bluuebunny/crossref_metadata_2025 huggingface dataset:
From Gold Nanoseeds to Nanorods: The Microscopic Origin of the Anisotropic Growth
Authors: Meena Santosh Kumar , Sulpizi Marialore
Published: August 2016

Directly manipulating and controlling the size and shape of metal nanoparticles is a key step for their tailored applications. In this work, molecular dynamics simulations were applied to understand the microscopic origin of the asymmetric growth mechanism in gold nanorods. Different factors influencing the growth were selectively included in the models to unravel the role of the surfactants and ions. In the early stage of the growth, when the seed is only a few nanometers large, a dramatic symmetry breaking occurs as the surfactant layer preferentially covers the (100) and (110) facets, leaving the (111) facets unprotected. This anisotropic surfactant layer in turn promotes anisotropic growth with the less protected tips growing faster. When silver salt is added to the growth solution, the asymmetry of the facets is preserved, but the Br− concentration at the interface increases, resulting in increased surface passivation.
A Molecular Necklace: Threading β‐Cyclodextrins onto Polymers Derived from Bile Acids
Authors: Jia Yong‐Guang , Malveau Cedric , Mezour Mohamed A. , Perepichka Dmitrii F. , Zhu X. X.
Published: August 2016

A molecular necklace of polypseudorotaxanes was prepared by threading β‐cyclodextrins (β‐CD) onto biodegradable and thermoresponsive polyurethanes derived from bile acids. These polyurethanes were synthesized via a simple step condensation of bile acid‐based dicarbonate with poly(ethylene glycol)‐diamine. The β‐CD rings slide onto the poly(ethylene glycol) segments and selectively recognize the bile acid units of the polyurethane chains, whereas the poly(ethylene glycol) segments remain crystalline with a lower crystallinity. This bio‐compound‐derived molecular necklace can be visualized by scanning tunneling microscopy. The polypseudorotaxanes show thermosensitivity in water and the phase transition temperature may be fine‐tuned by varying the molar ratios of β‐CD to the bile acid units. Such an interesting necklace model of polypseudorotaxane constructed from natural compounds may lead to the further exploration of their applications, such as as an enzyme model, due to their biological nature.
5‐Formylcytosine Could Be a Semipermanent Base in Specific Genome Sites
Authors: Su Meng , Kirchner Angie , Stazzoni Samuele , Müller Markus , Wagner Mirko , Schröder Arne , Carell Thomas
Published: August 2016

5‐Formyl‐2′‐deoxycytosine (fdC) is a recently discovered epigenetic base in the genome of stem cells, with yet unknown functions. Sequencing data show that the base is enriched in CpG islands of promoters and hence likely involved in the regulation of transcription during cellular differentiation. fdC is known to be recognized and excised by the enzyme thymine‐DNA‐glycosylase (Tdg). As such, fdC is believed to function as an intermediate during active demethylation. In order to understand the function of the new epigenetic base fdC, it is important to analyze its formation and removal at defined genomic sites. Here, we report a new method that combines sequence‐specific chemical derivatization of fdC with droplet digital PCR that enables such analysis. We show initial data, indicating that the repair protein Tdg removes only 50 % of the fdCs at a given genomic site, arguing that fdC is a semipermanent base.
Asymmetric Hydrogenation of Azaindoles: Chemo‐ and Enantioselective Reduction of Fused Aromatic Ring Systems Consisting of Two Heteroarenes
Authors: Makida Yusuke , Saita Masahiro , Kuramoto Takahiro , Ishizuka Kentaro , Kuwano Ryoichi
Published: August 2016

High enantioselectivity was achieved for the hydrogenation of azaindoles by using the chiral catalyst, which was prepared from [Ru(η3‐methallyl)2(cod)] and a trans‐chelating bis(phosphine) ligand (PhTRAP). The dearomative reaction exclusively occurred on the five‐membered ring, thus giving the corresponding azaindolines with up to 97:3 enantiomer ratio.
Wearable Thermocells Based on Gel Electrolytes for the Utilization of Body Heat
Authors: Yang Peihua , Liu Kang , Chen Qian , Mo Xiaobao , Zhou Yishu , Li Song , Feng Guang , Zhou Jun
Published: August 2016

Converting body heat into electricity is a promising strategy for supplying power to wearable electronics. To avoid the limitations of traditional solid‐state thermoelectric materials, such as frangibility and complex fabrication processes, we fabricated two types of thermogalvanic gel electrolytes with positive and negative thermo‐electrochemical Seebeck coefficients, respectively, which correspond to the n‐type and p‐type elements of a conventional thermoelectric generator. Such gel electrolytes exhibit not only moderate thermoelectric performance but also good mechanical properties. Based on these electrolytes, a flexible and wearable thermocell was designed with an output voltage approaching 1 V by utilizing body heat. This work may offer a new train of thought for the development of self‐powered wearable systems by harvesting low‐grade body heat.
Ultrafast Click Chemistry with Fluorosydnones
Authors: Liu Hui , Audisio Davide , Plougastel Lucie , Decuypere Elodie , Buisson David‐Alexandre , Koniev Oleksandr , Kolodych Sergii , Wagner Alain , Elhabiri Mourad , Krzyczmonik Anna , Forsback Sarita , Solin Olof , Gouverneur Véronique , Taran Frédéric
Published: August 2016

We report the synthesis and reactivity of 4‐fluorosydnones, a unique class of mesoionic dipoles displaying exquisite reactivity towards both copper‐catalyzed and strain‐promoted cycloaddition reactions with alkynes. Synthetic access to these new mesoionic compounds was granted by electrophilic fluorination of σ‐sydnone PdII precursors in the presence of Selectfluor. Their reactions with terminal and cyclic alkynes were found to proceed very rapidly and selectively, affording 5‐fluoro‐1,4‐pyrazoles with bimolecular rate constants up to 104 m−1 s−1, surpassing those documented in the literature with cycloalkynes. Kinetic studies were carried out to unravel the mechanism of the reaction, and the value of 4‐fluorosydnones was further highlighted by successful radiolabeling with [18F]Selectfluor.
Synthesis and Characterization of [XeOXe]2+in the Adduct‐Cation Salt, [CH3CN‐ ‐ ‐XeOXe‐ ‐ ‐NCCH3][AsF6]2
Authors: De Backere John R. , Bortolus Mark R. , Schrobilgen Gary J.
Published: August 2016

Acetonitrile and [FXeOXe‐ ‐ ‐FXeF][AsF6] react at −60 °C in anhydrous HF (aHF) to form the CH3CN adduct of the previously unknown [XeOXe]2+cation. The low‐temperature X‐ray structure of [CH3CN‐ ‐ ‐XeOXe‐ ‐ ‐NCCH3][AsF6]2exhibits a well‐isolated adduct‐cation that has among the shortest Xe−N distances obtained for an sp‐hybridized nitrogen base adducted to xenon. The Raman spectrum was fully assigned by comparison with the calculated vibrational frequencies and with the aid of18O‐enrichment studies. Natural bond orbital (NBO), atoms in molecules (AIM), electron localization function (ELF), and molecular electrostatic potential surface (MEPS) analyses show that the Xe−O bonds are semi‐ionic whereas the Xe−N bonds may be described as strong electrostatic (σ‐hole) interactions.
ZnCl2 supported on Fe3O4@SiO2 core–shell nanocatalyst for the synthesis of quinolines via Friedländer synthesis under solvent‐free condition
Authors: Soleimani Ebrahim , Naderi Namivandi Mahbobeh , Sepahvand Heshmatollah
Published: August 2016

A magnetic nanocatalyst of Fe3O4@SiO2/ZnCl2 was prepared by supporting ZnCl2 on silica‐coated magnetic nanoparticles of Fe3O4. This recoverable catalyst was used for the synthesis of quinolines via Friedländer synthesis from 2‐aminoaryl ketones and α‐methylene ketones under solvent‐free condition. The prepared catalyst was characterized by FT‐IR, TEM, SEM, XRD, EDX, ICP‐OES, VSM and BET. It was found that Fe3O4@SiO2/ZnCl2 showed higher catalytic activity than homogenous ZnCl2, and could be reused several times without significant loss of activity.
Synthesis, characterization, DNA interaction, apoptosis and molecular docking of Cu(II) and Mn(II) complexes with endo‐norbornene‐cis‐5,6‐dicarboxylic acid
Authors: Gao Enjun , Ding Yuqing , Sun Na , Zhang Shaozhong , Qiu Xue , Zhan Yang , Zhu Mingchang
Published: August 2016

Two new novel complexes, [Cu4(Endc)4(phen)4]⋅7(H2O)⋅2(O) and [Mn2(Endc)2(phen)2(H2O)2]⋅(H2O) (phen =1,10‐phenanthroline, H2Endc = endo‐norbornene‐cis‐5,6‐dicarboxylic acid), were synthesized and structurally characterized using IR and 1H NMR spectroscopies, elemental analysis and single‐crystal X‐ray diffractometry. Their reactivity with calf thymus DNA and HeLa cell DNA was measured using UV absorption and fluorescence spectroscopies. The results indicated that these complexes can bind to DNA with different binding affinity. Gel electrophoresis assay demonstrated the ability of the complexes to cleave pBR322 plasmid DNA. Apoptotic study showed that the complexes exhibit significant cancer cell inhibitory rates. Eventually, the complexes can suitably dock with a special DNA (PDB ID: 1AIO).
Novel conjugated nanoporous alkynyl metalloporphyrin framework as effective catalyst for oxidation of toluene with molecular oxygen
Authors: Li Yongjin , Sun Baoshuai , Zhou Yuanrong , Yang Weijun
Published: August 2016

A porous alkynylporphyrin conjugated organic polymer (MnE‐TPP) was synthesized by Sonogashira coupling reaction with Mn(II) 5,10,15,20‐tetrakis(4′‐ethynylphenyl)porphyrin and Mn(II) 5,10,15,20‐tetrakis(4′‐bromophenyl)porphyrin as building blocks. The polymer was characterized using nitrogen adsorption–desorption isotherms, field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, Fourier transform infrared and UV–visible spectroscopies, X‐ray diffraction, thermogravimetry and inductively coupled plasma atomic emission spectrometry. The electrochemical behaviors of MnE‐TPP were investigated by cyclic voltammetry. MnE‐TPP was developed as a heterogeneous catalyst for the activation of molecular oxygen to oxidize toluene under mild conditions. The selectivity of total benzaldehyde and benzyl alcohol remained above 70.0% with a conversion of toluene up to 10.2%. The turnover number was as high as 13 653. Also, MnE‐TPP remained structurally stable and the toluene conversion rate hardly decreased after 5 h of reaction and five cycles of reuse.
BMDREDD REGULATES THE APOPTOSIS COORDINATING WITH BMDAXX, BMCIDE‐B, BMFADD, AND BMCREB IN BMN CELLS
Authors: Chen Rui‐ting , Jiao Peng , Lu Yan , Xin Hu‐hu , Zhang Deng‐pan , Wang Mei‐xian , Liang Shuang , Miao Yun‐gen
Published: August 2016

The apoptosis mechanisms in mammals were investigated relatively clearly. However, little is known about how apoptosis is achieved at a molecular level in silkworm cells. We cloned a caspase homologous gene named BmDredd (where Bm is Bombyx mori and Dredd is death‐related ced‐3/Nedd2‐like caspase) in BmN cells from the ovary of Bm and analyzed its biological information. We constructed the N‐terminal, C‐terminal, and overexpression vector of BmDredd, respectively. Our results showed that the transcriptional expression level of BmDredd was increased in the apoptotic BmN cells. Furthermore, overexpression of BmDredd increased the caspase‐3/7 activity. Simultaneously, RNAi of BmDredd could save BmN cells from apoptosis. The immunofluorescence study showed that BmDredd located at the cytoplasm in normal cell otherwise is found at the nucleus when cells undergo apoptosis. Moreover, we quantified the transcriptional expressions of apoptosis‐related genes including BmDredd, BmDaxx (where Daxx is death‐domain associated protein), BmCide‐b (where Cide‐b is cell death inducing DFF45‐like effector), BmFadd (Fadd is fas‐associated via death domain), and BmCreb (where Creb is cAMP‐response element binding protein) in BmN cells with dsRNA interferences to detect the molecular mechanism of apoptosis. In conclusion, BmDredd may function for promoting apoptosis and there are various regulatory interactions among these apoptosis‐related genes.
Divergent Synthesis of Hydro‐γ‐Carbolines and Multisubstituted Indoles through Grob Fragmentation/Mannich Cyclization
Authors: Jiang Long , Yu Yuanyuan , Li Guang , Zu Liansuo
Published: August 2016

A distinct strategy for the divergent synthesis of hydro‐γ‐carbolines and multisubstituted indoles is reported. The stereochemical outcomes and a control experiment indicate that the reactions likely proceed through Grob fragmentation/Mannich cyclization rather than a concerted aza‐pinacol rearrangement.
Photolysis of Carbonyl Diisocyanate: Generation of Isocyanatocarbonyl Nitrene and Diazomethanone
Authors: Liu Qifan , Li Hongmin , Wu Zhuang , Li Dingqing , Beckers Helmut , Rauhut Guntram , Zeng Xiaoqing
Published: August 2016

The stepwise decomposition of carbonyl diisocyanate, OC(NCO)2, has been studied by using IR spectroscopy in solid argon matrices at 16 K. Upon irradiation with an ArF laser (λ=193 nm), carbonyl diisocyanate split off CO and furnished a new carbonyl nitrene, OCNC(O)N, in its triplet ground state. Two conformers of the nitrene, syn and anti, that were derived from the two conformers of OC(NCO)2 (62 % syn–syn and 38 % syn–anti) were identified and characterized by combining IR spectroscopy and quantum chemical calculations. Subsequent irradiation with visible light (λ>395 nm) caused the Curtius rearrangement of the nitrene into OCNNCO. In addition to the expected decomposition products, N2 and CO, further photolysis of OCNNCO with the ArF laser yielded NOCN, through a diazomethanone (NNCO) intermediate. To further validate our proposed reaction mechanism, ArF‐laser photolysis of the closely related NNNNCO and cyclo‐N2CO in solid argon matrices were also studied. The observations of NOCN and in situ CO‐trapped product OCNNCO provided indirect evidence to support the initial generation of NNCO as a common intermediate during the laser photolysis of OCNNCO, NNNNCO, and cyclo‐N2CO.
Chemical Genetic Screen Identifies Natural Products that Modulate Centriole Number
Authors: Graciotti Michele , Fang Zhou , Johnsson Kai , Gönczy Pierre
Published: August 2016

Centrioles are microtubule‐based organelles found in most eukaryotic cells and that are critical for the formation of cilia and flagella, as well as of centrosomes in animal cells. The number of centrioles must be strictly regulated in proliferating cells in order to ensure genome integrity upon cell division. Despite their importance, however, the mechanisms governing centriole assembly and number control remain incompletely understood, owing in part to a paucity of available small‐molecule compounds for dissection and alteration of the underlying processes. Here we have developed a chemical genetic approach to identify small‐molecule compounds capable of modulating centriole numbers in human cells. High‐throughput screening of ≈2600 natural compounds identified 14 candidate molecules that either diminish (ten compounds) or augment (four compounds) the number of centrioles per cell. We investigated the mechanisms of action of four of these compounds and discovered that two of them potentially reduce centriole number through effects on NF‐κB signalling. Moreover, we established that one further compound blocks cell cycle progression and probably indirectly causes an augmentation of centriole number. The last compound analysed induces, in addition to excess centrioles, exceptionally long primary cilia‐like structures. Overall, our analysis demonstrates that natural products constitute a rich source of tool compounds useful for unravelling and manipulating the mechanisms governing centriole assembly and number control.
Childhood trauma heightens risk for teen drug misuse
Authors: Knopf Alison
Published: August 2016

Trauma is a known risk factor for substance use disorders (SUDs) among adults, but less is known about how childhood trauma affects adolescent SUDs. This is particularly important, as adolescence is a target developmental stage for drug use prevention.
Timely autism diagnosis — before 4 years of age — improves treatment
Authors: Knopf Alison
Published: August 2016

Early diagnosis of an autism spectrum disorder (ASD) — before the age of 4 — means that behavioral therapy is more likely to be provided. After that age, children are less likely to receive behavioral therapy, and rather are more likely to receive medication, according to research published last month. If the delay is more than two years between the parents' first discussions with a provider and an autism diagnosis, the use of complementary and alternative medicine (CAM) — which is not evidence‐based — is more likely.
A High‐Performance Base‐Metal Approach for the Oxidative Esterification of 5‐Hydroxymethylfurfural
Authors: Sun Yuxia , Ma Hong , Jia Xiuquan , Ma Jiping , Luo Yang , Gao Jin , Xu Jie
Published: August 2016

Exploring high‐performance base‐metal approaches for the sustainable production of chemicals from biomass is presently attracting immense interest and is truly important to promote their industrialized application. Herein, CoOx‐N/C and α‐MnO2 were combined as a base‐metal catalyst that can achieve high yields of furan‐2,5‐dimethylcarboxylate (FDMC, 95.6 %) for the catalytic oxidative esterification of 5‐hydroxymethylfurfural (HMF) without basic additive. The reaction proceeds through fast conversion of HMF to diformylfuran (DFF) with α‐MnO2 and subsequent transformation of DFF to FDMC by CoOx‐N/C. Quantitative X‐ray photoelectron spectroscopy (XPS) analysis and density functional theory (DFT) calculations indicated that the pyridinic‐N present in doped carbon could behave as a Lewis base to promote the abstraction of hydrogen for the oxidative esterification reaction. Consequently, CoOx‐N/C is a high performance catalyst for the synthesis of FDMC from DFF in a neutral medium.
Solvent‐Free Synthesis of c‐Axis Oriented ZSM‐5 Crystals with Enhanced Methanol to Gasoline Catalytic Activity
Authors: Liu Ziyu , Wu Dan , Ren Shu , Chen Xinqing , Qiu Minghuang , Wu Xian , Yang Chengguang , Zeng Gaofeng , Sun Yuhan
Published: August 2016

ZSM‐5 crystals with controllable c‐axis length were successfully synthesized through a one‐pot solvent‐free route, with urea as an additive. X‐ray diffraction patterns (XRD) show that the prepared samples exhibit high crystallinity. N2 adsorption–desorption isotherms and mercury intrusion porosimetry (MIP) analysis together with TEM observations indicate that micro‐, meso‐, and macropores exist in the obtained samples. Catalytic tests for the methanol to gasoline (MTG) conversion showed that the prepared c‐axis oriented hierarchical ZSM‐5, which allow fast mass transfer, exhibited both 100 % methanol conversion and far longer lifetime (900 h) than those of ZSM‐5 with conventional morphology (350 h) in the MTG reaction. The enhanced MTG performance by the c‐axis oriented zeolite under one‐pot solvent‐free synthesis is of great importance as it is easily scaled‐up for industrial applications.
Control Strategy and Comparison of Tuning Methods for Continuous Lactide Ring‐Opening Polymerization
Authors: Costa Liborio I. , Trommsdorff Ulla
Published: August 2016

Polylactic acid is industrially produced by ring‐opening polymerization of lactide. This reaction is extremely sensitive to the level of monomer contaminants, thus posing some challenges for the operability of continuous processes. A control strategy was designed and the corresponding controller parameters were determined using gProms simulations by applying the Ziegler‐Nichols, Tyreus‐Luyben, and Cohen‐Coon methods. The simulation results show that the proposed strategy is effective in restoring the targeted process conditions after a sudden change in the level of contaminants, with the Cohen‐Coon controller providing the best results. Additionally, the simulations demonstrate that the use of automatic process control significantly reduces the pressure rise along the reactors after a feed disturbance, thus ensuring safer plant operation.
Stereoretentive Copper‐Catalyzed Directed Thioglycosylation of C(sp2)−H Bonds of Benzamides
Authors: Chabrier Amélie , Bruneau Alexandre , Benmahdjoub Sara , Benmerad Belkacem , Belaid Sabrina , Brion Jean‐Daniel , Alami Mouâd , Messaoudi Samir
Published: August 2016

An efficient thioglycosylation of C(sp2)−H bonds with thiosugars has been established for the first time. Using only Cu(OAc)2⋅H2O as a catalyst and Ag2CO3 as an additive in DMSO, the protocol proved to have broad scope, and a variety of complex thioglycosides have been prepared in good yields with exclusive β‐selectivity.
SuFEx Click: New Materials from SOxF and Silyl Ethers
Authors: Yatvin Jeremy , Brooks Karson , Locklin Jason
Published: August 2016

New forms of click chemistry present new opportunities in materials science. Sulfur(VI) fluoride exchange (SuFEx) is a recently discovered click reaction between molecules containing SOxF groups and silyl ethers, two functionalities that are orthogonal to all other known click chemistries, that generates sulfate or sulfonate connections upon the addition of certain organobases or fluoride sources. SuFEx also has several important advantages over other click reactions in that it is insensitive to ambient oxygen and water, and its precursor materials, especially SOxF, are chemically, UV, and thermally inert. This Concept article focuses on the unique reactivity of SuFEx and its relation to building high molecular weight polymers and surface coatings, both of which make it a powerful new tool for materials science.
Structures of Highly Twisted Amides Relevant to Amide N−C Cross‐Coupling: Evidence for Ground‐State Amide Destabilization
Authors: Pace Vittorio , Holzer Wolfgang , Meng Guangrong , Shi Shicheng , Lalancette Roger , Szostak Roman , Szostak Michal
Published: August 2016

Herein, we show that acyclic amides that have recently enabled a series of elusive transition‐metal‐catalyzed N−C activation/cross‐coupling reactions are highly twisted around the N−C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of theN‐glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α‐carbon atom. The15N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground‐state twist as a blueprint for activation of amides toward N−C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non‐planar amide bonds.
Influence of Polymer Electronics on Selective Dispersion of Single‐Walled Carbon Nanotubes
Authors: Fong Darryl , Bodnaryk William J. , Rice Nicole A. , Saem Sokunthearath , Moran‐Mirabal Jose M. , Adronov Alex
Published: August 2016

Invited for the cover of this issue is the group of Alex Adronov at McMaster University. The image depicts a stylized view of a metallic carbon nanotube that is being pulled into solution, and is related to the findings that the electronic nature of a conjugated polymer has an impact on its selectivity for metallic versus semiconducting single‐walled carbon nanotubes, allowing their selective dissolution. Read the full text of the article at 10.1002/chem.201602722.
Selenide‐Catalyzed Stereoselective Construction of Tetrasubstituted Trifluoromethylthiolated Alkenes with Alkynes
Authors: Wu Jin‐Ji , Xu Jia , Zhao Xiaodan
Published: August 2016

The efficient regio‐ and stereoselective construction of tetrasubstituted alkenes is challenging and very important. For this purpose, we have developed an efficient approach to synthesize tetrasubstituted trifluoromethylthiolated alkenes from simple alkynes in excellent regio‐ and stereoselectivities by selenide‐catalyzed multicomponent coupling. Using this method, trifluoromethylthiolated alkenyl triflates and arenes were achieved. In particular, the triflates could be further converted into carbofunctionalized alkenes by palladium‐catalyzed cross‐coupling reactions. Our method provides a new pathway for the construction of trifluoromethylthiolated tricarboalkenes. This work presents the first example of selenide‐catalyzed trifluoromethylthiolation of alkynes and enables the challenging functionalizations of alkynes.
ChemInform Abstract: Intramolecular Energy Transfer Studies of a New Mixed Isopolymolybdate [Eu(dmso)8] [Eu(η2‐NO3)2(dmso)4 (α‐Mo8O26)0.5] [Mo6O19]: Synthesis, Characterization and Europium(III) Luminescence Properties.
Authors: Ben Khelifa Arbia , Chekir‐Mzali Jalila , Ezzayani Khaireddine , Freslon Stephane , Belkhiria Mouhamed Salah
Published: August 2016

The title compound is obtained from DMSO solutions of [Bu4N][Mo6O19] and Eu(NO3)3 (333 K, 2 h, 75% yield).
ChemInform Abstract: A Gold(I)‐Catalyzed Substituent‐Controlled Cycloisomerization of Propargyl Vinylethers to Multi‐Substituted Furofuran and Furopyran Derivatives.
Authors: Liu Yongxiang , Jin Shengfei , Wang Yanshi , Cui Shanshan , Peng Xiaoshi , Niu Yuanyuan , Du Chuan , Cheng Maosheng
Published: August 2016

Compounds (IIIa), (IIIc), (IIIe), (Va), (Vc), (VIa), (VII), (VIIIa), and (IX) show antifungal activity.
ChemInform Abstract: Palladium‐Catalyzed Arylation of β‐Methylene C(sp3)—H Bonds at Room Temperature: Desymmetrization of Simple Cycloalkyl Carboxylic Acids.
Authors: Nack W. A. , Wang B. , Wu X. , Jiao R. , He G. , Chen G.
Published: August 2016

In most cases, the β methylene C—H bonds of cycloalkylcarboxamides of varied ring size are monoarylated giving products with excellent cis‐diastereoselectivity whereby, diarylated products are also observed as by‐products.
ChemInform Abstract: Rhodium(II)‐Catalyzed Isomerization of Cyclopropenylmethyl Esters into (Acyloxymethylene)cyclopropanes.
Authors: Archambeau Alexis , Nguyen Dinh‐Vu , Meyer Christophe , Cossy Janine
Published: August 2016

In the presence of a rhodium(II) catalyst, 3,3‐disubstituted cyclopropenylmethyl esters that possess an electron‐rich or neutral aromatic group undergo isomerization into (acyloxymethylene)cyclopropanes.
ChemInform Abstract: Direct Conversion of Haloarenes to Phenols under Mild, Transition‐Metal‐Free Conditions
Authors: Fier Patrick S. , Maloney Kevin M.
Published: August 2016

by a novel SNAr reaction/Lossen rearrangement sequence using acetohydroxamic acid as hydroxide source
ChemInform Abstract: Direct Conversion of Internal Alkynes into α‐Iodoenones: One‐Step Collaborative Iodination and Oxidation.
Authors: Wang Youliang , Genoux Alexandre , Ghorai Subir , Chen Hongyi , Todd Robert , Zhang Liming
Published: August 2016

2,6‐Dichloropyridine N‐oxide as oxidant and NIS as iodination agent in stoichiometric amounts promote the title reaction regioselectively in high yields with preferred formation of Z isomers.
ChemInform Abstract: Regioselective Alkoxycarbonylation of Allyl Phenyl Ethers Catalyzed by Pd/dppb under Syngas Conditions.
Authors: Amezquita‐Valencia Manuel , Alper Howard
Published: August 2016

The synthesis of phenoxy and phenylthio esters proceeds with excellent selectivity in favor of the linear product.
ChemInform Abstract: Highly Efficient and Regioselective Synthesis of Spirooxindolo Pyrrolizidines by Reaction of Isatin, Proline and Acrylonitrile/Methyl Acrylate in Water.
Authors: Tiwari Keshri Nath , Pandurang Taur Prakash , Pant Suyash , Kumar Rahul
Published: August 2016

The 1,3‐dipolar cycloaddition reaction of azomethine ylides generated in situ by isatin and L‐proline to acrylonitrile and methyl acrylate in water affords a series of spirooxindolo pyrrolizidines in good yields.
ChemInform Abstract: Ultrasound Assisted One‐Pot Synthesis of Benzo‐Fused Indole‐4,9‐dinones from 1,4‐Naphthoquinone and α‐Aminoacetals.
Authors: Luu Quang H. , Guerra Jorge D. , Castaneda Cecilio M. , Martinez Manuel A. , Saunders Jong , Garcia Benjamin A. , Gonzales Brenda V. , Aidunuthula Anushritha R. , Mito Shizue
Published: August 2016

The synthesis of benzo[f]indole‐4,9‐diones in one‐pot from 1,4‐naphthoquinone and α‐aminoacetals is reported.
ChemInform Abstract: Synthesis of 1,3‐Disubstituted Imidazo[1,5‐a]pyridines from Amino Acids via Catalytic Decarboxylative Intramolecular Cyclization.
Authors: Wang Huiqiao , Xu Wentao , Xin Lilan , Liu Wenmin , Wang Zhiqiang , Xu Kun
Published: August 2016

2‐Aryloylpyridines or quinolines efficiently react with aryl or alkyl substituted α‐amino acids, thus offering not only a novel approach to 1,3‐diaryl substituted imidazo[1,5‐a]pyridines, but also to 3‐alkyl‐1‐aryl substituted derivatives which are difficult to access by previously developed methods.
ChemInform Abstract: Efficient One‐Pot Synthesis of New Fused Pyridines and Bis‐pyridines Catalyzed by Triazine Diphosphonium Hydrogen Sulfate Ionic Liquid Supported on Functionalized Nano‐Silica.
Authors: Rahmani Fahime , Mohammadpoor‐Baltork Iraj , Khosropour Ahmad R. , Moghadam Majid , Tangestaninejad Shahram , Mirkhani Valiollah
Published: August 2016

A novel, facile, and highly efficient methodology for the synthesis of fused pyridines via a one‐pot three‐component reaction of aldehydes, kojic acid (I) and uracil (III) or pyrazole (VI) in the presence of a functionalized nano silica catalyst.
ChemInform Abstract: A Comparative Investigation: Group 9 Cp*M(III)‐Catalyzed Formal [4 + 2] Cycloaddition as an Atom‐Economic Approach to Quinazolines.
Authors: Wang Xiaoming , Lerchen Andreas , Glorius Frank
Published: August 2016

The cobalt catalyst exhibits excellent efficiency and selectivity in the novel formal [4 + 2] cycloaddition of arenes with a free imine unit and dioxazolones to quinazoline derivatives.
ChemInform Abstract: Microwave‐Assisted Synthesis of Pyridophenoxazinones, a Class of Antiproliferative Compounds.
Authors: De Nisco Mauro , Bolognese Adele , Sala Marina , Pedatella Silvana , Manfra Michele
Published: August 2016

Optimized microwave procedures are developed for the cyclocondensation of quinoline‐5,8‐dione (I) with ortho‐aminophenols (II) to give pyridophenoxazines (III).
ChemInform Abstract: Allylic Borylation of Tertiary Allylic Alcohols: A Divergent and Straightforward Access to Allylic Boronates.
Authors: Harada Kohei , Nogami Marina , Hirano Keiichi , Kurauchi Daisuke , Kato Hisano , Miyamoto Kazunori , Saito Tatsuo , Uchiyama Masanobu
Published: August 2016

A novel access to allylic boronates is described.
ChemInform Abstract: Identification of Two New Phosphorylated Polyketides from a Brazilian Streptomyces sp. Through the Use of LC‐SPE/NMR
Authors: Scherrer Thomasi Sergio , Ladeira Cecilia , Ferreira Douglas , da Fontoura Sprenger Ricardo , Colli Badino Alberto , Gilberto Ferreira Antonio , Venancio Tiago
Published: August 2016

Two new polyketide phosphate monoesters, phosdiecin A (I) and phosdiecin B (II), are isolated from a culture of the marine Streptomyces sp.
ChemInform Abstract: New Approaches to the Synthesis of Metal Carbenes
Authors: Jia Minqiang , Ma Shengming
Published: August 2016

Review: [257 refs.
ChemInform Abstract: Recent Advances in Catalytic CO2 Reduction by Organometal Complexes Anchored on Modified Electrodes
Authors: Sun Cunfa , Gobetto Roberto , Nervi Carlo
Published: August 2016

Review: 45 refs.
ChemInform Abstract: Ultrasound‐Assisted Bioalcohol Synthesis: Review and Analysis
Authors: Ranjan Amrita , Singh Shuchi , Malani Ritesh S. , Moholkar Vijayanand S.
Published: August 2016

Review: 72 refs.
ChemInform Abstract: Applications of Dimedone in the Synthesis of Heterocycles: An Update
Authors: Heravi Majid M. , Zadsirjan Vahideh , Fattahi Bahareh , Nazari Niousha
Published: August 2016

Review: 272 refs.
ChemInform Abstract: Unlocking the Potential of Supported Liquid Phase Catalysts with Supercritical Fluids: Low Temperature Continuous Flow Catalysis with Integrated Product Separation
Authors: Francio Giancarlo , Hintermair Ulrich , Leitner Walter
Published: August 2016

Review: 198 refs.
ChemInform Abstract: Halogen ′dance′: A Way to Extend the Boundaries of Arene Deprotolithiation
Authors: Erb William , Mongin Florence
Published: August 2016

Review: [36 refs.
ChemInform Abstract: 5‐Alkoxyoxazole — A Versatile Building Block in (Bio)organic Synthesis
Authors: Jouanno Laurie‐Anne , Renault Kevin , Sabot Cyrille , Renard Pierre‐Yves
Published: August 2016

Review: [80 refs.
ChemInform Abstract: Chemical Constituents of Plants from the Genus Psychotria
Authors: Yang Hongmei , Zhang Hongmei , Yang Caiqiong , Chen Yegao
Published: August 2016

Review: 75 refs.
ChemInform Abstract: Imaging and Therapeutic Applications of Zinc(II)‐Dipicolylamine Molecular Probes for Anionic Biomembranes
Authors: Rice Douglas R. , Clear Kasey J. , Smith Bradley D.
Published: August 2016

Review: 159 refs.
ChemInform Abstract: On the Outside Looking In: Redefining the Role of Analytical Chemistry in the Biosciences
Authors: Hare Dominic J. , New Elizabeth J.
Published: August 2016

Review: 173 refs.
ChemInform Abstract: Self‐Monitoring of Tear Glucose: The Development of a Tear Based Glucose Sensor as an Alternative to Self‐Monitoring of Blood Glucose
Authors: La Belle Jeffrey T. , Adams Anngela , Lin Chi‐En , Engelschall Erica , Pratt Breanna , Cook Curtiss B.
Published: August 2016

Review: 43 refs.
ChemInform Abstract: Graphene Oxide: Strategies for Synthesis, Reduction and Frontier Applications
Authors: Singh Rajesh Kumar , Kumar Rajesh , Singh Dinesh Pratap
Published: August 2016

Review: 263 refs.
ChemInform Abstract: Biomass into Chemicals: Green Chemical Conversion of Carbohydrates into 5‐Hydroxymethylfurfural in Ionic Liquids
Authors: Chinnappan Amutha , Baskar Chinnappan , Kim Hern
Published: August 2016

Review: 120 refs.
ChemInform Abstract: Modelling Spin Hamiltonian Parameters of Molecular Nanomagnets
Authors: Gupta Tulika , Rajaraman Gopalan
Published: August 2016

Review: [216 refs.
Immunoproteasome β5i‐Selective Dipeptidomimetic Inhibitors
Authors: Singh Pradeep K. , Fan Hao , Jiang Xiuju , Shi Lei , Nathan Carl F. , Lin Gang
Published: August 2016

N,C‐capped dipeptides belong to a class of noncovalent proteasome inhibitors. Herein we report that the insertion of a β‐amino acid into N,C‐capped dipeptides markedly decreases their inhibitory potency against human constitutive proteasome β5c, while maintaining potent inhibitory activity against human immunoproteasome β5i, thereby achieving thousands‐fold selectivity for β5i over β5c. Structure–activity relationship studies revealed that β5c does not tolerate the β‐amino acid based dipeptidomimetics as does β5i. In vitro, one such compound was found to inhibit human T cell proliferation. Compounds of this class may have potential as therapeutics for autoimmune and inflammatory diseases with less mechanism‐based cytotoxicity than agents that also inhibit the constitutive proteasome.
Membrane‐associated guanylate kinase scaffolds organize a horizontal cell synaptic complex restricted to invaginating contacts with photoreceptors
Authors: Vila Alejandro , Whitaker Christopher M. , O'Brien John
Published: August 2016

Synaptic processes and plasticity of synapses are mediated by large suites of proteins. In most cases, many of these proteins are tethered together by synaptic scaffold proteins. Scaffold proteins have a large number and typically a variety of protein interaction domains that allow many different proteins to be assembled into functional complexes. Because each scaffold protein has a different set of protein interaction domains and a unique set of interacting partners, the presence of synaptic scaffolds can provide insight into the molecular mechanisms that regulate synaptic processes. In studies of rabbit retina, we found SAP102 and Chapsyn110 selectively localized in the tips of B‐type horizontal cell processes, where they contact cone and rod photoreceptors. We further identified some known SAP102 binding partners, kainate receptor GluR6/7 and inward rectifier potassium channel Kir2.1, closely associated with SAP102 in photoreceptor invaginations. The kainate receptor occupies a position distinct from that of the majority of AMPA receptors that dominate the horizontal cell postsynaptic response. GluR6/7 and Kir2.1 presumably are involved in synaptic processes that govern cell‐to‐cell communication and could both contribute in different ways to synaptic currents that mediate feedback signaling. Notably, we failed to find evidence for the presence of Cx57 or Cx59 that might be involved in ephaptic feedback signaling in this complex. The presence of SAP102 and its binding partners in both cone and rod invaginating synapses suggests that whatever mechanism is supported by this protein complex is present in both types of photoreceptors. J. Comp. Neurol. 525:850–867, 2017. © 2016 Wiley Periodicals, Inc.
The pretectal connectome in lamprey
Authors: Capantini Lorenza , von Twickel Arndt , Robertson Brita , Grillner Sten
Published: August 2016

In vertebrates, the pretectum and optic tectum (superior colliculus in mammals) are visuomotor areas that process sensory information and shape motor responses. Whereas the tectum has been investigated in great detail, the pretectum has received far less attention. The present study provides a detailed analysis of the connectivity and neuronal properties of lamprey pretectal cells. The pretectum can be subdivided roughly into three areas based on cellular location and projection pattern: superficial, central, and periventricular. Three different types of pretectal cells could be distinguished based on neuronal firing patterns. One type, the rapid spike‐inactivation cells, preferentially lie within the periventricular zone; the other cell types are distributed more generally. In terms of afferentation, the pretectum receives electro‐ and mechanoreceptive inputs in addition to retinal input. Histological data reveal that a large number of pretectal cells in the superficial and central areas extend dendrites into the optic tract, suggesting a predominant retinal influence even outside of the normal retinal terminal areas. The pretectum receives inhibitory input from the basal ganglia, and input from the pallium (cortex in mammals) and torus semicircularis. In addition, the pretectum is reciprocally connected with the thalamus, tectum, octavolateral area, and habenula. The main pretectal output is to the reticulospinal nuclei, and thus the pretectum indirectly affects the control of movement. Efference copies of some of this output are relayed to the thalamus and tectum. Overall, its extensive circuitry—especially the reciprocal connectivity with other retinorecipient areas—underlines the importance of the pretectum for sensory integration and visuomotor functions. J. Comp. Neurol. 525:753–772, 2017. © 2016 Wiley Periodicals, Inc.
Late postnatal shifts of parvalbumin and nitric oxide synthase expression within the GABAergic and glutamatergic phenotypes of inferior colliculus neurons
Authors: Fujimoto Hisataka , Konno Kotaro , Watanabe Masahiko , Jinno Shozo
Published: August 2016

The inferior colliculus (IC) is partitioned into three subdivisions: the dorsal and lateral cortices (DC and LC) and the central nucleus (ICC), and serves as an integration center of auditory information. Recent studies indicate that a certain population of IC neurons may represent the non‐GABAergic phenotype, while they express well‐established cortical/hippocampal GABAergic neuron markers. In this study we used the optical disector to investigate the phenotype of IC neurons expressing parvalbumin (PV) and/or nitric oxide synthase (NOS) in C57BL/6J mice during the late postnatal period. Four major types of IC neurons were defined by the presence (+) or absence (–) of PV, NOS, and glutamic acid decarboxylase 67 (GAD67): PV+/NOS−/GAD67+, PV+/NOS+/GAD67+, PV+/NOS−/GAD67−, and PV−/NOS+/GAD67−. Fluorescent in situ hybridization for vesicular glutamate transporter 2 mRNA indicated that almost all GAD67− IC neurons represented the glutamatergic phenotype. The numerical densities (NDs) of total GAD67+ IC neurons remained unchanged in all subdivisions. The NDs of PV+/NOS−/GAD67+ neurons and PV−/NOS+/GAD67− neurons were reduced with age in the ICC, while they remained unchanged in the DC and LC. By contrast, the NDs of PV+/NOS+/GAD67+ neurons and PV+/NOS−/GAD67− neurons were increased with age in the ICC, although there were no changes in the DC and LC. The cell body size of GAD67+ IC neurons did not vary according to the expression of PV with or without NOS. The present findings indicate that the expression of PV and NOS may shift with age within the GABAergic and glutamatergic phenotypes of IC neurons during the late postnatal period. J. Comp. Neurol. 525:868–884, 2017. © 2016 Wiley Periodicals, Inc.
Self‐Assembly of “Chalcone” Type Push‐Pull Dye Molecules into Organic Single Crystalline Microribbons and Rigid Microrods for Vis/NIR Range Photonic Cavity Applications
Authors: Vattikunta Radhika , Venkatakrishnarao Dasari , Mohiddon Mahamad Ahamad , Chandrasekar Rajadurai
Published: August 2016

A novel supramolecular fluorescent donor–acceptor type dye molecule, (2E,4E)‐1‐(2‐hydroxyphenyl)‐5‐(pyren‐1‐yl)penta‐2,4‐dien‐1‐one (HPPD) self‐assembles in a mixture of ethanol/chloroform through intermolecular π–π stacking (distance ca. 3.384 Å) to form J‐aggregated single‐crystalline microribbons displaying Fabry–Pèrot (F‐P) type visible‐range optical resonance. The corresponding borondifluoride dye (HPPD‐BF), with a reduced HOMO–LUMO gap, self‐assembles into crystalline microrods acting as an F‐P type resonator in the near‐infrared (NIR) range.
Selectivity Control in the Tandem Aromatization of Bio‐Based Furanics Catalyzed by Solid Acids and Palladium
Authors: Genuino Homer C. , Thiyagarajan Shanmugam , van der Waal Jan C. , de Jong Ed , van Haveren Jacco , van Es Daan S. , Weckhuysen Bert M. , Bruijnincx Pieter C. A.
Published: August 2016

Bio‐based furanics can be aromatized efficiently by sequential Diels–Alder (DA) addition and hydrogenation steps followed by tandem catalytic aromatization. With a combination of zeolite H‐Y and Pd/C, the hydrogenated DA adduct of 2‐methylfuran and maleic anhydride can thus be aromatized in the liquid phase and, to a certain extent, decarboxylated to give high yields of the aromatic products 3‐methylphthalic anhydride and o‐ and m‐toluic acid. Here, it is shown that a variation in the acidity and textural properties of the solid acid as well as bifunctionality offers a handle on selectivity toward aromatic products. The zeolite component was found to dominate selectivity. Indeed, a linear correlation is found between 3‐methylphthalic anhydride yield and the product of (strong acid/total acidity) and mesopore volume of H‐Y, highlighting the need for balanced catalyst acidity and porosity. The efficient coupling of the dehydration and dehydrogenation steps by varying the zeolite‐to‐Pd/C ratio allowed the competitive decarboxylation reaction to be effectively suppressed, which led to an improved 3‐methylphthalic anhydride/total aromatics selectivity ratio of 80 % (89 % total aromatics yield). The incorporation of Pd nanoparticles in close proximity to the acid sites in bifunctional Pd/H‐Y catalysts also afforded a flexible means to control aromatic products selectivity, as further demonstrated in the aromatization of hydrogenated DA adducts from other diene/dienophile combinations.
An offset cancellation technique of complementary input pair buffers for continuous time applications
Authors: Mountrichas L. , Siskos S.
Published: August 2016

This letter describes an offset cancellation technique for rail‐to‐rail complementary input pair operational amplifiers in unity gain loop configuration that overcomes the variable offset and minimizes distortion. The simulated buffer exhibits up to 40 dB increase in spurious‐free dynamic range and up to 30 dB increase in signal‐to‐noise and distortion ratio. When used to buffer a continuous time modulator, the performance matches that of chopping. Measurement results verify the technique, illustrating effective offset cancellation regardless of the input signal level. Copyright © 2016 John Wiley & Sons, Ltd.
A supervised learning framework for pancreatic islet segmentation with multi‐scale color‐texture features and rolling guidance filters
Authors: Huang Yue , Liu Chi , Eisses John F. , Husain Sohail Z. , Rohde Gustavo K.
Published: August 2016

Islet cell quantification and function is important for developing novel therapeutic interventions for diabetes. Existing methods of pancreatic islet segmentation in histopathological images depend strongly on cell/nuclei detection, and thus are limited due to a wide variance in the appearance of pancreatic islets. In this paper, we propose a supervised learning pipeline to segment pancreatic islets in histopathological images, which does not require cell detection. The proposed framework firstly partitions images into superpixels, and then extracts multi‐scale color‐texture features from each superpixel and processes these features using rolling guidance filters, in order to simultaneously reduce inter‐class ambiguity and intra‐class variation. Finally, a linear support vector machine (SVM) is trained and applied to segment the testing images. A total of 23 hematoxylin‐and‐eosin‐stained histopathological images with pancreatic islets are used for verifying the framework. With an average accuracy of 95%, training time of 20 min and testing time of 1 min per image, the proposed framework outperforms existing approaches with better segmentation performance and lower computational cost. © 2016 International Society for Advancement of Cytometry
Sorting of chromosomes on FACSAriaTM SORP for the preparation of painting probes
Authors: Jia Yu‐Yan , Wu Hou‐Nan , Fang Liang , Liu Yun , Cheng Li , Liu Guang , Zhang Mei‐Li , Huang Yue
Published: August 2016

High purity chromosome sorting can be performed on instruments such as MoFlo MLS and BD influx, which are stream‐in‐air sorters equipped with water‐cooled high power lasers. The FACSAria is a true fixed alignment, low laser powered instrument with a quartz flow cell gel‐coupled to the collection optics. However, whether high purity mouse and human chromosomes can be obtained by sorting on the BD FACSAriaTM Special Order Research Product (FACSAria SORP) remains to be determined. Here, we report that the high resolution flow karyotype of mouse lymphocytes and normal male human peripheral blood mononuclear cells (hPBMCs) can be obtained on the FACSAria SORP using laser power settings of 50 mW for 355 nm and 20 mW for 444 nm excitation. Furthermore, the use of Fluorescence in situ hybridization (FISH) confirmed that chromosome paints prepared from the sorted chromosomes demonstrated high purity and signal specificity. Notably, human chromosome 12 was separated from the chromosome 9–12 cluster in the flow karyotype, and its identity was confirmed using FISH in trisomy 12 human ES cell lines B2‐C7 and B2‐B8. In addition, multicolor FISH (mFISH) with human chromosome painting probes to 13,18, 21, and sex chromosomes X and Y showed high signal specificity in hPBMCs. Taken together, our findings demonstrated that high resolution flow karyotype can be obtained using FACSAria SORP. Moreover, a FISH analysis confirmed high purity of the sorted chromosomes. Additionally, in contrast to centromeric satellite probes, chromosome painting probes with high specificity are more suitable for detection of chromosome aberrations, such as deletions and translocations, in prenatal diagnosis. © 2016 International Society for Advancement of Cytometry