bluuebunny/crossref_metadata_2025 huggingface dataset:
Epilogue
Authors: Balasubramaniam Dr. R , Venkatachaliah M N
Published: May 2018

Mudalimadiah is a very senior and respected chieftain of the Kadukuruba tribal community. Though I have known him since 1987, we became close only after 1996 when we had started our engagement with the National Human Rights Commission on the issue of displacement and rehabilitation of the tribals in Heggadadevanakote. It was a time when the tension between the forest department and the tribal communities was quite palpable, and even small incidents could potentially turn into explosive situations. The callous and insensitive attitudes of the forest department and the police were making the tribals increasingly restive as the struggle for justice kept becoming longer. Fatigue was creeping in and it was getting difficult to keep the spirits up and the agitation going. The younger generation was showing signs of turning the protests violent and were pushing me to take more visibly strident steps. I also had very little to show in terms of success and my arguments to continue with the non-violent struggle were either weakening or ceasing to have an impact. At times, I was myself feeling low and wanted to give up....
The Golden Age
Authors: Shaw Claire L.
Published: May 2018

This chapter considers the ‘golden age’ of the Soviet deaf community, from the early 1950s to the late 1970s. This period saw Soviet understandings of deafness undergo a profound change: no longer a negative symbol of “backwardness” to be compensated for, deafness was increasingly framed as a legitimate Soviet community identity, institutionalized in the structures and establishments of VOG and characterized by unique forms of language, culture and everyday life. As this chapter shows, however, this ‘golden age’ represented a complex intertwining of marginal cultural practices with the broader ideological constructs of the Soviet state. The assertion of a unique deaf identity was constantly tempered by the desire to show that identity to be fundamentally Soviet in its qualities, shaped by notions of “culturedness” – expressed increasingly in hearing terms – and permeated by values of collectivism, agency, and welfare.
Divergent and convergent evolution of housekeeping genes in human–pig lineage
Authors: Wei Kai , Zhang Tingting , Ma Lei
Published: May 2018

Housekeeping genes are ubiquitously expressed and maintain basic cellular functions across tissue/cell type conditions. The present study aimed to develop a set of pig housekeeping genes and compare the structure, evolution and function of housekeeping genes in the human–pig lineage. By using RNA sequencing data, we identified 3,136 pig housekeeping genes. Compared with human housekeeping genes, we found that pig housekeeping genes were longer and subjected to slightly weaker purifying selection pressure and faster neutral evolution. Common housekeeping genes, shared by the two species, achieve stronger purifying selection than species-specific genes. However, pig- and human-specific housekeeping genes have similar functions. Some species-specific housekeeping genes have evolved independently to form similar protein active sites or structure, such as the classical catalytic serine–histidine–aspartate triad, implying that they have converged for maintaining the basic cellular function, which allows them to adapt to the environment. Human and pig housekeeping genes have varied structures and gene lists, but they have converged to maintain basic cellular functions essential for the existence of a cell, regardless of its specific role in the species. The results of our study shed light on the evolutionary dynamics of housekeeping genes.
On the taxonomic status and distribution of African species ofOtomops(Chiroptera: Molossidae)
Authors: Patterson Bruce D. , Webala Paul W. , Bartonjo Michael , Nziza Julius , Dick Carl W. , Demos Terrence C.
Published: May 2018

Background

Free-tailed bats of the genusOtomopsare poorly known, and most species are documented from a handful of widely scattered localities. Recently, two allopatric species ofOtomopswere recognized in continental Africa:Otomops martiensseni(Matschie, 1897) in southern, central and western Africa, and the new speciesO. harrisoniRalph et al., 2015 in the northeast and in Yemen.

Methods

We collected additional samples ofOtomopsin Kenya and Rwanda where the ranges of these taxa approach one another to clarify their geographic ranges and taxonomic status. Mitochondrial and nuclear intron sequences served to identify and delimit species; we also documented their echolocation call variation and ectoparasite complements.

Results

Otomops martiensseni, the southern African species, was documented in northern Kenya in Marsabit National Park.O. harrisoni, the northeastern African–Arabian species, was documented in southern Kenya and in a cave in Musanze District, Rwanda. Moreover, individuals of both species were found together at the Musanze cave, establishing them in precise spatial and temporal sympatry. Analyses of mitochondrial and nuclear loci identify no evidence of admixture between these forms, although available samples limit the power of this analysis. Echolocation call differences are also apparent among the three localities we analyzed. Three orders of insects and two families of mites are newly reported as ectoparasites ofO. harrisoni.

Discussion

Our results corroborate species rank forO. harrisoniand establish a zone of potential geographic overlap withO. martienssenispanning at least 800 km of latitude. The new records establish the species in sympatry in northern Rwanda and add an additional species to the bat faunas of both Kenya and Rwanda. Future studies are needed to understandOtomopsroosting requirements and movements, thereby explaining the paucity of known colonies and yielding better estimates of their conservation status. The discovery of mixed roosting associations in Rwanda invites further investigation.
Re-examining Evidence Based Practice in Special Education: A Discussion
Authors: Williamson Robert L. , Jasper Andrea , Novak Jeanne , Smith Clinton , Hunter William , Casey Laura , Reeves Kay
Published: May 2018

The Council for Exceptional Children (CEC) recently released updated standards regarding how to determine whether any particular intervention may be deemed an evidence-based practice (EBP). As new criteria regarding the acceptance of any specific intervention as evidence-based become available, the question arises: Would the application of new standards to studies completed under the older guidelines result in changes to past conclusions? The current study examined if changes in EBP standards might change the classification of an exemplar practice that was previously designated as an EBP. In this case, we examined video modeling (VM), an accepted practice regarding skill acquisition in special education as an exemplar practice. In order to determine if the new CEC 2014 standards would impact a previously determined EBP finding, a re-examination of Bellini and Akullian's (2007) frequently cited meta-analysis that focused on VM as an intervention for individuals with autism spectrum disorders (ASD) was conducted. The results revealed that if Bellini and Akullian had conducted their review using updated CEC 2014 standards, VM applied to individuals with ASD would not have been classified as an EBP.
Modulation of STAT3 phosphorylation by PTPN2 inhibits naïve pluripotency of embryonic stem cells
Authors: Zhang Yan , Ding Huiwen , Wang Xiaohu , Ye Shou‐Dong
Published: May 2018

STAT3 phosphorylation at tyrosine 705 (STAT3pY705), triggered by the addition of the leukemia inhibitory factor (LIF), can maintain mouse embryonic stem cell (mESC) self‐renewal and reprogram mouse epiblast stem cells (EpiSCs) to enter a naïve pluripotent state. The activation of STAT3pY705 occurs mainly through Janus kinases. However, it remains unclear how STAT3pY705 levels are decreased in mESCs. Our study shows that upregulation of the protein tyrosine phosphatase (PTPN2) inhibits STAT3 activity by reducing its phosphorylation level and promotes mESC differentiation, whereas PTPN2 knockout by CRISPR/CAS9 delays mESC differentiation. Consistently, PTPN2 knockdown facilitates the generation of mESC‐like colonies in STAT3‐overexpressing EpiSCs. PTPN2‐mediated STAT3 activity, thus, contributes to the exit of ESCs from the pluripotent ground state. These findings expand the current understanding of the regulatory network of naïve pluripotency.
Ultracompliant Hydrogel‐Based Neural Interfaces Fabricated by Aqueous‐Phase Microtransfer Printing
Authors: Huang Wei‐Chen , Ong Xiao Chuan , Kwon Ik Soo , Gopinath Chaitanya , Fisher Lee E. , Wu Haosheng , Fedder Gary K. , Gaunt Robert A. , Bettinger Christopher J.
Published: May 2018

Hydrogel‐based electronics are ideally suited for neural interfaces because they exhibit ultracompliant mechanical properties that match that of excitable tissue in the brain and peripheral nerve. Hydrogel‐based multielectrode arrays (MEAs) can conformably interface with tissues to minimize inflammation and improve the reliability to enhance signal transduction. However, MEA substrates composed of swollen hydrogels exhibit low toughness and poor adhesion when laminated on the tissue surface and also present incompatibilities with processes commonly used in MEA fabrication. Here, a strategy to fabricate an ultracompliant MEA is described based on aqueous‐phase transfer printing. This technique employs redox active adhesive motifs in hygroscopic polymer precursors that simultaneously form hydrogels through sol–gel phase transitions and bond to materials in the underlying microelectronic structures. Specifically, in situ gelation of four‐arm‐polyethylene glycol‐grafted catechol [PEG‐Dopa]4 hydrogels induced by oxidation using Fe3+ produces conformal adhesive contact with the underlying MEA, robust adhesion to electronic sub‐structures, and rapid dissolution of water‐soluble sacrificial release layers. MEAs are integrated on hydrogel‐based substrates to produce free‐standing ultracompliant neural probes, which are then laminated to the surface of the dorsal root ganglia in feline subjects to record single‐unit neural activity.
Patterned Carbon Nitride–Based Hybrid Aerogel Membranes via 3D Printing for Broadband Solar Wastewater Remediation
Authors: He Peisheng , Tang Xingwei , Chen Liao , Xie Peiwen , He Lu , Zhou Han , Zhang Di , Fan Tongxiang
Published: May 2018

Controlled scalable assembly of 2D building blocks into macroscopic 3D architectures is highly significant. However, the assembly of g‐C3N4 into tailored, 3D architectures is not yet reported. Here, a 3D printing methodology to enable the programmable construction of carbon nitride–based hybrid aerogel membranes with patterned macroscopic architectures is proposed. g‐C3N4 nanosheets (CNNS) are used as the building block, and sodium alginate (SA) increases the viscosity of the ink to obtain the desired rheological properties. Three printing routes, including printing directly in air and in the supporting reservoirs composed of CaCl2/glycerol solution or Pluronic F127, are demonstrated for printing versatility. The printed Au nanobipyramid–CNNS–SA hybrid aerogels exhibit broadband visible‐light absorption and superior solar wastewater remediation performance with excellent cyclic stability and easy manipulation features. Remarkably, the activity of the 3D‐printed aerogel is about 2.5 times of that of the contrast sample, attributing to the enhanced liquid velocity and solution diffusion efficiency because of the 3D‐printed structure, which is demonstrated by experimental and theoretical simulations. This approach can be extended to the macroscopic assembly of other 2D materials for myriad applications.
High‐Performance Triphase Bio‐Photoelectrochemical Assay System Based on Superhydrophobic Substrate‐Supported TiO2 Nanowire Arrays
Authors: Chen Liping , Sheng Xia , Wang Dandan , Liu Jie , Sun Ruize , Jiang Lei , Feng Xinjian
Published: May 2018

The design and fabrication of bio‐photoelectrodes that simultaneously possess rapid charge and gas‐phase mass transport abilities are highly desirable for the development of high‐performance bio‐photoelectrochemical assay systems. Here, a solid–liquid–air triphase bio‐photoelectrode is demonstrated by immobilizing glucose oxidase, a model redox active enzyme, onto 1D single crystalline TiO2 nanowire arrays grown upon a superhydrophobic carbon textile substrate. Based on this triphase bio‐photoelectrode system, oxygen can be directly and constantly supplied from the air phase to sustain enzymatic reactions, leading to much enhanced oxidase kinetics. Further, the photogenerated electrons can transport rapidly and be efficiently collected along the nanowire arrays. The bio‐photoelectrochemical assay system demonstrates a significant wide detection range, high sensitivity, and selectivity as well as a low detection limit. The design principle is generally applicable to the fabrication of other triphase bio‐photoelectrodes, which offers an excellent opportunity for significant advances in environmental analysis and clinical diagnosis.
Mechanotargeting: Mechanics‐Dependent Cellular Uptake of Nanoparticles
Authors: Wei Qiong , Huang Changjin , Zhang Yao , Zhao Tiankai , Zhao Peng , Butler Peter , Zhang Sulin
Published: May 2018

Targeted delivery of nanoparticle (NP)‐based diagnostic and therapeutic agents to malignant cells and tissues has exclusively relied on chemotargeting, wherein NPs are surface‐coated with ligands that specifically bind to overexpressed receptors on malignant cells. Here, it is demonstrated that cellular uptake of NPs can also be biased to malignant cells based on the differential mechanical states of cells, enabling mechanotargeting. Owing to mechanotransduction, cell lines (HeLa and HCT‐8) cultured on hydrogels of various stiffness are directed into different stress states, measured by cellular force microscopies. In vitro NP delivery reveals that increases in cell stress suppress cellular uptake, counteracting the enhanced uptake that occurs with increases in exposed surface area of spread cells. Upon prolonged culture on stiff hydrogels, cohesive HCT‐8 cell colonies undergo metastatic phenotypic change and disperse into individual malignant cells. The metastatic cells are of extremely low stress state and adopt an unspread, 3D morphology, resulting in several‐fold higher uptake than the nonmetastatic counterparts. This study opens a new paradigm of harnessing mechanics for the design of future strategies in nanomedicine.
Reverse Saturable Absorption Induced by Phonon‐Assisted Anti‐Stokes Processes
Authors: Tian Xiangling , Wei Rongfei , Guo Qianyi , Zhao Yu‐Jun , Qiu Jianrong
Published: May 2018

In materials showing reverse saturable absorption (RSA), optical transmittance decreases at intense laser irradiation. One approach to application of these materials is to protect the sensors or human eyes from laser damage. To date, research has mainly concentrated on thin films and suspensions of graphite and its nanostructure (including nanotubes, graphene, and graphene oxides), which are mainly used as an optical limiter for nanosecond laser pulses. Moreover, thin individual pieces of semiconductor usually exhibit increased transmittance due to saturable absorption when the laser energy (Elaser) is higher than the band gap (EB). Here, it is shown that indirect gap semiconductor WSe2 exhibits high RSA on exposure to a femtosecond laser under Elaser > EB near band gap excitation, which is attributed to the longitudinal optical phonon‐assisted anti‐Stokes transition by the annihilation of phonons and the absorption of photons. An optical limiting threshold (≈21.6 mJ cm−2) lower than those reported for other optical‐limiting materials currently for femtosecond laser at 800 nm is observed.
Hypervalent Iodine(III)‐Mediated Solvent‐Free, Regioselective Synthesis of 3,4‐Disubstituted 5‐Imino‐1,2,4‐thiadiazoles and 2‐Aminobenzo[d]thiazoles
Authors: Tumula Nagaraju , Palakodety Radha Krishna , Balasubramanian Sridhar , Nakka Mangarao
Published: May 2018

A convenient approach for the synthesis of 3,4‐disubstituted 5‐imino‐1,2,4‐thiadiazoles and 2‐aminobenzo[d]thiazoles has been developed using phenyliodine diacetate (PIDA). This approach involves a metal‐free oxidative C−N, N−S and C−S bond formations under neat conditions. High regioselectivity, solvent‐free conditions, short reaction time and broad functional group compatibility are the notable features of this report.

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Recent Progress on Layered Double Hydroxides and Their Derivatives for Electrocatalytic Water Splitting
Authors: Wang Yanyong , Yan Dafeng , El Hankari Samir , Zou Yuqin , Wang Shuangyin
Published: May 2018

Layered double hydroxide (LDH)‐based materials have attracted widespread attention in various applications due to their unique layered structure with high specific surface area and unique electron distribution, resulting in a good electrocatalytic performance. Moreover, the existence of multiple metal cations invests a flexible tunability in the host layers; the unique intercalation characteristics lead to flexible ion exchange and exfoliation. Thus, their electrocatalytic performance can be tuned by regulating the morphology, composition, intercalation ion, and exfoliation. However, the poor conductivity limits their electrocatalytic performance, which therefore has motivated researchers to combine them with conductive materials to improve their electrocatalytic performance. Another factor hampering their electrocatalytic activity is their large lateral size and the bulk thickness of LDHs. Introducing defects and tuning electronic structure in LDH‐based materials are considered to be effective strategies to increase the number of active sites and enhance their intrinsic activity. Given the unique advantages of LDH‐based materials, their derivatives have been also used as advanced electrocatalysts for water splitting. Here, recent progress on LDHs and their derivatives as advanced electrocatalysts for water splitting is summarized, current strategies for their designing are proposed, and significant challenges and perspectives of LDHs are discussed.
Graphene–Polymer Nanocomposite‐Based Redox‐Induced Electricity for Flexible Self‐Powered Strain Sensors
Authors: Wang Yuanming , Wang Yang , Yang Ya
Published: May 2018

Graphene as a powerful inorganic material such as excellent conductivity and ideal mechanical strength has recently been extensively utilized to develop flexible strain sensors. However, graphene‐based strain sensors usually suffer from the deficiencies of stretchability, sensitivity, and sensing range, which can restrict their applications in wearable devices. Here, a novel strain sensor is designed by integrating graphene/ecoflex film and meandering zinc wire into the flexible base. The constructed strain sensor not only possesses high stretchability of up to 150% strain but can also self‐generates current signals from redox‐induced electricity, where the stable current and voltage signals of about 75 µA and 0.83 V can be obtained, respectively. Furthermore, the self‐powered sensor presents a broad and linear sensing range of 25% to 150% strains and a fast response time of less than 0.11 s. Attached on human body, the sensor has been utilized to realize the motion detection of knee joint.
The critical role of fossils in inferring deep‐node phylogenetic relationships and macroevolutionary patterns in Cornales
Authors: Atkinson Brian A.
Published: May 2018

Premise of the Study

The basal asterid order, Cornales, experienced a rapid radiation during the Cretaceous, which has made it difficult to elucidate the early evolution of the order using extant taxa only. Recent paleobotanical studies, however, have begun to shed light on the early diversification of Cornales. Herein, fossils are directly incorporated in phylogenetic and quantitative morphological analyses to reconstruct early cornalean evolution.

Methods

A morphological matrix of 77 fruit characters and 58 taxa (24 extinct) was assembled. Parsimony analyses including and excluding fossils were conducted. A fossil inclusive tree was time‐scaled to visualize the timing of the initial cornalean radiation. Disparity analyses were utilized to infer the morphological evolution of cornaleans with drupaceous fruits.

Key Results

Fossil inclusive and exclusive parsimony analyses resulted in well‐resolved deep‐node relationships within Cornales. Resolution in the fossil inclusive analysis is substantially higher, revealing a basal grade including Loasaceae, Hydrangeaceae, Hydrostachyaceae, Grubbiaceae, a Hironoia+Amersinia clade, and Curtisiaceae, respectively, that leads to a “core” group containing a clade comprising a Cretaceous grade leading to clade of Nyssaceae, Mastixiaceae, and Davidiaceae that is sister to a Cornaceae+Alangiaceae clade. The time‐scaled tree indicates that the initial cornalean diversification occurred before 89.8 Ma. Disparity analyses suggest the morphological diversity of Cornales peaked during the Paleogene.

Conclusions

Phylogenetic analyses clearly demonstrate that novel character mosaics of Cretaceous cornaleans play a critical role in resolving deep‐node relationships within Cornales. The post‐Cretaceous increase of cornalean disparity is associated with a shift in morphospace occupation, which can be explained from ecological and developmental perspectives.
Oxytocin‐ and arginine vasopressin‐containing fibers in the cortex of humans, chimpanzees, and rhesus macaques
Authors: Rogers Christina N. , Ross Amy P. , Sahu Shweta P. , Siegel Ethan R. , Dooyema Jeromy M. , Cree Mary Ann , Stopa Edward G. , Young Larry J. , Rilling James K. , Albers H. Elliott , Preuss Todd M.
Published: May 2018

Oxytocin (OT) and arginine‐vasopressin (AVP) are involved in the regulation of complex social behaviors across a wide range of taxa. Despite this, little is known about the neuroanatomy of the OT and AVP systems in most non‐human primates, and less in humans. The effects of OT and AVP on social behavior, including aggression, mating, and parental behavior, may be mediated primarily by the extensive connections of OT‐ and AVP‐producing neurons located in the hypothalamus with the basal forebrain and amygdala, as well as with the hypothalamus itself. However, OT and AVP also influence social cognition, including effects on social recognition, cooperation, communication, and in‐group altruism, which suggests connectivity with cortical structures. While OT and AVP V1a receptors have been demonstrated in the cortex of rodents and primates, and intranasal administration of OT and AVP has been shown to modulate cortical activity, there is to date little evidence that OT‐and AVP‐containing neurons project into the cortex. Here, we demonstrate the existence of OT‐ and AVP‐containing fibers in cortical regions relevant to social cognition using immunohistochemistry in humans, chimpanzees, and rhesus macaques. OT‐immunoreactive fibers were found in the straight gyrus of the orbitofrontal cortex as well as the anterior cingulate gyrus in human and chimpanzee brains, while no OT‐immunoreactive fibers were found in macaque cortex. AVP‐immunoreactive fibers were observed in the anterior cingulate gyrus in all species, as well as in the insular cortex in humans, and in a more restricted distribution in chimpanzees. This is the first report of OT and AVP fibers in the cortex in human and non‐human primates. Our findings provide a potential mechanism by which OT and AVP might exert effects on brain regions far from their production site in the hypothalamus, as well as potential species differences in the behavioral functions of these target regions.
Urinary oxytocin in capuchin monkeys: Validation and the influence of social behavior
Authors: Benítez Marcela E. , Sosnowski Meghan J. , Tomeo Olivia B. , Brosnan Sarah F.
Published: May 2018

In highly social species, like primates, oxytocin plays an important role in cooperation, and in the formation and maintenance of social relationships. Despite recent interest in the relationship between oxytocin and social behavior in nonhuman primates, relatively little is known about endogenous oxytocin in social New World Monkeys. In this paper, we investigate the relationship between oxytocin and affiliative behaviors in socially‐housed captive capuchin monkeys (Sapajus [Cebus] apella) by first validating methods of analysis of urinary oxytocin in this species and, second, examining the effects of grooming and fur‐rubbing behavior on oxytocin concentrations and further affiliative behavior. In the validation, we found that intranasal exogenous oxytocin significantly increased urinary oxytocin 15–60 min post‐administration. Oxytocin was also implicated in both grooming and fur‐rubbing behaviors. We found that oxytocin concentrations increased after subjects engaged in grooming or fur‐rubbing. In addition, we found that fur‐rubbing influenced affiliative behaviors, both during and after a social fur‐rubbing bout. While individuals spent more time in contact and proximity while fur‐rubbing, immediately following the fur‐rubbing event (15–30 min afterwards) all affiliative behaviors decreased. This supports previous research that oxytocin may, in fact, initially be related to increased social distance in this species. Yet, an increase in all affiliative behaviors 30–45 min after the onset of fur‐rubbing suggests that fur‐rubbing, like grooming, may ultimately function to strengthen social relationships. Overall, these results support a critical role for oxytocin in affiliative behaviors that maintain and strengthen social relationships in capuchin monkeys, and highlight the complexity of the interactions among oxytocin, affiliative behaviors, and social bonding.
Proteomic Analysis of Single Mammalian Cells Enabled by Microfluidic Nanodroplet Sample Preparation and Ultrasensitive NanoLC‐MS
Authors: Zhu Ying , Clair Geremy , Chrisler William B. , Shen Yufeng , Zhao Rui , Shukla Anil K. , Moore Ronald J. , Misra Ravi S. , Pryhuber Gloria S. , Smith Richard D. , Ansong Charles , Kelly Ryan T.
Published: May 2018

We report on the quantitative proteomic analysis of single mammalian cells. Fluorescence‐activated cell sorting was employed to deposit cells into a newly developed nanodroplet sample processing chip, after which samples were analyzed by ultrasensitive nanoLC‐MS. An average of circa 670 protein groups were confidently identified from single HeLa cells, which is a far greater level of proteome coverage for single cells than has been previously reported. We demonstrate that the single‐cell proteomics platform can be used to differentiate cell types from enzyme‐dissociated human lung primary cells and identify specific protein markers for epithelial and mesenchymal cells.
Selective ortho C−H Cyanoalkylation of (Diacetoxyiodo)arenes through [3,3]‐Sigmatropic Rearrangement
Authors: Tian Junsong , Luo Fan , Zhang Chaoshen , Huang Xin , Zhang Yage , Zhang Lei , Kong Lichun , Hu Xiaochun , Wang Zhi‐Xiang , Peng Bo
Published: May 2018

We herein report a robust catalyst‐free cross‐coupling between ArI(OAc)2 and α‐stannyl nitriles, aided by TMSOTf. The transformation introduces a cyanoalkyl group to the ortho position of ArI(OAc)2 and simultaneously reduces the aryl iodine(III) to iodide, thus providing α‐(2‐iodoaryl) nitrile as the product. This transformation could be completed within 5 min at −78 °C and features superb functional‐group tolerance and efficient scalability. DFT calculations indicate that the formation of a ketenimine(aryl)iodonium intermediate and subsequent [3,3]‐sigmatropic rearrangement are involved as key steps.
MnI/AgI Relay Catalysis: Traceless Diazo‐Assisted C(sp2)–H/C(sp3)–H Coupling to β‐(Hetero)Aryl/Alkenyl Ketones
Authors: Lu Qingquan , Mondal Shobhan , Cembellín Sara , Glorius Frank
Published: May 2018

An unprecedented MnI/AgI‐relay‐catalyzed C(sp2)−H/C(sp3)−H coupling of (vinyl)arenes with α‐diazoketones is reported, wherein the diazo group was exploited as a traceless auxiliary for control of regioselectivity. Challenging β‐(hetero)aryl/alkenyl ketones were obtained through this operationally simple approach. The cascade process merges denitrogenation, carbene rearrangement, C−H activation, and hydroarylation/hydroalkenylation. The robustness of this method was demonstrated at preparative scale and applied to late‐stage diversification of natural products.
Metal‐ and Reagent‐Free Dehydrogenative Formal Benzyl–Aryl Cross‐Coupling by Anodic Activation in 1,1,1,3,3,3‐Hexafluoropropan‐2‐ol
Authors: Imada Yasushi , Röckl Johannes L. , Wiebe Anton , Gieshoff Tile , Schollmeyer Dieter , Chiba Kazuhiro , Franke Robert , Waldvogel Siegfried R.
Published: May 2018

A selective dehydrogenative electrochemical functionalization of benzylic positions that employs 1,1,1,3,3,3‐hexafluoropropan‐2‐ol (HFIP) has been developed. The electrogenerated products are versatile intermediates for subsequent functionalizations as they act as masked benzylic cations that can be easily activated. Herein, we report a sustainable, scalable, and reagent‐ and metal‐free dehydrogenative formal benzyl–aryl cross‐coupling. Liberation of the benzylic cation was accomplished through the use of acid. Valuable diarylmethanes are accessible in the presence of aromatic nucleophiles. The direct application of electricity enables a safe and environmentally benign chemical transformation as oxidizers are replaced by electrons. A broad variety of different substrates and nucleophiles can be employed.
Numerical investigation of drop formation in a co‐current liquid–liquid flow for ice slurry making system
Authors: Zhang Tiantian , Xin Yi , Geng Fan , Han Dongtai , Peng Zhengbiao , Chai Hongli , Luo Gang , Ding Haiyan
Published: May 2018

Ice slurry is used widely as phase change materials (PCMs) to reduce the peak demand for power system. Drop formation plays a key role during ice slurry production in liquid–liquid circulating fluidized bed. In the present work, drop formation in a co‐current liquid–liquid flow was investigated via a 3D model. Volume of fluid method was adopted to study drop characteristics by tracking the interface. Major influences of the water velocity, the oil velocity, the jet size, and the jet number on drop formation were analyzed for drop characteristics. The results indicate that properties of drop formation vary significantly according to the different conditions. The drop size was distributed mainly as the normal distribution, and the average drop diameter varies with different conditions. The drop size varies from 0.7 to 1.9 mm at the water velocity of 0.5 m/s, whereas the size of drop size varies from 1.8 to about 2.65 mm at the water velocity of 1.5 m/s. Furthermore, the residence time of drop decreases obviously with the increase of the oil velocity. When the oil velocity is 0.1 m/s, a drop leaves the top outlet at about 0.44 s. When the oil velocity is 0.3 m/s, a drop reaches the outlet at about 0.15 s. Additionally, the simulated results were compared with the relevant experimental results and the previous simulated results. Reasonable agreements have been gained, which can validate the established model to some extent.
Synthesis, evaluation, and molecular docking studies of aryl urea‐triazole‐based derivatives as anti‐urease agents
Authors: Moghimi Setareh , Goli‐Garmroodi Fereshteh , Allahyari‐Devin Maryam , Pilali Hedieh , Hassanzadeh Malihe , Mahernia Shabnam , Mahdavi Mohammad , Firoozpour Loghman , Amanlou Massoud , Foroumadi Alireza
Published: May 2018

Considering the importance of urease inhibitors in the treatment of ureolytic bacterial infections, in this work, the synthesis of novel, aryl urea‐triazole‐based derivatives as effective urease inhibitors is described. Dichloro‐substituted derivative 4o, with IC50 = 22.81 ± 0.05 μM, is found to be the most potent urease inhibitor, determined by Berthelot colorimetric assay. Docking studies were also carried out for compound 4o to confirm the effective interactions with the urease active site.
Effects of combined magnetic fields on bacteria Rhodospirillum rubrum VKM B‐1621
Authors: Khokhlova Galina , Abashina Tatiana , Belova Nataliya , Panchelyuga Victor , Petrov Alexey , Abreu Fernanda , Vainshtein Mikhail
Published: May 2018

Bacteria are the simplest model of living organisms and thus are a convenient object for magnetobiological research. This paper describes some effects of combined magnetic fields (CMFs) on the bacterium Rhodospirillum rubrum strain VKM B‐1621, which is not a pathogen but was selected due to its wide spectrum of growth abilities. The authors chose magnetic field‐resonant phosphorus and iron (Fe3+) because P‐containing biochemical compounds (standard abbreviations PP1, AMP, ADP, ATP) provide energy flows in bacteria while iron could take part in formation of magnetosensitive intracellular inclusions. CMFs were produced by interaction of a geomagnetic field (ВDС) and an alternating electromagnetic field (ВАС), which were similar in their intensities. Their magnetic characteristics were as follows: (CMF‐1) ВDC = 46.80 µТ, ВАС = 86.11 µT, f = 807.0 Hz; (CMF‐2) ВDC = 46.80 µТ, ВАС = 86.11 µT, f = 38.3 Hz; that is, the frequencies of applied alternating electromagnetic fields coincided with cyclotron frequencies of phosphorus or ferric ions, respectively. The blank variants were exposed to the geomagnetic field. The CMFs increased bacterial consumption of dissolved iron as measured by residual concentrations of iron in the medium (P > 99%). An increase of bacterial nitrate reduction in the CMFs was statistically insignificant (P > 90%) when measured by residual concentrations of nitrate. Application of CMFs can influence bacterial activity and metabolism. Bioelectromagnetics. 2018;39:485–490, 2018. © 2018 Wiley Periodicals, Inc.
Development and validation of a UPLC–MS/MS method for determination of Sarsasapogenin‐AA22 in rat plasma and its application to a pharmacokinetic study
Authors: Pei Lixia , Ge Songlan , Ye Yiyi , Jiang Ziwei , Liang Xiaoqiang , Zhao Wenshu , Ma Lei
Published: May 2018

A sarsasapogenin derivative, sarsasapogenin‐AA22 (AA22), with cyclobutylamine at the 3‐hydroxyl position of sarsasapogenin, has great neuroprotective activity in PC12 cells and NO production inhibitory activity in RAW264.7 cell lines. A method was developed to determine AA22 in rat plasma which was further applied to evaluate the pharmacokinetics of AA22 after taking a single dose of AA22. Liquid chromatography tandem mass spectrometry was used in the method, while diosgenin was used as internal standard. A simple protein precipitation based on acetonitrile was utilized. A simple sample cleanup promoted the throughput of the method considerably. The method was validated over the range of 1–1000 ng/mL with a correlation coefficient > 0.99. The lower limit of quantification was 1 ng/mL for AA22 in plasma. Intra‐ and inter‐day accuracies for AA22 were 92–111 and 100–103%, respectively, and the inter‐day precision was <15%. After a single oral dose of 25 mg/kg of AA22, the mean peak plasma concentration of AA22 was 2114 ± 362 ng/mL at 6 h. The area under the plasma concentration–time curve was 196,098 ± 69,375 h ng/mL, and the elimination half‐life was 8.7 ± 2.2 h.
Multivariate optimization and characterization of simultaneous removal of binary mixture of Cu(II) and Pb(II) using Fe3O4@MoS2 nanoparticles
Authors: Zolgharnein Javad , Rastgordani Mahdieh
Published: May 2018

In this study, a facile hydrothermal method was used for the synthesis of Fe3O4@MoS2 magnetic nanoparticles. Then, this compound was used as an efficient adsorbent for the simultaneous removal of Cu(II) and Pb(II) ions from water. The prepared nanoparticles were characterized by scanning electron microscopy, X‐ray diffraction, vibrating sample magnetometer, and Fourier transform infrared spectroscopy. In addition, the effect of operational parameters on the adsorption process, such as initial pH, the concentration of metal ions, and sorbent mass, was investigated. The results of response surface methodology, obtained from Box‐Behnken design, was used to optimize the removal percent (%R) of Cu(II) and Pb(II). The effect of the different variables and their interactions was displayed by a regression model. A good agreement was seen between the proposed quadratic model resulting from Box‐Behnken design approach and the experimental data. According to the obtained results, the optimized conditions for the removal of metal ions were as follows: pH = 3, sorbent dose = 0.05 g, CPb (initial Pb(II) concentration) = 240.70 mg/L, and CCu (initial Cu(II) concentration) = 198 mg/L. The adsorption of both Freundlich and Langmuir isotherm models and pseudo‐second‐order kinetic model described the adsorption process well (R2 > 0.99). The obtained amounts of the thermodynamic parameters, such as ∆G°, ∆S°, and ∆H°, have proved that the adsorption of Pb(II) and Cu(II) ions on the surface of Fe3O4@MoS2 nanoparticles is spontaneous, feasible, and endothermic in nature.
Radical Cation π‐Dimers of Conjugated Oligomers as Molecular Wires: An Analysis Based on Nitronyl Nitroxide Spin Labels
Authors: Nishinaga Tohru , Kanzaki Yuki , Shiomi Daisuke , Matsuda Kenji , Suzuki Shuichi , Okada Keiji
Published: May 2018

Nitronyl nitroxide (NN)‐substituted conjugated oligomers, which were expected to self‐associate in biradical cation states, were designed to analyze the capability of π‐dimers as molecular wires. The oligomer moieties were composed of dithienyl‐N‐methylpyrrole with methoxy substituents at the inner β‐position of thiophene rings (DTP‐NN.) and its propylenedioxythiophene (ProDOT) inserted derivative (DTP‐P‐NN.), or two ethylenedioxythiophene (EDOT) and two ProDOT units (E2P2‐NN.). Among them, chemical one‐electron oxidation gave biradical cations (DTP‐P).+‐NN. and (E2P2).+‐NN. that formed π‐dimers (DTP‐P‐NN.)22+ and (E2P2‐NN.)22+ in dichloromethane at low temperatures. ESR studies of (DTP‐P‐NN.)22+ and (E2P2‐NN.)22+ showed the presence of a relatively strong exchange interaction between two NN radicals through the radical cation π‐dimer moieties. DFT calculations supported these experimental results and predicted that exchange interactions between two NN radicals were comparable or stronger than those through covalently linked quaterthiophene. Thus, the conjugated oligomer radical cation π‐dimers acted as efficient molecular wires for electronic communication.
Spiro‐epoxyglycosides as Activity‐Based Probes for Glycoside Hydrolase Family 99 Endomannosidase/Endomannanase
Authors: Schröder Sybrin P. , Kallemeijn Wouter W. , Debets Marjoke F. , Hansen Thomas , Sobala Lukasz F. , Hakki Zalihe , Williams Spencer J. , Beenakker Thomas J. M. , Aerts Johannes M. F. G. , van der Marel Gijsbert A. , Codée Jeroen D. C. , Davies Gideon J. , Overkleeft Herman S.
Published: May 2018

N‐Glycans direct protein function, stability, folding and targeting, and influence immunogenicity. While most glycosidases that process N‐glycans cleave a single sugar residue at a time, enzymes from glycoside hydrolase family 99 are endo‐acting enzymes that cleave within complex N‐glycans. Eukaryotic Golgi endo‐1,2‐α‐mannosidase cleaves glucose‐substituted mannose within immature glucosylated high‐mannose N‐glycans in the secretory pathway. Certain bacteria within the human gut microbiota produce endo‐1,2‐α‐mannanase, which cleaves related structures within fungal mannan, as part of nutrient acquisition. An unconventional mechanism of catalysis was proposed for enzymes of this family, hinted at by crystal structures of imino/azasugars complexed within the active site. Based on this mechanism, we developed the synthesis of two glycosides bearing a spiro‐epoxide at C‐2 as electrophilic trap, to covalently bind a mechanistically important, conserved GH99 catalytic residue. The spiro‐epoxyglycosides are equipped with a fluorescent tag, and following incubation with recombinant enzyme, allow concentration, time and pH dependent visualization of the bound enzyme using gel electrophoresis.
Immediate histopathologic follow‐up of cervista and aptima high‐risk HPV assays in women with LSIL cytology
Authors: Zhang Huina , Varma Kavita R. , Han Min , Matsko Jonee , Zhao Chengquan
Published: May 2018

BACKGROUND

Recent guidelines recommended the optional deferral of colposcopy for postmenopausal women with low‐grade squamous intraepithelial lesion (LSIL) Papanicolaou (Pap) test results and negative human papillomavirus (HPV) testing. The objective of the current study was to assess the histopathologic follow‐up of Cervista and Aptima high‐risk HPV (hrHPV) testing in patients with LSIL cytology.

METHODS

Women with LSIL Pap test results and Cervista or Aptima hrHPV testing results were retrospectively identified from June 2013 through July 2017. Histological follow‐up results within 6 months after LSIL Pap tests were analyzed.

RESULTS

A total of 1731 and 1906 cases of LSIL Pap tests, respectively, were tested on Cervista and Aptima platforms. Among the 2119 cases with histopathologic follow‐up, cervical intraepithelial neoplasia of types 2/3 (CIN2/3) was diagnosed in 184 women (8.9%) and the detection rate was significantly higher in women with positive HPV testing compared with those with a negative result on both assays. Both methods demonstrated comparable performance for detecting CIN2/3 lesions. However, in women aged ≥50 years, the specificity for the detection of CIN2/3 lesions by the Aptima assay was statistically significantly higher than that of the Cervista test (48.7% vs 23.1%; P<.01), although there were no significant differences in the sensitivity, positive predictive value, and negative predictive value between these 2 assays in this age group.

CONCLUSIONS

The Aptima assay was found to be statistically significantly more specific than the Cervista test for detecting CIN2/3 lesions among women aged ≥50 years. These findings not only further support the recommendations by the American Society for Colposcopy and Cervical Pathology that hrHPV triage is an acceptable option for postmenopausal women with LSIL cytology, but also provide additional evidence that HPV RNA testing may be more useful in clinical risk stratification due to its specificity in the postmenopausal population. Cancer Cytopathol 2018. © 2018 American Cancer Society.
Monitoring the Effects of Pharmacological Reagents on Mitochondrial Morphology
Authors: Fu Dong , Lippincott‐Schwartz Jennifer
Published: May 2018

This protocol describes how to apply appropriate pharmacological controls to induce mitochondrial fusion or fission in studies of mitochondria morphology for four different mammalian cell types, HepG2 human liver hepatocellular carcinoma cells, MCF7 human breast adenocarcinoma cells, HEK293 human embryonic kidney cells, and collagen sandwich culture of primary rat hepatocytes. The protocol provides methods of treating cells with these pharmacological controls, staining mitochondria with commercially available MitoTracker Green and TMRE dyes, and imaging the mitochondrial morphology in live cells using a confocal fluorescent microscope. It also describes the cell culture methods needed for this protocol. © 2018 by John Wiley & Sons, Inc.
Adsorption of Hydrogen Sulfide, Hydrosulfide and Sulfide at Cu(110) ‐ Polarizability and Cooperativity Effects. First Stages of Formation of a Sulfide Layer.
Authors: Lousada Cláudio M. , Johansson Adam Johannes , Korzhavyi Pavel A.
Published: May 2018

Understanding the surface site preference for single adsorbates, the interactions between adsorbates, how these interactions affect surface site specificity in adsorption and perturb the electronic states of surfaces is important for rationalizing the structure of interfaces and the growth of surface products. Herein, using density functional theory (DFT) calculations, we investigated the adsorption of H2S, HS and, S onto Cu(110). The surface site specificity observed for single adsorbates can be largely affected by the presence of other adsorbates, especially S that can affect the adsorption of other species even at distances of 13 Å. The large supercell employed with a surface periodicity of (6×6) allowed us to safely use the Helmholtz method for the determination of the dipole of the surface‐adsorbate complex at low adsorbate coverages. We found that the surface perturbation induced by S can be explained by the charge transfer model, H2S leads to a perturbation of the surface that arises mostly from Pauli exclusion effects, whereas HS shows a mix of charge transfer and Pauli exclusion effects. These effects have a large contribution to the long range adsorbate‐adsorbate interactions observed. Further support for the long range adsorbate‐adsorbate interactions are the values of the adsorption energies of adsorbate pairs that are larger than the sum of the adsorption energies of the single adsorbates that constitute the pair. This happens even for large distances and thus goes beyond the H‐bond contribution for the H‐bond capable adsorbate pairs. Exploiting this knowledge we investigated two models for describing the first stages of growth of a layer of S‐atoms at the surface: the formation of islands versus the formation of more homogeneous surface distributions of S‐atoms. We found that for coverages lower than 0.5 ML the S‐atoms prefer to cluster as islands that evolve to stripes along the [1
0] direction with increasing coverage. At 0.5 ML a homogeneous distribution of S‐atoms becomes more stable than the formation of stripes. For the coverage equivalent to 1 ML, the formation of two half‐monolayers of S‐atoms that disrupt the Cu−Cu bonds between the first and second layer is more favorable than the formation of 1 ML homogeneous coverage of S‐atoms. Here the S−Cu bond distances and geometries are reminiscent of pyrite, covellite, and to some extent chalcocite. The small energy difference of ≈0.1 eV that exists between this structure and the formation of 1 ML suggests that in a real system at finite temperature both structures may coexist leading to a structure with even lower symmetry.
Shigella Pathogenesis Modeling with Tissue Culture Assays
Authors: Koestler Benjamin J. , Ward Cara M. , Payne Shelley M.
Published: May 2018

Shigella is an enteroinvasive human pathogen that infects the colonic epithelium and causes Shigellosis, an infectious diarrheal disease. There is no vaccine for the prevention or treatment of Shigellosis and antibiotic‐resistant strains of Shigella are increasing, emphasizing the need for a deeper understanding of Shigella pathogenesis in order to design effective antimicrobial therapies. Small animal models do not recapitulate Shigellosis, therefore tissue‐cultured cells have served as model systems to study Shigella pathogenesis. Here, protocols to enumerate Shigella invasion, cell‐cell spread, and plaque formation in the tissue‐cultured cell lines Henle‐407 and CoN‐841 are described. Additionally, a new method to study Shigella invasion in primary intestinal enteroids is described. These protocols can be used to examine different aspects of Shigella virulence. © 2018 by John Wiley & Sons, Inc.
Organocatalytic Asymmetric Decarboxylative Addition of β‐Ketoacids to Methyleneindolinones Derivatives
Authors: Kumari Anita , Kaur Jasneet , Bhardwaj Vimal K. , Chimni Swapandeep Singh
Published: May 2018

The quinine squaramide‐catalyzed enantioselective decarboxylative addition reaction of various β‐keto acids with methyleneindolinones has been developed. Through this methodology, various oxindole derivatives were synthesized in good yields (up to 93 %) and excellent enantiomeric excess (up to 99 % ee) and moderate diastereoselectivity (up to 66:34).