bluuebunny/crossref_metadata_2025 huggingface dataset:
On the Origin of Energetic Disorder in Mixed Halides Lead Perovskites
Authors: Diez‐Cabanes Valentin , Giannini Samuele , Beljonne David , Quarti Claudio
Published: October 2023

Mixed halide perovskites are emerging as promising candidates for wide‐bandgap components in tandem solar cells and color‐tunable light‐emitting diodes. Yet, halide mixing poses a fundamental question of whether the inhomogeneous halide distribution impacts the intrinsic electronic disorder in these materials. To address this point, density functional theory (DFT)‐based molecular dynamics (MD) simulations are performed for pure and mixed halide perovskites, accounting for disorder stemming from inhomogeneous chemical composition associated with the halide component and from finite temperature effects. For pure halide perovskites, finite‐temperature band gap fluctuations from the MD simulations are in good agreement with the broadening measured using photoluminescence. Furthermore, these calculations confirm the natively modest inhomogeneous disorder in the electronic structure of these materials. Most notably, such a low degree of electronic disorder is preserved in models mimicking finely intermixed Br/I solid‐state solutions. In contrast, models featuring halide segregation show comparably wider band gap fluctuations, with a sizable contribution from inhomogeneous (static) broadening, which is associated, at least in part, with structural distortions stemming from lattice mismatch.
Indication of Intramolecular Triplet–Triplet Annihilation Upconversion in Organic Light‐Emitting Diodes
Authors: Sasaki Shoma , Goushi Kenichi , Mamada Masashi , Miyazaki Shiori , Miyata Kiyoshi , Onda Ken , Adachi Chihaya
Published: October 2023

It is well known that triplet–triplet annihilation upconversion (TTU) can enhance electroluminescence (EL) efficiency by converting two low‐energy triplet excitons into one high‐energy singlet exciton. However, conventional intermolecular TTU requires high doping concentration to activate, limiting device architecture. Here, six dimer molecules comprised of two anthracene units connected by a spacer unit are investigated, which have a possibility of the intramolecular TTU process. As a result, two dimer molecules show high TTU efficiencies close to the theoretical maximum even in dispersed, diluted conditions. By comparing these molecular conformations, a correlation is found between the dimer structures of two anthracene units and the TTU activity in the diluted condition, i.e., the 3D molecular structure with the exciton utilizing efficiency.
Protein‐Nanocaged Selenium Induces t(8;21) Leukemia Cell Differentiation via Epigenetic Regulation
Authors: Fang Long , Zhang Ruofei , Shi Lin , Xie Jiaying , Ma Long , Yang Yili , Yan Xiyun , Fan Kelong
Published: October 2023

The success of arsenic in degrading PML‐RARα oncoprotein illustrates the great anti‐leukemia value of inorganics. Inspired by this, the therapeutic effect of inorganic selenium on t(8; 21) leukemia is studied, which has shown promising anti‐cancer effects on solid tumors. A leukemia‐targeting selenium nanomedicine is rationally built with bioengineered protein nanocage and is demonstrated to be an effective epigenetic drug for inducing the differentiation of t(8;21) leukemia. The selenium drug significantly induces the differentiation of t(8;21) leukemia cells into more mature myeloid cells. Mechanistic analysis shows that the selenium is metabolized into bioactive forms in cells, which drives the degradation of the AML1‐ETO oncoprotein by inhibiting histone deacetylases activity, resulting in the regulation of AML1‐ETO target genes. The regulation results in a significant increase in the expression levels of myeloid differentiation transcription factors PU.1 and C/EBPα, and a significant decrease in the expression level of C‐KIT protein, a member of the type III receptor tyrosine kinase family. This study demonstrates that this protein‐nanocaged selenium is a potential therapeutic drug against t(8;21) leukemia through epigenetic regulation.
Deubiquitylating Enzymes in Cancer and Immunity
Authors: Ren Jiang , Yu Peng , Liu Sijia , Li Ran , Niu Xin , Chen Yan , Zhang Zhenyu , Zhou Fangfang , Zhang Long
Published: October 2023

Deubiquitylating enzymes (DUBs) maintain relative homeostasis of the cellular ubiquitome by removing the post‐translational modification ubiquitin moiety from substrates. Numerous DUBs have been demonstrated specificity for cleaving a certain type of ubiquitin linkage or positions within ubiquitin chains. Moreover, several DUBs perform functions through specific protein–protein interactions in a catalytically independent manner, which further expands the versatility and complexity of DUBs’ functions. Dysregulation of DUBs disrupts the dynamic equilibrium of ubiquitome and causes various diseases, especially cancer and immune disorders. This review summarizes the Janus‐faced roles of DUBs in cancer including proteasomal degradation, DNA repair, apoptosis, and tumor metastasis, as well as in immunity involving innate immune receptor signaling and inflammatory and autoimmune disorders. The prospects and challenges for the clinical development of DUB inhibitors are further discussed. The review provides a comprehensive understanding of the multi‐faced roles of DUBs in cancer and immunity.
Acoustic Streaming‐Induced Multimodal Locomotion of Bubble‐Based Microrobots
Authors: Mahkam Nima , Aghakhani Amirreza , Sheehan Devin , Gardi Gaurav , Katzschmann Robert , Sitti Metin
Published: October 2023

Acoustically‐driven bubbles at the micron scale can generate strong microstreaming flows in its surrounding fluidic medium. The tunable acoustic streaming strength of oscillating microbubbles and the diversity of the generated flow patterns enable the design of fast‐moving microrobots with multimodal locomotion suitable for biomedical applications. The acoustic microrobots holding two coupled microbubbles inside a rigid body are presented; trapped bubbles inside the L‐shaped structure with different orifices generate various streaming flows, thus allowing multiple degrees of freedom in locomotion. The streaming pattern and mean streaming speed depend on the intensity and frequency of the acoustic wave, which can trigger four dominant locomotion modes in the microrobot, denoted as translational and rotational, spinning, rotational, and translational modes. Next, the effect of various geometrical and actuation parameters on the control and navigation of the microrobot is investigated. Furthermore, the surface‐slipping multimodal locomotion, flow mixing, particle manipulation capabilities, the effective interaction of high flow rates with cells, and subsequent cancerous cell lysing abilities of the proposed microrobot are demonstrated. Overall, these results introduce a design toolbox for the next generation of acoustic microrobots with higher degrees of freedom with multimodal locomotion in biomedical applications.
Developments and Challenges of Miniature Piezoelectric Robots: A Review
Authors: Li Jing , Deng Jie , Zhang Shijing , Chen Weishan , Zhao Jie , Liu Yingxiang
Published: October 2023

Miniature robots have been widely studied and applied in the fields of search and rescue, reconnaissance, micromanipulation, and even the interior of the human body benefiting from their highlight features of small size, light weight, and agile movement. With the development of new smart materials, many functional actuating elements have been proposed to construct miniature robots. Compared with other actuating elements, piezoelectric actuating elements have the advantages of compact structure, high power density, fast response, high resolution, and no electromagnetic interference, which make them greatly suitable for actuating miniature robots, and capture the attentions and favor of numerous scholars. In this paper, a comprehensive review of recent developments in miniature piezoelectric robots (MPRs) is provided. The MPRs are classified and summarized in detail from three aspects of operating environment, structure of piezoelectric actuating element, and working principle. In addition, new manufacturing methods and piezoelectric materials in MPRs, as well as the application situations, are sorted out and outlined. Finally, the challenges and future trends of MPRs are evaluated and discussed. It is hoped that this review will be of great assistance for determining appropriate designs and guiding future developments of MPRs, and provide a destination board to the researchers interested in MPRs.
Giant Thermoelectric Performance of N‐Type Ionogels by Synergistic Dopings of Cations and Anions
Authors: Le Qiujian , Chen Zhijun , Cheng Hanlin , Ouyang Jianyong
Published: October 2023

It is of great significance to develop high‐performance n‐type ionic thermoelectric materials. Herein, the turnover from p‐ to n‐type and great improvement in the n‐type ionic Seebeck coefficient of ionogels through synergistic dopings of cations and anions, is reported. Doping with silver trifluoromethanesulfonate (AgOTf) can turn the ionic Seebeck coefficient of the ionogels consisting of poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate (BMIM:BF4) from 5.52 to −26.4 mV K−1 under a relative humidity (RH) of 75%. The TE performances can be further improved through the combination with the anti‐solvent method, and the ZTi value can be up to 1.7 under 91% RH, the highest for n‐type ionogels. Such p‐ to n‐type turnover and great improvement in the n‐type ionic Seebeck coefficient can be attributed to synergistic doping by Ag+ and OTf−. Ag+ can form a complex with BMIM+, and OTf− can have strong Coulomb interaction to BMIM+. Both can retard the migration of the BMIM+ cations and thus increase the difference in the mobilities of BMIM+ and BF4−. This is the first time that synergistic dopings by both cations and anions for ionic TE materials has been observed.
Social networks and violence victimization and perpetration among youth: A longitudinal analysis
Authors: Mullet Natira , Waterman Emily A. , Edwards Katie M. , Banyard Victoria , Valente Thomas W.
Published: October 2023

Interpersonal violence (IV) is a serious concern for adolescents in the United States that has devastating impacts for individuals and communities. Given the increased importance placed on friendships during adolescence, the purpose of the current study was to examine the extent to which IV experiences cluster within youths' friendship networks. Participants were students (N = 1303) in grades 7th to 10th who completed surveys at the beginning and end of an academic year. Results showed that friends' average perpetration (i.e., the percentage of the friends they nominated who perpetrated IV) was strongly associated with likelihood of individual perpetration at baseline but not at the follow‐up. For victimization, friends' average report of victimization (i.e., the percentage of the friends they nominated who were victimized) was associated with higher likelihood reporting of victimization (at both baseline and follow‐up). Although future research is needed to understand explanatory mechanisms underlying these findings, it is possible that the effectiveness of prevention initiatives may be enhanced by incorporating peer group information.
The now and future of human biology at the extremes: An introduction to the special issue
Authors: Niclou Alexandra , Sarma Mallika S.
Published: October 2023

Objectives

A hallmark of the human species is our adaptability to a wide range of different ecologies and ecosystems, including some of the most extreme settings. Human biologists have long studied how humans have successfully (and sometimes unsuccessfully) adapted to such extremes, particularly ecological extremes like environments at lower limits of temperature and high altitude. In this special issue, we revisit traditional definitions and explore new conceptions of work in extreme environments. We argue that our definitions of extremes should change with our changing world, and account for extremes unique to the Anthropocene, including environments of inequality and precarity, pandemic landscapes, climate‐impacted settings, obesogenic environments, and the environments of human spaceflight. We also explore the future of work at the extremes and provide some suggested guidelines on how human biologists can continue to build and expand on foundational work in this area.

Conclusion

While human biologists have done critical work on groups living in extreme environments, our definitions of humans at the limits continue to change as the world around us also changes. Scholars in this area have a responsibility to re‐examine the parameters of extremes to stay at the forefront of scientific exploration and collaboration so human biology, as a discipline, can continue to shape our understanding of adaptability, and thus contribute to the continued thriving of all humans as we endure new climatic, environmental, and societal extremes.
Ligand Engineering Enables Efficient Pure Red Tin‐Based Perovskite Light‐Emitting Diodes
Authors: Bai Wenhao , Liang Mingming , Xuan Tongtong , Gong Ting , Bian Liang , Li Huili , Xie Rong‐Jun
Published: October 2023

With increasing ecological and environmental concerns, tin (Sn)‐based perovskite light‐emitting diodes (PeLEDs) are competitive candidates for future displays because of their environmental friendliness, excellent photoelectric properties, and low‐cost solution‐processed fabrication. Nonetheless, their electroluminescence (EL) performance still lags behind that of lead (Pb)‐based PeLEDs due to the fast crystallization rate of Sn‐based perovskite films and undesired oxidation from Sn2+ to Sn4+, leading to poor film morphology and coverage, as well as high density defects. Here, we propose a ligand engineering strategy to construct high‐quality phenethylammonium tin iodide (PEA2SnI4) perovskite films by using L‐glutathione reduced (GSH) as surface ligands toward efficient pure red PEA2SnI4‐based PeLEDs. We show that the hydrogen‐bond and coordinate interactions between GSH and PEA2SnI4 effectively reduce the crystallization rate of the perovskites and suppress the oxidation of Sn2+ and formation of defects. The improved pure red perovskite films not only show excellent uniformity, density, and coverage but also exhibit enhanced optical properties and stability. Finally, state‐of‐the‐art pure red PeLEDs achieve a record external quantum efficiency of 9.32 % in the field of PEA2SnI4‐based devices. This work demonstrates that ligand engineering represents a feasible route to enhance the EL performance of Sn‐based PeLEDs.
Crystallizing Self‐Standing Covalent Organic Framework Membranes for Ultrafast Proton Transport in Flow Batteries
Authors: Wu Yulin , Wang Yixing , Zhang Dezhu , Xu Fang , Dai Liheng , Qu Kai , Cao Hongyan , Xia Yu , Li Siyao , Huang Kang , Xu Zhi
Published: October 2023

Covalent organic frameworks (COFs) display great potential to be assembled into proton conductive membranes for their uniform and controllable pore structure, yet constructing self‐standing COF membrane with high crystallinity to fully exploit their ordered crystalline channels for efficient ionic conduction remains a great challenge. Here, a macromolecular‐mediated crystallization strategy is designed to manipulate the crystallization of self‐standing COF membrane, where the −SO3H groups in introduced sulfonated macromolecule chains function as the sites to interact with the precursors of COF and thus offer long‐range ordered template for membrane crystallization. The optimized self‐standing COF membrane composed of highly‐ordered nanopores exhibits high proton conductivity (75 mS cm−1 at 100 % relative humidity and 20 °C) and excellent flow battery performance, outperforming Nafion 212 and reported membranes. Meanwhile, the long‐term run of membrane is achieved with the help of the anchoring effect of flexible macromolecule chains. Our work provides inspiration to design self‐standing COF membranes with ordered channels for permselective application.
Significant Strain Dissipation via Stiff‐Tough Solid Electrolyte Interphase Design for Highly Stable Alloying Anodes
Authors: Jiang Chunlei , Yan Jiaxiao , Wang Doufeng , Yan Kunye , Shi Lei , Zheng Yongping , Xie Chengde , Cheng Hui‐Ming , Tang Yongbing
Published: October 2023

The pulverization of alloying anodes significantly restricts their use in lithium‐ion batteries (LIBs). This study presents a dual‐phase solid electrolyte interphase (SEI) design that incorporates finely dispersed Al nanoparticles within the LiPON matrix. This distinctive dual‐phase structure imparts high stiffness and toughness to the integrated SEI film. In comparison to single‐phase LiPON film, the optimized Al/LiPON dual‐phase SEI film demonstrates a remarkable increase in fracture toughness by 317.8 %, while maintaining stiffness, achieved through the substantial dissipation of strain energy. Application of the dual‐phase SEI film on an Al anode leads to a 450 % enhancement in cycling stability for lithium storage in dual‐ion batteries. A similar enhancement in cycling stability for silicon anodes, which face severe volume expansion issues, is also observed, demonstrating the broad applicability of the dual‐phase SEI design. Specifically, homogeneous Li−Al alloying has been observed in conventional LIBs, even when paired with a high mass loading LiNi0.5Co0.3Mn0.2O2 cathode (7 mg cm−2). The dual‐phase SEI film design can also accelerate the diffusion kinetics of Li‐ions through interface electronic structure regulation. This dual‐phase design can integrate stiffness and toughness into a single SEI film, providing a pathway to enhance both the structural stability and rate capability of alloying anodes.
Hydrogenation Catalysis by Hydrogen Spillover on Platinum‐Functionalized Heterogeneous Boronic Acid‐Polyoxometalates
Authors: Li Shujun , Ma Yubin , Zhao Yue , Liu Rongji , Zhao Yupeng , Dai Xusheng , Ma Nana , Streb Carsten , Chen Xuenian
Published: October 2023

The activation of molecular hydrogen is a key process in catalysis. Here, we demonstrate how polyoxometalate (POM)‐based heterogeneous compounds functionalized with Platinum particles activate H2 by synergism between a hydrogen spillover mechanism and electron‐proton transfer by the POM. This interplay facilitates the selective catalytic reduction of olefins and nitroarenes with high functional group tolerance. A family of polyoxotungstates covalently functionalized with boronic acids is reported. In the solid‐state, the compounds are held together by non‐covalent interactions (π–π stacking and hydrogen bonding). The resulting heterogeneous nanoscale particles form stable colloidal dispersions in acetonitrile and can be surface‐functionalized with platinum nanoparticles by in situ photoreduction. The resulting materials show excellent catalytic activity in hydrogenation of olefins and nitrobenzene derivatives under mild conditions (1 bar H2 and room temperature).
Forests as Social Mirrors: What do Approaches to Forest Management Tell us About Human Social Relations?
Authors: Walton Andrew
Published: October 2023

There is evidence to suggest that the nature of human impact upon forests, measured both quantitatively and qualitatively, tells a story about dominant social paradigms throughout recent history. In this sense, forests are social mirrors. Collectively, we are consuming ecological resources at 1.5 times the rate they can be replenished, while often simplifying or adversely impacting forest ecosystems. At the same time, ecocentric and enlightened self‐interest movements are emerging, manifest in woodland management approaches that embrace multiple values, ecological sensitivity, and traditional ecological knowledge. The evidence therefore shows that contradictory paradigms exist alongside each other, exerting influence over landscapes at shared temporal and spatial scales simultaneously. Consequently, forest management reflects the sociocultural dynamics of a species experiencing cognitive dissonance; responding to human ideals around the need to tread lightly and the contradictory reality of an ever‐increasing economic output.
Bi‐cuspid TAVR; bye or buy!
Authors: Zahr Firas , Lantz Gurion
Published: October 2023

Key Points

Mid term data of TAVR in stenotic bicuspid aortic valves is promising both in term of mortality and valve performance.

Many factors should be considered before we generalize these results to all types of bicuspid native valves, TAVR valves, and patient populations.

A randomized trial to SAVR versus TAVR remains the missing piece before we solve this complex clinical equation.
Molybdenum Carbide for Catalytic De/hydrogenation Process: Synthesis, Modulation and Applications
Authors: Jiang Shan , Wu Xiaoping , Liu Xinrui , Ma Wanbing , Song Jiajie , Shu Riyang , Zhang Qian , Qiu Songbai
Published: October 2023

The catalytic de/hydrogenation process is important in the fields of petrochemical refining, fuel synthesis, drug synthesis, CO2 conversion, and hydrogen synthesis, where the construction of low‐cost and high‐efficiency de/hydrogenation catalysts attracting significant attentions. Molybdenum carbide (MoxC), as a non‐noble transition metal carbide catalyst, has been widely investigated for hydrogen activation. Herein, research progress and achievements of molybdenum carbide for catalytic de/hydrogenation are reviewed. Additional attention is paid to the structure and crystal phase of molybdenum carbide, and various modification strategies related to the catalytic activity regulation are summarized. Finally, the application prospect of molybdenum carbide catalysts is also discussed. This review provides a framework reference for further understanding the design and utilization of molybdenum carbide catalysts for catalytic de/hydrogenation and the key research problems to be addressed.
Deposited PtGe Clusters as Active and Durable Catalysts for CO Oxidation**
Authors: Ugartemendia Andoni , Mercero Jose M. , de Cózar Abel , Melander Marko M. , Akola Jaakko , Jimenez‐Izal Elisa
Published: October 2023

Control of CO emissions raises serious environmental concerns in the current chemical industry, as well as in nascent technologies based on hydrogen such as electrolyzers and fuel cells. As for now, Pt remains one of the state‐of‐the‐art catalysts for the CO oxidation reaction, but unfortunately, it suffers from CO self‐poisoning. Recently, Pt−Ge alloys were proposed to be an excellent alternative to reduce CO poisoning. This work investigates the impact of Ge content on the CO oxidation kinetics of Pt4Gen subnanoclusters supported on MgO. A Ge concentration dependence of the reaction kinetics is found due to a strong synergy between Pt and Ge. Pt−Ge nanoalloys act as a bifunctional catalyst by displaying dual adsorption sites; i. e., CO is adsorbed on Pt whereas oxygen binds to Ge, forming an alternative oxygen source GeOx. Besides, Ge alloying modifies the electronic structure of Pt (ligand effects) and reduces the affinity to CO. In this way, the competition between CO and O2 adsorption and the overbinding of CO is alleviated, achieving a CO poisoning‐free kinetic regime. Our calculations suggest that Pt4Ge3 is the optimal catalyst, evidencing that alloying composition is a parameter of extreme importance in nanocatalyst design. The work relies on global optimization search techniques to determine the accessibility of multiple structures at different conditions, mechanistic studies and microkinetic modeling.
Molecular packing tuning via chlorinated end group enables efficient binary organic solar cells over 18.5%
Authors: Li Yafeng , Chen Zhenyu , Yan Xingzheng , Ge Ziyi
Published: October 2023

Designing novel nonfullerene acceptors (NFAs) is of vital importance for the development of organic solar cells (OSC). Modification on the side chain and end group are two powerful tools to construct efficient NFAs. Here, based on the high‐performance L8BO, we selected 3‐ethylheptyl to substitute the inner chain of 2‐ethylhexyl, obtaining the backbone of BON3. Then we introduced different halogen atoms of fluorine and chlorine on 2‐(3‐oxo‐2,3‐dihydro‐1H‐inden‐1‐ylidene) malononitrile end group (EG) to construct efficient NFAs named BON3‐F and BON3‐Cl, respectively. Polymer donor D18 was chosen to combine with two novel NFAs to construct OSC devices. Impressively, D18:BON3‐Cl‐based device shows a remarkable power conversion efficiency (PCE) of 18.57%, with a high open‐circuit voltage (VOC) of 0.907 V and an excellent fill factor (FF) of 80.44%, which is one of the highest binary PCE of devices based on D18 as the donor. However, BON3‐F‐based device shows a relatively lower PCE of 17.79% with a decreased FF of 79.05%. The better photovoltaic performance is mainly attributed to the red‐shifted absorption, higher electron and hole mobilities, reduced charge recombination, and enhanced molecular packing in the D18:BON3‐Cl films. Also, we performed stability tests on two binary systems; the D18:BON3‐Cl and D18:BON3‐F devices maintain 88.1% and 85.5% of their initial efficiencies after 169 h of storage at 85°C in an N2‐filled glove box, respectively. Our work demonstrates the importance of selecting halogen atoms on EG and provides an efficient binary system of D18:BON3‐Cl for further improvement of PCE.
Improving In Vivo Tumor Accumulation and Efficacy of Platinum Antitumor Agents by Electronic Tuning of the Kinetic Lability
Authors: M Manikandan , Chhatar Sushanta , Gadre Shubhankar , Paul Subhadeep , Vaidya Shreyas P. , Khatri Subhash , Duari Prakash , Kode Jyoti , Ingle Arvind , Kolthur‐Seetharam Ullas , Patra Malay
Published: October 2023

The impact of kinetic lability or reactivity on in vitro cytotoxicity, stability in plasma, in vivo tumor and tissue accumulation, and antitumor efficacy of functional platinum(II) (Pt) anticancer agents containing a O˄O β‐diketonate leaving ligand remain largely unexplored. To investigate this, we synthesized Pt complexes [(NH3)2Pt(L1‐H)]NO3 and [(DACH)Pt(L1‐H)]NO3 (L1=4,4,4‐trifluoro‐1‐ferrocenylbutane‐1,3‐dione, DACH=1R,2R‐cyclohexane‐1,2‐diamine) containing an electron deficient [L1‐H]– O˄O leaving ligand and [(NH3)2Pt(L2‐H)]NO3 and [(DACH)Pt(L2‐H)]NO3 (L2=1‐ferrocenylbutane‐1,3‐dione) containing an electron‐rich [L2‐H]– O˄O leaving ligand. While all four complexes have comparable lipophilicity, the presence of the electron‐withdrawing CF3 group was found to dramatically enhance the reactivity of these complexes toward nucleophilic biomolecules. In vitro cellular assays revealed that the more reactive complexes have higher cellular uptake and higher anticancer potency as compared to their less reactive analogs. But the scenario is opposite in vivo, where the less reactive complex showed improved tissue and tumor accumulation and better anticancer efficacy in mice bearing ovarian xenograft when compared to its more reactive analog. Finally, in addition to demonstrating the profound but contrasting impact of kinetic lability on in vitro and in vivo antitumor potencies, we also described the impact of kinetic lability on the mechanism of action of this class of promising antitumor agents.
Discotic Star Mesogen with Thymine Nucleobases Exhibiting a Rare Gyroid Cubic Mesophase with 3D Conductivity
Authors: Noll Katja , Lambov Martin , Singh Dharmendra Pratap , Lehmann Matthias
Published: October 2023

A unique gyroid cubic phase has been discovered for a discotic star mesogen with three covalently attached DNA bases. In this cubic
phase, the conjugated core of the mesogens and the thymine pseudo guests self‐assemble in mirror image continuous networks, representing a semiconducting material with three‐dimensional transport pathways. The hole carrier mobilities are found to be in the typical range of poly(phenylenevinylene) scaffolds. This structure is stabilized by a weak hydrogen bonding between the thymine bases and can be switched to a columnar liquid crystal – thermally and by the addition of complementary adenine guests.
Recent Advances in Zeolites‐Catalyzed Biomass Conversion to Hydroxymethylfurfural: The Role of Porosity and Acidity
Authors: Wang Yanan , Yuan Xiaoxian , Liu Jianxin , Jia Xicheng
Published: October 2023

Biomass is an attractive raw material for the production of fuel oil and chemical intermediates due to its abundant reserves, low price, easy biodegradability, and renewable use. Hydroxymethylfurfural (5‐HMF) is a valuable platform chemically derived from biomass that has gained significant research interest owing to its economic and environmental benefits. In this review, recent advances in biomass catalytic conversion systems for 5‐HMF production were examined with a focus on the catalysts selection and feedstocks’ impact on the 5‐HMF selectivity and yield. Specifically, the potential of zeolite‐based catalysts for efficient biomass catalysis was evaluated given their unique pore structure and tunable (Lewis and Brønsted) acidity. The benefits of hierarchical modifications and the interactions between porosity and acidity in zeolites, which are critical factors for the development of green catalytic systems to convert biomass to 5‐HMF efficiently, were summarized and assessed. This Review suggests that zeolite‐based catalysts hold significant promise in facilitating the sustainable utilization of biomass resources.
Rescuing Drugs That are Discontinued in Adult Oncology Development for the Benefit of Children and Adolescents With Cancer – An ACCELERATE Multistakeholder Consensus
Authors: de Rojas Teresa , Chiodin Davy , Pearson Andrew D.J. , Heenen Delphine , Adamson Peter , Caron Hubert , Vassal Gilles
Published: October 2023

Better therapies for childhood cancer remain an unmet need to improve the dismal prognosis of certain malignancies and to reduce the burden of toxicity. Rescuing discontinued or shelved drugs for children, adolescents, and young adults is a strategy to identify new uses for approved or investigational medicines outside the scope of their original medical indication. Our proposed multistakeholder consensus focuses on the development of innovative, patent‐protected targeted agents, sourced from previously shelved or discontinued programs that have the potential to provide significant benefit to underserved patient populations, with unmet medical needs. There are several challenges to continuing/rescuing drugs for pediatric oncology development, which include the lack of information for decision making, corporate strategy considerations underlying the decision to invest in pediatric development, and the contracting and technology transfer complexities required to enable divestment and subsequent development. The multistakeholder approach for drug development has the advantage of conveying a consensus among academia, patient advocates, and importantly industry itself. We propose three areas of action to facilitate rescuing potentially beneficial drugs for children and adolescents with cancer: (i) initiatives to provide information to companies considering developing these drugs and a standards framework; (ii) incentives both in Europe and in the United States to encourage companies to develop pediatric‐only drugs, with the reform of the EU Pharmaceutical Legislation posing an important opportunity; and (iii) communication of the issues to all stakeholders. Ultimately, this will benefit children and adolescents with cancer.
From mental strain to gut pain: A brain‐gut pathway transducing psychological stress to intestinal inflammation
Authors: Schneider Kai Markus , Blank Niklas , Thaiss Christoph A.
Published: October 2023

Psychological stress can trigger inflammatory bowel disease (IBD) flares, but the molecular mechanisms have remained unclear. We recently discovered an unexpected function of the enteric nervous system as a relay between stress signals from the brain and intestinal inflammation. Our findings highlight targeting stress‐induced signaling networks as a possible new pillar in the clinical management of IBD.
A case of extranodal NK/T‐cell lymphoma, nasal type, diagnosed by scraping cytology of the maxillary gingiva
Authors: Niwa Hiroe , Mukai Kazumi , Kimura Iyo , Imura Johji
Published: October 2023

Extranodal NK/T‐cell lymphoma (ENKTL), nasal type, is often seen in the head and neck region, but there have been rare instances of this disease with initial presentation as a lesion in the oral mucosa. The patient, a woman in her seventh decade of life, presented with an ulcer in the maxillary gingiva, and scraping cytology and biopsy were performed. Cytological specimens showed solitary or small aggregating cells with marked atypia in a necrotic background. Tumor cells were detected that had various nuclear shapes and azure granules in the cytoplasm. Biopsy showed that the tumor cells had diffusely infiltrated or interdigitated into the subepithelium. Immunohistochemistry revealed that the tumor cells had T‐ and NK cell phenotypes and were Epstein–Barr virus‐encoded small RNA (EBER) positive, leading to a diagnosis of ENKTL. Thus, when nonepithelial tumor cells in a necrotic background and prominent atypia are found, as in this case, it is important to carefully observe for azurophil granules in the cytoplasm for differential diagnosis considerations.
One third of cases of new‐onset diabetic ketosis in adults are associated with ketosis‐prone type 2 diabetes—A systematic review and meta‐analysis
Authors: Kovacs Adrienn , Bunduc Stefania , Veres Daniel S. , Palinkas Daniel , Gagyi Endre B. , Hegyi Peter J. , Eross Balint , Mihaly Emese , Hegyi Peter , Hosszufalusi Nora
Published: October 2023

Aims

Ketosis‐prone type 2 diabetes was defined by the World Health Organization in 2019. According to the literature, the diagnosis is based on the presence of ketosis, islet autoantibody negativity and preserved insulin secretion. Our meta‐analysis assessed the prevalence and clinical characteristics of ketosis‐prone type 2 diabetes among patients hospitalised with diabetic ketoacidosis (DKA) or ketosis.

Methods

The systematic search was performed in five main databases as of 15 October 2021 without restrictions. We calculated the pooled prevalence of ketosis‐prone type 2 diabetes (exposed group) within the diabetic population under examination, patients with ketoacidosis or ketosis, to identify the clinical characteristics, and we compared it to type 1 diabetes (the comparator group). The random effects model provided pooled estimates as prevalence, odds ratio and mean difference (MD) with 95% confidence intervals.

Results

Eleven articles were eligible for meta‐analysis, thus incorporating 2010 patients of various ethnic backgrounds. Among patients presenting with DKA or ketosis at the onset of diabetes, 35% (95% CI: 24%–49%) had ketosis‐prone type 2 diabetes. These patients were older (MD = 11.55 years; 95% CI: 5.5–17.6) and had a significantly higher body mass index (BMI) (MD = 5.48 kg/m2; 95% CI: 3.25–7.72) than those with type 1 diabetes.

Conclusions

Ketosis‐prone type 2 diabetes accounts for one third of DKA or ketosis at the onset of diabetes in adults. These patients are characterised by islet autoantibody negativity and preserved insulin secretion. They are older and have a higher BMI compared with type 1 diabetes. C‐peptide and diabetes‐related autoantibody measurement is essential to identify this subgroup among patients with ketosis at the onset of diabetes.
Stem cell‐mediated development, regeneration, chimerism, and aging in the colonial chordate Botryllus schlosseri
Authors: Voskoboynik Ayelet
Published: October 2023

Stem cells are units of biological organization, responsible for tissue and organ development and regeneration. I study stem cell biology, aging, and the evolution of immunity using the colonial chordate Botryllus schlosseri as a model system. This organism is uniquely suited for this study because it is closely related to vertebrates, undergoes weekly cycles of stem cell mediated regeneration, is long lived and has a recognition system and robust immune system. I have led the Botryllus genome project and developed a novel method to obtain a synthetic long read sequence, identified Botryllus stem cells and stem cell niches, isolated the gene that controls self/non self‐recognition and characterized its immune system on the cellular and molecular levels. Recently, I led the Botryllus atlas project to characterize the two developmental pathways, embryogenesis (sexual) and blastogenesis (asexual), revealing the unique molecular landscapes for each developmental mode and investigated the molecular clock and neurodegeneration pathways in young and old colonies and investigated the molecular clock and neurodegeneration pathways in young and old colonies. These results and the resources we developed are used by my lab and others to further study stem cell and immune cell properties during development, regeneration, transplantation, and aging.
Synthesis, Structural Elucidation, and Cytotoxicity Studies of New Triazolyl Half‐Sandwich RuII, OsII, RhIII and IrIII Complexes
Authors: Chu William K. , Rono Charles K. , Makhubela Banothile C. E.
Published: October 2023

Herein, we report the synthesis of a series of nine novel cationic triazole‐based complexes C1–C9 and their anticancer assays against cervical cancer cells (Hela), kidney cancer cells (HEK293), lung cancer cells (A549), and leukemia cells (MT4). The complexes have the formula [MCl(Ar)L]+X−, where M is a platinum group metal‐based cation (RuII, OsII, RhIII, or IrIII), Ar is Cp* for Rh and Ir and p‐cymene for Ru and Os, L is the
‐chelating ligands 1‐benzyl‐4‐(aminomethyl)‐1H‐1,2,3‐triazole (L1) and 1‐picolyl‐4‐phenyl‐1H‐1,2,3‐triazole (L2), and X− is Cl−, BF4−, or BPh4−. The reaction of ligands L1 and L2 with [Ru(p‐cymene)Cl2]2, [Os(p‐cymene)Cl2]2, [Rh(Cp*)Cl2]2, and [Ir(Cp*)Cl2]2 produced the nine cationic complexes (C1–C9) cumulatively. Normal kidney cell lines (BHK21) were included in the assays to assess the selectivity aspect of these complexes to cancer cells. In general, all the compounds displayed low cytotoxicity except for the ruthenium(II) complex C7 (with BPh4− as the counterion), which showed good activity against all the cancer cell lines (EC50 values as low as 9±1.8 μM. Complex C1 with EC50=16±0.5 μM against MT4 gave the highest selectivity towards cancer cells. C7 was also shown to interact with L‐histidine (L‐His), NADH, bovine serum album (BSA) and guanosine 5’‐monophosphate (5’‐GMP). Due to the observed non‐toxicity of most of the complexes against normal cells, selectivity against specific cancer cells, and interaction with imidazole containing biomolecules, this class of complexes may serve as templates in drug development for targeted therapeutics.
Nickel Metallaphotoredox Buchwald–Hartwig Amination Reactions: A Perspective on Irradiation Light Wavelength
Authors: Kuai Meiying , Jia Zihan , Chen Lijie , Gao Shuang , Fang Weiwei
Published: October 2023

The construction of C−N bonds is considered one of the most useful reactions in synthetic chemistry due to their widespread presence in pharmaceuticals, natural products, etc. Pd‐catalyzed Buchwald–Hartwig amination (BHA) has provided the most efficient method to form (hetero)aryl amines but it required strong base and sophisticated ligands. In comparison, the combination of photocatalysis and nickel chemistry has revolutionized catalytic strategies and is emerging as a quintessence to realize BHA, termed as Ni‐metallaphotoredox BHA. To pursue a universal protocol, diverse photocatalysts were designed and employed in Ni‐metallaphotoredox BHA, and smoothly promoted C−N bond formations under irradiation of light from ultraviolet to red light, respectively. Note that the matching of photocatalyst and light was critical for success. Therefore, this review mainly focuses on the discussion of Ni‐metallaphotoredox BHA according to the irradiation light's wavelength, covering ultraviolet, purple, blue, red, and white light as well as solar light. We try to find a clue in the relationship of structure‐photophysical behaviors of photocatalysts under the same or different irradiation light. At last, current limitations and potential trends for advancing Ni‐metallaphotoredox BHA are highlighted. We deem that it could encourage chemists to continue designing suitable photocatalyst for C−N bond formations under sunlight mimicking plants’ photosynthesis.
The qualities of a good enrollment manager
Authors: Dennis Marguerite J.
Published: October 2023

In 1976, in an article in Boston College's Bridge Magazine, Dean of Admission, John Maguire, defined enrollment management as a process that brings together disparate functions related to recruiting, funding, tracking, and retaining students as they enroll, progress, and graduate.
Spatial regression modeling via the R2D2 framework
Authors: Yanchenko Eric , Bondell Howard D. , Reich Brian J.
Published: October 2023

Spatially dependent data arises in many applications, and Gaussian processes are a popular modeling choice for these scenarios. While Bayesian analyses of these problems have proven to be successful, selecting prior distributions for these complex models remains a difficult task. In this work, we propose a principled approach for setting prior distributions on model variance components by placing a prior distribution on a measure of model fit. In particular, we derive the distribution of the prior coefficient of determination. Placing a beta prior distribution on this measure induces a generalized beta prime prior distribution on the global variance of the linear predictor in the model. This method can also be thought of as shrinking the fit towards the intercept‐only (null) model. We derive an efficient Gibbs sampler for the majority of the parameters and use Metropolis–Hasting updates for the others. Finally, the method is applied to a marine protection area dataset. We estimate the effect of marine policies on biodiversity and conclude that no‐take restrictions lead to a slight increase in biodiversity and that the majority of the variance in the linear predictor comes from the spatial effect.
Foreign exchange hedging using regime‐switching models: The case of pound sterling
Authors: Lee Taehyun , Moutzouris Ioannis C. , Papapostolou Nikos C. , Fatouh Mahmoud
Published: October 2023

We develop a four‐state regime‐switching model for optimal foreign exchange (FX) hedging using forward contracts. The states correspond to four distinct market conditions, each defined by the direction and magnitude of deviation of the prevailing FX spot rate from its long‐term trends. The model's performance is evaluated for five currencies against the pound sterling for various horizons. Our examination compares the hedging outcomes of the proposed model to those of other commonly employed hedging methods. The empirical results suggest that our model demonstrates the highest level of risk reduction for the US dollar, euro, Japanese yen and Turkish lira and the second‐best performance for the Indian rupee. The risk reduction is significantly higher for lira compared with the other approaches, implying that the proposed model might be able to provide much more effective hedging for highly volatile currencies. The improved performance of the model can be attributed to the adjustability of the estimation horizon for the optimal hedge ratio based on the prevailing market conditions. This, in turn, allows it to better capture fat‐tail properties that are frequently observed in FX returns. Our findings suggest that FX investors tend to use short‐term memory during low market conditions (relative to trend) and long‐term memory in high ones.   The results would be also useful to build a better understanding of how investor behaviour depends on market conditions and mitigate the adverse behavioural implications of short‐term memory, such as panic.
Love and Justice in the Family
Authors: Glover Jackie
Published: October 2023

The Patient in the Family: An Ethics of Medicine and Families. By Hilde Lindemann Nelson and James Lindemann Nelson.
Intranasal Desmopressin‐Induced Hyponatremia
Authors: Williford Stephen L. , Bernstein Stephen A.
Published: October 2023

Desmopressin is a commonly used, well‐tolerated agent for the treatment of primary nocturnal enuresis and central diabetes insipidus. Intranasal desmopressin provides symptomatic relief with few serious complications. A 29‐year‐old woman with a long history of primary nocturnal enuresis began treatment with intranasal desmopressin. Although the enuresis ceased, she developed throbbing headaches, nausea, vomiting, paresthesia, lethargy, fatigue, and altered mental status over the next 7 days. When she came to the emergency room her sodium concentration was 127 mmol/L. The history of desmopressin use was not obtained at that time. She was treated with intravenous fluids and discharged. The symptoms returned and worsened over the next 4 days, and she returned to the emergency room stuporous. A repeat sodium was 124 mmol/L, and she was admitted. The history of desmopressin use was still not available. Medical evaluations included computerized tomography, lumbar puncture, complete blood counts, serum chemistries, and serologies. The next morning the woman was improved and informed clinicians of her desmopressin use. Without other causes for the hyponatremia, she was diagnosed with the syndrome of inappropriate antidiuretic hormone, presumably caused by desmopressin. Within 24 hours of fluid restriction and cessation of desmopressin, her symptoms and hyponatremia resolved. A review of the literature found 11 children and 2 adults in whom intranasal desmopressin was associated with hyponatremia, all of whom experienced seizures or altered mental status. Our patient illustrates the importance of early recognition and treatment of hyponatremia before the onset of seizures. When vague symptoms develop during desmopressin therapy, hyponatremia must be considered as part of the differential diagnosis. It may also be prudent to screen for electrolyte abnormalities in patients taking this agent to prevent serious iatrogenic complications.
Intravenous Ketorolac for Pain Management in a Ventilator‐Dependent Patient With Thermal Injury
Authors: Tran Hieu T. , Ackerman Bruce H. , Wardius Patricia A. , Haith Linwood R. , Patton Mary Lou
Published: October 2023

A patient with a long‐standing history of chronic obstructive pulmonary disease suffered a thermal injury over 20% of his total body surface area. He required opiates for pain management and benzodiazepines for anxiety associated with dressing changes. The narcotics compromised his pulmonary function and level of consciousness, and interfered with several attempts to wean him from ventilator support. Intravenous ketorolac instead of narcotics before dressing changes alleviated the respiratory depression and returned his partial pressure of carbon dioxide‐mediated respiratory drive to normal. With these changes, including changes in respiratory rate to tidal volume, he was successfully weaned from ventilatory support. In addition, the patient's level of consciousness improved. These changes increased his participation in his daily physical therapy sessions.
A Review of NMDA Receptors and the Phencyclidine Model of Schizophrenia
Authors: Thornberg Sheri A. , Saklad Stephen R.
Published: October 2023

Current models of drug‐induced psychosis insufficiently describe the symptoms of schizophrenia. Phencyclidine‐induced psychosis is a model that more completely reflects the pathophysiology of the disease. By decreasing glutamatergic neurotransmission, phencyclidine decreases 7‐aminobutyric acid release from the nucleus accumbens, striatum, and hippocampus (manifested by MK‐801); may inhibit tonic release of dopamine from the nucleus accumbens and striatum, resulting in increased dopamine phasic reactivity; and decreases long‐term potentiation. Glutamatergic system dysfunction may be involved, but pharmacologic manipulation has not revealed a clear mechanism of this dysfunction.