of next‐generation CDT. Hopefully, this Scientific Perspective can inspire new ideas and advances for CDT and provide a reference for breaking down the interdisciplinary barriers in the field of nanomedicine.
Manganese(II)‐Guided Separation in the Sub‐Nanometer Regime for Precise Identification of In Vivo Size Dependence
Authors: Cai Wei , Tan Yue , He Kui , Tang Bing , Liu Jinbin
Published: January 2023

A precise understanding of nano‐bio interactions in the sub‐nanometer regime is necessary for advancements in nanomedicine. However, this is currently hindered by the control of the nanoparticle size in the sub‐nanometer regime. Herein, we report a facile in situ Mn2+‐guided centrifugation strategy for the synthesis of large‐scale ultrasmall gold nanoparticles (AuNPs) with a precisely controlled size gradient at the sub‐nanometer regime. With the discovery that [Mn(OH)]+, especially metallic manganese (Mn0@[Mn(OH)]+) nanoparticles, could selectively interact with larger AuNPs through synergistic coordination and hydrogen bonding to form aggregates, we also realized the fast (<1 h) synthesis of water‐soluble atomically precise Au25 with high yields (>56 %). We further demonstrated that sub‐nanometer size differences (approximately 0.5 nm) significantly alter non‐specific phagocytosis of AuNPs in the reticuloendothelial system macrophages, elimination rate, and nanotoxicology.
Molecular Lanthanide Switches for Magnetism and Photoluminescence
Authors: Münzfeld Luca , Dahlen Milena , Hauser Adrian , Mahieu Nolwenn , Kuppusamy Senthil Kumar , Moutet Jules , Tricoire Maxime , Köppe Ralf , La Droitte Léo , Cador Olivier , Le Guennic Boris , Nocton Grégory , Moreno‐Pineda Eufemio , Ruben Mario , Roesky Peter W.
Published: January 2023

Solvation of [(CNT)Ln(η8‐COT)] (Ln=La, Ce, Nd, Tb, Er; CNT=cyclononatetraenyl, i.e., C9H9−; COT=cyclooctatetraendiid, i.e., C8H82−) complexes with tetrahydrofuran (THF) gives rise to neutral [(η4‐CNT)Ln(thf)2(η8‐COT)] (Ln=La, Ce) and ionic [Ln(thf)x(η8‐COT)][CNT] (x=4 (Ce, Nd, Tb), 3 (Er)) species in a solid‐to‐solid transformation. Due to the severe distortion of the ligand sphere upon solvation, these species act as switchable luminophores and single‐molecule magnets. The desolvation of the coordinated solvents can be triggered by applying a dynamic vacuum, as well as a temperature gradient stimulus. Raman spectroscopic investigations revealed fast and fully reversible solvation and desolvation processes. Moreover, we also show that a Nd:YAG laser can induce the necessary temperature gradient for a self‐sufficient switching process of the Ce(III) analogue in a spatially resolved manner.
Dynamic Reconfigurable DNA Nanostructures, Networks and Materials
Authors: Wang Jianbang , Li Zhenzhen , Willner Itamar
Published: January 2023

DNA nanotechnology relies on the structural and functional information encoded in nucleic acids. Specifically, the sequence‐guided reconfiguration of nucleic acids by auxiliary triggers provides a means to develop DNA switches, machines and stimuli‐responsive materials. The present Review addresses recent advances in the construction and applications of dynamic reconfigurable DNA nanostructures, networks and materials. Dynamic transformations proceeding within engineered origami frames or between origami tiles, and the triggered dynamic reconfiguration of scaled supramolecular origami structures are addressed. The use of origami frameworks to assemble dynamic chiroplasmonic optical devices and to operate switchable chemical processes are discussed. Also, the dynamic operation of DNA networks is addressed, and the design of “smart” stimuli‐responsive all‐DNA materials and their applications are introduced. Future perspectives and applications of dynamic reconfigurable DNA nanostructures are presented.
Direct Monitoring of Li2S2 Evolution and Its Influence on the Reversible Capacities of Lithium‐Sulfur Batteries
Authors: Luo Yufeng , Fang Zhenhan , Duan Shaorong , Wu Hengcai , Liu Haitao , Zhao Yuxing , Wang Ke , Li Qunqing , Fan Shoushan , Zheng Zijian , Duan Wenhui , Zhang Yuegang , Wang Jiaping
Published: January 2023

The polysulfide (PS) dissolution and low conductivity of lithium sulfides (Li2S) are generally considered the main reasons for limiting the reversible capacity of the lithium‐sulfur (Li‐S) system. However, as the inevitable intermediate between PSs and Li2S, lithium disulfide (Li2S2) evolutions are always overlooked. Herein, Li2S2 evolutions are monitored from the operando measurements on the pouch cell level. Results indicate that Li2S2 undergoes slow electrochemical reduction and chemical disproportionation simultaneously during the discharging process, leading to further PS dissolution and Li2S generation without capacity contribution. Compared with the fully oxidized Li2S, Li2S2 still residues at the end of the charging state. Therefore, instead of the considered Li2S and PSs, slow electrochemical conversions and side chemical reactions of Li2S2 are the determining factors in limiting the sulfur utilization, corresponding to the poor reversible capacity of Li‐S batteries.
Boron‐Thioketonates: A New Class of S,O‐Chelated Boranes as Acceptors in Optoelectronic Devices
Authors: Murali Anna Chandrasekar , Nayak Prakash , Nayak Shashwat , Das Sabyasachi , Senanayak Satyaprasad P. , Venkatasubbaiah Krishnan
Published: January 2023

Development of new n‐type semiconductors with tunable band gap and dielectric constant has significant implication in dissociating bound charge carrier relevant for demonstrating high performance optoelectronic devices. Boron‐β‐thioketonates (MTDKB), analogues to boron‐β‐diketonates containing a sulfur atom in the framework of β‐diketones were synthesized. Bulk transport measurement exhibited an outstanding bulk electron mobility of ≈0.003 cm2 V−1 s−1, which is among the best values reported till date in these class of semiconducting materials and correspondingly a single junction photo responsivity of upto 6 mA W−1 was obtained. This new family of O,S‐chelated boron compounds exhibited luminescence in the far red/near‐infrared region. The remarkable red shift of 89 nm (fluorescence) observed for 4 a in comparison with analogues boron‐β‐diketonate signifies the importance of sulfur in these molecules. MTDKBs with amine functionality have also been investigated as an ON/OFF fluorescent sensor.
Imidazolium organometallic complex of palladium on Fe3O4 nanoparticles as selective and magnetically recoverable nanocatalyst for C‐C cross‐coupling reactions
Authors: Nouri Kheirollah , Ghassemzadeh Mitra , Mohsenzadeh Farshid , Afsharpour Maryam
Published: January 2023

The synthesis of an efficient heterogeneous nanocatalyst was prepared by the anchoring of palladium complex on the surface of an imidazolium‐based ionic liquid‐functionalized Fe3O4 (Pd‐imidazolium@Fe3O4 NPs). The nanocatalyst, Pd‐imidazolium@Fe3O4 NPs, was characterized by Raman, X‐ray diffraction  (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy‐dispersive X‐ray spectroscopy (EDX), fourier transform infrared (FT‐IR), inductively coupled plasma (ICP), and vibrating sample magnetometer (VSM) techniques. The catalytic performance of this novel nanocatalyst was evaluated in the Heck––Mizoroki and Suzuki–Miyaura cross‐coupling reactions under mild conditions using PEG‐400 as a green and biodegradable solvent. The nanocatalyst exhibited high catalytic activity for both cross‐coupling reactions. Furthermore, this stable nanocatalyst can be easily removed and recovered from the reaction mixture and reused for at least eight consecutive cycles without a discernible decrease in the catalytic activity. Also, the recovered Pd‐imidazolium@Fe3O4 NPs was characterized by FT‐IR, XRD, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and atomic absorption spectroscopy techniques.
Metal and nitrogen co‐doped carbon dots in the sensitized solar cells
Authors: Hezarkhani Zeinab , Saei Paria‐Sadat , Sabri Alireza , Kong Fantai , Ghadari Rahim
Published: January 2023

Doped carbon dots are used to upgrade the efficiency of the porphyrin‐sensitized solar cells (PSSCs). Nitrogen‐doped carbon dots (NCDs) and metal and nitrogen co‐doped carbon dots ([M]NCDs; M: manganese, iron, cobalt, nickel, copper, and zinc) are applied in the PSSCs structure to improve the performance. Study on the substituted porphyrins is showing the effect of the substitutions of the porphyrins on the performance of PSSCs in the presence of NCDs as co‐sensitizer. The ZnTCPP/NCDs has made the biggest impact on the performance of the solar cell relative to other porphyrins; increase from 0.76% to 1.84% in PCE (power conversion efficiency) relative to ZnTPP/NCDs can be seen. The results that are related to the use of NCDs and (M)NCDs as co‐sensitizer are showing the impact of impurity doping in CDs on the PSSCs' efficiency. In the case of doped CDs in the presence of ZnTCPP, the performance of PSSCs using (Ni)NCDs and (Zn)NCDs is showing more increase relative to the use of other prepared carbon dots as co‐sensitizer. PCE of the solar cells sensitized by ZnTCPP/(Ni)NCDs and ZnTCPP/(Zn)NCDs was increased from 1.10% to 2.75% and 3.09%, respectively, in comparison with only ZnTCPP. Based on computational results, the Zn2+ and Ni2+ are playing a direct role on the highest occupied molecular orbital (HOMO) and (lowest unoccupied molecular orbital) LUMO of (Zn)NCDs and (Ni)NCDs, respectively. Also, based on the partial density of states analysis, the metal ions such as Zn2+ and Ni2+ in the (Zn)NCDs and (Ni)NCDs, respectively, are playing an important role in HOMO and LUMO of investigated systems, and these two metals have high amount of contributions in the mentioned levels.
Regioselective Direct C−H Phosphorylation of Benzofulvenes
Authors: Hore Soumyadip , Singh Abhijeet , Singh Ravi P.
Published: January 2023

A practical and straightforward protocol to access site‐selective C‐3 phosphorylated benzofulvenes by means of cross‐dehydrogenative coupling of two nucleophilic moieties, employing silver as a promoter, is described here. Remarkably, this protocol provides a broad, structurally diverse phosphorylated benzofulvene. Initial mechanistic studies shed light on its radical coupling nature, and late‐stage transformations offer highly diversified benzofulvenes core.
Covalent Organic Frameworks as Emerging Battery Materials
Authors: Wang Zhiqiang , Hu Jing , Lu Zhouguang
Published: January 2023

Covalent organic frameworks (COFs) are emerging as promising energy storage materials due to their unique characteristics, such as adjustable thickness, designable topology, superior stability and controllable pore size distribution. Consequently, COFs can provide diversified high‐rate carrier transport pathways, and the performance of COFs can be easily improved by adjusting conjugated skeleton types, overlapping p‐electron clouds between stacks, and modifying open channels with functional groups. The state‐of‐the‐art COFs electrode materials based on synthetic method and electrochemical performance in recent years are summarized and discussed in this review. The synthesis method, topological structure and application in metal ion (such as Li+, Na+, K+, Zn2+, Mg2+, Al3+, et. al) batteries of COFs electrodes are critically accounted. Finally, we briefly discuss the major challenges in the field that needs to be addressed to pave the way for industrial applications. Although there are still many arduous tasks to be tackled, the burgeoning of COFs‐related technologies and applications in batteries provide a ponderable field for commercial process in the short run.
Robotic‐assisted versus laparoscopic nephroureterectomy; a systematic review and meta‐analysis
Authors: O'Sullivan Niall J. , Naughton Ailish , Temperley Hugo C. , Casey Rowan G.
Published: January 2023

Background

Upper tract urothelial carcinoma (UTUC) is the malignant transformation of urothelial cells, from the renal calyces to the ureteral orifices. While the benefits of minimally invasive nephroureterectomy over their open counterpart have been established, the optimal technique remains a debate. We aimed to assess current evidence in the literature and compare outcomes between robotic‐assisted (RANU) and laparoscopic nephroureterectomy (LNU).

Methods

A systematic review of the literature was performed for studies comparing RANU and LNU for bladder cancer. Outcome measurements were recurrence rates (local and distal), positive margins, positive lymph node yield and perioperative outcomes. Meta‐analysis was performed using Review Manager 5.

Results

Our results demonstrate a significantly higher mortality rate in patients undergoing laparoscopic nephroureterectomy when compared with the robotic‐assisted approach for the treatment of UTUC (1.8% vs. 1.1%, p = 0.008); however, these results were inconsistent on sensitivity analysis and should therefore be interpreted with caution. No significant difference was observed for other outcomes.

Conclusion

The ideal approach to minimally invasive radical nephroureterectomy remains undetermined. Future research, ideally prospective randomised studies, should focus on long‐term outcomes, in particular recurrence, recurrence‐free survival, overall survival and the correlation between surgical technique and survival.
Development and validation of a dried plasma spot LC–MS/MS method for therapeutic monitoring of vancomycin and comparison with enzyme‐multiplied immunoassay
Authors: Vidal Fernanda Ribeiro , Ossanes Daniela Souza , Birk Letícia , Scheid Camila , Barbosa Fábio Souza , Dallegrave Eliane , Merib Josias , Eller Sarah , de Oliveira Tiago Franco
Published: January 2023

Vancomycin is used as an antimicrobial agent for the treatment of severe gram‐positive infections. The importance of therapeutic monitoring of antimicrobials has led to the development of more specific sample preparation techniques capable of identifying with accuracy the concentration of this substance in the organism. An aliquot of 10 μl of plasma was transferred to Whatman 903 paper and dried at room temperature. The extraction method was performed by cutting and transferring the paper to a microtube and adding sodium phosphate buffer and internal standard. The mixture was shaken and centrifuged, and a 5‐μl aliquot was injected into the analytical system. The optimization of the main parameters that can influence the extraction efficiency was performed using multivariate approaches to obtain the best conditions. The method developed was validated, providing coefficients of determination higher than 0.994 and a lower limit of quantification of 1 mg/L. Within‐ and between‐run precision ranged from 11.4 to 17.30% and from 6.65 to 13.51%, respectively. This method was successfully applied to 75 samples of patients undergoing vancomycin therapy. The method was rapid, simple, and environmentally friendly with satisfactory analytical performance and was advantageous over the laborious and time‐consuming methodologies used in therapeutic drug monitoring routine analyses.
Clustering of prostate cancer healthcare pathways in the French National Healthcare database
Authors: Baulain Roméo , Jové Jérémy , Sakr Dunia , Gross‐Goupil Marine , Rouyer Magali , Puel Marius , Blin Patrick , Droz‐Perroteau Cécile , Lassalle Régis , Thurin Nicolas H.
Published: January 2023

Background

Healthcare pathways of patients with prostate cancer are heterogeneous and complex to apprehend using traditional descriptive statistics. Clustering and visualization methods can enhance their characterization.

Methods

Patients with prostate cancer in 2014 were identified in the French National Healthcare database (Système National des Données de Santé—SNDS) and their data were extracted with up to 5 years of history and 4 years of follow‐up. Fifty‐one‐specific encounters constitutive of prostate cancer management were synthesized into four macro‐variables using a clustering approach. Their values over patient follow‐ups constituted healthcare pathways. Optimal matching was applied to calculate distances between pathways. Partitioning around medoids was then used to define consistent groups across four exclusive cohorts of incident prostate cancer patients: Hormone‐sensitive (HSPC), metastatic hormone‐sensitive (mHSPC), castration‐resistant (CRPC), and metastatic castration‐resistant (mCRPC). Index plots were used to represent pathways clusters.

Results

The repartition of macro‐variables values—surveillance, local treatment, androgenic deprivation, and advanced treatment—appeared to be consistent with prostate cancer status. Two to five clusters of healthcare pathways were observed in each of the different cohorts, corresponding for most of them to relevant clinical patterns, although some heterogeneity remained. For instance, clustering allowed to distinguish patients undergoing active surveillance, or treated according to cancer progression risk in HSPC, and patients receiving treatment for potentially curative or palliative purposes in mHSPC and mCRPC.

Conclusion

Visualization methods combined with a clustering approach enabled the identification of clinically relevant patterns of prostate cancer management. Characterization of these care pathways is an essential element for the comprehension and the robust assessment of healthcare technology effectiveness.
Integrated Lipidomics and Network Pharmacology Reveal Mechanism of Memory Impairment Improvement by Yuanzhi San
Authors: Zhao Fuxia , Li Pei , Deng Fanying , Wang Jiamin , Cheng Yangang , Pei Ke , Wang Yingli , Wang Yan
Published: January 2023

Memory impairment (MI) is caused by a variety of causes, endangering human health. Yuanzhi San (YZS) is a common prescription used for the treatment of MI, but its mechanism of action needs further exploration. The purpose of this study was to investigate this mechanism through lipidomics and network pharmacology. Sprague Dawley (SD) rats were divided randomly into the normal, model, and YZS groups. The rats were gavaged with aluminum chloride (200 mg/kg) and intraperitoneally injected with D‐galactose (400 mg/kg) every day for 60 days, except for the normal group. From the 30th day, YZS (13.34 g/kg) was gavaged once a day to the rats in the YZS group. Post‐YZS treatment, ultra‐high‐performance liquid chromatography‐mass spectrometry (UHPLC/MS) analysis was implemented to conduct a lipidomics study in the hippocampus of rats with memory impairment induced by aluminum chloride and D‐galactose. Eight differential metabolites were identified between the normal group and the model group, whereas between the model group and the YZS group, 20 differential metabolites were established. Metabolic pathway analysis was performed on the aforementioned lipid metabolites, all of which were involved in sphingolipid and glycerophospholipid metabolism. Furthermore, serum pharmacochemistry analysis of YZS was carried out at the early stage of our research, which discovered 62 YZS prototype components. The results of the network pharmacology analysis showed that they were related to 1030 genes, and 451 disease genes were related to MI. There were 73 intersections between the YZS and MI targets. Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis showed that these targets were closely related to the sphingolipid metabolic, calcium signaling, and other pathways. The integrated approach of lipidomics and network pharmacology was then focused on four major targets, including PHK2, GBA, SPTLC1, and AChE, as well as their essential metabolites (glucosylceramide, N‐acylsphingosine, phosphatidylserine, phosphatidylcholine, and phosphatidylcholine) and pathways (sphingolipid, glycerophospholipid, and arachidonic acid metabolism). The significant affinity of the primary target for YZS was confirmed by molecular docking. The obtained results revealed that the combination of lipidomics and network pharmacology could be used to determine the effect of YZS on the MI biological network and metabolic state, and evaluate the drug efficacy of YZS and its related mechanisms of action.
A Nucleophilic Activity‐Based Probe Enables Profiling of PLP‐Dependent Enzymes
Authors: Brody Scott I. , Buonomo Joseph A. , Orimoloye Moyosore O. , Jia Ziyi , Sharma Sachin , Brown Christopher D. , Baughn Anthony D. , Aldrich Courtney C.
Published: January 2023

PLP‐dependent enzymes represent an important class of highly “druggable” enzymes that perform a wide array of critical reactions to support all organisms. Inhibition of individual members of this family of enzymes has been validated as a therapeutic target for pathologies ranging from infection with Mycobacterium tuberculosis to epilepsy. Given the broad nature of the activities within this family of enzymes, we envisioned a universally acting probe to characterize existing and putative members of the family that also includes the necessary chemical moieties to enable activity‐based protein profiling experiments. Hence, we developed a probe that contains an N‐hydroxyalanine warhead that acts as a covalent inhibitor of PLP‐dependent enzymes, a linear diazirine for UV crosslinking, and an alkyne moiety to enable enrichment of crosslinked proteins. Our molecule was used to study PLP‐dependent enzymes in vitro as well as look at whole‐cell lysates of M. tuberculosis and assess inhibitory activity. The probe was able to enrich and identify LysA, a PLP‐dependent enzyme crucial for lysine biosynthesis, through mass spectrometry. Overall, our study shows the utility of this trifunctional first‐generation probe. We anticipate further optimization of probes for PLP‐dependent enzymes will enable the characterization of rationally designed covalent inhibitors of PLP‐dependent enzymes, which will expedite the preclinical characterization of these important therapeutic targets.
Prolactin regulates RANKL expression via signal transducer and activator of transcription 5a signaling in mammary epithelial cells of dairy cows
Authors: Mao Yongjin , Yang Huilin , Ma Xiaocong , Wang Chunmei , Zhang Li , Cui Yingjun
Published: January 2023

Receptor of activated nuclear factor kappa B ligand (RANKL) is regulated by prolactin in the mammary gland. However, the intrinsic molecular mechanism is not well understood. Herein, mammary epithelial cells (MECs) of dairy cows were isolated to characterize the molecular mechanism of prolactin in vitro. We demonstrated that prolactin stimulation increased the expression of RANKL in MECs. Moreover, the expression of RANKL induced by prolactin was inhibited by the prolactin receptor or signal transducer and activator of transcription 5A (STAT5a) knockdown. Furthermore, prolactin markedly increased RANKL‐Luciferase reporter activity in MECs. We identified a putative gamma‐interferon activated site (GAS) in the region between residues −883 to −239 bp of the RANKL promoter. Subsequently, we found that the mutated GAS sequence failed to respond to prolactin stimulation. In addition, STAT5a knockdown markedly decreased prolactin‐stimulated RANKL promoter activity. Western blot results revealed that RANKL overexpression markedly decreased the STAT5a phosphorylation level in MECs. These findings indicate that prolactin could regulate RANKL promoter activity via STAT5a, contributing to increased RANKL expression in MECs. RANKL may have a negative regulatory effect on STAT5a activity.
Visible‐Light Induced Fixation of SO2 into Organic Molecules with Polypyridine Chromium(III) Complexes
Authors: Sittel Steven , Sell Arne Christian , Hofmann Kamil , Wiedemann Christina , Nau Jan Philipp , Kerzig Christoph , Manolikakes Georg , Heinze Katja
Published: January 2023

Incorporation of sulfur dioxide into organic compounds is achieved by a photocatalytic approach using sensitizers made from earth‐abundant chromium(III) ions and visible light leading to sulfones and sulfonamides. We employed three different chromium(III) sensitizers [Cr(ddpd)2]3+, [Cr(bpmp)2]3+ and [Cr(tpe)2]3+ with long excited state lifetimes and different ground and excited state redox potentials as well as varying stability under the reaction conditions (ddpd=N,N’‐dimethyl‐N,N’‐dipyridin‐2‐yl‐pyridine‐2,6‐diamine; bpmp=2,6‐bis(2‐pyridylmethyl)pyridine; tpe=1,1,1‐tris(pyrid‐2‐yl)ethane). Key reaction steps of the catalytic cycles are identified by electrochemical, luminescence quenching, photolysis, laser flash photolysis and catalytic experiments delivering a detailed picture of the challenges in these transformations. The reactivity of the reduced chromium complex was identified as a key property to explain the reaction outcomes. Initial cage escape yield determinations with [Cr(tpe)2]3+ revealed that desired photoreactions occur with unusually high quantum efficiencies, whereas side reactions are almost unproductive.
Configuration‐dependent stretchable all‐solid‐state supercapacitors and hybrid supercapacitors
Authors: Amiri Ahmad , Bruno Ashley , Polycarpou Andreas A.
Published: January 2023

Given the rise in the popularity of wearable electronics that are able to deform into desirable configurations while maintaining electrochemical functionality, stretchable and flexible (hybrid) supercapacitors (SCs) have become increasingly of interest as innovative energy storage devices. Their outstanding power density, long lifetime with low capacitance loss, and appropriate energy density, in particular in hybrid cases make them ideal candidates for flexible electronics. The aim of this review paper is to provide an in‐depth discussion of these stretchable and flexible SCs ranging from fabrication to electro‐mechanical properties. This review paper begins with a short overview of the fundamentals of charge storage mechanisms and different types of multivalent metal‐ion hybrid SCs. The research methods leading up to the current state of these stretchable and flexible SCs are then presented. This is followed by an in‐depth presentation of the challenges associated with the fabrication methods for different configurations. Proposed novel strategies to maximize the elastic and electrochemical properties of stretchable/flexible or quasi‐solid‐state SCs are classified and the pros and cons associated with each are shown. The advances in mechanical properties and the expected advancements for the future of these SCs are discussed in the last section.
Expanding the Horizon of Bio‐Inspired Catalyst Design with Tactical Incorporation of Drug Molecules
Authors: Afshan Gul , Ghorai Santanu , Rai Surabhi , Pandey Aman , Majumder Piyali , Patwari G. Naresh , Dutta Arnab
Published: January 2023

The development of potent H2 production catalysts is a key aspect in our journey toward the establishment of a sustainable carbon‐neutral power infrastructure. Hydrogenase enzymes provide the blueprint for designing efficient catalysts by the rational combination of central metal core and protein scaffold‐based outer coordination sphere (OCS). Traditionally, a biomimetic catalyst is crafted by including natural amino acids as OCS features around a synthetic metal motif to functionally imitate the metalloenzyme activity. Here, we have pursued an unconventional approach and implanted two distinct drug molecules (isoniazid and nicotine hydrazide) at the axial position of a cobalt core to create a new genre of synthetic catalysts. The resultant cobalt complexes are active for both electrocatalytic and photocatalytic H2 production in near‐neutral water, where they significantly enhance the catalytic performance of the unfunctionalized parent cobalt complex. The drug molecules showcased a dual effect as they influence the catalytic HER by improving the surrounding proton relay along and exerting subtle electronic effects. The isoniazid‐ligated catalyst C1 outperformed the nicotine hydrazide‐bound complex C2, as it produced H2 from water (pH 6.0) at a rate of 3960 s−1 while exhibiting Faradaic efficiency of about 90 %. This strategy opens up newer avenues of bio‐inspired catalyst design beyond amino acid‐based OCS features.
Distinct Reactivity of Trimethylytterbium toward AlMe3 and GaMe3: Synthesis of Donor‐Stabilized Dimethylytterbium
Authors: Mortis Alexandros , Maichle‐Mössmer Cäcilia , Anwander Reiner
Published: January 2023

Me3TACN (1,4,7‐trimethyl‐1,4,7‐triazacyclononane)‐stabilized trimethylytterbium was obtained via a salt‐metathesis protocol employing [(Me3TACN)YbCl3] and methyllithium. Complex [(Me3TACN)YbMe3] seems not to engage in redox chemistry with potassium graphite and is thermally quite stable in the solid state. Treatment of trivalent [(Me3TACN)YbMe3] with 3 equiv. of AlMe3 afforded divalent tetramethylaluminate complex [(Me3TACN)Yb(AlMe4)2]. The reaction of [(Me3TACN)YbMe3] with GaMe3 in THF gave trivalent ion pair [(Me3TACN)YbMe2(thf)][GaMe4], which is susceptible to reduction with KC8. The thermally very labile divalent [(Me3TACN)YbMe(μ‐Me)]2 is the first discrete donor adduct of a divalent dimethyl rare‐earth‐metal complex.
A Non Expected Alternative Ni(0) Species in the Ni‐Catalytic Aldehyde and Alcohol Arylation Reactions Facilitated by a 1,5‐Diaza‐3,7‐diphosphacyclooctane Ligand
Authors: Heitkämper Juliane , Posada‐Pérez Sergio , Escayola Sílvia , Solà Miquel , Kästner Johannes , Poater Albert
Published: January 2023

For decades there were many attempts to dispense with stoichiometric amounts of metal reagents for the synthesis of secondary alcohols. In 2021, the synthetic results of Newman and collaborators pioneered a synthesis still with metals, but not as reactants. Instead, they serverd as catalytic engines. Here we present a description by means of Density Functional Theory calculations of how this process can occur, and an attempt is made to shed light on the mechanism that facilitates the attainment of secondary alcohols, emphasizing the eternal cross‐coupling debate of whether the catalytically active species is Ni(0) or they are really taking shortcuts following the course of Ni(II). Effective Orbital analyses give a clear picture. Furthermore, this paper provides insight not only into the nature of the ligands of the metal catalyst but also the role of the base.
An investigation on worst‐case spectral reconstruction from RGB images via Radiance Mondrian World assumption
Authors: Lin Yi‐Tun , Finlayson Graham D.
Published: January 2023

Spectral reconstruction (SR) algorithms recover hyperspectral measurements from RGB camera responses. Statistical models at different levels of complexity are used to solve the SR problem—from the simplest closed‐form regression, to sparse coding, to the complex deep neural networks (DNN). Recently, these methods were benchmarked based on the mean performance of the models and on a fixed set of real‐world scenes, suggesting that more complex (more non‐linear) models generally deliver better SR. In this paper, we investigate the relative performances of these models in terms of a real‐world worst‐case imaging condition called the Radiance Mondrian World (RMW) assumption. Under the RMW, testing hyperspectral images are composed of randomly‐arranged and overlapping rectangular patches, where each patch is filled with one random radiance spectrum uniformly sampled from the convex closure of all natural radiances (i.e., all spectra in the concerned hyperspectral image dataset). Surprisingly, we show that all compared algorithms—regardless of their model complexity—degrade to broadly the same level of performance on our RMW testing set. Further, by retraining all models with an RMW training set, we show that increasing model complexity also does not help learning better SR mappings from the RMW images. That is, using simple regression is as good as using a DNN. This similarity of performance is also shown to hold for images adhering to the conventional Mondrian World assumption (random reflectances lit by a single, per scene, randomly selected light source).
Quorum sensing centered bacterial horde algorithm for global optimization
Authors: Raviprabhakaran Vijay
Published: January 2023

This article proposes an intellectual quorum sensing‐centered bacterial horde optimization (QBHO) exert for assessing and authenticating the optimization problems. Quorum detection realizes the finest place of the bacteria by apprehending the most awful point within the hunt area. This mechanism is utilized in this study for problem‐solving. With this bacterial behavior and location perceptive, the superlative optimum result is obtained. In this anticipated QBHO algorithm, the competence of bacteria is enhanced to be beneficial so that results can be enhanced. The fundamental group‐built optimization procedures for instance, particle swarm, ant cluster, biogeography‐built algorithm, simulated bee constellation procedure and typical bacterial herd optimization through the distinctive considerations remain simulated and then associated through the intended practice for its ratification of results with QBHO. The projected QBHO practice is exploited to ensue with the seven‐typical benchmark with unimodal and multimodal trial functions intended to prove its practicability and ideality. The realized findings imply that the suggested QBHO approach surpasses the deemed optimization procedures for complex standard functions. Furthermore, the intended procedure might be appropriate to several engineering challenges, notably intended for intricate concurrent optimization problems.
C−H Activation by Iron‐Vanadium Bimetallic Oxide Cluster Anions FeV3O10− and FeV5O15−: A Comparison with Scandium‐Vanadium Oxide Clusters
Authors: Wei Gong‐Ping , Liu Qing‐Yu , Zhao Yan‐Xia , He Sheng‐Gui
Published: January 2023

Late transition metal‐bonded atomic oxygen radicals (LTM−O⋅−) have been frequently proposed as important active sites to selectively activate and transform inert alkane molecules. However, it is extremely challenging to characterize the LTM−O⋅−‐mediated elementary reactions for clarifying the underlying mechanisms limited by the low activity of LTM−O⋅− radicals that is inaccessible by the traditional experimental methods. Herein, benefiting from our newly‐designed ship‐lock type reactor, the reactivity of iron‐vanadium bimetallic oxide cluster anions FeV3O10− and FeV5O15− featuring with Fe−O⋅− radicals to abstract a hydrogen atom from C2−C4 alkanes has been experimentally characterized at 298 K, and the rate constants are determined in the orders of magnitude of 10−14 to 10−16 cm3 molecule−1 s−1, which are four orders of magnitude slower than the values of counterpart ScV3O10− and ScV5O15− clusters bearing Sc−O⋅− radicals. Theoretical results reveal that the rearrangements of the electronic and geometric structures during the reaction process function to modulate the activity of Fe−O⋅−. This study not only quantitatively characterizes the elementary reactions of LTM−O⋅− radicals with alkanes, but also provides new insights into structure‐activity relationship of M−O⋅− radicals.
Digital economy development, corporate social responsibility and low‐carbon innovation
Authors: Chen Wen
Published: January 2023

The coordinated development of digitization and greening is the internal demand for the comprehensive transformation and upgrading of enterprises worldwide. Based on data of China's A‐share listed companies from 2012 to 2019, this article empirically confirms the stimulating effect of digital economy development on corporate low‐carbon innovation. The mechanism tests show that the above stimulating effect is due to both the reduction effects of financing constraints and environmental uncertainty brought by the rapid development of the digital economy. In addition, this article discusses the value of corporate social responsibility (CSR) and finds that the promotion of CSR can significantly improve the policy effect of digital economy development in enabling corporate low‐carbon innovation, especially for private listed enterprises in high‐pollution industries. The findings of this article deepen our understanding of how to promote corporate low‐carbon sustainable development in the digital era.
Flow cytometric assessment for minimal/measurable residual disease in B lymphoblastic leukemia/lymphoma in the era of immunotherapy
Authors: Chen Xueyan , Gao Qi , Roshal Mikhail , Cherian Sindhu
Published: January 2023

Minimal/measurable residual disease (MRD) is the most important independent prognostic factor for patients with B‐lymphoblastic leukemia (B‐LL). MRD post therapy has been incorporated into risk stratification and clinical management, resulting in substantially improved outcomes in pediatric and adult patients. Currently, MRD in B‐ALL is most commonly assessed by multiparametric flow cytometry and molecular (polymerase chain reaction or high‐throughput sequencing based) methods. The detection of MRD by flow cytometry in B‐ALL often begins with B cell antigen‐based gating strategies. Over the past several years, targeted immunotherapy directed against B cell markers has been introduced in patients with relapsed or refractory B‐ALL and has demonstrated encouraging results. However, targeted therapies have significant impact on the immunophenotype of leukemic blasts, in particular, downregulation or loss of targeted antigens on blasts and normal B cell precursors, posing challenges for MRD detection using standard gating strategies. Novel flow cytometric approaches, using alternative strategies for population identification, sometimes including alternative gating reagents, have been developed and implemented to monitor MRD in the setting of post targeted therapy.