bluuebunny/crossref_metadata_2025 huggingface dataset:
Comparative Clinical Observation of Arthroscopic Microfracture in the Presence and Absence of a Stromal Vascular Fraction Injection for Osteoarthritis
Authors: Nguyen Phu Dinh , Tran Tung Dang-Xuan , Nguyen Huynh Ton-Ngoc , Vu Hieu Trung , Le Phuong Thi-Bich , Phan Nhan Lu-Chinh , Vu Ngoc Bich , Phan Ngoc Kim , Van Pham Phuc
Published: August 2016

Osteoarthritis (OA) is a degenerative cartilage disease that is characterized by a local inflammatory reaction. Consequently, many studies have been performed to identify suitable prevention and treatment interventions. In recent years, both arthroscopic microfracture (AM) and stem cell therapy have been used clinically to treat OA. This study aimed to evaluate the clinical effects of AM in the presence and absence of a stromal vascular fraction (SVF) injection in the management of patients with OA. Thirty patients with grade 2 or 3 (Lawrence scale) OA of the knee participated in this study. Placebo group patients (n = 15) received AM alone; treatment group patients (n = 15) received AM and an adipose tissue-derived SVF injection. The SVF was suspended in platelet-rich plasma (PRP) before injection into the joint. Patient groups were monitored and scored with the Western Ontario and McMaster Universities Arthritis Index (WOMAC), Lysholm, Visual Analog Pain Scale (VAS), and modified Outerbridge classifications before treatment and at 6, 12, and 18 months post-treatment. Bone marrow edema was also assessed at these time points. Patients were evaluated for knee activity (joint motion amplitude) and adverse effects relating to surgery and stem cell injection. Treatment efficacy was significantly different between placebo and treatment groups. All treatment group patients had significantly reduced pain and WOMAC scores, and increased Lysholm and VAS scores compared with the placebo group. These findings suggest that the SVF/PRP injection efficiently improved OA for 18 months after treatment. This study will be continuously monitored for additional 24 months.
Multimodality, Synaesthesia and Intersemiotic Translation
Authors: Maier Carmen Daniela
Published: August 2016

No abstract.
The Ki-67 and RepoMan mitotic phosphatases assemble via an identical, yet novel mechanism
Authors: Kumar Ganesan Senthil , Gokhan Ezgi , De Munter Sofie , Bollen Mathieu , Vagnarelli Paola , Peti Wolfgang , Page Rebecca
Published: August 2016

Ki-67 and RepoMan have key roles during mitotic exit. Previously, we showed that Ki-67 organizes the mitotic chromosome periphery and recruits protein phosphatase 1 (PP1) to chromatin at anaphase onset, in a similar manner as RepoMan (Booth et al., 2014). Here we show how Ki-67 and RepoMan form mitotic exit phosphatases by recruiting PP1, how they distinguish between distinct PP1 isoforms and how the assembly of these two holoenzymes are dynamically regulated by Aurora B kinase during mitosis. Unexpectedly, our data also reveal that Ki-67 and RepoMan bind PP1 using an identical, yet novel mechanism, interacting with a PP1 pocket that is engaged only by these two PP1 regulators. These findings not only show how two distinct mitotic exit phosphatases are recruited to their substrates, but also provide immediate opportunities for the design of novel cancer therapeutics that selectively target the Ki-67:PP1 and RepoMan:PP1 holoenzymes.
Proton currents constrain structural models of voltage sensor activation
Authors: Randolph Aaron L , Mokrab Younes , Bennett Ashley L , Sansom Mark SP , Ramsey Ian Scott
Published: August 2016

The Hv1 proton channel is evidently unique among voltage sensor domain proteins in mediating an intrinsic ‘aqueous’ H+ conductance (GAQ). Mutation of a highly conserved ‘gating charge’ residue in the S4 helix (R1H) confers a resting-state H+ ‘shuttle’ conductance (GSH) in VGCs and Ci VSP, and we now report that R1H is sufficient to reconstitute GSH in Hv1 without abrogating GAQ. Second-site mutations in S3 (D185A/H) and S4 (N4R) experimentally separate GSH and GAQ gating, which report thermodynamically distinct initial and final steps, respectively, in the Hv1 activation pathway. The effects of Hv1 mutations on GSH and GAQ are used to constrain the positions of key side chains in resting- and activated-state VS model structures, providing new insights into the structural basis of VS activation and H+ transfer mechanisms in Hv1.
Osteology of the Late Triassic aetosaurScutarx deltatylus(Archosauria: Pseudosuchia)
Authors: Parker William G.
Published: August 2016

Aetosaurians are some of the most common fossils collected from the Upper Triassic Chinle Formation of Arizona, especially at the Petrified Forest National Park (PEFO). Aetosaurians collected from lower levels of the park includeDesmatosuchus spurensis,Paratypothorax,Adamanasuchus eisenhardtae,Calyptosuchus wellesi, andScutarx deltatylus. Four partial skeletons collected from the park between 2002 and 2009 represent the holotype and referred specimens ofScutarx deltatylus. These specimens include much of the carapace, as well as the vertebral column, and shoulder and pelvic girdles, and a new naming convention proposed for osteoderms descriptions better differentiates portions of the carapace and ventral armor. A partial skull from the holotype specimen represents the first aetosaur skull recovered and described from Arizona since the 1930s. The key morphological feature distinguishingScutarx deltatylusis the presence of a prominent, triangular boss located in the posteromedial corner of the dorsal surface of the dorsal paramedian osteoderms.Scutarx deltatyluscan be distinguished from closely related formsCalyptosuchus wellesiandAdamanasuchus eisenhardtaenot only morphologically, but also stratigraphically. Thus,Scutarx deltatylusis potentially an index taxon for the upper part of the Adamanian biozone.
The Influence of Neighborhood Aesthetics, Safety, and Social Cohesion on Perceived Stress in Disadvantaged Communities
Authors: Henderson Heather , Child Stephanie , Moore Spencer , Moore Justin B. , Kaczynski Andrew T.
Published: August 2016

Limited research has explored how specific elements of physical and social environments influence mental health indicators such as perceived stress, or whether such associations are moderated by gender. This study examined the relationship between selected neighborhood characteristics and perceived stress levels within a primarily low‐income, older, African‐American population in a mid‐sized city in the Southeastern U.S. Residents (n = 394; mean age=55.3 years, 70.9% female, 89.3% African American) from eight historically disadvantaged neighborhoods completed surveys measuring perceptions of neighborhood safety, social cohesion, aesthetics, and stress. Multivariate linear regression models examined the association between each of the three neighborhood characteristics and perceived stress. Greater perceived safety, improved neighborhood aesthetics, and social cohesion were significantly associated with lower perceived stress. These associations were not moderated by gender. These findings suggest that improving social attributes of neighborhoods may have positive impacts on stress and related benefits for population health. Future research should examine how neighborhood characteristics influence stress over time.
Peripheral blood blast clearance is an independent prognostic factor for survival and response to acute myeloid leukemia induction chemotherapy
Authors: Short Nicholas J. , Benton Christopher B. , Chen Hsiang‐Chun , Qiu Peng , Gu Lisa , Pierce Sherry , Brandt Mark , Maiti Abhishek , Min Taejin L. , Naqvi Kiran , Quintas‐Cardama Alfonso , Konopleva Marina , Kadia Tapan , Cortes Jorge , Garcia‐Manero Guillermo , Ravandi Farhad , Jabbour Elias , Kantarjian Hagop , Andreeff Michael
Published: August 2016

In patients with acute myeloid leukemia (AML), rapid reduction of circulating blasts with induction chemotherapy may serve as an in vivo marker of chemosensitivity. We performed a retrospective analysis of 363 patients with untreated AML who received induction chemotherapy in order to determine the relationship between day of blast disappearance (DOBD) and complete remission (CR) rates, event‐free survival (EFS), and overall survival (OS). DOBD ≤ 5 vs. >5 was identified as the most discriminating cutoff for OS. DOBD > 5 was observed in 35 patients (9.6%). The CR rate for patients with DOBD ≤ 5 vs. >5 was 74.0 and 28.6%, median EFS was 9.4 and 1.8 months, and median OS was 17.1 and 5.8 months, respectively (P < 0.001 for all). DOBD > 5 was independently associated with a lower CR rate and shorter EFS and OS (P < 0.001 for all). DOBD > 5 retained prognostic significance for EFS and OS when patients were stratified by cytogenetic risk group, de novo vs. secondary or therapy‐related AML, European LeukemiaNet‐based risk groups, and whether CR was achieved. We propose DOBD > 5 as a simple and early marker of disease resistance that identifies patients with poor prognosis who otherwise may not be identified with existing risk stratification systems. Am. J. Hematol. 91:1221–1226, 2016. © 2016 Wiley Periodicals, Inc.
GaCl3‐Mediated Reactions of Donor–Acceptor Cyclopropanes with Aromatic Aldehydes
Authors: Borisov Denis D. , Novikov Roman A. , Tomilov Yury V.
Published: August 2016

A new strategy for cascade assembly of substituted indenes and polycyclic lactones based on reactions of donor–acceptor cyclopropanes and styrylmalonates with aromatic aldehydes in the presence of GaCl3 has been developed. The use of GaCl3 makes it possible to principally change the direction of the reaction known in this series of substrates and to perform the process in a multicomponent version. Generation of formal 1,2‐zwitterionic intermediates owing to complexation of dicarboxylate groups with GaCl3 is the driving force of the reactions discovered. This method makes it possible to assemble indenylmalonates or indano[1′,2′:2,3]indano[2,1‐b]furan‐2‐ones in one synthetic stage from readily available starting compounds with high regio‐ and diastereoselectivity. A mechanism of the reactions has been suggested using the 18O label in benzaldehyde.
Evaluierung neuer Reaktionen zur Steuerung der Wirkstoff‐Forschung: ein Eignungstest
Authors: Foley Daniel J. , Nelson Adam , Marsden Stephen P.
Published: August 2016

Mit der Verbesserung unserer Kenntnisse zur Bedeutung bestimmter Moleküleigenschaften bei Anwendungen im Rahmen der Wirkstoffsuche wird das Ausmaß immer klarer, in dem veröffentlichte Synthesemethoden erwünschten Kriterien genügen (oder nicht genügen). Wir beschreiben hier, wie die Anwendung einfacher (und in vielen Fällen frei verfügbarer) Rechenprogramme genutzt werden kann, um ein semiquantitatives Verständnis des Potenzials von neuen Methoden in der Wirkstoff‐Forschung zu entwickeln. Diese Analyse kann sich unter anderem auf die Planung verbesserter Studien zum Substratspektrum auswirken, die Priorisierung von bestimmten Beispielstrukturen für die Synthese leiten und Ansprüche für potenzielle künftige Anwendungen von neuen Methoden begründen.
Organic‐Stabilizer‐Free Polyol Synthesis of Silver Nanowires for Electrode Applications
Authors: Sim Hwansu , Bok Shingyu , Kim Bongsung , Kim Minha , Lim Guh‐Hwan , Cho Sung Min , Lim Byungkwon
Published: August 2016

The polyol reduction of a Ag precursor in the presence of an organic stabilizer, such as poly(vinylpyrrolidone), is a widely used method for the production of Ag nanowires (NWs). However, organic capping molecules introduce insulating layers around each NW. Herein we demonstrate that Ag NWs can be produced in high yield without any organic stabilizers simply by introducing trace amounts of NaCl and Fe(NO3)3 during low‐temperature polyol synthesis. The heterogeneous nucleation and growth of Ag NWs on initially formed AgCl particles, combined with oxidative etching of unwanted Ag nanoparticles, resulted in the selective formation of long NWs with an average length of about 40 μm in the absence of a capping or stabilizing effect provided by surface‐adsorbing molecules. These organic‐stabilizer‐free Ag NWs were directly used for the fabrication of high‐performance transparent or stretchable electrodes without a complicated process for the removal of capping molecules from the NW surface.
Targeted Delivery and Sustained Antitumor Activity of Triptolide through Glucose Conjugation
Authors: He Qing‐Li , Minn Il , Wang Qiaoling , Xu Peng , Head Sarah A. , Datan Emmanuel , Yu Biao , Pomper Martin G. , Liu Jun O.
Published: August 2016

Triptolide, a key ingredient from the traditional Chinese medicinal plant thunder god vine, which has been used to treat inflammation and autoimmune diseases for centuries, has been shown to be an irreversible inhibitor of the XPB subunit of the transcription factor TFIIH and initiation of RNA polymerase II mediated transcription. The clinical development of triptolide over the past two decades has been limited by its toxicity and low water solubility. Herein, we report the development of a glucose conjugate of triptolide, named glutriptolide, which was intended to target tumor cells overexpressing glucose transporters selectively. Glutriptolide did not inhibit XPB activity in vitro but demonstrated significantly higher cytotoxicity against tumor cells over normal cells with greater water solubility than triptolide. Furthermore, it exhibited remarkable tumor control in vivo, which is likely due to sustained stepwise release of active triptolide within cancer cells. These findings indicate that glutriptolide may serve as a promising lead for developing a new mechanistic class of anticancer drugs.
Hochaktive und selektive Mangankatalysatoren zur Hydrierung von C=O‐Bindungen – die Bedeutung des mehrzähnigen Liganden, der Coliganden und der Oxidationsstufe
Authors: Kallmeier Fabian , Irrgang Torsten , Dietel Thomas , Kempe Rhett
Published: August 2016

Der Ersatz teurer Edelmetalle durch in der Erde reichlich vorkommende Übergangsmetalle ist ein zentrales Thema in der Katalyse. Hier wird ein hochaktiver und selektiver, homogener, Mn‐basierter Hydrierkatalysator von C=O‐Bindungen vorgestellt. Der Katalysator verfügt über ein breites Substratspektrum und ist in der Lage, Aryl‐alkyl‐, Diaryl‐, Dialkyl‐ und Cycloalkylketone sowie Aldehyde zu hydrieren. Eine sehr gute Verträglichkeit mit funktionellen Gruppen, einschließlich der quantitativen und selektiven Hydrierung eines Ketons in Gegenwart eines nicht abgeschirmten Olefins, wird beobachtet. In der Mn‐Hydrierkatalyse ist die Kombination aus mehrzähnigem Liganden, Oxidationszustand des Metalls und richtigem Hilfsliganden wahrscheinlich entscheidend für eine hohe Aktivität. Diese Beobachtung unterstreicht einen Vorteil von Homogenkatalysatoren in der 3d‐Metallkatalyse. Für Koordinationsverbindungen ist eine Feinabstimmung einer komplexen Koordinationsumgebung leichter durchführbar als für Enzyme und/oder Heterogenkatalysatoren.
Nickel‐Catalyzed Enantioselective Reductive Amination of Ketones with Both Arylamines and Benzhydrazide
Authors: Yang Peng , Lim Li Hui , Chuanprasit Pratanphorn , Hirao Hajime , Zhou Jianrong (Steve)
Published: August 2016

An asymmetric reductive amination of ketones using both arylamines and benzhydrazide in the presence of nickel catalysts was developed. A one‐pot synthesis of tetrahydroquinoxalines was also developed starting directly from α‐ketoaldehydes and 1,2‐diaminobenzene. Formic acid was used as a safe and economic surrogate for high‐pressure hydrogen gas. Strongly σ‐donating bis(alkylphosphine)s are crucial ancillary ligands for both stereoselective hydride insertion and decarboxylation of the formate.
Evaluating New Chemistry to Drive Molecular Discovery: Fit for Purpose?
Authors: Foley Daniel J. , Nelson Adam , Marsden Stephen P.
Published: August 2016

As our understanding of the impact of specific molecular properties on applications in discovery‐based disciplines improves, the extent to which published synthetic methods meet (or do not meet) desirable criteria is ever clearer. Herein, we show how the application of simple (and in many cases freely available) computational tools can be used to develop a semiquantitative understanding of the potential of new methods to support molecular discovery. This analysis can, among other things, inform the design of improved substrate scoping studies; direct the prioritization of specific exemplar structures for synthesis; and substantiate claims of potential future applications for new methods.
Highly Active and Selective Manganese C=O Bond Hydrogenation Catalysts: The Importance of the Multidentate Ligand, the Ancillary Ligands, and the Oxidation State
Authors: Kallmeier Fabian , Irrgang Torsten , Dietel Thomas , Kempe Rhett
Published: August 2016

The replacement of expensive noble metals by earth‐abundant transition metals is a central topic in catalysis. Herein, we introduce a highly active and selective homogeneous manganese‐based C=O bond hydrogenation catalyst. Our catalyst has a broad substrate scope, it is able to hydrogenate aryl–alkyl, diaryl, dialkyl, and cycloalkyl ketones as well as aldehydes. A very good functional group tolerance including the quantitative and selective hydrogenation of a ketone in the presence of a non‐shielded olefin is observed. In Mn hydrogenation catalysis, the combination of the multidentate ligand, the oxidation state of the metal, and the choice of the right ancillary ligand is crucial for high activity. This observation emphasizes an advantage and the importance of homogeneous catalysts in 3d‐metal catalysis. For coordination compounds, fine‐tuning of a complex coordination environment is easily accomplished in comparison to enzyme and/or heterogeneous catalysts.
Influence of rubber content on mechanical, thermal, and morphological behavior of natural rubber toughened poly(lactic acid)–multiwalled carbon nanotube nanocomposites
Authors: Mat Desa Mohd Shaiful Zaidi , Hassan Azman , Arsad Agus , Arjmandi Reza , Mohammad Nor Nisa Balqis
Published: August 2016

The effects of natural rubber (NR) on the mechanical, thermal, and morphological properties of multiwalled carbon nanotube (CNT) reinforced poly(lactic acid) (PLA) nanocomposites prepared by melt blending were investigated. A PLA/NR blend and PLA/CNT nanocomposites were also produced for comparison. The tensile strength and Young's modulus of PLA/CNT nanocomposites improved significantly, whereas the impact strength decreased compared to neat PLA. The incorporation of NR into PLA/CNT significantly improved the impact strength and elongation at break of the nanocomposites, which showed approximately 200% and 850% increases at 20 wt % NR, respectively. However, the tensile strength and Young's modulus of PLA/NR/CNT nanocomposites decreased compared to PLA/CNT nanocomposites. The morphology analysis showed the homogeneous dispersion of NR particles in PLA/NR/CNT nanocomposites, while CNTs preferentially reside in the NR phase rather than the PLA matrix. In addition, the incorporation of NR into PLA/CNT lowered the thermal stability and glass‐transition temperature of the nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44344.
Surface modification of microcrystalline cellulose (MCC) and its application in LDPE‐based composites
Authors: Chartrand Ariane , Lavoie Jean‐Michel , Huneault Michel A.
Published: August 2016

Microcrystalline cellulose (MCC) was modified by grafting onto its surface ferulic acid, methacryloyl chloride and oleoyl chloride. The efficacy of the chemical modification was confirmed by X‐ray photoelectron spectroscopy. In addition, the size distribution of the cellulosic particles was investigated by optical microscopy and laser granulometry and its hydrophobicity was evaluated using a contact angle method. Finally, to investigate the affinity of modified MCC with a nonpolar polymer and to assess its potential as a biobased reinforcing filler, the modified MCC was compounded into low‐density polyethylene. An organic peroxide, dicumyl peroxide, was added at selected formulations to see if it could further enhance mechanical bonding between the polymer and the particulates. The dispersion was assessed by scanning electron microscopy. Mechanical properties were investigated through tensile testing while the melt rheology of the composites was monitored by small angle oscillatory shear rheology. The acylation modification of the MCC improved the dispersion within LDPE and enhanced the mechanical properties of the composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 44348.
Chemoselective, Substrate‐directed Fluorination of Functionalized Cyclopentane β‐Amino Acids
Authors: Kiss Loránd , Nonn Melinda , Sillanpää Reijo , Haukka Matti , Fustero Santos , Fülöp Ferenc
Published: August 2016

This work describes a substrate‐directed fluorination of some highly functionalized cyclopentane derivatives. The cyclic products incorporating CH2F or CHF2 moieties in their structure have been synthesized from diexo‐ or diendo‐norbornene β‐amino acids following a stereocontrolled strategy. The synthetic study was based on an oxidative transformation of the ring carbon–carbon double bond of the norbornene β‐amino acids, followed by transformation of the resulted „all cis“ and „trans“ diformyl intermediates by fluorination with „chemodifferentiation“.
Microscale temperature and SAR measurements in cell monolayer models exposed to millimeter waves
Authors: Zhadobov Maxim , Alekseev Stanislav I. , Sauleau Ronan , Le Page Yann , Le Dréan Yves , Fesenko Evgeny E.
Published: August 2016

Due to shallow penetration of millimeter waves (MMW) and convection in liquid medium surrounding cells, the problem of accurate assessment of local MMW heating in in vitro experiments remains unsolved. Conventional dosimetric MMW techniques, such as infrared imaging or fiber optic (FO) sensors, face several inherent limits. Here we propose a methodology for accurate local temperature measurement and subsequent specific absorption rate (SAR) retrieval using microscale thermocouples (TC). SAR was retrieved by fitting the measured initial temperature rise to the numerical solution of an equivalent thermal model. It was found that the accuracy of temperature measurement depends on thermosensor size, that is, the smaller TC, the more accurate the temperature measurement. SAR determined using TC with lead diameters of 25 and 75 μm demonstrated 98.5% and 80.4% match with computed SAR, respectively. However, both TC provided the same temperature rises in long run (> 10 min). FO probe failed to measure adequately local heating both for short and long exposures due to the relatively large size of the probe sensor (400 μm) and time constant (0.6 s). Calculated SAR in the cell monolayer was almost two times lower than that in the surrounding liquid. It was shown that the impact of the cell monolayer on heating due to its small thickness (5 to 10 μm) can be considered as negligible. Moreover, we demonstrated the possibility of accurate measurement of MMW‐induced thermal pulses (up to 10 °C) using 25 μm TC. Bioelectromagnetics. 38:11–21, 2017. © 2016 Wiley Periodicals, Inc.
Enhanced noradrenergic axon regeneration into schwann cell‐filled PVDF‐TrFE conduits after complete spinal cord transection
Authors: Lee Yee‐Shuan , Wu Siliang , Arinzeh Treena Livingston , Bunge Mary Bartlett
Published: August 2016

Schwann cell (SC) transplantation has been utilized for spinal cord repair and demonstrated to be a promising therapeutic strategy. In this study, we investigated the feasibility of combining SC transplantation with novel conduits to bridge the completely transected adult rat spinal cord. This is the first and initial study to evaluate the potential of using a fibrous piezoelectric polyvinylidene fluoride trifluoroethylene (PVDF‐TrFE) conduit with SCs for spinal cord repair. PVDF‐TrFE has been shown to enhance neurite growth in vitro and peripheral nerve repair in vivo. In this study, SCs adhered and proliferated when seeded onto PVDF‐TrFE scaffolds in vitro. SCs and PVDF‐TrFE conduits, consisting of random or aligned fibrous inner walls, were transplanted into transected rat spinal cords for 3 weeks to examine early repair. Glial fibrillary acidic protein (GFAP)+astrocyte processes and GFP (green fluorescent protein)‐SCs were interdigitated at both rostral and caudal spinal cord/SC transplant interfaces in both types of conduits, indicative of permissivity to axon growth. More noradrenergic/DβH+(dopamine‐beta‐hydroxylase) brainstem axons regenerated across the transplant when greater numbers of GFAP+astrocyte processes were present. Aligned conduits promoted extension of DβH+axons and GFAP+processes farther into the transplant than random conduits. Sensory CGRP+(calcitonin gene‐related peptide) axons were present at the caudal interface. Blood vessels formed throughout the transplant in both conduits. This study demonstrates that PVDF‐TrFE conduits harboring SCs are promising for spinal cord repair and deserve further investigation. Biotechnol. Bioeng. 2017;114: 444–456. © 2016 Wiley Periodicals, Inc.
Novel Solid‐phase and Solution‐phase Synthetic Methods for Trisubstituted Thieno[3,2‐d]pyrimidine Derivatives
Authors: Jeon Moon‐Kook , Kim Jung‐Gyu , Lee Duck‐Hyung
Published: August 2016

The coupling of 7‐aryl‐3,4‐dihydro‐4‐oxothieno[3,2‐d]pyrimidine‐2‐carboxylic acid with a primary alkylamine‐loaded acid‐sensitive methoxy benzaldehyde (AMEBA) resin, a benzotriazol‐1‐yloxytris(dimethylamino)phosphonium hexafluorophosphate (BOP)‐mediated amination reaction, and cleavage from the solid support yielded N‐alkyl‐4‐(alkylamino)‐7‐arylthieno[3,2‐d]pyrimidine‐2‐carboxamide derivatives. The progress of the reactions on solid phase was monitored through attenuated total reflectance‐FTIR spectroscopy and was compared with representative solution‐phase surrogates. Additionally, N‐acylation (acid chloride, InF3
, CH3CN, room temperature) and cyclization (DBN, 1,4‐dioxane, 80°C) of a 3‐amino‐4‐(4‐t‐butoxycarbonylphenyl)thiophene‐2‐carboxamide intermediate under previously unreported conditions provided 2‐substituted thieno[3,2‐d]pyrimidin‐4(3H)‐one derivatives, which were subsequently converted to 2‐substituted 4‐alkylamino‐7‐[4‐(alkylaminocarbonyl)phenyl]thieno[3,2‐d]pyrimidine derivatives through a reaction sequence consisting of a BOP‐mediated amination reaction, t‐butyl deprotection, and amide formation.
Synthesis of Benzoisoxazole Derivatives and Evaluation of Inhibitory Potency against Cholinesterase for Alzheimer's Disease Therapeutics
Authors: Park Jung‐Youl , Shin Sujeong , Kim Jae‐kwan , Park Kyoung Chan , Park Jeong Ho
Published: August 2016

To improve Alzheimer's disease (AD) therapeutics, we have designed and synthesized new benzoisoxazole derivatives that are potent inhibitors of cholinesterase (acetylcholinesterase [AChE] and butyrylcholinesterase [BuChE]). Since inhibition of cholinesterase (ChE) is still considered to be one of the most effective ways of treating AD patients, many new classes of ChE inhibitors have been synthesized. To identify a new type of cholinergic drug, the benzoisoxazole moiety which is the pharmacophore moiety of Risperidone was coupled with natural antioxidants. Some benzoisoxazole derivatives (26–28 and 30) were found to effectively inhibit BuChE (IC50 < 20 μM), and some (20 and 26–28) to moderately inhibit AChE (IC50 < 100 μM). Furthermore, compound 28 showed better inhibitory activity against BuChE (IC50 = 0.72 ± 0.11 μM) than galantamine (IC50 = 8.4 ± 0.1 μM). The new benzoisoxazole derivatives showing BuChE inhibitory activity represent a new class of ChE inhibitor and can be used to create novel compound derivative drugs for treating AD patients.
Determination of eurycomanone in rat plasma using hydrophilic interaction liquid chromatography–tandem mass spectrometry for pharmacokinetic study
Authors: Rehman Shaheed Ur , Choi Min Sun , Han Young Min , Kim In Sook , Kim Seung Hyun , Piao Xiang‐Lan , Yoo Hye Hyun
Published: August 2016

In this study, a rapid, sensitive, and reliable hydrophilic interaction liquid chromatography–tandem mass spectrometry (HILIC‐MS/MS) method for the determination of eurycomanone in rat plasma was developed and validated. Plasma samples were pretreated with a protein precipitation method and quercitrin was used as an internal standard (IS). A HILIC silica column (2.1 × 100 mm, 3 μm) was used for hydrophilic‐based chromatographic separation, using the mobile phase of 0.1% formic acid with acetonitrile in gradient elution at a flow rate of 0.25 mL/min. Precursor–product ion pairs for multiple‐reaction monitoring were m/z 409.1 → 391.0 for eurycomanone and m/z 449.1 → 303.0 for IS. The linear range was 2–120 ng/mL. The intra‐ and inter‐day accuracies were between 95.5 and 103.4% with a precision of <4.2%. The developed method was successfully applied to the pharmacokinetic analysis of eurycomanone in rat plasma after oral dosing with pure compound and E. longifolia extract. The Cmax and AUC0–t, respectively, were 40.43 ± 16.08 ng/mL and 161.09 ± 37.63 ng h/mL for 10 mg/kg eurycomanone, and 9.90 ± 3.97 ng/mL and 37.15 ± 6.80 ng h/mL for E. longifolia extract (2 mg/kg as eurycomanone). The pharmacokinetic results were comparable with each other, based on the dose as eurycomanone.
Photocatalytic Decontamination of Wastewater Containing Organic Dyes by Metal–Organic Frameworks and their Derivatives
Authors: Wu Zhibin , Yuan Xingzhong , Zhang Jin , Wang Hou , Jiang Longbo , Zeng Guangming
Published: August 2016

Photoactive metal–organic frameworks (MOFs) have lately emerged as a class of crystalline porous materials, which provides an advanced platform to develop catalysts for the photocatalytic decolorization of wastewater. Controllable integration of pure MOFs into other active materials creates fabrication protocols for new multifunctional hybrids with superior photocatalytic properties for dye degradation into individual components, and the calcination of transition‐metal MOF precursors affords a convenient and practical route for preparation of nanosized photocatalysts with novel structures and good purity. Although the application of pure MOFs for organic pollutant decomposition has been reviewed previously, there have been significant advances in diverse MOF‐based composites and their derivatives for dye degradation, which have rarely been reviewed. This review aims to fill this gap and discuss the various influencing factors, the reaction kinetics, and mechanisms of dye degradation, considering the period from 2014 to 2016. Finally, the challenges and outlooks for dye decomposition by MOF‐based materials are suggested.
Carbon Self‐Doping Induced Activation of n–π* Electronic Transitions of g‐C3N4 Nanosheets for Efficient Photocatalytic H2 Evolution
Authors: Su Feng‐Yun , Xu Cheng‐Qun , Yu Yu‐Xiang , Zhang Wei‐De
Published: August 2016

This paper reports a facile one‐pot synthesis strategy to prepare carbon self‐doped g‐C3N4 (C‐g‐C3N4) nanosheets by using supramolecular networks consisting of cyanuric acid, ethylene glycol (EG), and melamine (CEM) bonded through hydrogen bonding as the thermal polycondensation precursor, in which EG serves as a solvent for cyanuric acid and melamine, and as a source of the doped carbon simultaneously. The threedimensional structure of CEM resulted in the distortion of C‐g‐C3N4, which is capable of motivating the n–π* electronic transition involving the N lone pairs to give an additional absorption region from 450 to 600 nm. The hydrogen evolution rate of C‐g‐C3N4 reaches 73.09 μmol h−1, which is about 15 times of that over the g‐C3N4 obtained from direct thermal polycondensation of melamine owing to its extended light harvesting and faster separation of photogenerated electrons and holes.
A Heterogeneous Photocatalytic Hydrogen Evolution Dyad: [(tpy
Authors: Zhao Weiwei , Huang Yi , Liu Yang , Cao Liming , Zhang Fang , Guo Yamei , Zhang Bin
Published: August 2016

The development of an artificial heterogeneous dyad by covalently anchoring a hydrogen‐evolving molecule catalyst to a semiconductor photosensitizer through a bridging ligand is highly challenging. Herein, we adopt the inorganic–organic hybrid CdS–DETA NSs (DETA=diethylenetriamine, NSs=nanosheets) as initial matrix to successfully construct an imine bond (‐CH=N‐) linked heterogeneous dyad [CdS−N=CH−Ni] through the condensation reaction between the amino groups of CdS–DETA and the aldehyde group of the water reduction molecular catalyst, [(tpy‐CHO)2Ni]Cl2 (tpy=terpyridine). The [CdS−N=CH−Ni] enables a turnover number (TON) of about 43 815 versus Ni catalysts and an initial turnover frequency (TOF) of approximately 0.47 s−1 in 26 h under visible‐light irradiation (λ>420 nm). The apparent quantum yield (AQY) reaches (9.9±0.8) % at 420 nm. Under optical conditions, the [CdS−N=CH−Ni] can achieve a considerable amount of hydrogen production, 507.1±27 μmol H2 for 6 h, which is 1.27 times that generated from the mechanically mixed system of CdS–DETA NSs and [(tpy‐CH=NR)2Ni]Cl2 (III) under otherwise identical conditions. Furthermore, its TON value based on Ni species is also higher than that of the mixed system of CdS–DETA and III.
Surface Chemistry of tert‐Butylphosphine (TBP) on Si(001) in the Nucleation Phase of Thin‐Film Growth
Authors: Stegmüller Andreas , Werner Katharina , Reutzel Marcel , Beyer Andreas , Rosenow Phil , Höfer Ulrich , Stolz Wolfgang , Volz Kerstin , Dürr Michael , Tonner Ralf
Published: August 2016

We combine density functional theory calculations and scanning tunneling microscopy investigations to identify the relevant chemical species and reactions in the nucleation phase of chemical vapor deposition. tert‐Butylphosphine (TBP) was deposited on a silicon substrate under conditions typical for surface functionalization and growth of semiconductor materials. On the activated hydrogen‐covered surface H/Si(001) it forms a strong covalent P−Si bond without loss of the tert‐butyl group. Calculations show that site preference for multiple adsorption of TBP is influenced by steric repulsion of the adsorbate's bulky substituent. STM imaging furthermore revealed an anisotropic distribution of TBP with a preference for adsorption perpendicular to the surface dimer rows. The adsorption patterns found can be understood by a mechanism invoking stabilization of surface hydrogen vacancies through electron donation by an adsorbate. The now improved understanding of nucleation in thin‐film growth may help to optimize molecular precursors and experimental conditions and will ultimately lead to higher quality materials.
α‐Aminoxy Oligopeptides: Synthesis, Secondary Structure, and Cytotoxicity of a New Class of Anticancer Foldamers
Authors: Diedrich Daniela , Moita Ana J. Rodrigues , Rüther Anja , Frieg Benedikt , Reiss Guido J. , Hoeppner Astrid , Kurz Thomas , Gohlke Holger , Lüdeke Steffen , Kassack Matthias U. , Hansen Finn K.
Published: August 2016

α‐Aminoxy peptides are peptidomimetic foldamers with high proteolytic and conformational stability. To gain an improved synthetic access to α‐aminoxy oligopeptides we used a straightforward combination of solution‐ and solid‐phase‐supported methods and obtained oligomers that showed a remarkable anticancer activity against a panel of cancer cell lines. We solved the first X‐ray crystal structure of an α‐aminoxy peptide with multiple turns around the helical axis. The crystal structure revealed a right‐handed 28‐helical conformation with precisely two residues per turn and a helical pitch of 5.8 Å. By 2D ROESY experiments, molecular dynamics simulations, and CD spectroscopy we were able to identify the 28‐helix as the predominant conformation in organic solvents. In aqueous solution, the α‐aminoxy peptides exist in the 28‐helical conformation at acidic pH, but exhibit remarkable changes in the secondary structure with increasing pH. The most cytotoxic α‐aminoxy peptides have an increased propensity to take up a 28‐helical conformation in the presence of a model membrane. This indicates a correlation between the 28‐helical conformation and the membranolytic activity observed in mode of action studies, thereby providing novel insights in the folding properties and the biological activity of α‐aminoxy peptides.
Oxidation Chemistry of Inorganic Benzene Complexes
Authors: Fleischmann Martin , Dielmann Fabian , Balázs Gábor , Scheer Manfred
Published: August 2016

The oxidation of the 28 VE cyclo‐E6 triple‐decker complexes [(CpRMo)2(μ,η6:η6‐E6)] (E=P, CpR=Cp(2 a), Cp*(2 b), CpBn(2 c)=C5(CH2Ph)5; E=As, CpR=Cp*(3)) by Cu+ or Ag+ leads to cationic 27 VE complexes that retain their general triple‐decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single‐crystal X‐ray diffraction. The cyclo‐E6 middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ‐system of the cyclo‐E6 ligands in 2 a–3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization.
A Photoswitchable Fluorophore for the Real‐Time Monitoring of Dynamic Events in Living Organisms
Authors: Zhang Yang , Tang Sicheng , Sansalone Lorenzo , Baker James D. , Raymo Françisco M.
Published: August 2016

This study reports the synthesis of a photoactivatable fluorophore with optimal photochemical and photophysical properties for the real‐time tracking of motion in vivo. The photoactivation mechanism designed into this particular compound permits the conversion of an emissive reactant into an emissive product with resolved fluorescence, under mild illumination conditions that are impossible to replicate with conventional switching schemes based on bleaching. Indeed, the supramolecular delivery of these photoswitchable probes into the cellular blastoderm of Drosophila melanogaster embryos allows the real‐time visualization of translocating molecules with no detrimental effects on the developing organisms. Thus, this innovative mechanism for fluorescence photoactivation can evolve into a general chemical tool to monitor dynamic processes in living biological specimens.
Rhodium‐Catalyzed Enantioselective Intramolecular Hydroacylation of Trisubstituted Alkenes
Authors: Johnson Kirsten F. , Schneider Eugene A. , Schumacher Brian P. , Ellern Arkady , Scanlon Joseph D. , Stanley Levi M.
Published: August 2016

We report the first examples of transition metal‐catalyzed enantioselective alkene hydroacylations with 1,1,2‐trisubstituted alkenes. DFT and mechanistic studies are consistent with a reaction pathway for these rhodium‐catalyzed processes including intramolecular alkene hydroacylation and α‐epimerization to generate highly enantioenriched, polycyclic architectures. This reaction sequence enables the hydroacylation of 2‐(cyclohex‐1‐en‐1‐yl)benzaldehydes to form hexahydro‐9H‐fluoren‐9‐ones in moderate to high yields (68–91 %) with high enantioselectivities (up to 99 % ee) and diastereoselectivities (typically >20:1).
MgII‐Catalyzed Desymmetrization Reaction of meso‐Aziridines with Hydroxylamines: Synthesis of Novel Chiral 1,2‐Diamine Skeletons
Authors: Li Dan , Yang Dongxu , Wang Linqing , Liu Xihong , Jiang Xianxing , Wang Rui
Published: August 2016

A MgII‐catalyzed desymmetrization reaction of meso‐aziridines with hydroxylamines has been disclosed for the first time. A series of novel chiral 1,2‐diamine skeletons were obtained in good yields and enantioselectivities. The reaction employed magnesium catalysis generated in situ from a simple oxazoline‐OH chiral ligand. Obviously, the diverse structures of the obtained chiral 1,2‐diamine compounds could allow them to be potential chiral ligands in future catalytic asymmetric synthesis studies.
Unusual Reactivity of Sodium Tetramesityltetraphosphanediide towards Cyclohexyl Isocyanide
Authors: Adhikari Anup K. , Sárosi Menyhárt B. , Grell Toni , Lönnecke Peter , Hey‐Hawkins Evamarie
Published: August 2016

The reaction of [Na2(thf)4(P4Mes4)] (Mes=2,4,6‐Me3C6H2) with cyclohexyl isocyanide (2:5) resulted in the formation of the heterocyclic N‐(tetramesityltetraphosphacyclopentylidene)cyclohexylamine [cyclo‐{P4Mes4C(NCy)}] (2) (30–35 %), the unusual 1,3,5‐triphospha‐1,4‐pentadiene (3) (40–45 %), and small amounts of the dimeric iminomethylidenephosphane cyclo‐{PMesC(NCy)}2 (4). With catalytic amounts of AgBF4, 2 was the major product. The reaction of 2 with [CuBr(SMe2)] (1:1) produced bromido‐bridged dimeric CuI complex 5. Molecular structures of compounds 3, 4, and 5 were obtained.
Bewertung von Adsorbenzien zur Kraftstoffdampfnachbehandlung in Adsorbern für Personenkraftwagen
Authors: Hedwig Michael , Breitkopf Cornelia
Published: August 2016

Die Herausforderungen an die Kraftstoffdampfnachbehandlung in Adsorbern ottomotorisch betriebener PKW steigen infolge zunehmender Emissionsrestriktionen an. Die Arbeitskapazität des Adsorbers ist maßgeblich durch die Sorptionsfähigkeit des darin enthaltenen Adsorbens limitiert und von dem zu adsorbierenden Kraftstoffdampf abhängig. Anhand einer Charakterisierung repräsentativer Kraftstoffe werden hier die dazugehörigen Adsorptivgemische erschlossen. Darauf aufbauend erfolgt in Form einer Gegenüberstellung charakteristischer Stoffeigenschaften eine Bewertung und Auswahl geeigneter Absorbenzien.
Complete identification of four giant interneurons supplying mushroom body calyces in the cockroach Periplaneta americana
Authors: Takahashi Naomi , Katoh Ko , Watanabe Hidehiro , Nakayama Yuta , Iwasaki Masazumi , Mizunami Makoto , Nishino Hiroshi
Published: August 2016

Global inhibition is a fundamental physiological mechanism that has been proposed to shape odor representation in higher‐order olfactory centers. A pair of mushroom bodies (MBs) in insect brains, an analog of the mammalian olfactory cortex, are implicated in multisensory integration and associative memory formation. With the use of single/multiple intracellular recording and staining in the cockroach Periplaneta americana, we succeeded in unambiguous identification of four tightly bundled GABA‐immunoreactive giant interneurons that are presumably involved in global inhibitory control of the MB. These neurons, including three spiking neurons and one nonspiking neuron, possess dendrites in termination fields of MB output neurons and send axon terminals back to MB input sites, calyces, suggesting feedback roles onto the MB. The largest spiking neuron innervates almost exclusively the basal region of calyces, while the two smaller spiking neurons and the second‐largest nonspiking neuron innervate more profusely the peripheral (lip) region of the calyces than the basal region. This subdivision corresponds well to the calycal zonation made by axon terminals of two populations of uniglomerular projection neurons with dendrites in distinct glomerular groups in the antennal lobe. The four giant neurons exhibited excitatory responses to every odor tested in a neuron‐specific fashion, and two of the neurons also exhibited inhibitory responses in some recording sessions. Our results suggest that two parallel olfactory inputs to the MB undergo different forms of inhibitory control by the giant neurons, which may, in turn, be involved in different aspects of odor discrimination, plasticity, and state‐dependent gain control. J. Comp. Neurol. 525:204–230, 2017. © 2016 Wiley Periodicals, Inc.
Synthesis and Photoinduced Electron‐Transfer Reactions in a La2@Ih‐C80–Phenoxazine Conjugate
Authors: Akasaka Takeshi , Nakata Akira , Rudolf Marc , Wang Wei‐Wei , Yamada Michio , Suzuki Mitsuaki , Maeda Yutaka , Aoyama Ryo , Tsuchiya Takahiro , Nagase Shigeru , Guldi Dirk M.
Published: August 2016

A newly designed electron donor–acceptor conjugate consisting of an endohedral dimetallofullerene (La2@Ih‐C80) and phenoxazine (POZ) was successfully synthesized under Prato conditions. Our results document that the 1,3‐dipolar cycloaddition took place across the [5,6] junction to afford exclusively the corresponding [5,6] cycloadduct. The structure of the conjugate was characterized by means of NMR spectroscopy, absorption spectroscopy, and electrochemical studies. Computational calculations suggest that the electron density of the highest occupied molecular orbital (HOMO) is distributed on the POZ moiety, whereas that of the lowest unoccupied molecular orbital (LUMO) is located at the endohedral La atoms, leading to efficient separation of the HOMO and LUMO in the conjugate. Time‐resolved absorption spectroscopic investigations and spectroelectrochemical measurements corroborate the formation of the energetically low‐lying (La2@Ih‐C80).−–(POZ).+ radical‐ion‐pair state by means of ultrafast through‐space electron transfer.
Contagion processes on urban bus networks in Indian cities
Authors: Chatterjee Atanu , Ramadurai Gitakrishnan , Jagannathan Krishna
Published: August 2016

Bus transportation is the most convenient and cheapest way of public transportation in Indian cities. Due to cost‐effectiveness and wide reachability, buses bring people to their destinations every day. Although the bus transportation has numerous advantages over other ways of public transportation, this mode of transportation also poses a serious threat of spreading contagious diseases throughout the city. It is extremely difficult to predict the extent and spread of such an epidemic. Earlier studies have focused on the contagion processes on scale‐free network topologies; whereas, real‐world networks such as bus networks exhibit a wide‐spectrum of network topology. Therefore, we aim in this study to understand this complex dynamical process of epidemic outbreak and information diffusion on the bus networks for six different Indian cities using SI and SIR models. We identify epidemic thresholds for these networks which help us in controlling outbreaks by developing node‐based immunization techniques. © 2016 Wiley Periodicals, Inc. Complexity 21: 451–458, 2016
Fe/W Co‐Doped BiVO4 Photoanodes with a Metal–Organic Framework Cocatalyst for Improved Photoelectrochemical Stability and Activity
Authors: Jiao Zhengbo , Zheng Jingjing , Feng Chenchen , Wang Zeli , Wang Xuesen , Lu Gongxuan , Bi Yingpu
Published: August 2016

BiVO4 has been identified as one of the excellent visible light responsive photoanodes for use in photoelectrochemical (PEC) water splitting. However, pristine BiVO4 usually exhibits relative low photocatalytic properties owing to insufficient charge separation and transport characteristics. Although the marginal n‐type doping of higher valence ions can obviously raise the photocurrent value, it by no means improves the PEC stability. In this work, we successfully enhanced the PEC stability of BiVO4 by doping Fe ions in substitution of Bi. Density functional theory calculations have illustrated that Fe‐doping would result in an impurity band in the forbidden gap, and thus narrow its energy gap. More importantly, Fe‐doping can synergize with other means to further improve the PEC activities of BiVO4. Therefore, we fabricated a nanoporous Fe/W co‐doped BiVO4 photoelectrode, and then loaded the metal–organic framework (MOF) MIL‐100(Fe) as cocatalyst to further promote the separation of charge carriers. To the best of our knowledge, MOFs have not yet been utilized as a cocatalyst to facilitate the charge separation, which could increase the photocurrent density of Fe/W co‐doped BiVO4.