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Keywords = IPRs

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12 pages, 1314 KiB  
Article
Evaluating the Inflammatory Protein Ratio (IPR) as an Inflammation-Based Biomarker for Cancer Diagnosis
by Aurelio Lo Buglio, Francesco Bellanti, Rosanna Maria Carapellese, Rosanna Villani, Moris Sangineto, Antonino Davide Romano, Gianluigi Vendemiale and Gaetano Serviddio
Int. J. Mol. Sci. 2025, 26(9), 4375; https://doi.org/10.3390/ijms26094375 - 5 May 2025
Viewed by 420
Abstract
Chronic inflammation is increasingly recognized as a key driver of tumorigenesis, affecting both the tumor microenvironment and host response. In this context, circulating inflammatory proteins may provide valuable insights into cancer activity. This study evaluated the diagnostic performance of the inflammatory protein ratio [...] Read more.
Chronic inflammation is increasingly recognized as a key driver of tumorigenesis, affecting both the tumor microenvironment and host response. In this context, circulating inflammatory proteins may provide valuable insights into cancer activity. This study evaluated the diagnostic performance of the inflammatory protein ratio (IPR), a composite index derived from serum protein electrophoresis, in detecting active cancer among hospitalized patients. We retrospectively analyzed clinical and laboratory data from 312 adult patients admitted to the Internal Medicine and Aging Department at Policlinico Foggia, Italy, between November 2023 and July 2024. Patients were stratified according to the presence of active cancer, defined by NICE criteria. The diagnostic accuracy of the IPR was compared with that of conventional inflammatory markers, including C-reactive protein (CRP) and the neutrophil–lymphocyte ratio (NLR), platelet–lymphocyte ratio (PLR), monocyte–lymphocyte ratio (MLR), and systemic immune–inflammation index (SII). The IPR showed the highest diagnostic performance, with a sensitivity of 88.1%, a specificity of 75.2%, and an area under the receiver operating characteristic curve (AUC) of 0.868. Its negative predictive value reached 97.6%, underscoring its potential as a rule-out tool for malignancy in hospitalized patients. These findings support the IPR as a promising and cost-effective inflammation-based biomarker for cancer detection, warranting further validation in prospective and molecularly characterized cohorts. Full article
(This article belongs to the Section Molecular Biology)
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17 pages, 1553 KiB  
Article
Chemical Profiling and Bioactivity of Microalgae Extracts for Enhancing Growth and Anthracnose Resistance in the Common Bean (Phaseolus vulgaris L.)
by Alessandro A. dos Santos, Camila Nader, Mateus B. de Freitas, César F. Ribeiro, Geovanna de Oliveira Costa, Louis P. Sandjo, Alex S. Poltronieri, Roberto B. Derner and Marciel J. Stadnik
BioTech 2025, 14(1), 17; https://doi.org/10.3390/biotech14010017 - 8 Mar 2025
Viewed by 603
Abstract
The present study aimed to chemically profile the hydroalcoholic extracts from the microalgae (MEs) Nannochloropsis oculata, Phaeodactylum tricornutum, Tetradesmus obliquus, and Tetraselmis tetrathele and evaluate their effects on the development of Colletotrichum lindemuthianum and anthracnose symptoms, as well as on the [...] Read more.
The present study aimed to chemically profile the hydroalcoholic extracts from the microalgae (MEs) Nannochloropsis oculata, Phaeodactylum tricornutum, Tetradesmus obliquus, and Tetraselmis tetrathele and evaluate their effects on the development of Colletotrichum lindemuthianum and anthracnose symptoms, as well as on the initial growth of bean plants. For this, MEs were analyzed using UPLC coupled with a mass spectrometer, allowing the identification of peaks and annotation of potential metabolites. Fungal mycelial growth was assessed seven days after inoculation, and conidial germination was measured 72 h after incubation, using ME concentrations of 0, 0.1, 0.5, and 1.0 mg·mL−1. Bean seeds of the IPR Uirapuru cultivar were sown and treated with 3 mL of extracts at four time points: at sowing and 72 h after each previous treatment. After 11 days of cultivation in a growth chamber, the plants were divided into two groups: one for anthracnose control assessment and the other for evaluating growth promotion by MEs. Plant length as well as fresh and dry weights of shoots and roots were determined, leaf pigments were quantified, and anthracnose severity was assessed using a diagrammatic scale. The UPLC analysis identified 32 compounds in the extracts of the four microalgae, belonging to different chemical and functional groups, with lipids being the most significant fraction. The extracts exhibited variability and diversity in chemical composition depending on the microalgal species. MEs did not affect mycelial growth yet increased the germination of C. lindemuthianum conidia, regardless of the dose or species used. Anthracnose severity was not affected by the microalgae extracts. Regarding growth promotion, the extracts showed varying effects but generally increased shoot and root length, fresh biomass, and leaf pigment content. Full article
(This article belongs to the Section Industry, Agriculture and Food Biotechnology)
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19 pages, 4839 KiB  
Article
Synergizing Machine Learning and Physical Models for Enhanced Gas Production Forecasting: A Comparative Study of Short- and Long-Term Feasibility
by Bafren K. Raoof, Ali Rabia, Usama Alameedy, Pshtiwan Shakor and Moses Karakouzian
Energies 2025, 18(5), 1187; https://doi.org/10.3390/en18051187 - 28 Feb 2025
Cited by 1 | Viewed by 584
Abstract
Advanced strategies for production forecasting, operational optimization, and decision-making enhancement have been employed through reservoir management and machine learning (ML) techniques. A hybrid model is established to predict future gas output in a gas reservoir through historical production data, including reservoir pressure, cumulative [...] Read more.
Advanced strategies for production forecasting, operational optimization, and decision-making enhancement have been employed through reservoir management and machine learning (ML) techniques. A hybrid model is established to predict future gas output in a gas reservoir through historical production data, including reservoir pressure, cumulative gas production, and cumulative water production for 67 months. The procedure starts with data preprocessing and applies seasonal exponential smoothing (SES) to capture seasonality and trends in production data, while an Artificial Neural Network (ANN) captures complicated spatiotemporal connections. The history replication in the models is quantified for accuracy through metric keys such as mean absolute error (MAE), root mean square error (RMSE), and R-squared. The future forecast is compared with an outcome of a previous physical model that integrates wells and reservoir properties to simulate gas production using regressions and forecasts based on empirical and theoretical relationships. Regression analysis ensures alignment between historical data and model predictions, forming a baseline for hybrid model performance evaluation. The results reveal the complementary attributes of these methodologies, providing insights into integrating data-driven and physics-based approaches for optimal reservoir management. The hybrid model captured the production rate conservatively with an extra margin of three years in favor of the physical model. Full article
(This article belongs to the Section H: Geo-Energy)
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9 pages, 2301 KiB  
Communication
Heteroleptic Cobalt Complexes with Catecholate and 1,4-Diaza-1,3-butadiene Ligands
by Irina V. Ershova, Maxim V. Arsenyev, Ilya A. Yakushev and Alexandr V. Piskunov
Molbank 2025, 2025(1), M1972; https://doi.org/10.3390/M1972 - 23 Feb 2025
Viewed by 563
Abstract
Two new heteroleptic cobalt(II) complexes (3,6-Cat)Co(R-DAD) (where (3,6-Cat)2− is a dianion of 3,6-di-tert-butyl-o-benzoquinone, R-DAD is diisopropyl-1,4-diaza-1,3-butadiene (R = i-Pr (1)) or dicyclohexyl-1,4-diaza-1,3-butadiene (R = c-Hex (2)) have been synthesized and characterized in [...] Read more.
Two new heteroleptic cobalt(II) complexes (3,6-Cat)Co(R-DAD) (where (3,6-Cat)2− is a dianion of 3,6-di-tert-butyl-o-benzoquinone, R-DAD is diisopropyl-1,4-diaza-1,3-butadiene (R = i-Pr (1)) or dicyclohexyl-1,4-diaza-1,3-butadiene (R = c-Hex (2)) have been synthesized and characterized in detail by IR, UV–Vis–NIR spectroscopy, and elemental analysis. The molecular structure of 1 was determined by X-ray diffraction analysis. Magnetic properties of 1 and 2 were measured both in a solid state and in a solution. According to the single-crystal X-ray diffraction analysis, the metal ion in 1 has a planar coordination environment, but magnetic susceptibility measurements of the microcrystalline samples of 1 and 2 indicate the formation of both forms with tetrahedral (d7, h.s., SCo = 3/2) and planar (d7, l.s., SCo = ½) coordination environments of the metal ion. Absorption spectra of crystalline samples of 1 and 2 possess intense absorption band in the NIR region. Electrochemical measurements of 1 and 2 were also performed. Full article
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42 pages, 11528 KiB  
Article
A Framework for Iterative Phase Retrieval Technique Integration into Atmospheric Adaptive Optics—Part II: High Resolution Wavefront Control in Strong Scintillations
by Mikhail A. Vorontsov and Ernst Polnau
Photonics 2025, 12(3), 185; https://doi.org/10.3390/photonics12030185 - 23 Feb 2025
Viewed by 523
Abstract
In this paper, we introduce atmospheric adaptive optics (AO) system architectures that utilize scintillation-resistant wavefront sensors based on iterative phase retrieval (IPR) techniques (described in detail in Part I) for closed-loop mitigation of atmospheric turbulence-induced wavefront aberrations in strong intensity scintillation conditions. The [...] Read more.
In this paper, we introduce atmospheric adaptive optics (AO) system architectures that utilize scintillation-resistant wavefront sensors based on iterative phase retrieval (IPR) techniques (described in detail in Part I) for closed-loop mitigation of atmospheric turbulence-induced wavefront aberrations in strong intensity scintillation conditions. The objective is to provide a framework (mathematical and numerical models, performance metrics, control algorithms, and wave-optics modeling and simulation results) for the potential integration of IPR-based wavefront sensing techniques into the following major atmospheric optics system types: directed energy laser beam projection, remote laser power delivery (remote power beaming), and free-space optical communications. Theoretical analysis and numerical simulation results demonstrate that the proposed closed-loop AO system architectures and control algorithms can be uniquely applicable for addressing one of the most challenging AO problems of turbulence effects mitigation in the presence of strong-intensity scintillations. Full article
(This article belongs to the Special Issue Challenges and Future Directions in Adaptive Optics Technology)
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11 pages, 712 KiB  
Article
Validation of Methodology for Quantifying Caffeic and Ferulic Acids in Raw and Roasted Coffee Extracts by High-Performance Liquid Chromatography
by Walace Breno da Silva, Larissa Martins Rocha, Marcio Santos Soares, Pedro Ivo Vieira Good God, Sabrina Alves da Silva, Daniele Birck Moreira and Geraldo Humberto Silva
J 2025, 8(1), 8; https://doi.org/10.3390/j8010008 - 21 Feb 2025
Viewed by 821
Abstract
Caffeic and ferulic acids are critical phenolic compounds in coffee beans, known for their antioxidant properties and influence on coffee’s acidity. This study developed and validated a rapid and simple analytical method to quantify these acids in raw and roasted coffee extracts using [...] Read more.
Caffeic and ferulic acids are critical phenolic compounds in coffee beans, known for their antioxidant properties and influence on coffee’s acidity. This study developed and validated a rapid and simple analytical method to quantify these acids in raw and roasted coffee extracts using high-performance liquid chromatography with a violet detector (HPLC-UV). Parameters such as linearity, accuracy, precision, robustness, limit of quantification, and detection were analyzed. The two acids were quantified in five Coffea arabica cultivars (Red catucai, Siriema, IPR 98, Yellow catuai, and Yellow catucai), and the results were within the standards recommended by ANVISA and INMETRO. The concentrations of caffeic acid ranged from 1.43 to 1.93 mg/g in roasted grains and from 0.16 to 0.38 mg/g in raw grains; for ferulic acid, the concentrations ranged from 0.13 to 0.16 mg/g in raw grains and from 0.27 to 0.50 mg/g in roasted grains. According to the Tukey test, only cultivar IPR 98 showed a statistically significant difference in roasted grains. The proposed method offers a rapid and accurate analysis, contributing to the study of bioactive properties and the relationship between beverage quality and the presence of these compounds in coffee beans. Full article
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11 pages, 2098 KiB  
Article
The Facile Synthesis of Exogenous Lewis-Base-Free Amidoalanes: A Structural Comparison
by Jake Hemsworth, Andrej Vinogradov, William Lewis, Simon Woodward and Darren Willcox
Molecules 2025, 30(5), 986; https://doi.org/10.3390/molecules30050986 - 20 Feb 2025
Viewed by 357
Abstract
A simple one-pot reaction of LiAlH4, AlCl3, and a secondary amine HNR2 [R = Et, iPr, iBu, cyclo-C6H11, (CH2)4, and (CH2)5] in hydrocarbon solvents [...] Read more.
A simple one-pot reaction of LiAlH4, AlCl3, and a secondary amine HNR2 [R = Et, iPr, iBu, cyclo-C6H11, (CH2)4, and (CH2)5] in hydrocarbon solvents results in the formation of exogenous Lewis-base-free amidoalanes [H2Al(NR2)]n (n = 2 or 3) as crystalline solids (35–85% yield). In the solid state (seven X-ray structures), all the amidoalanes exist as dimers, with the exception of the pyrrolidine-derived alane which exists as a trimer. As solids, these amidoalanes exhibit significant kinetic stability towards oxygen/moisture allowing the brief (ca. 5 min.) handling of [H2Al(NiPr2)]2 in air. Full article
(This article belongs to the Section Organometallic Chemistry)
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19 pages, 3452 KiB  
Article
Sensorless Control of Ultra-High-Speed PMSM via Improved PR and Adaptive Position Observer
by Xiyue Bai, Weiguang Huang, Chuang Gao and Yingna Wu
Sensors 2025, 25(5), 1290; https://doi.org/10.3390/s25051290 - 20 Feb 2025
Cited by 1 | Viewed by 919
Abstract
To improve the precision of the position and speed estimation in ultra-high-speed (UHS) permanent magnet synchronous motors (PMSM) without position sensors, multiple refinements to the traditional extended electromotive force (EEMF) estimation algorithm are proposed in this paper. The key improvements include discretization compensation, [...] Read more.
To improve the precision of the position and speed estimation in ultra-high-speed (UHS) permanent magnet synchronous motors (PMSM) without position sensors, multiple refinements to the traditional extended electromotive force (EEMF) estimation algorithm are proposed in this paper. The key improvements include discretization compensation, high-frequency harmonic filtering, and the real-time adjustment of the phase-locked loop (PLL) bandwidth. Firstly, a discrete model is introduced to address EMF cross-coupling issues. Secondly, an improved proportional resonant (IPR) controller eliminating static errors is utilized in place of the conventional proportional-integral (PI) controller and low-pass filter (LPF) to enable precise electromotive force extraction, effectively filtering high-frequency harmonics that arise in low carrier ratio conditions. Based on a standard PR design, the IPR controller offers a streamlined calculation for target leading angles in delay compensation schemes to effectively mitigate discretization and delay errors. Additionally, an adaptive phase-locked loop (AQPLL) dynamically adjusts its bandwidth during acceleration to balance noise rejection and phase delay, reducing position estimation errors and optimizing torque. Simulations and experimental analyses on a motor (90,000 rpm, 30 kW) validate the effectiveness of the proposed sensorless driving techniques and demonstrate enhanced performance in position and velocity estimation, compared to the conventional EEMF approach. Full article
(This article belongs to the Section Physical Sensors)
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23 pages, 8630 KiB  
Article
Finely-Tuned Bis(imino)pyridylcobalt Complexes Enhance Ethylene Polymerization: The Role of Bulky and Halogen Substituents
by Elizabeth Ogbe, Yanping Ma, Yizhou Wang, Jiahao Gao, Yang Sun and Wen-Hua Sun
Molecules 2025, 30(4), 859; https://doi.org/10.3390/molecules30040859 - 13 Feb 2025
Viewed by 558
Abstract
The bis(imino)pyridylcobalt complexes have been finely tuned through using the aniline derivative bearing a meta-chloro substituent, besides its ortho- and para-di(4-fluorophenyl)methyl and ortho-methyl substituents for the series of 2-[1-(3-chloro-4,6-bis((di(4-fluorophenyl)methyl)-2-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) chlorides (2,6-Me2Ph, Co1; 2,6-Et2Ph, Co2 [...] Read more.
The bis(imino)pyridylcobalt complexes have been finely tuned through using the aniline derivative bearing a meta-chloro substituent, besides its ortho- and para-di(4-fluorophenyl)methyl and ortho-methyl substituents for the series of 2-[1-(3-chloro-4,6-bis((di(4-fluorophenyl)methyl)-2-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) chlorides (2,6-Me2Ph, Co1; 2,6-Et2Ph, Co2; 2,6-iPr2Ph, Co3; 2,4,6-Me3Ph, Co4; and 2,6-Et2-4-MePh, Co5). The compounds were characterized using elemental analysis, 1H/13C NMR, FT-IR spectroscopy, and the single-crystal X-ray diffraction used in confirming the molecular structures of Co1, Co2, Co4, and Co5. The newly synthesized precatalysts, maintaining steric influences with the addition of an electron-withdrawing meta-chloro group, achieved higher activities along with better thermal stability, and controlled molecular weights of polyethylenes obtained. Upon activation with either MAO or MMAO, all catalysts exhibited remarkable activity for ethylene polymerization, for example, 9.2 × 106 g mol−1 h−1 by Co1 at 70 °C with 30 min and 18.0 × 106 g mol−1 h−1 by Co4 with the first 5 min. Co4 demonstrated exceptionally thermal stability with the peak activity of 8.9 × 106 g mol−1 h−1 at 70 °C and slightly decreased to 7.2 × 106 g mol−1 h−1 at 80 °C, and even maintained an activity of 1.6 × 106 g mol−1 h−1 at 100 °C. More importantly, all resultant polyethylenes were characterized as having vinyl-terminal and high-linear feature along with narrow dispersity; the molecular weights could be adapted in the ranges from 6.4 to 50.0 kg mol−1. In comparison with previous cobalt analogs, the current system performed better thermal stability and polymerization efficiency. Therefore, such robust complex catalysts are potentially considered for the polyethylene industry. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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24 pages, 2211 KiB  
Review
Mechanisms of Resistance to Anti-PD-1 Immunotherapy in Melanoma and Strategies to Overcome It
by Magdalena K. Zielińska, Magdalena Ciążyńska, Dorota Sulejczak, Piotr Rutkowski and Anna M. Czarnecka
Biomolecules 2025, 15(2), 269; https://doi.org/10.3390/biom15020269 - 12 Feb 2025
Viewed by 2969
Abstract
Resistance to anti-PD-1 therapy in melanoma remains a major obstacle in achieving effective and durable treatment outcomes, highlighting the need to understand and address the underlying mechanisms. The first key factor is innate anti-PD-1 resistance signature (IPRES), an expression of a group of [...] Read more.
Resistance to anti-PD-1 therapy in melanoma remains a major obstacle in achieving effective and durable treatment outcomes, highlighting the need to understand and address the underlying mechanisms. The first key factor is innate anti-PD-1 resistance signature (IPRES), an expression of a group of genes associated with tumor plasticity and immune evasion. IPRES promotes epithelial-to-mesenchymal transition (EMT), increasing melanoma cells’ invasiveness and survival. Overexpressed AXL, TWIST2, and WNT5a induce phenotypic changes. The upregulation of pro-inflammatory cytokines frequently coincides with EMT-related changes, further promoting a resistant and aggressive tumor phenotype. Inflamed tumor microenvironment may also drive the expression of resistance. The complexity of immune resistance development suggests that combination therapies are necessary to overcome it. Furthermore, targeting epigenetic regulation and exploring novel approaches such as miR-146a modulation may provide new strategies to counter resistance in melanoma. Full article
(This article belongs to the Special Issue Cancer Immunotherapy and the PD-1/PD-L1 Checkpoint Pathway)
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16 pages, 5789 KiB  
Article
Arabica coffee Intercropped with Urochloa decumbens Improved Nutrient Uptake and Yield in the Brazilian Cerrado
by Thais Rodrigues de Sousa, Arminda Moreira de Carvalho, Maria Lucrecia Gerosa Ramos, Douglas Rodrigues de Jesus, Ana Caroline Pereira da Fonseca, Fernanda Rodrigues da Costa Silva, Alexsandra Duarte de Oliveira, Heloisa Carvalho Ribeiro, Adriano Delly Veiga, Robélio Leandro Marchão, Raíssa de Araujo Dantas and Fabiana Piontekowski Ribeiro
Plants 2025, 14(4), 496; https://doi.org/10.3390/plants14040496 - 7 Feb 2025
Viewed by 745
Abstract
Coffee intercropped with Urochloa decumbens modifies nutrient uptake, and consequently the yield and quality of coffee, by the greater release of nutrients and efficient nutrient cycling. There is little information about the increasing nutrient content in Arabica coffee plants intercropped with Urochloa decumbens [...] Read more.
Coffee intercropped with Urochloa decumbens modifies nutrient uptake, and consequently the yield and quality of coffee, by the greater release of nutrients and efficient nutrient cycling. There is little information about the increasing nutrient content in Arabica coffee plants intercropped with Urochloa decumbens. The objective of this study was to evaluate the effect of Urochloa decumbens intercropped with two coffee cultivars (Coffea arabica L.) on the levels of macro- and micronutrients and coffee crop yield. The experiment was conducted at Embrapa Cerrados, Planaltina-DF, and was arranged in a completely randomized block design with three replications, in a factorial design. The first factor consists of two management systems: with (WB) and without (NB) Urochloa decumbens intercropped; the second factor is composed of Arabica coffee cultivars ‘IPR-103’ and ‘IPR-99’. There was no significant difference in yield of the coffee cultivars with and without Urochloa decumbens intercropped between the rows. The treatment with ‘IPR-99’ coffee cultivar intercropped with Urochloa decumbens achieved 400 kg ha−1 (8 bags) more than the other treatments. The presence of Urochloa decumbens increased leaf nutrient contents of the macronutrients Ca and Mg and micronutrients Mn and Fe. Thus, the Arabica coffee–Urochloa decumbens intercropping system is an efficiency management strategy which improves nutrient content for the main crop with consequent yield gains. Full article
(This article belongs to the Section Plant Nutrition)
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16 pages, 467 KiB  
Article
A Zero-Shot Framework for Low-Resource Relation Extraction via Distant Supervision and Large Language Models
by Peisheng Han, Geng Liang and Yongfei Wang
Electronics 2025, 14(3), 593; https://doi.org/10.3390/electronics14030593 - 2 Feb 2025
Viewed by 791
Abstract
While Large Language Models (LLMs) have significantly advanced various benchmarks in Natural Language Processing (NLP), the challenge of low-resource tasks persists, primarily due to the scarcity of data and difficulties in annotation. This study introduces LoRE, a framework designed for zero-shot relation extraction [...] Read more.
While Large Language Models (LLMs) have significantly advanced various benchmarks in Natural Language Processing (NLP), the challenge of low-resource tasks persists, primarily due to the scarcity of data and difficulties in annotation. This study introduces LoRE, a framework designed for zero-shot relation extraction in low-resource settings, which blends distant supervision with the powerful capabilities of LLMs. LoRE addresses the challenges of data sparsity and noise inherent in traditional distant supervision methods, enabling high-quality relation extraction without requiring extensive labeled data. By leveraging LLMs for zero-shot open information extraction and incorporating heuristic entity and relation alignment with semantic disambiguation, LoRE enhances the accuracy and relevance of the extracted data. Low-resource tasks refer to scenarios where labeled data are extremely limited, making traditional supervised learning approaches impractical. This study aims to develop a robust framework that not only tackles these challenges but also demonstrates the theoretical and practical implications of zero-shot relation extraction. The Chinese Person Relationship Extraction (CPRE) dataset, developed under this framework, demonstrates LoRE’s proficiency in extracting person-related triples. The CPRE dataset consists of 1000 word pairs, capturing diverse semantic relationships. Extensive experiments on the CPRE, IPRE, and DuIE datasets show significant improvements in dataset quality and a reduction in manual annotation efforts. These findings highlight the potential of LoRE to advance both the theoretical understanding and practical applications of relation extraction in low-resource settings. Notably, the performance of LoRE on the manually annotated DuIE dataset attests to the quality of the CPRE dataset, rivaling that of manually curated datasets, and highlights LoRE’s potential for reducing the complexities and costs associated with dataset construction for zero-shot and low-resource tasks. Full article
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24 pages, 5030 KiB  
Article
EtIDip (EtIPr)—Synthesis, Characterisation and Reactivity of a Robust, Backbone-Modified N-Heterocyclic Carbene and Group 13 Element Complexes
by Huanhuan Dong, Albert Martinez-Segura, Riley W. Kelehan, Connor Bourne, Aidan P. McKay, Alexandra M. Z. Slawin, David B. Cordes and Andreas Stasch
Inorganics 2025, 13(1), 27; https://doi.org/10.3390/inorganics13010027 - 17 Jan 2025
Viewed by 866
Abstract
We report the synthesis, characterisation and reactivity of the stable imidazol-2-ylidene EtIDip (EtIPr), {EtCN(Dip)}2C:, Dip = 2,6-iPr2C6H3, as a chemically robust alternative to IDip (IPr), {HCN(Dip)}2C:. The N-heterocyclic [...] Read more.
We report the synthesis, characterisation and reactivity of the stable imidazol-2-ylidene EtIDip (EtIPr), {EtCN(Dip)}2C:, Dip = 2,6-iPr2C6H3, as a chemically robust alternative to IDip (IPr), {HCN(Dip)}2C:. The N-heterocyclic carbene EtIDip could be further converted to the oxidised species [EtIDipCl]Cl, EtIDipF2, EtIDipO, and EtIDipSe, and the group 13 element complexes EtIDipEX3, with E = B, X = Br; E = Al, X = I; E = Ga, X = I; E = Al, X = H. The properties of the EtIDip and IDip ligands are compared and the molecular structures of (DipNCEt)2, [EtIDipH]Cl, [EtIDipH]I, EtIDip, [EtIDipCl]Cl, EtIDipF2, EtIDipO, EtIDipBBr3, EtIDipAlI3, EtIDipGaI3, and EtIDipAlH3 have been determined. Full article
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12 pages, 3093 KiB  
Article
Tetrazenyl-, Imido-, and Azidoaluminate Derivatives of a Sterically Demanding Bis-Silazide Ligand
by Han-Ying Liu, Ryan J. Schwamm, Jakub Kenar, Mary F. Mahon and Michael S. Hill
Inorganics 2025, 13(1), 25; https://doi.org/10.3390/inorganics13010025 - 16 Jan 2025
Viewed by 709
Abstract
The potassium alumanyl [{SiNDipp}AlK]2 (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-i-Pr2C6H3) reacts with organic azides via reductive N2 elimination. With the less sterically encumbered azides [...] Read more.
The potassium alumanyl [{SiNDipp}AlK]2 (SiNDipp = {CH2SiMe2NDipp}2; Dipp = 2,6-i-Pr2C6H3) reacts with organic azides via reductive N2 elimination. With the less sterically encumbered azides PhN3 and C10H15N3 (1-azidoadamantane), the putative initially formed aluminium imide undergoes facile [2 + 3] cycloaddition to provide the tetrazenylaluminates [{SiNDipp}Al-κ2-N,N′-({N(R)}2N2)]K (R = Ph, C10H15). In contrast, each Al(I) centre of [{SiNDipp}AlK]2 only reacts with a single equivalent of 2,4,6-Me3C6H2N3 to provide the imidoaluminate [{SiNDipp}AlN(2,4,6-Me3C6H2)(K∙C6H6)], which crystallises as a monomer and displays a short Al-N distance of 1.7040(13) Å. Attempts to synthesise the azide [{SiNDipp}AlN3] by reaction of [{SiNDipp}AlI] with an excess of KN3 resulted in exclusive formation of the bis(azido)aluminate [{SiNDipp}Al(N3)2K], which crystallises as an infinite 1-dimensional polymer propagated by μ-(1,3)-N3 bridging interactions between the potassium cations and azide anions. Although the THF-adducted azide [{SiNDipp}AlN3(THF)] may be synthesised and characterised by more stringent control of the reaction stoichiometry, the synthetic viability of this route remains compromised by competitive generation of [{SiNDipp}Al(N3)2K]. Full article
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20 pages, 5000 KiB  
Article
The Effect of Alkyl Substituents on the Formation and Structure of Homochiral (R*,R*)-[R2Ga(µ-OCH(Me)CO2R′)]2 Species—Towards the Factors Controlling the Stereoselectivity of Dialkylgallium Alkoxides in the Ring-Opening Polymerization of rac-Lactide
by Magdalena Kaźmierczak, Łukasz Dobrzycki, Maciej Dranka and Paweł Horeglad
Molecules 2025, 30(1), 190; https://doi.org/10.3390/molecules30010190 - 6 Jan 2025
Viewed by 784
Abstract
Building on our previous studies, which have demonstrated that homochiral propagating species—(R*,R*)-[Me2Ga(µ-OCH(Me)CO2R)]2—were crucial for the heteroselectivity of [Me2Ga(µ-OCH(Me)CO2Me)]2 in the ring-opening polymerization (ROP) of [...] Read more.
Building on our previous studies, which have demonstrated that homochiral propagating species—(R*,R*)-[Me2Ga(µ-OCH(Me)CO2R)]2—were crucial for the heteroselectivity of [Me2Ga(µ-OCH(Me)CO2Me)]2 in the ring-opening polymerization (ROP) of racemic lactide (rac-LA), we have investigated the effect of alkyl groups on the structure and catalytic properties of dialkylgallium alkoxides in the ROP of rac-LA. Therefore, we have isolated and characterized the rac-[R2Ga(µ-OCH(Me)CO2Me]2 (R = Et (1), iPr (2) and rac-[R2Ga(µ-OCH(Me)C5H4N]2 (R = Et (3), iPr (4)) complexes, to demonstrate the effect of alkyl groups on the chiral recognition induced the formation of the respective homochiaral species—(R*,R*)-[R2Ga(µ-OCH(Me)CO2Me)]2 and (R*,R*)-[R2Ga(µ-OCH(Me)C5H4N]2. Moreover, we have investigated the structure of (S,S)-[R2Ga(µ-OCH(Me)CO2Me]2 (R = Et ((S,S)-1, R = iPr ((S,S)-2,) and their catalytic activity in the ROP of rac-LA. With an increase in the bulkiness of alkyl substituents on gallium the following can be observed: (a) the tendency for the formation of homochiral complexes decreased, (b) the symmetry of homochiral (S,S)-[R2Ga(µ-OCH(Me)CO2Me]2 (M = Me, Et (S,S)-1), iPr (S,S)-2) changed, and both have resulted in (c) lower or no heteroselectivtity across these complexes in the ROP of rac-LA. Importantly, the results have confirmed the crucial role of the chiral-induced formation of homochiral asymmetric dimers on the heteroselectivity of dialkylgallium alkoxides in the ROP of rac-LA. Full article
(This article belongs to the Special Issue Organometallic Compounds: Design, Synthesis and Application)
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