bluuebunny/crossref_metadata_2025_split huggingface dataset:
Donor–Acceptor–Donor Triads with Flexible Spacers: Deciphering Complex Photophysics for Targeted Materials Design
Authors: Feng Siyang , Wang Liangxuan , Milián‐Medina Begoña , Meixner Alfred J. , Kwon Min Sang , Park Soo Young , Wannemacher Reinhold , Gierschner Johannes 
Published: August 2023

AbstractThe complex photokinetics of donor–acceptor–donor triads with varying flexible spacer lengths (n = 4–10 carbon atoms) are investigated in liquid and solid solution, as well as in crystals, by steady‐state and transient fluorescence spectroscopy combined with computational studies. For the short spacer (n = 4) in a liquid solution, dynamic charge‐transfer (CT) state formation with subsequent, efficient exciplex emission is observed, effectively competing with quenching through electron transfer (eT) via a radical ion pair. In a solid solution, a fluorescent CT static complex is formed upon freezing for all spacer lengths. This allows the observations of a former seminal report on stimuli‐responsive high‐contrast fluorescence on/off switching in films of the triads to be reassigned (Adv. Mater. 2012, 24, 5487), now providing a holistic picture on varying spacer length. In fact, external stimuli of the film by modulating the geometry of the CT complex, which results in on/off fluorescence switching (for n > 4) or in a change of the emission color (n = 4). The work thus demonstrates how in‐depth analysis of complex photophysics can be put to practical use in materials science.
Visible Light Induced EDA‐mediated Deaminative C‐2 Alkylation of Heterocyclic‐N‐Oxides using Katritzky salts
Authors: Singh Nihal , Sharma Shivani , Sharma Anuj 
Published: August 2023

AbstractHerein, a direct C‐2 alkylation of Heterocyclic‐N‐oxides with alkyl amines as Katritzky salts via visible‐light induced deaminative approach was developed. Mechanistic studies revealed that Katritzky salts and base were involved to generate an EDA complex, which underwent intermolecular single electron transfer (SET) to give an alkyl radical intermediate. Finally, the alkyl radical intermediate further underwent‐addition with heterocyclic‐N‐oxide substrates to access the desired products with 63–94% yield. The method worked well with quinoline‐N‐oxides, pyridine‐N‐oxides, and benzopyrazine‐N‐oxides.
An S=1 Iron(IV) Intermediate Revealed in a Non‐Heme Iron Enzyme‐Catalyzed Oxidative C−S Bond Formation
Authors: Paris Jared C. , Hu Sha , Wen Aiwen , Weitz Andrew C. , Cheng Ronghai , Gee Leland B. , Tang Yijie , Kim Hyomin , Vegas Arturo , Chang Wei‐chen , Elliott Sean J. , Liu Pinghua , Guo Yisong 
Published: August 2023

AbstractErgothioneine (ESH) and ovothiol A (OSHA) are two natural thiol‐histidine derivatives. ESH has been implicated as a longevity vitamin and OSHA inhibits the proliferation of hepatocarcinoma. The key biosynthetic step of ESH and OSHA in the aerobic pathways is the O2‐dependent C−S bond formation catalyzed by non‐heme iron enzymes (e.g., OvoA in ovothiol biosynthesis), but due to the lack of identification of key reactive intermediate the mechanism of this novel reaction is unresolved. In this study, we report the identification and characterization of a kinetically competent S=1 iron(IV) intermediate supported by a four‐histidine ligand environment (three from the protein residues and one from the substrate) in enabling C−S bond formation in OvoA from Methyloversatilis thermotoleran, which represents the first experimentally observed intermediate spin iron(IV) species in non‐heme iron enzymes. Results reported in this study thus set the stage to further dissect the mechanism of enzymatic oxidative C−S bond formation in the OSHA biosynthesis pathway. They also afford new opportunities to study the structure‐function relationship of high‐valent iron intermediates supported by a histidine rich ligand environment.
Polydopamine surface modified Ti3C2Tx/PLA biocomposites with enhanced mechanical, thermal, and tribological properties
Authors: Khan Fazal Maula , Sun Mingchen , Liu Zhiwei , Li Guanlong , Bhagat Waheed Ali , Wang Kai , Zhao Yan 
Published: August 2023

AbstractThe industry desires to create robust, resilient, thermally stable, and environmentally friendly composites. In this study, we created a poly (lactic acid) (PLA) composite via a straightforward method. The Ti3C2TX was surface‐coated with polydopamine (PDA) via a bioinspired approach and was then reinforced in the PLA using melt blending. The PDA layer adorned on the Ti3C2TX provided several functional groups for the MXene nanosheets and strengthened the PLA‐MXene interaction by hydrogen bonding. The well‐dispersed PDA@Ti3C2TX in the PLA improved mechanical, thermal, and tribological properties. For PLA/PDA@Ti3C2TX‐1, the tensile strength and elongation at the break of the nano‐composite were 9.03% and 25.5% higher than pure PLA, respectively. The flexural strength and modulus were increased by 49.5% over pure PLA, reaching 148.8 and 6702 MPa, respectively. The nanocomposite toughness increased by up to 53.3%. The nanocomposites had 3.8% and 49.08% lower friction coefficient and specific wear rate, respectively, than pure PLA. The addition of Ti3C2TX and PDA@Ti3C2TX increased the thermal stability of PLA at lower temperatures and promoted carbonization. PLA/PDA@Ti3C2TX‐1 showed the maximum char yield of 10 wt.% at 800°C, proving the highest thermal barrier effect due to MXene exfoliation during PDA and increased PLA dispersion state.
Factors influencing the mobility control ability of diutan gum‐enhanced foam in porous media
Authors: Lai Nanjun , Wang Zhouxin , Wang Junqi , Guan Xiaoxu , Tang Lei , Xian Xiaokang 
Published: August 2023

AbstractDiutan gum (DG) is an anionic polysaccharide produced by Sphingomonas sp. ATCC 53159. The DG‐enhanced foam (DGEF) formed by the DG and foam has great application potential in enhanced oil recovery. In this research, the influence of injection parameters on DGEF was studied by conducting orthogonal experiment, with residual resistance coefficient (Rff) as the main evaluation index. The micro‐state of the foam was observed using an etching model and scanning electron microscope. The mechanism of different factors on the mobility control ability of the foam was discussed based on the apparent viscosity and surfactant depletion. The results show that the Rff of foam is correlated with the apparent viscosity, and the foam with high apparent viscosity had a good flow control ability. The calculation of the surfactant depletion shows that the bubble stability decreased significantly when the concentration of Sodium alpha‐olefin sulfonate (AOS) cannot meet the minimum stabilization concentration, thus weakening the mobility control ability. Based on the study of crude oils, the presence of oil phase will seriously weaken the mobility control ability of DGEF, but the effect of oil with higher content of resin and asphaltene will be relatively weak.
RootBot: High‐throughput root stress phenotyping robot
Authors: Ruppel Mia , Nelson Sven K. , Sidberry Grace , Mitchell Madison , Kick Daniel , Thomas Shawn K. , Guill Katherine E. , Oliver Melvin J. , Washburn Jacob D. 
Published: August 2023

AbstractPremiseHigher temperatures across the globe are causing an increase in the frequency and severity of droughts. In agricultural crops, this results in reduced yields, financial losses, and increased food costs at the supermarket. Root growth maintenance in drying soils plays a major role in a plant's ability to survive and perform under drought, but phenotyping root growth is extremely difficult due to roots being under the soil.Methods and ResultsRootBot is an automated high‐throughput phenotyping robot that eliminates many of the difficulties and reduces the time required for performing drought‐stress studies on primary roots. RootBot simulates root growth conditions using transparent plates to create a gap that is filled with soil and polyethylene glycol (PEG) to simulate low soil moisture. RootBot has a gantry system with vertical slots to hold the transparent plates, which theoretically allows for evaluating more than 50 plates at a time. Software pipelines were also co‐opted, developed, tested, and extensively refined for running the RootBot imaging process, storing and organizing the images, and analyzing and extracting data.ConclusionsThe RootBot platform and the lessons learned from its design and testing represent a valuable resource for better understanding drought tolerance mechanisms in roots, as well as for identifying breeding and genetic engineering targets for crop plants.
Indefinite LQ optimal control for stochastic Takagi–Sugeno fuzzy system under sensor data scheduling: Finite‐horizon case
Authors: Tan Cheng , Zhu Binlian , Qi Qingyuan , Chen Ziran 
Published: August 2023

AbstractThe present paper considers the finite‐horizon indefinite linear quadratic (LQ) control problem for stochastic Takagi–Sugeno (T‐S) fuzzy systems with input delay. In this paper, we consider the presence of sensor data scheduling, which imposes a communication energy constraint and necessitates optimal state estimation for measurements. Then, by utilizing dynamic programming principles, the stochastic LQ problem under consideration can be solved, while the optimal control policy is developed in terms of the unique solutions to a set of coupled difference Riccati equations (CDREs). Specifically, for simple delay‐free case, the linear matrix inequalities based conditions are also proposed, whose feasibility is shown to be equivalent to the well‐posedness of the indefinite LQ control under consideration. As an application, our theoretic analysis is extended to study the intermittent observation model caused by random denial‐of‐service attack.
A green approach for the analysis of emtricitabine bictegravir and tenofovir in a pharmaceutical preparation using novel HPLC and spectrophotometric methods
Authors: Tiris Gizem , Genc Asena Ayse , Oven Elifnaz , Erk Nevin 
Published: August 2023

AbstractTwo spectrophotometric techniques and a novel HPLC method were consecutively applied for the simultaneous quantification of the active ingredients of emtricitabine (EMC), tenofovir (TNF), and bictegravir (BIC). The first spectrophotometric method is the dual amplitude difference method coupled with the ratio difference method. TNF was determined using the dual amplitude difference method, while BIC and EMC were determined using the ratio difference method. The second spectrophotometric method was the constant multiplication with absorbance extraction method, and was applied for the determination of active substances used in the treatment of human immunodeficiency virus (HIV) infection. BIC was determined by the constant multiplication method, whereas EMC and TNF were determined using the absorbance extraction method. For the HPLC method, the XBridge C18 column was used. The solvent system comprised acetonitrile:phosphate buffer (pH 6.8; 30:70 v/v). All active ingredients were detected at 260.0 nm, and the flow rate was 0.5 mL/min. The experiment was completed within 5.5 min. The experiments carried out enabled the simultaneous analysis of the three active substances and they were economical, fast, environmentally friendly, and simple. The methods have been successfully applied to prepare mixtures and tablets without matrix interference. The methods were evaluated in terms of green chemistry. The methods have been validated according to International Council for Harmonisation (ICH) guidelines.
MYC overexpression but not MYC/BCL2 double expression predicts survival in bulky mass diffuse large B‐cell lymphoma patients
Authors: Wang Yanjie , Liu Donglin , Zhang Xudong , Zhang Mingzhi , Li Shenglei , Feng Xiaoyan , Dong Meng , Ma Shanshan , Qian Siyu , Wang Zeyuan , Zhang Yue , Wang Pengyuan , Mei Shuhao , Chen Qingjiang 
Published: August 2023

AbstractPurposeThe prognostic factors for diffuse large B‐cell lymphoma (DLBCL) have been fully explored, but prognostic information for bulky mass DLBCL patients is limited. This study aimed to analyze the prognostic value of MYC protein expression and other biological parameters in bulky mass DLBCL patients.MethodsWe defined a bulky mass as a maximum tumor diameter ≥7.5 cm and studied 227 patients with de novo bulky mass DLBCL.ResultsIn all patients with bulky mass DLBCL, the 1‐year and 3‐year OS rates were 72.7% and 57.1%, respectively, and the 1‐year and 3‐year PFS rates were 52.0% and 42.5%, respectively. The MYC overexpression group (n = 140) showed significantly worse overall survival (OS; p = 0.019) and progression‐free survival (PFS; p = 0.001) than the non‐MYC overexpression group (n = 87). Subgroup analyses demonstrated that the MYC overexpression group was associated with inferior OS and PFS in the subgroups with the International Prognostic Index score of 3–5 (OS: p = 0.011; PFS: p < 0.001), Ann Arbor stage 3–4 (OS: p = 0.014; PFS: p < 0.001) and GCB subtype (OS: p = 0.014; PFS: p = 0.010). Consolidation radiotherapy improved OS and PFS in patients with bulky mass DLBCL (OS: p = 0.008; PFS: p = 0.004) as well as in those with MYC overexpression (OS: p = 0.001; PFS: p = 0.001). The prognostic value of MYC overexpression was maintained in a multivariate model adjusted for the International Prognostic Index.ConclusionMYC overexpression is a poor predictor for bulky mass DLBCL patients. Consolidation radiotherapy for residual disease after induction therapy may improve outcomes for patients with bulky mass DLBCL.
Role of plasma angiogenesis factors in the efficacy of first‐line chemotherapy combined with biologics in RAS wild‐type metastatic colorectal cancer: Results from the GI‐SCREEN CRC‐Ukit study
Authors: Yuki Satoshi , Yamazaki Kentaro , Sunakawa Yu , Taniguchi Hiroya , Bando Hideaki , Shiozawa Manabu , Nishina Tomohiro , Yasui Hisateru , Kagawa Yoshinori , Takahashi Naoki , Denda Tadamichi , Esaki Taito , Kawakami Hisato , Satake Hironaga , Takashima Atsuo , Matsuhashi Nobuhisa , Kato Takeshi , Asano Chiharu , Abe Yukiko , Nomura Shogo , Yoshino Takayuki 
Published: August 2023

AbstractBackgroundSeveral biomarkers have been established for metastatic colorectal cancer (mCRC). We investigated whether plasma angiogenesis factors could predict the efficacy of biologics combined with chemotherapy in first‐line (1L) treatment in patients with RAS wild‐type mCRC and the dynamics of plasma angiogenesis factors at progression during 1L treatment.MethodsIn this multicenter prospective observational study, serial plasma samples were prospectively collected at pretreatment and progression stages; 17 plasma angiogenesis factors were analyzed using the multiplex assay with Luminex® technology. Interactions between the pretreatment measurements and treatment groups on progression‐free survival (PFS) and overall survival (OS) in patients with RAS wild‐type were assessed using the propensity‐score weighted Cox proportional hazards model.ResultsFrom February 2018 to September 2020, 202 patients were enrolled in the 1L cohort; 133 patients had RAS wild‐type (chemotherapy plus bevacizumab [BEV group, n = 33] and plus anti‐epidermal growth factor receptor monoclonal antibodies [aEGFR group, n = 100]). A trend of strong interaction on PFS was observed for interleukin‐8 (IL‐8) (p = 0.0752) and soluble vascular cell adhesion molecule‐1 (sVCAM‐1) (p = 0.0156). Regarding OS, IL‐8 (p = 0.0283), soluble vascular endothelial growth factor‐receptor‐1 (sVEGFR‐1) (p = 0.0777) and sVCAM‐1 (p = 0.0011) tended to differentiate the treatment effect. In 112 patients, plasma samples were evaluable for dynamic analysis (57 and 55 from the BEV and aEGFR groups, respectively). In the BEV group, six factors significantly increased during progression, whereas two decreased. In the aEGFR group, three factors significantly increased, and six decreased.ConclusionPretreatment plasma IL‐8 and sVCAM‐1 levels could be predictive biomarkers to distinguish BEV and anti‐EGFR mAbs when combined with chemotherapy in the 1L treatment of RAS wild‐type mCRC. Several plasma angiogenesis factors showed significant change at progression in 1L chemotherapy plus biologics for RAS wild‐type mCRC, which are potential biomarkers for selecting an optimal angiogenesis inhibitor in second‐line treatment.
Charles Bonnet syndrome in an elderly blind man with recurrent pituitary macroadenoma and optic nerve atrophy: A case report
Authors: Aslan Suluma , Ngajilo Gloria , Nyundo Azan 
Published: August 2023

Key Clinical MessageCharles Bonnet syndrome presents with complex visual hallucinations in a visually impaired or blind person. The case highlights complex neuropsychiatric manifestations due to pituitary macroadenoma in geriatrics requiring multi‐collaborative care.AbstractAn 81‐year‐old man presented with a 3‐year history of vivid visual hallucinations preceded by visual impairment and recurrence of a pituitary macroadenoma. Remission of hallucination occurred within 2 weeks of 1.5 mg of haloperidol per oral once daily; this is a rare case of Charles Bonnet syndrome after recurrent pituitary macroadenoma.
Cationic ordering transition in oxygen‐redox layered oxide cathodes
Authors: Li Xinyan , Gao Ang , Zhang Qinghua , Yu Hao , Ji Pengxiang , Xiao Dongdong , Wang Xuefeng , Su Dong , Rong Xiaohui , Yu Xiqian , Li Hong , Hu Yong‐Sheng , Gu Lin 
Published: August 2023

AbstractUnderstanding the structural origin of the competition between oxygen 2p and transition‐metal 3d orbitals in oxygen‐redox (OR) layered oxides is eminently desirable for exploring reversible and high‐energy‐density Li/Na‐ion cathodes. Here, we reveal the correlation between cationic ordering transition and OR degradation in ribbon‐ordered P3‐Na0.6Li0.2Mn0.8O2 via in situ structural analysis. Comparing two different voltage windows, the OR capacity can be improved approximately twofold when suppressing the in‐plane cationic ordering transition. We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn4+ to Jahn–Teller Mn3+ and the concomitant NaO6 stacking transformation from triangular prisms to octahedra, resulting in the loss of ribbon ordering and electrochemical decay. First‐principles calculations reveal that Mn4+/Mn3+ charge ordering and alignment of the degenerate eg orbital induce lattice‐level collective Jahn–Teller distortion, which favors intralayer Mn‐ion migration and thereby accelerates OR degradation. These findings unravel the relationship between in‐plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR‐active layered oxide cathodes.
Improved Catalytic Performance toward Selective Oxidation of Benzyl Alcohols Originated from New Open‐Framework Copper Molybdovanadate with a Unique V/Mo Ratio
Authors: Feng Yuquan , Zhong Zhiguo , Chen Shuyang , Liu Kecheng , Meng Zhaohui 
Published: August 2023

AbstractA new organic‐inorganic hybrid open‐framework molybdovanadate with mixed‐valences of vanadium (V4+/V5+=4/3) and molybdenum (Mo5+/Mo6+=8/2) cations has been synthesized. The complex possesses the unique V/Mo ratio (7/10), fascinating 8‐C topological network and 1D 4‐MR channels (7.793 Å×6.699 Å). Importantly, its catalytic activities for the selective oxidation of benzyl alcohol to benzaldehyde (oxidant: H2O2, 30 wt %) have been well evaluated. The results indicated that it exhibited improved catalytic activities (conv.: 96.8 %) compared with the catalyst (Cpyr)5PV2Mo5W5O40 [conv.: 88.51 %, Cpyr=(C16H32C5H4N)+)], high recyclability and structural stability. Moreover, the conversions and selectivities (conv.: 82.4–92.5 %; sele.: 91.5–95.7 %) of the substrates containing electron donating groups (−OH, −CH3, −OCH3 and −Cl) were significantly higher than those of the substrate containing electron withdrawing group (−NO2) (conv. 67.4 %; sele.: 80.8 %). This is due to the fact that the −NO2 with a large Hammett substituent constant is not conducive to the generation of transition state products. The studies revealed the complex could act as a highly efficient heterogeneous catalyst in selective oxidation of benzyl alcohols.
Genomic and tumour microenvironmental biomarkers of immune checkpoint inhibitor response in advanced Taiwanese melanoma
Authors: Chang John Wen‐Cheng , Huang Chien‐Jung , Huang Wen‐Kuan , Wang Yu‐Chao , Hsieh Jia‐Juan , Chang Yao‐Yu , Huang Yen‐Lin , Wu Chia‐Ling , Wang Yeh‐Han , Chen Shu‐Jen , Tan Kien Thiam , Chen Chiao‐Ping , Wu Chiao‐En 
Published: August 2023

AbstractObjectiveGenomic biomarkers predicting immune checkpoint inhibitor (ICI) treatment outcomes for Asian metastatic melanoma have been rarely reported. This study presents data on next‐generation sequencing (NGS) and tumour microenvironment biomarkers in 33 cases.MethodsThirty‐three patients with advanced melanoma, who underwent ICI treatment at the Chang Gung Memorial Hospital in Taiwan, were recruited. The study evaluated clinical outcomes, including response rate, disease control rate, progression‐free survival (PFS) rate and overall survival (OS) rate. Archived tissue samples from 33 cases were subjected to NGS by ACTOnco, and ACTTME was employed in 25 cases.ResultsThe most prevalent driver mutations were BRAF mutations (24.2%), followed by NRAS (15.2%), KIT (12.1%), KRAS (9.1%) and NF1 (9.1%) mutations. Acral/mucosal melanomas exhibited distinct mutation patterns compared to non‐acral melanomas. Tumour mutational burden estimated using ACTOnco was not associated with ICI efficacy. Notably, genetic alterations in the p53 pathway (CDKNA2 loss, MDM2 gain/amplification and TP53 mutation) accounted for 36.4% and were significantly associated with unfavourable PFS (median PFS 2.7 months vs. 3.9 months, P = 0.0394). Moreover, 26 genes were identified as differentially expressed genes that were upregulated in patients with clinical benefits compared to those without benefits. Four genes, GZMH, GZMK, AIM2 and CTLA4, were found to be associated with both PFS and OS.ConclusionGenetic alterations in the p53 pathway may be critical in Asian patients with melanoma undergoing ICI treatment. Further investigation is required to explore this mechanism and validate these findings.
Efficient signal transmission algorithms for remote sensing gamma radiation over developed mobil WiMax network
Authors: El_Tokhy Mohamed S. 
Published: August 2023

SummaryThis paper overcomes two key issues within radiation monitoring networks. Secure and accurate transmission of detected gamma radiation in remote areas is the first challenge. The second one is related to the robustness of transmitted signal under different fading scenarios. These issues are handled during signal transmission over worldwide interoperability for microwave access (WiMax) networks. The signals are experimentally captured using a 137Cs point source, a NaI (TI) detector, and an analog‐to‐digital converter with 16 MS/s. For the first issue, several algorithms are implemented for secure and efficient transmission of gamma‐based signals. These algorithms include encoding of captured signal, decoding, interleaving, and frequency transformation of modulated signal. Encoding and decoding of target signals are conducted using the Reed Solomon technique and convolutional encoding with a Viterbi decoder. A superior algorithm for channel interleaver using the combinational interleaving method is introduced. Fast lifting transform (FLT) is applied for transforming modulated signal into frequency domain. The results declare that CC = 1/2 with BPSK‐1/2 coding rate introduces a better BER of 0.00068. A higher SNR of 1.5 dB is accomplished by the combinational interleaving algorithm. For the second issue, several models are suggested for overcoming channel degradations under gamma, exponential, Poisson, and geometric fading. Closed‐form expressions that describe outage probability, bit error rate (BER), and symbol error rate (SER) are suggested. Geometric and gamma fading achieve respectively a lower BER of 0.18 and 0.48. These channels demonstrate similar channel performances at 3.6 dB. The proposed models are validated through comparison with published work. Finally, the proposed algorithms enable higher data rate transmission of detected 137Cs signals under higher robustness using WiMax networks.