bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation
Authors: Gulyaeva Ekaterina S. , Buhaibeh Ruqaya , Boundor Mohamed , Azouzi Karim , Willot Jérémy , Bastin Stéphanie , Duhayon Carine , Lugan Noël , Filippov Oleg A. , Sortais Jean‐Baptiste , Valyaev Dmitry A. , Canac Yves
Published: February 2024

Systematic modification of the chelating NHC‐phosphine ligand (NHC = N‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac‐[(Ph2PCH2NHC)Mn(CO)3Br] has been performed and the catalytic activity of the resulting complexes was evaluated using acetophenone as a benchmark substrate. While the variation of phosphine and NHC moieties led to inferior results than for a parent system, the incorporation of a phenyl substituent into the ligand methylene bridge improved catalytic performance by ca. 3 times providing maximal TON values in the range of 15000–20000. Mechanistic investigation combining experimental and computational studies allowed to rationalize this beneficial effect as an enhanced stabilization of reaction intermediates including anionic hydride species fac‐[(Ph2PC(Ph)NHC)Mn(CO)3H]− playing a crucial role in the hydrogenation process. These results highlight the interest of such carbon bridge substitution strategy being rarely employed in the design of chemically non‐innocent ligands.
Palladium‐Catalyzed C‐H Olefination of Imidazo[1,2a] pyridine Carboxamide in Aqueous Ethanol under Oxygen
Authors: Balaso Mohite Sachin , Kousin Mirza Yafia , Kumar Vishal , Partap Sangh , Baji Baba Shaik , Alake John , Bera Milan , Karpoormath Rajshekhar
Published: February 2024

The advancement of sustainable chemistry and changes in the economy are strongly intertwined. Reaction time, cost savings, moderate temperatures, and generation of the fewest byproducts are frequently achieved by using catalytic processes. Herein, we report the C−H olefination of imidazo[1,2a] pyridine carboxamides with various acrylates in the presence of Pd (OAc)2 with O2 as the oxidant in aqueous ethanol rather than using non‐ecofriendly solvents. The C−H activation features most user‐friendly reaction conditions, excellent yield as well as plenty substrate scope and applicable for C−H deuteriation of the corresponding heteroarenes with D2O. Experimental mechanistic studies indicate that C−H activation step succeeded after formation of tetra coordinated square planer Pd‐substrate adduct.
A Versatile, Functional Group‐Tolerant, and Bench‐Stable Iron Precatalyst for Building Arene and Triazine Rings by [2+2+2] Cycloadditions
Authors: Parisot William , Haddad Mansour , Phansavath Phannarath , Lefèvre Guillaume , Ratovelomanana‐Vidal Virginie
Published: February 2024

We report an efficient iron‐catalyzed cycloaddition procedure leading to the construction of (hetero)aromatic rings by alkyne [2+2+2] cycloisomerization. This method relies on the use of an air‐stable (N,N)Fe(II) precursor easily prepared from a commercially available ligand derived from 1,10‐phenanthroline, reduced in situ into a catalytically active non‐innocent (N,N ⋅−)2Fe(II) species. This system displays a large scope application, operates under mild conditions and at low catalytic charges (25 cycloadducts formed, up to 1.5 mol% catalyst). Moreover, this method also enables access to 29 cycloadducts by cross‐cycloisomerization between 1,6‐ or 1,7‐diynes and alkynes in near‐equimolar conditions. 1,3,5‐Triazines can also be prepared with this procedure starting from the corresponding cyanamides. Scale‐up reactions and post‐functionalization of several cycloadducts also show that this [2+2+2] cycloaddition can be used in multistep sequences.
Synthesis of [1]Benzothieno[3,2‐b][1]benzothiophenes through Iodine‐Mediated Sulfur Insertion Reaction
Authors: Ito Kazuki , Nakamura Kohei , Yoshida Kazuhiro
Published: February 2024

[1]Benzothieno[3,2‐b][1]benzothiophenes (BTBTs) are important molecules that have been extensively studied as high‐performance organic field‐effect transistors (OFETs). Therefore, it is important to develop a simple synthetic method for these molecules. In this paper, a synthetic method to obtain the BTBTs from 2‐arylbenzo[b]thiophenes and elemental sulfur, in which two C−S bonds are formed at once, is described. In this method, molecular iodine plays a very important role as an additive. The role of iodine is discussed in the presumed reaction pathways.
Photochemical Synthesis of Lactones, Cyclopropanes and ATRA Products: Revealing the Role of Sodium Ascorbate**
Authors: Rrapi Marie , Batsika Charikleia S. , Nikitas Nikolaos F. , Tappin Nicholas D. C. , Triandafillidi Ierasia , Renaud Philippe , Kokotos Christoforos G.
Published: February 2024

Light‐mediated processes have received significant attention, since they have re‐surfaced unconventional reactivity platforms, complementary to conventional polar chemistry. γ‐Lactones and cyclopropanes are prevalent moieties, found in numerous natural products and pharmaceuticals. Among various methods for their synthesis, light‐mediated protocols are coming to the spotlight, although these are contingent upon the use of photoorgano‐ or metal‐based catalysts. Herein, we introduce a novel photochemical activation of iodo‐reagents via the use of cheap sodium ascorbate or ascorbic acid to enable their homolytic scission and addition onto double bonds. The developed protocol was applied successfully to the formal [3+2] cycloaddition for the synthesis of γ‐lactones, traditional atom transfer radical addition (ATRA) reactions and the one‐pot two‐step conversion of alkenes to cyclopropanes. In all cases, the desired products were obtained in good to high yields, while the reaction mechanism was thoroughly investigated. Depending on the nature of the iodo‐reagent, a halogen or a hydrogen‐bonded complex is formed, which initiates the process.
Kraft‐Wärme‐Kopplung für Hybridspeicher
Authors: Kupper Christian
Published: February 2024

Der Ausbau erneuerbarer Energien erfordert zukünftig große Kapazitäten von Energiespeichern. Alternativen zur Lithium‐Ionen‐Technologie sind Flüssigbatterie bzw. Flow‐Batterie. Im Projekt BiFlow hat das Karlsruher Institut für Technologie (KIT) gemeinsam mit dem Fraunhofer Institut für Chemische Technologie ICT und der 1st Flow Energy Solutions ein neuartiges Hybridspeichersystem entwickelt, welches die spezifischen Vorteile der Lithium‐Ionen‐Batterie und der Flow‐Batterie kombinier und dabei die Abwärme nutzt.
Determination of vapour pressures of FAME industrial mixtures by ebullioscopic and thermogravimetric experimental methods
Authors: Tonsi Giulia , Zanella Elisa , Grainca Arian , Tondelli Giacomo , Capelli Sofia , Albertini Stefano , Pirola Carlo
Published: February 2024

Vapour pressure (VP) is a parameter that characterizes, by principle, only pure compounds. Nevertheless, it can refer also to mixtures in order to characterize their volatility or to be inserted in technical documents. The measurement of VP for mixtures is strongly dependent on the possible variation of the composition, during experiments, due to the different volatility of the constituent compounds. It is possible to calculate the VP of the mixture starting from its composition, but different thermodynamic scenarios must be considered. Moreover, for industrial samples, possible effects due to the presence of impurities must be considered. In this work, two different experimental methods have been employed to determine VP of some acetates esters and two industrial mixtures of fatty acid methyl esters (FAME). The first method is a direct ebullioscopic method, while the second is an indirect thermogravimetric analysis (TGA). An error function was calculated to compare the experimental results of VPs obtained with the two methodologies with the theoretical ones. Ebullioscopic measures resulted suitable only for acetates esters, as FAME mixtures are characterized by VPs too low to be quantified with this technique. On the contrary, TGA methodology is more accurate for FAME than acetates. It allows the collection of a great number of VP values with a very fast analysis. This method is less accurate than others, but it can be useful for a fast screening of the FAME mixtures, also contaminated with light impurities.
A review of Faisal Khan's contribution to process monitoring
Authors: Amin Md Tanjin , Qian Yutian
Published: February 2024

Process monitoring is pivotal in process system engineering for abnormal situation management and ensuring process safety. This paper presents a review of Professor Khan's works on process monitoring. It examines (i) the number of publications, (ii) the type of publications, (iii) key sources, (iv) focused areas and their evolvement, and (v) the research impact by Professor Khan in process monitoring. The results suggest that journals are the primary sources he has used to disseminate research results. Over the years, his research focus evolved from detection to root cause diagnosis, fault propagation pathway analysis, and failure prognosis. Professor Khan has immensely impacted his peers, evidenced by his theoretical contributions, a higher number of recognitions by other researchers, and diversified workforce development.
Twisted Phosphors that Violate Kasha's Exciton Model in Organic Systems
Authors: Fu Boyi , Wang Guangming , Li Jiuyang , Li Junbo , Li Xun , Zhao Xiaoya , Ding Shuhui , Yan Guoping , Yan Qianqian , Zhang Kaka
Published: February 2024

Comprehensive Summary

Kasha's exciton model proposes that T1 energy levels of organic compounds are insensitive to molecular aggregation and microenvironment change because of negligible small transition dipole moments of T1 states. This model holds true in most organic systems till now. Here we report the fabrication of twisted organic phosphors with intramolecular charge transfer characters and flexible molecular structures. When doped into different organic matrices, the twisted phosphor adopts different conformation, exhibits distinct phosphorescence colors and T1 energy levels, which violates Kasha's exciton model in organic system. Given that the change of phosphorescence colors and maxima can be readily distinguished by human eyes and conventional instrument, the twisted phosphors would be exploited as a new type of molecular probe, which would exhibit potential application in optical sensing and stimuli‐responsive systems.
Visible‐Light‐Mediated Photocatalyst‐Free Hydroacylation of Azodicarboxylic Acid Derivatives with 4‐Acyl‐1,4‐dihydropyridines
Authors: Liu Li , Wang Jing , Feng Xiaoying , Xu Kun , Liu Wei , Peng Xia , Du Hongguang , Tan Jiajing
Published: February 2024

Comprehensive Summary

A visible‐light‐enabled, photocatalyst‐free hydroacylation reaction of azodicarboxylic acid derivatives was described. This radical conjugate addition (RCA) protocol relied on the dual role of 4‐acyl‐1,4‐dihydropyridine (acyl‐DHP) reagents that besides being as radical reservoirs, they also enabled the conversion of radical adducts to anion intermediates via reduction. Under “catalyst‐oxidant‐additive free” conditions, a wide range of structurally different acyl hydrazide products were readily obtained in 56%—99% yields. The utility of this transformation was further demonstrated by the scale‐up synthesis and downstream derivatization.
Applying ensemble climate models to predict the fate of marginal coral reefs already existing at thermal and turbidity limits in arid tropical Australia
Authors: Cartwright Paula , Browne Nicola , Fearns Peter , O'Leary Mick , Lowe Ryan
Published: February 2024

Marine fauna, including coral reefs, exist under particular oceanographic and meteorological (metocean) processes that maintain water quality within the range limits to which they have adapted over millennia. Climate‐induced changes to these metocean processes could alter ambient marine water quality to ranges beyond those limits and at rates faster than species can adapt. Extreme (or marginal) coral reefs, such as those in arid tropical regions, already exist at the limits of their ranges for water quality parameters such as temperature and turbidity. Here, we apply projected anomalies from ensemble climate models to the metocean processes that drive turbidity in the Exmouth Gulf region of north Western Australia where habitats of significant environmental value exist. We also apply projected sea surface temperature anomalies to look at how a combined effect of turbidity and temperature might impact important habitats. We find that turbidity is predicted to increase in some parts of the Gulf and decrease in others due to differing metocean drivers of turbidity throughout the region. Temperature anomalies reveal year‐round increases in temperature consistent with current summer marine heat wave events (>2.5°C above mean temperatures). Climate models used in the predictions varied between themselves underscoring the importance of model choice and of using ensembles.
Effective Anticancer Potential of a New Sulfonamide as a Carbonic Anhydrase IX Inhibitor Against Aggressive Tumors
Authors: Koyuncu Ismail , Temiz Ebru , Güler Eray Metin , Durgun Mustafa , Yuksekdag Ozgür , Giovannuzzi Simone , Supuran Claudiu T.
Published: February 2024

This study examines efficiency of a newly synthesized sulfonamide derivative 2‐bromo‐N‐(4‐sulfamoylphenyl)propanamide (MMH‐1) on the inhibition of Carbonic Anhydrase IX (CA IX), which is overexpressed in many solid tumors including breast cancer. The inhibitory potential of MMH‐1 compound against its four major isoforms, including cytosolic isoforms hCA I and II, as well as tumor‐associated membrane‐bound isoforms hCA IX and XII, was evaluated. To this context, the cytotoxic effect of MMH‐1 on cancer and normal cells was tested and found to selectively affect MDA‐MB‐231 cells. MMH‐1 reduced cell proliferation by holding cells in the G0/G1 phase (72 %) and slowed the cells′ wound healing capacity. MMH‐1 inhibited CA IX under both hypoxic and normoxic conditions and altered the morphology of triple negative breast cancer cells. In MDA‐MB‐231 cells, inhibition of CA IX was accompanied by a decrease in extracellular pH acidity (7.2), disruption of mitochondrial membrane integrity (80 %), an increase in reactive oxygen levels (25 %), and the triggering of apoptosis (40 %). In addition, the caspase cascade (CASP‐3, ‐8, ‐9) was activated in MDA‐MB‐231 cells, triggering both the extrinsic and intrinsic apoptotic pathways. The expression of pro‐apoptotic regulatory proteins (Bad, Bax, Bid, Bim, Cyt‐c, Fas, FasL, TNF‐a, TNF‐R1, HTRA, SMAC, Casp‐3, ‐8, P21, P27, and P53) was increased, while the expression of anti‐apoptotic proteins, apoptosis inhibitor proteins (IAPs), and heat shock proteins (HSPs) (Bcl‐2, Bcl‐w, cIAP‐2, HSP27, HSP60, HSP70, Survivin, Livin, and XIAP) was decreased. These results propose that the MMH‐1 compound could triggers apoptosis in MDA‐MB‐231 cells via the pH/MMP/ROS pathway through the inhibition of CA IX. This compound is thought to have high potential and promising anticancer properties in the treatment of aggressive tumors.
Comparison of long‐term outcomes between imatinib and dasatinib prophylaxis after allogeneic stem cell transplantation in patients with Philadelphia‐positive acute lymphoblastic leukemia: A multicenter retrospective study
Authors: Guan Fangshu , Yang Luxin , Chen Yi , Shi Jimin , Song Xiaolu , Lai Xiaoyu , Lu Ying , Liu Lizhen , Ouyang Guifang , Zhao Yanmin , Yu Jian , Xu Yang , Lan Jianping , Fu Huarui , Zhao Yi , Qiu Xi , Zhu Panpan , Cai Zhen , Huang He , Luo Yi
Published: February 2024

Background

Although the prognosis of Philadelphia‐positive acute lymphoblastic leukemia (Ph+ ALL) has improved with the introduction of tyrosine kinase inhibitors (TKIs) and stem cell transplantation, prevention of relapse after transplantation remains a concern. The aim of this study was to compare the impact of TKI prophylaxis with imatinib and dasatinib on long‐term outcomes after transplantation.

Methods

Patients with Ph+ ALL who underwent allogeneic hematopoietic stem cell transplantation (allo‐HSCT) at first complete remission (CR1) and received TKI prophylaxis after allo‐HSCT were included in this retrospective analysis. Two cohorts were established based on the choice of TKI prophylaxis: the imatinib (Ima) and dasatinib (Das) cohorts. The survival and safety outcomes of these cohorts were compared.

Results

Ninety‐one patients in the Ima cohort and 50 in the Das cohort were included. After a median follow‐up of 50.6 months, the 5‐year cumulative incidence of relapse, nonrelapse mortality rate, and overall survival in the Ima and Das cohorts were 16.1% and 12.5%, 5.2% and 9.8%, and 86.5% and 77.6%, respectively, with no statistical differences. The cumulative incidence of mild chronic graft‐versus‐host disease was higher in the Das cohort. The most common adverse event was neutropenia (64.7% vs. 69.5%). The Das cohort had a higher incidence of gastrointestinal bleeding (25.5% vs. 2.3%) and gastrointestinal reaction (48.9% vs. 31.4%) than the Ima cohort. The proportion of patients treated on schedule was significantly lower in the Das cohort than in the Ima cohort, and drug intolerance was the main reason for protocol violation.

Conclusions

For patients with Ph+ ALL undergoing allo‐HSCT in CR1, imatinib prophylaxis achieved long‐term outcomes similar to those of dasatinib.
Research on the application of bilateral collaborative algorithm in hotel tourism consumption preference recommendation
Authors: Wang Qi
Published: February 2024

The continuous expansion of the domestic tourism market has driven the development of the hotel related industry. It is a key focus of the hotel industry to provide accurate supporting services to tourists based on their preferences. However, the current recommendation model mainly considers tourist factors and lacks consideration for hotel factors. In order to address the concerns of recommendation services, a bilateral collaborative recommendation model is proposed, which first analyzes tourist feature data through comprehensive similarity calculation. Firstly, the comprehensive similarity calculation is used to analyze tourist feature data, and the K‐means Clustering Algorithm (K‐means) is introduced to improve the clustering effect between data. And to better distinguish tourist preferences, the Gale Shapley (G‐S) bilateral matching model is introduced to achieve preference matching of consumer features. In the Mean Absolute Error (MAE) analysis of the model, the User‐based Collaborative Filtering (UBCF) model performs the worst. When the k value is 90, the minimum MAE value is 0.7896. The Item‐based Collaborative Filtering (IBCF) model is 0.7776, with the best performance being the improved G‐S model of 0.7325. In the performance testing of three models' preference recommendations, the improved G‐S model achieves an accuracy of over 90% in all three types of feature data recommendations, with the lowest accuracy of 62.5% for UBCF and 71.3% for IBCF. It can be seen that the proposed improved G‐S model can accurately identify tourist and hotel preference data and accurately recommend corresponding projects. The research content provides important technical references for the digital transformation and development of the tourism industry.
Graphene Exfoliation in Binary NMP/Water Mixtures by Molecular Dynamics Simulations
Authors: Gotzias A. , Lazarou Y. G.
Published: February 2024

We investigate the molecular mechanism underlying the liquid‐phase exfoliation of graphene in aqueous/N‐methyl‐2‐pyrrolidone (NMP) solvent mixtures and calculate the associated free energies, considering different NMP concentrations and exfoliation temperatures. We employ steered molecular dynamics to establish a path for the exfoliation of a graphene sheet from graphite within each solvent environment. Then, we conduct umbrella sampling simulations throughout the created paths to compute the potential of mean force (PMF) of the graphene sheet. As the exfoliated nanosheet disperses into the liquid, it becomes fully covered by an adsorbed solvent monolayer. We analyze the composition of the monolayer by measuring the direct contacts of either NMP or water molecules with the carbon surface. The carbon surface exhibits a preference for adsorbing NMP over water. The NMP molecules form a hydrophobic compact monolayer structure, effectively protecting the carbon interface from unfavorable interactions with water. The creation of the hydrophobic monolayer is a key factor in the exfoliation process, as it effectively inhibits the restacking of exfoliated nanosheets. An adequate level of graphene solubility is achieved through the addition of 20 % to 30 % water by weight to the NMP solvent. This finding holds significant importance for improving production efficiency and reducing dependence on organic solvents in the industrial manufacturing of graphene.
GFN‐xTB‐Based Computations Provide Comprehensive Insights into Emulsion Radiation‐Induced Graft Polymerization
Authors: Matsubara Kiho , Takahashi Kei , Matsuda Takeshi , Ueki Yuji , Seko Noriaki , Kakuchi Ryohei
Published: February 2024

Invited for this month's cover are the collaborating groups of Dr. Ryohei Kakuchi and Ms. Kiho Matsubara at Gunma University, Japan, Prof. Kei Takahashi at Fukuoka Institute of Technology and The Institute of Statistical Mathematics, Japan, Prof. Takeshi Matsuda at Hannan University, Japan, Dr. Noriaki Seko and Dr. Yuji Ueki at National Institutes for Quantum Science and Technology, Japan. The cover picture shows the machine learning‐based optimization and interpretation of radiation‐induced graft polymerizations under emulsion conditions based on realistic information for monomers calculated by the state‐of‐the‐art semiempirical method. More information can be found in the Research Article by Kiho Matsubara, Kei Takahashi, Ryohei Kakuchi, and co‐workers.
Antifungal and genotoxic effects of Thymus serpyllum as a root canal irrigant
Authors: Kameri Ariana , Dragidella Agime , Haziri Arben , Hashani Zeqir , Kurteshi Kemajl , Kurti Arsim
Published: February 2024

Objectives

The aim of this study was the assessment of the efficiency of the ethyl acetate (EthOAc) extract of Thymus serpyllum against Candida albicans and to compare it with sodium hypochlorite (NaOCl) and chlorhexidine (CHX), as well as their genotoxic effect.

Material and Methods

The antifungal effectiveness of the EthOAc extract of Thymus serpyllum was determined using the agar disk diffusion method. The inhibition zones induced by the EthOAc extract were compared after 5 min, 60 min, and 24 h to those induced by standard solutions (2% CHX and 2% NaOCl). An in vitro genotoxicity assay was performed in cultured lymphocytes from the blood of human volunteers to observe micronuclei formation. Statistical analysis of the results was performed using the Kruskal–Wallis test and one‐way analysis of variance.

Results

The inhibition zone of combination of CHX with EthOAc extract of Thymus serpyllum against C. albicans was 29.7 mm after 5 min, 28.3 mm after 60 min, and 29 mm after 24 h. The inhibition zone of NaOCl in combination with EthOAc extract of Thymus serpyllum against C. albicans was 0 mm. The EthOAc extract of Thymus serpyllum did not show a genotoxic effect on lymphocyte cells.

Conclusions

The EthOAc extract of Thymus serpyllum in combination with CHX may be a useful root canal disinfection in endodontic therapy.
Effectiveness of mechanical and chemical decontamination methods for the treatment of dental implant surfaces affected by peri‐implantitis: A systematic review and meta‐analysis
Authors: Hart Iain , Wells Christine , Tsigarida Alexandra , Bezerra Beatriz
Published: February 2024

Objective

To assess which decontamination method(s) used for the debridement of titanium surfaces (disks and dental implants) contaminated with bacterial, most efficiently eliminate bacterial biofilms.

Material and Methods

A systematic search was conducted in four electronic databases between January 1, 2010 and October 31, 2022. The search strategy followed the PICOS format and included only in vitro studies completed on either dental implant or titanium disk samples. The assessed outcome variable consisted of the most effective method(s)—chemical or mechanical— removing bacterial biofilm from titanium surfaces. A meta‐analysis was conducted, and data was summarized through single‐ and multi‐level random effects model (p < .05).

Results

The initial search resulted in 5260 articles after the removal of duplicates. After assessment by title, abstract, and full‐text review, a total of 13 articles met the inclusion criteria for this review. Different decontamination methods were assessed, including both mechanical and chemical, with the most common method across studies being chlorhexidine (CHX). Significant heterogeneity was noted across the included studies. The meta‐analyses only identified a significant difference in biofilm reduction when CHX treatment was compared against PBS. The remaining comparisons did not identify significant differences between the various decontamination methods.

Conclusions

The present results do not demonstrate that one method of decontamination is superior in eliminating bacterial biofilm from titanium disk and implant surfaces.
Prehydrated collagenated cortico‐cancellous heterologous bone gel and papillae tunneling for isolated intrabony defects: 12‐month noninferiority trial
Authors: Kobe Tom , Povšič Katja , Gašperšič Rok
Published: February 2024

Objectives

This study assessed the effectiveness of prehydrated collagenated xenogenic bone gel and a collagenated cortico‐cancellous heterologous bone mixture in conjunction with papillae tunneling techniques (PTT) for treating isolated periodontal intraosseous defects.

Materials and Methods

Twenty patients with periodontitis stage III/IV and at least one deep isolated interdental 2/3‐wall intraosseous defect were included in the study. Surgical incisions were made vertically at the adjacent tooth or horizontally at the mucogingival junction. A full‐thickness flap was then carefully lifted under the papillae using special tunneling instruments. The root surfaces were completely cleaned, and the defects were randomly filled with either prehydrated collagenated bone gel (test group; n = 10) or collagenated cortico‐cancellous heterologous bone mixture (control group; n = 10). Wounds were closed with microsurgical sutures. We predicted that the lower 95% confidence interval for the difference between the two procedures would exceed a prespecified noninferiority threshold.

Results

All wounds closed sufficiently to prevent biomaterial exposure. The test and control groups showed similar mean pocket depth reduction (3.5 ± 1.0 vs. 3.9 ± 1.7 mm; p = 0.52), similar gingival recession (−0.10 ± 0.99 vs. 0.2 ± 0.8 mm; p = 0.46), and similar clinical attachment gain (3.6 ± 1.51 vs. 3.7 ± 1.8 mm; p = 0.89) at the 12‐month follow‐up. All results were below the noninferiority margin of the sample.

Conclusions

At 12 months, prehydrated collagenous bone gel performed similarly to collagenous heterologous bone granules in the treatment of intraosseous lesions with PTT. In addition, both biomaterials preserved soft tissue with minimal further recession at 1 year.

Clinical Relevance

When combined with PTT, collagenous xenogeneic bone granules and prehydrated collagenous bone gel achieve comparable clinical outcomes in intrabony defects. The study was registered under the NCT 04782921 on ClinicalTrails.
A single‐source nine‐level solar‐PV inverter with quadruple voltage boosting and high reliability
Authors: Zaid Mohammad , Tayyab Mohammad , Sarwer Zeeshan , Ali Mohammad , Sarwar Adil , Anwar Md Nishat , Tariq Mohd , Khalid Muhammad
Published: February 2024

An increase in generation from distributed energy sources like solar PV has motivated researchers to explore better electrical energy conversion solutions. Multilevel inverters with fewer component count and boosting capabilities contribute to a reliable and efficient single‐stage solution. This work proposes a reliable single‐source switched capacitor multilevel inverter capable of producing nine‐level boosted AC voltage with its stand‐alone and grid‐connected operation. It employs 11 switches, three diodes, and three switched capacitors. The main feature of the proposed topology is its ability to produce quadruple boosting with respect to the DC input voltage. Another advantage is the exhibition of low capacitor currents due to frequent charging durations in one operational cycle. The selection criterion for the switched capacitors is also presented. The topology's performance is evaluated in MATLAB/Simulink under various conditions and in PLECS environments for its efficiency. It was then realized on an experimental prototype in stand‐alone mode. The topology is then modified in terms of topology and modulation to mitigate the leakage current, thus making it suitable for grid‐connected operation. This operation is validated on the hardware‐in‐the‐loop platform. Further, the reliability analysis explores a high total mean time to failure (MTTFT) of nearly 253,164 hours/failures compared to recent switched capacitor topologies and an efficiency of above 95%. The low inrush currents, high MTTFT value, and better efficiency make it a suitable topology for renewable microgrids' stand‐alone and grid‐integrated operation.
Reconfigured passivity‐based control strategy of LCL‐type grid‐connected inverter under complex grid conditions
Authors: Huang Min , Lin Wei , Zhang Zhicheng , Wu Weimin , Yao Zhilei
Published: February 2024

LCL‐type grid‐connected inverters have seen extensive use of the passivity‐based control (PBC) system. However, traditional PBC systems rarely take time delay into account while designing the system or doing a stability study. Therefore, utilizing Lyapunov's criterion to conclude that the system is stable is not accurate. The analysis revealed that the differential terms of PBC loops with the Euler–Lagrange (EL) mathematical model could induce instability considered control delay for LCL‐type grid‐connected inverter system. Compared with traditional EL‐PBC method, this paper proposed a reconstructed EL‐PBC scheme by properly optimizing the noise term. Then, the equivalent output impedance of the grid‐connected inverter system with proposed controller is analyzed with frequency domain passivity theory. The controller parameters are also optimized to ensure both the internal stability of LCL‐type grid‐connected inverter and the risk of interactive resonance in complex weak and nonideal grid. Results from simulation and experimentation support the modified control structure's efficacy and performance.
Genetically inspired organoids prevent joint degeneration and alleviate chondrocyte senescence via Col11a1–HIF1α‐mediated glycolysis–OXPHOS metabolism shift
Authors: Sun Ye , You Yongqing , Wu Qiang , Hu Rui , Dai Kerong
Published: February 2024

Introduction

Developmental dysplasia of hip (DDH) is a hip joint disorder leading to subsequent osteoarthritis. Previous studies suggested collagen XI alpha 1 (COL11A1) as a potential gene in hip dysplasia and chondrocyte degeneration. However, no genetic association has reported COL11A1‐related cellular therapy as treatment of DDH and joint degeneration.

Methods and Results

We report identified genetic association between COL11A1 locus and DDH with genome‐wide association study (GWAS). Further exome sequencing for familial DDH patients was conducted in different populations to identify potential pathogenic Col11A1 variants for familiar DDH. Further studies demonstrated involvement of COL11A1 expression was down‐regulated in femoral head cartilage of DDH patients and Col11a1‐KO mice with induced DDH. Col11a1‐KO mice demonstrated aggravated joint degeneration and severe OA phenotype. To explore the underlying mechanism of Col11a1 in cartilage and DDH development, we generated scRNA‐seq profiles for DDH and Col11a1‐KO cartilage, demonstrating disrupted chondrocyte homeostasis and cellular senescence caused by Col11a1–HIF1α‐mediated glycolysis–OXPHOS shift in chondrocytes. Genetically and biologically inspired, we further fabricated an intra‐articular injection therapy to preventing cartilage degeneration by generating a Col11a1‐over‐expressed (OE) SMSC mini‐organoids. Col11a1‐OE organoids demonstrated superior chondrogenesis and ameliorated cartilage degeneration in DDH mice via regulating cellular senescence by up‐regulated Col11a1/HIF1α‐mediated glycolysis in chondrocytes.

Conclusion

We reported association between COL11A1 loci and DDH with GWAS and exome sequencing. Further studies demonstrated involvement of COL11A1 in DDH patients and Col11a1‐KO mice. ScRNA‐seq for DDH and Col11a1‐KO cartilage demonstrated disrupted chondrocyte homeostasis and cellular senescence caused by Col11a1–HIF1α‐mediated glycolysis–OXPHOS shift in chondrocytes. Genetically and biologically inspired, an intra‐articular injection therapy was fabricated to prevent cartilage degeneration with Col11a1‐OE SMSC organoids. Col11a1‐OE organoids ameliorated cartilage degeneration in DDH mice via regulating cellular senescence by up‐regulated Col11a1/HIF1α‐mediated glycolysis in chondrocytes.
Taylor Tuna Optimizer‐based hybrid deep Q‐network for channel assignment in cognitive radio networks with user mobility and power control
Authors: Sekar Hemalatha , Appranchi Sumathi
Published: February 2024

Cognitive radio networks (CRNs) have emerged as a promising solution to address the spectrum scarcity problem by allowing unlicensed secondary users (SUs) to opportunistically access the underutilized licensed spectrum bands. However, efficient channel assignment in CRNs, especially with user mobility and power control considerations, remains a challenging problem. Traditional channel assignment algorithms often struggle to adapt to changing network conditions, resulting in suboptimal performance. To address these challenges, this research presents a novel Taylor Tuna Optimizer‐based hybrid deep Q‐network (TayTO‐based HDQNet) for channel assignment in CRNs with user mobility and power control considerations. The proposed TayTO‐based HDQNet combines the Elman neural network architecture with the reinforcement learning framework of deep Q‐networks, tuned using the Taylor Tuna Optimizer. This hybrid approach enables intelligent channel assignment decisions while considering power consumption constraints, leading to efficient communication in CRNs. To train the HDQNet agent, a comprehensive dataset is generated through simulations of various CRN scenarios, incorporating channel availability, interference levels, and power consumption for different channel assignment decisions. The HDQNet agent undergoes iterative training using this dataset to develop an optimal channel assignment policy. Experimental results demonstrate the effectiveness of the proposed TayTO‐based HDQNet approach done by MATLAB, achieving a high success rate of 98.47% and surpassing the reliability scores of previous studies. This highlights the improved performance and reliability of the proposed approach for channel assignment in CRNs.
Harem size should be measured by more than the sum of its parts: Phenology‐based measurements reveal joint effects of intrinsic and extrinsic factors on a polygamous herbivore under non‐stationary climatic conditions
Authors: Szemán Karola , Végvári Zsolt , Gőri Szilvia , Kapocsi István , Székely Tamás , Manning Jeffrey A.
Published: February 2024

Social behaviour is thought to be a major component of survival, reproduction, and resilience of populations. Thus, it is a key component in management and conservation of wild populations. In polygynous breeding species, group size influences the reproductive success of males and females, and hence it is essential to understand the environmental and demographic factors that shape the phenology of group size within populations. Here, we investigate harem size and its determinants using a 15‐year dataset of annual harem size phenology‐based metrics from a reintroduced population of wild Przewalski horses in Hortobágy National Park, Hungary. From the initial reintroduction of 21 animals in 1997, the population grew to 174 animals in 2012. During that same period, the number of harems increased from three to 23. Despite the 8‐fold increase in population size, harem sizes remained stable, and variability among harems within years decreased. The annual phenological cycle of harem size was not consistent over the 15‐year period, and the associated annual phenology‐based metrics varied differently over the years. The best predictors of our phenology‐based harem size metrics were adult sex ratio, annual adult mortality and annual mean number of harems, with some evidence that mean age of harem stallions and drought severity were contributing factors. Our findings reveal that complex interactions between demography, climate, and harem size can emerge in social animals. Taken together, our results demonstrate that intrinsic population processes can regulate group size even in the presence of non‐stationary climatic conditions during periods of growth in human‐introduced, semi‐free ranging animal populations.
Physiological and microbiome adaptation of coral Turbinaria peltata in response to marine heatwaves
Authors: Zhai Xin , Zhang YanPing , Zhou Jie , Li Hao , Wang Ao , Liu Li
Published: February 2024

Against the backdrop of global warming, marine heatwaves are projected to become increasingly intense and frequent. This trend poses a potential threat to the survival of corals and the maintenance of entire coral reef ecosystems. Despite extensive evidence for the resilience of corals to heat stress, their ability to withstand repeated heatwave events has not been determined. In this study, we examined the responses and resilience of Turbinaria peltata to repeated exposure to marine heatwaves, with a focus on physiological parameters and symbiotic microorganisms. In the first heatwave, from a physiological perspective, T. peltata showed decreases in the Chl a content and endosymbiont density and significant increases in GST, caspase‐3, CAT, and SOD levels (p < .05), while the effects of repeated exposure on heatwaves were weaker than those of the initial exposure. In terms of bacteria, the abundance of Leptospira, with the potential for pathogenicity and intracellular parasitism, increased significantly during the initial exposure. Beneficial bacteria, such as Achromobacter arsenitoxydans and Halomonas desiderata increased significantly during re‐exposure to the heatwave. Overall, these results indicate that T. peltata might adapt to marine heatwaves through physiological regulation and microbial community alterations.
Incorporating small‐scale disturbances in models of forest structure and aboveground biomass of tropical mountains
Authors: Uscanga Adriana , Shuler Sophia , Silva Lucas C. R.
Published: February 2024

Several efforts have been made to model forest structure and estimate global aboveground biomass (AGB) magnitude and distribution. However, AGB models still show large uncertainties, especially over tropical mountains that are difficult to survey and understudied. Although forest disturbance and land use greatly influence forest structure and AGB accumulation, they are rarely considered in forest structure and AGB models. Including the effect of forest disturbance and land use could improve model performance. In this study, we used Landsat time series analysis and forest inventory data to assess and model the effect of small‐scale disturbance and land use on tropical montane forest structure and AGB. We explored two approaches: abrupt forest change detection, using the algorithm Breaks For Additive Seasonal Trend (BFAST), and gradual vegetation change by calculating the variation of remote sensing vegetation indices over time. We found that tropical montane landscapes are very dynamic and heterogenous. Out of the 284 forest plots analyzed, 27% had abrupt disturbances at least once between 1993 and 2014, and some of them showed abrupt disturbances several times. Forest plots with abrupt disturbances exhibit statistically significant lower basal area, tree height, and AGB than plots without abrupt disturbances. Using linear mixed‐effects models, we found that the number of breakpoints, annual Normalized Difference Vegetation Index SD, and Normalized Difference Water Index minimum values over time were the most informative variables for predicting forest structure, particularly basal area (adjusted R2 = 0.61). These variables are easy to calculate and could add significant power to forest structure and AGB models. In conclusion, incorporating small‐scale disturbance to model forest structure and AGB at regional scales is feasible through the identification of recent abrupt and gradual forest change using remote sensing time series. Including recent forest disturbance variables as predictors in forest structure models can greatly improve biomass predictability and mapping in dynamic landscapes.
Evidence from interpretable machine learning to inform spatial management of Palau's tuna fisheries
Authors: Gilman Eric , Chaloupka Milani
Published: February 2024

Static and dynamic area‐based management tools hold substantial potential to balance socioeconomic benefits derived from fisheries and costs from bycatch mortality of at‐risk species. Palau longline fisheries have high bycatch of at‐risk species including the olive ridley marine turtle and silky and blue sharks. This study analyzed a two decades‐long time series of observer and electronic monitoring datasets from the Palau distant‐water and locally‐based pelagic longline fisheries. An interpretable or explainable machine learning‐based modeling approach was used to derive spatially resolved species‐specific catch rate predictions. These models were conditioned on a suite of potentially informative environmental, bathymetric, ocean‐climate metric, vessel, monitoring system, and set‐specific operational predictors. Overall, there would be limited ecological tradeoffs from focusing fishing effort within primary catch rate hotspots for target bigeye and yellowfin tunas. Mean field prediction surfaces also defined catch rate hotspots for at‐risk species of silky and blue sharks, olive ridley turtle, and pelagic stingray, which did not overlap the hotspots for target species. The predicted target species hotspots, however, overlap olive ridley and pelagic stingray warmspots. Results also identify opportunities for temporally dynamic spatial management to control catch rates of target and bycatch species. Management of fishery operational predictors of fishing depth and soak duration present additional opportunities to balance catch rates of at‐risk bycatch and target species. A transition to employing fleetwide or vessel‐based output controls that effectively constrain the fishery would alter the spatial management strategy to focus on zones with the lowest ratio of at‐risk bycatch to commercial catch. Our findings support evidence‐informed evaluation of spatial management strategies and complementary measures to meet objectives for balancing socioeconomic benefits derived from target species catch with costs to threatened species.
Impact of vutrisiran on exploratory cardiac parameters in hereditary transthyretin‐mediated amyloidosis with polyneuropathy
Authors: Garcia‐Pavia Pablo , Grogan Martha , Kale Parag , Berk John L. , Maurer Mathew S. , Conceição Isabel , Di Carli Marcelo , Solomon Scott D. , Chen Chongshu , Yureneva Elena , Vest John , Gillmore Julian D.
Published: February 2024

Aims

HELIOS‐A was a Phase 3, open‐label study of vutrisiran, an RNA interference therapeutic, in patients with hereditary transthyretin (ATTRv) amyloidosis with polyneuropathy. This analysis evaluated vutrisiran's impact on exploratory cardiac endpoints in HELIOS‐A patients.

Methods and results

Patients were randomized 3:1 to subcutaneous vutrisiran 25 mg every 3 months or intravenous patisiran 0.3 mg/kg every 3 weeks (reference group) for 18 months. Exploratory cardiac endpoints included change from baseline in N‐terminal prohormone of brain‐type natriuretic peptide (NT‐proBNP) and echocardiographic parameters versus external placebo (APOLLO study). The modified intent‐to‐treat (mITT) population comprised randomized patients receiving any study drug (n = 122). A cardiac subpopulation with evidence of cardiac amyloid involvement (n = 40) was prespecified. 99mTc scintigraphy exploratory assessments in a planned vutrisiran‐treated cohort at select sites were compared with baseline. At Month 18, vutrisiran demonstrated beneficial effects on NT‐proBNP versus external placebo in the mITT and cardiac subpopulations (adjusted geometric mean fold change ratio [95% confidence interval] 0.480 [0.383–0.600], p = 9.606 × 10−10 and 0.491 [0.337–0.716], p = 0.0004, respectively). Benefits or trends towards benefit in echocardiographic parameters versus external placebo were observed for both populations. In 99mTc scintigraphy assessments, 32/47 (68.1%) and 31/48 (64.6%) patients exhibited reduced normalized left ventricular total uptake and heart‐to‐contralateral lung ratio, respectively. Perugini grade was reduced or unchanged versus baseline in 55/57 (96.5%) evaluable patients. No increase in cardiac adverse events was observed with vutrisiran versus external placebo.

Conclusions

Vutrisiran demonstrated evidence of potential benefit on cardiac manifestations in patients with ATTRv amyloidosis with polyneuropathy, with an acceptable safety profile.
Fcgr2b and Fcgr3 are the major genetic factors for cartilage antibody‐induced arthritis, overriding the effect of Hc encoding complement C5
Authors: Xu Zhongwei , Moreno‐Giró Àlex , Zhao Danxia , Krämer Alexander , Pandey Rajan Kumar , Xu Bingze , Lundström Susanna L. , Holmdahl Rikard
Published: February 2024

Like rheumatoid arthritis (RA) in humans, collagen‐induced arthritis (CIA) in mice is associated with not only MHC class II genetic polymorphism but also, to some extent, with other loci including genes encoding Fc gamma receptors (FCGRs) and complement C5. In this study, we used a cartilage antibody‐induced arthritis (CAIA) model in which arthritis develops within a 12‐h timeframe, to determine the relative importance of FCGRs and C5 (Hc). In CAIA, inhibiting or deleting FCGR3 substantially hindered arthritis development, underscoring the crucial role of this receptor. Blocking FCGR3 also reduced the levels of FCGR4, and vice versa. When employing an IgG1 arthritogenic cocktail that exclusively interacts with FCGR2B and FCGR3, joint inflammation was promptly initiated in Fcgr2b−− mice but not in Fcgr3−− mice, suggesting that FCGR3 is sufficient for CAIA development. Regarding complement activation, Fcgr2b++.Hc** mice with C5 mutated were fully resistant to CAIA, whereas Fcgr2b−−.Hc** mice developed arthritis rapidly. We conclude that FCGR3 is essential and sufficient for CAIA development, particularly when induced by IgG1 antibodies. The human ortholog of mouse FCGR3, FCGR2A, may be associated with RA pathogenesis. FCGR2B deficiency allows for rapid arthritis progression and overrides the resistance conferred by C5 deficiency.
Controllably Modulating Oxygen Vacancies on Nonstoichiometric Nd−Ce−O Binary Oxides for Low‐temperature Oxidative Coupling of Methane
Authors: Gong Ying , Lu Chengxin , Zhong Xusheng , Xu Junwei , Ouyang Rumeng , Fang Xiuzhong , Xu Xianglan , Deng Chunhui , Wang Xiang
Published: February 2024

Herein, we synthesised a series of nonstoichiometric Nd−Ce−O composite oxides with a fluorite or rare‐earth C‐type phase structure using the glycine combustion method for the oxidative coupling of methane (OCM) reaction. As the amount of Nd3+ increases, the oxygen vacancies in this series of composite oxides gradually increase, leading to an amount increasing in the C2‐selective oxygen species O2− generated by the oxygen vacancies. In addition, with the increase in Nd3+, the number of moderate basic sites on the catalyst surface also improves, another significant factor affecting the OCM reaction performance of the composite oxides. Nd0.9Ce0.1O1.55 possesses optimal low‐temperature OCM reaction performance, achieving 8.0 % C2 yield at 450 °C and 14.1 % C2 yield at 700 °C. This can be attributed to the nonstoichiometric rare‐earth C‐type crystalline phase structure of Nd0.9Ce0.1O1.55, which exhibits the highest abundance of oxygen vacancies, selective oxygen species O2−, and moderate basic sites.