bluuebunny/crossref_metadata_2025 huggingface dataset:
Analytic expressions for the isosteric heat of adsorption from adsorption isotherm models and two‐dimensional SAFT‐VR equation of state
Authors: Siperstein Flor R. , Avendaño Carlos , Ortiz Jordan J. , Gil‐Villegas Alejandro
Published: January 2021

The isosteric heat of adsorption is an important thermodynamic property used to characterize and optimize adsorption processes. In this work, analytic expressions for isosteric heats of adsorption are derived for a collection of commonly used isotherm models and a two‐dimensional molecular equation of state based on the SAFT‐VR approach. The use of these expressions is presented with an example of adsorption of nitrous oxide, N2O, on biochar, which is a waste biomass charcoal that exhibits high adsorption potential. The results show that accurate fitting of the adsorption isotherms leads to consistent results obtained with different approaches; however, the predicted isosteric heat of adsorption exhibits strong variations in the regions where experimental data is insufficient such in the region of low pressure/low coverage. Convergence on the prediction of the isosteric heat of adsorption by the different models is only observed in the region where no extrapolation of experimental data is needed.
True nectar or stigmatic secretion? Structural evidence elucidates an old controversy regarding nectaries in Anthurium
Authors: Paiva Élder Antônio Sousa , Ballego‐Campos Igor , Gibernau Marc
Published: January 2021

Premise

Floral rewards are essential in understanding floral function and evolution of the relationships between flowers and pollinators. Whether sugars are present in stigmatic exudates in Anthurium and whether it has floral nectaries have remained controversial because of the scarcity of structural studies. To solve these questions, we investigated the floral anatomy of A. andraeanum to elucidate whether (1) tepals are secretory organs, (2) tepals possess a structurally recognizable nectary, and (3) tepalar secretion differs from stigmatic secretion.

Methods

Floral structure was assessed through light and electron microscopy of samples of immature, pistillate, and staminate flowers. The dynamics of the starch reserve was investigated using histochemical tests, and the sugar content in the floral exudates was assessed using thin‐layer chromatography.

Results

Sugar analysis did not detect sucrose, glucose, or fructose in stigmatic secretions, but confirmed their presence in tepalar secretions. Stigmatic secretion was produced by secretory stigmatic papillae; tepalar exudates were produced by nonvascularized nectaries in the apex of tepals. These nectaries were characterized by modified stomata and cells with cytoplasm rich in organelles, and a high content of calcium oxalate crystals.

Conclusions

Our results showed for the first time nectaries on tepals and true nectar secretion for A. andraeanum. Stigmatic secretion appears to be a distinct substance, and its often‐reported sugar content seems to be a result of sample contamination. Nectar and stigmatic secretions have been often mistaken in other Anthurium species and deserve a revision for this genus.
Sequential One‐pot Method for the Synthesis of 4‐(Hydroxymethyl)oxazoles and their Application in Phosphonates Synthesis
Authors: Kajol Km , Ramesh Chintakunta
Published: January 2021

A sequential one‐pot method for the synthesis of 4‐(hydroxymethyl)oxazoles from readily available benzamides has been developed. Various substituted benzamides well‐tolerated and furnished 4‐(hydroxymethyl)oxazoles in moderate to good yields under the present reaction conditions. In order to demonstrate the usefulness of the present methodology, the resulting 4‐(hydroxymethyl)oxazoles were successfully transformed into its corresponding phosphonates under Michaelis‐Arbuzov reaction conditions. This methodology features a broad substrate scope, step economy, ease of execution, and scalability.
Research progress on the structure and function of endomucin
Authors: Zhang Guoxin , Yang Xingjiu , Gao Ran
Published: January 2021

Endomucin is a type I integral membrane glycoprotein, which is expressed in venous and capillary endothelial cells. It consists of 261 amino acids with an extracellular domain that is highly O‐glycosylated at serine and threonine residues and has several potential N‐glycosylation sites. Endomucin plays an important role in biological processes such as cell interaction, molecular cell signaling, angiogenesis and cell migration, and in recent years it has also been identified as an anti‐adhesion molecule and a marker of endothelial cells. While it has been shown to be involved in a number of physiological and pathological mechanisms, many of its functions remain unknown, and further study is needed. This article reviews research progress on the function of endomucin to date, in order to provide guidance for future studies.
A Novel Homozygous VPS11 Variant May Cause Generalized Dystonia
Authors: Monfrini Edoardo , Cogiamanian Filippo , Salani Sabrina , Straniero Letizia , Fagiolari Gigliola , Garbellini Manuela , Carsana Emma , Borellini Linda , Biella Fabio , Moggio Maurizio , Bresolin Nereo , Corti Stefania , Duga Stefano , Comi Giacomo P. , Aureli Massimo , Di Fonzo Alessio
Published: January 2021

In this work, we describe the association of a novel homozygous VPS11 variant with adult‐onset generalized dystonia, providing a detailed clinical report and biological evidence of disease mechanism. Vps11 is a subunit of the homotypic fusion and protein sorting (HOPS) complex, which promotes the fusion of late endosomes and autophagosomes with the lysosome. Functional studies on mutated fibroblasts showed marked lysosomal and autophagic abnormalities, which improved after overexpression of the wild type Vps11 protein. In conclusion, a deleterious VPS11 variant, damaging the autophagic and lysosomal pathways, is the probable genetic cause of a novel form of generalized dystonia. ANN NEUROL 2021;89:834–839
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

Actin 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

Die 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

Phosphorescent 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

The 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

Acquiring 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

Storage 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

Enzyme 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.
Water oxidation activity of azo‐azomethine‐based Ni (II), Co (II), and Cu (II) complexes
Authors: Shaghaghi Zohreh , Kouhsangini Parya Sallakh , Mohammad‐Rezaei Rahim
Published: January 2021

Nickel, cobalt, and copper complexes were synthesized by the reaction of metal acetate salts and azo‐azomethine‐type ligand H2L (H2L = 4‐chloro‐1,2‐bis[2‐hydroxy‐5‐(phenylazo)benzylideneamino]benzene). The complexes were characterized by spectroscopic methods, molar conductivity measurements, and elemental analysis. The complexes were investigated as water oxidizing catalysts by several electrochemical techniques. Our findings revealed that the nature of the central metal ion plays an essential role in the stability of the complexes and their electrocatalytic activity. Although all modified electrodes with complexes showed good activities for water oxidation compared with bare carbon paste electrode, nevertheless, NiL showed a much superior electrocatalytic activity in basic solution in terms of onset potential and Tafel slope. Experiments indicated that at pH = 11, NiOx is probably a heterogeneous catalyst for the oxidizing of water in the presence of NiL. However, about CoL, it was revealed that a high valent cobalt oxo intermediate is active in the electrocatalytic process. On the other hand, field‐emission scanning electron microscope images showed the formation of nanorods on the electrode surface. However, upon our observations, it was difficult to determine the real role of CoL in the water oxidation reaction. Surprisingly, the results indicated that CuL is not stable under electrochemical conditions, and after performing the amperometry for a long time, its electrocatalytic activity decreases.
Fe3O4/ZnO/MWCNTs magnetic nanocomposites promoted synthesis of new chromeno pyrano [2,3‐d]thiazins: Investigation of antioxidant and antibacterial activities
Authors: Dadashi Hani , Hajinasiri Rahimeh , Hossaini Zinatossadat
Published: January 2021

The Fe3O4/ZnO/MWCNTs magnetic nanocomposites as a high‐performance organomettalic catalyst were employed for the preparation of new chromeno pyrano [2,3‐d]thiazins derivatives in high yields via the five component reactions of 2‐hydroxyacetophenone or its derivatives, dimethyl carbonate, aldehydes, malononitrile or ethyl 2‐cyanoacetate, and isothiocyanates in ionic liquid at room temperature. The Fe3O4/ZnO/MWCNTs MNCs were synthesized using ionic liquid [OMIM]Br as a stabilizer and soft template. As well Fe3O4/ZnO/MWCNTs MNCs show a good improvement in the yield of the product and showed significant reusable ability. Due to having NH group in synthesized compounds, we investigate antioxidant property of some synthesized compounds by diphenyl‐picrylhydrazine (DPPH) radical trapping and power of ferric reduction experiment. Furthermore, the disk diffusion test on Gram‐positive and Gram‐negative bacteria is utilized for investigation of antimicrobial activity of some chromeno pyrano [2,3‐d]thiazins. The achieved outcomes of this experiment demonstrate that these synthesized compounds could prevent from growth of bacteria. Short time of reaction, high yields of product, easy separation of catalyst, and products are some benefits of this process.
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

Recent 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

Bionanocomposite 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

Celluloid 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

Objective

Canakinumab 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.

Methods

We 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.

Results

We 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.

Conclusion

Here, 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

Objective

To compare immune cell phenotype and function in psoriatic arthritis (PsA) versus psoriasis in order to better understand the pathogenesis of PsA.

Methods

In‐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.

Results

Compared 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.

Conclusion

Tissue‐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

Cost‐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

We 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

Aims

Adenoid 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 Results

The 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).

Conclusions

ACC 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

Background

Malignant 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.

Methods

This 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.

Results

Responders 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.

Conclusions

Our 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.
Application of DNA‐Alkylating Pyrrole‐Imidazole Polyamides for Cancer Treatment
Authors: Maeda Rina , Bando Toshikazu , Sugiyama Hiroshi
Published: January 2021

Pyrrole‐imidazole (PI) polyamides, which target specific DNA sequences, have been studied as a class of DNA minor‐groove‐binding molecules. To investigate the potential of compounds for cancer treatment, PI polyamides were conjugated with DNA‐alkylating agents, such as seco‐CBI and chlorambucil. DNA‐alkylating PI polyamides have attracted attention because of their sequence‐specific alkylating activities, which contribute to reducing the severe side effects of current DNA‐damaging drugs. Many of these types of conjugates have been developed as new candidates for anticancer drugs. Herein, we review recent progress into research on DNA‐alkylating PI polyamides and their sequence‐specific action on targets associated with cancer development.
Activation, Structure, Biosynthesis and Bioactivity of Glidobactin‐like Proteasome Inhibitors from Photorhabdus laumondii
Authors: Zhao Lei , Le Chapelain Camille , Brachmann Alexander O. , Kaiser Marcel , Groll Michael , Bode Helge B.
Published: January 2021

The glidobactin‐like natural products (GLNPs) glidobactin A and cepafungin I have been reported to be potent proteasome inhibitors and are regarded as promising candidates for anticancer drug development. Their biosynthetic gene cluster (BGC) plu1881–1877 is present in entomopathogenic Photorhabdus laumondii but silent under standard laboratory conditions. Here we show the largest subset of GLNPs, which are produced and identified after activation of the silent BGC in the native host and following heterologous expression of the BGC in Escherichia coli. Their chemical diversity results from a relaxed substrate specificity and flexible product release in the assembly line of GLNPs. Crystal structure analysis of the yeast proteasome in complex with new GLNPs suggests that the degree of unsaturation and the length of the aliphatic tail are critical for their bioactivity. The results in this study provide the basis to engineer the BGC for the generation of new GLNPs and to optimize these natural products resulting in potential drugs for cancer therapy.
Clinical efficacy of dupilumab in the treatment of severe chronic rhinosinusitis: The first case outside of a clinical trial
Authors: Trimarchi Matteo , Indelicato Pietro , Vinciguerra Alessandro , Bussi Mario
Published: January 2021

Treatment options for severe CRSwNP are limited. Dupilumab is a safe, well‐tolerated, and effective alternative in patients with poor control of symptoms, corticosteroid‐dependent disease, and high rates of recurrence of nasal polyps after surgery.
Hierarchical Carbon Nanocages Embedding High‐loading Sulfur for Catalyzing Oxygen Reduction Reactions
Authors: She Yiyi , Wang An , Liu Jin , Zhou Jinsong , Li Li , Wang Hongkang , Leung Michael K. H.
Published: January 2021

The carbon‐based nanomaterials have attracted intensive interests as promising metal‐free electrocatalysts to reduce or even eliminate the use of precious‐metal catalysts on oxygen reduction reactions (ORR). In this regard, we developed 3D hollow carbon nanocages confining high‐loading sulfur fabricated by chemical vapor deposition (CVD) method employing self‐sacrificial templates (basic magnesium carbonate). Under different fabrication temperatures, the as‐designed samples obtained different morphologies, compositions and structural properties. With the largest specific surface area (1306 m2 g−1), highest heteroatom doping content (6.04 at.% of S) and well‐balanced pore distribution, the electrocatalysts synthesized under 800 °C could catalyze the ORR process through the ideally efficient four‐electron transfer pathway. The remarkable catalytic selectivity and stability of the optimal material in alkaline electrolyte resulted from the synergistic effects of structural and chemical characteristics. Moreover, primary Zn‐air batteries built with the sulfur loaded carbon nanocage air electrodes revealed high open‐circuit voltage (1.42 V) and good stability in comparison with the counterpart using commercial Pt/C catalyst. These findings provide a new avenue for designing the metal‐free electrocatalysts for various renewable energy storage and conversion technologies.
Optimized the Carrier Transport Path and Separation Efficiency of 2D/2D Heterojunction in Photoelectrochemical Water Splitting
Authors: Qian Hongxia , Liu Zhifeng , Zhang Bo , Li Junwei , Ya Jing
Published: January 2021

It is a promising strategy that the photoelectrode with high charge transfer rate and separation efficiency is designed in the photoelectrochemical (PEC) water splitting. Herein, the nanoflakes/nanoflakes (2D/2D) MoS2/ZnIn2S4 heterojunction is synthesized by two‐step hydrothermal methods. The carrier transport path in heterojunction is optimized through the Schottky contact calculated by density functional theory (DFT) and large specific surface area between 2D nanoflakes MoS2 and ZnIn2S4. Besides, the bimetallic oxyhydroxide NiFeOOH can be used as co‐catalyst to improve the separation of carriers. The results exhibit that MoS2/ZnIn2S4/NiFeOOH photoelectrode with dramatically enhanced photocurrent density of 0.74 mA/cm2 at 1.23 V versus the reversible hydrogen electrode (VRHE), which is 2.6 and 5.7 times higher than the bare MoS2 and ZnIn2S4, respectively. And it has the largest charge separation efficiency (ηbulk) (22.8 %) and charge transfer efficiency (ηsurface) (64.6 %) in the as‐prepared samples. This work provides a strategy for design of the photoelectrode with excellent charge transfer efficiency and separation efficiency in PEC water splitting.
Highly Dispersed Ruthenium Nanoparticles on Y2O3 as Superior Catalyst for Ammonia Decomposition
Authors: Feng Ji , Liu Lin , Ju Xiaohua , Wang Jiemin , Zhang Xilun , He Teng , Chen Ping
Published: January 2021

Design of highly active and stable catalysts for ammonia decomposition to produce COx‐free hydrogen is an urgent task for the utilization of NH3 as H2 carrier. Herein, Yttrium oxide (Y2O3) has been demonstrated to be capable of dispersing and stabilizing Ru nanoparticles as a functional support. Highly dispersed Ru nanoparticles on Y2O3 (Ru/Y2O3) was prepared and investigated as catalyst for NH3 decomposition. Under a relatively high weight gas hourly space velocity (30000 mL gcat−1 h−1), the Ru/Y2O3 with Ru content of 5 wt. % can catalyze NH3 decomposition with excellent catalytic activity and can achieve nearly complete NH3 conversion at 475 °C, superior to many typical oxides supported Ru catalysts. The Ru/Y2O3 catalyst is also highly stable for NH3 decomposition, and the activity can be well maintained in a period of 100 hours. Characterization results reveal that the superior catalytic performance of Ru/Y2O3 for NH3 decomposition reaction may originate from the high dispersion of Ru nanoparticles as well as their strong interaction with Y2O3 support. This work offers opportunity to achieve new kind of active and stable oxide supported Ru catalysts for NH3 decomposition reaction.
Tunnel‐Type Sodium Manganese Oxide Cathodes for Sodium‐Ion Batteries
Authors: Chae Munseok S. , Elias Yuval , Aurbach Doron
Published: January 2021

Tunnel‐type sodium manganese oxide is attracting attention as a cheap and earth‐abundant cathode material for sodium‐ion batteries, offering more stable cycling performance than other layered materials due to its special structural ordering. Developments and applications in aqueous and nonaqueous electrolyte solutions are reviewed, and problems and possible solutions are discussed in detail.
A Comparative Study on the Photophysical Properties of Anthocyanins and Pyranoanthocyanins
Authors: Phan Kim , De Meester Steven , Raes Katleen , De Clerck Karen , Van Speybroeck Veronique
Published: January 2021

Anthocyanins and pyranoanthocyanins are flavonoids that are present in various food products (e.g., fruit, vegetables, wine, etc.). The large chemical diversity amongst these molecules leads to compound‐specific properties such as color and stability towards external conditions. These properties are also attractive for food and non‐food applications. The photophysical experimental characterization is not easy as this generally demands advanced analytical techniques along with optimized separation procedures. Molecular modeling can provide insights into the fundamental understanding of the photophysical properties of these compounds in a uniform way for a broad set of compounds. However, the current literature is quite fragmented on this topic. Herein, a large set of 140 naturally derived anthocyanins was evaluated in a systematic way with three functionals (B3LYP, PBE0, and CAM‐B3LYP). The accuracy of these functionals was determined with experimental literatureλmax,visvalues. In addition toλmax,visvalues, time‐dependent (TD)‐DFT calculations also provided oscillator strengths, molar absorption coefficients, and orbital energies, which define whether specific natural anthocyanin‐based compounds can be deployed in food and non‐food applications such as food additives/colorants, textile dyeing, analytical standards, and dye‐sensitized solar cells (DSSCs).
f‐Block Phospholyl and Arsolyl Chemistry
Authors: Mills David P. , Evans Peter
Published: January 2021

The f‐block chemistry of phospholyl and arsolyl ligands, heavier p‐block analogues of substituted cyclopentadienyls (CpR, C5R5) where one or more CR groups are replaced by P or As atoms, is less developed than for lighter isoelectronic C5R5 rings. Heterocyclopentadienyl complexes can exhibit properties that complement and contrast with CpR chemistry. Given that there has been renewed interest in phospholyl and arsolyl f‐block chemistry in the last two decades, coinciding with a renaissance in f‐block solution chemistry, a review of this field is timely. Here, the syntheses of all structurally characterised examples of lanthanide and actinide phospholyl and arsolyl complexes to date are covered, including benzannulated derivatives, and together with group 3 complexes for completeness. The physicochemical properties of these complexes are reviewed, with the intention of motivating further research in this field.
Molecular Solar Thermal Batteries through Combination of Magnetic Nanoparticle Catalysts and Tailored Norbornadiene Photoswitches
Authors: Lorenz Patrick , Luchs Tobias , Hirsch Andreas
Published: January 2021

Cobalt catalysts are immobilized on the surface of iron oxide nanoparticles for the preparation of highly active quasi‐homogeneous catalysts toward an efficient release of photochemically stored energy in norbornadiene‐based photoswitches. The facile separation of the iron oxide nanoparticles through exploitation of the intrinsic magnetic properties of this material enables efficient cyclization of energy storage and release. Through the transition from cobalt (II) salphen to cobalt porphyrins, a 22.6‐fold increase in the catalytic efficiency of the QC‐NBD back‐conversion is achieved, with an initial TOF of up to 3.64 s−1 and excellent TON of over 3305. In addition, a series of novel “push–pull” functionalized norbornadiene derivatives is prepared, featuring excellent absorption properties with maxima up to 366 nm, quantum yields around 70 %, high energy storage capacities of up to 98.0 kJ mol−1, and outstanding thermal stability with t1/2 (25 °C) over 100 days. Finally, the energy storage potential of these molecular solar thermal (MOST) systems is harnessed in a heat release experiment. This demonstrates the potential of norbornadiene‐based photoswitches in combination with efficient magnetic catalysts for the generation of environmentally benign process heat.
Initial treatment of patients with thyroid cancer: Outcomes and factors associated with care at academic versus nonacademic cancer centers
Authors: Alhumaidi Hebah , Manochakian Rami , Cochuyt Jordan , Chindris Ana , Hodge David , Abdulazeez Mays F. , David Shishir , Biswas Suman , Aggarwal Chander Shekher , Smallridge Robert C. , Ailawadhi Sikander
Published: January 2021

Background

Factors associated with receiving initial care for thyroid cancer (TC) at academic centers (ACs) versus nonacademic centers (NACs) and their impact on patient outcomes have not been reported.

Methods

The National Cancer Database with TC cases from 2004 to 2013 was evaluated for association of type of center for initial care with socioeconomic factors and disease and treatment characteristics, as well as overall survival (OS; all‐cause mortality).

Results

The patients with TC (n = 200,824) included were predominantly women (74%), non‐Hispanic Whites (85%), and from metro areas (84%). Sixty percent received initial care at a NAC. There were no significant differences between treatment groups by age or gender. Among those treated at an AC, a higher proportion belonged to racial/ethnic minorities (16.5%) versus at a NAC (11.6%). Hormone therapy was used more in an AC versus a NAC (60% vs 47%). Patients with all TC pathologies combined had a lower likelihood of death when they received initial care at an AC (hazard ratio [HR], 0.948; P = .0006). Among individual pathologic subtypes, a lower likelihood of death was noted when initial care was received at an AC for follicular (HR, 0.828, P = .0010) and Hurthle cell cancers (HR, 792; P = .0008), as well as stage II papillary thyroid cancer (HR, 0.828; P = .0026), but not for other histopathologic subtypes.

Conclusions

Initial care at an AC was associated with lower likelihood of death for patients with TC, especially for those with follicular or Hurthle cell subtypes. Optimal resource use with consideration of patients' socioeconomic and demographic factors is imperative to ensure the most appropriate management of patients with TC in various treatment settings.