bluuebunny/crossref_metadata_2025 huggingface dataset:
Effects of Message Framing on Patients’ Perceptions and Willingness to Change to a Biosimilar in a Hypothetical Drug Switch
Authors: Gasteiger Chiara , Jones Annie S. K. , Kleinstäuber Maria , Lobo Maria , Horne Rob , Dalbeth Nicola , Petrie Keith J.
Published: June 2019

Objective

Patients often hold negative perceptions toward biosimilars that can create barriers to their uptake. Physicians also report uncertainty in how best to explain biosimilars. The aim of this study was to measure the effect of differently framed explanations on patients’ perceptions of and willingness to change to a biosimilar in a hypothetical drug switch.

Methods

Ninety‐six patients with rheumatic diseases taking an originator biologic were randomized to receive 1 of 4 biosimilar explanations: positive framing with and without an analogy, and negative framing with and without an analogy. Willingness to switch to a biosimilar, perceptions about biosimilars, and the effectiveness of the explanation were measured after the information delivery.

Results

Positive framing led to more participants being willing to switch (67%) than negative framing (46%). Framing significantly predicted willingness to switch to a biosimilar, with participants in the positive framing group being 2.36 times more willing to switch (P = 0.041). The positive framing group also reported significantly greater perceived efficacy of biosimilars (P = 0.046) and thought the explanation was more convincing (P = 0.030). The analogy did not enhance willingness to switch or increase understanding (P > 0.05).

Conclusion

Positive framing can improve perceptions of and willingness to switch to a biosimilar in patients currently taking biologic treatments.
Associations of Amino Acid and Acylcarnitine Profiles With Incident Hyperuricemia in Middle‐Aged and Older Chinese Individuals
Authors: Wang Feijie , Sun Liang , Zong Geng , Gao Xianfu , Zhang Huiping , Xiong Quan , Huo Shaofeng , Niu Zhenhua , Sun Qi , Zeng Rong , Lin Xu
Published: June 2019

Objective

Little is known about how metabolic perturbations are linked to hyperuricemia in the general population. Therefore we aimed to examine metabolomics profiles in relation to uric acid change and incident hyperuricemia.

Methods

This study included 1,621 community‐dwelling Chinese participants ages 50–70 years without hyperuricemia at baseline, with a mean duration of follow‐up of 6 years. A total of 56 metabolites (22 amino acids and 34 acylcarnitines) at baseline were quantified by gas or liquid chromatography coupled to mass spectrometry. Annual change in uric acid was calculated, and incident hyperuricemia was defined as plasma uric acid >420 μmoles/liter in men and >360 μmoles/liter in women.

Results

The mean ± SD annual change in uric acid was 9.6 ± 12.1 μmoles/liter and the incidence of hyperuricemia was 23.1% (375 of 1,621). After adjustment for conventional risk factors, 9 metabolites (cysteine, glutamine, phenylalanine, threonine, and long‐chain acylcarnitines C14:1OH, C18, C18:2, C20, and C20:4) were significantly associated with uric acid change (Bonferroni corrected P < 0.05) and with incident hyperuricemia (relative risks ranged from 1.14 to 1.21 per SD increment of metabolites; P < 0.05). A network analysis showed significant associations between the module containing long‐chain acylcarnitines and incident hyperuricemia. Moreover, levels of these 9 metabolites were specifically correlated with intake of foods, including red and processed meat or soy products.

Conclusion

Plasma cysteine, glutamine, phenylalanine, threonine, and long‐chain acylcarnitines are positively associated with incident hyperuricemia. The levels of these metabolites may be partially driven by intakes of meat and soy products that are associated with hyperuricemia.
Natural History of Radiographic First Metatarsophalangeal Joint Osteoarthritis: A Nineteen‐Year Population‐Based Cohort Study
Authors: Bowen Catherine , Gates Lucy , McQueen Peter , Daniels Maxine , Delmestri Antonella , Drechsler Wendy , Stephensen David , Doherty Michael , Arden Nigel
Published: June 2019

Objective

To assess the long‐term prevalence, natural history, progression, and incidence of radiographic first metatarsophalangeal (MTP) joint osteoarthritis (OA).

Methods

A longitudinal cohort design was used in which radiographic OA at the first MTP joint was investigated in participants from the Chingford 1,000 Women Study at year 6 (1995) and year 23 (2013–2015). Radiographic features of osteophytes (OPs) and/or joint space narrowing (JSN) at the first MTP joint were scored according to a validated foot atlas. Natural history was determined by the change in prevalence, incidence, progression, and worsening of OA in the first MTP joint.

Results

Complete case‐matched foot radiographic data were available for 193 of the women currently enrolled in the study (mean ± SD age 75.7 ± 5.2 years [range 69–90 years]). At the level of the first MTP joint, prevalence of OA at year 6 was 21.76% in the left and 24.35% in the right; at year 23, it was 23.83% in the left and 32.64% in the right. Over the 19‐year period, 13.5% of the women developed incident OA in the right first MTP joint and 8.3% in the left. Both progression and worsening of OA were more evident for OPs and in the right first MTP joints.

Conclusion

In this study of the natural history of radiographic first MTP joint OA, which to our knowledge is the longest study to date, the prevalence and incidence of first MTP joint OA increased over a 19‐year period. Progression and/or worsening of OA at the first MTP joint over time appears to be driven by OP development rather than JSN, which suggests a biomechanical cause.
Linear Dichroism Conversion in Quasi‐1D Perovskite Chalcogenide
Authors: Wu Jiangbin , Cong Xin , Niu Shanyuan , Liu Fanxin , Zhao Huan , Du Zhonghao , Ravichandran Jayakanth , Tan Ping‐Heng , Wang Han
Published: June 2019

Anisotropic photonic materials with linear dichroism are crucial components in many sensing, imaging, and communication applications. Such materials play an important role as polarizers, filters, and waveplates in photonic devices and circuits. Conventional crystalline materials with optical anisotropy typically show unidirectional linear dichroism over a broad wavelength range. The linear dichroism conversion phenomenon has not been observed in crystalline materials. The investigation of the unique linear dichroism conversion phenomenon in quasi‐1D hexagonal perovskite chalcogenide BaTiS3is reported. This material shows a record level of optical anisotropy within the visible wavelength range. In contrast to conventional anisotropic optical materials, the linear dichroism polarity in BaTiS3makes an orthogonal change at an optical wavelength corresponding to the photon energy of 1.78 eV. First‐principles calculations reveal that this anomalous linear dichroism conversion behavior originates from the different selection rules of the parallel energy bands in the BaTiS3material. Wavelength‐dependent polarized Raman spectroscopy further confirms this phenomenon. Such a material, with linear dichroism conversion properties, could facilitate the sensing and control of the energy and polarization of light, and lead to novel photonic devices such as polarization‐wavelength selective detectors and lasers for multispectral imaging, sensing, and optical communication applications.
Solution‐Processed Organic Transistors with Excellent Electrical Stability under Ambient Conditions
Authors: Kettner Michel , Mi Zhou , Kälblein Daniel , Brill Jochen , Blom Paul W. M. , Weitz R. Thomas
Published: June 2019

The application of organic transistors in backplane technology is strongly hindered by their perceived instability to current and bias stress. High‐performance polymer organic semiconductors with unprecedented electrical stability under ambient conditions are demonstrated. Remarkably, these unencapsulated, solution‐processed organic transistors show slightly better bias stress stability than even the the current benchmarks for flat panel displays, a‐Si and IGZO. Moreover, the transistors show a high mobility of about 3 cm2 V−1 s−1 and high on/off ratio of 106, combined with excellent reproducibility. These results demonstrate that solution‐processed organic thin‐film transistors have reached a stage that makes them suitable for commercialization in flexible backplane technology.
Ethylene Carbonate‐Free Electrolytes for High‐Nickel Layered Oxide Cathodes in Lithium‐Ion Batteries
Authors: Li Wangda , Dolocan Andrei , Li Jianyu , Xie Qiang , Manthiram Arumugam
Published: June 2019

Layered lithium nickel oxide (LiNiO2) can provide very high energy density among intercalation cathode materials for lithium‐ion batteries, but suffers from poor cycle life and thermal‐abuse tolerance with large lithium utilization. In addition to stabilization of the active cathode material, a concurrent development of electrolyte systems of better compatibility is critical to overcome these limitations for practical applications. Here, with nonaqueous electrolytes based on exclusively aprotic acyclic carbonates free of ethylene carbonate (EC), superior electrochemical and thermal characteristics are obtained with an ultrahigh‐nickel cathode (LiNi0.94Co0.06O2), capable of reaching a 235 mA h g−1 specific capacity. Pouch‐type graphite|LiNi0.94Co0.06O2 cells in EC‐free electrolytes withstand several hundred charge–discharge cycles with minor degradation at both ambient and elevated temperatures. In thermal‐abuse tests, the cathode at full charge, while reacting aggressively with EC‐based electrolytes below 200 °C, shows suppressed self‐heating without EC. Through 3D chemical and structural analyses, the intriguing impact of EC is visualized in aggravating unwanted surface parasitic reactions and irreversible bulk structural degradation of the cathode at high voltages. These results provide important insights in designing high‐energy electrodes for long‐lasting and reliable lithium‐ion batteries.
Breast firmness is of greater importance for women's attractiveness than breast size
Authors: Kościński Krzysztof
Published: June 2019

Objectives

Male preferences are believed to have played a role in the evolution of permanently enlarged breasts in human females. Although breast size and shape are proven to affect women's attractiveness, their relative importance has not been investigated thus far. We aime to address this gap.

Methods

We prepared two sets of stimuli, each comprising 49 high‐quality color images of a topless woman in a three‐quarter view that varied in breast size (from 1 to 7) and firmness (from 1 to 7). Set A depicted the glandular ptosis (ie, breast shape being manipulated but the nipple always directed forward), while Set B depicted true ptosis (both breast shape and nipple position being manipulated). Participants (aged 18‐45) were assigned to Set A (62 women, 60 men) or Set B (76 women, 52 men). First, each participant indicated the most attractive woman in the set of images. Next, the participant chose the more attractive woman from pairs in which one female deviated from the participant's ideal in breast size and the other in breast firmness.

Results

Both men and women preferred breasts of average or slightly above‐average size and high or extreme firmness. Glandular ptosis was as important for attractiveness as breast size, but true ptosis was of much greater importance. Men preferred slightly bigger breasts than women.

Conclusions

Further attempts to explain evolution of permanent breasts in human females should give greater attention to breast shape than has previously been the case.
Efficacy of clopidogrel for stroke depends on CYP2C19 genotype and risk profile
Authors: Xu Jie , Wang Anxin , Wangqin Runqi , Mo Jinglin , Chen Zimo , Dai Liye , Meng Xia , Zhao Xingquan , Wang Yilong , Li Hao , Chen Wei , Xian Ying , Wang Yongjun ,   for the CHANCE investigators
Published: June 2019

Objective

Dual antiplatelet therapy (DAT) with clopidogrel plus aspirin has been suggested by American Heart Association/American Stroke Association guidelines for minor stroke (MS) and transient ischemic attack (TIA) patients. The purpose of this study was to find the potential subgroups that benefit from DAT. We aimed to compare the efficacy of clopidogrel–aspirin therapy with that of aspirin therapy in MS/TIA patients stratified by CYP2C19 genotype and risk profiles.

Methods

CYP2C19 loss‐of‐function allele (LoFA) carriers were defined as patients with LoFA of either *2 or *3. Low‐ and high‐risk profile was defined as Essen Stroke Risk Score (ESRS) <3 and ≥3, respectively. Stroke recurrence at 1 year was considered primary outcome.

Results

Of a total 2,933 MS/TIA patients, there were 1,726 (58.8%) LoFA carriers and 1,068 (36.4%) patients at high risk (ESRS ≥3). No significant difference for stroke recurrence between the clopidogrel–aspirin group and aspirin alone group was found in LoFA carriers (11.2% vs 13.3%, hazard ratio [HR] = 0.83, 95% confidence interval [CI] = 0.64~1.09). In stratified analyses by CYP2C19 genotype and ESRS, HRs (95% CIs) of the clopidogrel–aspirin therapy for stroke recurrence were 1.00 (0.70~1.42), 0.63 (0.41~0.97), 0.62 (0.40~0.96), and 0.52 (0.31~0.88) among subgroups of LoFA carriers at low risk, LoFA carriers at high risk, LoFA noncarriers at low risk, and LoFA noncarriers at high risk, respectively, with p = 0.021 for interaction.

Interpretation

Overall, LoFA carriers do not benefit from DAT, but there is significant benefit for LoFA carriers who are at high risk. The benefit of clopidogrel in Chinese MS/TIA patients depends on CYP2C19 genotype and risk profile. ANN NEUROL 2019;86:419–426
Double Negatively Curved C70 Growth through a Heptagon‐Involving Pathway
Authors: Zhong Yuan‐Yuan , Chen Zuo‐Chang , Du Peng , Cui Cun‐Hao , Tian Han‐Rui , Shi Xiang‐Mei , Deng Shun‐Liu , Gao Fei , Zhang Qianyan , Gao Cong‐Li , Zhang Xin , Xie Su‐Yuan , Huang Rong‐Bin , Zheng Lan‐Sun
Published: June 2019

All previously reported C70 isomers have positive curvature and contain 12 pentagons in addition to hexagons. Herein, we report a new C70 species with two negatively curved heptagon moieties and 14 pentagons. This unconventional heptafullerene[70] containing two symmetric heptagons, referred to as dihept‐C70, grows in the carbon arc by a theoretically supported pathway in which the carbon cluster of a previously reported C66 species undergoes successive C2 insertion via a known heptafullerene[68] intermediate with low energy barriers. As identified by X‐ray crystallography, the occurrence of heptagons facilitates a reduction in the angle of the π‐orbital axis vector in the fused pentagons to stabilize dihept‐C70. Chlorination at the intersection of a heptagon and two adjacent pentagons can greatly enlarge the HOMO–LUMO gap, which makes dihept‐C70Cl6 isolable by chromatography. The synthesis of dihept‐C70Cl6 offers precious clues with respect to the fullerene formation mechanism in the carbon‐clustering process.
Photochemical C−H Amination of Ethers and Geminal Difunctionalization Reactions in One Pot
Authors: Hernández‐Guerra Daniel , Hlavačková Anna , Pramthaisong Chiranan , Vespoli Ilaria , Pohl Radek , Slanina Tomáš , Jahn Ullrich
Published: June 2019

A mild, atom‐economic, and metal‐free α‐C−H amination of ethers using relatively stable nonafluorobutanesulfonyl (nonaflyl, Nf) azide as the aminating reagent to give N‐sulfonyl hemiaminals is reported. This enables unprecedented C(sp3) difunctionalization reactions, leading to diverse functionalized amino group containing compounds starting from simple ethers in one pot.
Long‐Lived Room‐Temperature Phosphorescence for Visual and Quantitative Detection of Oxygen
Authors: Zhou Yusheng , Qin Wei , Du Cheng , Gao Haiyang , Zhu Fangming , Liang Guodong
Published: June 2019

An unconventional organic molecule (TBBU) showing obvious long‐lived room temperature phosphorescence (RTP) is reported. X‐ray single crystal analysis demonstrates that TBBU molecules are packed in a unique fashion with side‐by‐side arranged intermolecular aromatic rings, which is entirely different from the RTP molecules reported to date. Theoretical calculations verify that the extraordinary intermolecular interaction between neighboring molecules plays an important role in RTP of TBBU crystals. More importantly, the polymer film doped with TBBU inherits its distinctive RTP property, which is highly sensitive to oxygen. The color of the doped film changes and its RTP lifetime drops abruptly through a dynamic collisional quenching mechanism with increasing oxygen fraction, enabling visual and quantitative detection of oxygen. Through analyzing the grayscale of the phosphorescence images, a facile method is developed for rapid, visual, and quantitative detection of oxygen in the air.
Main path analysis on cyclic citation networks
Authors: Jiang Xiaorui , Zhu Xinghao , Chen Jingqiang
Published: June 2019

Main path analysis is a famous network‐based method for understanding the evolution of a scientific domain. Most existing methods have two steps, weighting citation arcs based on search path counting and exploring main paths in a greedy fashion, with the assumption that citation networks are acyclic. The only available proposal that avoids manual cycle removal is to preprint transform a cyclic network to an acyclic counterpart. Through a detailed discussion about the issues concerning this approach, especially deriving the “de‐preprinted” main paths for the original network, this article proposes an alternative solution with two‐fold contributions. Based on the argument that a publication cannot influence itself through a citation cycle, the SimSPC algorithm is proposed to weight citation arcs by counting simple search paths. A set of algorithms are further proposed for main path exploration and extraction directly from cyclic networks based on a novel data structure main path tree. The experiments on two cyclic citation networks demonstrate the usefulness of the alternative solution. In the meanwhile, experiments show that publications in strongly connected components may sit on the turning points of main path networks, which signifies the necessity of a systematic way of dealing with citation cycles.
Mouse whole embryo culture: Evaluating the requirement for rat serum as culture medium
Authors: Culshaw Lucy H. , Savery Dawn , Greene Nicholas D. E. , Copp Andrew J.
Published: June 2019

Background

Whole embryo culture is a valuable research method in mammalian developmental biology and birth defects research, enabling longitudinal studies of explanted organogenesis‐stage rodent embryos. Rat serum is the primary culture medium, and can sustain growth and development over limited periods as in utero. However, the cost, labor, and time to produce culture serum are factors limiting the uptake of the methodology. The goal of replacing or at least reducing rat serum usage in culture would be in accordance with the principles of “replacement, reduction, and refinement” of animals in research (the 3Rs).

Methods

We performed cultures of mouse embryos for 24 hr from embryonic day 8.5 in serum‐free media or in rat serum diluted with defined media, compared with 100% rat serum. Developmental parameters scored after culture included yolk sac circulation, dorsal axial length, somite number, protein content, and completion of cranial neural tube closure.

Results

A literature review revealed use of both serum‐free and diluted rat serum‐based media in whole embryo culture studies, but with almost no formal comparisons of culture success against 100% rat serum. Two serum‐free media were tested, but neither could sustain development as in 100% rat serum. Dilution of rat serum 1:1 with Glasgow Minimum Essential Medium plus defined supplements supported growth and development as well as whole rat serum, whereas other diluent media yielded substandard outcomes.

Conclusion

Rat serum usage cannot be avoided, to achieve high quality mouse embryo cultures, but rat usage can be reduced using medium containing diluted serum.
The Performance Investigation of Bimodal Cation Exchange/Hydrophilic Interaction Liquid Chromatography–Electrospray Ionization Mass Spectrometry by Modifying Mobile Phase Composition in Amino Acid Separation
Authors: Lee Seunghwa , Kim Hee Won , Han Sang Moon , Han Sang Yun , Kim Byungjoo , Moon Myeong Hee , Kim Ki Hun , Lee Jaeick
Published: June 2019

Owing to its unique selectivity, mixed‐mode chromatography (MMC) has been extended to the analysis of biological fluids. Among various MMC applications, ion exchange/hydrophilic interaction liquid chromatography (IEX/HILIC) is particularly beneficial for the analysis of polar compounds without derivatization or ion pairing. Nevertheless, no practical information about the retention behavior is discussed. In this study, the chromatographic behavior of amino acids in a CEX/hydrophilic interaction mixed‐mode column via the modification of the mobile phase was investigated. A low buffer salt concentration led to increased retention; particularly, positively charged amino acids were not eluted by excessive interactions with the negatively charged stationary phase at a moderate salt concentration (<20 mM). An acid modifier of formic acid or acetic acid exhibited a similar effect on the separation, and a low acid concentration (<0.5%) led to peak broadening by additional ion exchange with a silanol group at high pH. With respect to the composition of organic solvents, aprotic solvents such as tetrahydrofuran or acetonitrile afforded appropriate retention. However, protic solvents led to the considerably reduced retention except positively charged amino acids. Novel, practical information for the optimization or development of applications with a CEX/HILIC column for polar analytes such as amino acids was obtained.
PLGA Microsphere Addition to 1‐Hydroxy‐2‐napthoic Acid Enhances the Sustained Release of Escitalopram
Authors: Kang Seok Hee , Kim Bo Yeon , Kwon Hyuk Il , Kim Hye Min , Cho Sun Hang , Park Jeong Sook , Han Hee Dong , Shin Byung Cheol
Published: June 2019

Escitalopram (ET), a selective serotonin reuptake inhibitor, has been utilized for the treatment of depression and anxiety. However, ET has serious side effects such as nausea, leading to an increased therapeutic dose, needing multiple administrations. Therefore, to overcome these issues, we developed ET encapsulated poly (d,l‐lactic‐co‐glycolic acid) (PLGA) microspheres (PLGA‐MS) as a sustained release carrier to maintain therapeutic efficacy. The mean particle size of the PLGA‐MSs was measured by microscopy. Loading efficiency was measured by high performance liquid chromatography (HPLC). Morphologies were determined by microscopy and scanning electron microscopy (SEM). Differential scanning calorimetry (DSC) was used for thermal analysis and glass transition temperature determination. Mean particle size of the ET‐loaded PLGA‐MSs was 129 ± 14 μm, loading efficiency was 36.8 ± 9.1%, and encapsulation efficiency was up to 70.6 ± 6.8%. Loading efficiency and encapsulation efficiency were increased by the addition of 1‐hydroxy‐2‐naphthoic acid (HNA). ET was released from PLGA‐MS for 4 weeks, which was longer than ET release from PLGA‐MS without the addition of HNA. Taken together, we demonstrate the optimum condition for sustained release of ET from PLGA‐MS with the addition of HNA, and that this approach may be useful for depression therapy.
Green innovation to respond to environmental regulation: How external knowledge adoption and green absorptive capacity matter?
Authors: Zhang Jianming , Liang Gongqian , Feng Taiwen , Yuan Chunlin , Jiang Wenbo
Published: June 2019

Although environmental regulations have been considered as important forces of conducting green innovation, how and under what conditions they affect green innovation are still unclear. Drawing from institutional theory, this study used survey data from 237 manufacturing firms in China to investigate how two dimensions of environmental regulations (i.e., command and control regulation and market‐based regulation) affect green product innovation and green process innovation. Further, this article examined the mediating role of external knowledge adoption and the moderating role of green absorptive capacity. Our results indicate that both command and control regulation and market‐based regulation have positive influences on external knowledge adoption. External knowledge adoption fully mediates these positive relationships. In addition, green absorptive capacity only strengthens the positive impact of market‐based regulation on external knowledge adoption. Our study contributes to institutional theory and green innovation literature.
In vitro cytotoxic activity of microalgal extracts loaded nano–micro particles produced via electrospraying and microemulsion methods
Authors: Karakaş Canan Y. , Tekarslan Şahin Hande , İnan Benan , Özçimen Didem , Erginer Yıldız Ö.
Published: June 2019

Reactive oxygen species can bind protein, DNA, lipids, and carbohydrates and thus cause an oxidation reaction that induces various syndromes such as cardiovascular diseases, degenerative disease, and cancer types in the human body. Bioactive compounds, such as PUFA, EPA, DHA, and carotenoids in algae, have a chain ring and protect the tissue from chemical damage and reverse the symptoms of some diseases. Algal bioactives also have various biological properties such as anticoagulants, antiviral, antiangiogenic, antitumor, anti‐inflammatory, antioxidant, antiproliferative, and immune modulation properties. This study aimed to show in vitro cytotoxic activity effect ofChlorella protothecoidesandNannochloropsis oculatamicroalgal extracts loaded nano–microparticles on A‐172 (Homo sapiensbrain glioblastoma) and HCT‐116 (H. sapienscolon colorectal carcinoma) cell lines because of the increasing importance of algal biotechnology. MTT viability tests were performed on HUVEC, A172, and HCT 116 cells with particles obtained at optimum process parameters. The cell viability rates of encapsulated particles were also compared with pure algae extracts. Microalgal extracts loaded nano–micro particles showed very promising results for cytotoxic effect on cancer cells.
Synthetic Phosphodiester‐Linked 4‐Amino‐4‐deoxy‐l‐arabinose Derivatives Demonstrate that ArnT is an Inverting Aminoarabinosyl Transferase
Authors: Olagnon Charlotte , Monjaras Feria Julia , Grünwald‐Gruber Clemens , Blaukopf Markus , Valvano Miguel A. , Kosma Paul
Published: June 2019

4‐Amino‐4‐deoxy‐l‐arabinopyranose (Ara4N) residues have been linked to antibiotic resistance due to reduction of the negative charge in the lipid A and core regions of the bacterial lipopolysaccharide (LPS). To study the enzymatic transfer of Ara4N onto lipid A, which is catalysed by the ArnT transferase, we chemically synthesised a series of anomeric phosphodiester‐linked lipid Ara4N derivatives containing linear aliphatic chains as well as E‐ and Z‐configured monoterpene units. Coupling reactions were based on sugar‐derived H‐phosphonates, followed by oxidation and global deprotection. The enzymatic Ara4N transfer was performed in vitro with crude membranes from a deep‐rough mutant from Escherichia coli as acceptor. Product formation was detected by TLC and LC‐ESI‐QTOF mass spectrometry. Out of seven analogues tested, only the α‐neryl derivative was accepted by the Burkholderia cenocepacia ArnT protein, leading to substitution of the Kdo2‐lipid A acceptor and thus affording evidence that ArnT is an inverting glycosyl transferase that requires the Z‐configured double bond next to the anomeric phosphate moiety. This approach provides an easily accessible donor substrate for biochemical studies relating to modifications of bacterial LPS that modulate antibiotic resistance and immune recognition.
Gender‐related differences in patients undergoing transcatheter mitral valve interventions in clinical practice: 1‐year results from the German TRAMI registry
Authors: Werner Nicolas , Puls Miriam , Baldus Stephan , Lubos Edith , Bekeredjian Raffi , Sievert Horst , Schofer Joachim , Kuck Karl‐Heinz , Möllmann Helge , Hehrlein Christoph , Nickenig Georg , Boekstegers Peter , Ouarrak Taoufik , Senges Jochen , Zahn Ralf ,   for the German Transcatheter Mitral Valve Intervention (TRAMI) investigators
Published: June 2019

Objectives

Information on gender‐related differences in terms of baseline characteristics and clinical outcome of patients undergoing MitraClip® implantation in daily clinical practice have been studied in smaller populations previously. This study sought to additionally evaluate gender‐related differences in a larger German real‐world patient population.

Methods and results

We analyzed data from the prospective and multicenter German TRAMI Registry. Between 08/2010 and 07/2013 327 women and 501 men underwent MitraClip® implantation for significant mitral valve regurgitation. Female patients were significantly older and showed higher rates of frailty compared to men. In contrast, men had significantly higher rates of comorbidities compared to women. The majority of patients underwent MitraClip® implantation for secondary mitral regurgitation, with no significant gender‐related differences. MitraClip® treatment was equally effective in terms of procedural results and residual mitral regurgitation in women and men and complication rates were low. However, in this real‐world analysis severe bleeding complications were significantly higher in women (p = .02) and re‐intervention rates were significantly higher in men after MitraClip® treatment (p = .02). Women showed less improvement in functional NYHA class after MitraClip® treatment compared to men at 1‐year follow‐up (FU; p < .001). No significant differences between female and male patients were found in 1‐year mortality and in re‐hospitalization rates.

Conclusion

In this analysis from a large prospective, multicenter real‐world registry MitraClip® implantation is safe and effective for treatment of significant mitral regurgitation with equal postprocedural results and mortality rates during 1‐year follow‐up. Men and women showed a persisting and significant clinical benefit at 1‐year FU after treatment. Complication and re‐intervention rates were low. Additional studies are needed to further evaluate our findings on increased bleeding complications and decreased functional improvement in women at 1‐year follow‐up after MitraClip® therapy.
Successful catheter cryoablation for premature ventricular contractions originating from the para‐Hisian region
Authors: Suzuki George , Yotsukura Akihiko , Nanbu Tadafumi , Sakurai Masayuki
Published: June 2019

We achieved successful catheter cryoablation in a patient with para‐Hisian premature ventricular contractions (PVCs) without conduction disturbance using the freeze‐thaw‐freeze method while observing the atrial‐His bundle interval. Cryoablation could be considered an alternative to radiofrequency ablation for patients with para‐Hisian PVCs.
Electrochemical‐/Photoredox Aspects of Transition Metal‐Catalyzed Directed C−H Bond Activation
Authors: Dwivedi Vikas , Kalsi Deepti , Sundararaju Basker
Published: June 2019

C−H activation and functionalization have caused a paradigm shift in molecular design as a result of its selective and atom‐economical nature. Despite significant major advances, C−H functionalization regime had the disadvantage of employing (super) stoichiometric amounts of expensive and toxic metal oxidants for oxidative functionalization. Hence, various protocols were introduced to improve the sustainability of C−H bond functionalization, such as employing molecular oxygen, metal oxidants or tethered oxidants that get cleaved during the reaction, in addition to the use of suitable solvents or additives. The most recent and proficient advance is the use of electro‐ or photo‐redox catalysis. In this Review, we highlight the recent advances towards a green catalytic approach for oxidative C−H bond functionalization using light and photosensitizers or electricity as sources of oxidant to regenerate the active species.
Data Driven Determination of Reaction Conditions in Oxidative Coupling of Methane via Machine Learning
Authors: Ohyama Junya , Nishimura Shun , Takahashi Keisuke
Published: June 2019

The challenge in catalytic reactions lies within its complexity coming from high dimensional experimental factors. In order to solve such complexity, machine learning is implemented to treat experimental conditions in high dimensions. Oxidative coupling of methane, methane to C2 compounds (ethylene and ethane), is chosen as the prototype reaction where 156 data consisting of various experimental conditions is prepared. Machine learning reveals that the relationship between experimental conditions and C2 yield is non‐linear matter. In particular, extreme tree regression is found to accurately reproduce the experimental data. In addition, machine learning predictions can be a good indicator for designing experiments. Thus, machine learning can be a powerful approach towards understanding and determining experimental conditions in high dimension.
Facile Synthesis of Peapod‐Like Cu3Ge/Ge@C as a High‐Capacity and Long‐Life Anode for Li‐Ion Batteries
Authors: Wang Xinyi , Xu Xijun , Liu Jun , Liu Zhengbo , Shen Jiadong , Li Fangkun , Hu Renzong , Yang Lichun , Ouyang Liuzhang , Zhu Min
Published: June 2019

As anode materials for high‐performance Li‐ion batteries, peapod‐like Ge‐based composites, including Ge, a Li‐inactive conducting Cu3Ge, and a porous carbon matrix are synthesized simply by annealing CuGeO3@dopamine in a H2/Ar atmosphere. The introduction of the carbon layer and inactive alloying phase Cu3Ge not only enhances the electrical conductivity of the Ge anode, but also reduces the volume change of Ge during the cell cycle as a buffer. In particular, the anode of this peapod‐like Cu3Ge/Ge@C shows an excellent long cycle life as well as outstanding capacity performance, with a discharge specific capacity up to 934 mA h g−1 after 500 cycles.
Effects of Spacers on Photoinduced Reversible Solid‐to‐Liquid Transitions of Azobenzene‐Containing Polymers
Authors: Weis Philipp , Hess Andreas , Kircher Gunnar , Huang Shilin , Auernhammer Günter K. , Koynov Kaloian , Butt Hans‐Jürgen , Wu Si
Published: June 2019

Photoisomerization in some azobenzene‐containing polymers (azopolymers) results in reversible solid‐to‐liquid transitions becausetrans‐ andcis‐azopolymers have different glass transition temperatures. This property enables photoinduced healing and processing of azopolymers with high spatiotemporal resolution. However, a general lack of knowledge about the influence of the polymer structure on photoinduced reversible solid‐to‐liquid transitions hinders the design of such novel polymers. Herein, the synthesis and photoresponsive behavior of new azopolymers with different lengths of spacers between the polymer backbone and the azobenzene group on the side chain are reported. Azopolymers with no and 20 methylene spacers did not show photoinduced solid‐to‐liquid transitions. Azopolymers with 6 or 12 methylene spacers showed photoinduced solid‐to‐liquid transitions. This study demonstrates that spacers are essential for azopolymers with photoinduced reversible solid‐to‐liquid transitions, and thus, gives an insight into how to design azopolymers for photoinduced healing and processing.
The Distinct Conformational Landscapes of 4S‐Substituted Prolines That Promote an endo Ring Pucker
Authors: Costantini Nicholas V. , Ganguly Himal K. , Martin Maxwell I. , Wenzell Nicole A. , Yap Glenn P. A. , Zondlo Neal J.
Published: June 2019

4‐Substitution on proline directly impacts protein main chain conformational preferences. The structural effects of N‐acyl substitution and of 4‐substitution were examined by NMR spectroscopy and X‐ray crystallography on minimal molecules with a proline 4S‐nitrobenzoate. The effects of N‐acyl substitution on conformation were attenuated in the 4S‐nitrobenzoate context, due to the minimal role of the n→π* interaction in stabilizing extended conformations. By X‐ray crystallography, an extended conformation was observed for most molecules. The formyl derivative adopted a δ conformation that is observed at the i+2 position of β‐turns. Computational analysis indicated that the structures observed crystallographically represent the inherent conformational preferences of 4S‐substituted prolines with electron‐withdrawing 4‐position substituents. The divergent conformational preferences of 4R‐ and 4S‐substituted prolines suggest their wider structure‐specific application in molecular design. In particular, the proline endo ring pucker favored by 4S‐substituted prolines uniquely promotes the δ conformation [(ϕ, ψ) ≈(−80°, 0°)] found in β‐turns. In contrast to other acyl capping groups, the pivaloyl group strongly promoted trans amide bond and polyproline II helix conformation, with a close n→π* interaction in the crystalline state, despite the endo ring pucker, suggesting its special capabilities in promoting compact conformations in ϕ due to its strongly electron‐donating character.
High immune cytolytic activity in tumor‐free tongue tissue confers better prognosis in patients with squamous cell carcinoma of the oral tongue
Authors: Gu Xiaolian , Boldrup Linda , Coates Philip J , Fahraeus Robin , Wang Lixiao , Wilms Torben , Norberg‐Spaak Lena , Sgaramella Nicola , Nylander Karin
Published: June 2019

Immune cells and cytolytic activity within the tumor microenvironment are being intensively studied. Through transcriptome profiling, immune cell enumeration using the xCell tool and cytolytic activity quantification according to granzyme A (GZMA) and perforin (PRF1) mRNA levels, we investigated immunoreactivity in tumor and/or tumor‐free tongue tissue samples from 31 patients with squamous cell carcinoma of the oral tongue and 14 healthy individuals (control tongue tissues). We found significantly altered immune cell compositions (p < 0.001) and elevated cytolytic activity (p < 0.001) in tumor compared to tumor‐free samples, and altered infiltration of a subset of immune cells (e.g. CD8+ T cells, p < 0.01) as well as increased cytolytic activity (p < 0.001) in tumor‐free compared to control samples. Controlling for patient age at diagnosis and tumor stage, Cox regression analysis showed that high cytolytic activity in tumor‐free samples associated with improved disease‐free survival (hazard ratio= 4.20, 95% CI = 1.09–16.20, p = 0.037). However, the degree of cytolytic activity in tumor samples did not provide prognostic information. Taken together, our results show the presence of cancer‐related immune responses in clinically tumor‐free tongue in patients with squamous cell carcinoma of the oral tongue. Measuring cytolytic activity in tumor‐free tongue samples contralateral to tumor might thus be an effective approach to predict clinical outcome.
Porous Cupric Oxide: Efficient Photocathode for Photoelectrochemical Water Splitting
Authors: Basu Mrinmoyee
Published: June 2019

Photoelectrochemical (PEC) water splitting is considered as an effective approach to generate hydrogen at the cathode, and can be used as a means to generate green energy. A simple electrochemical deposition technique is developed for the synthesis of CuO nanostructures. CuO with different morphologies like porous 2D sheets, porous bipyramids, particles, and spheres are developed after oxidation of the electrodeposited Cu nanostructure. Among them, CuO porous 2D nanosheets show the best activity as photocathode towards PEC water splitting due to the high light absorbance and high electrochemically active surface area (ECSA). CuO porous 2D sheets contains three times higher ECSA compared to CuO particles, indicating their higher electrochemical activity. CuO porous 2D sheets can generate a current density of 3.09 mA cm−2 at an applied potential of −0.1 V vs RHE in 0.5 M Na2SO4 solution. Furthermore, Mott‐Schottky measurements demonstrate that CuO porous 2D sheets possess high carrier density, 8.18×1020 cm−3, and a high flat band potential of 1.215 V vs. RHE. Thus, CuO porous 2D sheets have excellent conductivity and a high degree of band bending. After PEC water splitting, XRD analysis was carried out to reconfirm the photostability of the CuO porous 2D sheets. It may be due to the higher charge transportation in the porous structures.
Density of Feed Rod Dependence of the PrB6 Single Crystal Grown by the Optical Floating Zone Technique
Authors: Wang Yan , Zhao Jingjing , Yang Xinyu , Cheng Hefa , Xu Bing , Ning Shuyu , Zhang Jiuxing
Published: June 2019

Rare‐earth hexaboride single crystals praseodymium hexaboride (PrB6) are successfully grown by the optical floating zone technique using the feed rods with different densities sintered by spark plasma sintering (SPS). Single crystal X‐ray diffraction and transmission electron microscopy analysis have found that the as‐grown PrB6 adopts a single crystalline structure which has a primitive cubic structure, and has grown along the <100> direction. Particular attentions are given to the effect of density of feed rod on the crystal quality and thermionic emission performance of PrB6 single crystals. The result of X‐ray rocking curve indicates that the quality of the as‐grown single crystals get better with increase in the density of feed rod, and an ultralow full‐width at half‐maximum of 0.066°, confirming the good crystal integrality, is resulted from the single crystal using the feed rod with relative density of 97.17%. Similarly, the result of thermionic emission shows that the PrB6 single crystal grown here using a high‐density feed rod has a large current density. The density of feed rod plays an important role in PrB6 single crystal growth by the optical floating zone technique.
Synthesis of Biomass‐Derived Ethers for Use as Fuels and Lubricants
Authors: Rorrer Julie E. , Bell Alexis T. , Toste F. Dean
Published: June 2019

Ethers synthesized from biomass‐derived compounds have exceptional properties as fuels, lubricants, and specialty chemicals and can serve as replacements for petroleum‐derived products. Recent efforts have identified heterogeneous catalysts for the selective synthesis of ethers from alcohols, aldehydes, ketones, furans, esters, olefins, carboxylic acids, and other molecules derived from biomass. This Review highlights the scope of etherification reactions and provides insights into the choice of catalysts and reaction conditions best suited for producing targeted ethers from the available starting materials. First, the properties of ethers for specific applications and the methods by which synthons for ether synthesis can be obtained from biomass are discussed. Then the progress that has been made on the synthesis of ethers via the following methods is summarized: direct etherification of alcohols; reductive etherification of alcohols with aldehydes or ketones; etherification of furanic compounds, esters, and carboxylic acids; and the addition of alcohols to olefins. Next, the mechanisms of these reactions and catalyst properties required to promote them are discussed, with the goal of understanding how reaction conditions can be tuned to optimize catalyst activity and selectivity towards desired ethers. The Review closes by examining the tradeoffs between catalyst selectivity, activity, stability, and reaction conditions required to achieve the most economically and environmentally favorable routes to biomass‐derived ethers.
Impacts of “supermoon” events on the physiology of a wild bird
Authors: Portugal Steven J. , White Craig R. , Frappell Peter B. , Green Jonathan A. , Butler Patrick J.
Published: June 2019

The position of the Moon in relation to the Earth and the Sun gives rise to several predictable cycles, and natural changes in nighttime light intensity are known to cause alterations to physiological processes and behaviors in many animals. The limited research undertaken to date on the physiological responses of animals to the lunar illumination has exclusively focused on the synodic lunar cycle (full moon to full moon, or moon phase) but the moon's orbit—its distance from the Earth—may also be relevant. Every month, the moon moves from apogee, its most distant point from Earth—and then to perigee, its closest point to Earth. Here, we studied wild barnacle geese (Branta leucopsis) to investigate the influence of multiple interacting lunar cycles on the physiology of diurnally active animals. Our study, which uses biologging technology to continually monitor body temperature and heart rate for an entire annual cycle, asks whether there is evidence for a physiological response to natural cycles in lunar brightness in wild birds, particularly “supermoon” phenomena, where perigee coincides with a full moon. There was a three‐way interaction between lunar phase, lunar distance, and cloud cover as predictors of nighttime mean body temperature, such that body temperature was highest on clear nights when the full moon coincided with perigee moon. Our study is the first to report the physiological responses of wild birds to “supermoon” events; the wild geese responded to the combination of two independent lunar cycles, by significantly increasing their body temperature at night. That wild birds respond to natural fluctuations in nighttime ambient light levels support the documented responses of many species to anthropogenic sources of artificial light, that birds seem unable to override. As most biological systems are arguably organized foremost by light, this suggests that any interactions between lunar cycles and local weather conditions could have significant impacts on the energy budgets of birds.
Copper‐Catalyzed Dimerization of Sulfoxonium Ylides with 3‐Diazoindolin‐2‐imines: A Practical and Efficient Approach to Spiro[cyclopropane‐1,3′‐indolin]‐2′‐imines
Authors: Suleman Muhammad , Li Zhenmin , Lu Ping , Wang Yanguang
Published: June 2019

A novel copper‐catalyzed dimerization of sulfoxonium ylides with 3‐diazoindolin‐2‐imines is described. Our reaction discriminates between the reactivity of sulfoxonium ylides and diazo compounds as both these classes are carbene precursors as well as nucleophiles. A wide range of spiro[cyclopropane‐1,3′‐indolin]‐2′‐imines were obtained in good to excellent yields with high diastereoselectivity under mild reaction conditions.
Studies on Toxicity of Suspensions of CdTe Quantum Dots to Biomphalaria glabrata Mollusks
Authors: de Vasconcelos Lima Maíra , de Andrade Pereira Maria Isabela , Cabral Filho Paulo Euzébio , Nascimento de Siqueira Williams , Milca Fagundes Silva Hianna Arely , de França Elvis Joacir , Saegesser Santos Beate , Mendonça de Albuquerque Melo Ana Maria , Fontes Adriana
Published: June 2019

Quantum dots have generated great interest because of their optical properties, both to life sciences and electronics applications. However, possible risks to the environment associated with these nanoparticles are still under investigation. The present study aimed to evaluate the toxicity of suspensions of cadmium telluride (CdTe) quantum dots to Biomphalaria glabrata mollusks, a very sensitive aquatic environmental bioindicator for physical and chemical agents. Toxicity was examined by using embryos and adult mollusks as well as hemocytes. The distribution of cadmium in the organs of adults was also assessed. Effects of the stabilizing agent of the quantum dots were also evaluated. Animals were exposed to suspensions of quantum dots for 24 h, at concentrations varying from 1.2 to 20 nM for embryos and from 50 to 400 nM for adult mollusks. Results showed that suspensions of quantum dots induced malformations and mortality in embryos and mortality in adults, depending on the concentration applied. In the cytotoxicity study, hemocyte apoptosis was observed in adults exposed to the highest concentration of quantum dots applied as well as to the stabilizing agent. Cell binucleation and micronucleus frequencies were not significative. Bioaccumulation evaluation revealed that quantum dots targeted the digestive gland (hepatopancreas). Taken together, outcomes suggested that specific nano-effects related directly not only to composition but also to the aggregation of quantum dots may be mediating the observed toxicity. Thus B. glabrata was determined to be a very sensitive species for interpreting possible nano-effects in aquatic environments. Environ Toxicol Chem 2019;38:2128–2136. © 2019 SETAC.