bluuebunny/crossref_metadata_2025_split huggingface dataset:
Two-Year Outcomes After Variable Duration of Drug Cessation in Patients With Maculopathy Associated With Pentosan Polysulfate Use
Authors: Jung Emily H. , Lindeke-Myers Aaron , Jain Nieraj 
Published: February 2023

ImportancePrior retrospective studies have provided limited evidence on disease progression following drug cessation in patients with maculopathy associated with pentosan polysulfate (PPS).ObjectiveTo evaluate the 2-year evolution of maculopathy associated with PPS use after drug cessation.Design, Setting, and ParticipantsThis cohort study prospectively evaluated the natural history of patients with maculopathy associated with PPS use. Participants seen at the Emory Eye Center were enrolled between December 1, 2018, and December 1, 2019, and data were collected through November 30, 2021.Main Outcomes and MeasuresThe main outcomes were changes in visual function and structure. Visual function was assessed annually with refraction and Early Treatment Diabetic Retinopathy Study (ETDRS) best-corrected visual acuity (BCVA), mesopic microperimetry, and dark adaptometry. Structural outcomes included presence and extent of complete retinal pigment epithelium and outer retinal atrophy (cRORA), macular central subfield thickness (CST), and subfoveal choroidal thickness (SFCT).ResultsOf the 12 participants (23 eyes), 11 (91.7%) were female (1 [8.3%] male), 11 (91.7%) were White (1 [8.3%] Black), and median (IQR) age at enrollment was 58 (47-64) years. Median (IQR) time from PPS discontinuation to initial visit was 0.6 (0.4-1.9) years. Median baseline ETDRS BCVA letter score was 83 (Snellen equivalent, 20/20) (IQR, 80-86.5 [20/25-20/20]), with a median 2-year change of −3 (IQR, −6 to −0.5; P = .08). Four eyes (17.4%) had a letter score decline of 15 or more, all associated with progressive cRORA. Median change in microperimetry average threshold was −3.5 dB (IQR, −4.1 to −2.5 dB; P = .001), and percent reduced threshold was 32.5% (IQR, 20.3%-52.8%; P = .004). Nine eyes (39%) had macular cRORA at baseline, with a median linearized growth rate of 0.23 mm/y (IQR, 0.22-0.25 mm/y). Two eyes (8.7%) without atrophy at baseline developed new-onset cRORA. Median baseline CST was 284 μm (IQR, 253-291 μm), with a median 2-year change of −5 μm (IQR, −13 to 0.5 μm; P = .0497). Median 2-year change in SFCT was 1 μm (IQR, −18 to 16 μm; P = .91).Conclusions and RelevanceThe findings of this cohort study suggest that functional and structural deficits continue to progress in PPS-associated maculopathy even after drug cessation. Additional study is needed to determine whether these findings can be generalized to other patients with PPS-associated maculopathy and whether longer follow-up could determine subsequent disease course.
Four‐dimensional computed tomography‐based ventilation imaging in intensity‐modulated radiation therapy treatment planning for pulmonary functional avoidance
Authors: Iqbal Gazi Md Daud , Zhang Hao , D'Souza Wareen , Ha Lidan , Rosenberger Jay M. 
Published: February 2023

AbstractPurposeTo incorporate four‐dimensional computed tomography (4DCT)‐based ventilation imaging into intensity‐modulated radiation therapy (IMRT) treatment planning for pulmonary functional avoidance.Methods and MaterialsNineteen locally advanced lung cancer patients are retrospectively studied. 4DCT images are employed to create ventilation maps for each patient via a density‐change‐based algorithm with mass correction. The regional ventilation is directly incorporated into the mathematical formulation of a direct aperture optimization model in IMRT treatment planning to achieve functional avoidance and a voxel‐based treatment plan. The proposed functional avoidance planning and voxel‐based planning are compared to the conventional treatment planning approach purely based on the anatomy of patients. Paired sample t‐tests are conducted to see whether dosimetric differences among the three approaches are significant.ResultsSimilar planning target volume (PTV) coverage is achieved by anatomical, functional avoidance, and voxel‐based approaches. The voxel‐based treatment planning performs better than both functional avoidance and anatomical planning to the lung. For a total lung, the average volume reductions in a functional avoidance plan from an anatomical plan, a voxel‐based plan from an anatomical plan, and a voxel‐based plan from a functional avoidance plan are 7.0%, 16.8%, and 10.6%, respectively for V40; and 0.4%, 6.4%, and 6.0%, respectively for mean Lung Dose (MLD). For a functional lung, the reductions are 8.8%, 17.2%, and 9.2%, respectively, for fV40; and 1.1%, 6.2%, and 5.2%, respectively, for functional mean lung dose (fMLD). These reductions are obtained without significantly increasing doses to other organs‐at‐risk. All the pairwise treatment planning comparisons for both total lung and functional lung are statistically significant (p‐value ) except for the functional avoidance plan with the anatomical plan pair in which the p‐value . From these results, we can conclude that voxel‐based treatment planning outperforms both anatomical and functional‐avoidance planning.ConclusionsWe propose a treatment planning framework that directly utilizes functional images and compares voxel‐based treatment planning with functional avoidance and anatomical treatment planning.
Molecular Engineering for Shortening the Pt···Pt Distances in Pt(II) Dinuclear Complexes and Enhancing the Efficiencies of these Complexes for Application in Deep‐Red and Near‐IR OLEDs
Authors: Rajakannu Palanisamy , Lee Woochan , Park Sanghoon , Kim Hyung Suk , Mubarok Hanif , Lee Min Hyung , Yoo Seunghyup 
Published: February 2023

AbstractDeep‐red (DR)‐to‐near‐infrared (NIR) phosphorescent organic light‐emitting diodes (OLEDs) have potentials for application in various fields ranging from phototherapy to sensing. Accordingly, herein, phenylpyridazine‐based bidentate ligands are synthesized and subsequently utilized for the preparation of dinuclear Pt(II) complexes (1–6). The molecular structures of 1–3 is investigated by single‐crystal X‐ray diffraction, and the results suggest that these complexes have substantially shortened Pt···Pt distances (2.906–2.911 Å). Complexes 1–6 exhibit intense emissions in the NIR region (700–726 nm), high photoluminescence quantum yield (PLQY) (0.11–0.18), and short phosphorescence decay lifetimes (τ = 0.64–0.95 µs) in a CH2Cl2 solution. To examine the effect of N‐substitution on the dinuclear Pt complexes, the phenylpyrimidine‐based Pt(II) emitters 7 and 8 are prepared and discovered to have Pt···Pt distances of 2.933 Å. 7 and 8 demonstrate strong emissions in the 628–650 nm range with high PLQY of 0.52–0.65. Theoretical studies indicate that the functional groups or atoms in the ligands play crucial roles in the formation of emitters with significantly shortened Pt···Pt distances. 3 and 7 are employed as non‐doped emitters to fabricate NIR OLEDs, and the resulting OLEDs exhibit electroluminescence peaks at 754 and 692 nm with maximum external quantum efficiencies of 3.0 and 4.4%, respectively.
Coordination‐Precipitation Synthesis of Metal Sulfide with Phase Transformation Enhanced Reactivity against Antibiotic‐Resistant Bacteria
Authors: Liu Yuan , Wang Xiaonan , Fan Xiaowan , Ge Mengyue , Fang Ling , Yuan Ye , Chen Lei , Jiang Jing , Cao Anmin , Gao Lizeng 
Published: February 2023

AbstractGiven the challenge of bacterial resistance to antibiotics, there is an urgent need to develop alternative antibacterial agents. While some metal sulfides are promising candidates against bacterial resistance, their fundamental mechanism of action (MoA) remains unclear. Herein, a “coordination‐precipitation” method is developed for the synthesis of a metal sulfide library and the evaluation of antibacterial consistency. Employing ethylenediamine as a coordination agent and thioglycolic acid as a precipitation agent, 12 different metal sulfide nanocrystals following the same procedure are synthesized. Antibacterial assessment reveals that six metal sulfides with bactericidal potency perform a common feature of phase transformation. In particular, in the process of manganese sulfide (MnS) transformation to Mn3O4, a highly reactive complex of high‐valance manganese (Mn3+) and polysulfide (S32−) accompanied by superoxide is sustainably generated, which synergistically induces bacterial death with a hallmark of lipid peroxidation (named liperoptosis) specifically toward Gram‐positive Staphylococcus aureus (S. aureus). In addition, this MoA confers MnS with therapeutic effects superior to vancomycin in a methicillin‐resistant S. aureus‐infected skin wound model. This study reveals the correlation between phase transformation and the antibacterial MoA of metal sulfides and provides a general fundamental to design a non‐antibiotic antibacterial candidate against bacterial resistance.
Molecular Modulation of Sequestered Copper Sites for Efficient Electroreduction of Carbon Dioxide to Methane
Authors: Zhang Kefan , Xu Jie , Yan Tianran , Jia Lin , Zhang Jie , Shao Chaochen , Zhang Liang , Han Na , Li Yanguang 
Published: February 2023

AbstractThe sustainable production of methane (CH4) via the electrochemical conversion of carbon dioxide (CO2) is an appealing approach to simultaneously mitigating carbon emissions and achieving energy storage in chemical bonds. Copper (Cu) is a unique material to produce hydrocarbons and oxygenates. However, selective methane generation on Cu remains a great challenge due to the preferential *CO dimerization pathway toward multi‐carbon (C2+) products at neighboring catalytic sites. Herein, a conjugated copper phthalocyanine polymer (CuPPc) is designed by a facile solid‐state method for highly selective CO2‐to‐CH4 conversion. The spatially isolated CuN4 sites in CuPPc favor the *CO protonation to generate the key *CHO intermediate, thus significantly promoting the formation of CH4. As a result, the CuPPc catalyst exhibits a high CH4 Faradaic efficiency of 55% and a partial current density of 18 mA cm−2 at −1.25 V versus the reversible hydrogen electrode. It also stably operates for 12 h. This study may offer a new solution to regulating the chemical environment of the active sites for the development of highly efficient copper‐based catalysts for electrochemical CO2 reduction.
FeCl2‐Catalyzed Rearrangement of Aryl Peroxyoxindole into 1,3‐Benzooxazin‐4‐One
Authors: Mohanta Nirmala , Paramita Samal Pragnya , Krishnamurty Sailaja , Gnanaprakasam Boopathy 
Published: February 2023

AbstractWe report an FeCl2‐catalyzed radical rearrangement of aryl peroxyoxindoles into 1,3‐benzooxazin‐2‐ones to obtain a variety of aryl substituted 1,3‐benzooxazin‐4‐ones in moderate to good yields. Mechanistically, this skeletal rearrangement of peroxyoxindoles proceeded via radical pathway and was well supported with a series of experimental findings and DFT studies.magnified image
4D Printing of Humidity‐Driven Seed Inspired Soft Robots
Authors: Cecchini Luca , Mariani Stefano , Ronzan Marilena , Mondini Alessio , Pugno Nicola M. , Mazzolai Barbara 
Published: February 2023

AbstractGeraniaceae seeds represent a role model in soft robotics thanks to their ability to move autonomously across and into the soil driven by humidity changes. The secret behind their mobility and adaptivity is embodied in the hierarchical structures and anatomical features of the biological hygroscopic tissues, geometrically designed to be selectively responsive to environmental humidity. Following a bioinspired approach, the internal structure and biomechanics of Pelargonium appendiculatum (L.f.) Willd seeds are investigated to develop a model for the design of a soft robot. The authors exploit the re‐shaping ability of 4D printed materials to fabricate a seed‐like soft robot, according to the natural specifications and model, and using biodegradable and hygroscopic polymers. The robot mimics the movement and performances of the natural seed, reaching a torque value of ≈30 µN m, an extensional force of ≈2.5 mN and it is capable to lift ≈100 times its own weight. Driven by environmental humidity changes, the artificial seed is able to explore a sample soil, adapting its morphology to interact with soil roughness and cracks.
Low‐Cost, High‐Pressure‐Synthesized Oxygen‐Entrapping Materials to Improve Treatment of Solid Tumors
Authors: Bi Jianling , Witt Emily , Voltarelli Vanessa A. , Feig Vivian R. , Venkatachalam Veena , Boyce Hannah , McGovern Megan , Gutierrez Wade R. , Rytlewski Jeffrey D. , Bowman Kate R. , Rhodes Ashley C. , Cook Austin N. , Muller Benjamin N. , Smith Matthew G. , Ramos Alexis Rebecca , Panchal Heena , Dodd Rebecca D. , Henry Michael D. , Mailloux Adam , Traverso Giovanni , Otterbein Leo E. , Byrne James D. 
Published: February 2023

AbstractTumor hypoxia drives resistance to many cancer therapies, including radiotherapy and chemotherapy. Methods that increase tumor oxygen pressures, such as hyperbaric oxygen therapy and microbubble infusion, are utilized to improve the responses to current standard‐of‐care therapies. However, key obstacles remain, in particular delivery of oxygen at the appropriate dose and with optimal pharmacokinetics. Toward overcoming these hurdles, gas‐entrapping materials (GeMs) that are capable of tunable oxygen release are formulated. It is shown that injection or implantation of these materials into tumors can mitigate tumor hypoxia by delivering oxygen locally and that these GeMs enhance responsiveness to radiation and chemotherapy in multiple tumor types. This paper also demonstrates, by comparing an oxygen (O2)‐GeM to a sham GeM, that the former generates an antitumorigenic and immunogenic tumor microenvironment in malignant peripheral nerve sheath tumors. Collectively the results indicate that the use of O2‐GeMs is promising as an adjunctive strategy for the treatment of solid tumors.
Molecular Trap Engineering Enables Superior High‐Temperature Capacitive Energy Storage Performance in All‐Organic Composite at 200 °C
Authors: Zhou Yao , Zhu Yujie , Xu Wenhan , Wang Qing 
Published: February 2023

AbstractDielectric capacitors are essential components of advanced high‐power electrical and electronic systems for electrical energy storage. The drastic reductions in the energy density and the charge‐discharge efficiency of dielectric polymers at elevated temperatures, owing to sharply increased electrical conduction, remain a major challenge. While substantial progress has been made in enhancing the high‐temperature capacitive performance of dielectric polymers, the improvement has been rather limited when the temperature exceeds 150 °C. Here, a universal approach to the control of the energy level of charge traps in all‐organic polymer composites by substituent engineering of organic semiconductors, leading to significantly suppressed high‐field high‐temperature conduction loss and improved capacitive performance is reported. At 200 °C, the polymer/organic semiconductor composite delivers ultrahigh energy densities of 3.4 and 5.0 J cm−3 with an efficiency >90% at 10 and 100 Hz, respectively, outperforming the current dielectric polymers and composites. The underlying mechanism of the improved performance is revealed experimentally and confirmed computationally. Moreover, excellent cyclability and the ability to be fabricated into large‐area high‐quality films with uniform performance, along with an ultralow filler loading, further demonstrate the potential of molecularly engineered organic semiconductors for dielectric polymer composites operating under extreme conditions.
Evaluation of foliar‐applied post‐emergence corn–soybean herbicides on giant ragweed and waterhemp control in Wisconsin
Authors: Werle Rodrigo , Mobli Ahmadreza , DeWerff Ryan P. , Arneson Nicholas J. 
Published: February 2023

AbstractGiant ragweed (Ambrosia trifida L.) and waterhemp (Amaranthus tuberculatus [Moq.] J.D.Sauer) are highly competitive and the most troublesome weeds in corn (Zea mays L.) and soybean (Glycine max Merr.) cropping systems in Wisconsin. Field experiments were conducted to evaluate the efficacy of multiple foliar‐applied POST‐emergence herbicides on giant ragweed at Janesville, WI (2020 and 2021), and on groups 2‐ and 9‐resistant waterhemp at Brooklyn, WI (2019 and 2020), respectively. Several herbicides from site of action groups 2, 4, 5, 6, 9, 10, 14, and 27 were evaluated. Herbicide treatments were applied when giant ragweed and waterhemp reached ~10 cm in height. Herbicide efficacy (0‐100% visual control) was evaluated 14 days after treatment (DAT). Group 2 herbicides provided poor (<45%) control of giant ragweed and waterhemp 14 DAT. Several herbicides encompassing different sites of action provided >90% giant ragweed control. Certain herbicides from groups 4, 10, 14, and 27 provided the best control (74‐87%) of waterhemp, but no herbicide evaluated in this study provided = 90% waterhemp control. Weed management programs containing multiple effective herbicide sites of action PRE‐ and POST‐emergence accompanied by non‐chemical strategies are recommended to extend the spectrum of chemical control and reduce the risk of selection of further herbicide‐resistant biotypes for both giant ragweed and waterhemp in Wisconsin and beyond.
Locally Concentrated Ionic Liquid Electrolytes for Lithium‐Metal Batteries
Authors: Liu Xu , Mariani Alessandro , Adenusi Henry , Passerini Stefano 
Published: February 2023

AbstractNon‐flammable ionic liquid electrolytes (ILEs) are well‐known candidates for safer and long‐lifespan lithium metal batteries (LMBs). However, the high viscosity and insufficient Li+ transport limit their practical application. Recently, non‐solvating and low‐viscosity co‐solvents diluting ILEs without affecting the local Li+ solvation structure are employed to solve these problems. The diluted electrolytes, i.e., locally concentrated ionic liquid electrolytes (LCILEs), exhibiting lower viscosity, faster Li+ transport, and enhanced compatibility toward lithium metal anodes, are feasible options for the next‐generation high‐energy‐density LMBs. Herein, the progress of the recently developed LCILEs are summarised, including their physicochemical properties, solution structures, and applications in LMBs with a variety of high‐energy cathode materials. Lastly, a perspective on the future research directions of LCILEs to further understanding and achieve improved cell performances is outlined.
Supramolecular Capsule Catalysis Enables the Exploration of Terpenoid Chemical Space Untapped by Nature
Authors: Némethová Ivana , Schmid Dario , Tiefenbacher Konrad 
Published: February 2023

AbstractTerpenes represent the largest and the most diverse class of natural compounds. This is remarkable as the whole variety is accessed from just a handful of highly conserved linear precursors. Modification of the cyclization precursors would enable a dramatic expansion of the accessible chemical space. However, natural enzymes do not enable us to tap into this potential, as they do not tolerate larger deviations from the prototypical substrate structure. Herein we report that supramolecular capsule catalysis enables facile access to diverse and novel terpenoid skeletons that formally can be traced back to C3‐phenyl, benzyl, and homoprenyl derivatives of farnesol. Novel skeletons related to the presilphiperfolane core structure, as well as novel neoclovene derivatives were accessed efficiently in only four synthetic steps. Importantly, the products obtained carry functional groups that may be readily derivatized further.
Broadening the product portfolio with cellulose and lignin nanoparticles in an elephant grass biorefinery
Authors: Scopel Eupidio , Camargos Camilla H. M. , Pinto Lidiane O. , Trevisan Henrique , Ferreira Elisa S. , Rezende Camila A. 
Published: February 2023

AbstractCellulose and lignin nanoparticles are high‐value‐added products obtained from lignocellulosic biomasses through several steps of cellulose purification and lignin extraction. These steps drastically reduce the potential feedstock revenue when carried out as stand‐alone methodologies. To increase biomass yields, we describe here a strategy to design a biorefinery focused on producing cellulose and lignin nanoparticles as main products, but also aim to recover and benefit from other biomass components using only water‐based processes. Sequential pressurized liquid extractions and diluted acid and alkaline treatments were carried out to fractionate elephant grass biomass, yielding (for every 100 g of biomass): 30 g of cellulose pulp (converted to 9 g of cellulose nanocrystals and 9 g of cellulose nanofibers); 10 g of lignin (used to produce 8.5 g of stable colloidal lignin nanoparticles by probe‐sonication in water); 7.5 g of extractives (e.g. sterols and phenolics) and 23 g of xylose (converted to 4.1 g of furfural). Alternatively, to allow for the flexible use of the cellulose fraction in the proposed biorefinery, 22 g of glucose could be produced by enzymatic hydrolysis. The results demonstrate that water‐based processes are suitable for a holistic use of biomass, providing a comprehensive set of high‐value‐added co‐products that are renewable and cost‐effective chemical, cosmetic, food, polymer and pharmaceutical solutions.
Sterile filtration of a multi‐serotype glycoconjugate vaccine drug product
Authors: Du Zhuoshi , Gill Kanwaldeep , Toprani Vishal , Zydney Andrew L. 
Published: February 2023

AbstractGlycoconjugate vaccines consisting of multiple serotypes of the bacterial capsular polysaccharide can provide strong protection against infection by significant pathogens. Previous studies of the sterile filtration behavior of these glycoconjugates have been limited to experiments with individual serotypes even though the formulated vaccines contain several different serotypes to provide broad immunization. The objective of this study was to explore the fouling behavior of a glycoconjugate vaccine drug product consisting of four different polysaccharide serotypes. Sterile filtration data were obtained with 0.22 µm Durapore® membranes at both constant flux and constant pressure for both the individual serotypes and the drug product containing multiple serotypes. Fouled membranes were examined by confocal microscopy, demonstrating that all four serotypes deposit in a narrow band near the filter inlet. The different ionic composition of the formulation buffer (compared to the buffers used with the drug substance) had a large effect on the fouling behavior. In addition, the fouling resistance associated with the drug product was greater than the sum of the resistances of the individual serotypes. These results provide important insights into the sterile filtration behavior of these multivalent glycoconjugate vaccines.
Comprehensive Overview: The Effect of Using Different Solvents for Barley Extraction with Its Anti‐Inflammatory and Antioxidant Activity
Authors: Eid Omneya , Elkady Wafaa M. , Ezzat Shahira , El Sayed Abeer , Abd elsattar Essam 
Published: February 2023

AbstractBarley (Hordeum vulgare L.) is one of the world's oldest cereal crops. There is considerable interest in barley's potential usage in human diets. Barley is rich in bioactive metabolites such as high content of β‐glucan, fiber, and vitamin E. It is also well‐known as a rich source of phytochemical derivatives, namely, phenolic acids, flavonols, chalcones, flavones, proanthocyanidins, and flavanones. Phenolic compounds are recognized as excellent dietary materials with antioxidant and anti‐inflammatory activities. This review was written to give an overview of the main components that are separated from barley using different solvents. Even though there were numerous biological activities for barely, the antioxidant, as well as the anti‐inflammatory, are the main focus of this review.