bluuebunny/crossref_metadata_2025 huggingface dataset:
Web-mining conceitos e aplicações
Authors:   Universidade do Estado de Santa Catarina, Scoz Diogo Pietro
Published: April 2015

A grande quantidade e variedade de dados disponíveis na web cria a oportunidade da aplicação de técnicas de mineração de dados na Internet, isso é conhecido como web-mining. Quando uma pessoa necessita encontrar alguma informação na web, normalmente ela irá recorrer a algum motor de busca, e um dos maiores problemas é encontrar os dados relevantes dentre tantos resultados da busca de modo a conseguir extrair conhecimento util. Por isso, são necessárias técnicas para aumentar a eficiência das respostas, visto que as pessoas possuem padrões diferentes de preferências e atividades que realizam online. Tais padrões e dados sobre os usuários podem ser “minerados” com o objetivo de tornar a experiência do próprio usuário em algum site mais eficiente. O objetivo deste artigo é explanar os conceitos básicos necessários para compreensão do tema de web-mining.
Trickle-Down Technology and Screening of a Durable Goods Monopolist
Authors: Huang Su-Chen , Yu Shih-Ti , Chi Woody Chih-Yi , Yang Wen-Ben
Published: April 2015

We show that when it takes time for a durable goods monopolist to make its high-end new technology accessible to low-end market (the trickle-down technology constraint), the monopolist's high-end product might have a higher-than-optimum quality. This result differs from conventional screening models, in which the qualities of non-durable goods supplied by a monopolist never exceed the optimum, and only consumers with the highest valuation consume the efficient quality. In another literature discussing a durable goods monopolist who delays the introduction of low-end product as a marketing strategy, but not due to the trickle-down constraint, the qualities will not exceed the optimum either. Our results show that the trickle-down constraint will make the monopolist chooses a higher-than-optimum quality when the difference of the valuations of high demand and low demand consumers are in certain ranges. The intuition follows Spence (1975): the efficient quality is determined by the marginal cost and the average of all consumers' marginal valuations, while the monopolist chooses quality such that the marginal cost equals the marginal consumer's marginal valuation.
Plant defense phenotypes determine the consequences of volatile emission for individuals and neighbors
Authors: Schuman Meredith C , Allmann Silke , Baldwin Ian T
Published: April 2015

Plants are at the trophic base of terrestrial ecosystems, and the diversity of plant species in an ecosystem is a principle determinant of community structure. This may arise from diverse functional traits among species. In fact, genetic diversity within species can have similarly large effects. However, studies of intraspecific genetic diversity have used genotypes varying in several complex traits, obscuring the specific phenotypic variation responsible for community-level effects. Using lines of the wild tobacco Nicotiana attenuata genetically altered in specific well-characterized defense traits and planted into experimental populations in their native habitat, we investigated community-level effects of trait diversity in populations of otherwise isogenic plants. We conclude that the frequency of defense traits in a population can determine the outcomes of these traits for individuals. Furthermore, our results suggest that some ecosystem-level services afforded by genetically diverse plant populations could be recaptured in intensive monocultures engineered to be functionally diverse.
Verification of Inferior Right Hepatic Vein–Conserving Segments 7 to 8 Resection of the Liver
Authors: Nakayama Hisashi , Takayama Tadatoshi , Higaki Tokio , Okubo Takao , Moriguchi Masamichi , Yoshida Nao , Kuronuma Akiko
Published: April 2015

This study aims to investigate the safety of inferior right hepatic vein (IRHV)–conserving surgery by comparing the surgical data and postoperative complications between IRHV-conserving segments 7 to 8 (S7 to S8) resection and conventional right hemihepatectomy (RH). Five patients who underwent IRHV-conserving S7 to S8 segmentectomy between 2007 and 2011 (IRHV group) and 25 liver cancer patients who underwent RH without biliary tract reconstruction during the same period (RH group) were investigated. The surgical data, postoperative complications, and duration of hospital stay were compared. The IRHV and RH groups included 2 (40%) and 13 (52%) hepatocellular carcinoma patients, respectively. There were no significant differences in liver function before surgery between the groups. The presence of the IRHV did not adversely affect the processing of the short hepatic vein or frontal dissection of the inferior vena cava. The operative time was shorter (median, 366 minutes versus 501 minutes; P = 0.0001), the postoperative bilirubin level was lower (12 mg/dL versus 1.8 mg/dL; P = 0.037), and the duration of hospital stay was shorter (10 days versus 14 days; P = 0.002) in the IRHV group. No significant differences were noted in the intraoperative blood loss, postoperative transaminase levels, or the incidence of severe complications (Clavien grade IIIb or higher) between the groups. IRHV-conserving resection of the liver is a safe surgical procedure that is useful in preventing postoperative elevation of bilirubin level and in shortening the duration of hospital stay.
Efficacy of Transversus Abdominis Plane Block and Rectus Sheath Block in Laparoscopic Inguinal Hernia Surgery
Authors: Takebayashi Katsushi , Matsumura Masakata , Kawai Yasuhiro , Hoashi Takahiko , Katsura Nagato , Fukuda Seijun , Shimizu Kenji , Inada Takuji , Sato Masugi
Published: April 2015

We aimed to assess the efficacy of transversus abdominis plane (TAP) block and rectus sheath (RS) block in patients undergoing laparoscopic inguinal hernia surgery. Few studies have addressed the efficacy and safety associated with TAP block and RS block for laparoscopic surgery. Thirty-two patients underwent laparoscopic inguinal hernia surgery, either with TAP and RS block (Block+ group, n = 18) or without peripheral nerve block (Block− group, n = 14). Preoperatively, TAP and RS block were performed through ultrasound guidance. We evaluated postoperative pain control and patient outcomes. The mean postoperative hospital stays were 1.56 days (Block+ group) and 2.07 days (Block− group; range, 1–3 days in both groups; P = 0.0038). A total of 11 patients and 1 patient underwent day surgery in the Block+ and Block− groups, respectively (P = 0.0012). Good postoperative pain control was more commonly observed in the Block+ group than in the Block− group (P = 0.011). TAP and RS block was effective in reducing postoperative pain and was associated with a fast recovery in patients undergoing laparoscopic inguinal hernia surgery.
A 45-Year-Old With Multiple Skin Lesions on Sun-Protected Areas of the Body
Authors: Liu Sheng-Wen , Wang Wei-Ming
Published: August 2024

A patient had multiple erythematous macules and patches on the trunk, hyperpigmented patches on the intergluteal cleft and subgluteal fold, and poikiloderma in the axillae; results of laboratory testing, including antinuclear antibody test, were unremarkable. What is the diagnosis and what would you do next?
Weight Gain After Adenotonsillectomy in Children With Mild Obstructive Sleep-Disordered Breathing
Authors: Kirkham Erin M. , Ishman Stacey , Baldassari Cristina M. , Mitchell Ron B. , Naqvi S. Kamal , Tapia Ignacio E. , Elden Lisa M. , Hassan Fauziya , Ibrahim Sally , Ross Kristie , Cen Mengqi , Wang Rui , Redline Susan , Chervin Ronald D.
Published: August 2024

Importance

It is unknown whether adenotonsillectomy causes undesirable weight gain in children with mild obstructive sleep-disordered breathing (oSDB).

Objective

To compare changes in anthropometric measures in children with mild oSDB treated with adenotonsillectomy vs watchful waiting.

Design, Setting, and Participants

This was an exploratory analysis of the Pediatric Adenotonsillectomy Trial for Snoring (PATS) randomized clinical trial of adenotonsillectomy vs watchful waiting for mild oSDB (snoring with obstructive apnea-hypopnea index of <3 events/hour) that took place at 7 pediatric tertiary care centers across the US and included 458 children aged 3.0 to 12.9 years with mild oSDB. Participants were recruited from June 29, 2016, to February 1, 2021. Anthropomorphic measures taken at baseline and 12 months after randomization were standardized for age and sex, including each participant’s percentage of the 95th body mass index percentile (%BMIp95). Data analyses were performed from March 15, 2023, to April 1, 2024.

Intervention

Early adenotonsillectomy (eAT) vs watchful waiting with supportive care (WWSC).

Main Outcomes and Measures

Twelve-month change in %BMIp95 from baseline and undesirable weight gain (defined as any weight gain in a child who already had overweight or obesity or an increase from baseline normal weight/underweight to overweight/obesity) at follow-up assessment.

Results

The study analysis included 375 children (mean [SD] age, 6.1 [2.3] years; 188 [50.2%] females), of whom 143 (38%) had overweight or obesity at baseline. At 12 months, children in the eAT group experienced a 1.25-point increase in %BMIp95 compared with a 0.59-point increase in the WWSC group (mean difference, 0.93; 95% CI, −0.39 to 2.25). Undesirable weight gain was also similar between the eAT (n = 120; 32%) and WWSC (n = 101; 27%) groups (mean difference, 4%; 95% CI, 5% to 14%).

Conclusions and Relevance

The findings of this exploratory analysis of the PATS trial indicate that adenotonsillectomy was not independently associated with an increased risk of undesirable weight gain in children with mild oSDB. However, one-third of the children gained undesirable weight during the study, which suggests that there is an opportunity to address healthy weight management during the evaluation and treatment of children with mild oSDB.

Trial Registration

ClinicalTrials.gov Identifier: NCT02562040
Prediagnostic Amino Acid Metabolites and Risk of Gout, Accounting for Serum Urate: Prospective Cohort Study and Mendelian Randomization
Authors: McCormick Natalie , Joshi Amit D. , Yokose Chio , Yu Bing , Tin Adrienne , Terkeltaub Robert , Merriman Tony R. , Zeleznik Oana , Eliassen A. Heather , Curhan Gary C. , Ea Hang‐Korng , Nayor Matthew , Raffield Laura M. , Choi Hyon K.
Published: August 2024

Objective

Our objective was to prospectively investigate prediagnostic population‐based metabolome for risk of hospitalized gout (ie, most accurate, severe, and costly cases), accounting for serum urate.

Methods

We conducted prediagnostic metabolome‐wide analyses among 249,677 UK Biobank participants with nuclear magnetic resonance metabolomic profiling (N = 168 metabolites, including eight amino acids) from baseline blood samples (2006–2010) without a history of gout. We calculated multivariable hazard ratios (HRs) for hospitalized incident gout, before and after adjusting for serum urate levels; we included patients with nonhospitalized incident gout in a sensitivity analysis. Potential causal effects were evaluated with two‐sample Mendelian randomization.

Results

Correcting for multiple testing, 107 metabolites were associated with incidence of hospitalized gout (n = 2,735) before urate adjustment, including glycine and glutamine (glutamine HR 0.64, 95% confidence interval [CI] 0.54–0.75, P = 8.3 × 10−8; glycine HR 0.69, 95% CI 0.61–0.78, P = 3.3 × 10−9 between extreme quintiles), and glycoprotein acetyls (HR 2.48, 95% CI 2.15–2.87, P = 1.96 × 10−34). Associations remained significant and directionally consistent following urate adjustment (HR 0.83, 95% CI 0.70–0.98; HR 0.86, 95% CI 0.76–0.98; HR 1.41, 95% CI 1.21–1.63 between extreme quintiles), respectively; corresponding HRs per SD were 0.91 (95% CI 0.86–0.97), 0.94 (95% CI 0.91–0.98), and 1.10 (95% CI 1.06–1.14). Findings persisted when including patients with nonhospitalized incident gout. Mendelian randomization corroborated their potential causal role on hyperuricemia or gout risk; with change in urate levels of −0.05 mg/dL (95% CI −0.08 to −0.01) and −0.12 mg/dL (95% CI −0.22 to −0.03) per SD of glycine and glutamine, respectively, and odds ratios of 0.94 (95% CI 0.88–1.00) and 0.81 (95% CI 0.67–0.97) for gout.

Conclusion

These prospective findings with causal implications could lead to biomarker‐based risk prediction and potential supplementation‐based interventions with glycine or glutamine.
Designing Salen‐Based Porous Organic Polymers for Enhanced Electrolytic Water Splitting into Oxygen
Authors: Pal Hiranmoy , Karmakar Arun , Sadhukhan Arnab , Koner Kalipada , Karak Shayan , Sharma Rahul Kumar , Ghosh Manasi , Dey Krishna Kishor , Pathak Biswarup , Kundu Subrata , Banerjee Rahul
Published: August 2024

The development of electricity‐driven oxygen evolution reaction (OER) is a potent solution for energy storage applications. In recent years, there is a surge in interest in designing transition metal‐based catalysts with stable linkages, presenting an efficient alternative to noble metal‐based electrocatalysts. Transition metal complexes linked by salen ligands garner considerable attention due to their capacity to chelate and stabilize metal ions. This work presents a novel approach by strategically incorporating the metal–salen core into a porous organic polymer (POP) backbone, thereby fabricating a highly effective electrocatalyst for oxygen evolution. The judicious selection of metal–salen active sites, coupled with the intramolecular free volume (IMFV) of the triptycene core and the high specific surface area of the salen–POPs, result in superior OER activity. By precisely tuning the structure through variation of the transition metal in the salen unit, deep insights are gained into their electrocatalytic behavior. Notably, the most efficient catalyst, Ni‐DHDA‐TAT, exhibits an impressively low overpotential (η10) of ≈ 270 mV at a current density of 10 mA cm−2 for OER (in 1 m KOH). Further, Ni‐DHDA‐TAT retains its activity even after 50 h of chronoamperometry and 1000 cyclic voltammetry cycles with negligible degradation in its initial performance.
Adaptive No‐Tip Distribution of Rich Charge‐Density‐Clusters Guiding Confinement Deposition with Repair Function toward Highly Reversible Zinc Anode
Authors: Hu Xiaomeng , He Zhongqian , Zhao Qiwen , Zhou Jie , Wang Changding , Huang Shaozhen , Zhou Gang , Xu Bingang , Wang Bin , Chen Libao , Chen Yuejiao
Published: August 2024

The plating/stripping behavior of Zn ions on the Zn anode, driven by an electric field, is a key process in determining the performance of aqueous zinc ion batteries (AZIBs). Process‐induced unevenness of commercial Zn foils results in poor reversibility of Zn anodes. Herein, a self‐healing dynamic anode/electrolyte interface is constructed by incorporating hydroxyl‐rich alcohols with high charge density and zincophilicity into the original electrolyte. These alcohols selectively anchor on electron‐poor sites in the charging state, inducing domain‐limited deposition of Zn2+ to achieve a dense, uniform, and flat deposition state. As a result, a durable Zn anode with excellent electrochemical reversibility can be realized in practical cycling (average Coulombic efficiency of 99.5%). Even under deep plating/stripping conditions (5 mA cm−2 and 5mAh cm−2), the modified electrolyte exhibits a remarkable repair effect on corroded Zn anodes that have been cycled in base electrolyte, extending the lifespan to over 1,020 h. This represents a 15.6‐fold enhancement in lifespan compared to recycling in the base electrolyte. This strategy for electrolyte additive directly influences the design of ultra‐long‐life AZIBs and provides concrete concepts for the recovery of zinc anodes.
Achieving Ultrahigh Transparency and Superior Mechanical Properties in Flexible Polyimide Nanofoams Through CO2 Foaming for Thermal Insulation
Authors: Li Xin'ao , Zong Yumeng , Li Wenjuan , Qian Jin , Qiang Zhe , Ye Changhuai , Zhu Meifang
Published: August 2024

Transparent polymer nanofoams offer significant potential for thermal insulation, particularly for energy‐saving windows, where both transparency and low thermal conductivity are crucial. However, grand challenges remain in preparing polymer nanofoam monoliths with pore sizes smaller than 40 nm to achieve high optical transparency via minimized light scattering. Herein, the preparation of highly transparent nanofoam monoliths based on fluorinated polyimide (FPI) using CO2 foaming is reported for the first time. The high CO2 absorption capacity and robust melt strength of the FPI matrix significantly promote bubble nucleation while minimizing cell coalescence during CO2 foaming process, resulting in ultra‐small pore sizes down to sub‐10 nm. These FPI nanofoams, with a thickness of ≈0.2 mm, can exhibit high optical transmittance (>85% in the wavelength range of 500–700 nm) and low haze (≈18%), which is unprecedented for polymer foams prepared using foaming methods. Furthermore, these FPI nanofoams demonstrate superior mechanical and thermal insulation properties compared to micron‐sized FPI foams and maintain remarkable mechanical flexibility and structural stability even under harsh conditions, including extreme temperatures and water exposure. Transparent nanofoams prepared using a scalable CO2 foaming method can serve as the next‐generation thermal insulation materials, with broad potential applications in energy‐efficient buildings, and aerospace.
Unraveling the Role of Spacer Cations: Toward Constructing Ideal Dion–Jacobson Halide Perovskites
Authors: Lai Zhengxun , Shen Yi , Jiang Bei , Zhang Yuxuan , Meng You , Yin Di , Gao Boxiang , Wang Weijun , Xie Pengshan , Yan Yan , Yip SenPo , Liao Lei , Ho Johnny C.
Published: August 2024

Dion–Jacobson‐type 2D halide perovskites (DJPs) present an ideal alternative to their 3D counterparts due to their superior stability and exceptional optoelectronic properties. Despite the numerous DJPs proposed in recent years, the impact of different spacer cations on DJPs remains unclear. This understanding is crucial for researchers to select suitable materials and is an urgent requirement for the development of higher‐performance DJPs‐based devices. In this study, the influence of the chain‐like spacer cations with varying branch chains and chain lengths is thoroughly examined using both theoretical and experimental methods. The findings reveal that spacer cations with high polarity components along the main chain direction enhance the stability and photoelectric properties of DJPs. Additionally, it is found that the chain length of the spacer cation plays a critical role. Chain lengths that are too long or too short can detrimentally affect the photoelectric performance and stability of DJPs. These insights will guide researchers in selecting suitable spacer cations and in innovating new types of DJPs.
Tuning the Electronic and Electrochemical Properties of 3D Porous Laser‐Induced Graphene by Electrochemically Induced Deposition of Polyoxovanadate Nanoclusters for Flexible Supercapacitors
Authors: Arya Nikhil , Dinda Sirshendu , Diemant Thomas , Wang Ke , Fichtner Maximilian , Anjass Montaha
Published: August 2024

The advancement of microelectronic devices mandates the development of flexible energy storage systems to enable the fabrication of miniaturized and wearable electronics. Herein, a sustainable approach is demonstrated for tuning the electronic and electrochemical properties of hierarchically porous laser‐induced graphene (LIG) substrates. The methodology entails the electrochemical deposition of polyoxovanadate nanoclusters (K5(CH3CN)3[V12O32Cl] (= K5{V12}) onto the highly porous LIG matrix. The comprehensive characterization is integrated through micro‐Raman spectroscopy and in‐depth X‐ray photoelectron spectroscopy to elucidate the deposition mechanism and electronic properties of the fabricated electrode. The results indicate a significant correlation between the orientation of the deposited clusters and the non‐crystalline regions of the LIG structure. Additionally, the cluster deposition results in a reduction of grain boundary defects in the nano‐graphite lattice of LIG. The optimized electrode exhibits enhanced areal capacitance (CA) of 125 mF cm−2 at a current density of 0.1 mA cm−2, representing a fivefold improvement compared to the undoped LIG substrate. Furthermore, as a proof of concept, a flexible solid‐state symmetrical supercapacitor device, fabricated with a PVA‐H2SO4 gel electrolyte, demonstrates an areal capacitance of 24.92 mF cm−2 at current density of 0.1 mA cm−2 and exhibits exceptional cycling stability, enduring up to 5000 consecutive galvanostatic charge‐discharge cycles.
Lignosulfonate‐Derived Conducting Organohydrogel as Anisotrpic Bioadhesive for Motion‐Artifact‐Free Epidermal Bioelectronics
Authors: Shen Jinlai , Cai Minkun , Li Gang , Guo Chuan Fei , Qiu Xueqing , Qian Yong
Published: August 2024

Gel‐based adhesives show promising prospects in epidermal bioelectronics because of their potential applications in physiological signal collection and electrical stimulation. An ideal epidermal adhesive should exhibit robust adhesion for lamination and poor adhesion for easy peeling, in addition to strain‐insensitivity in electrical properties for motion‐artifact‐free physiological signal collection. Here, lignosulfonate‐derived organohydrogel adhesives with anisotropic and tunable adhesion, together with unprecedented strain‐insensitivity are synthesized. The organohydrogel exhibits a high interfacial toughness of 728 J m−2 on fresh porcine skin, while the adhesion can be screened by covering a denatured silk fibroin. An anisotropic adhesive with an adhesion heterogeneity is designed, showing a 14.2‐fold difference in adhesion strength along two different directions for on‐demand attachment and removal. The adhesive can transform into a highly porous structure, which has only a 3% resistance increase at 100% strain. The strain‐insensitivity of the adhesive lies in the strong interaction of ions and the 3D porous structure, which enables motion‐artifact‐free and high‐quality electrophysiological signal collection within the strain range of the human skin. The lignosulfonate‐derived on‐demand organohydrogel adhesive is expected to be used in epidermal bioelectronics, human‐machine interaction, metaverse, and beyond.
PAFerroptosis Combined with Metabolic Disturbance of Mito by p52‐ZER6 for Enhanced Cancer Immunotherapy induced by Nano‐Bacilliform‐Enzyme
Authors: Xi Zi‐yue , Fan Chuan‐yong , Zhu Shuang , Nie Gan‐yu , Xi Xin‐ran , Jiang Ying‐ying , Zhou Yao , Mei Yi‐hua , Xu Lu
Published: August 2024

The confused gene expressions and molecular mechanisms for mitochondrial dysfunction of traditional nanoenzymes is a challenge for tumor therapy. Herein, a nano‐bacilliform‐enzyme obtains the ability to inhibit p52‐ZER6 signal pathway, regulate the genes related to mitochondrial metabolism, and possess the GOx/CAT/POD‐like property. NBE acquires catalytic activity from the electronic energy transition. The tannin of NBE as a mitochondrial (Mito)‐targeting guide overloads MitoROS, and then metabolic disorder and lipid peroxidation of Mito membrane occurs, thus leading to a novel death pathway called PAFerroptosis (pyroptosis, apoptosis, and Ferroptosis). Simultaneously, in order to refrain from mitophagy, hydroxychloroquine is mixed with NBE to form a combo with strength pyroptosis. As a result, NBE/combo improves the PAFerroptosis obviously by activation of CD8+T cells and inactivation of MDSC cells, up‐regulating expression of caspase‐3 signal pathway, intercepting DHODH pathway to arrive excellent antitumor effect (93%). Therefore, this study establishes a rational nanoenzyme for mitochondrial dysfunction without mitophagy for effective antitumor therapy.
Encapsulation of Prussian Blue Analogues with Conductive Polymers for High‐Performance Ammonium‐Ion Storage
Authors: Liu Qiang , Zhang Dongzhi , Yang Yunting , Gu Yalan , Liang Zhenyan , Chen Wenshu , Wu Yuping , Hu Linfeng
Published: August 2024

Multivalent manganese‐based Prussian blue analogues (Mn‐PBA) possess multi‐electron transfer characteristics and exhibit unique properties for achieving high energy density in ammonium ion batteries (AIBs). However, the irreversible structural collapse and sluggish ionic diffusion kinetics result in inferior rate capability and undesirable lifespan. Herein, guided by theoretical calculations, a series of ultrafine Mn‐PBA@ conductive polymers core–shell composites through an in situ polymerization and encapsulation strategy are synthesized to solve the above existing issues for Mn‐PBA. Among various designed conductive polymers (including the poly‐pyrrole (ppy), polyaniline, and poly(3,4‐ethylenedioxythiophene)) coated on Mn‐PBA, the Mn‐PBA@ppy shows the strongest adsorption for ammonium ions and the highest manganese atom removal energy barrier. Acting as the cathode of AIBs, the designed Mn‐PBA@ppy exhibits a remarkable high capacity of 72 mAh g−1, a super‐stable discharge platform of 0.81 V, and excellent cycling stability of 94% retention for over 300 cycles (0.1 A g−1) with an ultrahigh NH4+ diffusion coefficient of ≈1.38 × 10−8 cm−2 s−1. This work offers an in situ polymer encapsulation approach to simultaneously enhance the ammonium ion diffusion kinetics and structural stability. More importantly, this organic/inorganic interfacial design can promote the development of cathode materials with rapid diffusion kinetics and excellent cyclic stability.
Recurrent carotid paragangliomas in a syndromic patient with a heterozygous missense variant in DNA Methyltransferase 3 Alpha
Authors: German Ryan J. , Vuocolo Blake , Vossaert Liesbeth , Saba Lisa , Fletcher Robin , Tedder Matthew L. , Sadikovic Bekim , Kerkhof Jennifer , Wangler Michael , Bacino Carlos A. ,   The Texome Project
Published: August 2024

We report a 40‐year‐old African American female with a novel variant in exon 8 of DNA methyltransferase 3 alpha (DNMT3A), (NM_022552.4: c.905G>C, p.G302A) who presented with a history of recurrent carotid paragangliomas, mediastinal mass, intellectual disability, dysarthria, cholelithiasis, diabetes mellitus, hypertension, and dysmorphic features. We interpret this novel variant as likely pathogenic and causative for the patient's syndromic features of Heyn–Sproul–Jackson syndrome. Heyn–Sproul–Jackson syndrome is a condition caused by gain‐of‐function genetic changes in DNMT3A. Paragangliomas have also been observed in non‐syndromic patients with genetic alterations in DNMT3A. We describe a patient with clinical features of Heyn–Sproul–Jackson syndrome such as intellectual disability, dysarthria, brachydactyly, and lack of brain MRI findings to add evidence to associate paragangliomas with DNMT3A and draw particular attention to the potential involvement of the proline‐tryptophan‐tryptophan‐proline domain of DNMT3A.
Nickel‐Catalyzed Reductive Protocol to Access Silacyclobutanes with Unprecedented Functional Group Tolerance
Authors: Yang Ling‐yun , Qin Ying , Zhao Zhihan , Zhao Dongbing
Published: August 2024

While significant progress has been made in the area of transition metal‐catalyzed ring‐opening and formal cycloaddition reactions of 1,1‐disubstituted silacyclobutanes (SCBs), synthesizing these SCBs—particularly those bearing additional functional groups—continues to present synthetic challenges. In this context, we present a novel Ni‐catalyzed reductive coupling reaction that combines 1‐chloro‐substituted silacyclobutanes with aryl or vinyl halides and pseudohalides, thereby obviating the need for organometallic reagents. This method facilitates the generation of 1,1‐disubstituted silacyclobutanes with a remarkable tolerance for various functional groups. This approach serves as a complementary and more step‐economical alternative to the commonly used yet moisture‐ and air‐sensitive nucleophilic substitution reactions involving Grignard or lithium reagents. Our initial mechanistic studies indicate that this reaction is initiated by oxidative cleavage of the Si−Cl bond in 1‐chlorosilacyclobutanes, which represents a distinct mechanism from the previously documented reductive coupling processes involving carbon electrophiles and chlorosilanes.
Non‐Equilibrium Dissipative Assembly with Switchable Biological Functions
Authors: Zhao Peng , Zhao Yuanfeng , Lu Yan , Xu Linjie , Li Bohan , Zhao Yingshuai , Zhou Wei , Yan Pu , Wang Youfu , Cao Kecheng , Zheng Yijun
Published: August 2024

Natural dissipative assembly (DSA) often exhibit energy‐driven shifts in natural functions. However, creating man‐made DSA that can mimic such biological activities transformation remains relatively rare. Herein, we introduce a cytomembrane‐like dissipative assembly system based on chiral supramolecules. This system employs benzoyl cysteine in an out of equilibrium manner, enabling the shifts in biofunctions while minimizing material use. Specifically, aroyl‐cystine derivatives primarily assemble into stable M‐helix nanofibers under equilibrium conditions. These nanofibers enhance fibroblast adhesion and proliferation through stereospecific interactions with chiral cellular membranes. Upon the addition of chemical fuels, these functional nanofibers temporarily transform into non‐equilibrium nanospheres, facilitating efficient drug delivery. Subsequently, these nanospheres revert to their original nanofiber state, effectively recycling the drug. The programmable function‐shifting ability of this DSA establishes it as a novel, fuel‐driven drug delivery vehicle. And the bioactive DSA not only addresses a gap in synthetic DSAs within biological applications but also sets the stage for innovative designs of ′living′ materials.
Structure‐Based Design of Bicyclic Helical Peptides That Target the Oncogene β‐Catenin
Authors: Yeste‐Vázquez Alejandro , Paulussen Felix M. , Wendt Mathias , Klintrot Rasmus , Schulte Clemens , Wallraven Kerstin , van Gijzel Lieke , Simeonov Boris , van der Gaag Maurice , Gerber Alan , Maric Hans M. , Hennig Sven , Grossmann Tom N.
Published: August 2024

The inhibition of intracellular protein‐protein interactions is challenging, in particular, when involved interfaces lack pronounced cavities. The transcriptional co‐activator protein and oncogene β‐catenin is a prime example of such a challenging target. Despite extensive targeting efforts, available high‐affinity binders comprise only large molecular weight inhibitors. This hampers the further development of therapeutically useful compounds. Herein, we report the design of a considerably smaller peptidomimetic scaffold derived from the α‐helical β‐catenin‐binding motif of Axin. Sequence maturation and bicyclization provided a stitched peptide with an unprecedented crosslink architecture. The binding mode and site were confirmed by a crystal structure. Further derivatization yielded a β‐catenin inhibitor with single‐digit micromolar activity in a cell‐based assay. This study sheds light on how to design helix mimetics with reduced molecular weight thereby improving their biological activity.
Molybdenum Disulfide Induced Phase Control Synthesis of Multi‐dimensional Co3S4‐MoS2 Heteronanostructures via Cation Exchange
Authors: He Yu‐Qing , Xu Hou‐Ming , Zhang Jian‐Ding , Zheng Dong , Zhang Gang , Fan Xu‐Zhuo , Ou‐Yang He , Liu Yu‐Qing , Lv An‐Chen , Zhao Jia‐Wei , Shi Cheng‐Wu , Han Shi‐Kui
Published: August 2024

Phase control over cation exchange (CE) reactions has emerged as an important approach for the synthesis of nanomaterials (NMs), enabling precise determination of their reactivity and properties. Although factors such as crystal structure and morphology have been studied for the phase engineering of CE reactions in NMs, there remains a lack of systematic investigation to reveal the impact for the factors in heterogeneous materials. Herein, we report a molybdenum disulfide induced phase control method for synthesizing multidimensional Co3S4‐MoS2 heteronanostructures (HNs) via cation exchange. MoS2 in parent Cu1.94S‐MoS2 HNs are proved to affect the thermodynamics and kinetics of CE reactions, and facilitate the formation of Co3S4‐MoS2 HNs with controlled phase. This MoS2 induced phase control method can be extended to other parent HNs with multiple dimensions, which shows its diversity. Further, theoretical calculations demonstrate that Co3S4 (111)/MoS2 (001) exhibits a higher adhesion work, providing further evidence that MoS2 enables phase control in the HNs CE reactions, inducing the generation of novel Co3S4‐MoS2 HNs. As a proof‐of‐concept application for crystal phase‐ and dimensionality‐dependent of cobalt sulfide based HNs, the obtained Co3S4‐MoS2 heteronanoplates (HNPls) show remarkable performance in hydrogen evolution reactions (HER) under alkaline media. This synthetic methodology provides a unique design strategy to control the crystal structure and fills the gap in the study of heterogeneous materials on CE reaction over phase engineering that are otherwise inaccessible.
Oscillating Structural Transformations in the Electrochemical Synthesis of Graphene Oxide from Graphite
Authors: Gurzęda Bartosz , Jeżowski Paweł , Boulanger Nicolas , Talyzin Alexandr V.
Published: August 2024

Electrochemical synthesis of graphene oxide (GO) is known to occur with potential oscillations, but the structural changes underlying these oscillations have remained unclear. In situ time‐resolved synchrotron radiation X‐ray diffraction demonstrates that the electrochemical synthesis of GO in aqueous H2SO4 can be described as an oscillating reaction. The transformation from graphite to GO proceeds through periodic structural oscillations that correlate with potential cycles. Stage‐1 graphite intercalation compound (GIC) is found only at the peak of the potential cycle, but not at the bottom of the cycle. Stage‐1 GIC is formed in the first half‐cycle from stage‐2 GIC and then transforms into “pristine graphite oxide” (PGO) on the lower side of the potential cycle, after which the cycle restarts with the formation of a new portion of stage‐1 GIC. Water‐washing results in the transformation of PGO into water‐swollen GO with d(001) ~11 Å. These periodic structural changes can be considered a new type of oscillating reaction. The presented results provide broad insights into the oscillating structural changes occurring during the anodic graphite oxidation in aqueous H2SO4 and allow to update of the mechanism of GO electrochemical formation.
Recognition and order of multiple sidechains by metal–organic framework enhances the separation of hexane isomers
Authors: Markad Datta , Kershaw Cook Laurence J. , Pétuya Rémi , Yan Yong , Gilford Oliver , Verma Ajay , Mali Bhupendra P. , Robertson Craig M. , Berry Neil G. , Darling George R. , Dyer Matthew S. , Antypov Dmytro , Katsoulidis Alexandros P. , Rosseinsky Matthew J.
Published: August 2024

Porous materials perform molecular sorting, separation and transformation by interaction between their framework structures and the substrates. Proteins also interact with molecules to effect chemical transformations, but rely on the precise sequence of the amino acid building units along a common polypeptide backbone to maximise their performance. Design strategies that positionally order sidechains over a defined porous framework to diversify the internal surface chemistry would enhance control of substrate processing. Here we show that different sidechains can be ordered over a metal–organic framework through recognition of their distinct chemistries during synthesis. The sidechains are recognised because each one forces the common building unit that defines the backbone of the framework into a different conformation in order to form the extended structure. The resulting sidechain ordering affords hexane isomer separation performance superior to that of the same framework decorated only with sidechains of a single kind. The separated molecules adopt distinct arrangements within the resulting modified pore geometry, reflecting their strongly differentiated environments precisely created by the ordered sidechains. The development of frameworks that recognize and order multiple sidechain functionality by conformational control offers tailoring of the internal surfaces within families of porous materials to direct interactions at the molecular level.
Insect cuticular protein; gene expression, genomic structure, transcriptional regulation, speculated cuticular structure, clarified through the genomic analysis of Bombyx mori
Authors: Kawasaki Hideki
Published: August 2024

JH and ecdysone signaling regulate insect metamorphosis through the master transcription factors, Krüppel homolog 1 (kr‐h1), Broad‐Complex (BR‐C), and E93. Ecdysone signaling activates successively expressed ecdysone responsive transcription factors (ERTFs), and the interaction between ERTFs determines the expression profiles of ERTFs themselves. Through the construction of expressed sequence tag (EST) database of Bombyx mori from many tissues, the existence of a large number of cuticular protein (CP) genes was identified in wing disc cDNA library of the 3 days after the start of wandering (W3). From the genomic analysis, 12 types of CP clusters of CP genes were identified. DNA sequences of CP genes revealed the duplication of CP genes, which suggests to reflect the insect evolution. These CP genes responded to ecdysone and ecdysone pulse; therefore, CP genes were applied for the analysis of transcriptional regulation by ERTF. The binding sites of ERTF have been reported to exist upstream of CP genes in several insects, and the activation of CP genes occurred by the binding of ERTFs. Through the analysis, the following were speculated; the successive appearance of ERTFs and the activation of target genes resulted in the successively produced CPs and cuticular layer. The sequence of the ERTF and CP gene expression was the same at larval to pupal and pupal to adult transformation. The involvement of several ERTFs in one CP gene expression was also clarified; BmorCPG12 belongs to group showing expression peak at W3 and was regulated by two ERTFs; BHR3 and ßFTZ‐F1, BmorCPH2 belongs to group showing expression peak at P0 and was regulated by two ERTFs; ßFTZ‐F1 and E74A. The involvement of BHR39 as a negative regulator of CP gene expression was found. Larval, pupal, and adult cuticular layers were supposed to be constructed by the combination of different and similar types of CPs, through the expressed timing of CP genes.
ChatGPT versus a customized AI chatbot (Anatbuddy) for anatomy education: A comparative pilot study
Authors: Arun Gautham , Perumal Vivek , Urias Francis Paul John Bato , Ler Yan En , Tan Bryan Wen Tao , Vallabhajosyula Ranganath , Tan Emmanuel , Ng Olivia , Ng Kian Bee , Mogali Sreenivasulu Reddy
Published: August 2024

Large Language Models (LLMs) have the potential to improve education by personalizing learning. However, ChatGPT‐generated content has been criticized for sometimes producing false, biased, and/or hallucinatory information. To evaluate AI's ability to return clear and accurate anatomy information, this study generated a custom interactive and intelligent chatbot (Anatbuddy) through an Open AI Application Programming Interface (API) that enables seamless AI‐driven interactions within a secured cloud infrastructure. Anatbuddy was programmed through a Retrieval Augmented Generation (RAG) method to provide context‐aware responses to user queries based on a predetermined knowledge base. To compare their outputs, various queries (i.e., prompts) on thoracic anatomy (n = 18) were fed into Anatbuddy and ChatGPT 3.5. A panel comprising three experienced anatomists evaluated both tools' responses for factual accuracy, relevance, completeness, coherence, and fluency on a 5‐point Likert scale. These ratings were reviewed by a third party blinded to the study, who revised and finalized scores as needed. Anatbuddy's factual accuracy (mean ± SD = 4.78/5.00 ± 0.43; median = 5.00) was rated significantly higher (U = 84, p = 0.01) than ChatGPT's accuracy (4.11 ± 0.83; median = 4.00). No statistically significant differences were detected between the chatbots for the other variables. Given ChatGPT's current content knowledge limitations, we strongly recommend the anatomy profession develop a custom AI chatbot for anatomy education utilizing a carefully curated knowledge base to ensure accuracy. Further research is needed to determine students' acceptance of custom chatbots for anatomy education and their influence on learning experiences and outcomes.
Creating new embryological models for teaching cardiac development in embryology
Authors: Fernquist Geoffery D. , Samonds Karen E.
Published: August 2024

Embryology is an essential component to understanding human anatomy. It requires an in‐depth understanding of 3D knowledge but is primarily taught with 2‐dimensional resources. In particular, the development of the human heart is a complex process and difficult to understand using traditional teaching methods. We present here a series of heart embryology models created to supplement embryology education and aid students in understanding this complex process. Using Polydoh moldable plastic, models representing six different critical steps in heart formation are described, including: the fusing of the heart tubes (days 21–23), beginning of the cardiac loop (early day 23), fully formed cardiac loop (late day 23), four‐week heart, formation of the endocardial cushions and septi (late fourth week), and heart with fully formed septi with functioning foramen ovale (sixth week). These models not only improve embryology education but also the understanding of heart pathologies. This method provides an affordable option for embryology education and provides students with learning tools that assist with the comprehension of the development of a complex organ.
Molecular Engineering Towards Efficient Aggregation‐Induced Delayed Fluorescence Luminogens as Emitters and Sensitizers for High‐Performance Organic Light‐Emitting Diodes
Authors: Wang Hongbo , Zou Peng , Xu Letian , Jiang Ruming , Shi Heping , Tang Ben Zhong , Zhao Zujin
Published: August 2024

Exploring efficient thermally‐activated delayed fluorescence materials having maximum external quantum efficiencies (ηext,maxs) exceeding 30 % for organic light‐emitting diodes (OLEDs) still remains challenging because it generally requires efficient reverse intersystem crossing (RISC), high photoluminescence quantum yield (ΦPL), and large optical out‐coupling efficiency (Φout) simultaneously. Herein, two green aggregation‐induced delayed fluorescence (AIDF) luminogens, named XTCz‐2 and XTCz‐3, are designed and constructed by using xanthone (XT) as electron acceptor and phenylcarbazole‐substituted carbazole as donors. XTCz‐2 and XTCz‐3 exhibit distinguished advantages of high thermal stability (439–560 °C), excellent ΦPLs (84–88 %) and fast RISC rates (1.9×105–4.2×105 s−1), and prefer horizontal dipole orientation and thus have high Φouts. Consequently, they can achieve the state‐of‐the‐art electroluminescence (EL) performances with ηext,maxs of up to 35.0 %. Moreover, XTCz‐3 is selected as a sensitizer for sky‐blue multi‐resonance delayed fluorescence emitter in hyperfluorescence OLEDs, providing narrow EL spectra and excellent ηext,maxs of up to 33.8 % with low efficiency roll‐offs. The splendid comprehensive performances demonstrate the significant application potential of these AIDF luminogens as both light‐emitting materials and sensitizers for OLEDs.
Stock market bubbles and the forecastability of gold returns and volatility
Authors: Gabauer David , Gupta Rangan , Karmakar Sayar , Nielsen Joshua
Published: August 2024

In this article, multi‐scale LPPLS confidence indicator approach is used to detect both positive and negative bubbles at short‐, medium‐, and long‐term horizons for the stock markets of the G7 and the BRICS countries. This enables detecting major crashes and rallies in the 12 stock markets over the period of the 1st week of January, 1973 to the 2nd week of September, 2020. Similar timing of strong (positive and negative) LPPLS indicator values across both G7 and BRICS countries was also observed, suggesting interconnectedness of the extreme movements in these stock markets. Next, these indicators were utilized to forecast gold returns and its volatility, using a method involving block means of residuals obtained from the popular LASSO routine, given that the number of covariates ranged between 42 and 72, and gold returns demonstrated a heavy upper tail. The finding was, these bubbles indicators, particularly when both positive and negative bubbles are considered simultaneously, can accurately forecast gold returns at short‐ to medium‐term, and also time‐varying estimates of gold returns volatility to a lesser extent. The results of this paper have important implications for the portfolio decisions of investors who seek a safe haven during boom‐bust cycles of major global stock markets.
Improving the extraction yield of essential oil from Pimenta dioica (L.) Merr. using Aspergillus niger ATCC 1004 enzyme blend
Authors: Tavares Iasnaia Maria de Carvalho , Santos Rândilla Regis Cordeiro dos , Costa Floriatan Santos , Jesus Gabriel Lucas Silva de , Sanches Alex‐William , Silva Fabiane Neves , Irfan Muhammad , Oliveira Rosilene Aparecida de , Franco Marcelo
Published: August 2024

The objective of this work was to optimize the application of an enzymatic blend produced by Aspergillus niger ATCC 1004 on the Pimenta dioica fruits for essential oil extraction. The enzyme blend was obtained from the fermentation of cocoa bean shells, an agro‐industrial residue. The effects of the enzymatic pre‐treatment on the extraction yield, the chemical composition of the oil through gas chromatography, and the fruit structure through scanning electron microscopy (SEM) were assessed. A Doehlert design was used to optimize the process conditions, resulting in an extraction with 117 mL of enzyme during 77 min, which increased the extraction yield by 387.5%. The chemical composition was not altered, which proves that the enzyme blend preserves the quality of the essential oil extracted. The content of eugenol (70%), the major compound in the P. dioica essential oil, had a great increase in its concentration (560%). The enzyme activity analyses showed the presence of endoglucanase (0.4 U/mL), exoglucanase (0.25 U/mL), β‐glucosidase (0.19 U/mL), and invertase (135.08 U/mL). The microscopy analyses revealed changes in the morphology of fruit surface due to the enzymatic action. These results demonstrate the great potential of using enzyme blends produced by filamentous fungi from agro‐industrial residues for the essential oils extraction of interest for the pharmaceutical and food industries.
Contamination in LIB Pouch Cells Promoting Self‐Discharge and Crosstalk
Authors: Löwe Robert , Smith Anna
Published: August 2024

Storage studies of lithium‐ion battery electrolyte within bags made of commercial pouch foils, commonly used as encasing material of battery cells, revealed the presence of contamination leaching from the pouch foil material into the electrolyte. By analyzing the stored electrolyte via GC‐MS the appearing compound was identified as 2,4‐di‐tert‐butylphenol (2,4‐DTBP). To investigate the influence of DTBP on the battery cell performance, full cells employing commercial LiNi1/3Mn1/3Co1/3O2 based cathodes and graphite‐type anodes were assembled using 1 M LiPF6 in ethylene carbonate/ dimethyl carbonate mixture as the electrolyte with/out the intentional addition of either 2,4‐DTBP or its constitutional isomer 2,6‐DTBP. Furthermore, dimethyl terephthalate (DMT), a literature known redox shuttle triggering impurity leaching from PET‐based fixing tape used in LIBs, was added to compare the effect of DMT to DTBPs. It was revealed that either DTBP contaminations have a significant impact on the self‐discharge behavior of the studied cells, which exceed the effect of present DMT. Moreover, all contaminants heavily increase transition metal dissolution‐migration‐deposition (TM DMD) processes and irreversible capacity loss. When vinylene carbonate, an SEI forming additive, is added to the electrolyte mixtures self‐discharge, as well as TM DMD are suppressed to a different degree depending on the type of contaminant added.