bluuebunny/crossref_metadata_2025_split huggingface dataset:
Nahinfrarot Fluoreszenz‐Lebensdauer Mikroskopie von Biomolekülen mit Kohlenstoffnanoröhren**
Authors: Sistemich Linda , Galonska Phillip , Stegemann Jan , Ackermann Julia , Kruss Sebastian 
Published: March 2023

AbstractEinwandige Kohlenstoffnanoröhren (single‐walled carbon nanotubes, SWCNTs) sind vielseitig einsetzbare Bausteine für Biosensoren, die im nahen Infrarot (NIR) fluoreszieren. Ihre Oberfläche kann chemisch so modifiziert werden, dass sie auf Analyten mit einer Veränderung ihrer Fluoreszenz reagieren. Intensitätsbasierte Signale werden jedoch leicht durch äußere Faktoren wie Bewegungen der Probe beeinflusst. Hier zeigen wir Fluoreszenz‐Lebensdauer Mikroskopie (fluorescence lifetime imaging microscopy, FLIM) von SWCNT‐basierten Sensoren im NIR. Dafür wurde ein konfokales Laser‐Scanning‐Mikroskop (CLSM) für NIR‐Signale (>800 nm) angepasst und zeitkorrelierte Einzelphotonenzählung von (GT)10‐DNA‐funktionalisierten SWCNTs verwendet. (GT)10‐SWCNTs fungieren als Sensoren für den wichtigen Neurotransmitter Dopamin. Ihre Fluoreszenzlebensdauer (>900 nm) fällt biexponentiell ab, wobei die längere Lebensdauerkomponente (370 ps) mit steigender Dopaminkonzentration um bis zu 25 % ansteigt. Mit diesen Sensoren können Zellen beschichtet werden, um extrazelluläres Dopamin in 3D mittels FLIM zu messen. Wir demonstrieren damit das Potenzial der Fluoreszenzlebensdauer als Messgröße für SWCNT‐basierte NIR‐Sensoren.
Assembly of an A6L6 Anion Trigonal Antiprism and Binding of Glucopyranosides and Polyethylene Glycols (PEGs)
Authors: Li Boyang , Wei Tianfu , Zhao Xiaotong , Wang Yue , Xu Lizheng , Yang Xiao‐Juan , Wu Biao 
Published: March 2023

AbstractAnion‐coordination‐driven assembly (ACDA) has proven to be a very effective strategy for the construction of polyhedral structures. Here we demonstrate that variation of the “angle” of the backbone of C3‐symmetric tris‐bis(urea) ligands, from triphenylamine to triphenylphosphine oxide, results in the change of the final construct from an A4L4 tetrahedron to a higher‐nuclearity, A6L6 trigonal antiprism (A=anion, herein PO43−; L=ligand). Most interestingly, this assembly features a huge hollow internal space that is divided into three compartments: one central cavity and two large outer pockets. This multi‐cavity character enables the binding of different guests, namely monosaccharides or polyethylene glycol molecules (PEG600, PEG1000 and PEG2000), respectively. The results prove that anion coordination by multiple hydrogen bonds may provide both sufficient strength and flexibility, thus making possible the formation of complicated structures with adaptive guest binding ability.
Dual‐Atomic‐Site Catalysts for Molecular Oxygen Activation in Heterogeneous Thermo‐/Electro‐catalysis
Authors: Wang Zhongsen , Cheng Ming , Liu Yi , Wu Zewei , Gu Huayu , Huang Yi , Zhang Lizhi , Liu Xiao 
Published: March 2023

AbstractEfficient molecular oxygen activation (MOA) is the key to environmentally friendly catalytic oxidation reactions. In the last decade, single‐atomic‐site catalysts (SASCs) with nearly 100 % atomic utilization and unique electronic structure have been widely investigated for MOA. However, the single active site makes the activation effect unsatisfactory and difficult to deal with complex catalytic reactions. Recently, dual‐atomic‐site catalysts (DASCs) have provided a new idea for the effective activation of molecular oxygen (O2) due to more diverse active sites and synergetic interactions among adjacent atoms. In this review, we systematically summarized the recent research progress of DASCs for MOA in heterogeneous thermo‐ and electrocatalysis. Finally, we look forward to the challenges and application prospects in the construction of DASCs for MOA.
High‐Performance and Self‐Powered X‐Ray Detectors Made of Smooth Perovskite Microcrystalline Films with 100 μm Grains
Authors: Li Ning , Li Yuyang , Xie Shengdan , Wu Jinming , Liu Nianqiao , Yu Yuan , Lin Qinglian , Liu Yang , Yang Shuang , Lian Gang , Fang Yanjun , Yang Deren , Chen Zhaolai , Tao Xutang 
Published: March 2023

AbstractPerovskite single crystals and polycrystalline films have complementary merits and deficiencies in X‐ray detection and imaging. Herein, we report preparation of dense and smooth perovskite microcrystalline films with both merits of single crystals and polycrystalline films through polycrystal‐induced growth and hot‐pressing treatment (HPT). Utilizing polycrystalline films as seeds, multi‐inch‐sized microcrystalline films can be in situ grown on diverse substrates with maximum grain size reaching 100 μm, which endows the microcrystalline films with comparable carrier mobility‐lifetime (μτ) product as single crystals. As a result, self‐powered X‐ray detectors with impressive sensitivity of 6.1×104 μC Gyair−1 cm−2 and low detection limit of 1.5 nGyair s−1 are achieved, leading to high‐contrast X‐ray imaging at an ultra‐low dose rate of 67 nGyair s−1. Combining with the fast response speed (186 μs), this work may contribute to the development of perovskite‐based low‐dose X‐ray imaging.
Post‐Nickelation of a Crystalline Trinuclear Copper Organic Framework for Synergistic Photocatalytic Carbon Dioxide Conversion
Authors: Wang Xinxin , Ding Xu , Jin Yucheng , Qi Dongdong , Wang Hailong , Han Yuesheng , Wang Tianyu , Jiang Jianzhuang 
Published: March 2023

AbstractRational regulation of electronic structures and functionalities of framework materials still remains challenging. Herein, reaction of 4,4′,4′′‐nitrilo‐tribenzhydrazide with tris(μ2‐4‐carboxaldehyde‐pyrazolato‐N,N′)‐tricopper (Cu3Py3) generates the crystalline copper organic framework USTB‐11(Cu). Post‐modification with divalent nickel ions affords the heterometallic framework USTB‐11(Cu,Ni). Powder X‐ray diffraction and theoretical simulations reveal their two‐dimensional hexagonal structure geometry. A series of advanced spectroscopic techniques disclose the mixed CuI/CuIIstate nature of Cu3Py3in USTB‐11(Cu,Ni) with a uniform bistable Cu34+(CuI2CuII) : Cu35+(CuICuII2) (ca. 1 : 3) oxidation state, resulting in a significantly improved formation efficiency of the charge‐separation state. This endows the Ni sites with enhanced activity and USTB‐11(Cu,Ni) with outstanding photocatalytic CO2to CO performance with a conversion rate of 22 130 μmol g−1 h−1and selectivity of 98 %.
A Near‐Infrared Light‐Activated Photocage Based on a Ruthenium Complex for Cancer Phototherapy
Authors: He Guangli , He Maomao , Wang Ran , Li Xuezhao , Hu Hanze , Wang Dongsheng , Wang Ziqian , Lu Yang , Xu Ning , Du Jianjun , Fan Jiangli , Peng Xiaojun , Sun Wen 
Published: March 2023

AbstractConventional photocages only respond to short wavelength light, which is a significant obstacle to developing efficient phototherapy in vivo. The development of photocages activated by near‐infrared (NIR) light at wavelengths from 700 to 950 nm is important for in vivo studies but remains challenging. Herein, we describe the synthesis of a photocage based on a ruthenium (Ru) complex with NIR light‐triggered photocleavage reaction. The commercial anticancer drug, tetrahydrocurcumin (THC), was coordinated to the RuII center to create the Ru‐based photocage that is readily responsive to NIR light at 760 nm. The photocage inherited the anticancer properties of THC. As a proof‐of‐concept, we further engineered a self‐assembled photocage‐based nanoparticle system with amphiphilic block copolymers. Upon exposure to NIR light at 760 nm, the Ru complex‐based photocages were released from the polymeric nanoparticles and efficiently inhibited tumor proliferation in vivo.
Near‐Infrared Fluorescence Lifetime Imaging of Biomolecules with Carbon Nanotubes**
Authors: Sistemich Linda , Galonska Phillip , Stegemann Jan , Ackermann Julia , Kruss Sebastian 
Published: March 2023

AbstractSingle‐walled carbon nanotubes (SWCNTs) are versatile near infrared (NIR) fluorescent building blocks for biosensors. Their surface is chemically tailored to respond to analytes by a change in fluorescence. However, intensity‐based signals are easily affected by external factors such as sample movements. Here, we demonstrate fluorescence lifetime imaging microscopy (FLIM) of SWCNT‐based sensors in the NIR. We tailor a confocal laser scanning microscope (CLSM) for NIR signals (>800 nm) and employ time correlated single photon counting of (GT)10‐DNA functionalized SWCNTs. They act as sensors for the important neurotransmitter dopamine. Their fluorescence lifetime (>900 nm) decays biexponentially and the longer lifetime component (370 ps) increases by up to 25 % with dopamine concentration. These sensors serve as paint to cover cells and report extracellular dopamine in 3D via FLIM. Therefore, we demonstrate the potential of fluorescence lifetime as a readout of SWCNT‐based NIR sensors.
Using critical fluid carbon dioxide to optimize the enzymatic transesterification of soybean oil and ethyl ferulate to feruloyl soy glycerides
Authors: Eller Fred J. , Compton David L. 
Published: March 2023

AbstractFeruloyl Soy Glyceride (FSG) is an all‐natural replacement for petroleum‐based ultraviolet absorbing ingredients currently used in sunscreens. It is produced by the Novozym® 435‐catalyzed transesterification of ethyl ferulate (EF) with triglycerides. By‐product fatty acid ethyl esters (FAEEs) are more soluble in CO2than the EF and triglyceride starting materials. It was hypothesized that the preferential removal of the FAEEs over EF would drive the enzymatic reaction towards the desired FSG product. The effect of CO2pressure and temperature on the solubilities of components of the FSG reaction mixture was studied to select optimized conditions for the enzymatic reaction and purification. Pressure–temperature conditions were then selected to use in a recycling system. The enzymatic products were analyzed for CO2with and without recycling CO2. The solubilities of all components of the reaction mixture were proportional to CO2density but the relative solubilities of individual components were not equal at all pressures and temperatures. At 60°C, the ratio of ethyl linoleate to EF was only 1.1 at 6.9 MPa but 3.1 at 13.8 MPa. The CO2was recycled through the reactor at 13.8 MPa (removing more FAEE by‐products) and through the receiver at 6.0 MPa (removing less FAEEs). In the recycling treatment, the material left behind in the reactor had 99.6% FSG content. The use of the reduced pressure receiver in a recycling CO2system effectively increased the amount of EF incorporated onto the soybean oil increasing the yield of the FSG product.
Scale‐down of oxygen and glucose fluctuations in a tubular photobioreactor operated under oxygen‐balanced mixotrophy
Authors: Moñino Fernández Pedro , Vidal García Albert , Jansen Tanisha , Evers Wendy , Barbosa Maria , Janssen Marcel 
Published: March 2023

AbstractOxygen‐balanced mixotrophy (OBM) is a novel type of microalgal cultivation that improves autotrophic productivity while reducing aeration costs and achieving high biomass yields on substrate. The scale‐up of this process is not straightforward, as nonideal mixing in large photobioreactors might have unwanted effects in cell physiology. We simulated at lab scale dissolved oxygen and glucose fluctuations in a tubular photobioreactor operated under OBM where glucose is injected at the beginning of the tubular section. We ran repeated batch experiments with the strain Galdieria sulphuraria ACUF 064 under glucose pulse feeding of different lengths, representing different retention times: 112, 71, and 21 min. During the long and medium tube retention time simulations, dissolved oxygen was depleted 15–25 min after every glucose pulse. These periods of oxygen limitation resulted in the accumulation of coproporphyrin III in the supernatant, an indication of disruption in the chlorophyll synthesis pathway. Accordingly, the absorption cross‐section of the cultures decreased steeply, going from values of 150–180 m2 kg−1 at the end of the first batch down to 50–70 m2 kg−1 in the last batches of both conditions. In the short tube retention time simulation, dissolved oxygen always stayed above 10% air saturation and no pigment reduction nor coproporphyrin III accumulation were observed. Concerning glucose utilization efficiency, glucose pulse feeding caused a reduction of biomass yield on substrate in the range of 4%–22% compared to the maximum levels previously obtained with continuous glucose feeding (0.9 C‐g C‐g−1). The missing carbon was excreted to the supernatant as extracellular polymeric substances constituted by carbohydrates and proteins. Overall, the results point out the importance of studying large‐scale conditions in a controlled environment and the need for a highly controlled glucose feeding strategy in the scale‐up of mixotrophic cultivation.
Preparation of lignin nanoparticles via ultra‐fast microwave‐assisted fractionation of lignocellulose using ternary deep eutectic solvents
Authors: Yan Zhiyan , Wang Zhongren , Chen Yuehui , Liu Chenrui , Liu Yun , Li Ruijie , Si Mengying , Shi Yan 
Published: March 2023

AbstractLignin separation from natural lignocellulose for the preparation of lignin nanoparticles (LNPs) is often challenging owing to the recalcitrant and complex structure of lignocellulose. This paper reports a strategy for the rapid synthesis of LNPs via microwave‐assisted lignocellulose fractionation using ternary deep eutectic solvents (DESs). A novel ternary DES with strong hydrogen bonding was prepared using choline chloride, oxalic acid, and lactic acid in a 1:0.5:1 ratio. Efficient fractionation of rice straw (0.5 × 2.0 cm) (RS) was realized by the ternary DES under microwave irradiation (680 W) within only 4 min, and 63.4% of lignin could be separated from the RS to prepare LNPs with a high lignin purity (86.8%), an average particle size of 48–95 nm, and a narrow size distribution. The mechanism of lignin conversion was also investigated, which revealed that dissolved lignin aggregated into LNPs via π–π stacking interactions.
Bioguided Fractionation and Isolation of an Antiplasmodial Saponin from the Roots of Nauclea xanthoxylon (A.Chev.) Aubrév. (Rubiaceae)
Authors: Nkouayeb Nangmou Brice Maxime , Maza Djomkam Hermine Laure , Bellier Tabekoueng Georges , Tékapi Tsopgni Willifred Dongmo , Mbahbou Bitchagno Gabin Thierry , Mbock Michel Arnaud , Kamkumo Raceline Gounoue , Frese Marcel , Ndjakou Lenta Bruno , Ngouela Silvère Augustin , Sewald Nobert , Blaise Azebaze Anatole Guy 
Published: March 2023

AbstractThe root extract of Nauclea xanthoxylon (A.Chev.) Aubrév. displayed significant 50 % inhibition concentration (IC50s) of 0.57 and 1.26 μg/mL against chloroquine resistant and sensitive Plasmodium falciparum (Pf) Dd2 and 3D7 strains, respectively. Bio‐guided fractionation led to an ethyl acetate fraction with IC50s of 2.68 and 1.85 μg/mL and subsequently, to the new quinovic acid saponin named xanthoxyloside (1) with IC50s of 0.33 and 1.30 μM, respectively against the tested strains. Further compounds obtained from ethyl acetate and hexane fractions were the known clethric acid (2), ursolic acid (3), quafrinoic acid (4), quinovic acid (5), quinovic acid 3‐O‐β‐D‐fucopyranoside (6), oleanolic acid (7), oleanolic acid 3‐acetate (8), friedelin (9), β‐sitosterol (10a), stigmasterol (10b) and stigmasterol 3‐O‐β‐D‐glucopyranoside (11). Their structures were characterised with the aid of comprehensive spectroscopic methods (1 and 2D NMR, Mass). Bio‐assays were performed using nucleic acid gel stain (SYBR green I)‐based fluorescence assay with chloroquine as reference. Extracts and compounds exhibited good selectivity indices (SIs) of >10. Significant antiplasmodial activities measured for the crude extract, the ethyl acetate fraction and xanthoxyloside (1) from that fraction can justify the use of the root of N. xanthoxylon in ethnomedicine to treat malaria.
Bioinformatic Analysis of Immobilized Enzymes: Towards a Better Understanding of The Guiding Forces
Authors: Padrosa David Roura , Paradisi Francesca 
Published: March 2023

AbstractProtein bioinformatics has been applied to a myriad of opportunities in biocatalysis from enzyme engineering to enzyme discovery, but its application in enzyme immobilization is still very limited. Enzyme immobilization brings clear advantages in terms of sustainability and cost‐efficiency but is still limited in its implementation. This, because it is a technique that remains tied to a quasi‐blind protocol of trial and error, and therefore, is regarded as a time‐intensive and costly approach. Here, we present the use of a set of bioinformatic tools to rationalize the results of protein immobilization that have been previously described. The study of proteins with these new tools allows the discovery of key driving forces in the process of immobilization that explain the obtained results, moving us a step closer to the final goal: predictive enzyme immobilization protocols.
Chemoenzymatic Synthesis of Glycopeptides to Explore the Role of Mucin 1 Glycosylation in Cell Adhesion
Authors: Bello Claudia , Pranzini Erica , Piemontese Emanuele , Schrems Maximilian , Taddei Maria Letizia , Giovannelli Lisa , Schubert Mario , Becker Christian F. W. , Rovero Paolo , Papini Anna Maria 
Published: March 2023

AbstractPost‐translational modifications affect protein biology under physiological and pathological conditions. Efficient methods for the preparation of peptides and proteins carrying defined, homogeneous modifications are fundamental tools for investigating these functions. In the case of mucin 1 (MUC1), an altered glycosylation pattern is observed in carcinogenesis. To better understand the role of MUC1 glycosylation in the interactions and adhesion of cancer cells, we prepared a panel of homogeneously O‐glycosylated MUC1 peptides by using a quantitative chemoenzymatic approach. Cell‐adhesion experiments with MCF‐7 cancer cells on surfaces carrying up to six differently glycosylated MUC1 peptides demonstrated that different glycans have a significant impact on adhesion. This finding suggests a distinct role for MUC1 glycosylation patterns in cancer cell migration and/or invasion. To decipher the molecular mechanism for the observed adhesion, we investigated the conformation of the glycosylated MUC1 peptides by NMR spectroscopy. These experiments revealed only minor differences in peptide structure, therefore clearly relating the adhesion behaviour to the type and number of glycans linked to MUC1.
Altering the Modular Architecture of Galectins Affects its Binding with Synthetic α‐Dystroglycan O‐Mannosylated Core M1 Glycoconjugates In situ
Authors: Villones Lareno L. , Ludwig Anna‐Kristin , Kikuchi Seiya , Ochi Rika , Nishimura Shin‐Ichiro , Gabius Hans‐Joachim , Kaltner Herbert , Hinou Hiroshi 
Published: March 2023

AbstractThe multifunctionality of galectins helps regulate a broad range of fundamental cellular processes via cis‐binding and trans‐bridging activities and has gained widespread attention with respect to the importance of the natural specificity/selectivity of this lectin family to its glycoconjugate receptors. Combining galectin (Gal)‐1, −3, −4, and −9 variant test panels, achieved via rational protein engineering, and a synthetic α‐dystroglycan (DG) O‐Mannosylated core M1 glycopeptide library, a detailed comparative analysis was performed, utilizing microarray experiments to delineate the design‐functionality relationships within this lectin family. Enhancement of prototype Gal‐1 and chimera‐type Gal‐3 cis‐binding toward the prepared ligands is possible by transforming these lectins into tandem‐repeat type and prototypes, respectively. Furthermore, Gal‐1 variants demonstrated improved trans‐bridging capabilities between core M1 α‐DG glycopeptides and laminins in microarray, suggesting the possible translational applications of these galectin variants in the treatment of some forms of α‐dystroglycanopathy.
Chemical Biology Approaches toward Precise Structure Control of IgG‐Based Antibody‐Oligonucleotide Conjugates
Authors: Shen Lin , Wu Yuanyuan , Xie Wenxue , Chen Guangyao , Xing Hang 
Published: March 2023

AbstractAntibody‐oligonucleotide conjugates (AOCs) are important tools for drug development and biochemical analysis. However, the structural heterogeneity of AOCs synthesized through conventional coupling methods raises reproducibility and safety concerns in clinical trials. To address these issues, different covalent coupling approaches have been developed to synthesize AOCs with precise site‐specificity and degree of conjugation. This Concept article categorizes these approaches as linker‐free or linker‐mediated and provides details on their chemistry and potential applications. Several factors, including site‐specificity, conjugation control, accessibility, stability, and efficiency, are highlighted when evaluating the pros and cons of these approaches. The article also discusses the future of AOCs, including the development of better conjugation approaches to ensure stimuli‐responsive release and the application of high‐throughput methods to facilitate their development.
Bioresorbable stents: We have more work to do
Authors: El Hajj Milad , Krajcer Zvonimir 
Published: March 2023

Key Points
The NeoVas sirolimus‐eluting bioresorbable stent is safe and efficacious for treating de novo coronary artery disease.
Lesion and patient‐specific characteristics may play a role in the long‐term safety profile of bioresorbable stents.
The role of bioresorbable scaffolds in complex coronary lesions needs to be further elucidated.
Exploring the Promotion of γ‐Al2O3 on Pd/CeO2‐Catalyzed Low‐Concentration Methane Oxidation Using Operando DRIFTS‐MS
Authors: Li Tao , Dong Mengling , Xu Jiacheng , Zhang Tiantian , Sun Yan , Li Ning , Wu Zuliang , Li Jing , Gao Erhao , Zhu Jiali , Yao Shuiliang , Huang Yong 
Published: March 2023

AbstractCeO2/γ‐Al2O3, Pd/CeO2, and Pd/CeO2/γ‐Al2O3 were used for catalyzing low‐concentration CH4 oxidation. It was found that nano‐sized Pd could obviously promote CH4 oxidation on CeO2/γ‐Al2O3. The interaction between Pd and CeO2 on γ‐Al2O3 resulted in higher ratios of Ce3+/(Ce3++Ce4+), Pd2+/(Pd2++Pdδ+), and Oads/(Oads+Olatt), those benefited the formation of more oxygen vacancies and surface reactive oxygen species for CH4 oxidation. γ‐Al2O3 not only supplied a high surface area and enhanced Pd/CeO2 dispersion on γ‐Al2O3, but also simulated the formation of bicarbonate, where bicarbonate is easier to gasify to CO2 than bidentate carbonate that formed on Pd/CeO2. Operando diffuse reflectance infrared Fourier transform spectroscopy‐mass spectrometer analysis results showed that CH4 oxidation could occur at a temperature as low as 180 °C due to the reaction with surface reactive OH, this reaction was also accompanied by the formation of bicarbonate. The mechanism of CH4 oxidation promoted by bicarbonate formation on γ‐Al2O3 was proposed.
Vanadium Pentafulvene Complexes: Synthon for Unprecedented VanadoceneIIIDerivatives
Authors: de Graaff Simon , Schwitalla Kevin , Thye Hermann , Yusufzadeh Zainab , Willms Michael , Schmidtmann Marc , Beckhaus Rüdiger 
Published: March 2023

AbstractThe benzene ligand at CpV(η6−C6H6) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2 aand2 b) and benzofulvene complexes (3 aand3 b). The molecular structures of the target compounds suggest a π‐η5:σ‐η1coordination mode with a vanadiumIIIcenter. With the sterically low demanding 6,6‐dimethylpentafulvene, a C−H activation at the leaving ligand is observed, yielding the ring‐substituted vanadoceneII4. The reactivity of the pentafulvene complexes was investigated. A series of unprecedented vanadoceneIIIcompounds were synthesized: Under mild conditions, E−H splitting of 4‐tert‐butylphenol, diphenylamine, and 2,6‐diisopropylaniline yield well characterized examples of rare vanadoceneIIIphenolate and amide complexes. Insertion reactions into the V−Cexobond of the pentafulvene complexes by multiple bond containing substrates were found for acetone, 4‐chlorobenzonitril andN,N’‐dicyclohexylcarbodiimide.