bluuebunny/crossref_metadata_2025 huggingface dataset:
Striving for Open Access publishing at KTH Royal Institute of Technology
Authors: Dubus Gaël , Fathli Margareta
Published: November 2022

Open Access publishing (OA) has been promoted by public institutions and research communities in many countries for some years now. Various categories encompassing different types and practices of OA are precisely described in definitions that now seem to be well-established. OA status is now available as part of a publication's metadata in all major publication databases, while some data sources such as Unpaywall are specifically dedicated to this type of information.
At KTH, we monitor and document the effects of this shifting landscape and of policies promoting OA by means of an annual OA report focused on scientific publications by our researchers. This allows us to observe potential effects of KTH policy changes and to identify areas that the KTH management or the KTH library could support or strengthen. To this end, we collect the OA status (open, closed) and OA type (gold, diamond, hybrid, green) from Unpaywall for several publication types (journal articles, conference proceedings, theses, book chapters) and aggregate these data both for KTH as a whole and for each of its five schools. We also identify the journals in which KTH researchers publish the most and calculate the OA proportion of KTH publications in these. Finally, we take a look at the evolution of publishing-related costs for KTH and KTH schools and relate them to changes in the university's publishing policy.
Results show that the OA share of KTH peer-reviewed publications has been globally increasing since 2011, strongly so for theses and journal articles. This is mainly due to the increase of gold and hybrid OA, despite the fact that journals where KTH authors publish the most are still mainly subscription-based. The increase in OA share is less pronounced for conference proceedings but nonetheless steady. A diversity of publishing practices in different research areas is revealed by the different OA publishing patterns at the different KTH schools. An overall increase in Article Processing Charges (APC) can be observed, related to both the increase of the number of hybrid and gold OA publications and to the implementation of new transformative agreements with several publishers.
We discuss the consequences of the current university policy and compare it to alternative policies supporting OA while limiting the increase of publishing costs. We also reflect upon the extent to which researchers can be guided towards better OA practices and the role a university library may play in the process. Considering the questions of sustainability in a foreseeable future and of equity in the scientific publishing landscape paramount, we strongly value input from various actors within open science communities in order to build a sound reference framework for OA-supporting policies.
The Effect of Public Participation on Performance of Devolved Governance System in Kenya: Case of the Government of the County of Kwale
Authors: Gwidi Juma Chidzangi , Kilei Peary
Published: November 2022

Public engagement, openness, and accountability are strongly emphasized in the 2010 Kenyan Constitution and the accompanying legislative framework on devolution as ways to increase the effectiveness, equity, and inclusivity of government and service delivery. The devolution framework includes many laws mandating county governments to interact with residents during planning, budgeting, and service delivery monitoring and to make information publicly available. The aim of this research was to how public participation affect devolved governance system in Kenya at Kwale County Government. Specific objectives were developed for the study and included; to determine the impact of fair notice and time on Kenya's decentralized government structure and public engagement, to evaluate the impact of appropriate and accessible information on Kenya's decentralized government system and public engagement, to ascertain the impact of fair and open  dialogue on Kenya's decentralized government structure and public engagement and to determine the impact of inclusive and Adequatet representation on Kenya's decentralized government system, public involvement. This research was guided by Agency Theory, Stewardship theory and Stakeholder Theory. This study applied descriptive survey design. Target population of this research was five hundred and eighty residents of the Kinango Sub County. Data was presented using tables as well as figures. To test how public participation and devolved governance system in Kenya are related, a linear multiple regression test was conducted and analysis was carried via coefficient of multiple regression. With a mean of (mean=3.81, SD=.782), the majority of respondents said that members are aware of the topics to be discussed. The least number of respondents, with a mean of (mean=2.89, SD=0.345), agreed that members had access to information on the topics to be addressed. The outcome implies that many legislations in Kenya have acknowledged public participation in governance issues. The researcher can conclude that the study came to the conclusion that the success of Kenya's devolved government system is positively impacted by public engagement. The researcher recommends that in order to ensure that everyone has an equal chance to participate, emphasis should be placed on using local language while engaging the public. To decide how long a member should remain in the forum, more research should be conducted. The county governments should establish and put into effect public participation statutes through their county assemblies. The Researcher recommends to the devolved government system in Kenya   to use the structured framework that incorporates the four independent variables as a model for how to conduct public involvement.
Morphological Characterization and Adaptive Trail of Two Prominent T. Aman Rice (Oryza sativa L.) Lines under Different Locations of Bangladesh
Authors: Reza Md. Selim , Ahmed Bulbul , Alim S. M. A. , Islam Md. Mohimenul , Hoque Md. Muzammal , Nadim Md. Kawsar Alam
Published: November 2022

Two advanced lines: BR8693-8-4-2-1 and BR8693-17-6-2-2, along with BRRI dhan49 (S. Ck) and BRRI dhan33 (R. Ck) as checks were tested at farmers’ field in eight locations such as West Byde (BRRI Gazipur), Khulna (Dumuria), Habiganj (Sadar), Chapainawabganj (Gomostapur), Rangpur (Sadar), Feni (Dagonbhuyan), Chattagram (Hathazari) and Barishal (Sadar) during the season of  Transplanting Aman 2018. The trial was replicated three times in each location. The unit plot size was 17.94 m2 (4.6m x 3.9m). Seeding emergence for eight locations varied from 11-17 July 2018. Seedling age varied from 25-30 days among the locations. Seedlings were transplanted at 20 cm x 15 cm spacing. NPKS and Zn fertilizers were applied at the rate of 0, 15, 50, 12 and 3.6 kg ha-1, respectively. All fertilizers except urea were applied as basal whereas, urea was applied in 3 equal splits at 10, 25 and 40 days after transplanting (DAT) Other standard management practices were followed as and when necessary. No insecticide was used because the two advanced lines were insect resistant and diseases were not controlled (to identify susceptibility and tolerance level of lines). Date of seeding, transplanting, flowering and maturity, lodging tolerance, pest and disease incidence, phenotypic acceptance at vegetative and ripening stage, yield and yield components were recorded. Among the two advanced lines, BR8693-8-4-2-1 line was statistically significant from BR8693-17-6-2-2, BRRI Dhan49 and BRRI Dhan33 respectively and the disease reaction, farmers’ opinion, and special character of insect resistant, BR8693-8-4-2-1 was found to be superior for further variety trial. The main purpose of the experiment is to recommended insect resistant rice genotype for proposed variety trail. For yield estimation, 9 m2 sample area from each plot was harvested at maturity and grain yields were adjusted to 14% moisture content.
Response of Growth and Yield of Garlic cv. PG-18 against Various Plant Growth Regulators and Mulching along with Its Consortium
Authors: Singh Navdeep , Yadav Kulveer Singh , Kaur Harmandeep , Kishor Sachin
Published: November 2022

An investigation was carried out to examine the effect of plant growth regulators and mulching along with their combinations on growth and yield attributes of garlic at Agriculture Farm, School of Agricultural Sciences & Technology, RIMT University, Mandi Gobindgarh, Punjab, India during 2019-20 by using cultivar PG-18. The study comprised plant growth regulators (GA3 25 ppm, IAA 40 ppm and NAA 60 ppm) and mulches (Black polythene mulch and Rice straw mulch) along with a control. The experiment was replicated thrice and subjected to statistical analysis by using RBD at 5% of CD. The results revealed that growth parameters i.e. plant height (56.83 cm), number of leaves/pant (8.00) and stem diameter (7.87 mm) were reported utmost with the application of BPM+GA3 @ 25 ppm while longest leaf length (38.59 cm) and diameter of pseudo stem (4.73 cm) were measured with BPM+NAA @ 60 ppm  and SM+NAA @ 60 ppm, respectively. However, maximum number of cloves/bulb (19.33),diameter of cloves (2.93 mm), clove weight (1.73 g), diameter of bulb (4.04 cm), fresh weight (29.96 g),dry weight (10.53 g), yield/plot (480.30 g) and yield/ha (70.21 q ) were resulted by BPM+IAA @ 40 ppm.
Knowledge Level of NICRA Beneficiaries on Climate Resilient Technologies and Its Relationship with Their Profile Characteristics
Authors: Singh Arvind Kumar , Mishra Y. D. , Gupta Shobhana , Jadon Priyanka
Published: November 2022

Present study was conducted during 2021-22 in four NICRA implementing districts of Madhya Pradesh. Main aim of the study was to know the knowledge level of NICRA beneficiaries regarding climate resilient technologies being advocated by the scientist’s implementing NICRA project in selected Villages. A survey was conducted among randomly selected 300 NICRA beneficiaries with the help of an interview schedule. The findings of the study conclude that knowledge level of respondents benefiting by NICRA has a significant relationship with selected profile characteristics and it also shows that majority of the NICRA farmers (63.0 %) had a medium level knowledge on climate resilient technologies followed by low (23.7 %) and high (13.3 %).Hence there is a need to strengthen capacity building activities targeted to improve the knowledge and skills of adopt climate resilient agricultural technologies for sustainable agriculture. (Randhir Singh et al. (2014).
Efficacy of Three Doses of Fungicide Ridomil Gold 66 WP in the Control of Phytophthora spp., Agent of Cocoa Tree Black Pod Disease in Côte d'Ivoire
Authors: Klotioloma Coulibaly , Adama Ouattara , Sidoine Essis Brice , Norbert Kouame , Françoise Gogbe , Brigitte Guiraud , Pierre N’guessan Walet , Kotaix Acka , Mathias Tahi , Maryse Assi , Daouda Kone , François N’guessan
Published: November 2022

Black pod disease is a major constraint to cocoa production in Côte d'Ivoire. Varietal selection and fungicide treatments are the principal means of control. Fungicide Ridomil Gold 66 WP (6% Metalaxyl and 60% copper oxide) is commonly used. This study aimed at evaluating the effectiveness of three doses of Ridomil Gold 66 WP in the control of black pod disease. An experiment on the rates of this fungicide was conducted in two localities (Aboisso and Duékoué). The experimental design was a randomized complete block with four treatments, replicated four times. The treatments comprised untreated or controlled, single dose (3.3 g/l) or recommended dose, double dose (6.6 g/l) or 2×recommanded dose and triple dose (9.9 g/l) or 3×recommanded dose. All data collected were subjected to ANOVA with the test of Student and Newmann-Keuls at the 5% threshold. As result, no significant difference was observed between the treatments of the three doses of Ridomil. But, a significant difference was observed between the fungicide treatments and the control. In Duékoué, black pod rates ranged from 4.5 to 9.52% in fungicide treated plots against 33.8% in control plots. In Aboisso, black pod rates ranged from 7.11 to 13.83% for fungicide treated plots against 30.83% for the control plots. Fungicide treatments increased healthy cocoa pod yields in both localities. The yields were increased by 51.35 to 89.63% in treated plots of Aboisso and by 34.63 to 101.06% in treated plots of Duékoué. This study confirmed the efficacy of the recommended dose (3.3 g/l) of Ridomil Gold 66 WP in the management of black pod disease. Yet, even if high doses of Ridomil Gold 66 WP improved yield, it could also be led to the development of resistant strains of Phytophthora spp. and increase production costs.
Biological nitrogen fixation in theory, practice, and reality: a perspective on the molybdenum nitrogenase system
Authors: Threatt Stephanie D. , Rees Douglas C.
Published: November 2022

Nitrogenase is the sole enzyme responsible for the ATP‐dependent conversion of atmospheric dinitrogen into the bioavailable form of ammonia (NH3), making this protein essential for the maintenance of the nitrogen cycle and thus life itself. Despite the widespread use of the Haber–Bosch process to industrially produce NH3, biological nitrogen fixation still accounts for half of the bioavailable nitrogen on Earth. An important feature of nitrogenase is that it operates under physiological conditions, where the equilibrium strongly favours ammonia production. This biological, multielectron reduction is a complex catalytic reaction that has perplexed scientists for decades. In this review, we explore the current understanding of the molybdenum nitrogenase system based on experimental and computational research, as well as the limitations of the crystallographic, spectroscopic, and computational techniques employed. Finally, essential outstanding questions regarding the nitrogenase system will be highlighted alongside suggestions for future experimental and computational work to elucidate this essential yet elusive process.
Evaluation of MRI‐only based online adaptive radiotherapy of abdominal region on MR‐linac
Authors: Nousiainen Katri , Santurio Grichar Valdes , Lundahl Nils , Cronholm Rickard , Siversson Carl , Edmund Jens M.
Published: November 2022

Purpose

A hybrid magnetic resonance linear accelerator (MRL) can perform magnetic resonance imaging (MRI) with high soft‐tissue contrast to be used for online adaptive radiotherapy (oART). To obtain electron densities needed for the oART dose calculation, a computed tomography (CT) is often deformably registered to MRI. Our aim was to evaluate an MRI‐only based synthetic CT (sCT) generation as an alternative to the deformed CT (dCT)‐based oART in the abdominal region.

Methods

The study data consisted of 57 patients who were treated on a 0.35 T MRL system mainly for abdominal tumors. Simulation MRI‐CT pairs of 43 patients were used for training and validation of a prototype convolutional neural network sCT‐generation algorithm, based on HighRes3DNet, for the abdominal region. For remaining test patients, sCT images were produced from simulation MRIs and daily MRIs. The dCT‐based plans were re‐calculated on sCT with identical calculation parameters. The sCT and dCT were compared in terms of geometric agreement and calculated dose.

Results

The mean and one standard deviation of the geometric agreement metrics over dCT–sCT‐pairs were: mean error of 8 ± 10 HU, mean absolute error of 49 ± 10 HU, and Dice similarity coefficient of 55 ± 12%, 60 ± 5%, and 82 ± 15% for bone, fat, and lung tissues, respectively. The dose differences between the sCT and dCT‐based dose for planning target volumes were 0.5 ± 0.9%, 0.6 ± 0.8%, and 0.5 ± 0.8% at D2%, D50%, and D98% in physical dose and 0.8 ± 1.4%, 0.8 ± 1.2%, and 0.6 ± 1.1% in biologically effective dose (BED). For organs‐at‐risk, the dose differences of all evaluated dose–volume histogram points were within [–4.5%, 7.8%] and [–1.1 Gy, 3.5 Gy] in both physical dose and BED.

Conclusions

The geometric agreement metrics were within typically reported values and most average relative dose differences were within 1%. Thus, an MRI‐only sCT‐based approach is a promising alternative to the current clinical practice of the abdominal oART on MRL.
Recognizing early MRI signs (or their absence) is crucial in diagnosing metachromatic leukodystrophy
Authors: Schoenmakers Daphne H. , Beerepoot Shanice , Krägeloh‐Mann Ingeborg , Elgün Saskia , Bender Benjamin , van der Knaap Marjo S. , Wolf Nicole I. , Groeschel Samuel
Published: November 2022

Objectives

Metachromatic leukodystrophy (MLD) has characteristic white matter (WM) changes on brain MRI, which often trigger biochemical and genetic confirmation of the diagnosis. In early or pre‐symptomatic disease stages, these typical MRI changes might be absent, hampering early diagnosis. This study aims to describe the characteristics of MRI WM abnormalities at diagnosis, related to clinical presentation.

Methods

We retrospectively reviewed brain MRIs of MLD patients followed in 2 centers at the time of diagnosis regarding MLD MRI score and presence of tigroid pattern. In addition, MLD subtype, symptom status, CNS/PNS phenotype, motor/cognitive/mixed phenotype, and the presence of CNS symptoms were evaluated.

Results

We included 104 brain MRIs from patients with late‐infantile (n = 43), early‐juvenile (n = 24), late‐juvenile (n = 20) and adult (n = 17) onset. Involvement of the corpus callosum was a characteristic early MRI sign and was present in 71% of the symptomatic late‐infantile patients, 94% of the symptomatic early‐juvenile patients and 100% of the symptomatic late‐juvenile and adult patients. Symptomatic early‐juvenile, late‐juvenile and adult patients generally had WM abnormalities on MRI suggestive of MLD. By contrast, 47% of the early‐symptomatic late‐infantile patients had no or only mild WM abnormalities on MRI, even in the presence of CNS symptoms including pyramidal signs.

Interpretation

Patients with late‐infantile MLD may have no or only mild, nonspecific abnormalities at brain MRI, partly suggestive of ‘delayed myelination’, even with clear clinical symptoms. This may lead to significant diagnostic delay. Knowledge of these early MRI signs (or their absence) is important for fast diagnosis.
Molecular Configuration Engineering in Hole‐Transporting Materials toward Efficient and Stable Perovskite Solar Cells
Authors: Tang Rong , Liu Haitao , Xu Yining , Chen Kaixing , Zhang Jin , Zhang Ping , Zhong Cheng , Wu Fei , Zhu Linna
Published: November 2022

The development of hole‐transporting materials (HTMs) that can passivate defects in perovskite is of great significance in improving the efficiency and long‐term stability of perovskite solar cells. To date, the investigation on HTMs mainly focus on exploring new structures, while molecular configuration is seldomly concerned. In this work, two small molecules are developed as HTMs with benzil and phenanthrene quinone as the core structure, respectively. With similar structure and the same defect passivation groups, whereas, the two molecules exhibit different configurations, thus distinct properties. Compared to 3,6‐bis(3,6‐bis(bis(4‐methoxyphenyl)amino)‐9H‐carbazol‐9‐yl)phenanthrene‐9,10‐dione (PQ) with a rigid core structure, the benzil group in 1,2‐bis(4‐(3,6‐bis(bis(4‐methoxyphenyl)amino)‐9H‐carbazol‐9‐yl)phenyl)ethane‐1,2‐dione (DB) is flexible and can adjust molecular configuration to efficiently interact with the underlying perovskite material, which is confirmed from both experimental results and theoretical simulations. The DB‐based device exhibits a high power conversion efficiency of 22.21% with excellent long‐term stability, superior to the PQ‐based device (20.22%). This study demonstrates that molecular configuration engineering will directly affect the properties of hole transport materials, as well as their interactions with perovskite, which should also be taken into consideration when devising HTMs.
Stem Cell‐Niche Engineering via Multifunctional Hydrogel Potentiates Stem Cell Therapies for Inflammatory Bone Loss
Authors: Li Gang , Li Zimeng , Li Lanlan , Liu Shan , Wu Peng , Zhou Min , Li Chenwen , Li Xiaodong , Luo Gaoxing , Zhang Jianxiang
Published: November 2022

Effective therapies capable of simultaneously inhibiting inflammation and promoting bone healing remain to be developed for inflammatory bone disease. Stem cell therapies hold great promise for a variety of diseases, but their translation is hampered by low cell survival, rapid clearance, and limited functional integration of transplanted stem cells in target tissues. Herein, a multifunctional hydrogel‐based stem cell niche engineering strategy is reported for the treatment of inflammatory bone loss. By rationally integrating different functional modules, an injectable hydrogel‐based stem niche is engineered, which possesses temperature‐triggered gelling performance, inflammation/oxidative stress‐resolving activity, stem‐cell binding and survival‐enhancing capacity, and osteogenesis‐promoting capability. Using ectomesenchymal stem cells (EMSCs), effectiveness of this functionally advanced synthetic stem cell niche is demonstrated in rats with periodontitis, a representative inflammatory bone loss disease. Synergistic effects of the multifunctional hydrogel and EMSCs are also confirmed, with respect to normalizing the pathological microenvironment and improving alveolar bone regeneration in the periodontal tissue. Mechanistically, inflammation/oxidative stress‐resolving and osteogenic differentiation promoting capacities of the synthetic stem cell niche are mainly achieved by an incorporated nanotherapy via the GDF15/Atf3/c‐Fos axis of the MAPK signaling pathway. Besides periodontitis, the newly engineered hydrogel‐stem cell therapies are promising for the treatment of other inflammatory bone defects.
Energy Transfer Induced by TADF Polymer Enables the Recycling of Excitons in Perovskite Solar Cells
Authors: Meng Yuanyuan , Zhang Jiasen , Liu Chang , Zheng Kanghui , Xie Lisha , Bu Shixiao , Han Bin , Cao Ruikun , Yin Xu , Liu Cuirong , Ge Ziyi
Published: November 2022

Formamidinium lead triiodide (FAPbI3) has been demonstrated as the most efficient perovskite system to date, due to its excellent thermal stability and an ideal bandgap approaching the Shockley‐Queisser limit. Whereas, there are intrinsic quantum confinement effects in FAPbI3, which lead to unwanted non‐radiative recombination. Additionally, the black α‐phase of FAPbI3 is unstable under room temperature due to the significant residual tensile stress in the film. To simultaneously address the above issues, a thermally‐activated delayed fluorescence polymer P1 is designed in the study to modify the FAPbI3 film. Owing to the spectral overlap between the photoluminescence of P1 and absorption of the above‐bandgap quantum wells of FAPbI3, the Förster energy transfer occurs at the P1/FAPbI3 interface, which further triggers the Dexter energy transfer within FAPbI3. The exciton “recycling” can thus be realized, which reduces the non‐radiative recombination losses in perovskite solar cells (PSCs). Moreover, P1 is found to introduce compressive stress into FAPbI3, which relieves the tensile stress in perovskite. Consequently, the PSCs with P1 treatment achieve an outstanding power conversion efficiency (PCE) of 23.51%. Moreover, with the alleviation of stress in the perovskite film, flexible PSCs (f‐PSCs) also deliver a high PCE of 21.40%.
Superwetting Injectable Hydrogel with Ultrastrong and Fast Tissue Adhesion for Minimally Invasive Hemostasis
Authors: Wei Congying , Shi Weili , Zhao Chuangqi , Yang Shuai , Zheng Jiajia , Zhong JinPan , Zhao Tianyi , Kong Simin , Gong Xi , Liu Mingjie
Published: November 2022

Injectable hydrogels have recently emerged as alternatives to sutures for various clinical indications. However, existing injectable hydrogels are unsuitable for hemostasis in minimally invasive surgery because of their weak interfacial adhesion and complex/prolonged processing. Herein, a superwetting injectable hydrogel composed of oppositely charged polysaccharides is developed. The spontaneous spreading of the injectable hydrogel on the surfaces achieves complete wetting and forms tight interfacial contact by absorbing the interfacial water. The superwetting ability and subsequent covalent crosslinking perform fast and ultrastrong wet adhesion (140 kPa) on the tissue surface. Ex vivo porcine and in vivo rat models show that the hydrogel successfully leads to the aggregation of erythrocytes for targeted hemostasis (in less than 12 s) without requiring external adjuncts, and no postsurgical adhesions to the peripheral tissues. This further demonstrates that hydrogel can act as an effective hemostasis agent in laparoscopic surgery in a rabbit model. Overall, the strong wet adhesion, antibacterial properties, and easy operability make this injectable hydrogel a promising candidate for hemostasis applications, as it can successfully combine clinical efficacy and transformation opportunities for minimally invasive surgery.
Colloidal Quantum Dot Infrared Lasers Featuring Sub‐Single‐Exciton Threshold and Very High Gain
Authors: Taghipour Nima , Dalmases Mariona , Whitworth Guy L. , Dosil Miguel , Othonos Andreas , Christodoulou Sotirios , Liga Shanti Maria , Konstantatos Gerasimos
Published: November 2022

The use of colloidal quantum dots (CQDs) as a gain medium in infrared laser devices has been underpinned by the need for high pumping intensities, very short gain lifetimes, and low gain coefficients. Here, PbS/PbSSe core/alloyed‐shell CQDs are employed as an infrared gain medium that results in highly suppressed Auger recombination with a lifetime of 485 ps, lowering the amplified spontaneous emission (ASE) threshold down to 300 µJ cm−2, and showing a record high net modal gain coefficient of 2180 cm−1. By doping these engineered core/shell CQDs up to nearly filling the first excited state, a significant reduction of optical gain threshold is demonstrated, measured by transient absorption, to an average‐exciton population‐per‐dot 〈Nth〉g of 0.45 due to bleaching of the ground state absorption. This in turn have led to a fivefold reduction in ASE threshold at 〈Nth〉ASE = 0.70 excitons‐per‐dot, associated with a gain lifetime of 280 ps. Finally, these heterostructured QDs are used to achieve near‐infrared lasing at 1670 nm at a pump fluences corresponding to sub‐single‐exciton‐per‐dot threshold (〈Nth〉Las = 0.87). This work brings infrared CQD lasing thresholds on par to their visible counterparts, and paves the way toward solution‐processed infrared laser diodes.
Advancing High‐Performance Mixed Matrix Membrane via Magnetically Aligned Polycrystalline Co0.5Ni0.5FeCrO4 Magnetic Spinel Nanoparticles for Effective H2/CO2 and O2/N2 Gas Separation
Authors: Ashtiani Saeed , Azadmanjiri Jalal , Hong Nguyen Vu , Floreková Jana , Regmi Chhbilal , Sofer Zdeněk , Khoshnamvand Mehdi , Friess Karel
Published: November 2022

Gas separation matrix membranes (MMMs) benefit from a combination of a polymer matrix and heterogeneous solid or liquid (nano) additives. However, improvements in mechanical strength of membrane permeability or gas selectivity are often overbalanced by morphological deficiencies, such as aggregation or sedimentation of the nanofiller, due to poor control at the nano level. Here, the controlled orthogonal magnetic field deposition of self‐invented spinel Co0.5Ni0.5FeCrO4 magnetic nanoparticles (SMNPs) into the cellulose triacetate (CTA) results in well‐defined gas transport pathways in the membrane and enhances gas separation performances by expanding the effective‐selective surface area. Contrariwise, the structural observation of the fabricated MMMs in the absence of the magnetic field shows precipitation and aggregation of the particles at the bottom of the membrane. The permeability and selectivity of the H2/CO2 and O2/N2 gas pairs surpass the 2008 and 2015 Robeson upper bounds for the controlled embedding of the SMNPs series (up to 15 wt.%) while the neat CTA or MMM with a random non‐controlled SMNPs distribution exhibits substantially lower permeability and selectivity values. This work contributes to the development of magnetic field casting as a facile technique that advances the gas transport properties of MMMs, efficient for air separation.
Stereoselective Synthesis of Structurally Diverse (S)‐Lactams via an Engineered Amine Dehydrogenase
Authors: Qian Yuanyi , Chu Liliang , Zhang Xiaoyan , Lu Zhiwen , Bai Yunpeng
Published: November 2022

Optically pure lactams have a wide diversity of applications, one of which is serving as important intermediates in the synthesis of agricultural bioactive compounds or pharmaceuticals. Efficient stereoselective synthesis of chiral lactams with low‐cost amine donors under mild conditions is desired for manufacturing of these important chemicals. Herein, a two‐step chemo‐enzymatic strategy has been designed to produce (S)‐lactams by engineering a natural amine dehydrogenase from Thermoanaerobacter thermohydrosulfuricus (TtherAmDH). TtherAmDH was subjected to eight cycles of directed evolution to enhance its reductive amination activity toward keto acid substrates. The variants showed improved specific activity toward 6 tested substrates and gave high stereoselectivities of up to 99% in the asymmetric synthesis of γ‐ and δ‐ lactams. In particular, TtherAmDHV8 showed a 237‐fold higher specific activity toward the model substrate levulinic acid and gave (S)‐5‐methyl‐2‐pyrrolidone in 99% ee with a space‐time yield of 75.3 g L−1 d−1. These results indicate that the engineered amine dehydrogenase TtherAmDH can serve as an efficient biocatalyst for the manufacture of highly valued chiral lactams.

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Copper‐Catalyzed Asymmetric 1,6‐Addition of Borylalkene‐Derived Nucleophiles to para‐Quinone Methides
Authors: Meng Deyuan , He Jing , Yoon Woojin , Yun Hoseop , Han Jung Tae , Yun Jaesook
Published: November 2022

Herein, we report the catalytic 1,6‐addition of chiral alkyl copper nucleophiles, in‐situ generated from borylalkenes and a copper‐hydride catalyst under mild conditions. Chemo‐ and stereoselective control was crucial in this reductive coupling process of borylalkenes and para‐quinone methides, sequentially forming adjacent stereogenic centers with good diastereo‐ and enantioselectivity. Through the multicomponent and catalytic tandem reactions, asymmetric 1,6‐adducts of p‐quinone methides were efficiently synthesized.

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Bias‐Free Solar‐Driven Syngas Production: A Fe2O3Photoanode Featuring Single‐Atom Cobalt Integrated with a Silver‐Palladium Cathode
Authors: Zhao Bin , Huang Xiaojuan , Ding Yong , Bi Yingpu
Published: November 2022

Photoelectrochemical syngas production from aqueous CO2is a promising technique for carbon capture and utilization. Herein, we demonstrate the efficient and tunable syngas production by integrating a single‐atom cobalt‐catalyst‐decorated α‐Fe2O3photoanode with a bimetallic Ag/Pd alloy cathode. A record syngas production activity of 81.9 μmol cm−2 h−1(CO/H2ratio: ≈1 : 1) was achieved under artificial sunlight (AM 1.5 G) with an excellent durability. Systematic studies reveal that the Co single atoms effectively extract the holes from Fe2O3photoanodes and serve as active sites for promoting oxygen evolution. Simultaneously, the Pd and Ag atoms in bimetallic cathodes selectively adsorb CO2and protons for facilitating CO production. Further incorporation with a photovoltaic, to allow solar light (>600 nm) to be utilized, yields a bias‐free CO2reduction device with solar‐to‐CO and solar‐to‐H2conversion efficiencies up to 1.33 and 1.36 %, respectively.
A Far‐Red Molecular Rotor Fluorogenic Trehalose Probe for Live Mycobacteria Detection and Drug‐Susceptibility Testing
Authors: Banahene Nicholas , Gepford Dana M. , Biegas Kyle J. , Swanson Daniel H. , Hsu Yen‐Pang , Murphy Brennan A. , Taylor Zachary E. , Lepori Irene , Siegrist M. Sloan , Obregón‐Henao Andrés , Van Nieuwenhze Michael S. , Swarts Benjamin M.
Published: November 2022

Increasing the speed, specificity, sensitivity, and accessibility of mycobacteria detection tools are important challenges for tuberculosis (TB) research and diagnosis. In this regard, previously reported fluorogenic trehalose analogues have shown potential, but their green‐emitting dyes may limit sensitivity and applications in complex settings. Here, we describe a trehalose‐based fluorogenic probe featuring a molecular rotor turn‐on fluorophore with bright far‐red emission (RMR‐Tre). RMR‐Tre, which exploits the unique biosynthetic enzymes and environment of the mycobacterial outer membrane to achieve fluorescence activation, enables fast, no‐wash, low‐background fluorescence detection of live mycobacteria. Aided by the red‐shifted molecular rotor fluorophore, RMR‐Tre exhibited up to a 100‐fold enhancement in M. tuberculosis labeling compared to existing fluorogenic trehalose probes. We show that RMR‐Tre reports on M. tuberculosis drug resistance in a facile assay, demonstrating its potential as a TB diagnostic tool.
Ordered Macro/Microporous Ionic Organic Framework for Efficient Separation of Toxic Pollutants from Water
Authors: Fajal Sahel , Hassan Atikur , Mandal Writakshi , Shirolkar Mandar M. , Let Sumanta , Das Neeladri , Ghosh Sujit K.
Published: November 2022

In case of pollutant segregation, fast mass diffusion is a fundamental criterion in order to achieve improved performance. The rapid mass transport through porous materials can be achieved by availing large open pores followed by easy and complete accessibility of functional sites. Inducing macroporosity into such materials could serve as ideal solution providing access to large macropores that offer unhindered transport of analyte and full exposure to interactive sites. Moreover, the challenge to configure the ionic‐functionality with macroporosity could emerge as an unparalleled avenue toward pollutants separation. Herein, we strategized a synthetic protocol for construction of a positively charged hierarchically‐porous ordered interconnected macro‐structure of organic framework where the size and number of macropores can easily be tuned. The ordered macropores with strong electrostatic interaction synergistically exhibited ultrafast removal efficiency towards various toxic pollutants.
Excitation‐Dependent Multicolour Luminescence of Organic Materials: Internal Mechanism and Potential Applications
Authors: Shen Yunxia , An Zhongfu , Liu Haichao , Yang Bing , Zhang Yujian
Published: November 2022

Excitation‐dependent emission (Ex‐de) materials have been of considerable academic interest and have potential applications in real life. Such multicolour luminescence is a characteristic exception to the ubiquitously accepted Kasha's rule. This phenomenon has been increasingly presented in some studies on different luminescence systems; however, a systematic overview of the mechanisms underlying this phenomenon is currently absent. Herein, we resolve this issue by classifying multicolour luminescence from single chromophores and dual/ternary chromophores, as well as multiple emitting species. The underlying processes are described based on electronic and/or geometrical conditions under which the phenomenon occurs. Before we present it in categories, related photophysical and photochemical foundations are introduced. This systematic overview will provide a clear approach to designing multicolour luminescence materials for special applications.
Anionic Magnesium and Calcium Hydrides: Transforming CO into Unsaturated Disilyl Ethers
Authors: McMullen Jacob S. , Huo Ryan , Vasko Petra , Edwards Alison J. , Hicks Jamie
Published: November 2022

The synthesis, characterisation and reactivity of two isostructural anionic magnesium and calcium complexes is reported. By X‐ray and neutron diffraction techniques, the anionic hydrides are shown to exist as dimers, held together by a range of interactions between the two anions and two bridging potassium cations. Unlike the vast proportion of previously reported dimeric group 2 hydrides, which have hydrides that bridge two group 2 centres, here the hydrides are shown to be “terminal”, but stabilised by interactions with the potassium cations. Both anionic hydrides were found to insert and couple CO under mild reaction conditions to give the corresponding group 2 cis‐ethenediolate complexes. These cis‐ethenediolate complexes were found to undergo salt elimination reactions with silyl chlorides, allowing access to small unsaturated disilyl ethers with a high percentage of their mass originating from the C1 source CO.
Confinement‐Driven Photophysics in Hydrazone‐Based Hierarchical Materials
Authors: Thaggard Grace C. , Leith Gabrielle A. , Sosnin Daniil , Martin Corey R. , Park Kyoung Chul , McBride Margaret K. , Lim Jaewoong , Yarbrough Brandon J. , Maldeni Kankanamalage Buddhima K. P. , Wilson Gina R. , Hill Austin R. , Smith Mark D. , Garashchuk Sophya , Greytak Andrew B. , Aprahamian Ivan , Shustova Natalia B.
Published: November 2022

Confinement‐imposed photophysics was probed for novel stimuli‐responsive hydrazone‐based compounds demonstrating a conceptual difference in their behavior within 2D versus 3D porous matrices for the first time. The challenges associated with photoswitch isomerization arising from host interactions with photochromic compounds in 2D scaffolds could be overcome in 3D materials. Solution‐like photoisomerization rate constants were realized for sterically demanding hydrazone derivatives in the solid state through their coordinative immobilization in 3D scaffolds. According to steady‐state and time‐resolved photophysical measurements and theoretical modeling, this approach provides access to hydrazone‐based materials with fast photoisomerization kinetics in the solid state. Fast isomerization of integrated hydrazone derivatives allows for probing and tailoring resonance energy transfer (ET) processes as a function of excitation wavelength, providing a novel pathway for ET modulation.
Highly Efficient Production of Nanoporous Block Copolymers with Arbitrary Structural Characteristics for Advanced Membranes
Authors: Guo Leiming , Ntetsikas Konstantinos , Zapsas Georgios , Thankamony Roshni , Lai Zhiping , Hadjichristidis Nikos
Published: November 2022

The great significance of boosting the design of percolating nanopore structures in block copolymers (BCPs) for various cases has been widely demonstrated in the past several decades. However, it still remains challenging to prepare the desired porous structures in a rapid, facile, and universal manner. Here we have developed an unconventional and benchtop strategy to rapidly generate the nanoporous polystyrene‐based BCPs with arbitrary structural characteristics regardless of the BCP bulk morphology. This universal pore‐forming strategy enables the sustainable CO2‐based BCPs to form advanced membranes after 1 s soaking for efficiently rejecting 94.2 % brilliant blue R (826 g mol−1). Meanwhile, the water permeance retains around 1020 L (m2 h bar)−1, which is 1–3 orders of magnitude higher than that of other membranes. This strategy may offer an excellent opportunity to introduce percolating pore structures in those newly developed BCPs with which the previously reported pore‐forming methods may not deal.
Phosphoric Acid‐Catalyzed Enantioselective Synthesis of Axially Chiral Anthrone‐based Compounds
Authors: He Shi‐Jiang , Zhu Shuai , Qiu Sheng‐Qi , Ding Wei‐Yi , Cheng Jun Kee , Xiang Shao‐Hua , Tan Bin
Published: November 2022

Anthrones and analogues are structural cores shared by diverse pharmacologically active natural and synthetic compounds. The sp2‐rich nature imposes inherent obstruction to introduce stereogenic element onto the tricyclic aromatic backbone. In our pursuit to expand the chemical space of axial chirality, a novel type of axially chiral anthrone‐derived skeleton was discovered. This work establishes oxime ether as suitable functionality to furnish axial chirality on symmetric anthrone skeletons through stereoselective condensation of the carbonyl entity with long‐range chirality control. The enantioenriched anthrones could be elaborated into dibenzo‐fused seven‐membered N‐heterocycles containing well‐defined stereogenic center via Beckmann rearrangement with axial‐to‐point chirality conversion.
Proton‐Reservoir Hydrogel Electrolyte for Long‐Term Cycling Zn/PANI Batteries in Wide Temperature Range
Authors: Feng Doudou , Jiao Yucong , Wu Peiyi
Published: November 2022

Advanced aqueous batteries are promising for next generation flexible devices owing to the high safety, yet still requiring better cycling stability and high capacities in wide temperature range. Herein, a polymeric acid hydrogel electrolyte (PAGE) with 3 M Zn(ClO4)2 was fabricated for high performance Zn/polyaniline (PANI) batteries. With PAGE, even at −35 °C the Zn/Zn symmetrical battery can keep stable for more than 1 500 h under 2 mA cm−2, and the Zn/PANI battery can provide ultra‐high stable specific capacity of 79.6 mAh g−1 for more than 70 000 cycles at 15 A g−1. This can be mainly ascribed to the −SO3−H+ function group in PAGE. It can generate constant protons and guide the (002) plane formation to accelerate the PANI redox reaction kinetics, increase the specific capacity, and suppress the side reaction and dendrites. This proton‐supplying strategy by polymeric acid hydrogel may further propel the development of high performance aqueous batteries.
Intramolecular Interception of the Remote Position of Vinylcarbene Silver Complex Intermediates by C(sp3)−H Bond Insertion
Authors: Díaz‐Jiménez Àlex , Monreal‐Corona Roger , Poater Albert , Álvarez María , Borrego Elena , Pérez Pedro J. , Caballero Ana , Roglans Anna , Pla‐Quintana Anna
Published: November 2022

The trapping of the elusive vinylogous position of a vinyl carbene with an aliphatic C(sp3)−H bond has been achieved for the first time during a silver‐catalyzed carbene/alkyne metathesis (CAM) process. A Tpx‐containing silver complex first promotes the generation of a donor‐acceptor silver carbene which triggers CAM, generating a subsequent donor‐donor vinyl silver carbene species, which then undergoes a selective vinylogous C(sp3)−H bond insertion, leading to the synthesis of a new family of benzoazepines. Density functional theory (DFT) calculations unveil the reaction mechanism, which allows proposing that the C−H bond insertion reaction takes place in a stepwise manner, with the hydrogen shift being the rate determining step.
α‐Synuclein as a Target for Metallo‐Anti‐Neurodegenerative Agents
Authors: Cao Kaiming , Zhu Yang , Hou Zhuanghao , Liu Manman , Yang Yanyan , Hu Hongze , Dai Yi , Wang Yu , Yuan Siming , Huang Guangming , Mei Jiaming , Sadler Peter J. , Liu Yangzhong
Published: November 2022

The unique thermodynamic and kinetic coordination chemistry of ruthenium allows it to modulate key adverse aggregation and membrane interactions of α‐synuclein (α‐syn) associated with Parkinson's disease. We show that the low‐toxic RuIII complex trans‐[ImH][RuCl4(Me2SO)(Im)] (NAMI‐A) has dual inhibitory effects on both aggregation and membrane interactions of α‐syn with submicromolar affinity, and disassembles pre‐formed fibrils. NAMI‐A abolishes the cytotoxicity of α‐syn towards neuronal cells and mitigates neurodegeneration and motor impairments in a rat model of Parkinson's. Multinuclear NMR and MS analyses show that NAMI‐A binds to residues involved in protein aggregation and membrane binding. NMR studies reveal the key steps in pro‐drug activation and the effect of activated NAMI‐A species on protein folding. Our findings provide a new basis for designing ruthenium complexes which could mitigate α‐syn‐induced Parkinson's pathology differently from organic agents.
Nitrenoid from Oxime: A Practical Synthesis of Planar Chiral Ferrocenyl Phenanthridines via Nitrene‐Involved Ring‐Expansion Reaction
Authors: Li Na , Hong Biqiong , Zhao Jinbo , Gu Zhenhua
Published: November 2022

Nitrenes and nitrenoids are highly reactive species and the proposed key intermediates in nitrogen‐containing heterocyclic compound synthesis. In this work, we developed a practical method for the synthesis of phenanthridines by the reaction of oximes and Grignard reagents (with or without diethylzinc) via ring‐expansion of magnesium coordinated nitrenoid complex as the key step. The method has been used to synthesize optically active planar chiral ferrocenyl phenanthridines.
Palmitoylated cellulose nanocrystal/polycarbonate composite with high mechanical performance and good transparency
Authors: Xie Zhongyuan , Wang Xingjuan , Chen Zhangyun , Jiang Hua
Published: November 2022

To fabricate polycarbonate (PC) composites with high mechanical and optical properties, PC composite films reinforced by cellulose nanocrystals esterified using palmitoyl chloride (palmitoylated cellulose nanocrystal [PAL‐CNCs]) were fabricated by casting‐evaporation and characterized by several techniques. It was shown that the PAL‐CNCs with a substitution degree of 0.43 and the crystalline index of 53.3% were better dispersed in chloroform and tetrahydrofuran, and achieved a water contact angle of 81.0°. The crystallite size and crystalline index of the PC in the composite film significantly increased to more than 5.2 nm and 51.5%, respectively, after the incorporation of the PAL‐CNCs. The PC composite film had an increase of 91.4% in tensile strength, 84.1% in Young's modulus, and a decrease of 5% in impact strength. Meanwhile, its UV–Vis‐light transmittance was above 90%. Therefore, the palmitoylated ‐CNCs were a better candidate for engineering PC composites with high mechanical performance and transparency.
Synthesis of fluorine contained hyperbranched polysiloxane and their effect on the thermal conductivity of epoxy resins
Authors: Jia Yuan , Yang Juxiang , Liu Zhen , Li Beibei
Published: November 2022

To improve the thermostability properties of epoxy (EP) resin, two kinds of novel hyperbranched polysiloxanes containing fluorine were prepared via the sol–gel process and the convenient transesterification process, respectively (F‐HBPSi‐1 and F‐HBPSi‐2). These two prepared F‐HBPSi were then used as modifier phased to blend with EP to obtain two new series polymer alloys F‐HBPSi‐1/EP and F‐HBPSi‐2/EP. The dielectric properties and thermal conductivities of the cured F‐HBPSi/EP resins were measured, while their thermal properties were also investigated by thermogravimetry (TG). The results showed that both the thermal conductivities and the thermostability properties of these two F‐HBPSi/EP were increased effectively, without further damaging their dielectric properties. Meanwhile, the F‐HBPSi‐2/EP exhibits better thermal conductivities and thermostability properties than that of F‐HBPSi‐1/EP. The improved overall performance of F‐HBPSi‐2/EP can be attributed to the low viscosity and excellent compatibility of F‐HBPSi‐2, as well as the good synergism between fluorine and silicon.
Synthesis and performance evaluation of carboxyl‐rich low phosphorus copolymer scale inhibitor
Authors: Ma Wentao , Zhang Yu , Li Huan
Published: November 2022

A novel low phosphorus terpolymer scale inhibitor P(IA‐MA‐SHP) was prepared by aqueous free radical polymerization using itaconic acid (IA), maleic acid (MA), and sodium hypophosphite (SHP) as raw materials. It was mainly used as an efficient scale inhibitor to inhibit CaCO3. The structures of the copolymers were characterized by Fourier transform infrared,1H‐NMR, and13C‐NMR, and the thermal properties, and scale sample crystal structure morphology of the copolymers were analyzed by thermogravimetric analysis, x‐ray diffraction (XRD), and scanning electron microscope (SEM). The effects of dosage, monomer ratio, temperature, and reaction time on the scale inhibition effect were investigated, and the optimal synthesis conditions were determined. The results show that: when the monomer ratio isn(IA):n(MA) = 1.0:1.0, the mass fraction of SHP is 10%, the amount of ammonium persulfate initiator is 12%, the reaction temperature is 90°C, and the reaction time is 4 h, when the dosage of the agent is 20 mg L−1, the scale inhibition rate of CaCO3is 94.30%, while it also has a favorable inhibitory effect on CaSO4. The results of SEM and XRD show that the copolymer scale inhibitor can distort the lattice and has a favorable adsorption and dispersion effect. In addition, it has a positive effect on controlling the scale.