bluuebunny/crossref_metadata_2025_split huggingface dataset:
Wavelength Selective Photocontrol of Hybrid Azobenzene‐Spiropyran Photoswitches with Overlapping Chromophores
Authors: Saßmannshausen Torben , Kunz Anne , Oberhof Nils , Schneider Friederike , Slavov Chavdar , Dreuw Andreas , Wachtveitl Josef , Wegner Hermann A. 
Published: December 2023

AbstractCompounds with multiple photoswitching units are appealing for complex photochemical control of molecular materials and nanostructures. Herein, we synthesized novel meta‐ and para‐ connected (related to the nitrogen of the indoline) azobenzene‐spiropyran dyads, in which the central benzene unit is shared by both switches. We investigated their photochemistry using static and time‐resolved transient absorption spectroscopy as well as quantum chemical calculations. In the meta‐compound, the individual components are photochemically decoupled due to the meta‐pattern. In the para‐compound the spiro‐connectivity leads to a bifunctional photoswitchable system with a red‐shifted absorption. The azobenzene and the spiropyran can thus be addressed and switched independently by light of appropriate wavelength. Through the different connectivity patterns two different orthogonally photoswitchable systems have been obtained which are promising candidates for complex applications of light control.
Counterion Effect in Cobaltate‐Catalyzed Alkene Hydrogenation
Authors: Gawron Martin , Gilch Franziska , Schmidhuber Daniel , Kelly John A. , Horsley Downie Thomas M. , Jacobi von Wangelin Axel , Rehbein Julia , Wolf Robert 
Published: December 2023

AbstractWe show that countercations exert a remarkable influence on the ability of anionic cobaltate salts to catalyze challenging alkene hydrogenations. An evaluation of the catalytic properties of [Cat][Co(η4‐cod)2] (Cat=K (1), Na (2), Li (3), (Depnacnac)Mg (4), and N(nBu)4 (5); cod=1,5‐cyclooctadiene, Depnacnac={2,6‐Et2C6H3NC(CH3)}2CH)]) demonstrated that the lithium salt 3 and magnesium salt 4 drastically outperform the other catalysts. Complex 4 was the most active catalyst, which readily promotes the hydrogenation of highly congested alkenes under mild conditions. A plausible catalytic mechanism is proposed based on density functional theory (DFT) investigations. Furthermore, combined molecular dynamics (MD) simulation and DFT studies were used to examine the turnover‐limiting migratory insertion step. The results of these studies suggest an active co‐catalytic role of the counterion in the hydrogenation reaction through the coordination to cobalt hydride intermediates.
Insulin‐like Growth Factor 2‐Tagged Aptamer Chimeras (ITACs) Modular Assembly for Targeted and Efficient Degradation of Two Membrane Proteins
Authors: Tian Yuan , Miao Yanyan , Guo Pei , Wang Junyan , Han Da 
Published: December 2023

AbstractOverexpression of pathogenic membrane proteins drives abnormal proliferation and invasion of tumor cells. Various strategies to durably knockdown membrane proteins with heterobifunctional degraders have been successfully developed, including LYTAC, KineTAC, and AbTAC. However, challenges including complicated synthetic procedures and the inability to simultaneously degrade multiple pathogenic proteins still exist. Herein, we developed insulin‐like growth factor 2 (IGF2)‐tagged aptamer chimeras (ITACs) that link the cell‐surface lysosome‐targeting receptor IGF2R and membrane proteins of interest (POIs) based on specific recognition of aptamers to the POIs and high‐affinity binding of IGF2 to IGF2R. We demonstrated that ITACs exhibit robust degradation efficiency of various membrane proteins in multiple cell lines. Furthermore, systematic studies revealed that a moderate cell‐surface IGF2R level is responsible for the excellent degradation performance of ITACs. Importantly, we further established a modular assembly strategy that allows assembly of one IGF2 with two aptamers with precise stoichiometry (dITACs), enabling cooperative and simultaneous degradation of two membrane proteins. This work provides an efficient and facile target membrane protein degradation platform and will shed light on the treatment of diseases related to the overexpression of membrane proteins.
Metal‐Free 1,3‐Boronate Rearrangement to Ketones Driven by Visible Light
Authors: Hao Kejia , Li Defang , Fu Dongmin , Zou Peng , Xie Shasha , Lan Yu , Chen Yiyun 
Published: December 2023

AbstractBoronate rearrangements, such as the Matteson and Petasis reactions, are valuable metal‐free reactions for the transfer of the carbo group on boron to intramolecular electrophilic sites. However, only highly reactive electrophiles are suitable, and ketones are too inactive for those boronate rearrangements due to the high energy barriers. We disclose here the 1,3‐boronate rearrangement to ketones, for which a high energy barrier (44.9 kcal/mol) is prohibitory for thermal reactions in the ground state. The reaction is enabled by the key keto‐enol‐boronate bidentate complex formation in situ, which absorbs visible light to reach the excited state for the chemoselective 1,3‐boronate rearrangement to ketones. Experimental and computational investigations exclude free radical intermediates from organoboronates. The aryl, alkenyl, and alkyl boronic acids react with various 1,3‐diketones driven by visible light irradiation to construct structurally diverse β‐keto tertiary alcohols under metal‐free conditions. The reaction demonstrates substrate diversity with 58 examples, yields up to 98 %, and it is suitable for gram‐scale synthesis.
Bifunctional Peptide Nanofibrils for Targeted Protein Degradation
Authors: Lin Zongtao , Garcia Benjamin A. , Lv Dongwen 
Published: December 2023

AbstractProteolysis targeting chimera (PROTAC) is a state‐of‐the‐art technology for ablating undruggable targets. A PROTAC degrader achieves targeted protein degradation (TPD) through the simultaneous binding of a protein of interest (POI) and an E3 ligase to form a ternary complex. A nanofibril‐based PROTAC strategy to form a polynary (E3)m : PROTAC : (POI)n complex has not been reported in the TPD field up to this point. A recent innovation shows that a POI ligand and E3 ligase ligand don't have to be within a fused degrader molecule. Instead, they can be recruited to cellular proximity by a self‐assembly‐driving peptide and click chemistry. The resulting nanofibrils can recruit multiple POI and E3 ligase molecules to form a polynary complex as a degradation center. The so‐called Nano‐PROTAC provides a novel approach for TPD in cancer therapy.
Triptycene Branched Poly(aryl‐co‐aryl piperidinium) Electrolytes for Alkaline Anion Exchange Membrane Fuel Cells and Water Electrolyzers
Authors: Hu Chuan , Kang Na Yoon , Kang Hyun Woo , Lee Ju Yeon , Zhang Xiaohua , Lee Yong Jun , Jung Seung Won , Park Jong Hyeong , Kim Myeong‐Geun , Yoo Sung Jong , Lee So Young , Park Chi Hoon , Lee Young Moo 
Published: December 2023

AbstractAlkaline polymer electrolytes (APEs) are essential materials for alkaline energy conversion devices such as anion exchange membrane fuel cells (AEMFCs) and water electrolyzers (AEMWEs). Here, we report a series of branched poly(aryl‐co‐aryl piperidinium) with different branching agents (triptycene: highly‐rigid, three‐dimensional structure; triphenylbenzene: planar, two‐dimensional structure) for high‐performance APEs. Among them, triptycene branched APEs showed excellent hydroxide conductivity (193.5 mS cm−1@80 °C), alkaline stability, mechanical properties, and dimensional stability due to the formation of branched network structures, and increased free volume. AEMFCs based on triptycene‐branched APEs reached promising peak power densities of 2.503 and 1.705 W cm−2 at 75/100 % and 30/30 % (anode/cathode) relative humidity, respectively. In addition, the fuel cells can run stably at a current density of 0.6 A cm−2 for 500 h with a low voltage decay rate of 46 μV h−1. Importantly, the related AEMWE achieved unprecedented current densities of 16 A cm−2 and 14.17 A cm−2 (@2 V, 80 °C, 1 M NaOH) using precious and non‐precious metal catalysts, respectively. Moreover, the AEMWE can be stably operated under 1.5 A cm−2 at 60 °C for 2000 h. The excellent results suggest that the triptycene‐branched APEs are promising candidates for future AEMFC and AEMWE applications.
Phenolics of mustard seeds: A review on composition, processing effect and their bioactvities
Authors: Nguyen Thu , Nandasiri Ruchira , Fadairo Olamide , Eskin N. A. Michael 
Published: December 2023

AbstractMustard seeds have been used since ancient times contributing great economic value to global agriculture. Canada, one of the world's top producers, grows three main mustard varieties, white /yellow, (Brassica hirta/Sinapis alba), black (Brassica nigra) and Oriental (Brassica juncea). Besides their high protein and lipid content, mustard varieties are a rich source of phenolic compounds. This review will cover mustard seed components including lipids, glucosinolates, and sinapates. The latter are the main phenolic compounds in mustard and include sinapine, sinapic acid and its conversion to canolol. The important bioactivities associated with mustard phenolics, has led to efforts to improve the methods for their extraction. The use of green technology is crucial for producing these phenolics while minimizing any detrimental effects to the environment. The important antioxidant and anticancer activities of these phenolics will also be reviewed.
Ecological correlates of three‐dimensional muscle architecture within the dietarily diverse Strepsirrhini
Authors: Dickinson Edwin , Manzo Madison , Davis Cassidy E. , Kolli Shruti , Schwenk Alysa , Carter Ashley , Liu Cindy , Vasipalli Nimi , Ratkiewicz Aleksandra , Deutsch Ashley R. , Granatosky Michael C. , Hartstone‐Rose Adam 
Published: December 2023

AbstractAnalysis of muscle architecture, traditionally conducted via gross dissection, has been used to evaluate adaptive relationships between anatomical form and behavioral function. However, gross dissection cannot preserve three‐dimensional relationships between myological structures for analysis. To analyze such data, we employ diffusible, iodine‐based contrast‐enhanced computed tomography (DiceCT) to explore the relationships between feeding ecology and masticatory muscle microanatomy in eight dietarily diverse strepsirrhines: allowing, for the first time, preservation of three‐dimensional fascicle orientation and tortuosity across a functional comparative sample. We find that fascicle properties derived from these digital analyses generally agree with those measured from gross‐dissected conspecifics. Physiological cross‐sectional area was greatest in species with mechanically challenging diets. Frugivorous taxa and the wood‐gouging species all exhibit long jaw adductor fascicles, while more folivorous species show the shortest relative jaw adductor fascicle lengths. Fascicle orientation in the parasagittal plane also seems to have a clear dietary association: most folivorous taxa have masseter and temporalis muscle vectors that intersect acutely while these vectors intersect obliquely in more frugivorous species. Finally, we observed notably greater magnitudes of fascicle tortuosity, as well as greater interspecific variation in tortuosity, within the jaw adductor musculature than in the jaw abductors. While the use of a single specimen per species precludes analysis of intraspecific variation, our data highlight the diversity of microanatomical variation that exists within the strepsirrhine feeding system and suggest that muscle architectural configurations are evolutionarily labile in response to dietary ecology—an observation to be explored across larger samples in the future.
Cross‐sectoral citrus sugarcane biorefinery: polyhydroxyalkanoates production in Brazil
Authors: Kanbe Mariana Teixeira , da Silva Luiziana Ferreira , Gomez José Gregório Cabrera 
Published: December 2023

AbstractPolyhydroxyalkanoates (PHA) are naturally occurring polyesters accumulated by bacteria under conditions of inorganic nutrient limitations and excess carbon. They offer renewable and biodegradable alternatives to petroleum‐based polymers, especially those used in transient single‐use applications. However, PHA still faces high production costs, primarily linked to the carbon source, lower productivity in processes and an early stage of technical development in comparison with well‐established fossil‐based polymers, which challenge its transition to a true commodity market. Recent research has highlighted the potential of renewable, inexpensive, abundant and non‐edible carbon‐rich residues from agriculture, municipal solid waste and industrial byproducts as alternative carbon sources in developing the production process. Recognizing Brazil's position as the leading producer of both citrus and sugarcane, this review introduces a novel citrus–sugarcane biorefinery model for PHA production, capitalizing on the geographical and operational synergies of both sectors. The proposed model integrates wet citrus pulp as a second‐generation carbon source, sugarcane industry fermenters, waste management, solvents and renewable energy from both sectors. Primary challenges involve the need for efficient, low‐cost biomass pre‐treatment to remove limonene and partially extract citric pectin, coupled with the partial hydrolysis of pectin to enhance solubility and reduce viscosity. Additional considerations include determining citrus biomass composition and sugar consumption, screening bacterial diversity for optimal PHA production, and deepening our understanding of the metabolic pathways underpinning the catabolism of citrus residues. Future research should focus on enhancing PHA concentrations and diversity and finally conducting life cycle assessment studies to evaluate the sustainability and feasibility of this proposed model.
A novel sustainable second‐derivative synchronous spectrofluorimetric method for the simultaneous determination of olmesartan medoxomil and rosuvastatin calcium in bulk and formulations: Integrated greenness and whiteness evaluation
Authors: Batakoushy Hany A. , Nasr Zeinab Adel , Soliman Marwa M. , Barghash Sona S. , Fouad Fatma A. , Barseem Aya 
Published: December 2023

AbstractThe present research has established a quick and highly sensitive second‐derivative synchronous fluorometric technique for the simultaneous quantification of a binary mixture of olmesartan medoxomil and rosuvastatin calcium. Simultaneously, the suggested approach was used to detect the synchronous fluorescence intensity of the cited drugs at Δ λ = 80 nm in ethanol to determine the concentrations of olmesartan medoxomil and rosuvastatin calcium at 265 and 240 nm, respectively. Various experimental conditions were tested, and each variable was analyzed and optimized. The calibration graphs were shown to be linear within ranges of 0.1–2.0 and 0.5–6.0 μg ml−1 for each drug concentration, respectively. The newly developed Green Solvents Selecting Tool (GSST) was utilized to assess the solvent's sustainability. Furthermore, the proposed method was found to be environmentally friendly after being evaluated with three different tools [the Green Analytical Procedure Index (GAPI), the Analytical Greenness Metric (AGREE), and the Analytical Eco‐Scale with Eco‐score equal to 95]. The whiteness qualities were also studied using the Red–Green–Blue (RGB12) model, which was recently designed and showed a high score equal to 92.9. The proposed method’s good findings, as well as its ongoing sustainability, simplicity, and economy, stimulate its application in QC laboratories.
Demonstrating the immunostimulatory and cytokine‐augmentation effects of bacterial ghosts on natural killer cells and Caenorhabditis Elegans
Authors: Narayanan Sreeja , Baburajan Adheena Panangattu , Muhammad Mumtaz , Joseph Andrea , Vemula Praveen Kumar , Bhat Sarita Ganapathy 
Published: December 2023

AbstractThe potential of bacteria‐based immunotherapy lies in its ability to inherently enhance immune responses. However, the “liveness” of bacteria poses risks of bacterial escape, nonspecific immuno‐stimulation, and ethical concerns, limiting their acceptability in immunotherapy. In this scenario, nonliving empty bacterial‐cell envelopes, named bacterial ghosts (BGs), have emerged as immuno‐stimulants with the potential to side‐step the limitations of live bacterial therapies. This study demonstrates the capability of BGs in modulating the functionality of NK‐92 cells and Caenorhabditis elegans (C. elegans), as well as perform as cytokine‐therapy adjuvants. BGs were obtained through a pH‐driven culture method, and were validated for their structural and chemical integrity via electron microscopy and spectroscopy. In NK‐92 cells, BGs have shown significant immuno‐stimulation by boosting the gene‐expression of perforin, granzyme‐B, Fas‐L, and interferon‐gamma by factors of 3.5‐, 1.5‐, 12.5‐, and 8.6‐folds, respectively. Combined BG and IL‐12 treatment yielded a notable 10.2‐fold increase in interferon‐gamma protein expression in 24 h. The BGs also significantly influenced the innate immune response in C. elegans through the upregulation of lysozyme genes viz., ilys‐3 (8.8‐fold) and lys‐2 (3.1‐fold). Our investigation into the impact of BGs on natural killer cells and C. elegans highlights its potential as a valid alternative approach for new‐age immunotherapy and cytokine augmentation.
The pathway towards circular economy: Measuring circular advantage of eco‐innovations
Authors: Brogi Stefano , Menichini Tamara 
Published: December 2023

AbstractEco‐Innovation (EI) emerges as an enabler of Circular Economy (CE). A shift to the CE is a powerful opportunity for companies to create significant financial and economic value for business and society: the so‐called “circular advantage”. Companies have a crucial role as accelerators of the CE transition, although the identification and exploitation of CE opportunities that derive from trasformative EI being essential. With the aim to develop a multidimensional and multi‐actor approach to innovation in CE the present paper proposes an integrated Multi‐Criteria Decision‐Making (MCDM) method based on fuzzy Analytic Hierarchy Process (AHP) and Interval‐Valued Triangular Fuzzy Numbers Additive Ratio ASsessment (IVTFN‐ARAS). The proposed method is conceived as a tool to evaluate the ability of Eco‐Innovative solutions to trigger company adoption of CE business models, the exploitation of disruptive technologies, and the enforcement of dynamic capabilities, which are all recognized as drivers of CE advantage. An illustrative application to a set of EU‐funded Eco‐Innovative projects is presented to clarify how the method works in practice. Discussion and suggestions for future research offer guidance to use the method as a policy‐making instrument.
Components of the tumor immune microenvironment based on m‐IHC correlate with prognosis and subtype of triple‐negative breast cancer
Authors: Lin Luyi , Li Haiming , Wang Xin , Wang Zezhou , Su Guanhua , Zhou Jiayin , Sun Shiyun , Ma Xiaowen , Chen Yan , You Chao , Gu Yajia 
Published: December 2023

AbstractBackground and AimThe spatial distribution and interactions of cells in the tumor immune microenvironment (TIME) might be related to the different responses of triple‐negative breast cancer (TNBC) to immunomodulators. The potential of multiplex IHC (m‐IHC) in evaluating the TIME has been reported, but the efficacy is insufficient. We aimed to research whether m‐IHC results could be used to reflect the TIME, and thus to predict prognosis and complement the TNBC subtyping system.MethodsThe clinical, imaging, and prognosis data for 86 TNBC patients were retrospectively reviewed. CD3, CD4, CD8, Foxp3, PD‐L1, and Pan‐CK markers were stained by m‐IHC. Particular cell spatial distributions and interactions in the TIME were evaluated with the HALO multispectral analysis platform. Then, we calculated the prognostic value of components of the TIME and their correlations with TNBC transcriptomic subtypes and MRI radiomic features reflecting TNBC subtypes.ResultsThe components of the TIME score were established by m‐IHC and demonstrated positive prognostic value for TNBC (p = 0.0047, 0.039, <0.0001 for DMFS, RFS, and OS). The score was calculated from several indicators, including Treg% in the tumor core (TC) or stromal area (SA), PD‐L1+ cell% in the SA, CD3 + cell% in the TC, and PD‐L1+/CD8+ cells in the invasive margin and SA. According to the TNBC subtyping system, a few TIME indicators were significantly different in different subtypes and significantly correlated with MRI radiomic features reflecting TNBC subtypes.ConclusionWe demonstrated that the m‐IHC‐based quantitative score and indicators related to the spatial distribution and interactions of cells in the TIME can aid in the accurate diagnosis of TNBC in terms of prognosis and classification.
Tryptophan metabolism enzymes are potential targets in ovarian clear cell carcinoma
Authors: Zhang Sumei , Gao Yike , Wang Pan , Wang Shu , Wang Yuming , Li Mei , Wang Anqi , Zhao Kun , Zhang Zixin , Sun Jian , Guo Dan , Liang Zhiyong 
Published: December 2023

AbstractAimAs the second most prevalent subtype of epithelial ovarian cancers, ovarian clear cell carcinoma (OCCC) is known for its chemoresistance to conventional platinum‐based therapy. In this work, we examined the tryptophan (Trp) metabolism enzymes' differential expression in patients with OCCC to assess the potential for personalised treatment.MethodsA total of 127 OCCC tissues were used to construct tissue microarrays, and immunohistochemistry (IHC) staining of the Trp enzymes IDO1, IDO2, TDO2 and IL4I1 was performed. The correlations between Trp enzyme expression and clinical characteristics were analysed.ResultsPositive IDO1, IDO2, TDO2 and IL4I1 staining was identified in 26.8%, 94.5%, 75.6% and 82.7% of OCCC respectively. IDO1‐positive samples were more common in the chemoresistant group than in the platinum‐sensitive group (46.7% vs. 19.8%). Moreover, positive expression of IDO1, TDO2 and IL4I1 was related to advanced stage, metastasis, bilateral tumours, endometriosis and tumour rupture (p < 0.05) respectively. Univariate analysis revealed a significant association between bilateral tumours, lymph node metastasis, advanced stage, distant metastasis and aberrant cytology with a poor prognosis for OCCC, while the absence of residual tumour was correlated with a favourable outcome (p < 0.05). However, only bilateral tumours and lymph node metastases were related to a poor prognosis after multivariate analysis.ConclusionThis is the first study to investigate the expression of the Trp enzymes IDO1, IDO2, TDO2 and IL4I1 in OCCC tissues. IDO2, TDO2 and IL4I1 were detected in the majority of OCCC. Clinical traits were correlated with IDO1, IDO2, TDO2 and IL4I1 expression. IDO1 may be used as a therapeutic target given the large percentage of chemoresistant cases with IDO1 expression. These results will aid the development of personalised therapies for OCCC.