bluuebunny/crossref_metadata_2025 huggingface dataset:
PbS/CdS/ZnS Quantum Dots: A Multifunctional Platform for In Vivo Near‐Infrared Low‐Dose Fluorescence Imaging
Authors: Benayas Antonio , Ren Fuqiang , Carrasco Elisa , Marzal Vicente , del Rosal Blanca , Gonfa Belete A. , Juarranz Ángeles , Sanz‐Rodríguez Francisco , Jaque Daniel , García‐Solé José , Ma Dongling , Vetrone Fiorenzo
Published: October 2015

Over the past decade, near‐infrared (NIR)‐emitting nanoparticles have increasingly been investigated in biomedical research for use as fluorescent imaging probes. Here, high‐quality water‐dispersible core/shell/shell PbS/CdS/ZnS quantum dots (hereafter QDs) as NIR imaging probes fabricated through a rapid, cost‐effective microwave‐assisted cation exchange procedure are reported. These QDs have proven to be water dispersible, stable, and are expected to be nontoxic, resulting from the growth of an outer ZnS shell and the simultaneous surface functionalization with mercaptopropionic acid ligands. Care is taken to design the emission wavelength of the QDs probe lying within the second biological window (1000–1350 nm), which leads to higher penetration depths because of the low extinction coefficient of biological tissues in this spectral range. Furthermore, their intense fluorescence emission enables to follow the real‐time evolution of QD biodistribution among different organs of living mice, after low‐dose intravenous administration. In this paper, QD platform has proven to be capable (ex vivo and in vitro) of high‐resolution thermal sensing in the physiological temperature range. The investigation, together with the lack of noticeable toxicity from these PbS/CdS/ZnS QDs after preliminary studies, paves the way for their use as outstanding multifunctional probes both for in vitro and in vivo applications in biomedicine.
Metal/Polymer Based Stretchable Antenna for Constant Frequency Far‐Field Communication in Wearable Electronics
Authors: Hussain Aftab M. , Ghaffar Farhan A. , Park Sung I. , Rogers John A. , Shamim Atif , Hussain Muhammad M.
Published: October 2015

Body integrated wearable electronics can be used for advanced health monitoring, security, and wellness. Due to the complex, asymmetric surface of human body and atypical motion such as stretching in elbow, finger joints, wrist, knee, ankle, etc. electronics integrated to body need to be physically flexible, conforming, and stretchable. In that context, state‐of‐the‐art electronics are unusable due to their bulky, rigid, and brittle framework. Therefore, it is critical to develop stretchable electronics which can physically stretch to absorb the strain associated with body movements. While research in stretchable electronics has started to gain momentum, a stretchable antenna which can perform far‐field communications and can operate at constant frequency, such that physical shape modulation will not compromise its functionality, is yet to be realized. Here, a stretchable antenna is shown, using a low‐cost metal (copper) on flexible polymeric platform, which functions at constant frequency of 2.45 GHz, for far‐field applications. While mounted on a stretchable fabric worn by a human subject, the fabricated antenna communicated at a distance of 80 m with 1.25 mW transmitted power. This work shows an integration strategy from compact antenna design to its practical experimentation for enhanced data communication capability in future generation wearable electronics.
Thrombocytopenia and Cornelia de Lange syndrome: Still an enigma?
Authors: Cavalleri Valeria , Bettini Laura R. , Barboni Chiara , Cereda Anna , Mariani Milena , Spinelli Marco , Gervasini Cristina , Russo Silvia , Biondi Andrea , Jankovic Momcilo , Selicorni Angelo
Published: October 2015

Cornelia de Lange Syndrome (CdLS) is a rare genetic disorder caused by mutations in the cohesion complex and its regulators. The syndrome is characterized by multiple organ system abnormalities, pre‐ and post‐natal growth retardation and typical facial features. Thrombocytopenia is a reduction in platelet count to <150 × 109 L. It can be caused by congenital or acquired decreased production, increased destruction, or sequestration of platelets. In recent years, several papers reported thrombocytopenia and immune thrombocytopenia in patients affected by CdLS. In 2011, Lambert et al. estimated the risk of idiopathic thrombocytopenia purpura in CdLS patients to be 31–633 times greater than in the general population. We describe the incidence of thrombocytopenia in 127 Italian CdLS patients, identifying patients with transient or persistent thrombocytopenia, but a lower incidence of true idiopathic thrombocytopenic purpura (ITP). © 2015 Wiley Periodicals, Inc.
Dermochondrocorneal dystrophy (Francois syndrome) in a Mexican patient and literature review
Authors: Hidalgo‐Bravo Alberto , Acosta‐Nieto Maria L. , Normendez‐Martinez Monica I. , Rodriguez‐Gonzalez Nubia F. , Paz‐Gomez Francisco , Valdes‐Flores Margarita , Kramis‐Hollands Mirelle
Published: October 2015

Dermochondrocorneal Dystrophy (OMIM 221800) is a very rare disease first described by Francois in 1949. It is characterized by the appearance of skin nodules, osteochondral deformities, and corneal opacities during childhood. Only a few cases have been reported. There is uncertainty about the inheritance pattern and no gene or genes have been associated to this disease. We report a patient from Mexican mestizo origin with the classic manifestations of Dermochondrocorneal Dystrophy. We perform a multidisciplinary assessment in order to contribute to the knowledge of the clinical presentation of this uncommon condition. Among the few documented patients, this is the third patient of Mexican ancestry reported with this syndrome. © 2015 Wiley Periodicals, Inc.
Genome‐wide significant linkage of schizophrenia‐related neuroanatomical trait to 12q24
Authors: Sprooten Emma , Gupta Cota Navin , Knowles Emma E.M. , McKay D. Reese , Mathias Samuel R. , Curran Joanne E. , Kent Jack W. , Carless Melanie A. , Almeida Marcio A. , Dyer Thomas D. , Göring Harald H.H. , Olvera Rene L. , Kochunov Peter , Fox Peter T. , Duggirala Ravi , Almasy Laura , Calhoun Vince D. , Blangero John , Turner Jessica A. , Glahn David C.
Published: October 2015

The insula and medial prefrontal cortex (mPFC) share functional, histological, transcriptional, and developmental characteristics, and they serve higher cognitive functions of theoretical relevance to schizophrenia and related disorders. Meta‐analyses and multivariate analysis of structural magnetic resonance imaging (MRI) scans indicate that gray matter density and volume reductions in schizophrenia are the most consistent and pronounced in a network primarily composed of the insula and mPFC. We used source‐based morphometry, a multivariate technique optimized for structural MRI, in a large sample of randomly ascertained pedigrees (N = 887) to derive an insula–mPFC component and to investigate its genetic determinants. Firstly, we replicated the insula–mPFC gray matter component as an independent source of gray matter variation in the general population, and verified its relevance to schizophrenia in an independent case‐control sample. Secondly, we showed that the neuroanatomical variation defined by this component is largely determined by additive genetic variation (h2 = 0.59), and genome‐wide linkage analysis resulted in a significant linkage peak at 12q24 (LOD = 3.76). This region has been of significant interest to psychiatric genetics as it contains the Darier's disease locus and other proposed susceptibility genes (e.g., DAO, NOS1), and it has been linked to affective disorders and schizophrenia in multiple populations. Thus, in conjunction with previous clinical studies, our data imply that one or more psychiatric risk variants at 12q24 are co‐inherited with reductions in mPFC and insula gray matter concentration. © 2015 Wiley Periodicals, Inc.
Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species
Authors: Perea‐Buceta Jesus E. , Fernández Israel , Heikkinen Sami , Axenov Kirill , King Alistair W. T. , Niemi Teemu , Nieger Martin , Leskelä Markku , Repo Timo
Published: October 2015

The addition of Barton's base has a dramatic effect on the classic rhodium(III)‐mediated hydrogenations promoted by Wilkinson′s catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.
Direct Air Capture of CO2 by Physisorbent Materials
Authors: Kumar Amrit , Madden David G. , Lusi Matteo , Chen Kai‐Jie , Daniels Emma A. , Curtin Teresa , Perry John J. , Zaworotko Michael J.
Published: October 2015

Sequestration of CO2, either from gas mixtures or directly from air (direct air capture, DAC), could mitigate carbon emissions. Here five materials are investigated for their ability to adsorb CO2 directly from air and other gas mixtures. The sorbents studied are benchmark materials that encompass four types of porous material, one chemisorbent, TEPA‐SBA‐15 (amine‐modified mesoporous silica) and four physisorbents: Zeolite 13X (inorganic); HKUST‐1 and Mg‐MOF‐74/Mg‐dobdc (metal–organic frameworks, MOFs); SIFSIX‐3‐Ni, (hybrid ultramicroporous material). Temperature‐programmed desorption (TPD) experiments afforded information about the contents of each sorbent under equilibrium conditions and their ease of recycling. Accelerated stability tests addressed projected shelf‐life of the five sorbents. The four physisorbents were found to be capable of carbon capture from CO2‐rich gas mixtures, but competition and reaction with atmospheric moisture significantly reduced their DAC performance.
An Autocatalytic System of Photooxidation‐Driven Substitution Reactions on a FeII4L6 Cage Framework
Authors: Neelakandan Prakash P. , Jiménez Azucena , Thoburn John D. , Nitschke Jonathan R.
Published: October 2015

The functions of life are accomplished by systems exhibiting nonlinear kinetics: autocatalysis, in particular, is integral to the signal amplification that allows for biological information processing. Novel synthetic autocatalytic systems provide a foundation for the design of artificial chemical networks capable of carrying out complex functions. Here we report a set of FeII4L6 cages containing BODIPY chromophores having tuneable photosensitizing properties. Electron‐rich anilines were observed to displace electron‐deficient anilines at the dynamic‐covalent imine bonds of these cages. When iodoaniline residues were incorporated, heavy‐atom effects led to enhanced 1O2 production. The incorporation of (methylthio)aniline residues into a cage allowed for the design of an autocatalytic system: oxidation of the methylthio groups into sulfoxides make them electron‐deficient and allows their displacement by iodoanilines, generating a better photocatalyst and accelerating the reaction.
Wrinkled Graphene Monoliths as Superabsorbing Building Blocks for Superhydrophobic and Superhydrophilic Surfaces
Authors: Lv Li‐Bing , Cui Tian‐Lu , Zhang Bing , Wang Hong‐Hui , Li Xin‐Hao , Chen Jie‐Sheng
Published: October 2015

Superhydrophobic and superhydrophilic surfaces are of great interest because of a large range of applications, for example, as antifogging and self‐cleaning coatings, as antibiofouling paints for boats, in metal refining, and for water–oil separation. An aqueous ink based on three‐dimensional graphene monoliths (Gr) can be used for constructing both superhydrophobic and superhydrophilic surfaces on arbitrary substrates with different surficial structures from the meso‐ to the macroscale. The surface wettability of a Gr‐coated surface mainly depends on which additional layers (air for a superhydrophobic surface and water for a superhydrophilic surface) are adsorbed on the surface of the graphene sheets. Switching a Gr‐coated surface between being superhydrophobic and superhydrophilic can thus be easily achieved by drying and prewetting with ethanol. The Gr‐based superhydrophobic membranes or films should have great potential as efficient separators for fast and gravity‐driven oil–water separation.
Delineating the Role of Helical Intermediates in Natively Unfolded Polypeptide Amyloid Assembly and Cytotoxicity
Authors: De Carufel Carole Anne , Quittot Noé , Nguyen Phuong Trang , Bourgault Steve
Published: October 2015

Amyloid deposition is a hallmark of many diseases, such as the Alzheimer’s disease. Numerous amyloidogenic proteins, including the islet amyloid polypeptide (IAPP) associated with type II diabetes, are natively unfolded and need to undergo conformational rearrangements allowing the formation of locally ordered structure(s) to initiate self‐assembly. Recent studies have indicated that the formation of α‐helical intermediates accelerates fibrillization, suggesting that these species are on‐pathway to amyloid assembly. By identifying an IAPP derivative with a restricted conformational ensemble that co‐assembles with IAPP, we observed that helical species were off‐pathway in homogenous environment and in presence of lipid bilayers or glycosaminoglycans. Moreover, preventing helical folding potentiated membrane perturbation and IAPP cytotoxicity, indicating that stabilization of helical motif(s) is a promising strategy to prevent cell degeneration associated with amyloidogenesis.
Disappearing Enantiomorphs: Single Handedness in Racemate Crystals
Authors: Parschau Manfred , Ernst Karl‐Heinz
Published: October 2015

Although crystallization is the most important method for the separation of enantiomers of chiral molecules in the chemical industry, the chiral recognition involved in this process is poorly understood at the molecular level. We report on the initial steps in the formation of layered racemate crystals from a racemic mixture, as observed by STM at submolecular resolution. Grown on a copper single‐crystal surface, the chiral hydrocarbon heptahelicene formed chiral racemic lattice structures within the first layer. In the second layer, enantiomerically pure domains were observed, underneath which the first layer contained exclusively the other enantiomer. Hence, the system changed from a 2D racemate into a 3D racemate with enantiomerically pure layers after exceeding monolayer‐saturation coverage. A chiral bias in form of a small enantiomeric excess suppressed the crystallization of one double‐layer enantiomorph so that the pure minor enantiomer crystallized only in the second layer.
Stable Encapsulated Air Nanobubbles in Water
Authors: Wang Yu , Liu Guojun , Hu Heng , Li Terry Yantian , Johri Amer M. , Li Xiaoyu , Wang Jian
Published: October 2015

The dispersion into water of nanocapsules bearing a highly hydrophobic fluorinated internal lining yielded encapsulated air nanobubbles. These bubbles, like their micrometer‐sized counterparts (microbubbles), effectively reflected ultrasound. More importantly, the nanobubbles survived under ultrasonication 100‐times longer than a commercial microbubble sample that is currently in clinical use. We justify this unprecedented stability theoretically. These nanobubbles, owing to their small size and potential ability to permeate the capillary networks of tissues, may expand the applications of microbubbles in diagnostic ultrasonography and find new applications in ultrasound‐regulated drug delivery.
Development of a Dinitrosyl Iron Complex Molecular Catalyst into a Hydrogen Evolution Cathode
Authors: Chiou Tzung‐Wen , Lu Tsai‐Te , Wu Ying‐Hao , Yu Yi‐Ju , Chu Li‐Kang , Liaw Wen‐Feng
Published: October 2015

Despite extensive efforts, the electrocatalytic reduction of water using homogeneous/heterogeneous Fe, Co, Ni, Cu, W, and Mo complexes remains challenging because of issues involving the development of efficient, recyclable, stable, and aqueous‐compatible catalysts. In this study, evolution of the de novo designed dinitrosyl iron complex DNIC‐PMDTA from a molecular catalyst into a solid‐state hydrogen evolution cathode, considering all the parameters to fulfill the electronic and structural requirements of each step of the catalytic cycle, is demonstrated. DNIC‐PMDTA reveals electrocatalytic reduction of water at neutral and basic media, whereas its deposit on electrode preserves exceptional longevity, 139 h. This discovery will initiate a systematic study on the assembly of [Fe(NO)2] motif into current collector for mass production of H2, whereas the efficiency remains tailored by its molecular precursor [(L)Fe(NO)2].
The effect of oxidized ferulic acid on physicochemical properties of bitter vetch (Vicia ervilia) protein‐based films
Authors: Arabestani Akram , Kadivar Mahdi , Shahedi Mohammad , Goli Sayed Amir Hossein , Porta Raffaele
Published: October 2015

The aim of the present study was to investigate the effect of oxidized ferulic acid on some physicochemical features of bitter vetch protein concentrate‐based films. Our results indicate that moisture content, total soluble matter, water vapor permeability, and mechanical resistance values of the films prepared in the presence of oxidized ferulic acid were significantly modified in comparison with the ones detected with films obtained in its absence. In fact, film moisture content, total soluble matter, and water vapor permeability significantly decreased when oxidized ferulic acid was added to the film forming solutions, whereas both film tensile strength and elongation at break resulted markedly higher. Moreover, atomic force and scanning electron microscopy analyses showed that film morphology was also markedly affected by the presence of oxidized ferulic acid, film surface roughness, and compactness resulting higher than the ones observed in control samples. Therefore, these findings show a marked improvement in obtaining edible films derived from cheap starting biopolymers, such as bitter vetch proteins, potentially useful for different food and pharmaceutical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42894.
PROTEOMICS ANALYSIS OF OVEREXPRESSED PLASMA PROTEINS IN RESPONSE TO COLD ACCLIMATION IN Ostrinia furnacalis
Authors: Shang Qingli , Pan Yiou , Peng Tianfei , Yang Shuang , Lu Xin , Wang Zhenying , Xi Jinghui
Published: October 2015

Many insects in temperate regions overwinter in diapause. In these insects, one of the metabolic adaptations to cold stress is the synthesis of responsive proteins. Using proteomic analysis, an investigation aimed to a better understanding of the molecular adaptation mechanisms to cold stress was carried out in Ostrinia furnacalis larva. Proteins were extracted from the larval hemolymph collected from both control and overwintering larva. By polyethylene glycol precipitation, approximately 560 protein spots were separated and visualized on two‐dimensional (2D) gels after silver staining. Eighteen protein spots were found to be upregulated in overwinter larval plasma in different patterns. As an initial work, 13 of these proteins were identified using MALDI TOF/TOF MS. The differentially overexpressed proteins include heat shock 70 kDa cognate protein, small heat shock protein (sHSP), putative aliphatic nitrilase, arginine kinase, phosphoglyceromutase, triosephosphateisomerase, and glutathione transferase. Alterations in the levels of these proteins were further confirmed by qPCR. This study is the first analysis of differentially expressed plasma proteins in O. furnacalis diapause larvae under extremely low temperature conditions and gives new insights into the acclimation mechanisms responsive to cold stress. Our results also support the idea that energy metabolism, alanine and proline metabolism, and antioxidative reaction act in the cold acclimation of O. furnacalis diapause larvae.
Slow intestinal transit contributes to elevate urinary p‐cresol level in Italian autistic children
Authors: Gabriele Stefano , Sacco Roberto , Altieri Laura , Neri Cristina , Urbani Andrea , Bravaccio Carmela , Riccio Maria Pia , Iovene Maria Rosaria , Bombace Francesca , De Magistris Laura , Persico Antonio M.
Published: October 2015

The uremic toxin p‐cresol (4‐methylphenol) is either of environmental origin or can be synthetized from tyrosine by cresol‐producing bacteria present in the gut lumen. Elevated p‐cresol amounts have been previously found in the urines of Italian and French autism spectrum disorder (ASD) children up until 8 years of age, and may be associated with autism severity or with the intensity of abnormal behaviors. This study aims to investigate the mechanism producing elevated urinary p‐cresol in ASD. Urinary p‐cresol levels were thus measured by High Performance Liquid Chromatography in a sample of 53 Italian ASD children assessed for (a) presence of Clostridium spp. strains in the gut by means of an in vitro fecal stool test and of Clostridium difficile‐derived toxin A/B in the feces, (b) intestinal permeability using the lactulose/mannitol (LA/MA) test, (c) frequent use of antibiotics due to recurrent infections during the first 2 years of postnatal life, and (d) stool habits with the Bristol Stool Form Scale. Chronic constipation was the only variable significantly associated with total urinary p‐cresol concentration (P < 0.05). No association was found with presence of Clostridium spp. in the gut flora (P = 0.92), augmented intestinal permeability (P = 0.18), or frequent use of antibiotics in early infancy (P = 0.47). No ASD child was found to carry C. difficile in the gut or to release toxin A/B in the feces. In conclusion, urinary p‐cresol levels are elevated in young ASD children with increased intestinal transit time and chronic constipation. Autism Res 2016, 9: 752–759. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
Autism screening and diagnosis in low resource settings: Challenges and opportunities to enhance research and services worldwide
Authors: Durkin Maureen S. , Elsabbagh Mayada , Barbaro Josephine , Gladstone Melissa , Happe Francesca , Hoekstra Rosa A. , Lee Li‐Ching , Rattazzi Alexia , Stapel‐Wax Jennifer , Stone Wendy L. , Tager‐Flusberg Helen , Thurm Audrey , Tomlinson Mark , Shih Andy
Published: October 2015

Most research into the epidemiology, etiology, clinical manifestations, diagnosis and treatment of autism is based on studies in high income countries. Moreover, within high income countries, individuals of high socioeconomic status are disproportionately represented among participants in autism research. Corresponding disparities in access to autism screening, diagnosis, and treatment exist globally. One of the barriers perpetuating this imbalance is the high cost of proprietary tools for diagnosing autism and for delivering evidence‐based therapies. Another barrier is the high cost of training of professionals and para‐professionals to use the tools. Open‐source and open access models provide a way to facilitate global collaboration and training. Using these models and technologies, the autism scientific community and clinicians worldwide should be able to work more effectively and efficiently than they have to date to address the global imbalance in autism knowledge and at the same time advance our understanding of autism and our ability to deliver cost‐effective services to everyone in need. Autism Res 2015, 8: 473–476. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
Tumor‐induced solid stress activates β‐catenin signaling to drive malignant behavior in normal, tumor‐adjacent cells
Authors: Ou Guanqing , Weaver Valerie Marie
Published: October 2015

Recent work by Fernández‐Sánchez and coworkers examining the impact of applied pressure on the malignant phenotype of murine colon tissue in vivo revealed that mechanical perturbations can drive malignant behavior in genetically normal cells. Their findings build upon an existing understanding of how the mechanical cues experienced by cells within a tissue become progressively modified as the tissue transforms. Using magnetically stimulated ultra‐magnetic liposomes to mimic tumor growth ‐induced solid stress, Fernández‐Sánchez and coworkers were able to stimulate β‐catenin to promote the cancerous behavior of both a normal and genetically modified colon epithelium. In this perspective, we discuss their findings in the context of what is currently known regarding the role of the mechanical landscape in cancer progression and β‐catenin as a mechanotransducer. We review data that suggest that mechanically regulated activation of β‐catenin fosters development of a malignant phenotype in tissue and predict that mechanical cues may contribute to tumor heterogeneity.
Asymptotically robust variance estimation for person‐time incidence rates
Authors: Scosyrev Emil
Published: October 2015

Person‐time incidence rates are frequently used in medical research. However, standard estimation theory for this measure of event occurrence is based on the assumption of independent and identically distributed (iid) exponential event times, which implies that the hazard function remains constant over time. Under this assumption and assuming independent censoring, observed person‐time incidence rate is the maximum‐likelihood estimator of the constant hazard, and asymptotic variance of the log rate can be estimated consistently by the inverse of the number of events. However, in many practical applications, the assumption of constant hazard is not very plausible. In the present paper, an average rate parameter is defined as the ratio of expected event count to the expected total time at risk. This rate parameter is equal to the hazard function under constant hazard. For inference about the average rate parameter, an asymptotically robust variance estimator of the log rate is proposed. Given some very general conditions, the robust variance estimator is consistent under arbitrary iid event times, and is also consistent or asymptotically conservative when event times are independent but nonidentically distributed. In contrast, the standard maximum‐likelihood estimator may become anticonservative under nonconstant hazard, producing confidence intervals with less‐than‐nominal asymptotic coverage. These results are derived analytically and illustrated with simulations. The two estimators are also compared in five datasets from oncology studies.
Esculetin induces apoptosis in human colon cancer cells by inducing endoplasmic reticulum stress
Authors: Kim Areum Daseul , Madduma Hewage Susara Ruwan Kumara , Piao Mei Jing , Kang Kyoung Ah , Cho Suk Ju , Hyun Jin Won
Published: October 2015

Colorectal cancer has become more common in many regions of the world. Recently, we showed that esculetin, a natural coumarin, induces apoptosis in HT‐29 colon cancer cells via the reactive oxygen species‐mediated mitochondrial pathway. The present study examined whether esculetin induces apoptosis in HT‐29 colon cancer cells by inducing endoplasmic reticulum (ER) stress. We found that esculetin induced characteristic signs of ER stress, confirmed by ER staining, mitochondrial calcium overload and expression of ER stress‐related proteins (i.e. glucose regulated protein 78, phosphorylated ribonucleic acid‐dependent protein kinase‐like ER kinase, phosphorylated inositol requiring enzyme 1, phosphorylated eukaryotic initiation factor‐2α, spliced X‐box binding protein 1 and cleaved activating transcription factor 6). Esculetin also induced the expression of the CCAAT/enhancer‐binding protein‐homologous protein (CHOP) and pro‐apoptotic factors caspase‐12. Moreover, transfection of colon cancer cells with a small interfering ribonucleic acid targeting CHOP attenuated esculetin‐induced apoptosis. Taken together, these results suggest that the ER stress response plays an important role in esculetin‐induced apoptosis in human colon cancer cells. Copyright © 2015 John Wiley & Sons, Ltd.
Development of Purification Concepts for Nutraceuticals from Algae – Part II: Design of Purification Strategies
Authors: Fröhlich Holger , Gasser Kurt , Gaul Simon , Grützner Thomas , Strube Jochen
Published: October 2015

Omega‐3 fatty acids are well‐known for health‐preserving effects like blood pressure reduction. Main source of fatty acids is fish oil which has recorded a significant price increase. This has stimulated research on recovering omega‐3 fatty acids from other sources, like the microalgae Ulkenia sp. These stems have in common that the fatty acids are built as storage lipids in the cell interior. Due to the cell wall stability of the cell systems, high disruption energies need to be applied which leads to formation of stable emulsions. Innovative downstream concepts are developed which in contrast to conventional processes are operated free from organic solvents. Several approaches are discussed and compared in terms of cost to common process concepts.
Limitations of the Zero‐Length Column Technique to Measure Diffusional Time Constants in Microporous Adsorbents
Authors: Silva José A. C. , Rodrigues Alírio E.
Published: October 2015

The zero‐length column (ZLC) technique has been developed to measure the intracrystalline diffusivity of strongly adsorbed species in large zeolite crystals above 50 μm in the Henry's law range of sorption equilibrium. The ZLC is a macroscopic technique, and there is a need of large crystallites or pellets to measure the intracrystalline diffusivity Dc of fast diffusion species or the macropore diffusivity DP of weakly adsorbed species, respectively. Another limitation is that ZLC desorption curves produce similar concentration profiles (linear isotherms) in bidisperse adsorbents (pellets) under macropore or micropore diffusion control. Moreover, the forms of the response curves are very similar in both diffusion‐ and nonlinear equilibrium‐controlled processes, leading to some misinterpretations of ZLC experiments. In this work, two criteria are developed showing that, in order to macroscopically measure the micropore diffusion time constant $ r_c^2/{D_c} $
or the macropore diffusion time constant $ R_p^2(1 + K)/{D_P} $
, the time of the ZLC experiments t should be higher than 7.0 × 10−2$ r_c^2/{D_c} $
or 7.0 × 10−2$ R_p^2(1 + K)/{D_P} $
, respectively. The interpretation of the ZLC response curve data is also checked in two completely different regimes, showing that a single ZLC response curve is not enough to conclude if a system is under a kinetic or an equilibrium regime.
Electrical Conductivity and Strong Luminescence in Copper Iodide Double Chains with Isonicotinato Derivatives
Authors: Hassanein Khaled , Conesa‐Egea Javier , Delgado Salome , Castillo Oscar , Benmansour Samia , Martínez José I. , Abellán Gonzalo , Gómez‐García Carlos J. , Zamora Félix , Amo‐Ochoa Pilar
Published: October 2015

Direct reactions between CuI and isonicotinic acid (HIN) or the corresponding esters, ethyl isonicotinate (EtIN) or methyl isonicotinate (MeIN), give rise to the formation of the coordination polymers [CuI(L)]n with L=EtIN (1), MeIN (2) and HIN (3). Polymers 1–3 show similar structures based on a CuI double chain in which ethyl‐, methyl isonicotinate or isonicotinic acid are coordinated as terminal ligands. Albeit, their supramolecular architecture differs considerably, affecting the distances and angles of the central CuI double chains and thereby their physical properties. Hence, the photoluminescence shows remarkable differences; 1 and 2 show a strong yellow emission, whereas 3 displays a weak emission; and 1 and 2 are semiconductors with moderate room temperature conductivities, whereas 3 has increased electrical conductivity up to 3×10−3 S cm−1. Additionally, 1 and 2 present an irreversible transition to a highly conducting phase with a conductivity almost 4 orders of magnitude higher and a quasi‐metallic behaviour. Thermogravimetric analysis (TGA) coupled to a mass spectrometer and magnetic measurements point to a partial thermally induced oxidation of the carboxylate groups of the ligands with CuI to Cu0 reduction. DFT calculations have been carried out to rationalise these observations.
Preparation, Structural Determination, and Characterization of Electronic Properties of Bis‐silylated and Bis‐germylated Lu3N@Ih‐C80
Authors: Kako Masahiro , Miyabe Kyosuke , Sato Kumiko , Suzuki Mitsuaki , Mizorogi Naomi , Wang Wei‐Wei , Yamada Michio , Maeda Yutaka , Olmstead Marilyn M. , Balch Alan L. , Nagase Shigeru , Akasaka Takeshi
Published: October 2015

Bis‐silylated and bis‐germylated derivatives of Lu3N@Ih‐C80 (3, 4, 5) were successfully synthesized by the photochemical addition of disiliranes 1 a, 1 b or digermirane 2, and fully characterized by spectroscopic, electrochemical, and theoretical studies. Interestingly, digermirane 2 reacts more efficiently than disiliranes 1 a and 1 b because of its good electron‐donor properties and lower steric hindrance around the GeGe bond. The 1,4‐adduct structures of 3, 4, 5 were unequivocally established by single‐crystal X‐ray crystallographic analyses. The electrochemical and theoretical studies reveal that the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the 1,4‐adducts are remarkably smaller than those of Lu3N@Ih‐C80, because the electron‐donating groups effectively raise the HOMO levels. It is also observed that germyl groups are slightly more electron‐donating than the silyl groups on the basis of the redox properties and the HOMO–LUMO energies of 4 and 5. Bis‐silylation and bis‐germylation are effective and versatile methods for tuning the electronic characteristics of endohedral metallofullerenes.
Exploratory Study on the RNA‐Binding Structural Motifs by Library Screening Targeting pre‐miRNA‐29 a
Authors: Fukuzumi Takeo , Murata Asako , Aikawa Haruo , Harada Yasue , Nakatani Kazuhiko
Published: October 2015

The metabolic stream of microRNA (miRNA) production, the so‐called maturation process of miRNAs, became one of important metabolic paths for drug‐targeting to modulate the expression of genes related to a number of diseases. We carried out discovery studies on small molecules binding to the precursor of miR‐29a (pre‐miR‐29a) from a chemical library containing 41 119 compounds (AQ library) by the fluorescent indicator displacement (FID) assay using the xanthone derivative X2SdiMe as a fluorescent indicator. The FID assay provided 1075 compounds, which showed an increase of fluorescence. These compounds were subsequently submitted to a binding analysis in a surface plasmon resonance (SPR) assay on a pre‐miR‐29a immobilized surface. 21 hit compounds were identified with a good reproducibility in the binding. These compounds have not been reported to bind to RNA until now and can be classified into two groups on the basis of the kinetics in the binding. To gain more information on the motif structures that could be necessary for the binding to pre‐miR‐29a, 19 substructures were selected from the hit compounds. The substructure library (SS library) which consisted of 362 compounds was prepared from the AQ library. An SPR assay of the SS library on pre‐miR‐29a‐immobilized surface suggested that five substructures could potentially be important structural motifs to bind to pre‐miR‐29a. These studies demonstrate that the combination of FID‐based screening of chemical library and subsequent SPR assay would be one way for obtaining practical solutions for the discovery of molecules which bind to the target pre‐miRNAs.
Catalytic Asymmetric Michael Reaction of 5H‐Oxazol‐4‐Ones with α,β‐Unsaturated Acyl Imidazoles
Authors: Zhang Bangzhi , Han Fengxia , Wang Linqing , Li Dan , Yang Dongxu , Yang Xiaoli , Yang Junxian , Li Xiaofang , Zhao Depeng , Wang Rui
Published: October 2015

The asymmetric Michael reaction between 5H‐oxazol‐4‐ones and α,β‐unsaturated acyl imidazoles is reported. A novel 2‐benzo[b]thiophenyl‐modified chiral ProPhenol species is synthesized and used as a ligand, leading to good enantioselectivities in this asymmetric conjugate addition reaction. Furthermore, the introduction of phenol additives as achiral co‐ligands is found to improve the reaction’s chemical yields, diastereoselectivities, and enantioselectivities.
To Transfer or Not to Transfer? Development of a Dinitrosyl Iron Complex as a Nitroxyl Donor for the Nitroxylation of an FeIII–Porphyrin Center
Authors: Tseng Yu‐Ting , Chen Chien‐Hong , Lin Jing‐Yu , Li Bing‐Han , Lu Yu‐Huan , Lin Chia‐Her , Chen Hsin‐Tsung , Weng Tsu‐Chien , Sokaras Dimosthenes , Chen Huang‐Yeh , Soo Yun‐Liang , Lu Tsai‐Te
Published: October 2015

A positive myocardial inotropic effect achieved using HNO/NO−, compared with NO⋅, triggered attempts to explore novel nitroxyl donors for use in clinical applications in vascular and myocardial pharmacology. To develop M‐NO complexes for nitroxyl chemistry and biology, modulation of direct nitroxyl‐transfer reactivity of dinitrosyl iron complexes (DNICs) is investigated in this study using a FeIII‐porphyrin complex and proteins as a specific probe. Stable dinuclear {Fe(NO)2}9 DNIC [Fe(μ‐MePyr)(NO)2]2 was discovered as a potent nitroxyl donor for nitroxylation of FeIII‐heme centers through an associative mechanism. Beyond the efficient nitroxyl transfer, transformation of DNICs into a chemical biology probe for nitroxyl and for pharmaceutical applications demands further efforts using in vitro/in vivo studies.
Instantaneous Click Chemistry by a Copper‐Containing Polymeric‐Membrane‐Installed Microflow Catalytic Reactor
Authors: Yamada Yoichi M. A. , Ohno Aya , Sato Takuma , Uozumi Yasuhiro
Published: October 2015

The copper(I)‐catalyzed Huisgen cycloaddition (azide–alkyne cycloaddition) is an important reaction in click chemistry that ideally proceeds instantaneously. An instantaneous Huisgen cycloaddition has been developed that uses a novel catalytic dinuclear copper complex‐containing polymeric membrane‐installed microflow device. A polymeric membranous copper catalyst was prepared from poly(4‐vinylpyridine), copper(II) sulfate, sodium chloride, and sodium ascorbate at the interface of two laminar flows inside microchannels. Elucidation of the structure by XANES, EXAFS, and elemental analysis, as well as second‐order Møller–Plesset perturbation theory (MP2) calculations and density functional theory (DFT) calculations assigned the local structure near Cu as a μ‐chloro dinuclear CuI complex. The microflow device promotes the instantaneous click reaction of a variety of alkynes and organic azides to afford the corresponding triazoles in quantitative yield.
Through‐Space 1,4‐Palladium Migration and 1,2‐Aryl Shift: Direct Access to Dibenzo[a,c]carbazoles through a Triple CH Functionalization Cascade
Authors: Bhunia Samir Kumar , Polley Arghya , Natarajan Ramalingam , Jana Ranjan
Published: October 2015

A palladium‐catalyzed expeditious synthesis of dibenzofused carbazoles from readily available 2‐arylindoles and diaryliodonium salts is reported. Interestingly, after the electrophilic C3 palladation of indole, an unexpected “through‐space” 1,4‐palladium migration to the 2‐aryl moiety, by remote CH bond activation followed by CH arylation with diaryliodonium salt, and an unprecedented 1,2‐aryl shift take place. Finally, an intramolecular cross‐dehydrogenative coupling (CDC) at the C2 position affords dibenzo[a,c]carbazoles in high yields. Remarkably, the present migratory annulation occurs through three CH bond activation one CC bond cleavage, and the simultaneous construction of three new CC bonds in a single operation.
Nonstoichiometric, Protic Azolium Azolate Ionic Liquids Provide Unique Environments for N‐Donor Coordination Chemistry
Authors: Kelley Steven P. , Nuss Joseph S. , Rogers Robin D.
Published: October 2015

Here we demonstrate that neat reactions of amphoteric azoles with more basic azoles give a family of finely tunable, nonstoichiometric liquids which are useful for N‐donor coordination chemistry. Reacting 4,5‐dicyanoimidazole (4,5‐DCNIm) with 1‐methylimidazole (1‐mim) gives new compounds with composition‐dependent speciation. Two crystalline compounds, a 1:1 protic salt, [H(1‐mim)][4,5‐DCNIm], and a 1:2 salt co‐crystal, [H(1‐mim)][4,5‐DCNIm]⋅4,5‐DCNIm, were isolated and structurally characterized, while differential scanning calorimetry revealed both suppression of crystallization and the presence of neutral and anionic species in the melt. Reactions of Cu(NO3)2⋅2.5 H2O, CuO, and ZnO with the neat 2:1 1‐mim/4,5‐DCNIm melt resulted in the isolation of entirely N‐donor ligated complexes of the formula M(4,5‐DCNIm)2(1‐mim)4 (M=Cu, Zn).
Direct Catalytic Asymmetric Mannich‐Type Reaction of α‐N3 Amide
Authors: Sun Zhongdong , Weidner Karin , Kumagai Naoya , Shibasaki Masakatsu
Published: October 2015

An α‐N3 7‐azaindoline amide serves as a latent enolate to directly engage in an asymmetric Mannich‐type reaction with N‐thiophosphinoyl imines by the action of a cooperative catalyst. The thus‐obtained highly enantioenriched anti‐adduct was transformed into β‐amino‐α‐azido acid in high yield by simple acidic treatment.
Chiral Pool‐Based Synthesis of Naphtho‐Fused Isocoumarins
Authors: Raza Abdul Rauf , Saddiqa Aisha , Çakmak Osman
Published: October 2015

A variety of chiral derivatives of benzo[d]naphtho[1,2‐b]pyran‐6‐one were prepared in a single step by Et3N‐mediated condensation of homophthalic anhydride with different derivatives of (S)‐amino acid chlorides at –5 °C by employing a chiral pool methodology. Chirality 27:951–957, 2015. © 2015 Wiley Periodicals, Inc.
Synthesis and properties of polyethylene/TiO2 nanocomposites using a vanadium catalyst
Authors: Bakather Omer Yahya , Al‐harthi Mamdouh A.
Published: October 2015

In this study, a vanadium (III) complex bearing a salicylaldiminato ligand of the general formula [RN=CH(2,4‐tBu2C6H2O)]VCl2(THF)2, where R = 2,6‐iPr2C6H3, was used as a catalyst. Titanium dioxide doped with iron nanofillers was synthesized by a sol‐gel process and used to investigate the effect of nanofillers on ethylene homopolymer and ethylene/propylene copolymer properties. To the best of our knowledge, this is the first time titanium dioxide doped with iron has been used as a nanofiller in ethylene polymerization and ethylene/propylene copolymerization using a vanadium complex with methyl aluminum dichloride as a cocatalyst. Besides catalyst activity, the molecular mass (Mw) of the obtained polymer, molecular mass distribution, copolymer composition, crystallinity, and thermal characteristics of polyethylene and polyethylene/polypropylene nanocomposites were investigated.
Mesozoic and Cenozoic Tectono‐Thermal Evolution History in the Chagan sag, Inner Mongolia
Authors: Yin‐Hui ZUO , Wang ZHANG , Zhao‐Ying LI , Jia‐Wei LI , Qing‐Qing HAO , Jie HU
Published: October 2015

The Chagan sag has the greatest oil and gas exploration potential among other sags in the Yingen‐Ejinaqi Basin, Inner Mongolia. To reveal the tectono‐thermal evolution history of the Chagan sag, this article utilized the combined forward and inversion method and 35 apatite fission track and 119 vitrinite reflectance data to reconstruct the Mesozoic and Cenozoic tectono‐thermal evolution history in the Chagan sag. The results show that the Chagan sag had a high geothermal gradient during the Cretaceous, and it experienced the following 4 stages of tectono‐thermal evolutions: (1) a rapid geothermal gradient increase stage from the Bayingebi Formation depositional period to the Suhongtu Formation depositional period, during which the geothermal gradient increased to 46∼52 °C/km at the end of the Suhongtu Formation depositional period; (2) a geothermal gradient peak stage during the Yingen Formation depositional period, with maximum geothermal gradient ranged from 50 to 58 °C/km; (3) a high geothermal gradient continuation stage during the Wulansuhai Formation depositional period, with maximum geothermal gradient ranged from 39 to 48 °C/km; and (4) a thermal subsidence stage during the Cenozoic, during which the Chagan sag is in the uplift and erosion stage due to the Himalayan movement and the geothermal gradient gradually decreased to 31∼34 °C/km at the present day. Moreover, the tectono‐thermal evolution was consistent with the tectonic evolution and volcanic activities in the Chagan sag. During the Early Cretaceous, the intraplate rift was developed, lithosphere was thinned and multi‐phase intense volcanic rocks were erupted in the Chagan sag, so a large amount of energy was released to the surface from the deep crust, resulting in a high geothermal gradient during this period. In addition, the high geothermal gradient during the Cretaceous was favorable for hydrocarbon generation, corresponding to a shallow paleo‐generation threshold, and the Early Cretaceous geothermal fields controlled the hydrocarbon generation of the Chagan sag. This work may provide new insights for the understanding of the oil and gas exploration potential of the Chagan sag.
The Relationship between High Conductive Layer in Upper Mantle and Endogenous Metallic Ore and Petroleum Reservoir
Authors: Qing ZHONG , Hui FANG , Pi‐Yuan YANG , Li LI , Yong‐Zhen YUAN , Fa‐Gen PEI
Published: October 2015

Based on the 1° × 1° depth map of the high conductive layers in upper mantle of China (1996), with the addition of magnetotelluric data, we created the new map of the high conductive layer in upper mantle of China. The depth of the upper mantle high conductive layers vary widely in China, the shallowest depth is about 50∼60 km, the deepest place is about 230 km, and the average depth can be about 100∼120 km. Through further study on the interface depth of high conductive layer in upper mantle as well as contrasting with the distribution of endogenous metallic minerals of the continent of China, we have found that most of the endogenous metallic ore deposits are located at the top of high conductive layer in upper mantle uplift or the top of the steep gradient zone of high conductive layer in upper mantle. Therefore, the depth and shape of the high‐conductive layer in upper mantle can be very useful for the prediction of endogenous metal ores. We also found that the structures which have mirror relationship with the high conductive layer in upper mantle such as shallow basin and rift are the best area to detecting inorganic mantle reservoirs. The lithosphere are thinning and stretching while the uplift of high conductive layer in upper mantle, meanwhile a series of nearly parallel beam steep crack can be formed to become the passway for the mass upwelling of magma, liquid and gas from the deep mantle, finally all those materials from deep mantle are accumulated and become inorganic mantle reservoirs, gas reservoirs and endogenous metal ores under certain situations.