bluuebunny/crossref_metadata_2025_split huggingface dataset:
ChemInform Abstract: Mechanistic Insights into the Post‐Cyclization Isomerization in Gold‐Catalyzed 7‐exo‐Dig‐Hydroarylations.
Authors: Pflaesterer Daniel , Schumacher Soeren , Rudolph Matthias , Hashmi A. Stephen K. 
Published: November 2015

AbstractThe gold catalyzed intramolecular hydroarylation of biphenyls and heteroaromatic analogs proceeds in the presence of a base to give the corresponding cyclization products with an exocyclic double bond.
ChemInform Abstract: Synthesis of New Bis‐spirooxindolopyrrolizidine(pyrrolidine) Derivatives via a Pseudo Five‐Component 1,3‐Dipolar Cycloaddition Reaction.
Authors: Taghizadeh Mohammad Javad , Javidan Abdollah , Keshipour Sajjad 
Published: November 2015

AbstractTitle compounds [(IV) and (VI)] are synthesized through a cycloaddition reaction characterized by mild reaction conditions, high yields, and easy products isolation.
ChemInform Abstract: anti‐Diastereoselective Synthesis of CF3‐Containing Spirooxazolines and Spirooxazines via Regiospecific Trifluoromethylative Spirocyclization by Photoredox Catalysis.
Authors: Noto Naoki , Miyazawa Kazuki , Koike Takashi , Akita Munetaka 
Published: November 2015

AbstractStarting from cyclic alkenes bearing an amide tether the title reaction provides trifluoromethylated spirooxazolines or spirooxazines in moderate to high yields and with moderate to high anti‐diastereoselectivity.
ChemInform Abstract: Copper‐Catalyzed Aerobic C—C Bond Cleavage of Lactols with N‐Hydroxy Phthalimide for Synthesis of Lactones.
Authors: Tnay Ya Lin , Chiba Shunsuke 
Published: November 2015

Abstractα,β‐Unsaturated lactones are obtained from various lactols through an unstrained C—Me bond cleavage as well as α,β‐unsaturation.
ChemInform Abstract: Divergent Synthesis of 2‐Aminofurans via Palladium‐Catalyzed Acetoxylative, Alkoxylative, and Hydroxylative Cycloisomerization of Homoallenyl Amides
Authors: Cheng Cungui , Liu Shuiyou , Zhu Gangguo 
Published: November 2015

Abstractusing hypervalent iodine organic compounds as oxidant
ChemInform Abstract: An Efficient and Straight Forward Strategy for the Synthesis of Enantiomerically Pure (S)‐1‐Benzyl‐5‐((alkyl/aryl amino)methyl)‐pyrrolidin‐2‐ones.
Authors: Panday Sharad Kumar , Pathak Manoher Bhushan , Prasad Jagdish 
Published: November 2015

AbstractTitle compounds (III) are conveniently synthesized starting from N‐benzyl‐5(S)‐pyroglutaminol (I) through Mitsunobu reaction.
ChemInform Abstract: Synthesis of Small 3‐Fluoro‐ and 3,3‐Difluoropyrrolidines Using Azomethine Ylide Chemistry.
Authors: McAlpine Indrawan , et al.  
Published: November 2015

AbstractA 1,3‐dipolar cycloaddition of an azomethine ylide with vinyl difluorides leads to 3,3‐difluoropyrrolidines.
ChemInform Abstract: Broensted Acid‐Catalyzed Three‐Component 1,3‐Dipolar Cycloadditions of 1,2‐Disubstituted Alkynes with Aldehyde‐Generated Azomethine Ylides
Authors: Tan Wei , Du Bai‐Xiang , Guo Lu , Li Mei , Xing Gui‐Juan , Shi Feng 
Published: November 2015

Abstractleading to a wide range of polysubstituted 2,5‐dihydropyrroles
ChemInform Abstract: Palladium‐Catalyzed Regioselective Alkynylation of Pyrroles and Azoles under Mild Conditions: Application to the Synthesis of a Dopamine D‐4 Receptor Agonist.
Authors: Brachet Etienne , Belmont Philippe 
Published: November 2015

AbstractVarious alkynyl residues are regioselectively introduced at the C‐2 position of pyrroles.
ChemInform Abstract: The Facile Construction of the Phthalazin‐1(2H)‐one Scaffold via Copper‐Mediated C—H(sp2)/C—H(sp) Coupling under Mild Conditions.
Authors: Zhu Wei , Wang Bao , Zhou Shengbin , Liu Hong 
Published: November 2015

AbstractThe reactions of benzamides [e.g. (I)] and terminal alkynes [e.g. (II)] give isoindolinones [e.g. (III)] via a Cu‐mediated cascade coupling and intramolecular annulation.
ChemInform Abstract: Synergistic Stereocontrol in the Enantioselective Ruthenium‐Catalyzed Sulfoxidation of Spirodithiolane‐Indolones.
Authors: Zhong Fangrui , Poethig Alexander , Bach Thorsten 
Published: November 2015

AbstractCatalysts of type (I) and (II) are developed which combine 2 elements of chirality: a chiral pybox ligand and a chiral bicyclic lactam unit where the latter is found to improve significantly the performance of the catalyst.
ChemInform Abstract: Regioselective Synthesis of Novel 2,3,4,4a‐Tetrahydro‐1H‐carbazoles and Their Cholinesterase Inhibitory Activities.
Authors: Khan Maria Aqeel , Fazal‐ur‐Rehman Saba , Hameed Abdul , Kousar Shazia , Dalvandi Kourosh , Yousuf Sammer , Choudhary Muhammad Iqbal , Basha Fatima Zehra 
Published: November 2015

AbstractThe carbazoles are synthesized from L‐menthone and substituted phenyl hydrazines in acetic acid and show promising inhibitory activities against acetyl‐ and butyrylcholinesterase.
ChemInform Abstract: Organocatalytic [4 + 1]‐Annulation Approach for the Synthesis of Densely Functionalized Pyrazolidine Carboxylates.
Authors: Lalwani Komal G. , Aher Ravindra D. , Sudalai Arumugam 
Published: November 2015

AbstractA cascade reaction of α‐amination/Wittig olefination and either Corey—Chaykovsky reaction or intramolecular Michael addition reaction in presence of L‐proline provides access to functionalized pyrazolidines in a highly enantio‐ and diastereoselective fashion.
ChemInform Abstract: Group 2 Catalysis for the Atom‐Efficient Synthesis of Imidazolidine and Thiazolidine Derivatives.
Authors: Arrowsmith Merle , Hill Michael S. , Kociok‐Koehn Gabriele 
Published: November 2015

AbstractAmong 3 alkaline earth bis(amide) precatalysts tested (M: Sr, Mg, Ca), the strontium compound is the most effective one.
ChemInform Abstract: Pseudoephedrine‐Directed Asymmetric α‐Arylation of α‐Amino Acid Derivatives.
Authors: Atkinson Rachel C. , Fernandez‐Nieto Fernando , Mas Rosello Josep , Clayden Jonathan 
Published: November 2015

AbstractAmino‐acid‐derived ureas (I) and (VI) are modified with pseudoephedrine as a chiral auxiliary to yield compounds (III) and (VII), which undergo LDA‐promoted rearrangement including an aryl shift to yield hydantoins (IV) and (VIII).
ChemInform Abstract: Highly Enantioselective and Diastereoselective Conjugate Addition of 5H‐Oxazol‐4‐ones to 2‐Chloroacrylonitrile Catalyzed by Chiral Guanidines.
Authors: Misaki Tomonori , Choi Na‐Rae , Morita Akane , Sugimura Takashi 
Published: November 2015

AbstractThe introduction of a 4‐methoxy substituent in substrate (I) inhibits undesirable side reactions and results in both high enantio‐ and diastereoselectivity for the conjugate addition.
ChemInform Abstract: Multicomponent Domino Reactions of Hydrazinecarbodithioates: Concise Access to 3‐Substituted 5‐Thiol‐1,3,4‐thiadiazolines.
Authors: Jia Huihui , Feng Huangdi , Sun Zhihua 
Published: November 2015

AbstractAn addition‐cycloaddition cascade of hydrazinecarbodithioates with formaldehyde and propynoic acids under mild conditions affords thiadiazole‐based thioethers.
ChemInform Abstract: A Highly Efficient Chirality Switchable Synthesis of Dihydropyran‐Fused Benzofurans by Fine‐Tuning the Phenolic Proton of β‐Isocupreidine (β‐ICD) Catalyst with Methyl.
Authors: Wang Feng , Yang Chen , Xue Xiao‐Song , Li Xin , Cheng Jin‐Pei 
Published: November 2015

AbstractA highly enaantioselective synthesis of the title heterocycles becomes possible in the presence of β‐ICD (Ia) with MeOH as the additive [cf.
ChemInform Abstract: Generation of ArS‐Substituted Flavone Derivatives Using Aryl Thiols as Sulfenylating Agents.
Authors: Zhao Wannian , Xie Ping , Bian Zhaogang , Zhou Aihua , Ge Haibo , Niu Ben , Ding Yingcai 
Published: November 2015

AbstractThe title sulfenylation is mediated by ammonium iodide under aerobic conditions.
ChemInform Abstract: Combined Claisen Rearrangement and Oxidative Cyclization as a Route to Hydroxymethyl Dihydrofuran‐Annulated Coumarins.
Authors: Jayaprakash Rao Y. , Chakravarthula Venu 
Published: November 2015

AbstractThe title compounds are efficiently and conveniently obtained by a tandem epoxidation/5‐exo‐tet intramolecular ring opening of allyl‐derivatives (I) using MCPBA as inexpensive oxidizing reagent.
ChemInform Abstract: Metal‐Free Synthesis of 2‐Alkenyl/Alkynyl‐5‐nitropyridines Using a Three‐Component Ring Transformation.
Authors: Le Song Thi , Asahara Haruyasu , Nishiwaki Nagatoshi 
Published: November 2015

AbstractThe novel metal‐free method for the synthesis of alkenylated and alkynylated nitropyridines is presented.
ChemInform Abstract: Design and Synthesis of Chiral Binaphthol‐Derived Bisphosphoric Acids and Their Application in the Catalytic Enantioselective Hydrogenation of Quinolines.
Authors: Wang Pei , Jia Yan‐E , Zhao Jia‐Zhen , Zhao Dan , Yuan Rui , Da Chao‐Shan 
Published: November 2015

AbstractAmong various bisphosphoric acids synthesized, the derivative BNPE is elaborated as the optimal one.
ChemInform Abstract: Rhodium(III)‐Catalyzed Cascade Oxidative Annulation Reactions of Aryl Imidazolium Salts with Alkynes Involving Multiple C—H Bond Activation.
Authors: Ge Qingmei , Li Bin , Song Haibin , Wang Baiquan 
Published: November 2015

AbstractA new and highly regioselective rhodium(III)‐catalyzed cascade oxidative annulation reaction of aryl imidazolium salts with alkynes is introduced.
ChemInform Abstract: Using N‐Substituted‐2‐amino‐4,6‐dimethoxypyrimidines in the Synthesis of Aliphatic Guanidines.
Authors: Shaw Julian W. , Barbance Laure , Grayson David H. , Rozas Isabel 
Published: November 2015

Abstract2‐Aminopyrimidines are easily prepared from aliphatic amines or imidazole and chloropyrimidine derivative (II).
ChemInform Abstract: Convenient and Scalable Synthesis of 2,3‐Dihydroquinazolin‐4(1H)‐one Derivatives and Their Anticancer Activities.
Authors: Rajaka Lingayya , Penumati Nageshwar Rao , Nagaiah K. , Poornachandra Y. , Kumar C. Ganesh 
Published: November 2015

AbstractA concise, efficient, mild and fast method for the synthesis of the title dihydroquinazolinone derivatives (III) (27 examples) is developed.
ChemInform Abstract: Synthesis of 2H‐Azolo[1,5‐a][1,2,3]triazolo[4,5‐e]pyrimidines.
Authors: Gorbunov Evgeny B. , Rusinov Gennady L. , Ulomskii Evgeny N. , Isenov Maksim L. , Charushin Valery N. 
Published: November 2015

AbstractTitle compounds are conveniently and in high yields synthesized by a regioselective reaction from 6‐nitroazolo[1,5‐a]pyrimidines with sodium azide.
ChemInform Abstract: A Simple, Convenient, One‐Pot Synthesis of Dihydro‐azolopyrimidines, DFT Calculation, and NMR Determination by Using H‐Ferrierite Zeolite as Catalyst.
Authors: Hassaneen H. M. E. , Farghaly T. A. 
Published: November 2015

AbstractTriazolopyrimidines and pyrimidobenzimidazoles are prepared by a three‐component reaction between aminotriazole or aminobenzimidazole with acetophenones and benzaldehyde.
ChemInform Abstract: Hetero‐Annulation Reaction Between 2‐Acylnaphthoquinones and 2‐Aminobenzothiazoles. A New Synthetic Route to Antiproliferative Benzo[g]benzothiazolo[2,3‐b]quinazoline‐7,12‐quinones.
Authors: Valderrama Jaime A. , Rios David , Muccioli Giulio G. , Buc Calderon Pedro , Brito Ivan , Benites Julio 
Published: November 2015

Abstract2‐Acylnaphtoquinones generated from substrates (I) react with 2‐aminobenzothiazoles to form the title compounds (III).
ChemInform Abstract: Broensted Acid‐Catalyzed Friedel—Crafts Reaction of Indoles to α‐Ketimino Esters.
Authors: Yang Jin‐Hui , Lou Qin‐Xin , Chen Yan‐Xue , Tang Kang‐Kang 
Published: November 2015

AbstractA huge number of indolylglycine derivatives (III) bearing a tetrasubstituted carbon center is efficiently synthesized camphorsulfonic acid catalyzed.
ChemInform Abstract: Organocatalytic Enantioselective Aza‐Friedel—Crafts Reaction of 2‐Naphthols with Benzoxathiazine 2,2‐Dioxides.
Authors: Montesinos‐Magraner Marc , Canton Ruben , Vila Carlos , Blay Gonzalo , Fernandez Isabel , Munoz M. Carmen , Pedro Jose R. 
Published: November 2015

AbstractA quinine‐derived bifunctional catalyst is used as the organocatalyst for the title reactions.
ChemInform Abstract: Unified Mild Reaction Conditions for C2‐Selective Pd‐Catalyzed Tryptophan Arylation, Including Tryptophan‐Containing Peptides.
Authors: Reay Alan J. , Williams Thomas J. , Fairlamb Ian J. S. 
Published: November 2015

AbstractMild reaction protocols for the regioselective arylation of tryptophan are reported.
ChemInform Abstract: Synthesis of Thiadiazolylaminoglycosides Through Ring Contraction of Triazinoglycosides Induced by [TBA‐Ox].
Authors: Kikelj Vincent , Julienne Karine , Chalopin Thibaut , Gouin Sebastien G. , Evain Michel , Deniaud David 
Published: November 2015

AbstractThree thiadiazolylaminoglycosides of type (II) are prepared from the corresponding triazinoglycosides (I).
ChemInform Abstract: Homogeneous Gold‐Catalyzed Glycosylations in Continuous Flow.
Authors: Matthies Stefan , McQuade D. Tyler , Seeberger Peter H. 
Published: November 2015

AbstractThe use of hexynylbenzoate‐containing glycosyl building blocks for the efficient O‐glycosylation of numerous compounds is described, including amino acids and amino alcohols, steroids, disaccharids as well as alkenyl and alkynyl group containing molecules.
ChemInform Abstract: New Metabolites from Endolichenic Fungus Pleosporales sp.
Authors: Jiao Yang , Li Gang , Wang Hai‐Ying , Liu Jing , Li Xiao‐Bin , Zhang Lu‐Lu , Zhao Zun‐Tian , Lou Hong‐Xiang 
Published: November 2015

Abstractisolation and structure elucidation of cucurbitarins A‐C (I, II), cucurbitarins D (III), and E (IV), benzocoumarins (V), and cyclohexanone (VI)
ChemInform Abstract: A Novel γ‐Lactone Derivative from the Twigs of Turraea pubescens.
Authors: Chang Yao‐Wen , Yuan Chun‐Mao , Zhang Jing , Zhang Yu , Hua Hui‐Ming , Di Ying‐Tong , Hao Xiao‐Jiang 
Published: November 2015

Abstractisolation, structure elucidation and cytotoxic as well as antiinflammatory activities of the novel γ‐lactone turranin G (I) and five known compounds
ChemInform Abstract: A Single‐Phase Full‐Color Phosphor Based on Ba3MgSi2O8 Co‐Activated with Eu2+, Tb3+, and Mn2+.
Authors: Birkel Alexander , DeCino Nicholas A. , Cozzan Clayton , Mikhailovsky Alexander A. , Hong Byung‐Chul , Seshadri Ram 
Published: November 2015

AbstractSamples of Ba2.97‐xEu0.03TbxMg1‐x LixSi2O8 are prepared by microwave‐assisted sol—gel reactions of BaCO3, Mg(NO3)2, (Et‐O)4Si, Tb(NO3)3, Eu(NO3)3, MnCO3, and Li2CO3 dissolved in a mixture of EtOH, H2O, AcOH, and citric acid (heating the obtained powder to 400 °C for 4 h and to 650 °C for 6 h).
ChemInform Abstract: Ultrasmall Black Phosphorus Quantum Dots: Synthesis and Use as Photothermal Agents.
Authors: Sun Zhengbo , Xie Hanhan , Tang Siying , Yu Xue‐Feng , Guo Zhinan , Shao Jundong , Zhang Han , Huang Hao , Wang Huaiyu , Chu Paul K. 
Published: November 2015

AbstractBlack P quantum dots (BPQDs) are prepared by probe sonication of a black P/NMP mixture (1200 W, 19—25 kHz, 3 h) combined with bath sonication (300 W, 10 h, 0 °C).
ChemInform Abstract: Advances in the Lanthanide Metallosupramolecular Chemistry of the Cucurbit[n]urils
Authors: Ni Xin‐Long , Xue Sai‐Feng , Tao Zhu , Zhu Qian‐Jiang , Lindoy Leonard F. , Wei Gang 
Published: November 2015

AbstractReview: 105 refs.
ChemInform Abstract: Structural Diversity and Photoluminescence of Copper(I) Carboxylates: From Discrete Complexes to Infinite Metal‐Based Wires and Helices
Authors: Hietsoi Oleksandr , Filatov Alexander S. , Dubceac Cristina , Petrukhina Marina A. 
Published: November 2015

AbstractReview: 86 refs.
ChemInform Abstract: Chemical Constituents of Plants from the Genus Eupatorium (1904—2014)
Authors: Liu Pei‐Yu , Liu Dan , Li Wei‐Huan , Zhao Ting , Sauriol Francoise , Gu Yu‐Cheng , Shi Qing‐Wen , Zhang Man‐Li 
Published: November 2015

AbstractReview: 97 refs.
ChemInform Abstract: Recent Advances of α‐Isothiocyanato Compounds in the Catalytic Asymmetric Reaction
Authors: Han Wen‐Yong , Zhao Jian‐Qiang , Zuo Jian , Xu Xiao‐Ying , Zhang Xiao‐Mei , Yuan Wei‐Cheng 
Published: November 2015

AbstractReview: [57 refs.
Katalysatorvergleich bei der Hydroesterifizierung von 10‐Undecensäuremethylester in thermomorphen Lösungsmittelsystemen
Authors: Gaide Tom , Behr Arno , Terhorst Michael , Arns Alexander , Benski Francesco , Vorholt Andreas J. 
Published: November 2015

AbstractZwei homogene Palladium‐Katalysatoren zur Hydroesterifizierung des nachwachsenden Rohstoffs 10‐Undecensäuremethylester zum Monomer Dodecandisäuredimethylester werden verglichen. Die Katalysatoren wurden auf ihre Reaktionsraten in thermomorphen Lösungsmittelsystemen untersucht und die Reaktionsparameter optimiert. Anschließend wurde die Abtrennbarkeit der Katalysatoren vom Produkt untersucht und schließlich die Anwendbarkeit des Konzeptes der thermomorphen Lösungsmittelsysteme in dieser Reaktion durch Recyclingexperimente mit beiden Katalysatoren validiert.
Phase 1 dose escalation trial of the safety and pharmacokinetics of cabozantinib concurrent with temozolomide and radiotherapy or temozolomide after radiotherapy in newly diagnosed patients with high‐grade gliomas
Authors: Schiff David , Desjardins Annick , Cloughesy Timothy , Mikkelsen Thomas , Glantz Michael , Chamberlain Marc C. , Reardon David A. , Wen Patrick Y. 
Published: November 2015

BACKGROUNDCabozantinib inhibits mesenchymal‐epithelial transition factor (MET) and vascular endothelial growth factor receptor 2 (VEGFR2) and has demonstrated activity in patients with recurrent glioblastoma, warranting evaluation of the addition of cabozantinib to radiotherapy (RT) and temozolomide (TMZ) for patients with newly diagnosed high‐grade glioma.METHODSCabozantinib doses of 40 mg and 60 mg were explored. Patients on the concurrent treatment arm received cabozantinib daily with standard TMZ and after RT continued cabozantinib daily with adjuvant TMZ. In the maintenance arm, patients who completed RT and ≥1 adjuvant cycle of TMZ continued adjuvant TMZ with added cabozantinib (3 schedules: days 1‐28, days 1‐14, or days 8‐21).RESULTSA total of 26 patients (25 with recurrent glioblastoma and 1 patient with anaplastic astrocytoma) aged 30 to 72 years were enrolled (10 to the concurrent arm and 16 to the maintenance arm). The median number of post‐RT TMZ cycles was 4.5 (range, 0‐14 cycles) in the concurrent arm and 5.5 (range, 1‐12 cycles) in the maintenance arm. Cabozantinib at a dose of 60 mg daily was the maximum administered dose and a dose of 40 mg daily was determined to be the maximum tolerated dose for both treatment arms (schedule of days 1‐28). The most frequent grade 3/4 adverse events were thrombocytopenia (31% of patients), leukopenia (27% of patients, including 5 patients with neutropenia), and deep vein thrombosis and/or pulmonary embolism (23% of patients) (adverse events were graded according to the National Cancer Institute Common Terminology Criteria for Adverse Events [version 3.0]).CONCLUSIONSCabozantinib at a dose of 40 mg daily with RT plus TMZ and post‐RT TMZ for patients with newly diagnosed high‐grade glioma was generally well tolerated, and demonstrated no pharmacokinetic interactions with concurrent TMZ. Given the strong theoretical rationale for combining anti‐VEGF and anti‐MET activity with standard therapy, cabozantinib at a dose of 40 mg daily warrants evaluation in combination with standard therapy for patients with newly diagnosed glioblastoma. Cancer 2016;122:582–587. © 2015 American Cancer Society.
Dopamine D1 receptor expression is bipolar cell type‐specific in the mouse retina
Authors: Farshi Pershang , Fyk‐Kolodziej Bozena , Krolewski David M. , Walker Paul D. , Ichinose Tomomi 
Published: November 2015

ABSTRACTIn the retina, dopamine is a key molecule for daytime vision. Dopamine is released by retinal dopaminergic amacrine cells and transmits signaling either by conventional synaptic or by volume transmission. By means of volume transmission, dopamine modulates all layers of retinal neurons; however, it is not well understood how dopamine modulates visual signaling pathways in bipolar cells. Here we analyzed Drd1a‐tdTomato BAC transgenic mice and found that the dopamine D1 receptor (D1R) is expressed in retinal bipolar cells in a type‐dependent manner. Strong tdTomato fluorescence was detected in the inner nuclear layer and localized to type 1, 3b, and 4 OFF bipolar cells and type 5‐2, XBC, 6, and 7 ON bipolar cells. In contrast, type 2, 3a, 5‐1, 9, and rod bipolar cells did not express Drd1a‐tdTomato. Other interneurons were also found to express tdTomato including horizontal cells and a subset (25%) of AII amacrine cells. Diverse visual processing pathways, such as color or motion‐coded pathways, are thought to be initiated in retinal bipolar cells. Our results indicate that dopamine sculpts bipolar cell performance in a type‐dependent manner to facilitate daytime vision. J. Comp. Neurol. 524:2059–2079, 2016. © 2015 Wiley Periodicals, Inc.
Switchable Surface Wettability by Using Boronic Ester Chemistry
Authors: Taleb Sabri , Noyer Elisabeth , Godeau Guilhem , Darmanin Thierry , Guittard Frédéric 
Published: November 2015

AbstractHere, we report for the first time the use of a boronic ester as an efficient tool for reversible surface post‐functionalization. The boronic ester bond allows surfaces to be reversibly switched from hydrophilic to hydrophobic. Based on the well‐known boronic acid/glycol affinity, this strategy offers the opportunity to play with surface hydrophobic properties by adding various boronic acids onto substrates bearing glycol groups. The post‐functionalization can then be reversed to regenerate the starting glycol surface. This pathway allows for the preparation of various switchable surfaces for a large range of applications in biosensors, liquid transportation, and separation membranes.
The Nature of the Singlet and Triplet States of Cyclobutadiene as Revealed by Quantum Interference
Authors: Fantuzzi Felipe , Cardozo Thiago M. , Nascimento Marco A. C. 
Published: November 2015

AbstractThe generalized product function energy partitioning (GPF‐EP) method is applied to the description of the cyclobutadiene molecule. The GPF wave function was built to reproduce generalized valence bond (GVB) and spin‐coupled (SC) wave functions. The influence of quasiclassical and quantum interference contributions to each chemical bond of the system are analyzed along the automerization reaction coordinate for the lowest singlet and triplet states. The results show that the interference effect on the π space reduces the electronic energy of the singlet cyclobutadiene relative to the second‐order Jahn–Teller distortion, which takes the molecule from a D4h to a D2h structure. Our results also suggest that the π space of the 1B1g state of the square cyclobutadiene is composed of a weak four center–four electron bond, whereas the 3A2g state has a four center–two electron π bond. Finally, we also show that, although strain effects are nonnegligible, the thermodynamics of the main decomposition pathway of cyclobutadiene in the gas phase is dominated by the π space interference.
Competing Insertion and External Binding Motifs in Hydrated Neurotransmitters: Infrared Spectra of Protonated Phenylethylamine Monohydrate
Authors: Bouchet Aude , Schütz Markus , Dopfer Otto 
Published: November 2015

AbstractHydration has a drastic impact on the structure and function of flexible biomolecules, such as aromatic ethylamino neurotransmitters. The structure of monohydrated protonated phenylethylamine (H+PEA−H2O) is investigated by infrared photodissociation (IRPD) spectroscopy of cold cluster ions by using rare‐gas (Rg=Ne and Ar) tagging and dispersion‐corrected density functional theory calculations at the B3LYP‐D3/aug‐cc‐pVTZ level. Monohydration of this prototypical neurotransmitter gives an insight into the first step of the formation of its solvation shell, especially regarding the competition between intra‐ and intermolecular interactions. The spectra of Rg‐tagged H+PEA−H2O reveal the presence of a stable insertion structure in which the water molecule is located between the positively charged ammonium group and the phenyl ring of H+PEA, acting both as a hydrogen bond acceptor (NH+⋅⋅⋅O) and donor (OH⋅⋅⋅π). Two other nearly equivalent isomers, in which water is externally H bonded to one of the free NH groups, are also identified. The balance between insertion and external hydration strongly depends on temperature.