bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cryo‐EM Resolves Molecular Recognition Of An Optojasp Photoswitch Bound To Actin Filaments In Both Switch States
Authors: Pospich Sabrina , Küllmer Florian , Nasufović Veselin , Funk Johanna , Belyy Alexander , Bieling Peter , Arndt Hans‐Dieter , Raunser Stefan 
Published: January 2021

AbstractActin is essential for key processes in all eukaryotic cells. Cellpermeable optojasps provide spatiotemporal control of the actin cytoskeleton, confining toxicity and potentially rendering F‐actin druggable by photopharmacology. Here, we report cryo electron microscopy (cryo‐EM) structures of both isomeric states of one optojasp bound to actin filaments. The high‐resolution structures reveal for the first time the pronounced effects of photoswitching a functionalized azobenzene. By characterizing the optojasp binding site and identifying conformational changes within F‐actin that depend on the optojasp isomeric state, we refine determinants for the design of functional F‐actin photoswitches.
Enzymkatalysierte späte Modifizierungen: Besser spät als nie
Authors: Romero Elvira , Jones Bethan S. , Hogg Bethany N. , Rué Casamajo Arnau , Hayes Martin A. , Flitsch Sabine L. , Turner Nicholas J. , Schnepel Christian 
Published: January 2021

AbstractDie Enzymkatalyse gewinnt zunehmend an Bedeutung in der Synthesechemie. Die durch Bioinformatik und Enzym‐Engineering stetig wachsende Zahl von Biokatalysatoren eröffnet eine große Vielfalt selektiver Reaktionen. Insbesondere für späte Funktionalisierungsreaktionen ist die Biokatalyse ein geeignetes Werkzeug, das oftmals der konventionellen De‐novo‐Synthese überlegen ist. Enzyme haben sich als nützlich erwiesen, um funktionelle Gruppen direkt in komplexe Molekülgerüste einzuführen sowie für die rasche Diversifizierung von Substanzbibliotheken. Biokatalytische Oxyfunktionalisierungen, Halogenierungen, Methylierungen, Reduktionen und Amidierungen sind von besonderem Interesse, da diese Strukturmotive häufig in Pharmazeutika vertreten sind. Dieser Aufsatz gibt einen Überblick über die Stärken und Schwächen der enzymkatalysierten späten Modifizierungen durch native und optimierte Enzyme in der Synthesechemie. Ebenso werden wichtige Beispiele in der Wirkstoffentwicklung hervorgehoben.
Bright and Robust Phosphorescence Achieved by Non‐Covalent Clipping
Authors: Li Zijian , Han Yifei , Nie Fude , Liu Mingyang , Zhong Hua , Wang Feng 
Published: January 2021

AbstractPhosphorescent materials with bright emission in versatile media are important for their practical applications, which require to lower the susceptibility of triplet excitons to surroundings. Herein a non‐covalent clipping strategy has been developed to attain this objective, by designing a tweezer receptor to encapsulate PtII‐based triplet emitters through two‐fold π‐stacking interactions. The PtII emitters display robust phosphorescence by virtue of synergistic rigidifying and shielding effects, which are hardly influenced by emitter concentration, oxygen content, and solvent polarity changes. The phosphorescent colors are elaborately modulated by varying ligand substitutes on PtII emitters. Circularly polarized phosphorescence is further amplified for chiral PtII emitters, by taking advantage of dual phosphorescence and chirality enhancement upon non‐covalent tweezer complexation. Overall, the clipping approach paves the way for the development of high‐performance phosphorescent materials with bright emission, environmental robustness, and facile color tunability.
The Total Synthesis of Chondrochloren A
Authors: Linne Yannick , Bonandi Elisa , Tabet Christopher , Geldsetzer Jan , Kalesse Markus 
Published: January 2021

AbstractThe first total synthesis of chondrochloren A is accomplished using a 1,2‐metallate rearrangement addition as an alternative for the Nozaki‐Hiyama‐Kishi reaction. This transformation also avoids the inherent challenges of this polyketide segment and provides a new, unprecedented strategy to assemble polyketidal frameworks. The formation of the Z‐enamide is accomplished using a Z‐selective cross coupling of the corresponding amide to a Z‐vinyl bromide.
Heterometallic Actinide‐Containing Photoresponsive Metal‐Organic Frameworks: Dynamic and Static Tuning of Electronic Properties
Authors: Martin Corey R. , Leith Gabrielle A. , Kittikhunnatham Preecha , Park Kyoung Chul , Ejegbavwo Otega A. , Mathur Abhijai , Callahan Cameron R. , Desmond Shelby L. , Keener Myles R. , Ahmed Fiaz , Pandey Shubham , Smith Mark D. , Phillpot Simon R. , Greytak Andrew B. , Shustova Natalia B. 
Published: January 2021

AbstractAcquiring fundamental knowledge of properties of actinide‐based materials is a necessary step to create new possibilities for addressing the current challenges in the nuclear energy and nuclear waste sectors. In this report, we established a photophysics–electronics correlation for actinide‐containing metal‐organic frameworks (An‐MOFs) as a function of excitation wavelength, for the first time. A stepwise approach for dynamically modulating electronic properties was applied for the first time towards actinide‐based heterometallic MOFs through integration of photochromic linkers. Optical cycling, modeling of density of states near the Fermi edge, conductivity measurements, and photoisomerization kinetics were employed to shed light on the process of tailoring optoelectronic properties of An‐MOFs. Furthermore, the first photochromic MOF‐based field‐effect transistor, in which the field‐effect response could be changed through light exposure, was constructed. As a demonstration, the change in current upon light exposure was sufficient to operate a two‐LED fail‐safe indicator circuit.
Enhanced Light‐Driven Hydrogen Production by Self‐Photosensitized Biohybrid Systems
Authors: Martins Mónica , Toste Catarina , Pereira Inês A. C. 
Published: January 2021

AbstractStorage of solar energy as hydrogen provides a platform towards decarbonizing our economy. One emerging strategy for the production of solar fuels is to use photocatalytic biohybrid systems that combine the high catalytic activity of non‐photosynthetic microorganisms with the high light‐harvesting efficiency of metal semiconductor nanoparticles. However, few such systems have been tested for H2 production. We investigated light‐driven H2 production by three novel organisms, Desulfovibrio desulfuricans, Citrobacter freundii, and Shewanella oneidensis, self‐photosensitized with cadmium sulfide nanoparticles, and compared their performance to Escherichia coli. All biohybrid systems produced H2 from light, with D. desulfuricans‐CdS demonstrating the best activity overall and outperforming the other microbial systems even in the absence of a mediator. With this system, H2 was continuously produced for more than 10 days with a specific rate of 36 μmol gdcw−1 h−1. High apparent quantum yields of 23 % and 4 % were obtained, with and without methyl viologen, respectively, exceeding values previously reported.
Enzymatic Late‐Stage Modifications: Better Late Than Never
Authors: Romero Elvira , Jones Bethan S. , Hogg Bethany N. , Rué Casamajo Arnau , Hayes Martin A. , Flitsch Sabine L. , Turner Nicholas J. , Schnepel Christian 
Published: January 2021

AbstractEnzyme catalysis is gaining increasing importance in synthetic chemistry. Nowadays, the growing number of biocatalysts accessible by means of bioinformatics and enzyme engineering opens up an immense variety of selective reactions. Biocatalysis especially provides excellent opportunities for late‐stage modification often superior to conventional de novo synthesis. Enzymes have proven to be useful for direct introduction of functional groups into complex scaffolds, as well as for rapid diversification of compound libraries. Particularly important and highly topical are enzyme‐catalysed oxyfunctionalisations, halogenations, methylations, reductions, and amide bond formations due to the high prevalence of these motifs in pharmaceuticals. This Review gives an overview of the strengths and limitations of enzymatic late‐stage modifications using native and engineered enzymes in synthesis while focusing on important examples in drug development.
Reversibly thermochromic and high strength core‐shell nanofibers fabricated by melt coaxial electrospinning
Authors: Wang Shuoshuo , Yi Liqiang , Fang Yini , Wang Lina , Yao Juming , Marek Jaromir , Zhang Ming 
Published: January 2021

AbstractRecent years, phase change materials (PCMs) with potential to store and transform energy have attracted broad attention, especially in the field of thermal energy storage. However, the instability and leak proneness of PCMs limit their universal application. In this paper, core‐shell fibers with 1‐tetradecanol (TD) as core and poly(vinylidene fluoride) (PVDF) as shell were prepared via melt coaxial electrospinning method, and for improvement, the dye composed of crystal violet lactone (CVL) and bisphenol A (BPA) was added to the core to endow the fiber the function of reversible thermochromism. During the preparation process, it was found that the addition of NaCl could regulate the fiber morphology and strength its mechanical property. By adjusting the concentration of shell solution and the flow rate of core solution, the high‐strength reversible thermochromic fibers were produced when polymer concentration was 24 wt% with a core feed rate of 0.4 ml/h. The latent heat of these fibers is up to 88.71 J/g. Besides, its color can change from blue to white when heated, and the transition temperature is around 38°C. And 100 thermal cycle tests of the fiber showed its strong thermal stability and thermochromic property.
Chitosan/nanocellulose‐based bionanocomposite films for controlled betamethasone and silver sulfadiazine delivery
Authors: Riccio Bruno Vincenzo Fiod , Klosowski Ana Beatriz , Prestes Eduardo , de Sousa Taynara Barbosa , de Assunção Morais Laís Caroline , Lemes Bruna Mikulis , Beltrame Flávio Luís , Campos Patrícia Mazureki , Ferrari Priscileila Colerato 
Published: January 2021

AbstractBionanocomposite films based on chitosan and nanocellulose (nanocrystals or nanofibrils) have gained considerable attention for biomedical applications, especially for wound dressings. However, the development of these films as controlled drug release dressings is still under‐exploited. Therefore, this work aimed to design chitosan/nanocellulose‐based bionanocomposite films, loaded by betamethasone or silver sulfadiazine, as functional dressings. The films were obtained by solvent casting and characterized by physicochemical, mechanical, barrier properties, in vitro drug release, and antimicrobial activity. The nanocellulose type, physical state, and content caused influence on the film's properties providing different physical, barrier, and drug release profiles. They are semi‐occlusive and mechanically resistant; the drug release is controlled, and possesses antimicrobial activity. In conclusion, the developed biodegradable bionanocomposite films are promising as active dressings for controlled drug delivery in the wound site and have specific applications according to their features to treat inflamed and purulent wounds, non‐infectious dry wounds, and infectious wounds.
Selection of thermal, spectroscopic, spectrometric, and chromatographic methods for characterizing historical celluloid
Authors: Elsässer Christina , Micheluz Anna , Pamplona Marisa , Kavda Stefani , Montag Peter 
Published: January 2021

AbstractCelluloid in museum collections is very unstable; therefore, heritage professionals carry out research studies dedicated to understanding its decay and prolonging its lifetime. This paper addresses the need to compare and select suitable analytical methods for that purpose. Thermogravimetric analysis coupled with Fourier transform infrared spectroscopy, evolved gas analysis–mass spectrometry, double shot – gas chromatography/mass spectrometry, and gel permeation chromatography (GPC) were employed to characterize the emission of gasses (decay products) and measure the molecular weight and camphor (plasticizer) content from unaged, artificially, and naturally aged celluloid samples. A pioneer GPC set‐up for the quantification of camphor was introduced for the first time in this study. Results demonstrated that GPC was the most suitable method for assessing material changes due to degradation. Both set‐ups, for measuring molecular weight and quantifying camphor, appear promising for assessing the effect of conservation treatments and investigating the heterogeneous degradation of celluloid objects in future studies.
Distinct Gene Expression Signatures Characterize Strong Clinical Responders Versus Nonresponders to Canakinumab in Children With Systemic Juvenile Idiopathic Arthritis
Authors: Verweyen Emely L. , Pickering Alex , Grom Alexei A. , Schulert Grant S. 
Published: January 2021

ObjectiveCanakinumab is a human anti–interleukin‐1β (anti–IL‐1β) blocking agent that effectively neutralizes IL‐1β–mediated signaling for treatment of systemic juvenile idiopathic arthritis (JIA). While many patients have dramatic clinical response to IL‐1 blockade, approximately one‐third fail to respond, but there are currently no validated clinical or immunologic predictors of response. We undertook this study to characterize distinct gene signatures for treatment response and nonresponse to canakinumab in systemic JIA patients.MethodsWe performed a secondary analysis of whole‐blood gene expression microarrays using blood samples obtained from healthy controls and systemic JIA patients at baseline and on day 3 after canakinumab treatment (GEO accession no. GSE80060). Patients were considered strong clinical responders if they met the ACR90 response (exhibited ≥90% improvement in the American College of Rheumatology [ACR] JIA response criteria; nonresponders were those who met ACR30 [exhibiting ≤30% improvement in the ACR JIA response criteria]). A random‐effects model with patient identity as the random variable was used for differential expression analysis.ResultsWe identified a distinct gene expression signature in patients with a strong clinical response to canakinumab treatment as compared to nonresponders, mediated by up‐regulation of neutrophil‐ and IL‐1–associated genes and characterized by increasing divergence from control transcriptomes with increasing clinical response. We also identified a signature including up‐regulated CD163 expression that was associated with canakinumab nonresponse. Intriguingly, canakinumab treatment induced either up‐ or down‐regulation of type I interferon (IFN) genes, independent of clinical response.ConclusionHere, we identify a gene signature in systemic JIA patients prior to receiving treatment that distinguishes strong responders to canakinumab from nonresponders. Further prospective studies are needed to assess the utility of these insights for treatment decisions in systemic JIA and to track the association of up‐regulated type I IFN signatures with systemic JIA complications.
Tissue‐Resident Memory CD8+ T Cells From Skin Differentiate Psoriatic Arthritis From Psoriasis
Authors: Leijten Emmerik F. , van Kempen Tessa S. , Olde Nordkamp Michel A. , Pouw Juliette N. , Kleinrensink Nienke J. , Vincken Nanette L. , Mertens Jorre , Balak Deepak M. W. , Verhagen Fleurieke H. , Hartgring Sarita A. , Lubberts Erik , Tekstra Janneke , Pandit Aridaman , Radstake Timothy R. , Boes Marianne 
Published: January 2021

ObjectiveTo compare immune cell phenotype and function in psoriatic arthritis (PsA) versus psoriasis in order to better understand the pathogenesis of PsA.MethodsIn‐depth immunophenotyping of different T cell and dendritic cell subsets was performed in patients with PsA, psoriasis, or axial spondyloarthritis and healthy controls. Subsequently, we analyzed cells from peripheral blood, synovial fluid (SF), and skin biopsy specimens using flow cytometry, along with high‐throughput transcriptome analyses and functional assays on the specific cell populations that appeared to differentiate PsA from psoriasis.ResultsCompared to healthy controls, the peripheral blood of patients with PsA was characterized by an increase in regulatory CD4+ T cells and interleukin‐17A (IL‐17A) and IL‐22 coproducing CD8+ T cells. One population specifically differentiated PsA from psoriasis: i.e., CD8+CCR10+ T cells were enriched in PsA. CD8+CCR10+ T cells expressed high levels of DNAX accessory molecule 1 and were effector memory cells that coexpressed skin‐homing receptors CCR4 and cutaneous lymphocyte antigen. CD8+CCR10+ T cells were detected under inflammatory and homeostatic conditions in skin, but were not enriched in SF. Gene profiling further revealed that CD8+CCR10+ T cells expressed GATA3, FOXP3, and core transcriptional signature of tissue‐resident memory T cells, including CD103. Specific genes, including RORC, IFNAR1, and ERAP1, were up‐regulated in PsA compared to psoriasis. CD8+CCR10+ T cells were endowed with a Tc2/22‐like cytokine profile, lacked cytotoxic potential, and displayed overall regulatory function.ConclusionTissue‐resident memory CD8+ T cells derived from the skin are enhanced in the circulation of patients with PsA compared to patients with psoriasis alone. This may indicate that aberrances in cutaneous tissue homeostasis contribute to arthritis development.
Photochemically Produced Superhydrophobic Silane@polystyrene‐Coated Polypropylene Fibrous Network for Oil/Water Separation
Authors: Baig Nadeem , Saleh Tawfik A. 
Published: January 2021

AbstractCost‐effective separation of oil and immiscible organic contaminants from water has become an urgent challenge to protect aquatic and human life from devastating effects. Therefore, it has become imperative to develop super‐selective materials for efficiently separating oil from water. In this work, a superhydrophobic surface has been formed that consists of a silane@polystyrene‐coated polypropylene fibrous network (silane@PS‐PPF) for efficient separation of accidentally spilled oil from water. The superhydrophobic PPFs were designed by a simple, cost‐effective two‐step process that includes photochemically controlled polymerization of styrene and subsequent dip coating in octadecyltrichlorosilane solution. The hydrophobic surface (CA=129°±4°) of the PS coated PPF after treating with silane was turned into a superhydrophobic body (CA=161°±2°). The achieved silane@PS‐PPF fibrous network selectively allowed the fast permeation of the oils and non‐polar organic liquids by altogether rejecting water during operation. The separation efficiency for various oils from the contaminated water was 96 to 99%, with a high flux in the range of 7606±312 L m−2h−1 to 9870±151 L m−2h−1. Apart from being used as a filter, the silane@PS‐PPF was also used as an oil absorber and has shown an absorption capacity in the range of 1185 to 1535% for various oils. We anticipate that the developed silane@PS‐PPF, due to its facile synthetic route, cost‐effectiveness, and high performance, can be effectively used in oily wastewater treatment and clean‐up of large oil spills from water.
Preparation and luminescence properties of Tb3+‐doped garnet Y2Mg2Al2Si2O12 luminescent materials
Authors: Gu Xuan , He Zheng , Sun Xiao‐Yu , Xu Li‐Dan , Shi Ming‐Fang 
Published: January 2021

AbstractWe prepared Y2Mg2Al2Si2O12:xTb3+ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12, 0.14 and 0.16) luminescent materials using a nodulizing procedure. The phase and luminescence properties of these materials were investigated. X‐ray diffraction results demonstrated that Tb3+ ions doped into Y2Mg2Al2Si2O12 hosts successfully and the Y2Mg2Al2Si2O12:xTb3+ materials showed a pure cubic phase. Y2Mg2Al2Si2O12:xTb3+ materials had the characteristic Tb3+ emission bands derived from 5D4→7F6, 7F5, 7F4, and 7F3 transitions when excited at 365 nm. The green emission band that derived from the 5D4→7F5 transition was highest due to the high possibility of both electric‐dipole and magnetic‐dipole transitions. Emission spectra indicated that the critical concentration of Tb3+ in the Y2Mg2Al2Si2O12 host was 0.14. The concentration quenching of Y2Mg2Al2Si2O12:Tb3+ was derived from a dipole–dipole interaction.
Multicentre clinicopathological study of adenoid cystic carcinoma: A report of 296 cases
Authors: Huang Zheng , Pan Juan , Chen Jiaorong , Wu Shidi , Wu Ting , Ye Haihua , Zhang Hongfeng , Nie Xiu , Huang Changzheng 
Published: January 2021

AbstractAimsAdenoid cystic carcinoma (ACC) is a distinctive tumour. Limited studies involving a large population have reported multicentre systematic analyses of the clinical, pathological and immunohistochemical (IHC) features of ACC as well as the potential role of IHC markers in the prognosis of ACC.Methods and ResultsThe clinical, histopathological and IHC data of 296 cases obtained from two tertiary hospitals were analysed. The age at onset ranged from 12 to 87 years with a median age of 52 years. The male‐to‐female ratio was 1:1.3. Patients with ACC arising from the lacrimal gland were younger than those with tumours arising from other sites. Patients with tumours in the extra auditory canal and nasopharynx were older than those with tumours in other locations. Histopathologically, solid type ACC was the most frequent in the nasal cavity and paranasal sinus (6/51) group. Tumours arising from the oral cavity most commonly showed perineural invasion (10/60) and margin positivity (11/60). IHC analyses showed that CK8/18, CK7, CK14, epithelial membrane antigen and CD117 were expressed in 35/35 (100%), 87/88 (98.8%), 26/27 (96.2%), 42/43 (97.6%) and 113/120 (94.1%) patients, respectively. CK5/6, P63, smooth muscle actin, calponin and S100 were positively expressed in 73/73 (100%), 111/124 (89.5%), 38/43 (88.3%), 41/50 (82.0%) and 61/92 (66.3%) cases, respectively. S100 proteins were expressed in 54 (54/77) primary cases and two (2/9) metastatic cases (p = 0.013).ConclusionsACC is a distinctive tumour that mainly affects middle‐aged and elderly individuals, with a mild female predominance. Loss of expression of S100 proteins may be a poor prognostic factor associated with metastasis.
Immune signature as predictive marker for response to checkpoint inhibitor immunotherapy and overall survival in melanoma
Authors: Krebs Franziska K. , Trzeciak Emily R. , Zimmer Sophia , Özistanbullu Deniz , Mitzel‐Rink Heidrun , Meissner Markus , Grabbe Stephan , Loquai Carmen , Tuettenberg Andrea 
Published: January 2021

AbstractBackgroundMalignant melanoma is an immunogenic skin cancer with an increasing global incidence. Advanced stages of melanoma have poor prognoses. Currently, there are no reliable parameters to predict a patient's response to immune checkpoint inhibitor (ICI) therapy.MethodsThis study highlights the relevance of a distinct immune signature in the blood for response to ICI therapy and overall survival (OS). Therefore, the immune cell composition in the peripheral blood of 45 melanoma patients prior to ICI therapy was analyzed by flow cytometry and complete blood count.ResultsResponders to ICI therapy displayed an abundance of proliferating CD4+ T cells, an increased lymphocyte‐to‐monocyte ratio, a low platelet‐to‐lymphocyte ratio, low levels of CTLA‐4+ Treg, and (arginase 1+) polymorphonuclear myeloid‐derived suppressor cells (PMN‐MDSC). Nevertheless, non‐responders with similar immune cell compositions also benefited from therapy displaying increased long‐term OS.ConclusionsOur study demonstrated that the observed immune signature in the peripheral blood of melanoma patients prior to treatment could identify responders as well as non‐responders that benefit from ICI immunotherapies.