bluuebunny/crossref_metadata_2025 huggingface dataset:
Association of Maternal Depression During Pregnancy and Recent Stress With Brain Age Among Adult Offspring
Authors: Mareckova Klara , Mareček Radek , Jani Martin , Zackova Lenka , Andryskova Lenka , Brazdil Milan , Nikolova Yuliya S.
Published: January 2023

Importance

Maternal mental health problems during pregnancy are associated with altered neurodevelopment in offspring, but the long-term relationship between these prenatal risk factors and offspring brain structure in adulthood remains incompletely understood due to a paucity of longitudinal studies.

Objective

To evaluate the association between exposure to maternal depression in utero and offspring brain age in the third decade of life, and to evaluate recent stressful life events as potential moderators of this association.

Design, Setting, and Participants

This cohort study examined the 30-year follow-up of a Czech prenatal birth cohort with a within-participant design neuroimaging component in young adulthood conducted from 1991 to 2022. Participants from the European Longitudinal Study of Pregnancy and Childhood prenatal birth cohort were recruited for 2 magnetic resonance imaging (MRI) follow-ups, one between ages 23 and 24 years (early 20s) and another between ages 28 and 30 years (late 20s).

Exposures

Maternal depression during pregnancy; stressful life events in the past year experienced by the young adult offspring.

Main Outcomes and Measures

Gap between estimated neuroanatomical vs chronological age at MRI scan (brain age gap estimation [BrainAGE]) calculated once in participants’ early 20s and once in their late 20s, and pace of aging calculated as the differences between BrainAGE at the 2 MRI sessions in young adulthood.

Results

A total of 260 individuals participated in the second neuroimaging follow-up (mean [SD] age, 29.5 [0.6] years; 135 [52%] male); MRI data for both time points and a history of maternal depression were available for 110 participants (mean [SD] age, 29.3 [0.6] years; 56 [51%] male). BrainAGE in participants’ early 20s was correlated with BrainAGE in their late 20s (r = 0.7, P < .001), and a previously observed association between maternal depression during pregnancy and BrainAGE in their early 20s persisted in their late 20s (adjusted R2 = 0.04; P = .04). However, no association emerged between maternal depression during pregnancy and the pace of aging between the 2 MRI sessions. The stability of the associations between maternal depression during pregnancy and BrainAGE was also supported by the lack of interactions with recent stress. In contrast, more recent stress was associated with greater pace of aging between the 2 MRI sessions, independent of maternal depression (adjusted R2 = 0.09; P = .01).

Conclusions and Relevance

The findings of this cohort study suggest that maternal depression and recent stress may have independent associations with brain age and the pace of aging, respectively, in young adulthood. Prevention and treatment of depression in pregnant mothers may have long-term implications for offspring brain development.
Initiation of and Escalation to High-Intensity Drinking in Young Adults
Authors: Patrick Megan E. , Evans-Polce Rebecca J. , Arterberry Brooke J. , Terry-McElrath Yvonne
Published: January 2023

Importance

High-intensity drinking (HID) (≥10 drinks in a row) is associated with acute negative outcomes. Identifying factors associated with HID initiation in adolescence and how it is associated with young adulthood outcomes can inform screening and prevention.

Objective

To identify when individuals initiate HID and speed of escalation from first drink and first binge to first HID; characteristics associated with initiation and escalation; and whether these characteristics are associated with weekly alcohol consumption, HID frequency, and symptoms of alcohol use disorder at age 20 years.

Design, Setting, and Participants

This cohort study analyzed web-based survey data from respondents in the US who reported alcohol use in the past 30 days recruited from the 2018 12th grade Monitoring the Future study and surveyed again from February 14 through April 17, 2020, at modal age 20 years in the Young Adult Daily Life Study. Only respondents who reported HID by modal age 20 years were included in the analyses.

Exposures

Retrospective alcohol use initiation and self-reported alcohol use measures.

Main Outcomes and Measures

Key retrospective measures included year of initiation for alcohol, first binge (≥5 drinks), and HID (≥10 drinks). Measures at age 20 years included weekly alcohol consumption, HID frequency, and Alcohol Use Disorders Identification Test (AUDIT) scores. Covariates included biologic sex, race and ethnicity, parental college education, family history of alcohol problems, and college status. Descriptive statistics and multivariable regression models were used, and all analyses were weighted.

Results

Of the 451 participants with data eligible for analysis, 62.0% were male (38.0% female). On average, alcohol, binge, and HID were initiated during high school. Mean time of escalation from first drink to first HID was 1.9 (95% CI, 1.8-2.1) years and between first binge and first HID, 0.7 (95% CI, 0.6-0.8) years. Initiating HID by grade 11 (vs later) was associated with higher average weekly alcohol consumption (adjusted incidence rate ratio [aIRR], 1.40; 95% CI, 1.10-1.79]), HID frequency (aIRR, 2.01; 95% CI, 1.25-3.22]), and AUDIT score (adjusted odds ratio, 1.17; 95% CI, 1.02-1.34]) at age 20 years. Escalation from first binge to first HID in the same year (vs ≥1 year) was associated with higher HID frequency at age 20 years (aIRR, 1.66; 95% CI, 1.06-2.61).

Conclusions and Relevance

These findings suggest that understanding ages and patterns of HID initiation and escalation associated with particular risk may facilitate screening for adolescents and young adults.
Efficacy and Safety of Dietary Therapies for Childhood Drug-Resistant Epilepsy
Authors: Devi Nagita , Madaan Priyanka , Kandoth Nidhun , Bansal Dipika , Sahu Jitendra Kumar
Published: January 2023

Importance

Despite advances in the understanding of dietary therapies in children with drug-resistant epilepsy, no quantitative comparison exists between different dietary interventions.

Objective

To evaluate the comparative efficacy and safety of various dietary therapies in childhood drug-resistant epilepsy.

Data Sources

Systematic review and network meta-analysis (frequentist) of studies in PubMed, Embase, Cochrane, and Ovid published from inception to April 2022 using the search terms ketogenic diet, medium chain triglyceride diet, modified Atkins diet, low glycemic index therapy, and refractory epilepsy.

Study Selection

Randomized clinical trials comparing different dietary therapies (ketogenic diet, modified Atkins diet, and low glycemic index therapy) with each other or care as usual in childhood drug-resistant epilepsy were included. Abstract, title, and full text were screened independently by 2 reviewers.

Data Extraction and Synthesis

Data extraction was conducted following Preferred Reporting Items for Systematic Reviews and Meta-analyses reporting guideline. Cochrane risk-of-bias tool was used to assess the study quality. Effect sizes were calculated as odds ratio with 95% CI using random-effects model. The hierarchy of competing interventions was defined using the surface under the cumulative ranking curve.

Main Outcomes and Measures

Short-term (≤3 months) 50% or higher and 90% or higher reduction in seizure frequency and treatment withdrawal due to adverse events were the primary efficacy and safety outcomes.

Results

Of 2158 citations, 12 randomized clinical trials (907 patients) qualified for inclusion. In the short term, all dietary interventions were more efficacious than care as usual for 50% or higher seizure reduction (low glycemic index therapy: odds ratio [OR], 24.7 [95% CI, 5.3-115.4]; modified Atkins diet: OR, 11.3 [95% CI, 5.1-25.1]; ketogenic diet: OR, 8.6 [95% CI, 3.7-20.0]), while ketogenic diet (OR, 6.5 [95% CI, 2.3-18.0]) and modified Atkins diet (OR, 5.1 [95% CI, 2.2-12.0]) were better than care as usual for seizure reduction of 90% or higher. However, adverse event–related discontinuation rates were significantly higher for ketogenic diet (OR, 8.6 [95% CI, 1.8-40.6]) and modified Atkins diet (OR, 6.5 [95% CI, 1.4-31.2]) compared with care as usual. Indirectly, there was no significant difference between dietary therapies in efficacy and safety outcomes.

Conclusions and Relevance

This study found that all dietary therapies are effective in the short term. However, modified Atkins diet had better tolerability, higher probability for 50% or higher seizure reduction, and comparable probability for 90% or higher seizure reduction and may be a sounder option than ketogenic diet. Direct head-to-head comparison studies are needed to confirm these findings.
Renenutet
Authors: Gillam Robyn
Published: January 2023

Renenutet, long identified as a nurturing snake deity watching over crops, originally safeguarded manufactured produce and goods stored in magazines and treasuries. Her Middle Kingdom temple in the Fayyum connected her directly with agriculture, wheat and viticulture in the early New Kingdom. In the later New Kingdom she was worshiped by the non‐elite, with stelae and votives. Many uninscribed cobra figurines from this period may represent other snake deities besides Renenutet. In the Ptolemaic period, her Greek form, Thermouthis, was identified with Isis as a universal god. Her worship continued into Roman times.
Effect of Systemic Lupus Erythematosus and Immunosuppressive Agents on COVID‐19 Vaccination Antibody Response
Authors: Petri Michelle , Joyce Daniel , Haag Kristin , Fava Andrea , Goldman Daniel W. , Zhong Diana , Xiao Shaoming , Milstone Aaron , Magder Laurence S.
Published: January 2023

Objective

The risk of COVID‐19 infection is increased in patients with systemic lupus erythematosus (SLE) versus those without SLE. Some immunosuppressive medications increase COVID‐19 infection and decrease the efficacy of vaccination. Consensus documents have suggested management strategies for handling immunosuppressive medications to increase vaccine efficacy, but the benefit of such strategies has not been proven. The current study was undertaken to determine the effect of immunosuppressive drugs on vaccine response in SLE.

Methods

We collected information on COVID‐19 infection, vaccination history, and COVID‐19 antibodies in the Hopkins Lupus Cohort. A cohort of health care workers was used for comparison. Outcome measures included SARS–CoV‐2 antibody IgG levels after vaccination over time in both cohorts and effect of immunosuppressive medications on postvaccination IgG levels in SLE patients.

Results

The analysis was based on 365 observations from 334 different patients in the SLE cohort, and 2,235 observations from 1,887 different health care workers. SLE patients taking immunosuppressive medications had lower vaccine IgG levels than SLE patients who were not; but both groups had lower levels than health care workers. Holding mycophenolate for 1 week after vaccination increased postvaccine IgG levels significantly without leading to clinical flares. In multiple variable models, mycophenolate mofetil, tacrolimus, and belimumab all significantly reduced antibody response to vaccination.

Conclusion

SLE patients, regardless of background immunosuppressive therapy, had lower vaccine IgG levels than health care workers. Mycophenolate, tacrolimus, and belimumab significantly reduced IgG response to vaccination. Holding mycophenolate for 1 week improved vaccine efficacy, providing clinical benefit on vaccine response without leading to clinical flares.
Disturbance rejection enhancement using predictive control for the fixed‐wing UAV with multiple ailerons
Authors: Sattar Abdul , Wang Liuping , Ansari Shahzeb , Hoshu Ayaz Ahmed , Khan Shah Khalid
Published: January 2023

The performance of small fixed‐wing unmanned aerial vehicles (UAVs) is easily degraded by exogenous disturbances. In an attempt to improve the performance, the structural change is made in conventional small fixed‐wing UAV through segmentation of each aileron control surface into multiples. Detailed system identification experiments are performed on each aileron pair in the wind tunnel to acquire linear dynamic models for the roll attitude of the UAV. These experiments have provided the transfer functions for the aileron control surfaces based on corresponding frequency response. Three distinctive model predictive controllers are designed and deployed in real‐time hardware to achieve the roll attitude control. The roll attitude control experiments are validated in wind tunnel under both normal and turbulent environments. The results show that multiple input and single output control system provides significant improvement in the roll attitude and disturbance rejection performance. The collective actuation of multiple control surfaces improves roll stability by to when compared to the single aileron pair based conventional control in the presence of turbulent flight conditions.
Controlling Magnetic Anisotropy in Amplitude Expansion of Phase Field Crystal Model
Authors: Backofen Rainer , Salvalaglio Marco , Voigt Axel
Published: January 2023

The amplitude expansion for a magnetic phase‐field‐crystal (magnetic APFC) model enables a convenient coarse‐grained description of crystalline structures under the influence of magnetic fields. Considering higher‐order magnetic coupling terms, the possibility of tuning the magnetic anisotropy in these models is demonstrated. This allows reproducing the easy and hard directions of magnetization. Such a result can be achieved without increasing the computational cost, enabling simulations of the manipulation of dislocation networks and microstructures in ferromagnetic materials. As a demonstration, the simulation of the shrinkage of a spherical grain with the magnetic anisotropy of Fe is reported.
Constructing Flexible Film Electrode with Porous Layered Structure by MXene/SWCNTs/PANI Ternary Composite for Efficient Low‐Grade Thermal Energy Harvest
Authors: Wei Shouhao , Ma Jiale , Wu Dianlun , Chen Bin , Du Chunyu , Liang Lirong , Huang Yang , Li Zhenyu , Rao Feng , Chen Guangming , Liu Zhuoxin
Published: January 2023

Thermal energy, constituting the majority of the energy lost through various inefficiencies, is abundant and ubiquitous. With thermogalvanic effect, thermocells (TECs) can directly convert thermal energy into electricity without producing vibration, noise or other waste emissions. This work presents a rational design of flexible film electrodes constructed on a ternary composite of Ti3C2Tx MXene (Tx represents surface terminations), polyaniline (PANI) and single‐wall carbon nanotubes for TECs, which exhibit notably enhanced thermoelectrochemical performance compared to the widely adopted noble platinum electrodes. The ternary composite electrodes form a porous layered structure with a large electrochemical‐active surface area. Experiment and simulation results reveal that synergistic effects of Ti3C2Tx and PANI are induced for promoting both mass and charge transport at the electrolyte‐electrode interface, resulting in a TEC with an output power of 13.15 µW cm−2 at the ΔT of 40 K. The TEC also shows a rapid response to the small temperature difference between the human body and the ambient, demonstrating high potential in harvesting low‐grade heat to power small electronics.
Stable, Cost‐Effective TiN‐Based Plasmonic Nanocomposites with over 99% Solar Steam Generation Efficiency
Authors: Wang Yong , Liu Xiaolei , Zhang Qingzhe , Wang Chen , Huang Shengyun , Liu Yannan , Yu Ting , Yang Ruiqi , Chen Guozhu , Chaker Mohamed , Ma Dongling
Published: January 2023

Plasmonic nanoparticles (NPs), such as Au, Ag, and Cu, are considered as promising photothermal materials and attract extensive attention for freshwater production by solar steam generation. However, high cost, narrow absorption range and/or poor stability greatly limit their practical applications. Herein, a high‐efficiency solar energy conversion material consisting of low‐cost non‐metal, extremely thermally‐stable plasmonic TiN NPs and hydrophilic semi‐reduced graphene oxide (semi‐rGO), with broadband solar absorption capability, by a fast in situ microwave reduction method is prepared. The 2D semi‐rGO serves as a support for the loading of plasmonic NPs, and meanwhile accelerates the transport and evaporation of water due to its hydrophilicity. Then, decoration of plasmonic TiN NPs further enhances the solar photon absorption and hydrophilicity while suppressing the heat loss, thanks to the layered structure of TiN/semi‐rGO, improving overall solar energy utilization. Owing to the enhanced absorption and unique layered nanostructure with strong interfacial interaction, the optimal sample of TiN/semi‐rGO‐25% absorber achieves a high and stable water evaporation rate of ≈1.76 kg m−2 h−1 with an energy efficiency as high as 99.1% under 1 sun illumination. Furthermore, this plasmonic TiN/semi‐rGO absorber is capable of producing high‐quality freshwater from sustainable seawater desalination and wastewater purification processes.
Crystallographic Insight of Reduced Lattice Volume Expansion in Mesoporous Cu2+‐Doped TiNb2O7 Microspheres during Li+ Insertion
Authors: Yang Chengfu , Ma Dongwei , Yang Jing , Manawan Maykel , Zhao Ting , Feng Yuanyuan , Li Jiahui , Liu Zhongzhu , Zhang Yong‐Wei , Von Dreele Robert B. , Toby Brian H. , Albarrán Carlos Ponce de León , Pan Jia Hong
Published: January 2023

TiNb2O7 represents a promising anode material for lithium‐ion batteries (LIBs), but its practical applications are currently hampered by the non‐negligible volumetric expansion and contraction during the charge/discharge process and the sluggish ion/electron kinetics. A combination technique is reported by systematically optimizing the porous and spherical morphology, crystal structure, and surface decoration of mesoporous Cu2+‐doped TiNb2O7 microspheres to enhance the electrochemical Li+ storage performance and stability simultaneously. The Cu2+ dopants preferentially replace Ti4+ in crystal lattices, which decreases the Li+ diffusion barrier and increases the electronic conductivity, as confirmed by density functional theory (DFT) calculation and demonstrated by diverse electrochemical characterizations. The successful Cu2+ doping significantly reduces the lattice expansion coefficient from 7.26% to 4.61% after Li+ insertion along the b‐axis of TiNb2O7, as visualized from in situ and ex situ XRD analysis. The optimal 5% Cu2+‐doped TiNb2O7 with surface coating of N‐doped carbon exhibits significantly enhanced specific capacity and rate and cyclic performances in both half‐ and full‐cell configurations, demonstrating an excellent electrochemical behavior for fast‐charging LIB applications.
Sonication‐Responsive Organic Afterglow Emulsions
Authors: Deng Xinjian , Huang Ju , Li Jiuyang , Wang Guangming , Zhang Kaka
Published: January 2023

In contrast to their fluorescence counterparts, stimuli‐responsive organic afterglow materials display distinct advantages to function normally in the presence of strong fluorescence background. However, most of the stimuli‐responsive afterglow materials can only work in their solid states with those in aqueous medium being rarely reported. In addition, the types of these materials are limited to mechanical force‐, pH‐, ion‐, and temperature‐responsive ones. Here, a serendipitous finding of sonication‐responsive organic afterglow emulsions in aqueous medium is reported. The afterglow emulsions are produced by dopant‐matrix strategy and emulsion technique. In‐depth studies reveal that the key to achieve the sonication responsiveness is the selection of a specialized organic matrix that can form microcrystalline particles in aqueous medium with the aid of surfactants. In matrix's microcrystalline state, the triplet excited states of luminescent dopant within the matrix can be protected to exhibit room‐temperature afterglow. Under sonication, matrix's microcrystalline structure can be disrupted and consequently the triplet excited states of luminescent dopants lose protection to show afterglow quenching. To the best of the authors’ knowledge, this study represents the first report of sonication‐responsive afterglow materials in aqueous medium, which show promising biomedical applications.
Tumor Cell Nanovaccines Based on Genetically Engineered Antibody‐Anchored Membrane
Authors: Li Yuanke , Zhang Haoqi , Wang Ruikun , Wang Yuan , Li Ruonan , Zhu Mingsheng , Zhang Xiangyun , Zhao Zhen , Wan Yajuan , Zhuang Jie , Zhang Hongkai , Huang Xinglu
Published: January 2023

Despite the promise in whole‐tumor cell vaccines, a key challenge is to overcome the lack of costimulatory signals. Here, agonistic‐antibody‐boosted tumor cell nanovaccines are reported by genetically engineered antibody‐anchored membrane (AAM) technology, capable of effectively activating costimulatory pathways. Specifically, the AAM can be stably constructed following genetic engineering of tumor cell membranes with anti‐CD40 single chain variable fragment (scFv), an agonistic antibody to induce costimulatory signals. The nanovaccines are versatilely designed and obtained based on the anti‐CD40 scFv‐anchored membrane and nanotechnology. Following vaccination, the anti‐CD40 scFv‐anchored membrane nanovaccine (Nano‐AAM/CD40) significantly facilitates dendritic cell maturation in CD40‐humanized transgenic mice and subsequent adaptive immune responses. Compared to membrane‐based nanovaccines alone, the enhanced antitumor efficacy in both “hot” and “cold” tumor models of the Nano‐AAM/CD40 demonstrates the importance of agonistic antibodies in development of tumor‐cell‐based vaccines. To expand the design of nanovaccines, further incorporation of cell lysates into the Nano‐AAM/CD40 to conceptually construct tumor cell‐like nanovaccines results in boosted immune responses and improved antitumor efficacy against malignant tumors inoculated into CD40‐humanized transgenic mice. Overall, this genetically engineered AAM technology provides a versatile design of nanovaccines by incorporation of tumor‐cell‐based components and agonistic antibodies of costimulatory immune checkpoints.
Graphene Induced High Thermoelectric Performance in ZnO/Graphene Heterostructure
Authors: Marfoua Brahim , Hong Jisang
Published: January 2023

Despite the low thermoelectric (TE) efficiency of graphene, its flexibility features are attractive for flexible and wearable next‐generation thermoelectric applications. So, it will be highly desirable to synthesize graphene‐based high TE material. Hence, the possibility of significant enhancement of the TE performance in ZnO/graphene heterostructure is investigated. The ZnO monolayer has a direct band gap of 3.3 eV, while a band gap of 5 meV in the ZnO/graphene heterostructure is found. The highest ZT ≈ 2.4 in the n‐doped ZnO/graphene heterostructure at 500 K is obtained, whereas the ZnO monolayer shows ZT ≈ 1.3 at 700 K. Particularly, this giant ZT in the ZnO/graphene heterostructure is found even at a low carrier concentration (≈1011 carrier cm−2). Besides, the ZnO/graphene heterostructure also displays a ZT ≈ 0.8 even at 300 K with a very low carrier concentration (≈1010 carrier cm−2). This outstanding TE performance originates from the TE coefficient advantages of each layer; high electrical conductivity from graphene and high Seebeck coefficient from ZnO incorporate with reduced thermal conductivity in the heterostructure. The findings will stimulate further studies to confirm the results as well as the development of flexible TE generators based on graphene for Internet of things thermoelectric applications.
An Eutectic Gel Based on Polymerizable Deep Eutectic Solvent with Self‐Adhesive, Self‐adaptive Cold and High Temperature Environments
Authors: Wang Rixuan , Chen Picheng , Zhou Xinjie , Sun Luyang , Wang Guoqing , Liu Yuetao , Gao Chuanhui
Published: January 2023

Ionic conductors have a wide range of development prospects in the field of flexible wearable electronics. The polymerizable deep eutectic solvent is more economical, resistant to extreme temperature, and less toxic than the traditional hydrogels and ionic liquids. In this paper, the supramolecular eutectic gel is prepared by introducing glycol/choline chloride deep eutectic solvent into acrylamide/choline chloride deep eutectic solvent as “hydrogen bond cross‐linking density regulator”. Deep eutectic solvents give eutectic gels the ability to resist the low (‐25 °C) and high (60 °C) temperatures. By introducing 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid into the gel, the adhesion ability of gel on copper sheet can reach 90 kPa and shows good reusability. Due to the complex hydrogen bond interaction in the gel, it has good mechanical properties (strain up to 2300%, stress up to 0.21 MPa). In addition, the ionic conductivity of the gel can reach 0.22 ms cm−1 due to the presence of choline chloride. In addition, since the polymerization is triggered quickly under UV light, this allowed us to print gels of any shape on any surface. Such deep eutectic gels with self‐adhesion, intrinsic conductivity, excellent mechanical properties and extreme temperature resistance may have a wide range of applications in the field of motion sensors.
Injectable Polysaccharide Hydrogels as Localized Nitric Oxide Delivery Formulations
Authors: Feura Evan S. , Maloney Sara E. , Conlon Ivie L. , Broberg Christopher A. , Yang Feichen , Schoenfisch Mark H.
Published: January 2023

A series of injectable polysaccharide hydrogels are prepared with oxidized dextran and diethylenetriamine‐modified carboxymethylcellulose (CMC) or hyaluronic acid (HA). Rheological evaluation reveals that CMC‐based hydrogels achieve storage moduli >1 kPa when prepared from 5 wt% solutions, while storage moduli >100 Pa are achievable from solutions with concentrations as low as 2 wt%. HA‐based hydrogels demonstrate smaller storage moduli but have swelling ratios more than four‐fold that of CMC systems at equal concentrations. The incorporation of N‐diazeniumdiolate nitric oxide (NO) donors into the hydrogels results in reduced hydrogel storage moduli as a function of NO donor concentration. The impact of the hydrogel architecture on NO‐release kinetics proves dependent on the identity of the NO donor. Hydrogel degradation over 14 d indicates that HA‐based hydrogels degrade more rapidly than CMC hydrogels and that the addition of NO to the hydrogels increases the rate at which they degrade. In vitro cytotoxicity of hydrogel extracts is minimal, with toxicity observed only at high NO‐donor concentrations for select cell lines. The diverse properties, versatility, and nontoxic characteristics of these injectable hydrogels should facilitate local delivery of nitric oxide for a range of biomedical applications.
“Z”‐Type Tilted Quasi‐One‐Dimensional Assembly of Actinide‐Embedded Coinage Metal Near‐Plane Superatoms and Their Optical Properties
Authors: Huang Wanrong , Yu Famin , Zhu Yu , Wang Rui , Li Jiarui , Zhang Sean Xiao‐An , Wang Zhigang
Published: January 2023

In this work, a novel discovery that the coinage‐metal near‐plane superatoms (CM‐NPSs) formed by embedding actinide elements into the coinage metal rings can realize the “Z”‐type tilted quasi‐one‐dimensional (1D) direct assembly is reported. This success can be attributed to the strong bonding between the overlapping parts of adjacent superatomic motifs. First‐principles calculations reveal that the motifs maintain their geometric and electronic structures robustly during the assembly process. With the accumulation of motifs, the intensity of the absorption peak increases continuously in the ultraviolet‐visible (UV‐Vis) absorption spectra range of 300–450 nm, resulting in the hyperchromic effect, which is closely related to the degree of the participation of Th atoms. Furthermore, the absorption spectra show a continuously tunable feature in the 450–900 nm range, as the interlayer stacking pattern leads to a pronounced redshift. More importantly, the valence 5f‐shells of Th atoms have an increased contribution to the final orbitals of electronic transition, which demonstrates the advantages of the active high angular momentum electrons of actinide elements in spectral properties. These findings provide a valuable reference for the direct artificial assembly of near‐plane superatoms and optical properties of superatomic assemblies embedded with rare elements.
Rapid and Energy‐Efficient Synthesis of Disordered Rocksalt Cathodes
Authors: Wu Vincent C. , Evans Hayden A. , Giovine Raynald , Preefer Molleigh B. , Ong Julia , Yoshida Eric , Cabelguen Pierre‐Etienne , Clément Raphaële J.
Published: January 2023

Lithium‐rich transition metal oxides with a cation‐disordered rocksalt structure (disordered rocksalt oxides or DRX) are promising candidates for sustainable, next‐generation Li‐ion cathodes due to their high energy densities and compositional flexibility, enabling Co‐ and Ni‐free battery chemistries. However, current methods to synthesize DRX compounds require either high temperature (≈1000 °C) sintering for several hours, or high energy ball milling for several days in an inert atmosphere. Both methods are time‐ and energy‐intensive, limiting the scale up of DRX production. The present study reports the rapid synthesis of various DRX compositions in ambient air via a microwave‐assisted solid‐state technique resulting in reaction times as short as 5 min, which are more than two orders of magnitude faster than current synthesis methods. The DRX compounds synthesized via microwave are phase‐pure and have a similar short‐ and long‐range structure as compared to DRX materials synthesized via a standard solid‐state route, resulting in nearly identical electrochemical performance. In some cases, microwave heating allows for better particle size and morphology control. Overall, the rapid and energy‐efficient microwave technique provides a more sustainable route to produce DRX materials, further incentivizes the development of next‐generation DRX cathodes, and is key to accelerating their optimization via high‐throughput studies.
Supramolecular Polyphenol‐DNA Microparticles for In Vivo Adjuvant and Antigen Co‐Delivery and Immune Stimulation
Authors: Qu Yijiao , De Rose Robert , Kim Chan‐Jin , Zhou Jiajing , Lin Zhixing , Ju Yi , Bhangu Sukhvir Kaur , Cortez‐Jugo Christina , Cavalieri Francesca , Caruso Frank
Published: January 2023

DNA‐based materials have attracted interest due to the tunable structure and encoded biological functionality of nucleic acids. A simple and general approach to synthesize DNA‐based materials with fine control over morphology and bioactivity is important to expand their applications. Here, we report the synthesis of DNA‐based particles via the supramolecular assembly of tannic acid (TA) and DNA. Uniform particles with different morphologies are obtained using a variety of DNA building blocks. The particles enable the co‐delivery of cytosine‐guanine adjuvant sequences and the antigen ovalbumin in model cells. Intramuscular injection of the particles in mice induces antigen‐specific antibody production and T cell responses with no apparent toxicity. Protein expression in cells is shown using capsules assembled from TA and plasmid DNA. This work highlights the potential of TA as a universal material for directing the supramolecular assembly of DNA into gene and vaccine delivery platforms.
A Two‐Dimensional Porphyrin Coordination Supramolecular Network Cathode for High‐Performance Aqueous Dual‐Ion Battery
Authors: Tan Yuanming , Chen Zhao , Tao Zengren , Wang Anding , Lai Shimei , Yang Yangyi
Published: January 2023

Iodine has great potential in the energy storage, but high solubility of I3− has seriously delayed its promotion. Benefited from abundant active sites and the open channel, two‐dimensional coordination supramolecular networks (2D CSNs) is considered to be a candidate for the energy storage. Herein, a 2D porphyrin‐CSN cathode named Zn‐TCPP for aqueous iodine dual‐ion battery (DIB) shows an excellent specific capacity of 278 mAh g−1, and a high energy density of 340 Wh kg−1 at 5 A g−1, as well as a durable cycle performance of 5000 cycles and a high Coulombic efficiency of 98 %. Molecular orbital theory, UV/VIS, Raman spectroscopy and density functional theory (DFT) calculations reveal charge‐transfer interaction between the donor of porphyrin nitrogen and the acceptor of I3−, and computational fluid dynamics (CFD) simulations demonstrate the contribution of 2D layered network structure of Zn‐TCPP to the penetration of I3−.
Sterically Hindered and Deconjugative α‐Regioselective Asymmetric Mannich Reaction of Meinwald Rearrangement‐Intermediate
Authors: Xu Jinxiu , Song Yanji , Yang Jia , Yang Bingqian , Su Zhishan , Lin Lili , Feng Xiaoming
Published: January 2023

Compared to γ‐addition, the α‐addition of α‐branched β,γ‐unsaturated aldehydes faces larger steric hindrance and disrupts the π–π conjugation, which might be why very few examples are reported. In this article, a highly diastereo‐ and enantioselective α‐regioselective Mannich reaction of isatin‐derived ketimines with α‐, β‐ or γ‐branched β,γ‐unsaturated aldehydes, generated in situ from Meinwald rearrangement of vinyl epoxides, is realized by using chiralN,N′‐dioxide/ScIIIcatalysts. A series of chiral α‐quaternary allyl aldehydes and homoallylic alcohols with vicinal multisubstituted stereocenters are constructed in excellent yields, good d.r. and excellenteevalues. Experimental studies and DFT (density functional theory) calculations reveal that the large steric hindrance of the ligand and the Boc (tButyloxy carbonyl) protecting group of imines are critical factors for the α‐regioselectivity.
Influencing Factors on Li‐ion Conductivity and Interfacial Stability of Solid Polymer Electrolytes, Exampled by Polycarbonates, Polyoxalates and Polymalonates
Authors: Xie Xiaoxin , Wang Zhaoxu , He Shuang , Chen Kejun , Huang Qiu , Zhang Peng , Hao Shu‐Meng , Wang Jiantao , Zhou Weidong
Published: January 2023

The application of solid polymer electrolytes (SPEs) in all‐solid‐state(ASS) batteries is hindered by lower Li+‐conductivity and narrower electrochemical window. Here, three families of ester‐based F‐modified SPEs of poly‐carbonate (PCE), poly‐oxalate (POE) and poly‐malonate (PME) were investigated. The Li+‐conductivity of these SPEs prepared from pentanediol are all higher than the counterparts made of butanediol, owing to the enhanced asymmetry and flexibility. Because of stronger chelating coordination with Li+, the Li+‐conductivity of PME and POE is around 10 and 5 times of PCE. The trifluoroacetyl‐units are observed more effective than −O−CH2−CF2−CF2−CH2−O− during the in situ passivation of Li‐metal. Using trifluoroacetyl terminated POE and PCE as SPE, the interfaces with Li‐metal and high‐voltage‐cathode are stabilized simultaneously, endowing stable cycling of ASS Li/LiNi0.6Co0.2Mn0.2O2(NCM622) cells. Owing to an enol isomerization of malonate, the cycling stability of Li/PME/NCM622 is deteriorated, which is recovered with the introduce of dimethyl‐group in malonate and the suppression of enol isomerization. The coordinating capability with Li+, molecular asymmetry and existing modes of elemental F, are all critical for the molecular design of SPEs.
Electrothermal Water‐Gas Shift Reaction at Room Temperature with a Silicomolybdate‐Based Palladium Single‐Atom Catalyst
Authors: Chang Jinquan , Hülsey Max J. , Wang Sikai , Li Maoshuai , Ma Xinbin , Yan Ning
Published: January 2023

The water‐gas shift (WGS) reaction is often conducted at elevated temperature and requires energy‐intensive separation of hydrogen (H2) from methane (CH4), carbon dioxide (CO2), and residual carbon monoxide (CO). Designing processes to decouple CO oxidation and H2 production provides an alternative strategy to obtain high‐purity H2 streams. We report an electrothermal WGS process combining thermal oxidation of CO on a silicomolybdic acid (SMA)‐supported Pd single‐atom catalyst (Pd1/CsSMA) and electrocatalytic H2 evolution. The two half‐reactions are coupled through phosphomolybdic acid (PMA) as a redox mediator at a moderate anodic potential of 0.6 V (versus Ag/AgCl). Under optimized conditions, our catalyst exhibited a TOF of 1.2 s−1 with turnover numbers above 40 000 mol
 molPd−1 achieving stable H2 production with a purity consistently exceeding 99.99 %.
Synthesis and application of a novel self‐smart sensor based on a modified amino‐functionalized Zr‐metal–organic framework for rapid and selective detection of some toxic metals in wastewater
Authors: El‐Bindary Mohamed A. , Shahat Ahmed , El‐Deen Ibrahim M. , El‐Afify Maher A. M. , Hassan Nader
Published: January 2023

In this study, a simple optical luminescence smart sensor derived from organic ligand‐based metal–organic framework material with high oxidation state central metal (Zr4+) was developed. It also was screened to achieve Fe3+, Pb2+, and Co2+ sensitive detection through the strong coordination of amino groups or nitrogen center with 2‐acetylpyridine ligand. The intrinsic optical and fluorescence intensities of sensor were regulated by the ligand‐to‐metal charge transfer effect. The new sensor exhibits an excellent selectivity, ultrafast detection of Fe3+, Pb2+, and Co2+ ions in water with good detection limits (LODs and LOQs). Fluorometric and UV–Vis absorption spectroscopies were used to conduct the study. Brunauer, Emmett, and Teller, Fourier transform infrared (FT‐IR); X‐ray diffraction spectrometry; and X‐ray Photoelectron Spectroscopy were used to confirm the structure of the novel sensor. A real industrial wastewater sample was investigated against the synthesized sensor with a powerful detection efficiency.
New phosphonium bromobismuthate as selective catalytic reagent in the heterocyclization reactions
Authors: Salmasi Reihaneh , Gholizadeh Mostafa , Salimi Alireza , Izadyar Mohammad , Nokhbeh Seyed Reza
Published: January 2023

A new hybrid phosphonium bromobismuthate compound was synthesized and characterized by 1H NMR, 13C NMR, 31P NMR, FT‐IR, differential scanning calorimetry (DSC) and single‐crystal X‐ray diffraction analysis. The crystal packing structures of title compound were stabilized by various intermolecular interactions especially of the type CH···Br hydrogen bonds between phosphonium cations and [Bi2Br9]3− anion. The relative contribution of various close contacts and 2D fingerprint plots of title compound and three analogous structures obtained from Cambridge Structural Database (CSD) were investigated by Hirshfeld surface analysis. Furthermore, the catalytic activity of title compound was investigated in heterocyclization reaction for the synthesis of significant and pharmacologically useful benzimidazole and benzoxazole derivatives. The results indicated that the yields of the product for aldehydes bearing p‐substituents and o‐substituents were higher than for m‐substituent ones. In addition to selectivity, simplicity of operation, waste minimization, ease of manipulation, short reaction time, excellent yield of product, and easy workup, this technique uses title compound as the catalyst, which is green, recyclable, soft, remarkably nontoxic, and easy to handle.
A facile strategy to construct multifunctional microencapsulated urea ammonium polyphosphate for epoxy resins towards satisfied fire safety, thermal stability and compatibility
Authors: Yi Liang , Long Miaotian , Yan Long , Tang Xinyu , Liao Jiahao
Published: January 2023

Enhancing the fire safety of epoxy resin (EP) concomitant with less mechanical performance degradation is still a challenge for traditional flame retardants. Hence, polypyrrole (PPy) was used as a film material to fabricate microencapsulated urea ammonium polyphosphate (UAPP) for simultaneously improving the fire safety, thermal stability and compatibility of epoxy composites. The obtained polypyrrole‐coated urea ammonium polyphosphate (PPy‐UAPP) at a load of 10 wt% endows the EP with a UL94 V‐0 rating and a limiting oxygen index (LOI) value of 32.3%, while 10 wt% ammonium polyphosphate (APP) only endows EP with a LOI of 28.5%. Furthermore, the peak heat release rate (PHRR) and peak smoke production rate (PSPR) of EP containing 10 wt% PPy‐UAPP are decreased by 12.3% and 21.4% compared to EP containing 10 wt% APP. The decreased fire hazard of EP/PPy‐UAPP is attributed to the reduction of hazardous gases including CO2 and CO and the generation of more incombustible gases including H2O and NH3 to reduce the combustion intensity. Meanwhile, the good compatibility between EP matrix and PPy‐UAPP endows the resulting EP composites with a superior balance between fire safety and mechanical properties.
The catalytic degradation of dyes using polyethersulfone/poly(vinylidene fluoride)/copper oxide composite nanofibers
Authors: Mapazi Odwa , Matabola Phillemon , Mokhena Teboho , van der Walt Hendriëtte
Published: January 2023

This work reports on the synthesis of copper oxide (CuO) nanoparticles and its incorporation into the polyethersulfone/poly(vinylidene fluoride) (PES/PVDF) nanofibers for both antibacterial and dyes degradation purposes. Transmission electron microscopy (TEM), X‐ray diffraction (XRD), ultraviolet (UV) and scanning electron microscope (SEM) characterized the materials' morphology and structure. Most notably, the CuO NPs exhibited low to mild toxicity toward different types of cells. The synthesis of CuO NPs and their subsequent incorporation into the PES/PVDF nanofibers was also successful, as illustrated by TEM, XRD and SEM characterizations. Moreover, the degradation and antibacterial studies were done using the methyl orange/coomassie blue dyes and E. coli bacterial strain, respectively. With respect to antibacterial properties, the CuO nanoparticles performed better as compared to the PES/PVDF/CuO composites. Furthermore, the bare nanoparticles emerged as excellent catalysts in comparison to the decorated nanofibers.
Identification of Cell‐Specific Differential DNA Methylation Associated With Methotrexate Treatment Response in Rheumatoid Arthritis
Authors: Adams Cameron , Nair Nisha , Plant Darren , Verstappen Suzanne M. M. , Quach Hong L. , Quach Diana L. , Carvidi Alex , Nititham Joanne , Nakamura Mary , Graf Jonathan , Barton Anne , Criswell Lindsey A. , Barcellos Lisa F.
Published: January 2023

Objective

We undertook this study to estimate changes in cell‐specific DNA methylation (DNAm) associated with methotrexate (MTX) response using whole blood samples collected from rheumatoid arthritis (RA) patients before and after initiation of MTX treatment.

Methods

Patients included in this study were from the Rheumatoid Arthritis Medication Study (n = 66) and the University of California San Francisco Rheumatoid Arthritis study (n = 11). All patients met the American College of Rheumatology RA classification criteria. Blood samples were collected at baseline and following treatment. Disease Activity Scores in 28 joints using the C‐reactive protein level were collected at baseline and after 3–6 months of treatment with MTX. Methylation profiles were generated using the Illumina Infinium HumanMethylation450 and MethylationEPIC v1.0 BeadChip arrays using DNA from whole blood. MTX response was defined using the EULAR response criteria (responders showed good/moderate response; nonresponders showed no response). Differentially methylated positions were identified using the Limma software package and Tensor Composition Analysis, which is a method for identifying cell‐specific differential DNAm at the CpG level from tissue‐level (“bulk”) data. Differentially methylated regions were identified using Comb‐p software.

Results

We found evidence of differential global methylation between treatment response groups. Further, we found patterns of cell‐specific differential global methylation associated with MTX response. After correction for multiple testing, 1 differentially methylated position was associated with differential DNAm between responders and nonresponders at baseline in CD4+ T cells, CD8+ T cells, and natural killer cells. Thirty‐nine cell‐specific differentially methylated regions associated with MTX treatment response were identified. There were no significant findings in analyses of whole blood samples.

Conclusion

We identified cell‐specific changes in DNAm that were associated with MTX treatment response in RA patients. Future studies of DNAm and MTX treatment response should include measurements of DNAm from sorted cells.

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Engineering of xylanases for the development of biotechnologically important characteristics
Authors: Sürmeli Yusuf , Şanlı‐Mohamed Gülşah
Published: January 2023

Xylanases are the main biocatalysts used for the reduction of the xylan backbone from hemicellulose, randomly splitting off β‐1,4‐glycosidic linkages between xylopyranosyl residues. Xylanase market has been annually estimated at 500 million US Dollars and they are potentially used in broad industrial process ranges such as paper pulp biobleaching, xylo‐oligosaccharide production, and biofuel manufacture from lignocellulose. The highly stable xylanases are preferred in the downstream procedure of industrial processes because they can tolerate severe conditions. Almost all native xylanases can not endure adverse conditions thus they are industrially not proper to be utilized. Protein engineering is a powerful technology for developing xylanases, which can effectively work in adverse conditions and can meet requirements for industrial processes. This study considered state‐of‐the‐art strategies of protein engineering for creating the xylanase gene diversity, high‐throughput screening systems toward upgraded traits of the xylanases, and the prediction and comprehensive analysis of the target mutations in xylanases by in silico methods. Also, key molecular factors have been elucidated for industrial characteristics (alkaliphilic enhancement, thermal stability, and catalytic performance) of GH11 family xylanases. The present review explores industrial characteristics improved by directed evolution, rational design, and semi‐rational design as protein engineering approaches for pulp bleaching process, xylooligosaccharides production, and biorefinery & bioenergy production.
Low‐volume plasma sampling for determination of dextromethorphan and dextrorphan in rat plasma: LC–MS/MS method and its application in pharmacokinetic study
Authors: Majhi Praful Kumar , Sayyad Samir , Mishra Pratyush , Kamte Sainath , Sahu Rajanikant , Ghosh Goutam , Subudhi Bharat Bhusan
Published: January 2023

Dextromethorphan (DM) and its metabolite dextrorphan (DX) continue to draw the attention of researchers owing to their diverse pharmacodynamics. Thus, there are possibilities for repurposing DM. Most of the pharmacodynamics of DM needs further validation in different preclinical models. Also, it is necessary to correlate the pharmacodynamics with relevant pharmacokinetics data. Multiple bioanalytical techniques developed for this purpose primarily use a high sample processing volume. Since sample volume is a limiting factor for many preclinical models, an effort was taken to develop an alternative method suitable for handling low sample processing volumes. An efficient solid‐phase extraction technique, robust liquid chromatographic (LC) separation and highly sensitive tandem mass spectrometric detection (MS/MS) showed suitability for use of a 30 μl sample processing volume. This led to the development of a highly specific, selective, accurate and precise‐bio‐analytical method for simultaneous quantification of DM and DX in rat plasma. The validated method was linear in the range of 0.196–403.356 ng/ml for DM and 0.102–209.017 ng/ml for DX. The application of the method was demonstrated through the estimation of pharmacokinetic parameters that showed good congruence with earlier studies.