bluuebunny/crossref_metadata_2025 huggingface dataset:
Tin and Mixed Lead–Tin Halide Perovskite Solar Cells: Progress and their Application in Tandem Solar Cells
Authors: Gu Shuai , Lin Renxing , Han Qiaolei , Gao Yuan , Tan Hairen , Zhu Jia
Published: February 2020

Metal halide perovskites have recently attracted enormous attention for photovoltaic applications due to their superior optical and electrical properties. Lead (Pb) halide perovskites stand out among this material series, with a power conversion efficiency (PCE) over 25%. According to the Shockley–Queisser (SQ) limit, lead halide perovskites typically exhibit bandgaps that are not within the optimal range for single‐junction solar cells. Partial or complete replacement of lead with tin (Sn) is gaining increasing research interest, due to the promise of further narrowing the bandgaps. This enables ideal solar utilization for single‐junction solar cells as well as the construction of all‐perovskite tandem solar cells. In addition, the usage of Sn provides a path to the fabrication of lead‐free or Pb‐reduced perovskite solar cells (PSCs). Recent progress in addressing the challenges of fabricating efficient Sn halide and mixed lead–tin (Pb–Sn) halide PSCs is summarized herein. Mixed Pb–Sn halide perovskites hold promise not only for higher efficiency and more stable single‐junction solar cells but also for efficient all‐perovskite monolithic tandem solar cells.
Integration of Ultrathin Silicon and Metal Nanowires for High‐Performance Transparent Electronics
Authors: Koo Jahyun , Lee Changsoo , Chu Cho Rong , Kang Seung‐Kyun , Lee Hyuck Mo
Published: February 2020

Transparent conducting electrodes (TCE) using metal (Cu and Ag) nanowires (NWs) have received great attention, due to their high conductivity, flexibility, and transparency, as alternatives for conventional conductive oxides. Hybridizing with semiconductor, the metal NWs TCE allows for transparent, flexible but high‐performance functional devices such as logical circuit and active device components. However, the electrical performance of hybrid metal NWs/organic semiconductor is still low compared to the hybrid with inorganic semiconductor, such as a‐Si, while the inorganic semiconductors have the limitation of flexibility and transparency. Ultrathin silicon nanomembranes (Si NMs) with thickness in the range of 10–300 nm offer new opportunities in flexible, transparent applications with enhanced electrical performance. Herein, integration strategy of metal (Cu and Ag) NWs with ultrathin (≈200 nm) Si NMs is presented. Vacuum filtering and hot‐rolling process of metal NWs to various inorganic semiconductors and its oxide and nitride substrates (e.g., Si, SiO2, SiNx, and a‐IGZO) yields high transfer rates (≈90% in all cases), which acts as a conductive, ohmic contacted, and transparent electrode. Optic and temperature sensors are demonstrated and the transparent and versatile functional uses of integrated layers of metal NWs and semiconductor substrates, using the transfer method are verified.
Noncationic Material Design for Nucleic Acid Delivery
Authors: Jiang Ziwen , Thayumanavan S.
Published: February 2020

Nucleic acid delivery provides effective options to control intracellular gene expression and protein production. Efficient delivery of nucleic acid typically requires delivery vehicles to facilitate the entry of nucleic acid into cells. Among nonviral delivery vehicles, cationic materials are favored because of their high loading capacity for nucleic acids and prominent cellular uptake efficiency through electrostatic interactions. However, cationic moieties at high dosage tend to induce severe cytotoxicity due to interference with cell membrane integrity. In contrast, noncationic materials present alternative delivery approaches with less safety concerns than cationic materials. In this Progress Report, principles of noncationic material design for nucleic acid delivery are discussed. Examples of such noncationic platforms are highlighted, including complexation or conjugation with nucleic acids and self‐assembled nucleic acid structures.
Multi‐Functional Hydrogel‐Interlayer RF/NFC Resonators as a Versatile Platform for Passive and Wireless Biosensing
Authors: Dautta Manik , Alshetaiwi Muhannad , Escobar Alberto , Torres Fredeswinda , Bernardo Nathan , Tseng Peter
Published: February 2020

Wearable sensors promise to transform human understanding of body state. However, despite many wearable sensor modalities that exist, few demonstrate the raw capabilities required for many emerging healthcare applications—passivity (and microelectronics‐free), wireless readout, long‐term operation, and specificity. Hydrogel‐interlayer radio‐frequency resonators are demonstrated as a versatile platform for passive and wireless biosensing. Fabricated using a simple vinyl cutter, the base resonator is composed of unanchored, broad‐side coupled coils interceded by multifunctional hydrogels—such resonators are tuned to be sensitive to specific analytical or physical signals by modifying hydrogel composition. These resonators are transformed into near‐field communication (NFC) sensor circuits through the simple attachment of an LED. These enable direct quantification of sensor state by cellphone and eye with no specialized electronics required. Resonator arrays are finally fused with silicone to form soft, wireless sensor skins that enable co‐readout of analytical to physical signals while molded to human subjects. Such low‐cost, accessible platforms can integrate with environments in transformative ways, enabling new applications in wireless sensing.
All‐Printed MnHCF‐MnOx‐Based High‐Performance Flexible Supercapacitors
Authors: Liang Jing , Tian Bin , Li Shuaiqi , Jiang Changzhong , Wu Wei
Published: February 2020

Here, a simple active materials synthesis method is presented that boosts electrode performance and utilizes a facile screen‐printing technique to prepare scalable patterned flexible supercapacitors based on manganese hexacyanoferrate‐manganese oxide and electrochemically reduced graphene oxide electrode materials (MnHCF‐MnOx/ErGO). A very simple in situ self‐reaction method is developed to introduce MnOx pseudocapacitor material into the MnHCF system by using NH4F. This MnHCF‐MnOx electrode materials can deliver excellent capacitance of 467 F g−1 at a current density of 1 A g−1, which is a 2.4 times capacitance increase compared to MnHCF. In addition a printed, patterned, flexible MnHCF‐MnOx/ErGO supercapacitor is fabricated, showing a remarkable areal capacitance of 16.8 mF cm−2 and considerable energy and power density of 0.5 mWh cm−2 and 0.0023 mW cm−2, respectively. Furthermore, the printed patterned flexible supercapacitors also exhibit exceptional flexibility, and the capacitance remains stable, even while bending to various angles (60°, 90°, and 180°) and for 100 cycles. The flexible supercapacitor arrays integrated by multiple prepared single supercapacitors can power various LEDs even in the bent states. This approach offers promising opportunities for the development of printable energy storage materials and devices with high energy density, large scalability, and excellent flexibility.
Is it necessary to manage falling number in the field?
Authors: Delwiche Stephen R. , Tao Haiying , Breslauer Rachel S. , Vinyard Bryan T. , Rausch Steven R.
Published: February 2020

Wheat (Triticum aestivum L.)‐growing areas of the U.S. Pacific Northwest, particularly eastern Washington and northern Idaho, are hillier than other wheat‐producing areas in the country. This may produce microclimate variation within a field due to differences in elevation and solar exposure thus causing corresponding variation in yield at harvest. It is unknown whether falling number (FN), an indirect indicator of endogenous α‐amylase activity and hence end‐product quality, is also affected. The aim of this study was to determine the utility of using local (subfield) topographical data to make decisions on segregating potentially low FN wheat produced from susceptible regions within a field. In two consecutive seasons, six large fields in commercial production were studied to reveal effects of elevation and solar exposure on FN. Elevation, slope, and aspect were determined through referencing land coordinates to U.S. Geological Survey (USGS) elevation datasets and ArcMap tools. Theoretical direct solar radiation flux energy increments were summed over the growing period. Findings indicate that for five of the six fields an elevation effect on FN was not significant despite a variation by as much as 50 m within a field. Direct energy flux was positively correlated with FN for two fields (r = .469 and .704) in the first season, but negatively correlated for one field in the second season (r = –.507). However, even in cases when energy flux or elevation trends were significant, these effects were minor. Thus, in‐field segregation of wheat during harvest is not necessary in favorable seasons.
Corn production under restricted irrigation in the Texas High Plains
Authors: Thapa Sushil , Xue Qingwu , Marek Thomas H. , Xu Wenwei , Porter Dana , Jessup Kirk E.
Published: February 2020

Sustainable corn (Zea mays L.) production in the semiarid Texas High Plains (THP) relies on irrigation water from the Ogallala Aquifer, but it is well known that the aquifer is declining. A 3‐yr (2010–2012) field study was conducted to find whether successful corn production is possible using only 60% (300 mm) of the current average irrigation for the region (500 mm). Three corn hybrids (Pioneer P31G96, Pioneer P33D49, and Monsanto DKC67‐87) were planted at four densities (5, 6, 7, and 8 plants m−2) under a center pivot sprinkler system. Seasonal precipitation was highest in 2010 (224 mm), followed by 2012 (132 mm), and 2011 (85 mm). Seasonal evapotranspiration for corn ranged between 426 and 635 mm. Yield was significantly lower in 2011 (2.4 Mg ha−1) and 2012 (6.0 Mg ha−1) than 2010 (13.3 Mg ha‐1) due to severe drought conditions combined with unusually high temperatures in those years. Increase in planting density increased biomass at silking but did not increase yield. Grain yield was related to biomass at maturity, harvest index, and biomass increase during grain filling. Results suggest that corn yields of about 13 Mg ha−1 are possible with only 300 mm of irrigation in the THP, but production risk is high due to frequent years with low seasonal precipitation.
Prevalence of type II workplace violence among home healthcare workers: A meta‐analysis
Authors: Byon Ha Do , Lee Mijung , Choi Min , Sagherian Knar , Crandall Mary , Lipscomb Jane
Published: February 2020

Background

Home healthcare workers (HHWs) provide medical and nonmedical services to home‐bound patients. They are at great risk of experiencing violence perpetrated by patients (type II violence). Establishing the reliable prevalence of such violence and identifying vulnerable subgroups are essential in enhancing HHWs’ safety. We, therefore, conducted meta‐analyses to synthesize the evidence for prevalence and identify vulnerable subgroups.

Methods

Five electronic databases were searched for journal articles published between 1 January 2005 and 20 March 2019. A total of 21 studies were identified for this study. Meta‐analyses of prevalence were conducted to obtain pooled estimates. Meta‐regression was performed to compare the prevalence between professionals and paraprofessionals.

Results

Prevalence estimates for HHWs were 0.223 for 12 months and 0.302 for over the career for combined violence types, 0.102 and 0.171, respectively, for physical violence, and 0.364 and 0.418, respectively, for nonphysical violence. The prevalence of nonphysical violence was higher than that of physical violence for professionals in 12 months (0.515 vs 0.135) and over the career (0.498 vs 0.224) and for paraprofessionals in 12 months (0.248 vs 0.086) and over the career (0.349 vs 0.113). Professionals reported significantly higher nonphysical violence for 12‐month prevalence than paraprofessionals did (0.515 vs 0.248, P = .015).

Conclusion

A considerable percentage of HHWs experience type II violence with higher prevalence among professionals. Further studies need to explore factors that can explain the differences in the prevalence between professionals and paraprofessionals. The findings provide support for the need for greater recognition of the violence hazard in the home healthcare workplace.
Ischemic Stroke despite Oral Anticoagulant Therapy in Patients with Atrial Fibrillation
Authors: Seiffge David J. , De Marchis Gian Marco , Koga Masatoshi , Paciaroni Maurizio , Wilson Duncan , Cappellari Manuel , Macha, MD Kosmas , Tsivgoulis Georgios , Ambler Gareth , Arihiro Shoji , Bonati Leo H. , Bonetti Bruno , Kallmünzer Bernd , Muir Keith W. , Bovi Paolo , Gensicke Henrik , Inoue Manabu , Schwab Stefan , Yaghi Shadi , Brown Martin M. , Lyrer Philippe , Takagi Masahito , Acciarrese Monica , Jager Hans Rolf , Polymeris Alexandros A. , Toyoda Kazunori , Venti Michele , Traenka Christopher , Yamagami Hiroshi , Alberti Andrea , Yoshimura Sohei , Caso Valeria , Engelter Stefan T. , Werring David J. ,   the RAF, RAF‐DOAC, CROMIS‐2, SAMURAI, NOACISP, Erlangen, and Verona registry collaborators
Published: February 2020

Objective

It is not known whether patients with atrial fibrillation (AF) with ischemic stroke despite oral anticoagulant therapy are at increased risk for further recurrent strokes or how ongoing secondary prevention should be managed.

Methods

We conducted an individual patient data pooled analysis of 7 prospective cohort studies that recruited patients with AF and recent cerebral ischemia. We compared patients taking oral anticoagulants (vitamin K antagonists [VKA] or direct oral anticoagulants [DOAC]) prior to index event (OACprior) with those without prior oral anticoagulation (OACnaive). We further compared those who changed the type (ie, from VKA or DOAC, vice versa, or DOAC to DOAC) of anticoagulation (OACchanged) with those who continued the same anticoagulation as secondary prevention (OACunchanged). Time to recurrent acute ischemic stroke (AIS) was analyzed using multivariate competing risk Fine–Gray models to calculate hazard ratios (HRs) and 95% confidence intervals (CIs).

Results

We included 5,413 patients (median age = 78 years [interquartile range (IQR) = 71–84 years]; 5,136 [96.7%] had ischemic stroke as the index event, median National Institutes of Health Stroke Scale on admission = 6 [IQR = 2–12]). The median CHA2DS2‐Vasc score (congestive heart failure, hypertension, age≥ 75 years, diabetes mellitus, stroke/transient ischemic attack, vascular disease, age 65–74 years, sex category) was 5 (IQR = 4–6) and was similar for OACprior (n = 1,195) and OACnaive (n = 4,119, p = 0.103). During 6,128 patient‐years of follow‐up, 289 patients had AIS (4.7% per year, 95% CI = 4.2–5.3%). OACprior was associated with an increased risk of AIS (HR = 1.6, 95% CI = 1.2–2.3, p = 0.005). OACchanged (n = 307) was not associated with decreased risk of AIS (HR = 1.2, 95% CI = 0.7–2.1, p = 0.415) compared with OACunchanged (n = 585).

Interpretation

Patients with AF who have an ischemic stroke despite previous oral anticoagulation are at a higher risk for recurrent ischemic stroke despite a CHA2DS2‐Vasc score similar to those without prior oral anticoagulation. Better prevention strategies are needed for this high‐risk patient group. ANN NEUROL 2020;87:677–687
Enhanced Propene/Propane Separation by Directional Decoration of the 12‐Membered Rings of Mordenite with ZIF Fragments
Authors: Wu Yaqi , Zeng Shu , Yuan Danhua , Xing Jiacheng , Liu Hanbang , Xu Shutao , Wei Yingxu , Xu Yunpeng , Liu Zhongmin
Published: February 2020

Propene/propane separation is challenging due to the very small difference in molecular sizes, boiling points and condensabilities between these molecules. Herein, we report a strategy of introducing ZIF fragments into traditional mordenite (MOR) zeolite to decorate the 12‐membered ring of MOR. After decoration, the originally ineffective zeolite MOR exhibited high kinetic propene/propane selectivities (139 at 25 °C) and achieved efficient propene/propane separation. The propene/propane separation potentials of the resulting adsorbents were further confirmed by breakthrough experiments with equimolar propene/propane (50/50) mixtures.
Tailored Palladium Catalysts for Selective Synthesis of Conjugated Enynes by Monocarbonylation of 1,3‐Diynes
Authors: Liu Jiawang , Yang Ji , Schneider Carolin , Franke Robert , Jackstell Ralf , Beller Matthias
Published: February 2020

For the first time, the monoalkoxycarbonylation of easily available 1,3‐diynes to give synthetically useful conjugated enynes has been realized. Key to success was the design and utilization of the new ligand 2,2′‐bis(tert‐butyl(pyridin‐2‐yl)phosphanyl)‐1,1′‐binaphthalene (Neolephos), which permits the palladium‐catalyzed selective carbonylation under mild conditions, providing a general preparation of functionalized 1,3‐enynes in good‐to‐high yields with excellent chemoselectivities. Synthetic applications that showcase the possibilities of this novel methodology include an efficient one‐pot synthesis of 4‐aryl‐4H‐pyrans as well as the rapid construction of various heterocyclic, bicyclic, and polycyclic compounds.
Dimensional Matching versus Induced‐Fit Distortions: Binding Affinities of Planar and Curved Polyaromatic Hydrocarbons with a Tetragold Metallorectangle
Authors: Ibáñez Susana , Peris Eduardo
Published: February 2020

A tetragold(I) rectangle‐like metallocage containing two pyrene‐bis‐imidazolylidene ligands and two carbazolyl‐bis‐alkynyl linkers is used for the encapsulation of a series of polycyclic aromatic hydrocarbons (PAHs), including corannulene. The binding affinities obtained for the encapsulation of the planar PAHs guests in CD2Cl2 are found to exponentially increase with the number of π‐electrons of the guest (1.3 > logK >6.6). For the bowl‐shaped molecule of corannulene, the association constant is much lower than the expected one according to its number of electrons. The molecular structure of the host–guest complex formed with corannulene shows that the molecule of the guest is compressed, while the host is expanded, thus showing an interesting case of artificial mutual induced‐fit arrangement.
A Photochemical Organocatalytic Strategy for the α‐Alkylation of Ketones by using Radicals
Authors: Spinnato Davide , Schweitzer‐Chaput Bertrand , Goti Giulio , Ošeka Maksim , Melchiorre Paolo
Published: February 2020

Reported herein is a visible‐light‐mediated radical approach to the α‐alkylation of ketones. This method exploits the ability of a nucleophilic organocatalyst to generate radicals upon SN2‐based activation of alkyl halides and blue light irradiation. The resulting open‐shell intermediates are then intercepted by weakly nucleophilic silyl enol ethers, which would be unable to directly attack the alkyl halides through a traditional two‐electron path. The mild reaction conditions allowed functionalization of the α position of ketones with functional groups that are not compatible with classical anionic strategies. In addition, the redox‐neutral nature of this process makes it compatible with a cinchona‐based primary amine catalyst, which was used to develop a rare example of enantioselective organocatalytic radical α‐alkylation of ketones.
Synthesis of α,β‐ and β‐Unsaturated Acids and Hydroxy Acids by Tandem Oxidation, Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives
Authors: Santhanaraj Daniel , Ruiz Maria P. , Komarneni Mallik R. , Pham Tu , Li Gengnan , Resasco Daniel E. , Faria Jimmy
Published: February 2020

We report a reaction platform for the synthesis of three different high‐value specialty chemical building blocks starting from bio‐ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde‐containing stream active for the production of C4 aldehydes via base‐catalyzed aldol‐condensation. Then, the resulting C4 adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of β‐hydroxy acid (3‐hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,β‐dihydroxy acid (2,3‐dihydroxybutanoic acid). Crotonic acid, 3‐hydroxybutanoic acid, and 2,3‐dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl‐co‐unsaturated acids resins, pharmaceutics, and bio‐degradable/ ‐compatible polymers, respectively.
Shear‐aided high‐throughput electrospinning: A needleless method with enhanced jet formation
Authors: Kara Yahya , He Haijun , Molnár Kolos
Published: February 2020

In this article, we introduce a novel high productivity electrospinning setup for scaling up the classical method. We propose a new spinneret concept, which allows the shearing of the polymer solution prior to electrospinning. Most of the solutions used in electrospinning are shear‐thinning, that is, as they are sheared, they show smaller resistance against the deformations caused by the electrostatic field. Therefore, enhanced Taylor‐cone formation can be achieved, and it also gives a hand in controlling the nanofiber morphology easily, even during operation. In this study, we investigated the influence of shearing on the electrospinning process and the fiber morphology. When shearing was applied by rotation, the operation became more stable and the fiber morphology improved. Multiple jets were observed along the circular edges of the spinneret, also became thinner as an effect of the shearing rotation. The average diameter of the electrospun nanofibers was decreased by 18% with rotation speed applied, compared to those of the nonrotating condition (0 rpm). Besides that, we found that the electrospun nanofiber diameter distribution was significantly different for the various rotation speeds for which we found an applicable explanation with the aid of high‐speed camera recordings.
Explaining Cu@Pt Bimetallic Nanoparticles Activity Based on NO Adsorption
Authors: Viñes Francesc , Görling Andreas
Published: February 2020

Cu@Pt nanoparticles (NPs) are experimentally regarded as improved catalysts for NOxstorage/reduction, with higher activities and selectivities compared with pure Pt or Cu NPs, and with inverse Pt@Cu NPs. Here, a density functional theory‐based study on such NP models with different sizes and shapes reveals that the observed enhanced stability of Cu@Pt compared with Pt@Cu NPs is due to energetic reasons. On both types of core@shell NPs, charge is transferred from Cu to Pt, strengthening the NP cohesion energy in Pt@Cu NPs, and spreading charge along the surface in Cu@Pt NPs. The negative surface Pt atoms in the latter diminish the NO bonding owing to an energetic rise of the Pt bands, as detected by the appliance of thed‐band model, although other factors, such as atomic low coordination or the presence of an immediate subsurface Pt atom do as well. A charge density difference analysis discloses a donation/back‐donation mechanism in the NO adsorption.
An Alumanylyttrium Complex with an Absorption due to a Transition from the Al−Y Bond to an Unoccupied d‐Orbital
Authors: Sugita Kengo , Yamashita Makoto
Published: February 2020

The reaction between a dialkyl‐substituted alumanyl anion and [Y(CH2SiMe3)2(thf)3][BPh4] resulted in the formation of (dialkylalumanyl)yttrium complex 2, which exhibits the first 2‐center–2‐electron (2 c‐2 e) Al−Y bond. The1H and13C NMR spectra of2together with an X‐ray crystallographic analysis indicated aC2vsymmetrical structure. DFT calculations on2revealed that its LUMO consists of overlapping 3 p‐ and 4 d‐orbitals of the Al and Y atoms, respectively, and that the HOMO–LUMO gap is narrow. The UV/Vis spectrum of2exhibited a visible absorption at 432 nm, which suggests that the strong σ‐donating and π‐accepting character of the three‐coordinate dialkylalumanyl ligand generates a colored d0‐complex that does not contain any π‐electrons.
Efficient Co‐Catalyzed Double Hydroboration of Nitriles: Application to One‐Pot Conversion of Nitriles to Aldimines
Authors: Gudun Kristina A. , Slamova Ainur , Hayrapetyan Davit , Khalimon Andrey Y.
Published: February 2020

The commercially available and bench‐stable Co(acac)2/dpephos system is employed as a precatalyst for selective and efficient room temperature hydroboration of organic nitriles with HBPin to produce a series of N,N‐diborylamines [RN(BPin)2], which react in situ with aldehydes to give aldimines. Formation of aldimines from N,N‐diborylamines does not require a dehydrating agent, is applicable to a wide range of N,N‐diborylamine and aldehyde substrates and is highly chemoselective, being unaffected by various common functional groups, such as alkenes, alkynes, secondary amines, ketones, esters, amides, carboxylic acids, pyridines, nitriles, and nitro compounds. The overall transformation represents a synthetically valuable approach to aldimines from nitriles and can be performed in a sequential one‐pot manner, tolerating ester, lactone, carboxamide and unactivated alkene functionalities.
Modelling the action potential propagation in a heart with structural heterogeneities: From high‐resolution MRI to numerical simulations
Authors: Davidović Anđela , Coudière Yves , Bourgault Yves
Published: February 2020

Mathematical modelling and numerical simulation in cardiac electrophysiology have already been studied extensively. However, there is a clear lack of techniques and methodologies for studying the propagation of action potential in a heart with structural defects. In this article, we present a modified version of the bidomain model, derived using homogenisation techniques with the assumption of existence of diffusive inclusions in the cardiac tissue. The diffusive inclusions represent regions without electrically active myocytes, for example, fat, fibrosis, and so forth. We present an application of this model to a rat heart. Starting from high‐resolution MRI, the geometry of the heart is built and meshed using image processing techniques. We perform a study of the effects of tissue heterogeneities induced by diffusive inclusions on the velocity and shape of the depolarisation wavefront. We present several test cases with different geometries of diffusive inclusions. We reach the conclusion that the conduction velocity is not affected in the best cases, while it is affected by up to 76% in the worst case scenario. Additionally, the shape of the wavefront was affected in some cases.
Preparation of Triple‐Responsive Porous Silica Carriers and Carbon Quantum Dots for Photodynamic‐/Chemotherapy and Multicolor Cell Imaging
Authors: Chen Yunyun , Li Xinli , Zhao Yanbao , Zhang Xu , Sun Lei
Published: February 2020

Photosensitive carbon quantum dots (CQDs) provide a new route to treat cancer owing to their ability to produce singlet oxygen. In this paper, pH/redox/enzyme‐responsive porous silica‐based carriers with CQDs were constructed for photodynamic‐chemical combination therapy. The porous silica (pSiO2) sample comprises uniform spheres with center‐radial channels, which is favorable for drug loading and delivery. CQDs with a size of 2.5 nm were synthesized and have the excellent ability to generate singlet oxygen. After loading CQDs and drug molecules, the channels of pSiO2 carrier were blocked with hyaluronic acid (HA)/chitosan (CHI) layer. The disulfide bonds, conjugating HA to the surface of pSiO2 carrier, would achieve redox‐responsive drug release, while breaking disulfide bonds and the HA/CHI layer could endow the pSiO2 carrier enzyme/pH‐responsive drug release. The prepared pSiO2 carriers display low cytotoxicity and good biocompatibility for multicolor imaging and photodynamic‐/chemotherapy.
The Atomic Partial Charges Arboretum: Trying to See the Forest for the Trees
Authors: Cho Minsik , Sylvetsky Nitai , Eshafi Sarah , Santra Golokesh , Efremenko Irena , Martin Jan M. L.
Published: February 2020

Atomic partial charges are among the most commonly used interpretive tools in quantum chemistry. Dozens of different ‘population analyses’ are in use, which are best seen as proxies (indirect gauges) rather than measurements of a ‘general ionicity’. For the GMTKN55 benchmark of nearly 2,500 main‐group molecules, which span a broad swathe of chemical space, some two dozen different charge distributions were evaluated at the PBE0 level near the 1‐particle basis set limit. The correlation matrix between the different charge distributions exhibits a block structure; blocking is, broadly speaking, by charge distribution class. A principal component analysis on the entire dataset suggests that nearly all variation can be accounted for by just two ‘principal components of ionicity’: one has all the distributions going in sync, while the second corresponds mainly to Bader QTAIM vs. all others. A weaker third component corresponds to electrostatic charge models in opposition to the orbital‐based ones. The single charge distributions that have the greatest statistical similarity to the first principal component are iterated Hirshfeld (Hirshfeld‐I) and a minimal‐basis projected modification of Bickelhaupt charges. If three individual variables, rather than three principal components, are to be identified that contain most of the information in the whole dataset, one representative for each of the three classes of Corminboeuf et al. is needed: one based on partitioning of the density (such as QTAIM), a second based on orbital partitioning (such as NPA), and a third based on the molecular electrostatic potential (such as HLY or CHELPG).
Redox Mechanisms in Li and Mg Batteries Containing Poly(phenanthrene quinone)/Graphene Cathodes using Operando ATR‐IR Spectroscopy
Authors: Vizintin Alen , Bitenc Jan , Kopač Lautar Anja , Grdadolnik Jože , Randon Vitanova Anna , Pirnat Klemen
Published: February 2020

The redox reaction mechanism of a poly(phenanthrene quinone)/graphene composite (PFQ/rGO) was investigated using operando attenuated total reflection infrared (ATR‐IR) spectroscopy during cycling of Li and Mg batteries. The reference phenanthrene quinone and the Li and Mg salts of the hydroquinone monomers were synthesized and their IR spectra were measured. Additionally, IR spectra were calculated using DFT. A comparison of all three spectra allowed us to accurately assign the C=O and C−O− vibration bands and confirm the redox mechanism of the quinone/Li salt of hydroquinone, with radical anion formation as the intermediate product. PFQ/rGO also showed exceptional performance in an Mg battery: A potential of 1.8 V versus Mg/Mg2+, maximum capacity of 186 mAh g−1 (335 Wh kg−1 of cathode material), and high capacity retention with only 8 % drop/100 cycles. Operando ATR‐IR spectroscopy was performed in a Mg/organic system, revealing an analogous redox mechanism to a Li/organic cell.
CD163+ tumor‐associated macrophage accumulation in breast cancer patients reflects both local differentiation signals and systemic skewing of monocytes
Authors: Ramos Rodrigo Nalio , Rodriguez Céline , Hubert Margaux , Ardin Maude , Treilleux Isabelle , Ries Carola H , Lavergne Emilie , Chabaud Sylvie , Colombe Amélie , Trédan Olivier , Guedes Henrique Gomes , Laginha Fábio , Richer Wilfrid , Piaggio Eliane , Barbuto José Alexandre M , Caux Christophe , Ménétrier‐Caux Christine , Bendriss‐Vermare Nathalie
Published: February 2020

Objectives

The accumulation of tumor‐associated macrophages (TAMs) is correlated with poor clinical outcome, but the mechanisms governing their differentiation from circulating monocytes remain unclear in humans.

Methods

Using multicolor flow cytometry, we evaluated TAMs phenotype in 93 breast cancer (BC) patients. Furthermore, monocytes from healthy donors were cultured in the presence of supernatants from dilacerated primary tumors to investigate their differentiation into macrophages (MΦ) in vitro. Additionally, we used transcriptomic analysis to evaluate BC patients’ blood monocytes profiles.

Results

We observed that high intra‐tumor CD163‐expressing TAM density is predictive of reduced survival in BC patients. In vitro, M‐CSF, TGF‐β and VEGF from primary tumor supernatants skewed the differentiation of healthy donor blood monocytes towards CD163highCD86lowIL‐10high M2‐like MΦ that strongly suppressed CD4+ T‐cell expansion via PD‐L1 and IL‐10. In addition, blood monocytes from about 40% of BC patients displayed an altered response to in vitro stimulation, being refractory to type‐1 MΦ (M1‐MΦ) differentiation and secreting higher amounts of immunosuppressive, metastatic‐related and angiogenic cytokines. Aside from showing that monocyte transcriptome is significantly altered by the presence of BC, we also demonstrated an overall metabolic de‐activation in refractory monocytes of BC patients. In contrast, monocytes from sensitive BC patients undergoing normal M1‐MΦ differentiation showed up‐regulation of IFN‐response genes and had no signs of metabolic alteration.

Conclusion

Altogether, our results suggest that systemic factors skew BC patient blood monocytes towards a pro‐metastatic profile, resulting in the accumulation of further polarised CD163high TAMs resembling type‐2 MΦ (M2‐MΦ) in the local BC microenvironment. These data indicate that monitoring circulating monocytes in BC patients may provide an indication of early systemic alterations induced by cancer and, thus, be instrumental in the development of improved personalised immunotherapeutic interventions.
The clinical and cytomorphological spectrum of hydatid disease
Authors: Kapatia Gargi , Tom Jesty P. , Rohilla Manish , Gupta Parikshaa , Gupta Nalini , Srinivasan Radhika , Rajwanshi Arvind , Dey Pranab
Published: February 2020

Introduction

Hydatid disease (HD) is caused by the tapeworm of the genus Echinococcus. Fine‐needle aspiration cytology (FNAC) is an expedient diagnostic technique that may be used for its rapid diagnosis.

Aim

To study the clinical and cytomorphological spectrum of HD diagnosed by cytology.

Material and methods

A total of 24 patients diagnosed with HD on FNAC and fluid were studied over a period of 5.5 years. May Grunwald Giemsa, Periodic acid Schiff, and Haematoxylin and Eosin stained smears were studied and analysed for the cytomorphological spectrum of HD.

Results

Amongst the 24 patients studied, the mean age was 29.8 years (range 6‐64 years). There was equal sex preponderance with 12 males and 12 females. The most common organ involved was lung (54.1% of cases) followed by liver (25% of cases). Presence of laminated membranes (n‐20, 83.3%) followed by presence of hooklets (n‐13, 54.1%) were the common cytological features. Scolices and protoscolices representing endocyst were seen in 37.5% of cases (n‐9).

Conclusion

Clinicians and pathologists should be aware of the clinical and morphological spectrum of HD respectively for immediate diagnosis followed by prompt management.
Early childhood cumulative risk is associated with decreased global brain measures, cortical thickness, and cognitive functioning in school‐age children
Authors: Chad‐Friedman Emma , Botdorf Morgan , Riggins Tracy , Dougherty Lea R.
Published: February 2020

Children exposed to multiple risk factors early in life are increasingly more likely to suffer from a host of cognitive impairments across development. However, little work has identified the neurobiological mechanisms linking early cumulative risk and cognitive functioning. The current study examined the impact of cumulative risk assessed during early childhood on neural and cognitive outcomes measured 3 years later when children were school‐aged. Participants included 63 children assessed during preschool (age: M = 4.23 years, SD = 0.84) and 3 years later (age: M = 7.19 years, SD = 0.89). Early cumulative risk was defined by the presence of low family income, a single parent household, low parental education, child exposure to parental depression, child exposure to high parental hostility, and high levels of stressful life events. Children's exposure to stressors in the past year, cognitive abilities, and brain structure were assessed at follow‐up. Early cumulative risk was prospectively associated with reduced total gray matter volume, cortex volume, right superior parietal and inferior parietal thickness, and poorer attention shifting and memory. Right superior parietal thickness mediated associations between early risk and recall memory. Results highlight neural variations associated with early cumulative risk and suggest potential neural pathways from early risk to later childhood cognitive impairments.
Timing, frequency, and duration of incubation recesses in dabbling ducks
Authors: Croston Rebecca , Hartman C. Alex , Herzog Mark P. , Casazza Michael L. , Feldheim Cliff L. , Ackerman Joshua T.
Published: February 2020

Nest attendance is an important determinant of avian reproductive success, and identifying factors that influence the frequency and duration of incubation recesses furthers our understanding of how incubating birds balance their needs with those of their offspring. We characterized the frequency and timing (start time, end time, and duration) of incubation recesses for mallard (Anas platyrhynchos) and gadwall (Mareca strepera) hens breeding in Suisun Marsh, California, USA, and examined the influences of day of year, ambient temperature at the nest, incubation day, and clutch size on recess frequency and timing using linear mixed models. Mallard, on average, took more recesses per day (1.69 ± 0.80, mean ± standard deviation) than did gadwall (1.39 ± 0.69), and 45% of mallard nest‐days were characterized by two recesses, while only 27% of gadwall nest‐days were characterized by two recesses. Mallard morning recesses started at 06:14 ± 02:46 and lasted 106.11 ± 2.01 min, whereas mallard afternoon recesses started at 16:39 ± 02:11 and lasted 155.39 ± 1.99 min. Gadwall morning recesses started at 06:30 ± 02:46 and lasted 91.28 ± 2.32 min, and gadwall afternoon recesses started at 16:31 ± 01:57 and lasted 192.69 ± 1.89 min. Mallard and gadwall started recesses earlier in the day with increasing ambient temperature, but later in the day as the season progressed. Recess duration decreased as the season progressed and as clutch size increased, and increased with ambient temperature at the nest. The impending darkness of sunset appeared to be a strong cue for ending a recess and returning to the nest, because hens returned to their nests earlier than expected when recesses were expected to end after sunset. Within hens, the timing of incubation recesses was repeatable across incubation days and was most repeatable for mallard afternoon recesses and on days in which hens took only one recess. Hens were most likely to be away from nests between 04:00 and 07:00 and between 16:00 and 19:00; therefore, investigators should search for nests between 07:00 and 16:00. Our analyses identified important factors influencing incubation recess timing in dabbling ducks and have important implications for nest monitoring programs.
FOE‐based regularization for optical flow estimation from an in‐vehicle event camera
Authors: Nagata Jun , Sekikawa Yusuke , Hara Kosuke , Aoki Yoshimitsu
Published: February 2020

Optical flow estimation from an in‐vehicle camera is an important task in automatic driving and advanced driver‐assistance systems. However, there is a problem that optical flow estimation is mistakable with high contrast and high speed. Event camera can overcome these situations because it reports only the per‐pixel intensity change with high dynamic range and low latency. However, the L1 smoothness regularization in the conventional optical flow estimation method is not suitable for radial optical flow in the driving scene. Therefore, we propose to use the focus of expansion (FOE) for regularization of optical flow estimation in event camera. The FOE is defined as the intersection of the translation vector of the camera and the image plane. The optical flow becomes radial from the FOE excluding the rotational component. Using the property, the optical flow can be regularized in the correct direction in the optimization process. We demonstrated that the optical flow was improved by introducing our regularization using the public dataset.
Gross nitrogen transformation rates in semiarid tropical soils under different salinity and vegetation conditions
Authors: Sharma Niharika , Kumar Sanjeev
Published: February 2020

Exacerbated inundations and saltwater intrusions due to sea‐level rise can significantly alter the ecology of low‐lying coastal drylands by affecting their nutrient cycling and productivity. During the present study, controls on production and consumption of nitrogen in soils of semiarid tropical climate with different levels of vegetation–salinity–moisture condition were investigated using 15N isotope dilution experiments. For this purpose, soils were collected from five land types including two in salt flat and one each in grassland (GL), wetland (WL), and an agricultural field. Soils with no vegetation, high salinity, and high moisture (salt flats) showed significant decline in gross production of nitrogen (mineralization rate: 0.21 ± 0.10 mg N·kg−1·d−1; nitrification rate: 0.27 ± 0.17 mg N·kg−1·d−1) compared to soils with vegetation, low salinity, and low moisture (GL, WL, and agricultural) (mineralization rate: 2.47 ± 1.74 mg N·kg−1·d−1; nitrification rate: 1.43 ± 1.30 mg N·kg−1·d−1). Backward stepwise regression analysis of the results indicated salinity to be the most important factor controlling nitrogen transformation rates. It is likely that soils undergoing frequent seawater exposure or excessive evaporation may experience slowdown in nitrogen cycling due to salinization leading to reduced nutrient production and consumption. Due to climate change, the areal extent of coastal drylands undergoing such decline in nutrient production is likely to increase, eventually leading to loss of productivity and desertification.
Reactions of HDDA Benzynes with C,N‐Diarylimines (ArCH=NAr')
Authors: Arora Sahil , Sneddon Dorian S. , Hoye Thomas R.
Published: February 2020

o‐Benzynes can be utilized to construct heterocyclic motifs using various nucleophilic and cycloaddition trapping reactions. Acridines have been synthesized by capture of C,N‐diarylimines with benzynes generated by classical methods (i.e., from ortho‐elimination of precursor arene compounds), although in poor yields. We report here that these imines can be trapped by benzynes generated by the hexadehydro‐Diels–Alder (HDDA) reaction in an efficient manner to produce 1,4‐dihydroacridine products. These dihydroacridines were subsequently aromatized using MnO2 to provide structurally complex acridines.
Heck Reactions of Acrolein or Enones and Aryl Bromides – Synthesis of 3‐Aryl Propenals or Propenones and Consecutive Application in Multicomponent Pyrazole Syntheses
Authors: Stephan Marvin , Panther Jesco , Wilbert Fabio , Ozog Pauline , Müller Thomas J. J.
Published: February 2020

3‐(Hetero)aryl propenals or propenones are efficiently prepared by a Heck reaction of (hetero)aryl bromides and acrolein or vinyl ketones using Beller's CataCXium® Ptb ligand under Jeffery's and Fu's conditions. The formation of these three‐carbon building blocks is embedded into consecutive three‐ and pseudo‐four‐component syntheses of 3‐(hetero)aryl and 3,5‐diarylpyrazoles with a broad substitution pattern in moderate to excellent yield.
Selective Conversion of Benzylic Phosphates into Diarylmethanes Through Al(OTf)3‐Catalyzed Friedel–Crafts‐Type Benzylation
Authors: Yurino Taiga , Hachiya Asuka , Suzuki Keisuke , Ohkuma Takeshi
Published: February 2020

Al(OTf)3 was identified as a high‐performance catalyst for Friedel–Crafts‐type benzylation using benzylic phosphates as electrophiles. The reaction proceeded even with 0.2 mol‐% of the catalyst. A series of diarylmethanes (21 examples) was obtained in moderate to high yield. The catalyst showed unique chemoselectivity, preferentially converting the benzylic phosphate motif, even with a benzylic acetate group existed in the same molecule.
Bone‐strengthening effects and safety of compound peptides from skin of Chiloscyllium plagiosum and Mustelus griseus
Authors: Xu Xin‐Heng , Lv Peng‐Fei , Wang Tong‐Xin , Wang Bao‐Xuan , Shi Yan , Wang Bi‐Xue , Meng Zheng‐Rou , Chen Qing‐Xi , Zhuang Jiang‐Xing , Wang Yule‐Yue
Published: February 2020

Fish processing produces a lot of by‐products highly containing large amount of proteins which mainly consist of collagen, implying great potential value for application as nutraceutical ingredients. In present study, two kinds of sharks, Chiloscyllium plagiosum and Mustelus griseus, were used as raw material to gain three kinds of “compound peptides” (CPs) by enzymolysis, FCP (CPs from the flesh of C. plagiosum), SCP (CPs from the skin of C. plagiosum), and SMG (CPs from the skin of M. griseus). According to a series of constituent analysis, the molecule weights of FCP, SCP, and SMG were under 800 Da; amino acids composition analysis of FCP, SCP, and SMG showed that there were high glycine, proline, and hydroxyproline and low cysteine contents in SCP and SMG, which is the characteristic of collagen peptides; their total protein contents were 87.500%, 91.875%, and 95.625%, respectively; and heavy metal contents of CPs were all beneath national standards. After three kinds of CPs were administrated intragastrically to C57BL/6 mice at a total dosage of 15 g/kg, bone‐strengthening effects of SCP and SMG were manifested by osteoblasts activity promotion, bone mineral density (BMD) increase, and marrow adipocyte number decrease, yet nonsignificant effects were shown in FCP group. No index showed toxicity of SCP and SMG in subacute toxicology trial, indicating their safety as functional foods. Herein, industrial application foundation of the skins from these two sharks was explored but more efforts should subsequently be implemented for further exploitation.
Farnesoid X Receptor Activation Protects Liver From Ischemia/Reperfusion Injury by Up‐Regulating Small Heterodimer Partner in Kupffer Cells
Authors: Jin Dan , Lu Tianfei , Ni Ming , Wang Han , Zhang Jiang , Zhong Chenpeng , Shen Chuan , Hao Jun , Busuttil Ronald W. , Kupiec‐Weglinski Jerzy W. , Zhang Jianjun , Xu Ning , Zhai Yuan
Published: February 2020

Farnesoid X receptor (FXR) is the nuclear receptor of bile acids and is involved in innate immune regulation. FXR agonists have been shown to protect multiple organs from inflammatory tissue injuries. Because liver expresses high levels of FXR, we explored the potential therapeutic benefits and underlying mechanisms of pharmacologic FXR activation in a murine model of partial liver warm ischemia. Pretreatment of mice with FXR agonist 3‐(2,6‐dichlorophenyl)‐4‐(3′‐carboxy‐2‐chlorostilben‐4‐yl)oxymethyl‐5‐isopropylisoxazole (GW4064) attenuated liver ischemia/reperfusion injuries (IRIs) in wild‐type but not FXR knockout mice. Posttreatment with GW4064 facilitated liver recovery from IRI. Mechanistically, Kupffer cells (KCs) expressed much higher levels of FXR than bone marrow‐derived macrophages (BMMs). Pretreatment of KCs but not BMMs with GW4064 resulted in lower tumor necrosis factor α but higher interleukin‐10 expressions following toll‐like receptor stimulation. FXR‐targeted gene small heterodimer partner (SHP) was critical for the regulation of KC response by GW4064. In vivo, the depletion of KCs but not cluster of differentiation (CD) 11b+ cells or knockdown of SHP diminished the immune regulatory effect of GW4064 in liver IRI. Thus, FXR activation protects liver from IRI by up‐regulating SHP in KCs to inhibit the liver proinflammatory response.