bluuebunny/crossref_metadata_2025 huggingface dataset:
Long‐Range Hydrophilic Attraction between Water and Polyelectrolyte Surfaces in Oil
Authors: Shi Chen , Yan Bin , Xie Lei , Zhang Ling , Wang Jingyi , Takahara Atsushi , Zeng Hongbo
Published: October 2016

The outstanding water wettability and the capability of polyelectrolyte surfaces to spontaneously clean oil fouling are determined by their wetting mechanism in the surrounding medium. Here, we have quantified the nanomechanics between three types of polyelectrolyte surfaces (i.e. zwitterionic, cationic, and anionic) and water or oil drops using an atomic force microscope (AFM) drop probe technique, and elucidated the intrinsic wetting mechanisms of the polyelectrolyte surfaces in oil and water media. The measured forces between oil drops and polyelectrolyte surfaces in water can be described by the Derjaguin‐Landau‐Verwey‐Overbeek (DLVO) theory. Surprisingly, strong long‐range attraction was discovered between polyelectrolyte surfaces and water drops in oil, and the strongest interaction was measured for the polyzwitterion. This unexpected long‐range “hydrophilic” attraction in oil could be attributed to a strong dipolar interaction because of the large dipole moment of the polyelectrolytes. Our results provide new nanomechanical insights into the development of novel polyelectrolyte‐based materials and coatings for a wide range of engineering, bioengineering, and environmental applications.
Brief Report: The Role of Rare Protein‐Coding Variants in Anti–Tumor Necrosis Factor Treatment Response in Rheumatoid Arthritis
Authors: Cui Jing , Diogo Dorothee , Stahl Eli A. , Canhao Helena , Mariette Xavier , Greenberg Jeffrey D. , Okada Yukinori , Pappas Dimitrios A. , Fulton Robert S. , Tak Paul P. , Nurmohamed Michael T. , Lee Annette , Larson David E. , Kurreeman Fina , Deluca Tracie L. , O'Laughlin Michelle , Fronick Catrina C. , Fulton Lucinda L. , Mardis Elaine R. , van der Horst‐Bruinsma Irene E. , Wolbink Gert‐Jan , Gregersen Peter K. , Kremer Joel M. , Crusius J. Bart A. , de Vries Niek , Huizinga Tom W. J. , Fonseca João Eurico , Miceli‐Richard Corinne , Karlson Elizabeth W. , Coenen Marieke J. H. , Barton Anne , Plenge Robert M. , Raychaudhuri Soumya
Published: October 2016

Objective

In many rheumatoid arthritis (RA) patients, disease is controlled with anti–tumor necrosis factor (anti‐TNF) biologic therapies. However, in a significant number of patients, the disease fails to respond to anti‐TNF therapy. We undertook the present study to examine the hypothesis that rare and low‐frequency genetic variants might influence response to anti‐TNF treatment.

Methods

We sequenced the coding region of 750 genes in 1,094 RA patients of European ancestry who were treated with anti‐TNF. After quality control, 690 genes were included in the analysis. We applied single‐variant association and gene‐based association tests to identify variants associated with anti‐TNF treatment response. In addition, given the key mechanistic role of TNF, we performed gene set analyses of 27 TNF pathway genes.

Results

We identified 14,420 functional variants, of which 6,934 were predicted as nonsynonymous 2,136 of which were further predicted to be “damaging.” Despite the fact that the study was well powered, no single variant or gene showed study‐wide significant association with change in the outcome measures disease activity or European League Against Rheumatism response. Intriguingly, we observed 3 genes, of 27 with nominal signals of association (P < 0.05), that were involved in the TNF signaling pathway. However, when we performed a rigorous gene set enrichment analysis based on association P value ranking, we observed no evidence of enrichment of association at genes involved in the TNF pathway (Penrichment = 0.15, based on phenotype permutations).

Conclusion

Our findings suggest that rare and low‐frequency protein‐coding variants in TNF signaling pathway genes or other genes do not contribute substantially to anti‐TNF treatment response in patients with RA.
Functional assessment of anomalous right coronary artery using fractional flow reserve
Authors: Boler Amber N. , Hilliard Anthony A. , Gordon Brent M.
Published: October 2016

Anomalous origin of a coronary artery is a recognized cause of sudden cardiac death (SCD). To date, there is no standard test to predict which patients are at increased risk for SCD. Fractional flow reserve (FFR) is an invasive technique used to qualify focal obstructive coronary lesions. We present a case where FFR was used to guide therapy in a young patient with anomalous right coronary artery (ARCA) when standard noninvasive testing showed ischemic discrepancy. © 2016 Wiley Periodicals, Inc.
Comparative data of single versus double proglide vascular preclose technique after percutaneous transfemoral transcatheter aortic valve implantation from the optimized catheter valvular intervention (OCEAN‐TAVI) japanese multicenter registry
Authors: Kodama Atsuko , Yamamoto Masanori , Shimura Tetsuro , Kagase Ai , Koyama Yutaka , Tada Norio , Takagi Kensuke , Araki Motoharu , Yamanaka Futoshi , Shirai Shinichi , Watanabe Yusuke , Hayashida Kentaro
Published: October 2016

Objectives

This study aimed to assess the feasibility of percutaneous arterial access site closure after percutaneous transfemoral transcatheter aortic valve implantation (TF‐TAVI) using single versus double Perclose ProGlide devices.

Backgrounds

Although suturing with the preclose technique has been widely adopted during TF‐TAVI, the optimal vascular closure strategy is still under debate.

Methods

Data from 279 patients who underwent TF‐TAVI, obtained from the Optimized CathEter vAlvular iNtervention (OCEAN‐TAVI) Japanese multicenter registry. Technical, procedural, and clinical outcomes were compared between the single ProGlide group (n = 99) and double ProGlide group (n = 180). They were also analyzed by propensity adjusted matching model (single [n = 69] vs. double [n = 69]). All patients were treated through a 16‐Fr to 20‐Fr eSheath. Technical success of the closure device was defined as hemostasis not requiring alternative invasive treatment. Access site‐related vascular complications, bleedings, and other procedural complications were defined according to the Valvular Academic Research Consortium‐2 (VARC‐2) criteria.

Results

The rates of technical success and access site‐related vascular complications were similar in the 2 groups (94.9% vs. 91.6%, p = 0.44; 5.0% vs. 7.7%, p = 0.54, respectively). The prevalence of bleeding complications did not differ between the 2 groups (1.0% vs. 3.3%, p = 0.43). Thirty‐day mortality rate also showed no difference between the 2 groups (2.0% vs. 1.1%, p = 0.95), although these events were not associated with access site failure. These results were not attenuated in the propensity matching model.

Conclusions

Vascular closure with a single ProGlide in TF‐TAVI could achieve equivalent, acceptable rates of technical success and procedural complications compared with the double ProGlide technique. © 2016 Wiley Periodicals, Inc.
SnO2/Sn Nanoparticles Embedded in an Ordered, Porous Carbon Framework for High‐Performance Lithium‐Ion Battery Anodes
Authors: Wang Zhi‐Qiang , Wang Ming‐Shan , Yang Zhen‐Liang , Bai Yong‐Shun , Ma Yan , Wang Guo‐Liang , Huang Yun , Li Xing
Published: October 2016

Tin dioxide (SnO2) is recognized as one of the most promising anode materials for lithium‐ion batteries. However, the large volume changes of pure SnO2 anodes during Li+ insertion/extraction inevitably result in rapid capacity decay. Herein, the fabrication of microsized, porous SnO2/Sn/carbon (p‐SnO2/Sn/C) composites by a straightforward one‐step hydrothermal process with triblock copolymer Pluronic F‐127 as templating agent and subsequent carbonization is reported. In this composite structure, SnO2/Sn nanoparticles (≈5 nm) are uniformly embedded in an ordered porous carbon matrix to form an interpenetrating framework structure. The ordered porous carbon matrix not only offers three‐dimensional channels for extraction/insertion of Li+ during cycling, but also buffers severe volume changes of the SnO2/Sn nanoparticles. Furthermore, the composite structure also ensures formation of stable solid electrolyte interface films as compared with isolated SnO2/Sn nanoparticles, which efficiently improves the electrochemical stability of the active materials. Thus, the p‐SnO2/Sn/C anode delivers a high reversible capacity of 1016.2 mAh g−1 at 100 mA g−1 after 100 cycles and has remarkable long‐term cycle stability (a charge capacity of 710 mAh g−1 even after 600 cycles at 1000 mA g−1).
Magnetoliposomes as Potential Carriers of Doxorubicin to Tumours
Authors: Joniec Aleksandra , Sek Slawomir , Krysinski Pawel
Published: October 2016

Studies on magnetoliposomes (MLUV) as potential carriers for magnetic‐field‐dependent drug delivery are presented. The systems were formed with hydrophobic superparamagnetic iron oxide nanoparticles (SPIONs) confined within the bilayer of the liposomes. The nanomechanical properties of bilayer lipid membranes were evaluated and related to the amount of incorporated SPIONs. It was found that the presence of SPIONs in the lipid membrane leads to overall stiffening and increases morphological inhomogeneity, facilitating rupture of the MLUV membrane in a low‐frequency alternating magnetic field (AMF). To verify the findings, doxorubicin release from MLUVs in the presence and absence of an AMF was measured. Under experimental conditions, drug release proceeds through MLUV rupture induced by mechanical vibration of SPIONs rather than through localized heating in the vicinity of the SPIONs.
Lithium Ion Mobility in Lithium Phosphidosilicates: Crystal Structure, 7Li, 29Si, and 31P MAS NMR Spectroscopy, and Impedance Spectroscopy of Li8SiP4 and Li2SiP2
Authors: Toffoletti Lorenzo , Kirchhain Holger , Landesfeind Johannes , Klein Wilhelm , van Wüllen Leo , Gasteiger Hubert A. , Fässler Thomas F.
Published: October 2016

The need to improve electrodes and Li‐ion conducting materials for rechargeable all‐solid‐state batteries has drawn enhanced attention to the investigation of lithium‐rich compounds. The study of the ternary system Li‐Si‐P revealed a series of new compounds, two of which, Li8SiP4 and Li2SiP2, are presented. Both phases represent members of a new family of Li ion conductors that display Li ion conductivity in the range from 1.15(7)×10−6 Scm−1 at 0 °C to 1.2(2)×10−4 Scm−1 at 75 °C (Li8SiP4) and from 6.1(7)×10−8 Scm−1 at 0 °C to 6(1)×10−6 Scm−1 at 75 °C (Li2SiP2), as determined by impedance measurements. Temperature‐dependent solid‐state 7Li NMR spectroscopy revealed low activation energies of about 36 kJ mol−1 for Li8SiP4 and about 47 kJ mol−1 for Li2SiP2. Both compounds were structurally characterized by X‐ray diffraction analysis (single crystal and powder methods) and by 7Li, 29Si, and 31P MAS NMR spectroscopy. Both phases consist of tetrahedral SiP4 anions and Li counterions. Li8SiP4 contains isolated SiP4 units surrounded by Li atoms, while Li2SiP2 comprises a three‐dimensional network based on corner‐sharing SiP4 tetrahedra, with the Li ions located in cavities and channels.
A Convenient Approach To Synthesize o‐Carborane‐Functionalized Phosphorescent Iridium(III) Complexes for Endocellular Hypoxia Imaging
Authors: Li Xiang , Tong Xiao , Yan Hong , Lu Changsheng , Zhao Qiang , Huang Wei
Published: October 2016

The structure–property relationship of carborane‐modified iridium(III) complexes was investigated. Firstly, an efficient approach for the synthesis of o‐carborane‐containing pyridine ligands a–f in high yields was developed by utilizing stable and cheap B10H10(Et4N)2 as the starting material. By using these ligands, iridium(III) complexes I–VII were efficiently prepared. In combination with DFT calculations, the photophysical and electrochemical properties of these complexes were studied. The hydrophilic nido‐o‐carborane‐based iridium(III) complex VII showed the highest phosphorescence efficiency (abs.
=0.48) among known water‐soluble homoleptic cyclometalated iridium(III) complexes and long emission lifetime (τ=1.24 μs) in aqueous solution. Both of them are sensitive to O2, and thus endocellular hypoxia imaging of complex VII was realized by time‐resolved luminescence imaging (TRLI). This is the first example of applying TRLI in endocellular oxygen detection with a water‐soluble nido‐carborane functionalized iridium(III) complex.
Parent, Unsubstituted Hemiporphycene: Synthesis and Properties
Authors: Ostapko Jakub , Nawara Krzysztof , Kijak Michał , Buczyńska Joanna , Leśniewska Barbara , Pietrzak Mariusz , Orzanowska Grażyna , Waluk Jacek
Published: October 2016

Among seven possible nitrogen‐in constitutional isomers of porphyrin only one, porphycene, has been obtained so far in the free, unsubstituted form. Herein, the synthesis of another isomer, parent hemiporphycene (HPc), and its thorough structural, spectral, photophysical, electrochemical, and theoretical characterization are reported. Most of the properties of HPc are intermediate between those of porphyrin and porphycene, as evidenced by the values of inner‐cavity dimensions, orbital‐energy splittings, absorption coefficients, magnetic circular dichroism parameters, NH‐stretching frequencies, fluorescence quantum yields, tautomerization rates, and redox potentials. The largest differences arise with respect to tautomerism, due to the low symmetry of HPc and inequivalence of the four nitrogen atoms that define the inner cavity. Two trans tautomers are observed, separated in energy by about 1 kcal mol−1. Tautomerization from the higher‐ to the lower‐energy form is detected in the lowest‐excited singlet state and occurs at a rate that is about four orders of magnitude lower than that observed for porphycene. Hemiporphycene is a very good model for the investigation of inequivalent intramolecular H‐bonds present in one molecule; two such bonds in HPc reveal unusual characteristics, and the bond strength results from the interplay between the N⋅⋅⋅N distance and the N−H−N angle.
Oxygenation Chemistry of Magnesium Alkyls Incorporating β‐Diketiminate Ligands Revisited
Authors: Pietrzak Tomasz , Kubisiak Marcin , Justyniak Iwona , Zelga Karolina , Bojarski Emil , Tratkiewicz Ewa , Ochal Zbigniew , Lewiński Janusz
Published: October 2016

Despite the fact that extensive research has been carried out, the oxygenation of alkyl magnesium species still remains a highly unexplored research area and significant uncertainties concerning the mechanism of these reactions and the composition of the resulting products persist. This case study compares the viability of the controlled oxygenation of alkylmagnesium complexes supported by β‐diketiminates. The structural tracking of the reactivity of (N,N)MgR‐type complexes towards O2 at low temperature showed that their oxygenation led exclusively to the formation of magnesium alkylperoxides (N,N)MgOOR. The results also highlight significant differences in the stability of the resulting alkylperoxides in solution and demonstrate that [(BDI)Mg(μ‐η2:η1‐OOBn)]2 (in which BDI=[(ArNCMe)2CH]− and Ar=C6H3iPr2‐2,6) can be easily transformed to the corresponding magnesium alkoxide [(BDI)MgOBn]2 at ambient temperature, whilst [(F3BDI)Mg(μ‐OOtBu)]2 (in which F3BDI=[(ArNCMe)2CH]− and Ar=C6H2F3‐2,4,6) is stable under similar conditions. The observed selective oxygenation of (N,N)MgR‐type complexes to the corresponding (N,N)MgOOR alkylperoxides strongly contradicts the widely accepted radical‐chain mechanism for the oxygenation of the main‐group‐metal alkyls. Furthermore, either the observed transformation of the alkylperoxide [(BDI)MgOOBn]2 to the alkoxide [(BDI)MgOBn]2 as well as the formation of an intractable mixture of products in the control reaction between the alkylperoxide [(F3BDI)MgOOtBu]2 and the parent alkylmagnesium [(F3BDI)MgtBu] complex are not in line with the common wisdom that magnesium alkoxide complexes’ formation results from the metathesis reaction between MgOOR and Mg−R species. In addition, a high catalytic activity of well‐defined magnesium alkylperoxides, in combination with tert‐butyl hydroperoxide (TBHP) as an oxygen source, in the epoxidation of trans‐chalcone is presented.
Layered Structural Co‐Based MOF with Conductive Network Frames as a New Supercapacitor Electrode
Authors: Yang Jie , Ma Zhihua , Gao Weixue , Wei Mingdeng
Published: October 2016

Layered structural Co‐MOF nanosheets were synthesized and then used as an electrode material for supercapacitors for the first time. This material exhibited a high specific capacitance, a good rate capability, and an excellent cycling stability. A maximum capacitance of 2564 F g−1 can be achieved at a current density of 1 Ag−1. Moreover, the capacitance retention can be kept at 95.8 % respectively of its initial value after 3000 cycles. To the best of our knowledge, both the specific capacitance and the capacitance retention were the highest values reported for MOF materials as supercapacitor electrodes until now. Such a high supercapacitive performance might be attributed to the intrinsic characteristics of this kind of Co‐MOF material, including its layered structure, conductive network frame, and thin nanosheet.
Emulating Natural Product Conformation by Cooperative, Non‐Covalent Fluorine Interactions
Authors: Scheidt Felix , Selter Philipp , Santschi Nico , Holland Mareike C. , Dudenko Dmytro V. , Daniliuc Constantin , Mück‐Lichtenfeld Christian , Hansen Michael Ryan , Gilmour Ryan
Published: October 2016

Pervasive in Nature, the propane unit is an essential component of numerous bioactive molecules. These range from acyclic systems, such as the neurotransmitter γ‐aminobutyric acid, through to the bicyclic nuclei of various chromanes and dihydrobenzofurans. In the latter case, cyclisation via cyclic ether formation ensures a highly pre‐organised structure, whilst linear scaffolds display more dynamic conformational behaviour resulting from rotation about the two internal C(sp3)–C(sp3) bonds. In this study, the replacement of ‐[CH2]‐ units by ‐[CHF]‐ centres is evaluated as a strategy to achieve acyclic conformational control by hindering these internal rotations. Reinforcing, non‐covalent fluorine interactions are validated as powerful design features that result in programmable conformational behaviours: These are encoded by the relative configuration of each centre. By exploiting cooperative neighbouring stereoelectronic effects in a multi‐vicinal fluoroalkane it is possible to emulate the overall conformation of the dihydrobenzofuran scaffold found in a variety of natural products with an acyclic mimic. This is described as a function of two bond vectors at the chain termini and validated by combined theoretical, crystallographic and spectroscopic analyses. In view of the favourable physicochemical properties associated with fluorine introduction, this approach to bioactive scaffold design may prove to be expansive.
Isomerization of Keggin Al13 Ions Followed by Diffusion Rates
Authors: Oliveri Anna F. , Colla Christopher A. , Perkins Cory K. , Akhavantabib Noushin , Callahan Joseph R. , Pilgrim Corey D. , Smart Scott E. , Cheong Paul H.‐Y. , Pan Long , Casey William H.
Published: October 2016

The solution chemistry of aluminum has long interested scientists due to its relevance to materials chemistry and geochemistry. The dynamic behavior of large aluminum–oxo‐hydroxo clusters, specifically [Al13O4(OH)24(H2O)12]7+ (Al13), is the focus of this paper. 27Al NMR, 1H NMR, and 1H DOSY techniques were used to follow the isomerization of the ϵ‐Al13 in the presence of glycine and Ca2+ at 90 °C. Although the conversion of ϵ‐Al13 to new clusters and/or Baker–Figgis–Keggin isomers has been studied previously, new 1H NMR and 1H DOSY analyses provided information about the role of glycine, the ligated intermediates, and the mechanism of isomerization. New 1H NMR data suggest that glycine plays a critical role in the isomerization. Surprisingly, glycine does not bind to Al30 clusters, which were previously proposed as an intermediate in the isomerization. Additionally, a highly symmetric tetrahedral signal (δ=72 ppm) appeared during the isomerization process, which evidence suggests corresponds to the long‐sought α‐Al13 isomer in solution.
ChemInform Abstract: EuAu3Al2: Crystal and Electronic Structures and Spectroscopic, Magnetic, and Magnetocaloric Properties.
Authors: Schmiegel Jan‐Patrick , Block Theresa , Gerke Birgit , Fickenscher Thomas , Touzani Rachid St. , Fokwa Boniface P. T. , Janka Oliver
Published: October 2016

The title compound is synthesized from the elements (Ta ampule, 1300 K for 10 min and 825 K for 2—8 h) and characterized by single crystal XRD, Moessbauer spectroscopy, magnetic measurements, and DFT calculations.
ChemInform Abstract: Mechanistic Studies and Expansion of the Substrate Scope of Direct Enantioselective Alkynylation of α‐Ketiminoesters Catalyzed by Adaptable (Phebox)Rhodium(III) Complexes.
Authors: Morisaki Kazuhiro , Sawa Masanao , Yonesaki Ryohei , Morimoto Hiroyuki , Mashima Kazushi , Ohshima Takashi
Published: October 2016

The use of (trimethylsilylethynyl)rhodium(III) complexes as catalysts significantly improves the catalysis of the reaction of α‐ketiminoesters (I) and related substrates (IV) and (VI) with terminal alkynes to yield products with quarternary stereocenters with good yields and enantioselectivities.
ChemInform Abstract: The Development of New Amine—Amide Ligands for Application in Cu(II)‐Catalyzed Enantioselective Henry Reactions.
Authors: Ao Chunyan , Men Jian , Wang Yang , Shao Tao , Huang Yuanyuan , Huo Junji , Gao Guowei
Published: October 2016

Combined with Cu(II) acetate, novel BINOL‐derived chiral tertiary amine ligands are developed as catalysts for the asymmetric Henry reaction of aromatic, heteroaromatic, and aliphatic aldehyde substrates.
ChemInform Abstract: Synthesis of β‐Phthalimido‐Alcohols via Regioselective Ring Opening of Epoxide by Using Reusable Basic Magnetic Nano Particles and Their Biological Investigation.
Authors: Zolfigol Mohammad Ali , Moosavi‐Zare Ahmad Reza , Zarei Mahmoud , Zare Abdolkarim , Noroozizadeh Ehsan , Karamian Roya , Asadbegy Mostafa
Published: October 2016

All phthalimido‐alcohols are tested for antioxidative properties in a radical scavenging assay showing efficacies similarly to that of ascorbic acid.
ChemInform Abstract: Palladium‐Catalyzed Regioselective C—H Acetoxylation of 2‐Aryloxypyridines with 2‐Pyridyloxy as a Removable Directing Group.
Authors: Wang Liang , Pan Liang , Huang Yibo , Chen Qun , He Mingyang
Published: October 2016

Yields of mono‐ as well as bis‐acetoxylated arenes depend significantly on the electronic nature of aryl substituents.
ChemInform Abstract: Hantzsch Ester as a Photosensitizer for the Visible‐Light‐Induced Debromination of Vicinal Dibromo Compounds.
Authors: Chen Wenxin , Tao Huachen , Huang Wenhao , Wang Guoqiang , Li Shuhua , Cheng Xu , Li Guigen
Published: October 2016

The scalable, robust, and catalyst‐free method has a broad substrate scope, thus offering access to a broad range of styrene derivatives, α,β‐unsaturated carbonyl compounds as well as 1,2 and 1,2‐disubstituted and even trisubstituted alkenes, including cyclic ones.
ChemInform Abstract: Preparation of Difluoromethylthioethers Through Difluoromethylation of Disulfides Using TMS‐CF2H.
Authors: Howard Joseph L. , Schotten Christiane , Alston Stephen T. , Browne Duncan L.
Published: October 2016

The operationally simple, metal‐free approach tolerates alkyl as well as aryl substituted disulfides which may contain diverse functional groups.
ChemInform Abstract: Practical Synthesis of Amides via Copper/ABNO‐Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.
Authors: Zultanski Susan L. , Zhao Jingyi , Stahl Shannon S.
Published: October 2016

Various catalyst systems are developed for the synthesis of a wide range of amides from alcohols and amines.
ChemInform Abstract: General Synthesis of Amino Acid Salts from Amino Alcohols and Basic Water Liberating H2.
Authors: Hu Peng , Ben‐David Yehoshoa , Milstein David
Published: October 2016

A simple and higlhy efficient method for the dehydrogenative conversion of amino alcohols to structurally diverse amino acids is developed using sodium or potassium hydroxide as base and a ruthenium pincer complex as catalyst.
ChemInform Abstract: NHC—Copper(I) Halide‐Catalyzed Direct Alkynylation of Trifluoromethyl Ketones on Water.
Authors: Czerwinski Pawel , Molga Edyta , Cavallo Luigi , Poater Albert , Michalak Michal
Published: October 2016

Aromatic and aliphatic trifluoroketone substrates can be used with success in the title process and a wide range of functional groups is tolerated in both reactant types (detailed theoretical calculations).
ChemInform Abstract: Diamination of Domino Aryne Precursor with Sulfonamides.
Authors: Qiu Dachuan , He Jia , Yue Xiao , Shi Jiarong , Li Yang
Published: October 2016

Variation of the reaction conditions allows for the preparation of 1,3‐diaminobenzenes or derivatives of the latter containing a triflic group in position 2.
ChemInform Abstract: Sonogashira Coupling Catalyzed by the Cu(Xantphos)I—Pd(OAc)2 System.
Authors: Liu Meilin , Ye Mingyan , Xue Yeye , Yin Guodong , Wang Dunjia , Huang Jinkun
Published: October 2016

Aryl bromides/iodides and electron‐poor aryl chlorides are suitable substrates for the title reaction.
ChemInform Abstract: Asymmetric Synthesis of Multisubstituted Dihydrobenzofurans by Intramolecular Conjugate Addition of Short‐Lived C—O Axially Chiral Enolates.
Authors: Tomohara Keisuke , Kasamatsu Koji , Yoshimura Tomoyuki , Furuta Takumi , Kawabata Takeo
Published: October 2016

The products are formed with high diastereomeric and enantiomeric excesses.
ChemInform Abstract: Stereoselective Synthesis of Alkylidene Phthalides.
Authors: Dragan Andrei , Jones D. Heulyn , Kennedy Alan R. , Tomkinson Nicholas C. O.
Published: October 2016

The products are formed as mixtures of E/Z isomers only the major isomer of which is isolated in moderate to high yields.
ChemInform Abstract: Synthesis of 5‐Hydroxy‐Δ1‐pyrrolines from Aryl Isoalkyl Ketoximes and Acetylene in a Tuned Superbase Medium.
Authors: Shabalin Dmitrii A. , Dvorko Marina Yu. , Schmidt Elena Yu. , Protsuk Nadezhda I. , Trofimov Boris A.
Published: October 2016

Title compounds (III) bearing aromatic substituents at the C—N double bond are synthesized in moderate yields by reaction of the corresponding ketoximes (I) and acetylene (II).
ChemInform Abstract: Detrifluoroacetylative in situ Generation of Free 3‐Fluoroindolin‐2‐one‐Derived Tertiary Enolates: Design, Synthesis, and Assessment of Reactivity Toward Asymmetric Mannich Reactions.
Authors: Xie Chen , Zhang Lijun , Sha Wanxing , Soloshonok Vadim A. , Han Jianlin , Pan Yi
Published: October 2016

The robust protocol displays a broad substrate scope and delivers the products in high yields and with very high diastereo‐ and enantioselectivities.
ChemInform Abstract: A Rhodium Catalyst Superior to Iridium Congeners for Enantioselective Radical Amination Activated by Visible Light.
Authors: Shen Xiaodong , Harms Klaus , Marsch Michael , Meggers Eric
Published: October 2016

The chiral Rh complex is highly efficient in the title reaction (detailed mechanism).
ChemInform Abstract: Isocyano Enones: Addition—Cyclization Cascade to Oxazoles.
Authors: Chao Allen , Lujan‐Montelongo J. Armando , Fleming Fraser F.
Published: October 2016

The modular and rapid synthesis is based on the reaction of various acyclic and 6‐7‐membered isocyano enones with diverse carbon or heteroatom nucleophiles such as dicarbonyl compounds, malonitrile, nitromethane, benzylamine and 4‐methylbenzenethiol.
ChemInform Abstract: One‐Pot Synthesis of Functionalized Benzo[c]coumarins and Their Precursors via the Reaction of 2‐(polyfluoroalkyl)chromones with 4‐Alkyl‐3‐cyanocoumarins.
Authors: Sosnovskikh Vyacheslav Ya. , Korotaev Vladislav Yu. , Kutyashev Igor B. , Barkov Alexey Yu. , Safrygin Alexander V.
Published: October 2016

The novel annulation reaction proceeds in the presence of triethylamine and provides directly benzo[c]coumarin derivatives or their ammonium salts.
ChemInform Abstract: Synthesis of Functionalized Tetrahydropyridazines via Catalyst‐Free Self [4 + 2] Cycloaddition of in situ Generated 1,2‐Diaza‐1,3‐dienes.
Authors: Zhang Zhimin , Zhang Li , Chen Qingqing , Lu Tao , Zhou Qingfa
Published: October 2016

The treatment of chlorides (I) with K2CO3 gives rise to tetrahydropyridazines (II) in high yields.
ChemInform Abstract: Silicon—Carbon Bond Formation via Nickel‐Catalyzed Cross‐Coupling of Silicon Nucleophiles with Unactivated Secondary and Tertiary Alkyl Electrophiles.
Authors: Chu Crystal K. , Liang Yufan , Fu Gregory C.
Published: October 2016

For the first time, the use of metal catalyst NiBr2·diglyme for the title reaction is described to yield a wide range of silylated compounds.
ChemInform Abstract: Pd‐Catalyzed C—P Coupling of Heteroaryl Boronic Acid with H‐Phosphonate Diester.
Authors: Geng Zhiyue , Zhang Yudan , Zheng Lu , Li Jingya , Zou Dapeng , Wu Yangjie , Wu Yusheng
Published: October 2016

A novel route to heteroaryl phosphonates (III) using a Pd/Ag‐catalyst system without addition of a base is described.
ChemInform Abstract: Mild and Efficient Oxidation of Phosphorus(III) Compounds with Selectfluor.
Authors: Chen Qian , Zeng Jiekun , Yan Xinxing , Huang Yulin , Du Zhiyun , Zhang Kun , Wen Chunxiao
Published: October 2016

Selectfluor is utilized to oxidize a variety of aryl‐, alkyl‐, and alkoxy‐substituted trivalent phosphorous compounds to the corresponding penta‐valent oxides.
ChemInform Abstract: Periplocain A, a New Naphthalene Derivative from Periploca aphylla Growing in Saudi Arabia.
Authors: Al Musayeib Nawal M. , Al‐Massarani Shaza M. , Amina Musarat , El Dib Rabab A. , Mohamed Gamal A. , Ibrahim Sabrin R. M.
Published: October 2016

isolation and structure elucidation
ChemInform Abstract: Antiinflammatory Activity of a Novel Acetylene Isolated from the Roots of Angelica tenuissima NAKAI.
Authors: Choi Hyun Gyu , Choi Hyukjae , Lee Jeong‐Hyung , Min Byung Sun , Kim Jeong Ah
Published: October 2016

The novel acetylene (I) shows potent inhibitory activity against LPS‐induced NO production as well as strong inhibitory activities against iNOS and COX‐2.
ChemInform Abstract: Eu2+‐Activated Alkaline‐Earth Halophosphates, M5(PO4)3X:Eu2+ (M: Ca, Sr, Ba; X : F, Cl, Br) for NUV‐LEDs: Site‐Selective Crystal Field Effect.
Authors: Kim Donghyeon , Kim Sung‐Chul , Bae Jong‐Seong , Kim Sungyun , Kim Seung‐Joo , Park Jung‐Chul
Published: October 2016

The title compounds are prepared from stoichiometric mixtures of MCO3 (M: Sr, Ca, Ba), Eu2O3, NH4X (X: F, Cl, Br), and (NH4)H2PO4 (4% H2/Ar, 1100 °C, 3 h) and characterized by powder XRD, XPS, photoluminescence, IR, and UV/VIS spectroscopy.
ChemInform Abstract: Coordination and Activation of E—H Bonds (E: B, Al, Ga) at Transition Metal Centers
Authors: Riddlestone Ian M. , Abdalla Joseph A. B. , Aldridge Simon
Published: October 2016

Review: 143 refs.
ChemInform Abstract: Electropolymerized Films of Redox‐Active Ruthenium Complexes for Multistate Near‐Infrared Electrochromism, Ion Sensing, and Information Storage
Authors: Shao Jiang‐Yang , Yao Chang‐Jiang , Cui Bin‐Bin , Gong Zhong‐Liang , Zhong Yu‐Wu
Published: October 2016

Review: 76 refs.
ChemInform Abstract: Rational Design of Dinuclear Complexes Binding at Two Neighboring Phosphate Esters of DNA
Authors: Glaser Thorsten , Fischer von Mollard Gabriele , Anselmetti Dario
Published: October 2016

Review: 120 refs.
ChemInform Abstract: Synthesis of α‐Ethynyl Glycines
Authors: Bolsakova Jekaterina , Jirgensons Aigars
Published: October 2016

Review: methods published from 1996 to 2015 for the syntheses of ethynyl glycines and synthetically equivalent ethynyl glycinols in racemic and enantioenriched form; 58 refs.
ChemInform Abstract: Transition‐Metal Catalyzed Asymmetric Carbon—Carbon Cross‐Coupling with Chiral Ligands
Authors: Yang He , Yang Xintong , Tang Wenjun
Published: October 2016

Review: 118 refs.
ChemInform Abstract: Recent Developments and Perspectives in the Ruthenium‐Catalyzed Olefin Epoxidation
Authors: Ujwaldev Sankuviruthiyil M. , Sindhu Kallikkakam S. , Thankachan Amrutha P. , Anilkumar Gopinathan
Published: October 2016

Review: [52 refs.
ChemInform Abstract: Regioselective Acylation, Alkylation, Silylation and Glycosylation of Monosaccharides
Authors: Lawandi Janice , Rocheleau Sylvain , Moitessier Nicolas
Published: October 2016

Review: 236 refs.
ChemInform Abstract: Recent Advances in Dual Transition Metal—Visible Light Photoredox Catalysis
Authors: Toth Balazs L. , Tischler Orsolya , Novak Zoltan
Published: October 2016

Review: [64 refs.
ChemInform Abstract: The Past, Present, and Future of the Yang Reaction
Authors: Chen Chuo
Published: October 2016

Review: 90 refs.
ChemInform Abstract: Catalytic and Mechanistic Insights into the Production of Ethyl Levulinate from Biorenewable Feedstocks
Authors: Ahmad Ejaz , Alam Md. Imteyaz , Pant K. K. , Haider M. Ali
Published: October 2016

Review: 175 refs.
ChemInform Abstract: Inverse Electron Demand Diels—Alder (IEDDA) Reactions: Synthesis of Heterocycles and Natural Products Along with Bioorthogonal and Material Sciences Applications
Authors: Brachet Etienne , Belmont Philippe
Published: October 2016

Review: bibliography data from 2013 to 2015; 49 refs.
ChemInform Abstract: Second Generation of Aldol Reaction
Authors: Gati Wafa , Yamamoto Hisashi
Published: October 2016

Review: 77 refs.
ChemInform Abstract: Alignment and Patterning of Organic Single Crystals for Field‐Effect Transistors
Authors: Li Qin‐Fen , Liu Shuang , Chen Hong‐Zheng , Li Han‐Ying
Published: October 2016

Review: 89 refs.
ChemInform Abstract: Principles that Govern Electronic Transport in Organic Conductors and Transistors
Authors: Mori Takehiko
Published: October 2016

Review: 128 refs + subrefs
ChemInform Abstract: Organic Reactions in Microdroplets: Reaction Acceleration Revealed by Mass Spectrometry
Authors: Yan Xin , Bain Ryan M. , Cooks R. Graham
Published: October 2016

Review: [77 refs.
ChemInform Abstract: Shell Biorefinery: Dream or Reality
Authors: Chen Xi , Yang Huiying , Yan Ning
Published: October 2016

Review: [127 refs.
ChemInform Abstract: Combustion Chemistry Diagnostics for Cleaner Processes
Authors: Kohse‐Hoeinghaus Katharina
Published: October 2016

Review: [87 refs.
ChemInform Abstract: An Approach to the Aromaticity Based on the Energy of the Occupied π Orbitals
Authors: D'Auria Maurizio
Published: October 2016

Review: 93 refs.
Fehlinterpretation der Fehling‐Probe auf reduzierende Zucker – Von der Beobachtung im Chemieunterricht zur Evidenz gegen die Oxidation der Aldehydgruppe
Authors: Fleischer Holger
Published: October 2016

Die im Chemieunterricht übliche Erklärung der positiven Fehling‐Probe auf reduzierende Zucker – Oxidation der Aldehyd‐ zur Carboxylgruppe – widerspricht der Beobachtung, dass Fructose dabei schneller reagiert als Glucose und Mannose. Primäres Oxidationsprodukt der Reaktion einer Kupfer(II)salz‐Lösung mit Glucose ist nicht die entsprechende Gluconsäure bzw. das Gluconat, sondern Glucoson (2‐Ketoglucose). Sie wird unter den Reaktionsbedingungen durch C−C Bindungsspaltung weiter oxidiert. Diese Tatsache ist seit fast 90 Jahren bekannt, hat sich aber in der Lehr‐ und Schulbuchliteratur nicht durchgesetzt. Für den Chemieunterricht bietet sich hier eine Chance, Erkenntnisgewinnung durch die Falsifizierung einer Hypothese zu vermitteln. Ferner wird erläutert, dass die Bildung von Glucoson aus Glucose nachvollziehbarer zu vermitteln ist als die Bildung von Gluconsäure. Es gibt somit keinen Grund, im Unterricht von der Oxidation der Aldehydgruppe als Ursache der reduzierenden Wirkung von Zuckern auszugehen.
Optimization of Acryloylphenylcarboxamides as Inhibitors of ABCG2 and Comparison with Acryloylphenylcarboxylates
Authors: Kraege Stefanie , Stefan Katja , Köhler Sebastian C. , Wiese Michael
Published: October 2016

ABCG2 belongs to the superfamily of ATP binding cassette (ABC) proteins and is associated with the limited success of anticancer chemotherapy, given its responsibility for the cross‐resistance of tumor cells, known as multidrug resistance (MDR). Several classes of ABCG2 inhibitors were developed for increasing the efficacy of chemotherapy. A series of chalcones coupled to an additional aromatic residue was synthesized and investigated for their inhibition of ABC transporters. In our previous work we determined the preferred position of the linker on the A‐ring to be ortho, and found several substitution patterns at the additional ring that improved potency. In this study we investigated whether a methoxy group that improved the inhibitory activity of chalcones would also be beneficial for the acryloylphenylcarboxamide scaffold. Indeed, this modification led to highly potent ABCG2 inhibitors. To support the hypothesis of a beneficial effect of the amide linker, six acryloylphenylcarboxylates were synthesized and investigated for their inhibitory activity. Replacement of the amide linker with an ester group resulted in decreased inhibition. Molecular modeling showed that the conformational preference of both series differs, thereby explaining the positive effect of the amide linker. Several compounds were characterized in detail by investigating their intrinsic cytotoxicity and capacity to reverse MDR in MTT assays and their effect on vanadate‐sensitive ATPase activity.
Results of a randomized controlled trial to increase cervical cancer screening among rural Latinas
Authors: Thompson Beti , Carosso Elizabeth A. , Jhingan Esther , Wang Lei , Holte Sarah E. , Byrd Theresa L. , Benavides Maria C. , Lopez Cathy , Martinez‐Gutierrez Javiera , Ibarra Genoveva , Gonzalez Virginia J. , Gonzalez Nora E. , Duggan Catherine R.
Published: October 2016

BACKGROUND

Latinas have the highest rates of cervical cancer in the United States and the second highest rate of cervical cancer mortality. One factor in the disparity is the relatively low rate of screening for cervical cancer in this population.

METHODS

Eligible women who were out of adherence with cervical cancer screening (>3 years since their last Papanicolaou [Pap] test) were identified via medical record review by a federally qualified local health center. The effects of a low‐intensity intervention (video delivered to participants' homes; n = 150) and a high‐intensity intervention (video plus a home‐based educational session; n = 146) on cervical cancer screening uptake in comparison with a control arm (usual care; n = 147) were investigated. A cost‐effectiveness analysis of the interventions was conducted: all intervention costs were calculated, and the incremental cost‐effectiveness ratio was computed. Finally, women with positive Pap tests were provided navigation by a community health educator to ensure that they received follow‐up care.

RESULTS

A total of 443 Latinas participated. Seven months after randomization, significantly more women in the high‐intensity arm received a Pap test (53.4%) in comparison with the low‐intensity arm (38.7%; P < .001) and the usual‐care arm (34.0%; P < .01). The incremental cost‐effectiveness ratio for high‐intensity women versus the control group amounted to $4.24. Twelve women had positive Pap tests, which encompassed diagnoses ranging from atypical squamous cells of unknown significance to invasive cancer; these women received navigation for follow‐up care.

CONCLUSIONS

A culturally appropriate, in‐home, promotora‐led educational intervention was successful in increasing cervical cancer screening among Latinas. Cancer 2017;123:666–674. © 2016 American Cancer Society.
Associations between use of the 21‐gene recurrence score assay and chemotherapy regimen selection in a statewide registry
Authors: Henry N. Lynn , Braun Thomas M. , Ali Haythem Y. , Munir Khan , Silver Samuel M. , Gorski David H. , Breslin Tara M. , Griggs Jennifer J.
Published: October 2016

BACKGROUND

The 21‐gene recurrence score (RS) assay predicts response to adjuvant chemotherapy in patients with early‐stage, hormone receptor‐positive, human epidermal growth factor receptor 2 (HER2)‐negative invasive breast cancer, but to the authors' knowledge, the role of the assay in guiding the selection of chemotherapy regimen has not been established. The current study was conducted to examine patterns of use of the RS assay for selecting chemotherapy regimens across a statewide registry from 2006 through 2013.

METHODS

Demographic, pathologic, and treatment data were abstracted from medical records for 16,666 women with breast cancer who were treated at 25 hospital systems across Michigan that were participating in the Michigan Breast Oncology Quality Initiative. Treatment patterns were examined based on the RS assay test result.

RESULTS

Approximately 25% of patients with lymph node‐negative disease who underwent testing with the RS assay and who were treated with chemotherapy received an anthracycline‐based regimen, compared with 49% of patients with lymph node‐negative disease who were treated with chemotherapy and who had not undergone testing with the RS assay. Of those patients with lymph node‐positive disease who underwent testing with the RS assay and who received chemotherapy, 31% received an anthracycline‐based regimen. In comparison, 71% of patients with lymph node‐positive, chemotherapy‐treated disease who did not undergo testing received an anthracycline. From 2006 through 2013, there was a statistically significant decrease in the use of anthracycline‐containing regimens in both patients with lymph node‐negative and lymph node‐positive disease.

CONCLUSIONS

Use of anthracycline‐containing chemotherapy regimens in eligible patients appears to vary with use of the RS assay, despite the lack of evidence supporting use of the assay to guide regimen selection. Results of ongoing prospective trials should help to define the role of the RS assay in this setting. Cancer 2017;123:948–56. © 2016 American Cancer Society.
Molecular Self‐Assembly of Cyclic Dipeptide Derivatives and Their Applications
Authors: Manchineella Shivaprasad , Govindaraju T.
Published: October 2016

Cyclic dipeptides (CDPs) are heterocyclic 2,5‐diketopiperazines with exceptional structural rigidity, enzymatic stability, and biological activity, exhibiting a substantial tendency to take part in intermolecular interactions. Strong intermolecular interactions driven by unique hydrogen bonding patterns render CDPs with a high propensity to undergo molecular self‐assembly. In this Review, the aim is to provide a comprehensive summary of design strategies used to engineer the molecular self‐assembly of CDPs into functional nano‐ and micro‐architectures and molecular gels with potential applications in biomedical and materials engineering fields.
Mechanistic Studies on Ruthenium(II)‐Catalyzed Base‐Free Transfer Hydrogenation Triggered by Roll‐Over Cyclometalation
Authors: Kerner Christian , Lang Johannes , Gaffga Maximilian , Menges Fabian S. , Sun Yu , Niedner‐Schatteburg Gereon , Thiel Werner R.
Published: October 2016

The synthesis of 2‐substituted pyridine–pyrimidine ligands and their complexation with arene ruthenium(II) chloride moieties is reported. Depending on the electronic and steric influences of the ligand, the catalysts undergo CH activation by roll‐over cyclometalation. This process opens up the route to the catalytic transfer hydrogenation of ketones with isopropanol as the hydrogen source under base‐free and mild conditions. Barriers related to the roll‐over cyclometalation process can be determined experimentally by collision‐induced dissociation ESI mass spectrometry. They are supported by DFT calculations and allow the classification of the ligands according to their electronic and steric properties, which is also in accordance with critical bond parameters derived from X‐ray structure data. DFT calculations furthermore reveal that the formation of a ruthenium(II) hydrido species is plausible through β‐hydride elimination from isopropanol.
Time‐aware and energy‐efficient opportunistic routing with residual energy collection in wireless sensor networks
Authors: Luo Haibo , He Minghua , Ruan Zhiqiang
Published: October 2016

In 1‐dimensional queue wireless sensor networks, how to balance end‐to‐end latency and energy consumption is a challenging problem. However, traditional best path routing and existing opportunistic routing protocols do not address them well because relay hop counts are usually much more, and the link appears more unreliable compared with general mesh topology. In this work, we formulate these 2 problems as a multiobjective optimization problem. Specifically, we first classify network packets into types of time tolerant and time critical and introduce a residual energy collection mechanism of neighboring nodes for forwarder set selection. We then propose a time‐aware and energy‐efficient opportunistic routing protocol (TE‐OR) to optimize energy consumption and to reduce latency for time‐critical packets. We evaluate TE‐OR by different parameters and compare it with existing protocols. The performance results show that TE‐OR achieves a trade‐off between energy consumption and time delay and balances energy consumption among nodes while guaranteeing the latency of time‐critical packets is minimized.
Risk of contrast induced nephropathy in diabetic patients affected by critical limb ischemia and diabetic foot ulcers treated by percutaneous transluminal angioplasty of lower limbs
Authors: Meloni Marco , Giurato Laura , Izzo Valentina , Stefanini Matteo , Gandini Roberto , Uccioli Luigi
Published: October 2016

Background

The aim of this study is to evaluate the risk of contrast induced nephropathy (CIN) in diabetic patients with critical limb ischemia (CLI) and foot ulcers (FUs) treated by percutaneous transluminal angioplasty of lower limbs.

Methods

The study group was composed of 145 diabetic patients who underwent a limb salvage protocol because of CLI and FUs between 2012 and 2015. All patients received a prophylactic strategy against the administration of contrast medium. Serum creatinine (SCr) levels were evaluated the day of procedure and for 3 days after. CIN was considered in case of increase of 25% of SCr in comparison to baseline value or an absolute increase of at least 0.5 mg/dl without other interfering factors.

Results

CIN occurred in 9% (14/145) of the cases. In the 1‐year follow‐up SCr returned to baseline values in 10 patients (71 %), 3 patients died (21%), and 1 patient had a major cardiovascular event (7%). No patients required dialysis. The risk was independent of chronic kidney disease stage. The rate of contrast nephropathy in each stage (X = 0.27) was as follows: 3/20 (15%) in stage 2; 3/66 (4.6%) in stage 3, 7/51 (13.7%) in stage 4; and 1/8 (12.5%) in stage 5. At the univariate analysis factors predicting this risk were anemia (HR 95% 2.5 [CI 1.8‐4.2] P = .039) and heart failure (HR 95% 2.6 [CI 2.1‐4.6] P = .038), while any significant variable was found at multivariate analysis.

Conclusions

Peripheral percutaneous transluminal angioplasty in diabetic patients with CLI and FUs can be performed with a good safety factor and a low risk of contrast medium toxicity.