bluuebunny/crossref_metadata_2025 huggingface dataset:
Donor or Acceptor: Molecular Engineering Based on dibenzo[a,c]phenazine Backbone for Highly Efficient Thermally‐Activated Delayed Fluorescence Organic Light‐Emitting Diodes
Authors: Liu Yanyan , Yang Jiaji , Mao Zhu , Ma Dongyu , Wang Yuyuan , Zhao Juan , Su Shi‐Jian , Chi Zhenguo
Published: November 2022

Thermally‐activated delayed fluorescence (TADF) emitters are usually constructed with twisted donor‐acceptor (D‐A) frameworks, while studies on the relationship between diverse D‐A structures are still in high demand to achieve high‐performance emitters. Herein, by adopting triphenylamine as electron donor and dibenzo[a,c]phenazine as electron acceptor, three TADF molecules are reported with different frameworks of D‐A (TPZ), D‐A‐D (DPZ) and D‐A‐A (APZ). Theoretical and experimental results demonstrate that different D‐A frameworks play significant effects on photophysical, horizontal dipole ratio, and electroluminescence properties of the TADF molecules. In comparison, the APZ‐OLED device achieves the best performance with a maximum external quantum efficiency of 27.5%, resulting from its low energy gap between the singlet and triplet, effective reverse intersystem crossing, high photoluminescence quantum yield, and horizontal dipole ratio. This work provides an insight into the relationship between efficient TADF emitters and rational molecular design engineering.
Rain Energy Harvesting Using Atomically Thin Gadolinium Telluride Decorated 3D Printed Nanogenerator
Authors: Kumbhakar Partha , Parui Arko , Ambekar Rushikesh S. , Mukherjee Madhubanti , Siddique Saif , Pugno Nicola M. , Singh Abhishek K. , Tiwary Chandra S.
Published: November 2022

The 3D printing (3DP) technology offers an innovative approach to developing energy storage devices to create facile and low‐cost customized electrodes for modern electronics. Generating electric potential by moving a droplet of ionic solution over 2D materials is a novel method for rain energy harvesting. This work demonstrates a liquid‐solid contact electrification‐based 3DP nanogenerator where raindrop passes through the positively charged ultrathin gadolinium telluride (Gd2Te3) sheets. The output efficiency of the nanogenerator is increased to ≈400% by enhancing the surface area of copious 3D‐printed porous structures. The density functional theory (DFT) calculations reveal that the high electrical conductivity of (112) surface of Gd2Te3 is due to the p‐type charge carriers, which help to generate electricity by interacting with the ionic solution. This work can open up a new avenue to advance scientific research on blue energy harvesting and tackle the energy crisis.
Risk factors for dementia in Brazil: Differences by region and race
Authors: Suemoto Claudia K. , Mukadam Naaheed , Brucki Sonia M.D. , Caramelli Paulo , Nitrini Ricardo , Laks Jerson , Livingston Gill , Ferri Cleusa P.
Published: November 2022

Introduction

Twelve risk factors (RFs) account for 40% of dementia cases worldwide. However, most data for population attributable fractions (PAFs) are from high‐income countries (HIC). We estimated how much these RFs account for dementia cases in Brazil, stratifying estimates by race and socioeconomic level.

Methods

We calculated the prevalence and communalities of 12 RFs using 9412 Brazilian Longitudinal Study of Aging participants, then stratified according to self‐reported race and country macro‐regions.

Results

The overall weighted PAF was 48.2%. Less education had the largest PAF (7.7%), followed by hypertension (7.6%), and hearing loss (6.8%). PAF was 49.0% and 54.0% in the richest and poorest regions, respectively. PAFs were similar among White and Black individuals (47.8% and 47.2%, respectively) but the importance of the main RF varied by race.

Discussion

Brazil's potential for dementia prevention is higher than in HIC. Education, hypertension, and hearing loss should be priority targets.
In Situ Observation of C−C Coupling and Step Poisoning During the Growth of Hydrocarbon Chains on Ni(111)
Authors: Zou Zhiyu , Sala Alessandro , Panighel Mirco , Tosi Ezequiel , Lacovig Paolo , Lizzit Silvano , Scardamaglia Mattia , Kokkonen Esko , Cepek Cinzia , Africh Cristina , Comelli Giovanni , Günther Sebastian , Patera Laerte L.
Published: November 2022

The synthesis of high‐value fuels and plastics starting from small hydrocarbon molecules plays a central role in the current transition towards renewable energy. However, the detailed mechanisms driving the growth of hydrocarbon chains remain to a large extent unknown. Here we investigated the formation of hydrocarbon chains resulting from acetylene polymerization on a Ni(111) model catalyst surface. Exploiting X‐ray photoelectron spectroscopy up to near‐ambient pressures, the intermediate species and reaction products have been identified. Complementary in situ scanning tunneling microscopy observations shed light onto the C−C coupling mechanism. While the step edges of the metal catalyst are commonly assumed to be the active sites for the C−C coupling, we showed that the polymerization occurs instead on the flat terraces of the metallic surface.
Spectroscopic Manifestations and Implications for Catalysis of Quasi‐d10Configurations in Formal Gold(III) Complexes
Authors: Trifonova Evgeniya A. , Leach Isaac F. , de Haas Winfried B. , Havenith Remco W. A. , Tromp Moniek , Klein Johannes E. M. N.
Published: November 2022

Several gold +I and +III complexes are investigated computationally and spectroscopically, focusing on the d‐configuration and physical oxidation state of the metal center. Density functional theory calculations reveal the non‐negligible electron‐sharing covalent character of the metal‐to‐ligand σ‐bonding framework. The bonding of gold(III) is shown to be isoelectronic to the formal CuIIIcomplex [Cu(CF3)4]1−, in which the metal center tries to populate its formally unoccupied 3dx2‐y2orbital via σ‐bonding, leading to a reduced d10CuIdescription. However, Au L3‐edge X‐ray absorption spectroscopy reveals excitation into the d‐orbital of the AuIIIspecies is still possible, showing that a genuine d10configuration is not achieved. We also find an increased electron‐sharing nature of the σ‐bonds in the AuIspecies, relative to their AgIand CuIanalogues, due to the low‐lying 6s orbital. We propose that gold +I and +III complexes form similar bonds with substrates, owing primarily to participation of the 5dx2‐y2or 6s orbital, respectively, in bonding, indicating why AuIand AuIIIcomplexes often have similar reactivity.
Spin‐Selective Charge Transport in Lead‐Free Chiral Perovskites: The Key towards High‐Anisotropy in Circularly‐Polarized Light Detection
Authors: Maiti Abhishek , Pal Amlan J.
Published: November 2022

A pair of zero‐dimensional lead‐free chiral perovskites is introduced towards the detection of circularly polarized light (CPL). Although spin‐polarized carriers are generated in the perovskites under the CPL, the absorption anisotropy remained low leading to mostly similar density of photogenerated carriers under the two CPLs. Interestingly, due to the intrinsic chirality in the perovskites, they exhibited chirality‐induced spin‐selectivity (CISS) allowing the transport of only one type of spin‐half states. A high anisotropy in photocurrent along the out‐of‐plane direction has therefore appeared resulting in a spin‐dependent photovoltaic effect in vertical heterojunction devices and making them suitable for CPL detection. While a self‐powered CPL detector showed a limited (but one of the highest to date) anisotropy factor of 0.3 due to possible spin‐flips during the transport process, the factor rose to 0.6 under bias prompting extension of the effective spin‐diffusion length.
The Marriage of Sierpiński Triangles and Platonic Polyhedra
Authors: Wang Jun , Jiang Zhilong , Liu Weiya , Wu Zihao , Miao Rui , Fu Fan , Yin Jia‐Fu , Chen Bangtang , Dong Qiangqiang , Zhao He , Li Kaixiu , Wang Guotao , Liu Die , Yin Panchao , Li Yiming , Chen Mingzhao , Wang Pingshan
Published: November 2022

Fractal structures with self‐similarity are of fundamental importance in the fields of aesthetic, chemistry and mathematics. Here, by taking advantage of constructs the rational geometry‐directed precursor design, we report the construction of two fascinating Platonic solids, the Sierpiński tetrahedron ST‐T and the Sierpiński octahedron ST‐O, in which each possesses a fractal Sierpiński triangle on their independent faces. These two discrete complexes are formed in near‐quantitative yield from the multi‐component self‐assembly of truncated Sierpiński triangular kernel L1 with tribenzotriquinacene‐based hexatopic and anthracene‐based tetratopic terpyridine ligands (L3 and L4) in the presence of metal ions, respectively. The enhanced stabilities of the 3D discrete structures were investigated by gradient tandem mass spectrometry (gMS2). This work provides new constructs for the imitation of complex virus assemblies and for the molecular encapsulation of giant guest molecules.
Conversion of Polyethylenes into Fungal Secondary Metabolites
Authors: Rabot Chris , Chen Yuhao , Bijlani Swati , Chiang Yi‐Ming , Oakley C. Elizabeth , Oakley Berl R. , Williams Travis J. , Wang Clay C. C.
Published: November 2022

Waste plastics represent major environmental and economic burdens due to their ubiquity, slow breakdown rates, and inadequacy of current recycling routes. Polyethylenes are particularly problematic, because they lack robust recycling approaches despite being the most abundant plastics in use today. We report a novel chemical and biological approach for the rapid conversion of polyethylenes into structurally complex and pharmacologically active compounds. We present conditions for aerobic, catalytic digestion of polyethylenes collected from post‐consumer and oceanic waste streams, creating carboxylic diacids that can then be used as a carbon source by the fungus Aspergillus nidulans. As a proof of principle, we have engineered strains of A. nidulans to synthesize the fungal secondary metabolites asperbenzaldehyde, citreoviridin, and mutilin when grown on these digestion products. This hybrid approach considerably expands the range of products to which polyethylenes can be upcycled.
Energy harvesting and temperature sensing thermoelectric devices based on the carbon template method
Authors: Jiang Nan , Qu Meijie , Wang Hai , Bin Yuezhen , Zhang Rui , Tang Ping
Published: November 2022

A series of self‐supporting carbon nanomaterial films with different morphologies were employed as conductive templates for n‐junction after polyethyleneimine (PEI) doping by taking advantages of the entanglement between carbon nanotubes. With the assistance of dimethyl sulfoxide (DMSO)‐treated poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) films as p‐junction, flexible and light‐weight thermoelectric generators (TEGs) were assembled. The effect of the morphology of the carbon nanomaterial, including multi‐walled carbon nanotube (MWCNT), whisker carbon nanotube (WSCNT), and graphene on the electrical conductivity, mechanical properties and morphology of n‐junction was investigated, on basis of which thermoelectric properties of TEG were evaluated. The properties of the three carbon‐based self‐supporting films show significant differences. The MWCNT/PEI film exhibits a tensile strength of up to 36.23 ± 0.57 MPa due to the high entanglement network density of MWCNT. The entanglement of WSCNT/MWCNT/PEI provides an ideal conductive template for PEI to prepare n‐junction material. TEGs with PEDOT:PSS‐DMSO and WSCNT/MWCNT/PEI as p‐ and n‐junctions show high power generation performance and cyclability. The output power density is up to 4.6 nW/cm2 at ΔT = 42.0 K, matched to a suitable load. With its fast response and slow recovery, this TEG is expected to be used for human health monitoring and energy storage.
Efficient production of glutathione in Saccharomyces cerevisiae via a synthetic isozyme system
Authors: Jeon Gi‐Beom , Lee Hyun‐Jae , Park Jong Pil , Park Kyeongsoon , Choi Chang‐Hyung , Kim Sun‐Ki
Published: November 2022

Glutathione, a tripeptide consisting of cysteine, glutamic acid, and glycine, has multiple beneficial effects on human health. Previous studies have focused on producing glutathione in Saccharomyces cerevisiae by overexpressing γ‐glutamylcysteine synthetase (GSH1) and glutathione synthetase (GSH2), which are the rate‐limiting enzymes involved in the glutathione biosynthetic pathway. However, the production yield and titer of glutathione remain low due to the feedback inhibition on GSH1. To overcome this limitation, a synthetic isozyme system consisting of a novel bifunctional enzyme (GshF) from Gram‐positive bacteria possessing both GSH1 and GSH2 activities, in addition to GSH1/GSH2, was introduced into S. cerevisiae, as GshF is insensitive to feedback inhibition. Given the HSP60 chaperonin system mismatch between bacteria and S. cerevisiae, co‐expression of Group‐I HSP60 chaperonins (GroEL and GroES) from Escherichia coli was required for functional expression of GshF. Among various strains constructed in this study, the SKSC222 strain capable of synthesizing glutathione with the synthetic isozyme system produced 240 mg L‐1 glutathione with glutathione content and yield of 4.3% and 25.6 mgglutathione/gglucose, respectively. These values were 6.6‐, 4.9‐, and 4.3‐fold higher than the corresponding values of the wild‐type strain. In a glucose‐limited fed‐batch fermentation, the SKSC222 strain produced 2.0 g L‐1 glutathione in 67 h. Therefore, this study highlights the benefits of the synthetic isozyme system in enhancing the production titer and yield of value‐added chemicals by engineered strains of S. cerevisiae.
Spatial organization of pathway enzymes via self‐assembly to improve 2′‐fucosyllactose biosynthesis in engineered Escherichia coli
Authors: Chen Roulin , Wan Li , Zhu Yingying , Liu Yuanlin , Zhang Wenli , Mu Wanmeng
Published: November 2022

As one of the most abundant components in human milk oligosaccharides, 2′‐fucosyllactose (2′‐FL) possesses versatile beneficial health effects. Although most studies focused on overexpressing or fine‐tuning the expression of pathway enzymes and achieved a striking increase of 2′‐FL production, directly facilitating the metabolic flux toward the key intermediate GDP‐l‐fucose seems to be ignored. Here, multienzyme complexes consisting of sequential pathway enzymes were constructed by using specific peptide interaction motifs in recombinant Escherichia coli to achieve a higher titer of 2′‐FL. Specifically, we first fine‐tuned the expression level of pathway enzymes and balanced the metabolic flux toward 2′‐FL synthesis. Then, two key enzymes (GDP‐mannose 4,6‐dehydratase and GDP‐
l‐fucose synthase) were self‐assembled into enzyme complexes in vivo via a short peptide interaction pair RIAD–RIDD (RI anchoring disruptor–RI dimer D/D domains), resulting in noticeable improvement of 2′‐FL production. Next, to further strengthen the metabolic flux toward 2′‐FL, three pathway enzymes were further aggregated into multienzyme assemblies by using another orthogonal protein interaction motif (Spycatcher–SpyTag or PDZ–PDZlig). Intracellular multienzyme assemblies remarkably enlarged the flux toward 2′‐FL biosynthesis and showed a 2.1‐fold increase of 2′‐FL production compared with a strain expressing free‐floating and unassembled enzymes. The optimally engineered strain EZJ23 accumulated 4.8 g/L 2′‐FL in shake flask fermentation and was capable of producing 25.1 g/L 2′‐FL by fed‐batch cultivation. This work provides novel approaches for further improvement and large‐scale production of 2′‐FL and demonstrates the effectiveness of spatial assembly of pathway enzymes to improve the production of valuable products in the engineered host strain.
Clinical and molecular characteristics of kinase domain duplications across diverse cancer types in the Chinese population
Authors: Lai Xiaojing , Yu Ruoying , Ou Qiuxiang , Bao Hua , Wu Xue , Shao Yang , Li Yang , Zhang Ying , Ding Qingqing
Published: November 2022

Background

Kinase domain duplications (KDDs) have recently been recognized as oncogenic mutations and possible association with drug resistance in cancers.

Method

Here, targeted sequencing was performed with the tumor tissue and/or plasma from 65 cancer patients with KDDs.

Result

Intact KDDs were identified in approximately 0.1% of the total population across multiple cancer types. EGFR KDD was first identified in colorectal cancer and breast cancer, whereas FGFR2 KDD was first identified in gastric cancer. Tumors with EGFR KDD displayed lower concurrent TP53 gene alterations (p = 0.03) and slightly higher chromosome instability (p = 0.27) compared to tumors with non‐EGFR‐KDDs. Immune pathway analysis further revealed the enrichment of the cytokine receptors pathway (93%) in the KDD carriers. Hyperprogression‐related gene mutations were identified in four cases.

Conclusion

Collectively, our data revealed the genomic features of KDD alterations in a multi‐cancer cohort, providing more information for the potential treatment application in the KDD carriers.
Evolution of lung adenocarcinoma from preneoplasia to invasive adenocarcinoma
Authors: Zhu Jianfei , Wang Wenchen , Xiong Yanlu , Xu Shuonan , Chen Jiankuan , Wen Miaomiao , Zhao Yabo , Lei Jie , Jiang Tao
Published: November 2022

Objective

Mutations in driver genes contribute to the development and progression of lung adenocarcinoma (LUAD). However, in the dynamic evolutionary process from adenocarcinoma in situ (AIS) to minimally invasive adenocarcinoma (MIA) and eventually to invasive adenocarcinoma (IAC), the role of driver genes is currently unclear. This study aimed to analyse the role of driver gene status in the progression of LUAD from preneoplasia to IAC.

Methods

Patients with LUAD who underwent surgery in our centre from March 2015 to December 2019 were retrospectively analysed, and LUAD patients with tumour sizes ≤3.0 cm and pN0 were included in the final analysis. The mutation status of common driver genes, including EGFR, ALK and ROS1, was detected. According to the pathological characteristics, the patients were divided into three stages: AIS, MIA and IAC. We analysed the distribution of driver gene mutation frequencies across three stages of LUAD. In addition, we performed univariate and multivariate analyses of IAC patients to screen for relevant variables (driver genes and clinicopathological features) affecting their prognosis.

Results

Ultimately, 759 patients with LUAD were enrolled, including 135, 130, and 494 cases of AIS, MIA, and IAC, respectively. EGFR mutations were identified in 359 (61.8%) patients, and with the transition from AIS to MIA, the frequency of EGFR mutations increased from 33.3% to 50.8%, p = 0.004, whereas the frequency of EGFR mutations was comparable for MIA and IAC (50.8% vs. 50.2%, p = 0.922). Moreover, ALK and ROS1 gene fusions were identified in 17 cases (2.2%) and 2 cases (3.0‰) respectively. For AIS, neither ALK gene nor ROS1 gene fusions were observed. When the tumour progressed to MIA, the ALK fusion frequency was 2.3% (3/130), which was basically consistent with the ALK fusion frequency of 2.8% in IAC, p = 0.143. For IAC, fusions of ROS1 fell into this category. In addition, we found that 40 patients (5.3%) developed metastasis/recurrence, and 14 patients (1.8%) died of cancer‐specific related diseases. Notably, for AIS, there were no recurrences and no deaths, and for MIA, only 1 patient died with LUAD. Finally, survival analysis was performed in patients with stage IA invasive adenocarcinoma, and EGFR‐mutant patients showed better DFS than EGFR‐wild‐type patients (p = 0.036). Conversely, patients with ALK fusions showed worse DFS than those with ALK wild‐type (p = 0.004), and the same results were found in OS analysis.

Conclusions

The accumulation of EGFR driver gene mutation frequencies mediates the progression of LUAD from AIS to MIA. When the tumour progresses to stage IA invasive adenocarcinoma, multivariate analysis based on driver gene status can be used as a pivotal prognostic factor.
Automatic hierarchical model builder
Authors: Marchi Lorenzo , Krylov Ivan , Roginski Robert T. , Wise Barry , Di Donato Francesca , Nieto‐Ortega Sonia , Pereira José Francielson Q. , Bro Rasmus
Published: November 2022

When building classification models of complex systems with many classes, the traditional chemometric approaches such as discriminant analysis or soft independent modeling of class analogy often fail. Some people resort to advanced deep neural network, but this is only an option if there is access to very many samples. Another alternative often used is to build hierarchical models where subclasses are sort of peeled off one or a few at a time. Such approaches often outperform classical classification as well as deep neural network on small multi‐class problems. The downside though is that it is very cumbersome to build such hierarchies of models. It requires substantial work of a skilled person. In this paper, we develop a fully automated approach for building hierarchical models and test the performance on a number of classification problems.
Hydrogen Bonding in Platinum Indolylphosphine Polyfluorido and Fluorido Complexes
Authors: Sander Stefan , Cosgrove Elizabeth J. , Müller Robert , Kaupp Martin , Braun Thomas
Published: November 2022

The reaction of the Pt complexescis‐[Pt(CH3)(Ar){Ph2P(Ind)}2] (Ind=2‐(3‐methyl)indolyl, Ar=4‐tBuC6H4(1 a),4‐CH3C6H4(1 b), Ph (1 c), 4‐FC6H4(1 d), 4‐ClC6H4(1 e), 4‐CF3C6H4(1 f)) with HF afforded the polyfluorido complexestrans‐[Pt(F(HF)2)(Ar){Ph2P(Ind)}2]2 a–f, which can be converted into the fluoride derivativestrans‐[Pt(F)(Ar){Ph2P(Ind)}2] (3 a–f) by treatment with CsF. The compounds2 a–fand3 a–fwere characterised thoroughly by multinuclear NMR spectroscopy. The data reveal hydrogen bonding of the fluorido ligand with HF molecules and the indolylphosphine ligand. Polyfluorido complexes2 a–fshow larger |1J(F,Pt)|, but lower1J(H,F) coupling constants when compared to the fluorido complexes3 a–f. Decreasing1J(P,Pt) coupling constants in2 a–fand3 a–fsuggest acisinfluence of the aryl ligands in the following order: 4‐tBuC6H4(a) ≈4‐CH3C6H4(b)<Ph (c)≪4‐FC6H4(d)<4‐ClC6H4(e)<4‐CF3C6H4(f). In addition, the largercisinfluence of aryl ligands bearing electron‐withdrawing groups in theparaposition correlates with decreasing magnitudes of |1J(F,Pt)| coupling constants. The interpretation of the experimental data was supported by quantum‐chemical DFT calculations.
Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′‐P3N5, δ‐P3N5 and PN2
Authors: Laniel Dominique , Trybel Florian , Néri Adrien , Yin Yuqing , Aslandukov Andrey , Fedotenko Timofey , Khandarkhaeva Saiana , Tasnádi Ferenc , Chariton Stella , Giacobbe Carlotta , Lawrence‐Bright Eleanor , Hanfland Michael , Prakapenka Vitali , Schnick Wolfgang , Abrikosov Igor A. , Dubrovinsky Leonid , Dubrovinskaia Natalia
Published: November 2022

Invited for the cover of this issue are Dominique Laniel (University of Edinburgh), Florian Trybel (University of Linköping), and their colleagues. The image depicts a bridge built of the newly discovered δ‐P3N5 solid with the structure featuring PN6 units, a previously missing connection between the carbon group elements nitrides and chalcogens nitrides. Read the full text of the article at 10.1002/chem.202201998.
Process‐aware data‐driven modelling and model predictive control of bioreactor for the production of monoclonal antibodies
Authors: Sarna Samardeep , Patel Nikesh , Corbett Brandon , McCready Chris , Mhaskar Prashant
Published: November 2022

This manuscript addresses the problem of controlling a bioreactor to maximize the production of a desired product while respecting the constraints imposed by the nature of the bio‐process. The approach is demonstrated by first building a data‐driven model and then formulating a model predictive controller (MPC) with the results illustrated by implementing a detailed monoclonal antibody production model (the test bed) created by Sartorius Inc. In particular, a recently developed data‐driven modelling approach using an adaptation of subspace identification techniques is utilized that enables the incorporation of known physical relationships in the data‐driven model development (constrained subspace model identification), making the data‐driven model process aware. The resultant controller implementation demonstrates a significant improvement in production compared to the existing proportional integral (PI) controller strategy used in the monoclonal antibody production. Simulation results also demonstrate the superiority of the process‐aware or constrained subspace MPC compared to traditional subspace MPC. Finally, the robustness of the controller design is illustrated via the implementation of a model developed using data from a test bed with a different set of parameters, thus showing the ability of the controller design to maintain good performance in the event of changes such as a different cell line or feed characteristics.
Considerations for Use of Pharmacodynamic Biomarkers to Support Biosimilar Development – (III) A Randomized Trial with Interferon Beta‐1a Products
Authors: Florian Jeffry , Gershuny Victoria , Sun Qin , Schrieber Sarah J. , Matta Murali K. , Hazel Anthony , Sheikhy Morasa , Weaver James L. , Hyland Paula L. , Hsiao Cheng‐Hui , Vegesna Giri , DePalma Ryan , Shah Aanchal , Prentice Kristin , Sanabria Carlos , Wang Yow‐Ming , Strauss David G.
Published: November 2022

The US Food and Drug Administration (FDA) has taken steps to bring efficiency to the development of biosimilars, including establishing guidance for the use of pharmacokinetic and pharmacodynamic (PD) similarity study data without a comparative clinical study with efficacy end point(s). To better understand the potential role for PD biomarkers in biosimilar development and inform best practices for biomarker selection and analysis, we conducted a randomized, double‐blinded, placebo‐controlled, single‐dose, parallel‐arm clinical study in healthy participants. Eighty‐four healthy participants (n = 12 per dose arm) received either placebo or one of three doses of either interferon β‐1a (7.5–30 μg) or pegylated interferon β‐1a (31.25–125 μg) to evaluate the maximum change from baseline and the baseline‐adjusted area under the effect curve for the biomarkers neopterin in serum and myxovirus resistance protein 1 in blood. Both PD biomarkers increased following product administration with clear separation from baseline (neopterin: 3.4‐fold and 3.9‐fold increase for interferon β‐1a and pegylated interferon β‐1a, respectively; myxovirus resistance protein 1: 19.0‐fold and 47.2‐fold increase for interferon β‐1a and pegylated interferon β‐1a, respectively). The dose–response curves support that therapeutic doses were adequately sensitive to detect differences in both PD biomarkers for consideration in a PD similarity study design. Because baseline levels of both biomarkers are low compared with on‐treatment values, there was little difference in using PD measures adjusted to baseline compared with the results without baseline adjustment. This study illustrates potential methodologies for evaluating PD biomarkers and an approach to address information gaps when limited information is publicly available for one or more PD biomarkers.
Behaviour‐based pain scales: Validity and interrater reliability of BPS‐NI and PAINAD‐G on general wards
Authors: Wandrey Jan D. , Behnel Niklas , Weidner Elisa , Dummin Ulrike , von Dincklage Falk , Tafelski Sascha
Published: November 2022

Background

Measuring pain intensity in patients unable to communicate is a challenge on general wards. Observation‐based pain scoring tools have been used for patients with dementia or in critically ill intensive care unit (ICU) patients. However, there is no established or validated assessment tool for non‐ICU patients without dementia related cognitive deficiencies who cannot communicate. The “Behavioural Pain Scale Non‐Intubated” (BPS‐NI) and the “Pain Assessment In Advanced Dementia‐German” (PAINAD‐G) are potential tools to fill this gap.

Methods

This study was performed with verbal non‐ICU patients on general wards at Charité Berlin. Two assessors independently rated pain intensity using the BPS‐NI and the PAINAD‐G along with patients' self‐ratings on the Numeric Rating Scale (NRS). The interrater‐reliability of BPS‐NI and PAINAD‐G was calculated and ROC‐analyses were performed to identify cut‐off values for medium and intense pain for each score. Effectiveness was calculated using percentage agreement. In total, 126 patients were included into analysis.

Results

The BPS‐NI showed substantial congruence in interrater‐reliability (Cohens‐Kappa 0.71), whereas the PAINAD‐G showed moderate congruence (Kappa 0.48). Based on ROC‐analyses, for medium pain levels a cut‐off 4 (BPS‐NI) or 2 (PAINAD‐G) and for severe pain levels cut‐off 5 (BPS‐NI) and 3 (PAINAD‐G) would result in good accordance with self‐reported NRS for pain.

Conclusion

The BPS‐NI shows a good validity in measuring pain intensity in patients on general wards and may possibly be used for patients unable to communicate. Using defined cut‐off values for BPS‐NI and PAINAD‐G, clinically relevant pain intensities in patients can reliably be detected.

Significance

Measuring the pain intensity in patients unable to communicate is a common challenge on general wards. This study assessed reliability and applicability BPS‐NI and the PAINAD‐G in a general ward setting. Furthermore, it provides cut‐off values in order to estimate pain intensity and support analgesic response.
Advances in Carbon Materials Applied to Carbon‐Based Perovskite Solar Cells
Authors: Kohlrausch Emerson Cristofer , de Vasconcelos Freitas Denilson , da Silva Filho Cícero Inácio , Fernandes Loguercio Lara , Santa-Cruz Larissa A. , Lins Maciel Leonardo José , Oliveira Maria Zilda , dos Santos Calink Indiara do Livramento , Machado Giovanna
Published: November 2022

Perovskite‐based solar cells (PSCs) are some of the most promising devices for capturing photovoltaic energy. Efficiency has increased from single digits to a certified 25.7%, an unprecedented improvement for any solar cell technology. Incorporating carbon materials into perovskite solar cells promises to be revolutionary in the solar cell field by increasing stability, decreasing manufacturing costs, and making them attractive for commercialization. Here, an overview of the advances in carbon‐based perovskite solar cells (C–PSCs) that incorporate different carbon materials as back contact on different device architectures is presented. An overview of PSC architectures and high‐ and low‐temperature C–PSCs is provided. Additionally, recent advances in the main carbon materials applied in the field, such as graphene, carbon nanotubes, carbon dots, and biocarbon, are presented. Finally, a summary of carbon materials applied to C–PSCs is provided.
Performance Analysis of a Novel Water/Electricity Cogeneration System Based on Plasma Waste Gasification and a Small Modular Reactor
Authors: Wu Haoran , Chen Heng , Yuan Xin , Li Tongyu , Pan Peiyuan , Xu Gang , Zhao Qinxin , Wang Xiuyan
Published: November 2022

A hybrid system consisting of plasma gasification, multistage flash (MSF) desalination, and a small modular reactor (SMR) power plant is proposed for power and water cogeneration. In the novel configuration, the syngas from the plasma gasifier is burned to drive the gas turbine to generate electricity. The exhaust from the gas turbine is used to heat the steam of the SMR power plant and the seawater. The new design is thoroughly evaluated from a thermodynamic and economic point of view. In the hybrid system, 36.12 MW of electricity is generated from medical waste, and 23.75 MW of heat that can be utilized by MSF desalination is also generated from medical waste, with waste‐to‐electricity efficiency and energy efficiency of medical waste being 40.39% and 52.88%, respectively. The exergy efficiency of medical waste is 37.99%. In addition, the new design has a short dynamic payback period of 3.7 years, and the project's net present value can reach 430036.07 k$ over a 20 year lifetime; internal rate of return can reach 54%. Meanwhile, the effects of equivalence ratio and plasma temperature on the performance of the hybrid system are discussed. These results confirm the feasibility of the new design.
Experimental study on combustion characteristics of a fischer‐tropsch diesel/methanol reactivity controlled compression ignition mode engine
Authors: Bai Zechuan , Wang Zhong , Li Ruina , Liu Shuai
Published: November 2022

F‐T diesel is an alternative fuel with a high cetane number (CN) for internal combustion engines. Methanol has a low CN and contains oxygen. F‐T diesel and methanol are potential fuels for the reactivity controlled compression ignition (RCCI) engines. In a single‐cylinder 186FA compression‐ignition engine with a combination of methanol inlet pipe injection and F‐T diesel in‐cylinder injection, the combustion characteristics of the F‐T diesel/methanol RCCI mode engine are investigated. The results show that as methanol premixed ratio (MPR) increases, the ignition delay (ID) is prolonged at low load conditions, the maximum in‐cylinder pressure (Pmax) and indicated thermal efficiency (ITE) a decreased. When the MPR increases from 0% to 60%, the ID is extended by 1.7°CA, the Pmax decreases by 8.1%, and the ITE decreases by 1.1%. At high load conditions, MPR rises from 0% to 60%, combustion duration (CD) is shortened by 2.4°CA, Pmax is increased by 8.3%, and the ITE is increased by 1.7%. The fuel injection advance angle (IAA) of F‐T diesel significantly influences the combustion process of the RCCI engine. As the IAA increases, the ID is shortened at high loads, and the Pmax and the ITE are increased. When the MPR is 60% and the IAA is 14°CA, the ITE of the engine is increased by 2.04%, and the equivalent indicated fuel consumption rate(be) is reduced by 5.68% compared with the engine fueled with F‐T diesel under high loads.
Hybrid simulation of a partial‐strength steel–concrete composite moment‐resisting frame endowed with hysteretic replaceable beam splices
Authors: Andreotti Roberto , Giuliani Giulia , Tondini Nicola , Bursi Oreste S.
Published: November 2022

This paper deals with the seismic response assessment of a steel–concrete moment‐resisting frame (MRF) equipped with special dissipative replaceable components (DRCs): the dissipative replaceable beam splices (DRBeS), which combine large energy dissipation with ease of replacement. The evaluation of the full potential of DRBeS requires a system‐level investigation, that is, a six‐story MRF, whereby the hysteretic effects of beam splices partial‐strength joints are considered on the global response of the structural system. Therefore, an OpenSees finite element (FE) frame model, based on previous experimental campaigns with cyclic displacements on partial‐strength joints, and a Matlab model validated on OpenSees, were used for a more complex experimental activity via hybrid simulation (HS). The aim of the simulations was twofold: (i) to increase knowledge of the non‐linear behaviour of steel‐concrete composite partial‐strength MRFs; and (ii) to study the effectiveness of the DRBeS components for increasing the recovery of functionality after a major seismic event. Therefore, to appreciate the performance of the partial‐strength MRF at damage limitation (DL), significant damage (SD) and near collapse (NC) within the performance‐based earthquake engineering (PBEE) approach, HSs were carried out. In such instances, the ground floor was physically tested at full scale in the laboratory and the remainder of the structure was numerically simulated. Relevant results showed that the DRBeS were capable of dissipating a significant amount of hysteretic energy and of protecting the non‐dissipative parts of partial‐strength joints and the overall structure with an ease of replacement.
Arroyo formation impacts on an early dryland agricultural community in Northeastern Utah, USA
Authors: Finley Judson Byrd , Robinson Erick , Justin DeRose R.
Published: November 2022

Indigenous Fremont farmers in Cub Creek, a part of northeastern Utah's Dinosaur National Monument, occupied the northern ecological margin of maize cultivation in western North America from A.D. 300 to 1300. Agriculture in Cub Creek was a response to multidecadal precipitation variability, but when precipitation stabilized between A.D. 750 and 1050, agricultural conditions improved and populations expanded to form villages along the floodplains of local dryland streams. Did the very same conditions (i.e., decreased precipitation variability) that allowed the growth of agricultural societies make them simultaneously vulnerable to arroyo formation, a key geomorphic risk to floodplain agriculturalists? Preliminary results from Cub Creek show that rapid sedimentation punctuated by episodic arroyo formation characterized the last 2000 years. We use stratigraphic and chronological evidence formalized in a Bayesian age model to develop a set of working hypotheses that a 2.5 m‐deep discontinuous arroyo formed before either A.D. 1020 or A.D. 1275. The earlier age corresponds with occupation of the Cub Creek village, while the later age corresponds with the end of Fremont agriculture in Cub Creek, and demonstrates regional synchronicity with arroyo formation across the Colorado Plateau. A second arroyo formed before A.D. 1490, indicating rapid alluvial cycling in Cub Creek. We conclude that floodplain instability and arroyo formation combined with the return of the dominant multidecadal precipitation variability regime beginning at A.D. 1050 was a key constraint on the growth potential of local populations. These findings have potential implications for the development of early Indigenous dryland agricultural systems throughout the interior of western North America.
Quorum Sensing Facilitates Interpopulation Signaling by Vibrio fischeri within the Light Organ of Euprymna scolopes
Authors: Yount Taylor A. , Murtha Andrew N. , Cecere Andrew G. , Miyashiro Tim I.
Published: November 2022

Quorum sensing is an intercellular signaling mechanism that enables bacterial cells to coordinate population‐level behaviors. How quorum sensing functions in natural habitats remains poorly understood. Vibrio fischeri is a bacterial symbiont of the Hawaiian bobtail squid Euprymna scolopes and depends on LuxI/LuxR quorum sensing to produce the symbiotic trait of bioluminescence. A previous study demonstrated that animals emit light when co‐colonized by a Δlux mutant, which lacks several genes within the lux operon that are necessary for bioluminescence production, and a LuxI− mutant, which cannot synthesize the quorum signaling molecule N‐3‐oxohexanoyl‐homoserine lactone. Here, we build upon that observation and show that populations of LuxI− feature elevated promoter activity for the lux operon. We find that population structures comprising of Δlux and LuxI− are attenuated within the squid, but a wild‐type strain enables the LuxI− strain type to be maintained in vivo. These experimental results support a model of interpopulation signaling, which provides basic insight into how quorum sensing functions within the natural habitats found within a host.
Income inequality and monetary policy in the euro area
Authors: Creel Jérôme , El Herradi Mehdi
Published: November 2022

This paper examines the distributional implications of ECB monetary policy on income inequality on a panel of 10 Euro area countries between 2000 and 2015. In contrast with the literature, we investigate different transmission channels and introduce several specifications (different monetary policy instruments, different indicators of income inequality, different data sources, parsimonious and larger models, shocks on monetary policy per se, on long‐term rates and on inflation rates) in a panel VAR setting to highlight the robustness of results. Results suggest that: (i) the distributional effects of ECB's monetary policy have been modest and (ii) mainly driven in times of conventional monetary policy measures, especially in countries with a high level of income inequality, while, overall, (iii) standard and non‐standard monetary policies do not significantly differ in terms of impact and (iv) baseline results persist when redistributive public policies are introduced. We further document that our results are more likely to be channelled via income composition effects.
Assessing the contribution of the Adhoc crop health surveillance tool on the food security and livelihoods of smallholder farmers in Uganda
Authors: Nameere‐Kivunike Florence , Gamukama Elly A. , Nakatumba‐Nabende Joyce , Mutembesa Daniel , Tusubira Jeremy Francis , Nsumba Solomon , Omongo Christopher A. , Namanya Gloria
Published: November 2022

One of the perennial causes of food insecurity in Sub‐Saharan African countries is crop pests and diseases that affect agricultural production. To address this concern in Uganda, a mobile phone crowdsourcing Adhoc surveillance tool, Adsurv, was deployed and used by smallholder farmers. Adsurv is a crop health surveillance and monitoring mobile application that facilitates diagnosing and managing crop pests and diseases. Existing literature has examined the impacts of mobile technologies on food security or livelihoods in isolation, but has not conducted a holistic assessment of both. This study on the other hand aimed at assessing the contribution Adsurv made towards improved food security and livelihood assets of the smallholder farmers, which were not fully understood. The study contributes to applying the sustainable livelihood framework (SLF) as theory in evaluating Mobile for Development (M4D) initiatives. The Analytic Hierarchy Process (AHP) was further adopted to facilitate the development of a hierarchical assessment model of the multidimensional food security and livelihood aspects using data collected from 56 out of the targeted 70 participants. Results show that Adsurv mainly contributed towards food availability rather than utilization or access. These gains mostly enhanced the human assets of the smallholder farmers, empowering them with skills that positively impacted all other assets to support the attainment of sustainable livelihoods. The implication of these results in both research and practice is the need for further research trials, which will motivate farmers to recognize the importance of the nutritional value of food in their agronomic practices.
Reactivities of silane coupling agents in the silica/rubber composites: Theoretical insights into the relationships between energy barriers and electronic characteristics
Authors: Ma Delong , Ma Song , Li Yunfeng , Yuan Jianyong , He Jionghao , Zhao Shuangliang
Published: November 2022

Si69 and Si75, typical commodities of silane coupling agents, are often employed in tire recipes to work as the bridges connecting silica and polymers, with which rolling resistance and wet traction are enhanced without loss in abrasion resistance. In this article, the reactivities of Si69 and Si75 with silica and various rubbers were theoretically investigated by using density functional theory (DFT). When the agents were coupled with silica, not only the acid+water condition but also the pure acid condition was confirmed to readily trigger the condensation reactions. The corresponding Gibbs free energy barriers were related to the charge distributions of reaction regions. As the agents suffered from the homolysis of central SS bonds, the generated single‐S‐tailer radicals (RS·) showed significantly higher reactivities of both the radical addition and the α‐H transfer reactions with rubbers, due to the stronger radical philicities of the terminal sulfur radicals with larger condensed local softnesses [s0(S)]. When the agents underwent the heterolysis of central SS bonds, the terminal sulfur anions with smaller s−(S) indices, however, facilitated the nucleophilic addition reactions with rubbers. Several derivative indices based on the condensed local softnesses were also proposed here to shed light on the reactivities from the viewpoint of the relationship between energy barriers and electronic characteristics. The above findings pave the way for the design of new kinds of silane coupling agents using computer‐aided techniques, and meanwhile, provide references for the practical application of Si69 and Si75 to the silica/rubbers systems.
IgG autoantibodies against ACE2 in SARS‐CoV‐2 infected patients
Authors: Hallmann Ewelina , Sikora Dominika , Poniedziałek Barbara , Szymański Karol , Kondratiuk Katarzyna , Żurawski Jakub , Brydak Lidia , Rzymski Piotr
Published: November 2022

How frequently autoantibodies against angiotensin‐converting enzyme 2 (ACE2) occur in patients infected by SARS‐CoV‐2 is understudied and limited to investigations on a small sample size. The presence of these antibodies may contribute to the long‐lasting effects of COVID‐19 observed in some individuals, particularly if IgG‐class antibodies would emerge in patients. This study assessed the prevalence of IgG autoantibodies against ACE2 in 1139 patients infected with SARS‐CoV‐2 and examined their relationship with severity, demographic characteristics, and status of vaccination against influenza. The overall prevalence of anti‐ACE IgG antibodies in our cohort was 1.5%. Most of these individuals were men (76.5%) and underwent mild COVID‐19, but some severe and asymptomatic cases were also observed. Patients with severe infection had twofold higher titers than mild and asymptomatic cases. Age, comorbidities, and influenza vaccination status were not related to antibody prevalence. The prevalence of IgG anti‐SARS‐CoV‐2 antibodies (against nucleocapsid protein and S2 subunit, but not against receptor‐binding domain) was higher in the subset with ACE2 autoantibodies. Further research is required to understand the potential spectrum and duration of effects of IgG autoantibodies against ACE2 in patients after SARS‐CoV‐2 infection, particularly concerning long COVID‐19.
Quantative MRI predicts tendon mechanical behavior, collagen composition, and organization
Authors: Zellers Jennifer A. , Edalati Masoud , Eekhoff Jeremy D. , McNish Reika , Tang Simon Y. , Lake Spencer P. , Mueller Michael J. , Hastings Mary K. , Zheng Jie
Published: November 2022

Quantitative magnetic resonance imaging (qMRI) measures have provided insights into the composition, quality, and structure‐function of musculoskeletal tissues. Low signal‐to‐noise ratio has limited application to tendon. Advances in scanning sequences and sample positioning have improved signal from tendon allowing for evaluation of structure and function. The purpose of this study was to elucidate relationships between tendon qMRI metrics (T1, T2, T1ρ and diffusion tensor imaging [DTI] metrics) with tendon tissue mechanics, collagen concentration and organization. Sixteen human Achilles tendon specimens were collected, imaged with qMRI, and subjected to mechanical testing with quantitative polarized light imaging. T2 values were related to tendon mechanics [peak stress (rsp = 0.51, p = 0.044), equilibrium stress (rsp = 0.54, p = 0.033), percent relaxation (rsp = −0.55, p = 0.027), hysteresis (rsp = −0.64, p = 0.007), linear modulus (rsp = 0.67, p = 0.009)]. T1ρ had a statistically significant relationship with percent relaxation (r = 0.50, p = 0.048). Collagen content was significantly related to DTI measures (range of r = 0.56–0.62). T2 values from a single slice of the midportion of human Achilles tendons were strongest predictors of tendon tensile mechanical metrics. DTI diffusivity indices (mean diffusivity, axial diffusivity, radial diffusivity) were strongly correlated with collagen content. These findings build on a growing body of literature supporting the feasibility of qMRI to characterize tendon tissue and noninvasively measure tendon structure and function. Statement of Clinical Significance: Quantitative MRI can be applied to characterize tendon tissue and is a noninvasive measure that relates to tendon composition and mechanical behavior.