bluuebunny/crossref_metadata_2025 huggingface dataset:
Copulatory Postures
Authors: Reagan Natalia
Published: April 2017

Primates, especially human primates, engage in a wide range of copulatory postures. One posture used by all species of primate is dorsoventral copulation, in which the male mounts the female from behind. However, there are variations on this type of copulatory position between species. Members of the family Hominidae and Hylobatidae also engage in ventroventral copulatory posture, in which the individuals face one another.
Eosimias
Authors: Beard Chris
Published: April 2017

The “dawn monkey”
Eosimias
is the oldest fossil primate to be widely recognized as being a member of the anthropoid clade, which includes living monkeys, apes, and humans. Species of
Eosimias
have been discovered at sites in central and eastern China, where they range in age from approximately 40–45 million years ago (middle Eocene). Species of
Eosimias
were small‐bodied primates, with adult body mass ranging from less than 100 grams to approximately 200 grams, making them smaller than even the smallest living anthropoids (
Cebuella
).
Eosimias
conforms to traditional concepts of a “transitional fossil” because it has a unique combination of primitive and derived features that is unknown among living primates.
Eosimias
is pivotal for reconstructing the earliest phases of anthropoid evolution, because it indicates an Asian origin for anthropoids that was millions of years earlier than was previously thought.
Prehensile Tail
Authors: Bezanson Michelle
Published: April 2017

A prehensile tail is one that is capable of grasping a substrate and sustaining the entire mass of an individual. Six primate genera exhibit tail prehensility:
Alouatta
(howling monkeys),
Ateles
(spider monkeys),
Brachyteles
(muriquis),
Cebus/Sapajus
(capuchin monkeys), and
Lagothrix
(woolly monkeys). It appears that the prehensile tail has evolved twice in these neotropical primates, once in the common ancestor of the Atelidae (
Alouatta
,
Ateles
,
Brachyteles
, and
Lagothrix
) and once in
Cebus
/
Sapajus
. In the Atelidae, the tail is relatively long and features a ventrodistal friction pad that is covered in dermatoglyphics. In
Cebus
/
Sapajus
, the tail is relatively shorter and fully furred. The prehensile tail is often described as a “fifth limb” that aids in support, balance, and maneuverability during feeding, foraging, travel, rest, and social behaviors. All prehensile‐tailed primates use their tail in both above‐branch and below‐branch feeding postures.
Ateles
and
Brachyteles
also employ their tail during below‐branch suspensory locomotion.
Primates in Urban Settings
Authors: Sinha Anindya , Vijayakrishnan Sreedhar
Published: April 2017

Nonhuman primates have coexisted with humans in urban habitats since historical times. While primate responses to human disturbances are variable and species‐specific, certain populations have adapted ecologically, behaviorally, or physiologically and appear to thrive in urban landscapes, depending on the availability, quality, and quantity of resources available. The ecological changes that urban primates face have also led to various behavioral innovations, especially in habitat selection and dietary preferences, which enable these populations to survive and persist in urban environments. Certain biological consequences of urbanization, however, include biological stress, cross‐species disease transmission, polyspecific associations and hybridization, and low population genetic variability. While urban human–nonhuman primate relationships are influenced by human cultural and individual attitudes, competition and conflict over resources is currently of great concern. Reactive and preventive management practices need to be introduced in order to reduce human–nonhuman primate conflict and ensure the conservation of the last remaining primate populations in urban spaces.
Megaladapidae
Authors: Godfrey Laurie R.
Published: April 2017

“Koala” lemurs (family Megaladapidae, genus
Megaladapis
) are members of a spectacular radiation of primates, the lemurs, on the island of Madagascar. All members of
Megaladapis
became extinct recently, well after humans colonized the island, and some possibly even after Europeans arrived.
Megaladapis
converged strikingly on koalas of Australia due primarily to similarities in diet and posture in trees. While
Megaladapis
is noted for its large size and peculiar cranial characters (especially its very long and narrow skull with laterally oriented orbits), its anatomical features are easily understood when its folivorous lifestyle is considered. Despite its peculiarities,
Megaladapis
is unquestionably a lemur, likely most closely related to the living lemurids.
Ape Language
Authors: Jensvold Mary Lee A.
Published: April 2017

In ape language studies, chimpanzees, bonobos, gorillas, and orangutans use sign language or artificial symbolic systems in interactions with humans and each other. These studies provide a tool to examine communication, behavior, and cognition of apes. Living conditions varied from cross‐fostering, homes, and laboratories. Sign language is an extension of natural ape communication behavior and acquisition occurred in patterns like human children. They showed conversational skills such as initiation and turn taking and a variety of communicative functions. One chimpanzee learned signs from other chimpanzees. Artificial language systems examined grammatical skill through plastic tokens and lexigrams. Bonobos and chimpanzees used these systems. Consideration in methodology includes conversational contexts, controls for cuing, and comparable conditions.
Hypertrophied Clitoris
Authors: Campbell Christina J.
Published: April 2017

A hypertrophied clitoris (or clitoral hypertrophy) is when the clitoris is enlarged beyond normal proportions. Nonhuman primate clitoral hypertrophy is restricted to five genera of New World Monkey—three genera in the Atelinae subfamily,
Ateles
(spider monkeys),
Brachyteles
(muriquis), and
Lagothrix
(woolly monkeys), and the capuchin monkey genera
Cebus
and
Sapajus
. It is smallest in the capuchin genera and largest in
Ateles
species. Explanations for the evolution of this feature have traditionally centered on the spread of olfactory cues of female reproductive state.
Molecular Diversity
Authors: Shattuck Milena R. , Disotell Todd R.
Published: April 2017

Recent advances in technology, along with ever lowering costs, have made it possible for a growing number of researchers to ascertain genetic diversity within and across primate species. Combined with observational data about primate behavior and morphology, measures of genetic diversity enable us to address important evolutionary questions to a degree that traditional approaches do not allow. In this entry we review some of the most commonly used measures of genetic diversity and a few of their potential applications in primate studies.
Estrus
Authors: Campbell Christina J.
Published: April 2017

Estrus refers to the cyclical occurring and typically brief period of time during which a female is willing and able to engage in sexual activity. In most mammalian species, female sexual activity coincides with ovulation, thus making conception feasible. Within the primates, female prosimians exhibit estrous cycles, while anthropoid females are more flexible in terms of the timing of sexual activity in relation to their ovarian cycle. As a result of this apparent decoupling of sexual behavior and hormonal control, the estrous concept as originally defined does not apply to anthropoids. While alternatives have been proposed, the term is still widely used by primatologists.
DNA
Sequencing
Authors: Disotell Todd R.
Published: April 2017

DNA sequencing is an important tool in primatology that provides the raw data for phylogenetic and population genetic analyses, inferring relatedness among organisms, examining functional aspects of physiology and development, identifying genes and genomes of commensals through analyses of microbiomes, dietary analyses, and even carrying out censuses and surveys in the broader environment.
Ape Diets
Authors: Morgan David B.
Published: April 2017

The three genera of great apes, gorillas (Gorilla), orangutans (Pongo), chimpanzees and bonobos (Pan), live in floristically diverse and dynamic environments. One of the main elements central to their ecology is diet. The breadth and selectivity of population diets are a facet of their altitude, local ecology, geology, and climate. As a result of their wide geographical distributions, dietary regimes vary, as do harvesting techniques. While all populations of great ape feature diverse diet repertoires, plant material makes up the bulk of the items consumed, with succulent high‐quality fruits preferred. Periodic shifts in climate cause fluctuations in most populations' foraging habits, and when preferred foods decline, items of lower nutritional value, or fallback foods (FBF), are relied upon. These dietary changes associated with seasonality have implications on social grouping and ranging patterns and potentially even cognitive abilities. The highly frugivorous species within the genusesPanandPongoare rather unique in the animal kingdom owing to their abilities to acquire hard‐to‐obtain embedded items such as insects and honey through the use of tool technology.
H
arlow,
H
arry
Authors: Arcus Doreen
Published: April 2017

Harry Harlow (1905–81) is best known for pioneering work on separation and attachment in rhesus macaques isolated during infancy, showing that, when threatened, these infants clung to terry cloth structures that did not provide nourishment. Infant preference for “contact comfort” provided an empirical challenge to Freudian and behavioral explanations of how humans learn to love.
Adolescent Sterility
Authors: Campbell Christina J.
Published: April 2017

Adolescent sterility, or adolescent subfecundity, refers to a period of time during which pubescent females experience irregular and/or anovulatory ovarian cycles, resulting in a lack of conception. In addition to this physiological explanation for reduced fertility, or perhaps as a result of it, pubescent females may be sexually unattractive to males, thus not conceiving because of a lack of sexual activity. Although female adolescent sterility has been documented for a number of primate species, it does not appear to occur in pubescent male primates.
Paleoenvironmental and Sea‐Level Change
Authors: Elton Sarah
Published: April 2017

Ancient environmental and sea‐level changes are very likely to have played key roles in primate speciation, extinction, adaptation, and dispersal. Most modern primates are ecologically dependent on trees and inhabit tropical environments, and the same was true for many extinct primates. In the warm Paleocene and Eocene when the tropical broadleaf forest biome extended to high latitudes, primates inhabited North America and northern Eurasia. Ranges then contracted into lower latitudes in the Eocene and Oligocene when global cooling caused a commensurate reduction in suitable tree cover, only to expand again in the Miocene, when most primates across Africa, Eurasia, and South America exploited diverse forest and woodland environments, which may have been very different to those observed in similar regions today. By the end of the Miocene through to the Pleistocene, grassland expansion allowed more terrestrial and open habitat primates to radiate, although most retained some ecological dependence on trees. Sea‐level changes occurring since the origin of primates, causing events such as the closure of the eastern Tethys Sea, appearance of the Isthmus of Panama, and shifts in Southeast Asian archipelagos, influenced primate dispersal and diversification. Changes to ocean circulation caused by sea‐level change may have impacted global climate, which in turn would have altered primate environments.
Environmental Stress
Authors: Lewis Alycia E.
Published: April 2017

Environmental stress refers to an external experience, ecological or anthropogenic, that disrupts an organism's equilibrium. Reactions to different stressors outline behavioral and physiological adaptations experienced by primate populations. Common environmental stressors are related to seasonality, food shortage, predation, and, more recently, anthropogenic disturbances. Presently, environmental stress is identified in nonhuman primates through observational and biological studies.
Daubentoniidae (Aye‐Aye)
Authors: Freed Benjamin Z.
Published: April 2017

Aye‐ayes are among the most specialized primates. They are represented by one extant 2.6‐kilogram species,
Daubentonia madagascariensis
, making them the largest extant nocturnal primates. Another extinct species,
D. robusta
, was much more robust and larger at 14 kilograms.
Sexual Dimorphism
Authors: Paciulli Lisa M.
Published: April 2017

Sexual dimorphism is a difference in secondary sex characteristics between males and females of the same species. Secondary sex differences are those not directly related to sexual structures or organs, mating, and/or parental investment (which are primary sex differences). Secondary sex differences include body size/mass, shape, color, and behavior, and are highly variable. In primates, sexual dimorphism is common in anthropoids (monkeys, apes, and humans) and less so in prosimians (lemurs, lorises, galagos, and tarsiers).
Evolution of Modern Strepsirhines
Authors: Masters Judith C. , Pozzi Luca , Godfrey Laurie R.
Published: April 2017

The modern strepsirhines (as distinct from the extinct Eocene strepsirhines, or Adapiformes, and including the recently extinct subfossil lemurs) make up a major proportion of Holocene primate diversity. Their current range includes the tropical and subtropical forests and woodlands of Africa, Madagascar, and Southeast Asia. By far the greatest diversity at both the species and family levels occurs on the island continent of Madagascar despite the fact that the area potentially available to strepsirhines on the continental mainland is at least 40 times as great. Like haplorhines, strepsirhines have an evolutionary history dating back at least 60 million years, and have evolved to survive and reproduce in modern environments and habitats.
Social System (Social Structure)
Authors: Loudon James E.
Published: April 2017

Primates live in dynamic, complex societies and exhibit a wide breadth of grouping patterns, mating systems, and inter‐ and intragroup social relationships. Traditionally, the social structures of primates have been placed in three broad categories consisting of pair‐living, group‐living, and solitary primates. Understanding primate social structures from ecological and evolutionary perspectives is of primary importance to the field of primatology. As such, a number of socioecological models have been developed to explain and understand primate social structures. These models have met with varying degrees of success, but have undoubtedly pushed the discipline of primatology significantly forward by providing testable frameworks by which primatologists can understand primate social organizations and behavior.
Abkhazian Primate Research Center
Authors: Lapin B. A. , Mikvabia Z. Ya.
Published: April 2017

After the Georgian–Abkhazian military conflict in the early 1990s, the monkey colony in Sukhum (Sukhumi) was significantly damaged. The Institute's material and technical resources had been destroyed, and the monkey population had decreased from 7,000 to 200 animals. Especially difficult was the disappearance of the hamadryas baboon, which had included representatives of ten generations. The branch of the monkey colony in Tamysh village and two reserves in Sukhum region vanished, and leading scientists resigned. The colony has since recovered, and the Institute is now the leading institution of the Abkhazian Academy of Sciences.
Arbitrarily Shaped 2.5D Circuits using Stretchable Interconnects Embedded in Thermoplastic Polymers
Authors: Plovie Bart , Yang Yang , Guillaume Joren , Dunphy Sheila , Dhaenens Kristof , Van Put Steven , Vandecasteele Björn , Vervust Thomas , Bossuyt Frederick , Vanfleteren Jan
Published: April 2017

A method to fabricate thermoplastically deformable electronic circuits is presented, with the intent of achieving low‐cost 2.5D free‐form rigid smart objects. This by utilizing existing flexible circuit technology based stretchable circuits, in combination with thermoplastic materials. After fabricating the circuit in a flat state, a thermoforming step shapes the device by heating it beyond its glass transition temperature, and pushing it against a mold. Preliminary tests show the feasibility to fabricate simple circuits using off‐the‐shelf circuit components; showing a minimal decrease in conductivity of the polyimide supported copper‐based interconnects.
Panitumumab‐Conjugated Pt‐Drug Nanomedicine for Enhanced Efficacy of Combination Targeted Chemotherapy against Colorectal Cancer
Authors: Tsai Ming‐Hsien , Pan Chao‐Hsuan , Peng Cheng‐Liang , Shieh Ming‐Jium
Published: April 2017

Targeted combination chemotherapy (TCT) has recently been used to increase the induction of tumor cell death. In particular, the combination of Panitumumab and the platinum (Pt)‐derived chemotherapeutic drug Oxaliplatin is clinically effective against KRAS and BRAF wild‐type colorectal cancer (CRC) cells that overexpress epidermal growth factor receptors, and significantly greater efficacy is observed than with either drug alone. However, low accumulation of Pt drug in tumor sites prevents achievement of ideal efficacy. To develop an alternative drug therapy that achieves the ideal efficacy of TCT, the novel nanomedicine NANOPt‐Pan using self‐assembled dichloro(1,2‐diaminocyclohexane)Pt(II)‐modified Panitumumab is generated. Treatments with NANOPt‐Pan lead to significant accumulation of Pt drug and Panitumumab in tumors, reflecting enhanced permeability and retention effect, active targeting, and sustained circulation of the Pt drug in the blood. In addition, NANOPt‐Pan has excellent in vivo anti‐CRC efficacy. These data indicate that NANOPt‐Pan has high potential as a candidate nanomedicine for CRC.
Anomalous Resistance Hysteresis in Oxide ReRAM: Oxygen Evolution and Reincorporation Revealed by In Situ TEM
Authors: Cooper David , Baeumer Christoph , Bernier Nicolas , Marchewka Astrid , La Torre Camilla , Dunin‐Borkowski Rafal E. , Menzel Stephan , Waser Rainer , Dittmann Regina
Published: April 2017

The control and rational design of redox‐based memristive devices, which are highly attractive candidates for next‐generation nonvolatile memory and logic applications, is complicated by competing and poorly understood switching mechanisms, which can result in two coexisting resistance hystereses that have opposite voltage polarity. These competing processes can be defined as regular and anomalous resistive switching. Despite significant characterization efforts, the complex nanoscale redox processes that drive anomalous resistive switching and their implications for current transport remain poorly understood. Here, lateral and vertical mapping of O vacancy concentrations is used during the operation of such devices in situ in an aberration corrected transmission electron microscope to explain the anomalous switching mechanism. It is found that an increase (decrease) in the overall O vacancy concentration within the device after positive (negative) biasing of the Schottky‐type electrode is associated with the electrocatalytic release and reincorporation of oxygen at the electrode/oxide interface and is responsible for the resistance change. This fundamental insight presents a novel perspective on resistive switching processes and opens up new technological opportunities for the implementation of memristive devices, as anomalous switching can now be suppressed selectively or used deliberately to achieve the desirable so‐called deep Reset.
Fast and Highly Sensitive Ionic‐Polymer‐Gated WS2–Graphene Photodetectors
Authors: Mehew Jake D. , Unal Selim , Torres Alonso Elias , Jones Gareth F. , Fadhil Ramadhan Saad , Craciun Monica F. , Russo Saverio
Published: April 2017

The combination of graphene with semiconductor materials in heterostructure photodetectors enables amplified detection of femtowatt light signals using micrometer‐scale electronic devices. Presently, long‐lived charge traps limit the speed of such detectors, and impractical strategies, e.g., the use of large gate‐voltage pulses, have been employed to achieve bandwidths suitable for applications such as video‐frame‐rate imaging. Here, atomically thin graphene–WS2 heterostructure photodetectors encapsulated in an ionic polymer are reported, which are uniquely able to operate at bandwidths up to 1.5 kHz whilst maintaining internal gain as large as 106. Highly mobile ions and the nanometer‐scale Debye length of the ionic polymer are used to screen charge traps and tune the Fermi level of the graphene over an unprecedented range at the interface with WS2. Responsivity R = 106 A W−1 and detectivity D* = 3.8 × 1011 Jones are observed, approaching that of single‐photon counters. The combination of both high responsivity and fast response times makes these photodetectors suitable for video‐frame‐rate imaging applications.
A Bioinspired Mineral Hydrogel as a Self‐Healable, Mechanically Adaptable Ionic Skin for Highly Sensitive Pressure Sensing
Authors: Lei Zhouyue , Wang Quankang , Sun Shengtong , Zhu Wencheng , Wu Peiyi
Published: April 2017

In the past two decades, artificial skin‐like materials have received increasing research interests for their broad applications in artificial intelligence, wearable devices, and soft robotics. However, profound challenges remain in terms of imitating human skin because of its unique combination of mechanical and sensory properties. In this work, a bioinspired mineral hydrogel is developed to fabricate a novel type of mechanically adaptable ionic skin sensor. Due to its unique viscoelastic properties, the hydrogel‐based capacitive sensor is compliant, self‐healable, and can sense subtle pressure changes, such as a gentle finger touch, human motion, or even small water droplets. It might not only show great potential in applications such as artificial intelligence, human/machine interactions, personal healthcare, and wearable devices, but also promote the development of next‐generation mechanically adaptable intelligent skin‐like devices.
Compressing Carbon Nanocages by Capillarity for Optimizing Porous Structures toward Ultrahigh‐Volumetric‐Performance Supercapacitors
Authors: Bu Yongfeng , Sun Tao , Cai Yuejin , Du Lingyu , Zhuo Ou , Yang Lijun , Wu Qiang , Wang Xizhang , Hu Zheng
Published: April 2017

High volumetric energy density combined with high power density is highly desired for electrical double‐layer capacitors. Usually the volumetric performance is improved by compressing carbon material to increase density but at the much expense of power density due to the deviation of the compressed porous structure from the ideal one. Herein the authors report an efficient approach to increase the density and optimize the porous structure by collapsing the carbon nanocages via capillarity. Three samples with decreasing sizes of meso‐ and macropores provide us an ideal model system to demonstrate the correlation of volumetric performance with porous structure. The results indicate that reducing the surplus macropores and, more importantly, the surplus mesopores is an efficient strategy to enhance the volumetric energy density while keeping the high power density. The optimized sample achieves a record‐high stack volumetric energy density of 73 Wh L−1 in ionic liquid with superb power density and cycling stability.
A Novel Approach to Fabricate Protective Layered Double Hydroxide Films on the Surface of Anodized Mg‐Al Alloy
Authors: Zhang Gen , Wu Liang , Tang Aitao , Zhang Shuo , Yuan Bo , Zheng Zhicheng , Pan Fusheng
Published: April 2017

In this work, anodic films consisted of a mixed oxide of aluminum and magnesium are developed on magnesium alloy by anodizing process. Then, MgAl‐layered double hydroxide (LDH) films are prepared by using this anodic film as a source of cations, without the introduction of any kinds of trivalent metal salts. After that, inhibitor anions of vanadate are intercalated into the interlayer galleries of LDHs through anion‐exchange process. LDH conversion films are investigated by scanning electron microscope, energy dispersive spectrum, X‐ray diffractometer, and Fourier transform infrared, respectively. Furthermore, the corrosion resistance of LDH conversion films are studied by potentiodynamic polarization, electrochemical impedance spectroscopy, and immersion test in NaCl solution, respectively. The results show that uniform and fine LDH films are successfully fabricated by using only anodic films, and the pores in anodic films are successfully sealed by LDHs. Moreover, the vanadate loaded LDHs exhibit better corrosion resistance compared to LDHs without vanadate.
Wearable Mechanotransduced Tactile Sensor for Haptic Perception
Authors: Yeo Joo Chuan , Liu Zhuangjian , Zhang Zhi‐Qian , Zhang Pan , Wang Zhiping , Lim Chwee Teck
Published: April 2017

Haptic tactile acuity is an important element for object recognition and manipulation. However, ascribing tactile acuity unto artificial systems is extremely challenging, as it requires active touch exploration involving multidirectional manipulation and sensing. This work reports a skin‐inspired liquid‐based microfluidic tactile sensor capable of haptic perception. The tactile sensor comprises a uniquely designed elastomeric structure with a microfluidic protrusion. Multidirectional forces on the protrusion result in unique fluid displacement that can be measured electrically. This unique architecture is sensitive enough to discriminate surface changes below 0.5 mm. Our sensor is thin, flexible, and robust, allowing adhesion to skin to directly discriminate surface features, contour changes, and object stiffness. We further show a proof of concept of our wearable tactile sensor for Braille reading, enabling the identification of letters by scanning across standard Braille codes. This technology has potential in enabling haptic perception for users affected by sensory neuropathy or for implementation in medical, social, and assistive robotics.
Crumpled Graphene Triboelectric Nanogenerators: Smaller Devices with Higher Output Performance
Authors: Chen Huamin , Xu Yun , Bai Lin , Jiang Yu , Zhang Jiushuang , Zhao Chen , Li Tong , Yu Hailong , Song Guofeng , Zhang Nan , Gan Qiaoqiang
Published: April 2017

The rapid growth of flexible and stretchable electronics paves the way toward compact and wearable power source devices. A shape‐adaptive and stretchable energy harvester is particularly attractive due to its mobility, sustainability, and availability. In this work, a crumpled‐graphene‐based stretchable triboelectric nanogenerator (TENG) to harvest mechanical energy under various deformations is reported. Due to the unique stretchability of crumpled graphene structures, the crumpled‐graphene‐based TENGs could operate under compressive mode, stretching mode, and, more uniquely, their hybridized mode. Importantly, by shrinking a given planar graphene layer into a smaller region, a more crumpled TENG device delivered a higher output voltage, revealing the superior potential to develop smaller and better performance power generators for emerging wearable electronics. Its application as the energy harvester and motion sensor was demonstrated using finger and wrist motions.
Rhodium(III)‐Catalyzed Cascade Redox‐Neutral C–H Functionalization and Aromatization: Synthesis of Unsymmetrical ortho‐Biphenols
Authors: Hu Zhiyong , Liu Guixia
Published: April 2017

An efficient rhodium(III)‐catalyzed coupling reaction of N‐aryloxyacetamides with 6‐diazo‐2‐cyclohexenones through a cascade redox‐neutral C–H functionalization and aromatization has been developed. This novel and scalable transformation provides a straightforward way to construct unsymmetrical ortho‐biphenols with broad substrate scope under mild and redox‐neutral conditions. The synthetic utility of this approach is demonstrated in the late‐stage functionalization of bioactive compounds and the synthesis of an optically active ortho‐biphenol.

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Recent Advances in Reactions of Azides
Authors: Huang Dayun , Yan Guobing
Published: April 2017

Azides are important intermediates in organic synthesis. They can function as precursors to form amines, amides, quinolones, pyridines, triazoles, amidines, indoles, and so on. Although there are some reviews about the applications of azides, few are concerned about their fundamental mechanisms. This review will focus on recent advances of azides based on three reactivity patterns, which may enlighten the further research.

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Diketopyrrolopyrrole‐Based Conjugated Polymer Entailing Triethylene Glycols as Side Chains with High Thin‐Film Charge Mobility without Post‐Treatments
Authors: Yang Si‐Fen , Liu Zi‐Tong , Cai Zheng‐Xu , Dyson Matthew J. , Stingelin Natalie , Chen Wei , Ju Hua‐Jun , Zhang Guan‐Xin , Zhang De‐Qing
Published: April 2017

Side chain engineering of conjugated donor–acceptor polymers is a new way to manipulate their optoelectronic properties. Two new diketopyrrolopyrrole (DPP)‐terthiophene‐based conjugated polymers PDPP3T‐1 and PDPP3T‐2, with both hydrophilic triethylene glycol (TEG) and hydrophobic alkyl chains, are reported. It is demonstrated that the incorporation of TEG chains has a significant effect on the interchain packing and thin‐film morphology with noticeable effect on charge transport. Polymer chains of PDPP3T‐1 in which TEG chains are uniformly distributed can self‐assemble spontaneously into a more ordered thin film. As a result, the thin film of PDPP3T‐1 exhibits high saturated hole mobility up to 2.6 cm2 V−1 s−1 without any post‐treatment. This is superior to those of PDPP3T with just alkyl chains and PDPP3T‐2. Moreover, the respective field effect transistors made of PDPP3T‐1 can be utilized for sensing ethanol vapor with high sensitivity (down to 100 ppb) and good selectivity.
Construction of Spiro[indene‐2,1′‐pyrrolo[2,1‐a]isoquinoline]s through a Visible‐Light‐Catalyzed Oxidative [3+2] Cycloaddition Reaction
Authors: Jiang Yan‐Hong , Sun Jing , Sun Qiu , Yan Chao‐Guo
Published: April 2017

Under visible‐light catalysis, a domino oxidative 1,3‐dipolar cycloaddition reaction of alkyl 2‐(3,4‐dihydroisoquinolin‐2‐yl)acetate with 2‐arylideneindane‐1,3‐diones has been developed that affords functionalized spiro[indene‐2,1′‐pyrrolo[2,1‐a]isoquinoline]s in satisfactory yields and high diastereoselectivities. Depending on the electronic properties of the aryl group, similar reactions with tert‐butyl 2‐(3,4‐dihydroisoquinolin‐2‐yl)acetate and 2‐(3,4‐dihydroisoquinolin‐2(1H)‐yl)acetonitrile selectively gave spiro[indene‐2,1′‐pyrrolo[2,1‐a]isoquinoline]s and 3‐arylspiro[indene‐2,2′‐oxirane]‐1,3‐diones, respectively.
Cobalt(II)/TFA‐Catalyzed Oxidative Esterification of Aldehydes and Alcohols: Dual Role of the Acid Co‐Catalyst
Authors: Mahmood Sajid , Li Ting , Xu Bao‐Hua , Guo Ya‐Fei , Zhang Suo‐Jiang
Published: April 2017

A CoII/CF3COOH (TFA)‐catalyzed oxidative esterification of aldehydes and alkanols by using tBuOOH as an oxidant is reported. A mechanistic investigation indicated that the oxidation reaction proceeded through the formation of a CoIII−OCH(OMe)R complex, followed by H‐atom abstraction by an in‐situ‐generated tBuO. radical. The former kinetic step was thought to be the selectivity‐determining step. Moreover, the strong acidity and TFA proton were beneficial for both the dehydrative formation of the CoIII−OCH(OMe)R complex and the redox properties of the cobalt atom, thereby offering high efficiency for the target oxidative cross‐coupling reaction.
Synthesis of Functionalized 4‐Fluoropyridazines
Authors: Feraldi‐Xypolia Alexandra , Fredj Gregory , Tran Gaël , Tsuchiya Tomoki , Vors Jean‐Pierre , Mykhailiuk Pavel , Gomez Pardo Domingo , Cossy Janine
Published: April 2017

A route to 4‐fluoropyridazines by a [2+1]/[3+2] cycloaddition sequence between an acetylenic derivative, a difluorocarbene source, and a diazo compound is reported. This approach is highly modular and compatible with a broad range of functional groups. The protocol does not require the isolation of any reactive intermediates and, thus, allows for access to a wide range of 4‐fluoropyridazines in a single synthetic step from simple alkynes. Furthermore, these fluorinated compounds can be easily diversified by nucleophilic aromatic substitution (SNAr) to displace the fluoro group to give a wider range of 3,4,6‐trisubstituted pyridazines. As a result of increasing interest in functionalized pyridazines as well as fluorinated derivatives, this efficient and concise approach to 4‐fluoropyridazines should be of value to medicinal chemists.
Cardiac arrest caused by rapidly increasing ascites in a patient with TAFRO syndrome: a case report
Authors: Okumura Masatoshi , Ujiro Atsushi , Otsuka Yasunori , Yamamoto Hiroshi , Wada Sho , Iwata Hirofumi , Kan Toshiaki , Miyauchi Seiji , Hashimoto Atsushi , Sato Yuko , Fujita Yoshihito , Fujiwara Yoshihiro , Shimaoka Hideki
Published: April 2017

Case

Thrombocytopenia, anasarca, fever, renal insufficiency, and organomegaly (TAFRO) syndrome is a newly defined systemic inflammatory disorder with gradual progression of symptoms. A 59‐year‐old man with fever and ascites of unknown cause developed sudden‐onset shock and respiratory failure in the general ward. Cardiac arrest immediately followed. Although he was resuscitated, frequent administration of adrenaline was required to maintain his blood pressure. His circulation was most effectively stabilized by drainage of fluid from his distended abdomen. The volume of discharged ascites reached 4,000 mL at that time, and several liters continued to be discharged for >1 month. The diagnosis of TAFRO syndrome was based on the clinical features and laboratory and histological findings.

Outcome

The ascites volume and concentrations of inflammatory parameters decreased with treatment using several immunosuppressive agents.

Conclusion

The newly defined TAFRO syndrome may be life‐threatening. Patients should be monitored for progression to shock and cardiac arrest, especially those with rapidly increasing ascites.
Von zweizähnigen Gallium‐Lewis‐Säuren zu supramolekularen Komplexen
Authors: Horstmann Jan , Hyseni Mentor , Mix Andreas , Neumann Beate , Stammler Hans‐Georg , Mitzel Norbert W.
Published: April 2017

Zweizähnige Gallium Lewis‐Säuren wurden ausgehend von Diethinyldiphenylsilan in reinem Trimethyl‐ oder Triethylgallium dargestellt. Bis[(dimethylgallanyl)ethinyl]diphenylsilan (1) und dessen Diethylgallanyl‐Derivat 2 wurden als Et2O‐ oder Pyridin‐Addukte NMR‐spektroskopisch charakterisiert; 2⋅2 Py wurde isoliert. Die Lewis‐Säuren 1 und 2 bilden Wirt‐Gast‐Addukte mit zweizähnigen Stickstoffbasen; dabei bilden sich nur bei passendem N⋅⋅⋅N‐Abstand cyclische 1:1‐Addukte aus 1 und 4,4′‐Dimethyl‐3,3′‐bipyridylacetylen (3), Bis[(pyrid‐3‐yl)ethinyl]diphenylsilan (4) oder Bis[(2‐methylpyrid‐5‐yl)ethyinyl]diphenylsilan (5). Die cyclischen Addukte 1⋅3, 1⋅4 und 1⋅5 wurde mittels Röntgenbeugungsexperimenten identifiziert. 2⋅2 Py reagiert mit DABCO zur polymeren Spezies (DABCO‐2‐)n.
Enantioselective Heck–Matsuda Arylations through Chiral Anion Phase‐Transfer of Aryl Diazonium Salts
Authors: Avila Carolina M. , Patel Jigar S. , Reddi Yernaidu , Saito Masato , Nelson Hosea M. , Shunatona Hunter P. , Sigman Matthew S. , Sunoj Raghavan B. , Toste F. Dean
Published: April 2017

A mild, asymmetric Heck–Matsuda reaction of five‐, six‐ and seven‐membered ring alkenes and aryl diazonium salts is presented. High yields and enantioselectivities were achieved using Pd0 and chiral anion co‐catalysts, the latter functioning as a chiral anion phase‐transfer (CAPT) reagent. For certain substrate classes, the chiral anion catalysts were modulated to minimize the formation of undesired by‐products. More specifically, BINAM‐derived phosphoric acid catalysts were shown to prevent alkene isomerization in cyclopentene and cycloheptene starting materials. DFT(B3LYP‐D3) computations revealed that increased product selectivity resulted from a chiral anion dependent lowering of the activation barrier for the desired pathway.
Cu/Pd Synergistic Dual Catalysis: Asymmetric α‐Allylation of an α‐CF3 Amide
Authors: Saito Akira , Kumagai Naoya , Shibasaki Masakatsu
Published: April 2017

Despite the burgeoning demand for fluorine‐containing chemical entities, the construction of CF3‐containing stereogenic centers has remained elusive. Herein, we report the strategic merger of CuI/base‐catalyzed enolization of an α‐CF3 amide and Pd0‐catalyzed allylic alkylation in an enantioselective manner to deliver chiral building blocks bearing a stereogenic carbon center connected to a CF3, an amide carbonyl, and a manipulable allylic group. The phosphine complexes of CuI and Pd0 engage in distinct catalytic roles without ligand scrambling to render the dual catalysis operative to achieve asymmetric α‐allylation of the amide. The stereoselective cyclization of the obtained α‐CF3‐γ,δ‐unsaturated amides to give tetrahydropyran and γ‐lactone‐fused cyclopropane skeletons highlights the synthetic utility of the present catalytic method as a new entry to non‐racemic CF3‐containing compounds.
Synthesis of Long Oxahelicenes by Polycyclization in a Flow Reactor
Authors: Nejedlý Jindřich , Šámal Michal , Rybáček Jiří , Tobrmanová Miroslava , Szydlo Florence , Coudret Christophe , Neumeier Maria , Vacek Jaroslav , Vacek Chocholoušová Jana , Buděšínský Miloš , Šaman David , Bednárová Lucie , Sieger Ladislav , Stará Irena G. , Starý Ivo
Published: April 2017

A series of oxahelicenes composed of ortho/meta‐annulated benzene/pyridine and 2H‐pyran rings were synthesized on the basis of the cobalt(I)‐mediated (or rhodium(I)‐ or nickel(0)‐mediated) double, triple, or quadruple [2+2+2] cycloisomerization of branched aromatic hexa‐, nona‐, or dodecaynes, thus allowing the construction of 6, 9, or 12 rings in a single operation. The use of a flow reactor was found to be beneficial for the multicyclization reactions. The stereogenic centers present in some of the oligoynes steered the helical folding in such a way that the final oxa[9]‐, [13]‐, [17]‐ and [19]helicenes were obtained in both enantiomerically and diastereomerically pure form. Specifically, the oxa[19]helicenes beat the current record in the length of a helicene backbone. Single‐molecule conductivity was studied by the mechanically controllable break‐junction method with a pyridooxa[9]helicene.
Catalytic Enantioselective Synthesis of 2,5‐Dihydrooxepines
Authors: Shim Su Yong , Cho Soo Min , Venkateswarlu Anipireddy , Ryu Do Hyun
Published: April 2017

A Michael addition initiated cyclopropanation/retro‐Claisen rearrangement tandem reaction was developed for the enantioselective synthesis of highly functionalized 2,5‐dihydrooxepines. In the presence of a chiral oxazaborolidinium ion (COBI) catalyst, the reaction proceeds to give good yields and high enantioselectivity.
Lewis Acid Promoted Single C–F Bond Activation of the CF3 Group: SN1′‐Type 3,3‐Difluoroallylation of Arenes with 2‐Trifluoromethyl‐1‐alkenes
Authors: Fuchibe Kohei , Hatta Hibiki , Oh Ken , Oki Rie , Ichikawa Junji
Published: April 2017

Activation of the sp3 C−F bond in 2‐trifluoromethyl‐1‐alkenes was accomplished through treatment with a Lewis acid. In the presence of an equimolar amount of EtAlCl2, the (trifluoromethyl)alkenes readily underwent an SN1′‐type reaction with arenes through a Friedel–Crafts‐type mechanism via elimination of a fluoride ion to afford 3,3‐difluoroallylated arenes in good yields. This selective activation of one C−F bond of the CF3 group provides a synthetic method for accessing biologically and synthetically important 1,1‐difluoro‐1‐alkenes.
Evaluation of Biological Activity and Computer‐Aided Design of New Soft Glucocorticoids
Authors: Dobričić Vladimir , Jaćević Vesna , Vučićević Jelica , Nikolic Katarina , Vladimirov Sote , Čudina Olivera
Published: April 2017

Soft glucocorticoids are compounds that are biotransformed to inactive and non‐toxic metabolites and have fewer side effects than traditional glucocorticoids. A new class of 17β‐carboxamide steroids has been recently introduced by our group. In this study, local anti‐inflammatory activity of these derivatives was evaluated by use of the croton oil‐induced ear edema test. Glucocorticoids with the highest maximal edema inhibition (MEI) were pointed out, and the systemic side effects of those with the lowest EC50 values were significantly lower in comparison to dexamethasone. A 3D‐QSAR model was created and employed for the design of 27 compounds. By use of the sequential combination of ligand‐based and structure‐based virtual screening, three compounds were selected from the ChEMBL library and used as a starting point for the design of 15 derivatives. Molecular docking analysis of the designed derivatives with the highest predicted MEI and relative glucocorticoid receptor binding affinity (20, 22, 24‐1, 25‐1, 27, VS7, VS13, and VS14) confirmed the presence of interactions with the glucocorticoid receptor that are important for the activity.
A Scalable and Versatile Synthesis of Oxime‐Based Hormone Dimers and Gels for Sustained Release
Authors: Bennett Christopher W. , Collins Joe , Xiao Zeyun , Klinger Daniel , Connal Luke A.
Published: April 2017

Well‐defined steroid hormone dimers and organogels were produced via a facile and scalable synthesis using oxime click chemistry. The versatile synthetic procedure extends to a wide range of hormones and linker groups exemplified here through the synthesis of cortisol‐ and progesterone‐dimers linked via hydrophobic, hydrophilic or functional groups. This method was also extended to the synthesis of cortisone‐based organogels. Owing to the dynamic nature of the oxime bond, the hormone‐based materials are degradable via acidic hydrolysis and transoximination representing new materials for the controlled release of steroid hormones.
Cyclometalated Iridium(III) Bipyridine–Phenylboronic Acid Complexes as Bioimaging Reagents and Luminescent Probes for Sialic Acids
Authors: Liu Hua‐Wei , Law Wendell Ho‐Tin , Lee Lawrence Cho‐Cheung , Lau Jonathan Chun‐Wai , Lo Kenneth Kam‐Wing
Published: April 2017

Sialic acids play important roles in mammalian development, cell–cell attachment, and signaling. As cancer cells utilize their overexpressed sialylated antigens to propagate metastases, the development of probes for sialic acids is of high importance. Herein, we report three luminescent cyclometalated iridium(III) bipyridine complexes bearing a phenylboronic acid (PBA) moiety. Spectrophotometric titrations revealed that the PBA complexes displayed higher binding affinity for the most common sialic acid N‐acetylneuraminic acid (Neu5Ac) compared with simple sugars that are commonly found on glycoproteins. Notably, cellular imaging and uptake experiments showed that the PBA complexes were able to recognize cellular sialic acid residues, resulting in more efficient uptake than the boronic acid‐free analogs. Additionally, one of the PBA complexes was shown to discriminate between cancerous and noncancerous cells.
Short Syntheses of 4‐Deoxycarbazomycin B, Sorazolon E, and (+)‐Sorazolon E2
Authors: Sako Makoto , Ichinose Kazuya , Takizawa Shinobu , Sasai Hiroaki
Published: April 2017

Short syntheses of 4‐deoxycarbazomycin B and sorazolon E were established through the condensation of cyclohexanone and commercially available 4‐methoxy‐2,3‐dimethylaniline, followed by PdII‐catalyzed dehydrogenative aromatization/intramolecular C−C bond coupling and deprotection. A chiral dinuclear vanadium complex (Ra,S,S)‐6 mediated the enantioselective oxidative coupling of sorazolon E, affording (+)‐sorazolon E2 in good enantioselectivity.
Distinguishing between order and chaos in a simple barred galaxy model
Authors: Zotos Euaggelos E.
Published: April 2017

We use a simple dynamical model to investigate the regular or chaotic character of orbits in a barred galaxy with a central, spherically symmetric, dense nucleus, and a flat disk. In particular, we explore how the total orbital energy influences the overall orbital structure of the system by computing in each case the percentage of regular, sticky and chaotic orbits. In an attempt to distinguish safely and with certainty between ordered and chaotic motion, we apply the Smaller Alignment Index (SALI) as a chaos detector to large samples of orbits obtained by integrating numerically the basic equations of motion as well as the variational equations. We integrate large sets of initial conditions of orbits in several types of two‐dimensional planes for understanding the orbital properties better. Our numerical calculations suggest that the value of the energy has a huge impact on the percentages of the orbits, thus indicating that a rotating barred galaxy is indeed a very interesting stellar entity.
Glutathione‐stabilized Cu nanocluster‐based fluorescent probe for sensitive and selective detection of Hg2+ in water
Authors: Luo Tingting , Zhang Shiting , Wang Yujue , Wang Meina , Liao Mei , Kou Xingming
Published: April 2017

In this paper, an innovative and facile one‐pot method for synthesizing water‐soluble and stable fluorescent Cu nanoclusters (CuNCs), in which glutathione (GSH) served as protecting ligand and ascorbic acid (AA) as reducing agent was reported. The resultant CuNCs emitted blue‐green fluorescence at 440 nm, with a quantum yield (QD) of about 3.08%. In addition, the prepared CuNCs exhibited excellent properties such as good water solubility, photostability and high stability toward high ionic strength. On the basis of the selective quenching of Hg2+ on CuNCs fluorescence, which may be the result of Hg2+ ion‐induced aggregation of the CuNCs, the CuNCs was used for the selective and sensitive determination of Hg2+ in aqueous solution. The proposed analytical strategy permitted detection of Hg2+ in a linear range of 4 × 10−8 to 6 × 10−5 M, with a detection limit of 2.2 × 10−8 M. Eventually, the practicability of this sensing approach was confirmed by its successful application to assay Hg2+ in tap water, Lotus lake water and river water samples with the quantitative spike recoveries ranging from 96.9% to 105.4%.