bluuebunny/crossref_metadata_2025 huggingface dataset:
Self‐Assembled Nanodielectrics for High‐Speed, Low‐Voltage Solution‐Processed Polymer Logic Circuits
Authors: Senanayak Satyaprasad P. , Sangwan Vinod K. , McMorrow Julian J. , Everaerts Ken , Chen Zhihua , Facchetti Antonio , Hersam Mark C. , Marks Tobin J. , Narayan K. S.
Published: October 2015

Solution‐processed polymer‐based logic circuits are typically associated with high operating voltage and slow switching speeds. Here, polymer field‐effect transistors (PFETs) fabricated on hybrid self‐assembled nanodielectric (SAND) structures are reported, the latter consisting of alternating organic–inorganic layers exhibiting low leakage current (≈10−9 A cm−2) and high capacitance (≈0.8 μF cm−2). Suitable device engineering, controllable dielectric parameters, and interface energetics enable PFET operation at ±1 V, field‐effect mobility (μ
FET) > 2.0 cm2 V−1 s−1, subthreshold swing ≈100 mV dec−1, and switching response ≈150 ns. These performance parameters are orders of magnitude higher than similar devices fabricated from other polymer dielectrics. Inverter and NAND logic circuits fabricated from these SAND‐based PFETs possess voltage gain up to 38 and maximum‐frequency bandwidth of 2 MHz. A systematic study comparing different classes of dielectric and semiconducting material attributes the enhanced performance to improved relaxation dynamics of the SAND layer and tunable chemically functionalized interfaces.
Testing of a new dynamic Ergun equation for transport with positron emission particle tracking
Authors: Tupper Gary B. , Govender Indresan , De Klerk David N. , Richter Max C. , Mainza Aubrey N.
Published: October 2015

The issue of formulating an Ergun‐like equation that applies to dynamic beds previously considered in Tupper et al. (2013) is revisited. Using new high quality positron emission particle tracking data, the volume and time averaged kinematic distributions of the granular (glass beads) and slurry (silica sand and water) mixture are computed. Incorporating these measured ingredients into the model then reveals that turbulence is not described by the usual effective viscosity, but nonetheless is negligible such that the new “Inertial Cell Equation” is first order in spatial derivatives. © 2015 American Institute of Chemical Engineers AIChE J, 62: 939–946, 2016
A Facile Synthesis of 1,5‐Disubstituted Tetrazole Peptidomimetics by Desulfurization/Electrocyclization of Thiopeptides
Authors: Prabhu Girish , Nagendra Govindappa , Sagar N. R. , Pal Rumpa , Guru Row Tayur N. , Sureshbabu Vommina V.
Published: October 2015

The cis‐amide bond isostere, 1,5‐disubstituted tetrazole,has been introduced in the peptide backbone by a simple route starting from the thiopeptide. The desired 1,5‐disubstituted tetrazole peptidomimetics were synthesized by the desulfurization of thiopeptides by using HgCl2 in the presence of NaN3/TEA in DMF in good yields. Various other thiophilic reagents including hypervalent iodine reagents failed to deliver the tetrazole product with the exception of CBr4/PPh3, which resulted in moderate yields. The advantage of the present protocol over previous methods has been demonstrated by the selective insertion of tetrazole into peptide–thiopeptide hybrids. Also, the protocol is compatible with commonly employed urethane protecting groups (Fmoc, Boc, and Cbz) in peptide chemistry. Thiopeptide Boc‐Pro‐ψ[CSNH]‐Val‐OMe (2 i) and two tetrazole peptidomimetics Cbz‐Ala‐ψ[CN4]‐Phe‐OMe (3 d) and Boc‐Pro‐ψ[CN4]‐Val‐OMe (3 i) were obtained as single crystals and their molecular structures have been confirmed by X‐ray crystallography.
Replacement of styrene with acrylated epoxidized soybean oil in an unsaturated polyester resin from propylene glycol, isophthalic acid, and maleic anhydride
Authors: Wu Yili , Li Kaichang
Published: October 2015

Commercial unsaturated polyester (UPE) resins typically contain a high amount of volatile toxic styrene. A non‐volatile acrylated epoxidized soybean oil (AESO) was found to be an excellent replacement of styrene in a commercially available UPE resin [designated as Styrene‐(PG‐IPA‐MA)] that is derived from propylene glycol (PG), isophthalic acid (IPA), and maleic anhydride (MA) in terms of the mechanical properties of the resulting kenaf fiber‐reinforced composites. The AESO‐(PG‐IPA‐MA) resins had low viscosity and long pot life below 70°C for a typical fiber‐reinforced composite application. AESO and PG‐IPA‐MA were not able to form a strong polymer matrix individually for fiber‐reinforced composites. However, a combination of AESO and PG‐IPA‐MA saw strong synergistic effects between them. The flexural, tensile, and water absorption properties of kenaf fiber‐reinforced composites made from AESO‐(PG‐IPA‐MA) resins were comparable with or even superior to those from the Styrene‐(PG‐IPA‐MA) resin. The AESO/(PG‐IPA‐MA) weight ratio was investigated for maximizing the mechanical properties of the kenaf fiber‐reinforced composites. The curing mechanism of the AESO‐(PG‐IPA‐MA) resins is discussed in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43052.
Altered kynurenine pathway metabolism in autism: Implication for immune‐induced glutamatergic activity
Authors: Lim Chai K. , Essa Musthafa M. , de Paula Martins Roberta , Lovejoy David B. , Bilgin Ayse A. , Waly Mostafa I. , Al‐Farsi Yahya M. , Al‐Sharbati Marwan , Al‐Shaffae Mohammed A. , Guillemin Gilles J.
Published: October 2015

Dysfunction of the serotoninergic and glutamatergic systems is implicated in the pathogenesis of autism spectrum disorder (ASD) together with various neuroinflammatory mediators. As the kynurenine pathway (KP) of tryptophan degradation is activated in neuroinflammatory states, we hypothesized that there may be a link between inflammation in ASD and enhanced KP activation resulting in reduced serotonin synthesis from tryptophan and production of KP metabolites capable of modulating glutamatergic activity. A cross‐sectional study of 15 different Omani families with newly diagnosed children with ASD (n = 15) and their age‐matched healthy siblings (n = 12) was designed. Immunological profile and the KP metabolic signature were characterized in the study participants. Our data indicated that there were alterations to the KP in ASD. Specifically, increased production of the downstream metabolite, quinolinic acid, which is capable of enhancing glutamatergic neurotransmission was noted. Correlation studies also demonstrated that the presence of inflammation induced KP activation in ASD. Until now, previous studies have failed to establish a link between inflammation, glutamatergic activity, and the KP. Our findings also suggest that increased quinolinic acid may be linked to 16p11.2 mutations leading to abnormal glutamatergic activity associated with ASD pathogenesis and may help rationalize the efficacy of sulforaphane treatment in ASD. Autism Res 2016, 9: 621–631. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
The fault lines of recontextualisation: the limits of constructivism in education
Authors: McPhail Graham
Published: October 2015

In this paper I explain and utilise Bernstein's theory of recontextualisation as a means to consider the influence of constructivism as one of the key ‘rulers of consciousness’ or recontextualising principles that has become hegemonic within education. In considering this influence I draw on the literature to clarify some of the confusion surrounding constructivism that has been utilised as a central theory for the curriculum and pedagogy. I suggest that in New Zealand there is a largely doxic acceptance of a romanticised and often confused view of constructivism developed in response to the lurking spectre of education as transmission. By drawing on three examples of tensions between official discourses and teacher autonomy I explore the lack of clarity surrounding constructivism and the implications for the ‘play’ of ideology and agency. I conclude by suggesting that constructivism has much to offer in developing approaches to pedagogy but serious limitations when applied to matters of epistemology and ontology. It is particularly important to clarify the limitations of constructivism before it morphs into a new twenty‐first century future focused version of itself.
Luminescence investigation of novel MgPbAl10O17:Tb3+ green‐emitting phosphor for solid‐state lighting
Authors: Panse V. R. , Kokode N. S. , Dhoble S. J. , Yerpude A. N.
Published: October 2015

In this work, we studied the luminescence properties of Tb3+‐doped MgPbAl10O17 green phosphor. To understand the excitation mechanism and corresponding emission of the prepared phosphor, its structural, morphological and photoluminescence properties were investigated. In general, for green emission, Tb3 is used as an activator and the obtained excitation and emission spectra indicated that this phosphor can be effectively excited by a wavelength of 380 nm, and exhibits bright green emission centered at 545 nm corresponding to the f → f transition of trivalent terbium ions. The chromaticity coordinates were (Cx = 0.263, Cy = 0.723). The impact of Tb3+ concentration on the relative emission intensity was investigated, and the best doping concentration was found to be 2 mol%. This study suggests that Tb3+‐doped MgPbAl10O17 phosphor is a strong candidate for a green component in phosphor‐converted white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.
Radioactive seed localization in breast cancer treatment
Authors: Janssen N N Y , Nijkamp J , Alderliesten T , Loo C E , Rutgers E J T , Sonke J-J , Vrancken Peeters M T F D
Published: October 2015

Background

Breast cancer screening, improved imaging and neoadjuvant systemic therapy (NST) have led to increased numbers of non-palpable tumours suitable for breast-conserving surgery (BCS). Accurate tumour localization is essential to achieve a complete resection in these patients. This study evaluated the role of radioactive seed localization (RSL) in improving breast- and axilla-conserving surgery in patients with breast cancer with or without NST.

Methods

Patients who underwent RSL between 2007 and 2014 were included. Learning curves were analysed by the rates of minimally involved (in situ/invasive tumour cells on a length of 0–4 mm on ink) and positive resection margins (over 4 mm on ink) after BCS, and the median resection volume over time.

Results

A total of 367 patients with in situ carcinomas and 199 with non-palpable invasive breast cancer underwent RSL before primary surgery. A further 697 patients had RSL before NST, of whom 206 also underwent RSL of a histologically verified axillary lymph node metastasis. BCS was performed in 93·2 and 87·9 per cent of patients undergoing primary surgery for in situ and invasive tumours respectively, and 57·5 per cent of those in the NST group. The rate of BCS with positive resection margins was low and stable over time in the three groups (9·1, 9·7 and 11·2 per cent respectively). The median resection volume decreased significantly with time in the invasive cancer and NST groups.

Conclusion

In the present study of more than 1200 patients and 7 years of experience, RSL was shown to facilitate breast- and axilla-conserving surgery in a diverse patient population. There was a significant reduction in resection volume while maintaining low positive resection margin rates after BCS.
Supramolecular Ligands for Histone Tails by Employing a Multivalent Display of Trisulfonated Calix[4]arenes
Authors: Kimura Yasuaki , Saito Nae , Hanada Kayo , Liu Jiaan , Okabe Takayoshi , Kawashima Shigehiro A. , Yamatsugu Kenzo , Kanai Motomu
Published: October 2015

Post‐translational modification of histone tails plays critical roles in gene regulation. Thus, molecules recognizing histone tails and controlling their epigenetic modification are desirable as biochemical tools to elucidate regulatory mechanisms. There are, however, only a few synthetic ligands that bind to histone tails with substantial affinity. We report CA2 and CA3, which exhibited sub‐micromolar affinity to histone tails (especially tails with a trimethylated lysine). Multivalent display of trisulfonated calix[4]arene was important for strong binding. CA2 was applicable not only to synthetic tail peptides but also to endogenous histone proteins, and was successfully used to pull‐down endogenous histones from nuclear extract. These findings indicate the utility of these supramolecular ligands as biochemical tools for studying chromatin regulator protein and as a targeting motif in ligand‐directed catalysis to control epigenetic modifications.
Progress in Understanding the Genetic Information and Biosynthetic Pathways behind Amycolatopsis Antibiotics, with Implications for the Continued Discovery of Novel Drugs
Authors: Chen Su , Wu Qihao , Shen Qingqing , Wang Hong
Published: October 2015

Species of Amycolatopsis, well recognized as producers of both vancomycin and rifamycin, are also known for producing other secondary metabolites, with wide usage in medicine and agriculture. The molecular genetics of natural antibiotics produced by this genus have been well studied. Since the rise of antibiotic resistance, finding new drugs to fight infection has become an urgent priority. Progress in understanding the biosynthesis of metabolites greatly helps the rational manipulation of biosynthetic pathways, and thus to achieve the goal of generating novel natural antibiotics. The efforts made in exploiting Amycolatopsis genome sequences for the discovery of novel natural products and biosynthetic pathways are summarized.
Small‐Sized Tungsten Nitride Particles Strongly Anchored on Carbon Nanotubes and their Use as Supports for Pt for Methanol Electro‐oxidation
Authors: Liu Yuan , Yan Haijing , Zhou Xiaoguang , Li Mingxia , Fu Honggang
Published: October 2015

The anchoring of small‐sized WN (tungsten nitride) nanoparticles (NPs) with good dispersion on carbon nanotubes (CNTs) offers an effective means of obtaining promising materials for use in electrocatalysis. Herein, an effective method based on grinding treatment followed by a nitridation process is proposed to realize this goal. In the synthesis, a solution containing H4[SiO4(W3O9)4] (SiW12) and CNTs modified with polyethylenimine (PEI‐CNTs) was ground to dryness. Small‐sized WN NPs were anchored onto the CNTs with good dispersion after calcination under NH3. Under hydrothermal assembly conditions (absence of grinding), WN particles of larger size and with inferior dispersion were obtained, demonstrating the important role of the grinding process. The benefit of the small‐sized WN has been demonstrated by using WN/CNTs as a support for Pt to catalyze the methanol electro‐oxidation reaction. The mass activity of Pt‐WN/CNTs‐G‐70 (where G denotes the grinding treatment, and 70 is the loading amount (%) of WN in the WN/CNTs) was evaluated as about 817 mA mg−1Pt, better that those of commercial Pt/C (340 mA mg−1Pt) and Pt/CNTs (162 mA mg−1Pt). The Pt‐WN/CNTs‐G also displayed good CO tolerance. In contrast, Pt‐WN/CNTs prepared without the grinding process displayed an activity of 344 mA mg−1Pt, verifying the key role of grinding treatment in the preparation of WN/CNTs with good co‐catalytic effect.
Enantioselective Synthesis of α‐Hydroxy Amides and β‐Amino Alcohols from α‐Keto Amides
Authors: Mamillapalli N. Chary , Sekar Govindasamy
Published: October 2015

Synthesis of enantiomerically enriched α‐hydroxy amides and β‐amino alcohols has been accomplished by enantioselective reduction of α‐keto amides with hydrosilanes. A series of α‐keto amides were reduced in the presence of chiral CuII/(S)‐DTBM‐SEGPHOS catalyst to give the corresponding optically active α‐hydroxy amides with excellent enantioselectivities by using (EtO)3SiH as a reducing agent. Furthermore, a one‐pot complete reduction of both ketone and amide groups of α‐keto amides has been achieved using the same chiral copper catalyst followed by tetra‐n‐butylammonium fluoride (TBAF) catalyst in presence of (EtO)3SiH to afford the corresponding chiral β‐amino alcohol derivatives.
Growth of Hollow Transition Metal (Fe, Co, Ni) Oxide Nanoparticles on Graphene Sheets through Kirkendall Effect as Anodes for High‐Performance Lithium‐Ion Batteries
Authors: Yu Xianbo , Qu Bin , Zhao Yang , Li Chunyan , Chen Yujin , Sun Chunwen , Gao Peng , Zhu Chunling
Published: October 2015

A general strategy based on the nanoscale Kirkendall effect has been developed to grow hollow transition metal (Fe, Co or Ni) oxide nanoparticles on graphene sheets. When applied as lithium‐ion battery anodes, these hollow transition metal oxide‐based composites exhibit excellent electrochemical performance, with high reversible capacities and long‐term stabilities at a high current density, superior to most transition metal oxides reported to date.
ChemInform Abstract: Superconductivity in the Niobium‐Rich Compound Nb5Se4.
Authors: Klimczuk T. , Baroudi K. , Krizan J. W. , Kozub A. L. , Cava R. J.
Published: October 2015

Polycrystalline Nb5Se4 is prepared by solid state reaction of a stoichiometric mixture of NbSe2 and Nb (Ta ampoule in vacuum furnace, 1620 K, 5 h).
ChemInform Abstract: Synthesis, Structure, and Rigid Unit Mode‐Like Anisotropic Thermal Expansion of BaIr2In9.
Authors: Calta Nicholas P. , Han Fei , Kanatzidis Mercouri G.
Published: October 2015

Large single crystals of the title compound are prepared from the elements using In as a reactive flux (alumina crucible, 1000 °C, 2 d, 50—70% yield based on Ba).
ChemInform Abstract: Enabling Asymmetric Alkynylation of Azaaryl Aldehydes with Soai Autocatalyst.
Authors: Funes‐Maldonado Matias , Sieng Bora , Amedjkouh Mohamed
Published: October 2015

A new sequence of autocatalysis—catalysis in asymmetric alkynylation of azaaryl aldehydes in the presence of Soai (5‐pyrimidyl)alkanol as chiral catalyst is documented.
ChemInform Abstract: A Synergistic Combinatorial and Chiroptical Study of Peptide Catalysts for Asymmetric Baeyer—Villiger Oxidation.
Authors: Giuliano Michael W. , Lin Chung‐Yon , Romney David K. , Miller Scott J. , Anslyn Eric V.
Published: October 2015

A combinatorial screening, rational library design, HPLC analysis, and a circular dichroism‐based assay lead to the identification of two families of peptide catalysts that induce opposite enantioselectivity in the asymmetric Baeyer—Villinger oxidation of cyclohexenone (I).
ChemInform Abstract: Lewis Acid/Rhodium‐Catalyzed Formal [3 + 3]‐Cycloaddition of Enoldiazoacetates with Donor—Acceptor Cyclopropanes.
Authors: Cheng Qing‐Qing , Qian Yu , Zavalij Peter Y. , Doyle Michael P.
Published: October 2015

The reaction proceeds via an initial Lewis acid‐catalyzed diastereoselective [3 + 2]‐cycloaddition followed by rhodium‐catalyzed chemoselective ring expansion.
ChemInform Abstract: An Aminopyridinato Titanium Catalyst for the Intramolecular Hydroaminoalkylation of Secondary Aminoalkenes.
Authors: Doerfler Jaika , Bytyqi Besnik , Hueller Sascha , Mann Nicola M. , Brahms Christian , Schmidtmann Marc , Doye Sven
Published: October 2015

2‐Methylcyclohexyl‐ or 2‐methylcyclopentylamines are obtained as mixtures of trans‐ and cis‐diastereomers.
ChemInform Abstract: Iron‐Catalyzed Amination of Alcohols Assisted by Lewis Acid.
Authors: Pan Hui‐Jie , Ng Teng Wei , Zhao Yu
Published: October 2015

A highly effective amination of primary and secondary alcohols with anilines, benzylamine, and piperidine is achieved using a catalytic amount of Knoelker′s complex (KNC) and AgF as co‐catalyst.
ChemInform Abstract: Nucleophilic Addition of (Difluoromethyl)trimethylsilane to Selected α‐Imino Ketones and Aryl Diketones.
Authors: Obijalska Emilia , Utecht Greta , Kowalski Marcin K. , Mloston Grzegorz , Rachwalski Michal
Published: October 2015

A chemoselective addition/reduction sequence allows the conversion of α‐imino ketones into difluoromethyl substituted aminoalcohols.
ChemInform Abstract: Rhodium‐Catalyzed Alkylation of C—H Bonds in Aromatic Amides with Styrenes via Bidentate—Chelation Assistance.
Authors: Shibata Kaname , Yamaguchi Takuma , Chatani Naoto
Published: October 2015

8‐Aminoquinoline is used as bidendate directing group in alkylation reactions of aromatic C(sp2)—H bonds.
ChemInform Abstract: Chiral Broensted Acid as a True Catalyst: Asymmetric Mukaiyama Aldol and Hosomi—Sakurai Allylation Reactions.
Authors: Sai Masahiro , Yamamoto Hisashi
Published: October 2015

A new chiral BINOL‐derived thiophosphoramide catalyst is prepared and applied for highly diastereo‐ and enantioselective Mukaiyama aldol reactions of various silyl enol ethers with aryl aldehydes.
ChemInform Abstract: Highly Enantioselective Asymmetric Transfer Hydrogenation (ATH) of α‐Phthalimide Ketones.
Authors: Xu Zhou , Li Yong , Liu Jing , Wu Nan , Li Ke , Zhu Songlei , Zhang Rongli , Liu Yi
Published: October 2015

Starting from phthalimide ketones carrying various aryl substituents optically active amino alcohols are delivered in high yields and with high enantiomeric excess.
ChemInform Abstract: Photoredox Cross‐Coupling: Ir/Ni Dual Catalysis for the Synthesis of Benzylic Ethers.
Authors: Karakaya Idris , Primer David N. , Molander Gary A.
Published: October 2015

The photoredox cross‐coupling of α‐alkoxymethyl trifluoroborates with aryl bromides is achieved under mild conditions using a combination of an iridium photoredox catalyst and a nickel cross‐coupling catalyst.
ChemInform Abstract: Chiral Lithium Binaphtholate for Enantioselective Michael Addition of Acyclic α‐Alkyl‐β‐Keto Esters to Vinyl Ketones.
Authors: Kotani Shunsuke , Moritani Miyuki , Nakajima Makoto
Published: October 2015

Asymmetric Michael addition of acyclic α‐alkyl‐β‐keto esters with vinyl ketones catalyzed by a chiral lithium binaphtholate is described.
ChemInform Abstract: Chiral N,N′‐Dioxide—FeCl3 Complex‐Catalyzed Asymmetric Intramolecular Cannizzaro Reaction.
Authors: Wu Wangbin , Liu Xiaohua , Zhang Yuheng , Ji Jie , Huang Tianyu , Lin Lili , Feng Xiaoming
Published: October 2015

An environmentally benign air‐insensitive asymmetric reaction of (het)aryl and alkyl glyoxals with various alkyl alcohols is developed which provides Cannizzaro products in high yields and with high enantioselectivities.
ChemInform Abstract: Suzuki Cross‐Coupling in Aqueous Media.
Authors: Hoffmann Ina , Blumenroeder Bettina , Onodi nee Thumann Silvia , Dommer Sabine , Schatz Juergen
Published: October 2015

A simple and efficient procedure for the Suzuki reaction of phenyl boronic acid or potassium phenyltrifluoroborate with aryl bromides and aryl iodides is reported The reaction can be conducted in pure water or aqueous media.
ChemInform Abstract: Rhodium‐Catalyzed Addition of Alkyltrifluoroborate Salts to Imines.
Authors: Lee Sumin , Lee Woo Lim , Yun Jaesook
Published: October 2015

γ‐Amino ester are efficiently synthesized under mild reaction conditions and converted to the corresponding β,γ‐substituted lactams by cyclization reactions.
ChemInform Abstract: Nickel‐Catalyzed Suzuki—Miyaura Type Cross‐Coupling Reactions of (2,2‐Difluorovinyl)benzene Derivatives with Arylboronic Acids.
Authors: Xiong Yang , Huang Tao , Ji Xinfei , Wu Jingjing , Cao Song
Published: October 2015

The reaction fails using gem‐difluoroalkenes bearing electron withdrawing groups, aliphatic or hetaryl substituents.
ChemInform Abstract: Catalytic Earthworms: In Three‐Component Cascade Mannich‐Michael Reactions.
Authors: He Yan‐Hong , Song Jian , Yang Da‐Cheng , Guan Zhi
Published: October 2015

Starting from cyclohex‐2‐en‐1‐one, arylamines and arylaldehydes the title reaction provides various isoquinuclidines in high yields as mixtures of endo/exo isomers.
ChemInform Abstract: An Efficient Synthesis of N‐(Hetero)arylcarbazoles: Palladium‐Catalyzed Coupling Reaction Between (Hetero)aryl Chlorides and N‐Carbazolylmagnesium Chloride.
Authors: Nakayama Yuji , Yokoyama Naota , Nara Hideki , Kobayashi Tohru , Fujiwhara Mitsuhiko
Published: October 2015

The reactions proceed quickly under mild conditions.
ChemInform Abstract: Modular Synthesis of Pyrazolones Using an Alkene Aminocarbonylation Reaction.
Authors: Lavergne Kaitlyn , Bongers Amanda , Betit Lyanne , Beauchemin Andre M.
Published: October 2015

A series of pyrazolones are obtained by reaction of enol ethers with hydrazones via aminocarbonylation of the enol ethers and subsequent nucleophile‐induced aromatization of the azomethine imine intermediates formed.
ChemInform Abstract: Tandem Alkyne Hydroacylation and Oxo‐Michael Addition: Diastereoselective Synthesis of 2,3‐Disubstituted Chroman‐4‐ones and Fluorinated Derivatives.
Authors: Du Xiang‐Wei , Stanley Levi M.
Published: October 2015

Salicylic aldehydes and internal alkynes undergo an efficient Pd‐catalyzed tandem alkyne hydroacylation/oxo‐Michael addition process to yield 2,3‐disubstituted chromanones with good trans‐selectivity.
ChemInform Abstract: Ecofriendly Synthesis of Some Benzothiazoles Containing Acridine Moiety and Their Antimicrobial Activity.
Authors: Kawle P. R. , Deohate P. P. , Berad B. N.
Published: October 2015

Almost all of the synthesized compounds are found to exhibit potent antimicrobial activities.
ChemInform Abstract: Rhodium(III)‐Catalyzed Double C—H Activation: A Straightforward Approach to Fused Imidazo[1,2‐a]pyridines from Internal Alkynes.
Authors: Kotla Siva K. Reddy , Choudhary Deepak , Tiwari Rakesh K. , Verma Akhilesh K.
Published: October 2015

Oxidative coupling of 2‐aryl‐imidazopyridines with alkynes affords polycyclic imidazopyridines.
ChemInform Abstract: Oxidative N‐Heterocyclic Carbene‐Catalyzed γ‐Carbon Addition of Enals to Imines: Mechanistic Studies and Access to Antimicrobial Compounds.
Authors: Zheng Peng‐Cheng , Cheng Jiajia , Su Shihu , Jin Zhichao , Wang Yu‐Huang , Yang Song , Jin Lin‐Hong , Song Bao‐An , Chi Yonggui Robin
Published: October 2015

Tricyclic sulfonyl amides are conveniently and highly enantioselectively synthesized via a sequence of oxidation, γ‐carbon deprotonation, and nucleophilic addition of the γ‐carbon to imines.
ChemInform Abstract: The B(C6F5)3 Boron Lewis Acid Route to Arene‐Annulated Pentalenes.
Authors: Chen Chao , Harhausen Marcel , Fukazawa Aiko , Yamaguchi Shigehiro , Froehlich Roland , Daniliuc Constantin G. , Petersen Jeffrey L. , Kehr Gerald , Erker Gerhard
Published: October 2015

The boron Lewis acid induced conversion of 1,2‐bis(arylethynyl)benzenes into substituted dibenzopentalenes and related systems is investigated.
ChemInform Abstract: Copper‐Catalyzed β‐Selective Hydroborylation of Ynamides: A Facile Access to (E)‐β‐Alkenylamide Boronates.
Authors: Bai Yihui , Zhang Fang , Shen Jiajia , Luo Fang , Zhu Gangguo
Published: October 2015

The entitled hydroboration of ynamides using bis(pinacolato)diboron as the borylating reagent, affords (E)‐β‐alkenylamide boronates in good yields with excellent regio‐ and stereoselectivity.
ChemInform Abstract: Asymmetric Synthesis of Tertiary α‐Hydroxy Phosphonic Acid Derivatives under Aerobic Oxidation Conditions.
Authors: Maji Biplab , Yamamoto Hisashi
Published: October 2015

Acyclic as well as cyclic β‐ketophosphonates react with N‐protected hydroxylamines to give the corresponding α‐aminoxy derivatives in high yields and excellent enantioselectivities.
ChemInform Abstract: Cyclization of Diaryl(hetaryl)alkynes under Selenobromination Conditions: Regioselectivity and Mechanistic Studies.
Authors: Paegle Edgars , Belyakov Sergey , Petrova Marina , Liepinsh Edvards , Arsenyan Pavel
Published: October 2015

Functionalized benzo[b]selenophene and selenophenothiophene derivatives are conveniently obtained from commercially available or easily accessible starting materials using in situ‐prepared SeBr4 and alkene additives as bromine scavenger.
ChemInform Abstract: Ring‐Closing Metathesis of (η5‐Alkenylcyclopentadienyl)(alkenylphosphine)manganese (I) Dicarbonyl Complexes.
Authors: Tseng Ya‐Yi , Kamikawa Ken , Wu Qian , Takahashi Tamotsu , Ogasawara Masamichi
Published: October 2015

Various substrates are applied for the facile ring‐closing metathesis in the coordination sphere of (η5‐cyclopentadienyl)manganese complexes leading to C3‐ or C4‐bridged manganese complexes.
ChemInform Abstract: Toxicity and Protective Effects of Cerium Oxide Nanoparticles (Nanoceria) Depending on Their Preparation Method, Particle Size, Cell Type, and Exposure Route
Authors: Gagnon Jacinthe , Fromm Katharina M.
Published: October 2015

Review: 82 refs.
ChemInform Abstract: Understanding the Role of Hyponitrite in Nitric Oxide Reduction
Authors: Wright Ashley M. , Hayton Trevor W.
Published: October 2015

Review: preparation and coordination chemsitry of cis and trans N2O22‐; 118 refs.
ChemInform Abstract: Catalysts Prepared by Confining Metal Nanoclusters in Metal Organic Frameworks
Authors: Huang Wenyu , Li Xinle , Xiao Chaoxian
Published: October 2015

Review: 4 refs.
ChemInform Abstract: Towards Multifunctional Magnetic Systems Through Molecular‐Programmed Self Assembly of Re(IV) Metaloligands
Authors: Martinez‐Lillo Jose , Faus Juan , Lloret Francesc , Julve Miguel
Published: October 2015

Review: 285 refs.
ChemInform Abstract: Recent Advances in Hybrid Periodic Mesostructured Organosilica Materials: Opportunities from Fundamental to Biomedical Applications
Authors: Wahab Mohammad A. , Beltramini Jorge N.
Published: October 2015

Review: 258 refs.
ChemInform Abstract: Metalation of Pyridazine, Cinnoline, and Phthalazine
Authors: Horkel Ernst
Published: October 2015

Review: 75 refs.
ChemInform Abstract: Metalation Reactions of Pyridines, Quinolines, and Isoquinolines with Ate Bases and Their Alkali Metal Salt‐Modified Congeners
Authors: Metallinos Costa , Stromski Kathryn
Published: October 2015

Review: data from 2006‐2011
ChemInform Abstract: Modern Organic Synthesis with α‐Diazocarbonyl Compounds
Authors: Ford Alan , Miel Hugues , Ring Aoife , Slattery Catherine N. , Maguire Anita R. , McKervey M. Anthony
Published: October 2015

Review: 768 refs.
ChemInform Abstract: Polyoxometalate‐Based Phase Transfer Catalysis for Liquid‐Solid Organic Reactions: A Review
Authors: Zhou Yu , Guo Zengjing , Hou Wei , Wang Qian , Wang Jun
Published: October 2015

Review: 79 refs.
ChemInform Abstract: Pulmonary Delivery of siRNA via Polymeric Vectors as Therapies of Asthma
Authors: Xie Yuran , Merkel Olivia M.
Published: October 2015

Review: 61 refs.
ChemInform Abstract: SOx/NOx Removal from Flue Gas Streams by Solid Adsorbents: A Review of Current Challenges and Future Directions
Authors: Rezaei Fateme , Rownaghi Ali A. , Monjezi Saman , Lively Ryan P. , Jones Christopher W.
Published: October 2015

Review: 111 refs.
Nottingham Prognostic Index Plus: Validation of a clinical decision making tool in breast cancer in an independent series
Authors: Green Andrew R , Soria Daniele , Stephen Jacqueline , Powe Desmond G , Nolan Christopher C , Kunkler Ian , Thomas Jeremy , Kerr Gillian R , Jack Wilma , Cameron David , Piper Tammy , Ball Graham R , Garibaldi Jonathan M , Rakha Emad A , Bartlett John MS , Ellis Ian O
Published: October 2015

The Nottingham Prognostic Index Plus (NPI+) is a clinical decision making tool in breast cancer (BC) that aims to provide improved patient outcome stratification superior to the traditional NPI. This study aimed to validate the NPI+ in an independent series of BC. Eight hundred and eighty five primary early stage BC cases from Edinburgh were semi‐quantitatively assessed for 10 biomarkers [Estrogen Receptor (ER), Progesterone Receptor (PgR), cytokeratin (CK) 5/6, CK7/8, epidermal growth factor receptor (EGFR), HER2, HER3, HER4, p53, and Mucin 1] using immunohistochemistry and classified into biological classes by fuzzy logic‐derived algorithms previously developed in the Nottingham series. Subsequently, NPI+ Prognostic Groups (PGs) were assigned for each class using bespoke NPI‐like formulae, previously developed in each NPI+ biological class of the Nottingham series, utilising clinicopathological parameters: number of positive nodes, pathological tumour size, stage, tubule formation, nuclear pleomorphism and mitotic counts. Biological classes and PGs were compared between the Edinburgh and Nottingham series using Cramer's V and their role in patient outcome prediction using Kaplan–Meier curves and tested using Log Rank. The NPI+ biomarker panel classified the Edinburgh series into seven biological classes similar to the Nottingham series (p > 0.01). The biological classes were significantly associated with patient outcome (p < 0.001). PGs were comparable in predicting patient outcome between series in Luminal A, Basal p53 altered, HER2+/ER+ tumours (p > 0.01). The good PGs were similarly validated in Luminal B, Basal p53 normal, HER2+/ER− tumours and the poor PG in the Luminal N class (p > 0.01). Due to small patient numbers assigned to the remaining PGs, Luminal N, Luminal B, Basal p53 normal and HER2+/ER− classes could not be validated. This study demonstrates the reproducibility of NPI+ and confirmed its prognostic value in an independent cohort of primary BC. Further validation in large randomised controlled trial material is warranted.
Division Design of Water Eco‐Functioning of the River Basin
Authors: Sheng Sheng , Xu Chi , Wen Teng , Wan Yun , An Shuqing
Published: October 2015

Regionalization plays an important role in delineating landscape heterogeneity and providing spatial frameworks for environmental management. Historically, the most widely used method for regionalization is qualitative synthesis of various mixes of environmental or biotic data as the whole. However, such methods based on expert judgment and whole data set are less repeatable and defensible than their quantitative counterparts. In this study, a comprehensive regionalization approach that integrated multiple quantitative techniques was developed to differentiate two distinct types of landscape variables, i.e., response attributes and driving factors. This approach was applied to the regionalization in the Huai River Basin (HRB), China. In the regionalization scheme, the sub‐watersheds of the basin were adopted as the basic spatial unit; different response attributes were used to characterize different water eco‐functioning. The sub‐watersheds were classified into a certain number of groups using the k‐means cluster analysis based on the response attributes. A goodness‐of‐fit index, calculated as the ratio of between‐group/within‐group variation, was employed as a quantitative criterion to assess the statistical performance of the classification results. Driving forces were used to assess the strengths of the forces operating at different spatial and temporal scales on water eco‐functioning. A general, quantitative, regionalization framework was developed; this framework can reveal underlying mechanisms of basin divisions and landscape patterns through integrating response attributes and driving factors. This framework was implemented by using a basin‐scale regionalization of Huai River Basin as an example; however, the framework can be adapted to other regionalization practices within broad contexts.
Massively parallel DNA sequencing from routinely processed cytological smears
Authors: Piqueret‐Stephan Laure , Marcaillou Charles , Reyes Cécile , Honoré Aurélie , Letexier Mélanie , Gentien David , Droin Nathalie , Lacroix Ludovic , Scoazec Jean‐Yves , Vielh Philippe
Published: October 2015

BACKGROUND

Data generated by next‐generation sequencing technologies have a pivotal role in precision medicine. These high‐throughput techniques are preferentially performed on fresh tissue, but there is an increasing need for protocols adapted to materials derived from formalin‐fixed, paraffin‐embedded tissue and cytology specimens.

METHODS

The aim of this work was to show that cytological material collected from archival smears processed for routine diagnoses could be used for massively parallel sequencing and array‐based genomic analysis for further studies.

RESULTS

As a proof of concept, data obtained from May‐Grünwald Giemsa– and Diff‐Quik–stained archival smears were shown to be in keeping with those obtained from matched frozen controls.

CONCLUSIONS

The quality of DNA extracted from routinely processed smears is compatible with the multitargeted sequencing of a large series of genes of interest with methods such as array‐based genomic analysis and whole‐exome sequencing. Cancer Cytopathol 2016;124:241–53. © 2015 American Cancer Society.
Take time to reflect upon your career
Authors: Hodges Dawn Z.
Published: October 2015

On July 1, I celebrated my 35th anniversary working in higher education. Around this time each year I take time to reflect upon my career. I suggest that you set an annual time to do the same. It might be around the new year, or on your work anniversary, or on your career anniversary, or any time that makes sense for you. It's important to do so if what you want is a meaningful, well‐planned‐out career and not just a string of jobs.
Deconvolution‐based nonlinear filtering for incompressible flows at moderately large Reynolds numbers
Authors: Bertagna L. , Quaini A. , Veneziani A.
Published: October 2015

We consider a Leray model with a deconvolution‐based indicator function for the simulation of incompressible fluid flow at moderately large Reynolds number (in the range of a few thousands) with under‐resolved meshes. For the implementation of the model, we adopt a three‐step algorithm called evolve–filter–relax that requires (i) the solution of a Navier–Stokes problem, (ii) the solution of a Stokes‐like problem to filter the Navier–Stokes velocity field, and (iii) a final relaxation step. We take advantage of a reformulation of the evolve–filter–relax algorithm as an operator‐splitting method to analyze the impact of the filter on the final solution versus a direct simulation of the Navier–Stokes equations.

In addition, we provide some direction for tuning the parameters involved in the model based on physical and numerical arguments. Our approach is validated against experimental data for fluid flow in an idealized medical device (consisting of a conical convergent, a narrow throat, and a sudden expansion, as recommended by the U.S. Food and Drug Administration). Numerical results are in good quantitative agreement with the measured axial components of the velocity and pressures for two different flow rates corresponding to turbulent regimes, even for meshes with a mesh size more than 40 times larger than the smallest turbulent scale. After several numerical experiments, we perform a preliminary sensitivity analysis of the computed solution to the parameters involved in the model. Copyright © 2015 John Wiley & Sons, Ltd.
Preparation and characterization of a biologic scaffold and hydrogel derived from colonic mucosa
Authors: Keane Timothy J. , Dziki Jenna , Castelton Arthur , Faulk Denver M. , Messerschmidt Victoria , Londono Ricardo , Reing Janet E. , Velankar Sachin S. , Badylak Stephen F.
Published: October 2015

Gastrointestinal pathologies, injuries, and defects affect millions of individuals each year. While there are diverse treatment options for these individuals, no ideal solution exists. The repair or replacement of gastrointestinal tissue, therefore, represents a large unmet clinical need. Biomaterials derived from extracellular matrix (ECM) scaffolds have been effectively used to repair or replace numerous tissues throughout the body in both preclinical and clinical studies. Such scaffolds are prepared from decellularized tissues, and the biochemical, structural, and biologic properties vary depending upon the source tissue from which the ECM is derived. Given the potential benefit of a site‐specific ECM scaffold for some applications, the objective of this study was to prepare, characterize, and determine the in vitro and in vivo cell response to ECM derived from porcine colon. Results of this study show that porcine colon can be effectively decellularized while retaining biochemical and structural constituents of the source tissue. Two forms of colonic ECM, scaffold and hydrogel, were shown to be cell friendly and facilitate the polarization of macrophages toward an M2 phenotype both in vitro and in vivo. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 291–306, 2017.
Hexahalogenated and their mixed benzene derivatives as prototypes for the understanding of halogen···halogen intramolecular interactions: New insights from combined DFT, QTAIM‐, and RDG‐based NCI analyses
Authors: Varadwaj Pradeep R. , Varadwaj Arpita , Jin Bih‐Yaw
Published: October 2015

A large number of fully halogenated benzene derivatives containing the fluorine, chlorine, bromine, and iodine atoms have been experimentally synthesized both as single‐ and co‐crystals (e.g., Desiraju et al., Chem. Eur. J. 2006, 12, 2222), yet the natures of the halogen ··· halogen interactions between the vicinal halogens in these compounds within the intramolecular domain are undisclosed. Given a fundamental understanding of these interactions is incredibly important in many areas of chemical, biological, supramolecular, and material sciences, we present here our newly discovered theoretical results that delineate whilst the nature of an F···F interaction in a pair of two adjacent fluorine atoms in either of the hexafluorobenzene and 1,4‐dibromotetrafluorobenzene compounds examined is almost unclear, each of the latter three hexahalogenated benzene derivatives (viz., C6Cl6, C6Br6, and C6I6), and each of the seven of their fully mixed hexahalogenated benzene analogues, are found to be stabilized by means of a number of halogen···halogen interactions, each a form of long‐range attraction within the intramolecular domain. The Molecular Electrostatic Surface Potential model was found to be unsurprisingly unsuitable in unraveling any of the aforesaid attractions between the halogen atoms. However, such interactions successfully enunciated by a set of noncovalent interaction descriptors of geometrical, topological, and electrostatic origins. These latter properties were extracted combining the results of the Density Functional Theory electronic structure calculations with those revealed from Atoms in Molecules, and Reduced Density Gradient charge density‐based topological calculations, and are expounded in detail to formalize the conclusions. © 2015 Wiley Periodicals, Inc.
Protein:Ligand binding free energies: A stringent test for computational protein design
Authors: Druart Karen , Palmai Zoltan , Omarjee Eyaz , Simonson Thomas
Published: October 2015

A computational protein design method is extended to allow Monte Carlo simulations where two ligands are titrated into a protein binding pocket, yielding binding free energy differences. These provide a stringent test of the physical model, including the energy surface and sidechain rotamer definition. As a test, we consider tyrosyl‐tRNA synthetase (TyrRS), which has been extensively redesigned experimentally. We consider its specificity for its substrate l‐tyrosine (l‐Tyr), compared to the analogs d‐Tyr, p‐acetyl‐, and p‐azido‐phenylalanine (ac‐Phe, az‐Phe). We simulate l‐ and d‐Tyr binding to TyrRS and six mutants, and compare the structures and binding free energies to a more rigorous “MD/GBSA” procedure: molecular dynamics with explicit solvent for structures and a Generalized Born + Surface Area model for binding free energies. Next, we consider l‐Tyr, ac‐ and az‐Phe binding to six other TyrRS variants. The titration results are sensitive to the precise rotamer definition, which involves a short energy minimization for each sidechain pair to help relax bad contacts induced by the discrete rotamer set. However, when designed mutant structures are rescored with a standard GBSA energy model, results agree well with the more rigorous MD/GBSA. As a third test, we redesign three amino acid positions in the substrate coordination sphere, with either l‐Tyr or d‐Tyr as the ligand. For two, we obtain good agreement with experiment, recovering the wildtype residue when l‐Tyr is the ligand and a d‐Tyr specific mutant when d‐Tyr is the ligand. For the third, we recover His with either ligand, instead of wildtype Gln. © 2015 Wiley Periodicals, Inc.
Cost and sensitivity of restricted active‐space calculations of metal L‐edge X‐ray absorption spectra
Authors: Pinjari Rahul V. , Delcey Mickaël G. , Guo Meiyuan , Odelius Michael , Lundberg Marcus
Published: October 2015

The restricted active‐space (RAS) approach can accurately simulate metal L‐edge X‐ray absorption spectra of first‐row transition metal complexes without the use of any fitting parameters. These characteristics provide a unique capability to identify unknown chemical species and to analyze their electronic structure. To find the best balance between cost and accuracy, the sensitivity of the simulated spectra with respect to the method variables has been tested for two models, [FeCl6]3– and [Fe(CN)6]3–. For these systems, the reference calculations give deviations, when compared with experiment, of ≤1 eV in peak positions, ≤30% for the relative intensity of major peaks, and ≤50% for minor peaks. When compared with these deviations, the simulated spectra are sensitive to the number of final states, the inclusion of dynamical correlation, and the ionization potential electron affinity shift, in addition to the selection of the active space. The spectra are less sensitive to the quality of the basis set and even a double‐ζ basis gives reasonable results. The inclusion of dynamical correlation through second‐order perturbation theory can be done efficiently using the state‐specific formalism without correlating the core orbitals. Although these observations are not directly transferable to other systems, they can, together with a cost analysis, aid in the design of RAS models and help to extend the use of this powerful approach to a wider range of transition metal systems. © 2015 Wiley Periodicals, Inc.
Improvement of L‐lactic acid production with a two‐step OUR control strategy
Authors: Tian Xiwei , Wang Yonghong , Chu Ju , Zhuang Yingping , Zhang Siliang
Published: October 2015

BACKGROUND

Oxygen metabolism plays an important role in cell growth, metabolism and survival of microorganism. This report describes the effects of different oxygen metabolism levels on L‐lactic acid production by Lactobacillus paracasei, and then a new oxygen uptake rate (OUR) strategy is proposed based on integrated process physiological and metabolic analyses.

RESULTS

Physiological parameter, OUR, was introduced to quantitatively characterize oxygen metabolism in a microaerobic bioprocess for the first time, and 0.14 mmol L−1 h−1 was adopted as control to simulate industrial lactic acid production. During the growth phase, moderate to high OUR (0.43 mmol L−1 h−1) could promote cell growth, glucose consumption and L‐lactic acid production with little decrease in yield. However, when cells entered the stationary phase, significant glycolysis inhibition and pyruvate metabolism shift from lactic acid to acetoin occurred with 0.43 and 0.85 mmol L−1 h−1, both of which led to further L‐lactic acid production limitation. Through a new two‐step OUR control strategy with 0.43 mmol L−1 h−1 during the growth phase and 0.14 mmol L−1 h−1 during the stationary phase, productivity was enhanced 12.7% and the same yield was achieved as in the control.

CONCLUSIONS

OUR was identified to be a feasible process control parameter for microaerobic lactic acid production, and the OUR control strategy efficiently improved L‐lactic acid production. © 2015 Society of Chemical Industry