bluuebunny/crossref_metadata_2025_split huggingface dataset:
One‐Pot Rh(III)‐Catalyzed Twofold C−H Activation/Oxidative Annulation of N‐Arylpyrroles with Alkynes to Fluorescent Ullazines
Authors: Otero‐Riesgo Sergio , Varela Jesús A. , Saá Carlos 
Published: March 2024

AbstractA range of densely functionalized ullazines have been synthesized by a one‐pot Rh(III)‐catalyzed twofold C−H activation/oxidative annulation of N‐arylpyrroles with alkynes. Electrophilic bromination at 5‐ or 5,7‐ positions of the EWG‐substituted ullazine core offers an interesting single or double entry for further extended functionalization. Mechanistic considerations suggest two complementary paths, EWG‐assisted and SEAr, for the C−H activations. All ullazines exhibit strong fluorescence emissions. Ullazines bearing thiophene and triarylamine units at 5‐ and 5,7‐ positions show a significant bathochromic shift in their emission spectra, attributed to the more extended electronic circuits present.
Water vapor effects on attrition and elemental migration of iron‐based oxygen carrier in chemical looping combustion
Authors: Huang Neng , Omosebi Ayokunle , Gao Xin , Koumoulis Dimitrios , Liu Kunlei 
Published: March 2024

AbstractChemical looping combustion (CLC) offers a novel approach to simultaneous power generation and carbon capture. However, the commercial viability of CLC depends on durable and cost‐effective oxygen carriers (OCs). This study assesses the impact of water vapor (WV) on the attrition of red mud OC, crucial for industrial CLC deployment. Findings indicate a significant reduction in the average attrition rate, from 0.06%/h to 0.03%/h, attributed to the limitation of Fe2O3 reduction, resulting in reduced volumetric and temperature changes in the presence of WV. A developed volume‐based model reveals attrition contributions in the order of chemical > mechanical >> thermal stresses, influencing OC particle surface morphology. Remarkably, the formation of the iron‐oxide layer remains unaffected by WV, reducing agents (CO or H2), or superficial velocities, suggesting scalable iron recovery from attrition with enhanced flexibility in future applications.
Establishment of light‐dependent photo‐thermal kinetic model for methane dry reforming and performance optimization in a cavity reactor
Authors: Yao Ji‐Long , Zhang Zhen‐Yu , Xu Bo‐Yu , Li Ting , Bai Pan‐Wei , Liang Wen‐Peng , Xie Tao 
Published: March 2024

AbstractSolar methane dry reforming (MDR) reaction is a highly promising technology for long‐term energy storage due to its eco‐friendly nature and high‐value‐added product. Numerous present works mainly focused on the photo‐thermal catalysts, few of them discussed photo‐thermal coupled kinetics. Therefore, this article proposed a light‐dependent kinetic model for MDR. In the model, not only the effect of temperature and species concentration were included, but also the radiation was considered, which is different from the conventional kinetic model. Solar radiation is divided into thermal‐effect and light‐promoted‐effect part and coupled with the heat and mass transportation and chemical reaction. The average relative error of established model is only 0.97% under dark condition, and 13.2% under light condition. Then, the impacts of operating condition in a cavity reactor were investigated by established coupled optical‐photo‐thermal dynamics–computational fluid dynamic model to improve the efficiency of chemical conversion. The results show that when GHSV is 48.21 h−1, light increased the reaction rate by 1.59 times and thermochemical energy storage efficiency by 18.5%. When CH4/CO2 = 1, the formation rates of syngas and thermochemical energy storage efficiency are the highest. This work provides a highly coupled photo‐thermal kinetic model and a method for modeling and condition optimization.
Patient experiences of receiving a diagnosis of hypermobile Ehlers–Danlos syndrome
Authors: Wang Yun‐Ting , Jahani Shiva , Morel‐Swols Dayna , Kapely Angelica , Rosen Ami , Forghani Irman 
Published: March 2024

AbstractHypermobile Ehlers–Danlos syndrome (hEDS) presents with a wide range of clinical symptoms and comorbidities that impact quality of life. The diagnosis is challenging and often delayed due to the heterogeneity of the disease and lack of diagnostic biomarkers, which adds to the disease burden by affecting patients' psychosocial adaptation and overall well‐being. Previous studies have revealed that healthcare professionals and the public have a limited understanding and familiarity with the condition, which leads to disapproval and skepticism that greatly impact patients' social spheres and welfare. While physical manifestations have been widely discussed, the psychosocial impact and the importance of receiving a diagnosis have not been fully studied in the current literature. This survey study investigated the impact of diagnosis in hEDS patients, selected from the University of Miami's hEDS registry. Survey questions were formulated based on clinical expertise and literature review. Descriptive statistics, Mann–Whitney test, and Spearman's correlation were used for data analysis. The median age at symptom presentation was 10 years, with a median gap of 4 years before the initial medical evaluation. On average, it took 10 years to receive a diagnosis of hEDS. Nearly all participants (95.2%) expressed receiving a diagnosis as “important” or “highly important,” with 81.9% agreeing that it helped them cope with their condition better, 76.8% could better manage their symptoms, and felt more in control of their long‐term care. Participants mostly had a positive emotional reaction and experienced an improvement in the support they were receiving from their caregivers and healthcare providers after receiving a diagnosis of hEDS. This study demonstrates that receiving a diagnosis could positively impact the patient's support, quality of care, and overall well‐being.
Photocatalytic CO2 Reduction Using an Osmium Complex as a Panchromatic Self‐Photosensitized Catalyst: Utilization of Blue, Green, and Red Light
Authors: Kamada Kenji , Jung Jieun , Yamada Chihiro , Wakabayashi Taku , Sekizawa Keita , Sato Shunsuke , Morikawa Takeshi , Fukuzumi Shunichi , Saito Susumu 
Published: March 2024

AbstractThe photocatalytic reduction of carbon dioxide (CO2) represents an attractive approach for solar‐energy storage and leads to the production of renewable fuels and valuable chemicals. Although some osmium (Os) photosensitizers absorb long wavelengths in the visible‐light region, a self‐photosensitized, mononuclear Os catalyst for red‐light‐driven CO2 reduction has not yet been exploited. Here, we discovered that the introduction of an Os metal to a PNNP‐type tetradentate ligand resulted in the absorption of light with longer‐wavelength (350–700 nm) and that can be applied to a panchromatic self‐photosensitized catalyst for CO2 reduction to give mainly carbon monoxide (CO) with a total turnover number (TON) of 625 under photoirradiation (λ≥400 nm). CO2 photoreduction also proceeded under irradiation with blue (λ0=405 nm), green (λ0=525 nm), or red (λ0=630 nm) light to give CO with >90 % selectivity. The quantum efficiency using red light was determined to be 12 % for the generation of CO. A catalytic mechanism is proposed based on the detection of intermediates using various spectroscopic techniques, including transient absorption, electron paramagnetic resonance, and UV/Vis spectroscopy.
Magneto‐chiral Nonlinear Optical Effect with Large Anisotropic Response in Two‐Dimensional Halide Perovskite
Authors: Okada Daichi , Araoka Fumito 
Published: March 2024

AbstractThe chiral organic–inorganic halide perovskites (OIHPs) are vital candidates for superior nonlinear optical (NLO) effects associated with circularly polarized (CP) light. NLO in chiral materials often couples with magnetic dipole (MD) transition, as well as the conventional electric dipole (ED) transition. However, the importance of MD transition in NLO process of chiral OIHPs has not yet been well recognized. Here, the circular polarized probe analysis of second harmonic generation circular dichroism (SHG‐CD) provides the direct evidence that the contribution of MD leads to a large anisotropic response to CP lights in chiral OIHPs, (R‐/S‐MBACl)2PbI4. The thin films exhibit great sensitivity to CP lights over a wide wavelength range, and the g‐value reaches up to 1.57 at the wavelength where the contribution of MD is maximized. Furthermore, it is also effective as CP light generator, outputting CP‐SHG with maximum g‐factor of 1.76 upon the stimulation of linearly polarized light. This study deepens the understanding of relation between chirality and magneto‐optical effect, and such an efficient discrimination and generation of CP light signal is highly applicable for chirality‐based sensor and optical communication devices.
Secondary Amine Catalysis in Enzyme Design: Broadening Protein Template Diversity through Genetic Code Expansion
Authors: Williams Thomas L. , Taily Irshad M. , Hatton Lewis , Berezin Andrey A , Wu Yi‐Lin , Moliner Vicent , Świderek Katarzyna , Tsai Yu‐Hsuan , Luk Louis Y. P. 
Published: March 2024

AbstractSecondary amines, due to their reactivity, can transform protein templates into catalytically active entities, accelerating the development of artificial enzymes. However, existing methods, predominantly reliant on modified ligands or N‐terminal prolines, impose significant limitations on template selection. In this study, genetic code expansion was used to break this boundary, enabling secondary amines to be incorporated into alternative proteins and positions of choice. Pyrrolysine analogues carrying different secondary amines could be incorporated into superfolder green fluorescent protein (sfGFP), multidrug‐binding LmrR and nucleotide‐binding dihydrofolate reductase (DHFR). Notably, the analogue containing a D‐proline moiety demonstrated both proteolytic stability and catalytic activity, conferring LmrR and DHFR with the desired transfer hydrogenation activity. While the LmrR variants were confined to the biomimetic 1‐benzyl‐1,4‐dihydronicotinamide (BNAH) as the hydride source, the optimal DHFR variant favorably used the pro‐R hydride from NADPH for stereoselective reactions (e.r. up to 92 : 8), highlighting that a switch of protein template could broaden the nucleophile option for catalysis. Owing to the cofactor compatibility, the DHFR‐based secondary amine catalysis could be integrated into an enzymatic recycling scheme. This established method shows substantial potential in enzyme design, applicable from studies on enzyme evolution to the development of new biocatalysts.
Regio‐ and Stereo‐Selective Isomerization of Borylated 1,3‐Dienes Enabled by Selective Energy Transfer Catalysis
Authors: Kweon Byeongseok , Blank Lukas , Soika Julia , Messara Amélia , Daniliuc Constantin G. , Gilmour Ryan 
Published: March 2024

AbstractConfigurationally‐defined dienes are pervasive across the bioactive natural product spectrum, where they typically manifest themselves as sorbic acid‐based fragments. These C5 motifs reflect the biosynthesis algorithms that facilitate their construction. To complement established biosynthetic paradigms, a chemical platform to facilitate the construction of stereochemically defined, functionalizable dienes by light‐enabled isomerization has been devised. Enabled by selective energy transfer catalysis, a variety of substituted β‐boryl sorbic acid derivatives can be isomerized in a regio‐ and stereo‐selective manner (up to 97 : 3). Directionality is guided by a stabilizing nO→pB interaction in the product: this constitutes a formal anti‐hydroboration of the starting alkyne. This operationally simple reaction employs low catalyst loadings (1 mol %) and is complete in 1 h. X‐ray analysis supports the hypothesis that the nO→pB interaction leads to chromophore bifurcation: this provides a structural foundation for selective energy transfer.
Polyacrylonitrile‐based porous polymer spheres and their conversion to N‐doped carbon materials for adsorption and electrocatalysis
Authors: Gao Zhuo , Sanjuán Ignacio , Hagemann Ulrich , Wittmar Alexandra S. M. , Andronescu Corina , Ulbricht Mathias 
Published: March 2024

AbstractBecause of their tunable porosity and specific surface area, porous materials are of high interest for the purification of wastewater by adsorption as well as in electrocatalysis, where, in particular, developing metal‐free carbon‐based catalysts for the oxygen reduction reaction (ORR) is researched. The carbon spheres presented here can meet these two requirements simultaneously. Porous polyacrylonitrile (PAN) spheres were firstly prepared by droplet shaping cum nonsolvent induced phase separation. Then, they were converted to nitrogen‐doped carbon spheres by two‐step carbonization via preoxidation and pyrolysis. During the pyrolysis step, carbon dioxide was used to reopen the pores of the materials that had been blocked after the preoxidation step. By this way, specific surface area values of carbon spheres of more than 1000 m2/g could be obtained. Best performing carbon materials (C#3) showed high adsorption capacity (e.g., 296 mg/g for methyl orange at solute equilibrium concentration of 24 mg/L in water). The XPS analysis revealed that only quaternary (N‐Q) and pyridinic (N‐6) nitrogen sites were found in these carbon spheres. The best ORR performance was found also for C#3 carbon spheres, with a potential of 0.81 V versus reversible hydrogen electrode (RHE) at −1 mA/cm2 and electron transfer number of 3.5 at 0.6–0.8 V versus RHE, as determined by rotating disk or rotating ring disk electrode tests. In conclusion, all results confirm that these PAN‐derived carbon spheres are potentially valuable materials for both wastewater treatment by adsorption and electrocatalytic oxygen reduction.
A room‐temperature self‐healing anticorrosion coating of supramolecular polyurethane based on dynamic reversible quadruple hydrogen bond
Authors: Yang Zhou , Wang Jixing , Li Geng , Gu Xiaomin , Yang Huan , Tang Quanwu , Su Gaoshen 
Published: March 2024

AbstractThe contradiction between the migration rate of molecular chains and mechanical strength has always been a key factor affecting the practical application of self‐healing anticorrosion coatings. In this paper, a series of supramolecular self‐healing elastomers (SPU‐MP) were prepared by the reaction of diphenylmethane diisocyanate and polyether amine. The results shown that the proportion of polyetheramine D230 (D230) in molecular segments affects the hydrogen bond density between molecular chains, thereby affecting the self‐healing efficiency and mechanical strength of SPU‐MP. When the ratio of D230 and polyetheramine D400 (D400) is 2:8, the tensile fracture strength of SPU‐MP8 is 5.08 MPa, and the self‐healing efficiency reaches 82.1% after 10 h of repair at room temperature. Further increasing the ratio of D230 increases the relaxation time of the molecular chain due to the increase in hydrogen bond density, resulting in a decrease in the self‐healing efficiency of SPU‐MP. The results of electrochemical experiments and neutral salt spray experiments indicate that the anticorrosion coating prepared by SPU‐MP8 exhibits good self‐healing performance. After immersing in 3.5 wt.% NaCl solution for 35 days, the low‐frequency impedance modulus of the intact coating and the scratch coating were both higher than 107 Ω cm2, still shown good anticorrosion ability.
Wear‐ and UV‐resistant polycarbonate‐based composite films reinforced by a novel inorganic–organic hybrid filler
Authors: Wang Songbin , Gao Xinlei , Weng Longfei , Huo Chunqing , Du Xueyu , Yin Xueqiong 
Published: March 2024

AbstractAs one of the five major engineering plastics, polycarbonate (PC) has been applied in many industrial fields. However, its poor wear‐ and UV‐ resistance greatly limit its further promotion. Inspired by the dual benefits of inorganic–organic hybrid filler, in this study, we developed a novel type of catechol group‐ and nano silica‐containing reinforcing filler (CFNS) for the preparation of wear‐ and UV‐resistant PC‐based composite films. With a low level of filler content (1%), the coefficient of friction (COF) was distinctly reduced from 0.14 (neat PC film) to 0.06 (composite film), benefiting from a wear‐resistant surface layer. On the basis of ensuring high and stable transmittance for visible light, the composite films also exhibit strengthened capacity of UV shielding for the waveband from 293 to 400 nm. In addition, the general performance of composite films including tensile strength, tensile modulus, and thermal stability have also been improved in different degrees. Therefore, the composite films reinforced by CFNS are highly promising for a wide range of applications, ascribed to their improved general properties as well as two additional functions of wear‐ and UV‐resistance.
Accomplishing sustainable development goals through international management system standards and multinational supply chains
Authors: Heriyati Pantri , Yadav Neeraj , Tamara Dewi 
Published: March 2024

AbstractThe United Nations has set up 17 sustainable development goals (SDGs) to be achieved by 2030. This research investigates the role of management system standards and multinational supply chains in achieving SDGs and targets, as well as whether these two paths produce varying degrees of effectiveness in achieving these goals. Questionnaire‐based research is conducted among 264 Indian manufacturing organisations based on their certification status and MNE supplier status. Comparison of the surveyed organisations is carried out on three parameters, namely, number of targets for each SDG, fulfilment levels of these targets and extension of established targets further in the supply chain. Analysis of variance and t‐test methods are used to compare survey responses. Results show that the role of management system standards and auditing frameworks used by multinational enterprises is statistically similar in achieving SDGs. The role of management system standards in achieving each of the SDGs has not yet been attempted so far by using the aforementioned factors. The comparison of management system standards' auditing approaches with the auditing frameworks of multinational enterprises also provides a novel addition. Both multinationals and their supplier organisations can save time, money and effort by following either of the two approaches and avoiding the duplicity that is currently prevalent in practice. The research has theoretical implications for sustainability, modernisation and globalisation theories.
Oncological and functional outcomes for transoral robotic surgery following previous radiation treatment for upper aerodigestive tract head and neck cancers. A French multicenter GETTEC group study
Authors: Malard Olivier , Karakachoff Matilde , Ferron Christophe , Hans Stéphane , Vergez Sébastien , Garrel Renaud , Gorphe Philippe , Ramin Lionel , Santini Laure , Villeneuve Alexandre , Lasne‐Cardon Audrey , Espitalier Florent , Hounkpatin Audrey 
Published: March 2024

AbstractBackgroundTransoral robotic surgery (TORS) opens new perspectives. We evaluated the outcomes for patients having undergone TORS after previous radiotherapy.MethodsA retrospective multicenter study (n = 138) in a previously irradiated area between 2009 and 2020. Survival was assessed with the Kaplan–Meier method. Prognostic factors were evaluated using a chi‐squared test, Fisher's test, or Wilcoxon's test.ResultsThe median length of hospital stay was 12.5 days. Bleeding was the most frequent postoperative complication (15.2%, n = 22). Prophylactic vessel ligation did not significantly decrease bleeding. Complications were significantly lower for Tis, T1, and N0 tumors. 91.6% (n = 120) of the patients with a perioperative tracheotomy could be decannulated. Larynx was functional for 65.94% of the patients. The median length of follow‐up was 26 months. The 5‐year overall and relapse‐free survival rates were respectively 59.9% and 43.4%.ConclusionOncological and functional results confirmed the value of TORS as a treatment in previously irradiated area.
A longitudinal study of symptom cluster latent profiles in ovarian cancer patients undergoing chemotherapy
Authors: Feng Yue , Lin Tangwei , Liu Xingcan , Guo Xiujing , Chen Jing , Deng Xue 
Published: March 2024

AbstractBackgroundThis study aimed to identify distinct patterns within the symptom cluster of fatigue, pain, and sleep disturbance among ovarian cancer patients receiving chemotherapy, to determine the factors predicting these patterns and their impact on quality of life.MethodsThe longitudinal study collected data from 151 ovarian cancer patients at three time points: before chemotherapy (T0), after the first chemotherapy cycle (T1), and following the completion of four cycles of chemotherapy (T2). Latent profile analysis and latent transition analysis were used to identify symptom patterns and evaluate changes in symptom patterns. A bias‐adjusted three‐step approach was utilized to examine predictor variables and distal outcomes associated with latent class membership.ResultsThree symptom patterns emerged: “All Low,” “Moderate” (T0)/“Low pain and high sleep disturbance” (T1 and T2), and “All High.” Patients with lower educational attainment and higher levels of anxiety and depression were found to be at an elevated risk of belonging to the “All High” class. All quality‐of‐life domains showed significant differences among the three subgroups, following an “All Low” > “All High” pattern (p < 0.05). Membership in three classes remained relatively stable over time, with probabilities of 0.749 staying within their groups from T0 to T2.ConclusionsThis study underscores the existence of a diverse and heterogeneous experience within the symptom cluster of fatigue, pain, and sleep disturbance among ovarian cancer patients. Importantly, these patterns were stable throughout chemotherapy. Recognizing and understanding these patterns can inform the development of targeted interventions to alleviate the burden of symptom clusters in this population.
Numerical study of doxorubicin transdermal delivery for breast cancer treatment using microneedles
Authors: Barhoumi Houda , Kouassi Marie Carole , Kallel Achraf 
Published: March 2024

AbstractThe lack of in vivo studies on the delivery of doxorubicin within human skin, especially the absence of data on the doxorubicin diffusion coefficient, has made understanding its transdermal delivery kinetics challenging. In this study, as a first step, governing equations and finite element methods were employed to reproduce Franz diffusion cell experiment in human cadaver skin. The application of this experiment representative model with a fitting method resulted in approximate values for the diffusivity of doxorubicin across various skin layers. The estimated values were used later to conduct a comprehensive examination of doxorubicin administration for breast tumor treatments. In a 2D axisymmetric model using Fick's Law and then a microneedles array 3D model, crucial parameters effects on delivery efficiency were examined, such as the microneedle tip diameter, tip‐to‐tip distance, and tumor depth. As highlighted by the findings of this study, these parameters have an impact on the effectiveness of doxorubicin delivery for treating breast tumors. The focus of this research is on the potential of numerical methods in biomedical engineering, which addresses the urgent need for data on doxorubicin diffusion in human skin and offers valuable insights into optimizing drug delivery strategies for enhanced therapeutic outcomes.