bluuebunny/crossref_metadata_2025 huggingface dataset:
Multidrug Resistance in Cancer Circumvented Using a Cytosolic Drug Reservoir
Authors: Fan Li , Zhang Silu , Zhang Chunyuan , Yin Chun , Chu Zhiqin , Song Chaojun , Lin Ge , Li Quan
Published: November 2017

It is discovered that sustained cytosolic drug release at a sufficient concentration is an effective mechanism to circumvent multidrug resistance and consequently enhance antitumor drug efficacy. It is showed that a simple way to enable this mechanism is to reach an intracellular kinetic balance of the drug movement between the drug released from the carrier into the cytosol and the one removed from the cell interior. By adopting nanoparticle (NP) as the drug carrier, a reservoir of drug can be maintained inside the cells upon effective cellular uptake of these NPs via endocytosis. This study shows that gradual release of the drug from the NP carrier provides a feasible scheme for sustained drug release in cells, resulting in relatively stable cytosolic drug concentration level, particularly in the drug resistant case. By implementing an “optical switch” with light irradiation on photosensitizer in the same nanoparticle carrier, cytosolic drug release is further promoted, which increases cytosolic drug concentration with good concentration retention. Enhanced drug efficacy in drug sensitive as well as resistant models is demonstrated both in vitro and in vivo. Such a mechanism is shown to efficiently circumvent multidrug resistance, and at the same time largely reduce the systemic toxicity of the anticancer drug.
A phase I study of lenalidomide plus chemotherapy with mitoxantrone, etoposide, and cytarabine for the reinduction of patients with acute myeloid leukemia
Authors: DeAngelo Daniel J. , Brunner Andrew M. , Werner Lillian , Avigan David , Fathi Amir T. , Sperling Adam S. , Washington Abigail , Stroopinsky Dina , Rosenblatt Jacalyn , McMasters Malgorzata , Luptakova Katarina , Wadleigh Martha , Steensma David P. , Hobbs Gabriela S. , Attar Eyal C. , Amrein Philip C. , Ebert Benjamin L. , Stone Richard M. , Ballen Karen K.
Published: November 2017

Patients with relapsed AML have a poor prognosis and limited responses to standard chemotherapy. Lenalidomide is an immunomodulatory drug that may modulate anti‐tumor immunity. We performed a study to evaluate the safety and tolerability of lenalidomide with mitoxantrone, etoposide and cytarabine (MEC) in relapsed/refractory AML. Adult patients with relapsed/refractory AML were eligible for this phase I dose‐escalation study. We enrolled 35 patients using a “3 + 3” design, with a 10 patient expansion cohort at the maximum tolerated dose (MTD). Lenalidomide was initially given days 1‐14 and MEC days 4‐8; due to delayed count recovery, the protocol was amended to administer lenalidomide days 1‐10. The dose of lenalidomide was then escalated starting at 5 mg/d (5‐10‐25‐50). The primary objective was tolerability and MTD determination, with secondary outcomes including overall survival (OS). The MTD of lenalidomide combined with MEC was 50 mg/d days 1‐10. Among the 35 enrolled patients, 12 achieved complete remission (CR) (34%, 90%CI 21‐50%); 30‐day mortality was 6% and 60‐day mortality 13%. The median OS for all patients was 11.5 months. Among 17 patients treated at the MTD, 7 attained CR (41%); the median OS was not reached while 12‐month OS was 61%. Following therapy with MEC and lenalidomide, patient CD4+ and CD8+ T‐cells demonstrated increased inflammatory responses to autologous tumor lysate. The combination of MEC and lenalidomide is tolerable with an RP2D of lenalidomide 50 mg/d days 1‐10, yielding encouraging response rates. Further studies are planned to explore the potential immunomodulatory effect of lenalidomide and MEC.
Elektrochemilumineszenz‐Bioassays können Fluoreszenzassays mithilfe eines wasserlöslichen Luminolderivats übertreffen
Authors: Mayer Michael , Takegami Shigehiko , Neumeier Michael , Rink Simone , Jacobi von Wangelin Axel , Schulte Silja , Vollmer Moritz , Griesbeck Axel G. , Duerkop Axel , Baeumner Antje J.
Published: November 2017

Die effizientesten und meistgenutzten Elektrochemilumineszenz(ECL)‐Moleküle sind Luminol, [Ru(bpy)3]2+ und dessen Derivate. Luminol zeichnet sich durch sein niedriges Anregungspotential aus, jedoch sind seine Anwendungen begrenzt aufgrund der sehr geringen Wasserlöslichkeit unter physiologischen Bedingungen. Das wasserlösliche m‐Carboxyluminol wurde in einer Ausbeute von 15 % synthetisiert und erreicht neben einer hohen Löslichkeit unter physiologischen Bedingungen einen vierfachen ECL‐Signalanstieg (gegenüber Luminol). Mittels Einschluss in DNA‐modifizierte Liposome wurde ein DNA‐Assay mit einer Nachweisgrenze von 3.2 pmol L−1 ermöglicht, die 150‐fach niedriger ist als die Nachweisgrenze des entsprechenden Fluoreszenzassays. Diese bemerkenswerte Steigerung der Empfindlichkeit sowie das niedrige Anregungspotential etablieren m‐Carboxyluminol als überlegene ECL‐Sonde mit Bedeutung für Chemilumineszenz‐ und enzymatische bioanalytische Anwendungen.
Thermally Activated Delayed Fluorescence in a Y3N@C80 Endohedral Fullerene: Time‐Resolved Luminescence and EPR Studies
Authors: Zalibera Michal , Krylov Denis S. , Karagiannis Dimitrios , Will Paul‐Anton , Ziegs Frank , Schiemenz Sandra , Lubitz Wolfgang , Reineke Sebastian , Savitsky Anton , Popov Alexey A.
Published: November 2017

The endohedral fullerene Y3N@C80 exhibits luminescence with reasonable quantum yield and extraordinary long lifetime. By variable‐temperature steady‐state and time‐resolved luminescence spectroscopy, it is demonstrated that above 60 K the Y3N@C80 exhibits thermally activated delayed fluorescence with maximum emission at 120 K and a negligible prompt fluorescence. Below 60 K, a phosphorescence with a lifetime of 192±1 ms is observed. Spin distribution and dynamics in the triplet excited state is investigated with X‐ and W‐band EPR and ENDOR spectroscopies and DFT computations. Finally, electroluminescence of the Y3N@C80/PFO film is demonstrated opening the possibility for red‐emitting fullerene‐based organic light‐emitting diodes (OLEDs).
MoB/g‐C3N4 Interface Materials as a Schottky Catalyst to Boost Hydrogen Evolution
Authors: Zhuang Zechao , Li Yong , Li Zilan , Lv Fan , Lang Zhiquan , Zhao Kangning , Zhou Liang , Moskaleva Lyudmila , Guo Shaojun , Mai Liqiang
Published: November 2017

Proton adsorption on metallic catalysts is a prerequisite for efficient hydrogen evolution reaction (HER). However, tuning proton adsorption without perturbing metallicity remains a challenge. A Schottky catalyst based on metal–semiconductor junction principles is presented. With metallic MoB, the introduction of n‐type semiconductive g‐C3N4 induces a vigorous charge transfer across the MoB/g‐C3N4 Schottky junction, and increases the local electron density in MoB surface, confirmed by multiple spectroscopic techniques. This Schottky catalyst exhibits a superior HER activity with a low Tafel slope of 46 mV dec−1 and a high exchange current density of 17 μA cm−2, which is far better than that of pristine MoB. First‐principle calculations reveal that the Schottky contact dramatically lowers the kinetic barriers of both proton adsorption and reduction coordinates, therefore benefiting surface hydrogen generation.
Supramolecular Polymerization Controlled through Kinetic Trapping
Authors: Chen Hao , Huang Zehuan , Wu Han , Xu Jiang‐Fei , Zhang Xi
Published: November 2017

A method of controllable supramolecular polymerization through kinetic trapping is developed. To this end, two bifunctional monomers with cucurbit[7]uril (CB[7]) and adamantane end groups were synthesized. The CB[7]‐containing monomer was presaturated with a pH‐responsive competitive guest for kinetic control. Then, the kinetics of supramolecular polymerization of the two monomers was easily controlled through the modulation of pH. As a result, supramolecular polymerization was kinetically trapped at certain stages, and supramolecular polymers with different molecular weights were obtained. It is anticipated that this research will enrich the methods of controllable supramolecular polymerization.
Podophyllotoxin extraction from Linum usitatissimum plant and its anticancer activity against HT‐29, A‐549 and MDA‐MB‐231 cell lines with and without the presence of gold nanoparticles
Authors: Safarpoor Mohammad , Ghaedi Mehrorang , Yousefinejad Masoume , Javadian Hamedreza , Asfaram Arash , Ghasemi Zahra , Jaberi Hajar , Rahimi Daruosh
Published: November 2017

In recent years, gold nanoparticles (Au‐NPs) have been taken into consideration in nanomedicine due to their excellent biocompatibility, chemical stability and promising optical properties. In this research, podophyllotoxin conjugated with gold nanoparticles (Au‐NPs‐POT) was synthesized and the conjugation of POT with Au‐NPs was confirmed using scanning electron microscopy, mass spectrometry and Fourier transform infrared spectroscopy. The anticancer effects of the product on preclinical models of lung, colon and breast cancers were investigated using MTT test. The analyses showed a direct dose–response relationship. It was found that higher concentrations of POT have more positive effects on the inhibition of cancer cell growth. At POT concentrations of 1, 2.5, 5, 7.5, 10, 15 and 20 ng ml−1, approximately 50% of the growth of colorectal, lung and breast cancer cell lines was inhibited, while similar results were obtained in the presence of 1, 2, 3, 4 and 5 μg ml−1 Au‐NPs‐POT. Au‐NPs‐POT exhibited the lowest cytotoxicity due to the presence of POT. The anticancer feature of Au‐NPs‐POT proved the potential to develop better anticancer therapeutics and to open new avenues for treatment of cancers.
Adsorption of metal ions by microwave assisted grafting of cross‐linked chitosan beads. Equilibrium, isotherm, thermodynamic and desorption studies
Authors: Igberase E. , Osifo P. , Ofomaja A.
Published: November 2017

Chemical modification of chitosan has become increasingly essential due to chitosan versatility that enables the material to be easily modified in a way of increasing its properties in adsorption processes. In this investigation, chitosan solution was cross‐linked with glutaraldehyde the cross‐linked solution was used in producing the beads and thereafter grafted with ethylene acrylic acid. The chemical functionalities of the beads were obtained by Fourier transform infrared spectroscopy (FTIR), Scanning electron microscope (SEM), X‐ray diffraction (XRD) and Thermogravimetric analysis (TGA). Adsorption of Pb2+, Cu2+, Ni2+, Zn2+, Cr6+ and Cd2+ ions from single component aqueous mixture by grafted cross‐linked chitosan beads (GXXB) was studied as a function of pH, temperature, initial concentration, contact time, agitation speed and ionic strength. Equilibrium data was obtained from the adsorption experiment, the data were applied in isotherm, thermodynamics and kinetic studies. The Langmuir, Temkin and Dubinin‐kaganer‐Radushkevich (DKR) model were successful in describing the isotherm data for the considered metal ions while the Freundlich model was not efficient in describing the experimental data. Pseudo‐second order and intra‐particle model described the kinetic data quite well. Thermodynamic parameters such as Gibb's free energy change (∆Go), enthalpy change (∆Ho) and entropy change (∆So) were calculated and the results showed the adsorption of Pb2+, Cu2+, Ni2+, Zn2+, Cr6+ and Cd2+ ions onto GXXB is spontaneous and endothermic in nature. Regeneration of the used adsorbent was effective for the studied metal ions.
Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones
Authors: Lan Wen‐Bo , Wang Xiao‐Feng , He Li‐Ping , Meng Yan‐Bin , Li Jun , Qiu Bin , Nie Chang‐Ming
Published: November 2017

The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein.
Structure and applications of organotin complex based on trimethyltin cation and quinaldic acid
Authors: El‐bendary Mohamed M. , Etaiw Safaa El‐din H.
Published: November 2017

The reaction between aqueous solution of Me3SnCl and acetonitrile solution of quinaldic acid (quinH) at room temperature affords a new organotin complex, [Me3Sn(quinH)(quin)]⋅6H2O (1). Complex 1 was structurally characterized using infrared, UV–visible and NMR spectra, thermogravimetric analysis and single‐crystal X‐ray analysis. The network structure of 1 is developed by a limitless number of discrete mononuclear molecules forming a one‐dimensional chain via hydrogen bonds. Extensive hydrogen bonds and π–π stacking associate the one‐dimensional chains creating a two‐dimensional array. The two‐dimensional arrays are additionally associated via hydrogen bonds through the water molecules and the methyl groups forming a three‐dimensional network. The cytotoxic impact of 1 on the viability of MCF‐7 cells was also examined using MTT assay, exhibiting great inhibiting action against MCF‐7 cells. Furthermore, the catalytic degradation performance of 1 towards methylene blue dye in the presence of H2O2 as oxidant was investigated. The reaction is first order with respect to methylene blue dye.
Solid‐state single‐ion conducting comb‐like siloxane copolymer electrolyte with improved conductivity and electrochemical window for lithium batteries
Authors: Ren Chaoshi , Liu Mingzhu , Zhang Jiawen , Zhang Qinghua , Zhan Xiaoli , Chen Fengqiu
Published: November 2017

Achievement of high conductivity and electrochemical window at ambient temperature for an all‐solid polymer electrolyte used in lithium ion batteries is a challenge. Here, we report the synthesis and characterization of a novel solid‐state single‐ion electrolytes based on comb‐like siloxane copolymer with pendant lithium 4‐styrenesulfonyl (perfluorobutylsulfonyl) imide and poly(ethylene glycol). The highly delocalized anionic charges of SO2N(–)C4F9 have a weak association with lithium ions, resulting in the increase of mobile lithium ions number. The designed polymer electrolytes possess ultra‐low glass transition temperature in the range from −73 to −54 °C due to the special flexible polysiloxane. Promising electrochemical properties have been obtained, including a remarkably high conductivity of 3.7 × 10−5 S/cm and electrochemical window of 5.2 V (vs. Li+/Li) at room temperature. A high lithium ion transference number of 0.80, and good compatibility with anode were also observed. These prominent characteristics endow the polymer electrolyte a potential for the application in high safety lithium ion batteries. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45848.
Effects of aging on poly(1‐trimethylsilyl‐1‐propyne) membranes irradiated with vacuum ultraviolet radiation for gas separation
Authors: Yoshioka Tetsuro , Miyashita Yoshiki , Motoo Taichi , Saito Kentaro , Nagai Kazukiyo
Published: November 2017

In this study, we investigated the effects of physical aging on the surface and gas‐transport properties of highly gas permeable poly(1‐trimethylsilyl‐1‐propyne) membranes irradiated with vacuum ultraviolet (VUV) radiation. VUV excimer lamp irradiation was performed on one side of the membrane for 6 or 60 min. The gas permeabilities for carbon dioxide (CO2) and nitrogen (N2) were determined through a volumetric measurement method at 23 °C. The gas permeabilities for CO2 and N2 increased temporarily at 7 days after 6 and 60 min of VUV irradiation of the membranes. The change in the gas permeability for N2 was more remarkable than that for CO2. These changes were related to the CO or SiOx ratio. The CO ratio was related to the gas permeability of the membranes VUV‐irradiated for 6 min, whereas the SiOx ratio was related to the gas permeability of the membranes VUV‐irradiated for 60 min. These changes affected the gas selectivities of the membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45973.
Rheological and mechanical properties of thermoplastic polyurethane elastomer derived from CO2 copolymer diol
Authors: Xian Wenqi , Song Lina , Liu Baohua , Ding Hulan , Li Zhao , Cheng Mengping , Ma Le
Published: November 2017

CO2 copolymer diol‐based thermal polyurethane elastomers (PPC‐TPU) were prepared by the reaction of CO2 copolymer diol and methylene diphenyl diisocyanate and chain extender (ethylene glycol/1,4‐butanediol/1,6‐hexanediol) (EG/BDO/HG). The rheological and mechanical properties of PPC‐TPU were analyzed. The effects of shear rate, shear temperature, hard segment content, and variety of chain extender on the properties of PPC‐TPU were studied. The results showed that the apparent viscosity (η) of PPC‐TPU decreased with the increasing shear rate (τ), and the non‐Newtonian index (n) was less than 1. PPC‐TPU exhibited a typical character of pseudoplastic non‐Newtonian rheological behavior. The degradation during the processing was obviously inhibited by adding plasticizer and antioxidant. It was also discovered that the apparent viscosity varied with the content of hard segment and chain extender. Under the same temperature (185 °C) and shear rate (50 s−1), the apparent viscosity increased considerably with the raise of hard segment content, and the apparent viscosity and tensile strength of PPC‐TPU with EG as chain extender was the maximum. It can be seen that with the apparent shear rate increasing, the variation tendency of apparent shear stress levels off, and the nonlinear relationship of τ–γ curve tended to be obvious. PPC‐TPU exhibited a typical character of pseudoplastic non‐Newtonian rheological behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 45974.
Visible‐Light Photoactive, Highly Efficient Triplet Sensitizers Based on Iodinated Aza‐BODIPYs: Synthesis, Photophysics and Redox Properties
Authors: Gut Arkadiusz , Łapok Łukasz , Drelinkiewicz Dawid , Pędziński Tomasz , Marciniak Bronisław , Nowakowska Maria
Published: November 2017

A series of novel iodinated NO2‐substituted aza‐BODIPYs have been synthesized and characterized. Highly desirable photophysical and photochemical properties were induced in NO2‐substituted aza‐BODIPYs by iodination of the pyrrole rings. In particular, high values of singlet oxygen quantum yields (ΦΔ) ranging from 0.79 to 0.85 were measured. The photooxygenation process proceeds via a Type II mechanism under the experimental conditions applied. The compounds studied exhibited an absorption band within the so‐called “therapeutic window”, with λmax located between 645 nm to 672 nm. They were non‐fluorescent at room temperature with excited singlet‐state lifetimes within the picosecond range as measured by femtosecond transient absorption. Nanosecond laser flash photolysis experiments revealed T1→Tn absorption spanning from ca. 400 nm to ca. 500 nm and allowed determination of the triplet‐state lifetimes. The estimated triplet lifetimes (τT) in deaerated acetonitrile ranged between 2.74 μs and 3.50 μs. As estimated by CV/DPV measurements, all iodinated aza‐BODIPYs studied exhibited one irreversible oxidation and two quasi‐reversible reductions processes. Estimation of the EHOMO gave the value of −6.06 to −6.26 eV while the ELUMO was found to be located at ca. −4.6 eV. Thermogravimetric (TGA) analysis revealed that iodinated aza‐BODIPYs were stable up to approximately 300 °C. All compounds studied exhibit high photostability in toluene solution.
Bounds for the reliability functions of coherent systems with heterogeneous components
Authors: Miziuła Patryk , Navarro Jorge
Published: November 2017

The computation of the reliability function of a (complex) coherent system is a difficult task. Hence, sometimes, we should simply work with some bounds (approximations). The computation of these bounds has been widely studied in the case of coherent systems with independent and identically distributed (IID) components. However, few results have been obtained in the case of heterogeneous (non ID) components. In this paper, we derive explicit bounds for systems with heterogeneous (independent or dependent) components. Also some stochastic comparisons are obtained. Some illustrative examples are included where we compare the different bounds proposed in the paper.
Joint effects of prenatal air pollutant exposure and maternal folic acid supplementation on risk of autism spectrum disorder
Authors: Goodrich Amanda J. , Volk Heather E. , Tancredi Daniel J. , McConnell Rob , Lurmann Fred W. , Hansen Robin L. , Schmidt Rebecca J.
Published: November 2017

Independent studies report that periconceptional folic acid (FA) may decrease the risk of autism spectrum disorder (ASD) while exposure to air pollution may increase ASD risk. We examined the joint effects of gestational FA and air pollution exposures in association with ASD. We studied 346 ASD cases and 260 typically developing controls from the CHARGE case‐control study. Self‐reported FA intake for each month of pregnancy was quantified. Estimates of exposure to near roadway air pollution (NRP) and criteria air pollutant measures were assigned based on maternal residential history. Among mothers with high FA intake (>800 μg) in the first pregnancy month, exposure to increasing levels of all air pollutants, except ozone, during the first trimester was associated with decreased ASD risk, while increased ASD risk was observed for the same pollutant among mothers with low FA intake (≤800 μg). This difference was statistically significant for NO2 (e.g., NO2 and low FA intake: OR = 1.53 (0.91, 2.56) vs NO2 and high FA intake: OR = 0.74 (0.46, 1.19), P‐interaction = 0.04). Mothers exposed to higher levels (≥ median) of any air pollutant during the first trimester of pregnancy and who reported low FA intake were at a higher ASD risk compared to mothers exposed to lower levels of that air pollutant and who reported high first month FA intake. Joint effects showed significant (alpha < 0.10) departures from expected interaction for NRP and NO2. Our results suggest that periconceptional FA intake may reduce ASD risk in those with high prenatal air pollution exposure. Further study is needed to replicate these findings in larger sample sizes and to understand mechanisms of this potential relationship.. Autism Res 2018, 11: 69–80. © 2017 International Society for Autism Research, Wiley Periodicals, Inc.

Lay Summary

We examined interactions between periconceptional folic acid (FA) and air pollution exposure on risk of ASD. Mothers exposed to higher levels of air pollution during the first trimester of pregnancy and who reported low supplemental FA intake during the first pregnancy month were at a higher ASD risk compared to mothers exposed to lower levels of air pollution and who reported high first month FA intake. Our results suggest that periconceptional FA intake may reduce ASD risk in those with high prenatal air pollution exposure.
The effects of a behavioral skills training and general‐case training package on caregiver implementation of a food selectivity intervention
Authors: Alaimo Christina , Seiverling Laura , Sarubbi Jaimie , Sturmey Peter
Published: November 2017

We used behavioral skills training with general‐case training to teach 3 caregivers to implement a behavioral feeding intervention with their children. The percentage of correctly performed steps of the feeding intervention increased for all 3 caregivers and was maintained at follow‐up. For all 3 children, the number of bites consumed increased and the number of bites with inappropriate mealtime behavior decreased across treatment. Increases in bites consumed and bites without behavior problems were maintained for 2 participants at follow‐up.
Using backward chaining and a physical guidance delay to teach self‐feeding
Authors: Rubio Emily K. , Pichardo Denise , Borrero Carrie S.W.
Published: November 2017

Many children with feeding disorders lack age‐appropriate self‐feeding without intervention, irrespective of whether refusal is a motivational or skill deficit. When a target behavior is infrequent or absent, multistep tasks can be shaped using chaining by targeting a preexisting step within an individual's behavioral repertoire. Studies suggest when the preexisting response is in the final step of the chain, backward chaining may increase mastery. In this study, we investigated the use of backward chaining to increase self‐feeding of solids of a 4‐year‐old male.
Avatar‐based counselling for young people within school counselling. Qualitative analysis of client experience
Authors: van Rijn Biljana , Cooper Mick , Chryssafidou Evi
Published: November 2017

Background

This study is a qualitative analysis of clients’ experiences of a new avatar based counselling intervention, based on the ‘ProReal’ software (www.proreal.world). The intervention was piloted in eight secondary schools in the UK in 2016.

Aims

Twenty‐nine participants (53% of the full sample) were interviewed about their use of the software, experience of the intervention, process of change and views about its helpfulness.

Materials and Methods

Interviews were semi‐structured and were analysed using thematic analysis.

Results

The analysis shows that the intervention was potentially attractive to these clients, particularly those enthusiastic about digital software and clients who found visual communication helpful. The software provided additional opportunities for clients to communicate their inner worlds to the counsellor and supported the development of insight. Male clients, in particular, commented on its helpfulness.

Discussion

There is an indication that digital imagery supported the process of change in counselling and the development of meaning bridges: both internally and with the counsellor (Stiles, 2011; Stiles et al., 1990). However, the software could be experienced as an obstacle when clients wanted to talk about specific problems or ‘vent’ their feelings. All clients who reported that they did not find the software helpful were female. There were a number of suggestions about developing the software to increase opportunities for expression as well as appropriateness for clients from different minority ethnic backgrounds.

Conclusion

Use of digital software in counselling has a potential to enhance communication and support a process of change, particularly with male clients, those who find visual communication helpful, and clients enthusiastic about digital technology. Further research is needed to develop the intervention and compare it to the use of other creative media in counselling.
Phage Display on the Anti‐infective Target 1‐Deoxy‐d‐xylulose‐5‐phosphate Synthase Leads to an Acceptor–Substrate Competitive Peptidic Inhibitor
Authors: Marcozzi Alessio , Masini Tiziana , Zhu Di , Pesce Diego , Illarionov Boris , Fischer Markus , Herrmann Andreas , Hirsch Anna K. H.
Published: November 2017

Enzymes of the 2‐C‐methyl‐d‐erythritol‐4‐phosphate pathway for the biosynthesis of isoprenoid precursors are validated drug targets. By performing phage display on 1‐deoxy‐d‐xylulose‐5‐phosphate synthase (DXS), which catalyzes the first step of this pathway, we discovered several peptide hits and recognized false‐positive hits. The enriched peptide binder P12 emerged as a substrate (d‐glyceraldehyde‐3‐phosphate)‐competitive inhibitor of Deinococcus radiodurans DXS. The results indicate possible overlap of the cofactor‐ and acceptor‐substrate‐binding pockets and provide inspiration for the design of inhibitors of DXS with a unique and novel mechanism of inhibition.
Improvement in the Thermostability of a β‐Amino Acid Converting ω‐Transaminase by Using FoldX
Authors: Buß Oliver , Muller Delphine , Jager Sven , Rudat Jens , Rabe Kersten S.
Published: November 2017

ω‐Transaminases (ω‐TAs) are important biocatalysts for the synthesis of active, chiral pharmaceutical ingredients containing amino groups, such as β‐amino acids, which are important in peptidomimetics and as building blocks for drugs. However, the application of ω‐TAs is limited by the availability and stability of enzymes with high conversion rates. One strategy for the synthesis and optical resolution of β‐phenylalanine and other important aromatic β‐amino acids is biotransformation by utilizing an ω‐transaminase from Variovorax paradoxus. We designed variants of this ω‐TA to gain higher process stability on the basis of predictions calculated by using the FoldX software. We herein report the first thermostabilization of a nonthermostable S‐selective ω‐TA by FoldX‐guided site‐directed mutagenesis. The melting point (Tm) of our best‐performing mutant was increased to 59.3 °C, an increase of 4.0 °C relative to the Tm value of the wild‐type enzyme, whereas the mutant fully retained its specific activity.
Magnetostructural Investigation of Orthogonal 1‐Aryl‐3‐Phenyl‐1,4‐Dihydrobenzo[e][1,2,4]triazin‐4‐yl Derivatives
Authors: Gardias Anita , Kaszyński Piotr , Obijalska Emilia , Trzybiński Damian , Domagała Sławomir , Woźniak Krzysztof , Szczytko Jacek
Published: November 2017

3‐Phenyl‐1,4‐dihydrobenzo[e][1,2,4]triazinyl radicals with the N(1) position substituted with naphth‐2‐yl (1 b), naphth‐1‐yl (1 c), pyren‐1‐yl (1 d), anthracen‐9‐yl (1 e), 2‐trifluoromethylphenyl (1 f), 3‐trifluoromethylphenyl (1 g), and 2‐iodophenyl (1 h) were characterized by using single‐crystal X‐ray diffraction, variable‐temperature magnetic susceptibility, and DFT computational methods. The substituent at N(1) is essentially orthogonal to the heterocycle plane in 1 f and 1 h, and with a high torsion angle in 1 c and 1 d. Radicals 1 c and 1 h form unusual infinite chains with crisscrossing hetero‐co‐facial π–π interactions, whereas radical 1 d forms analogous homo‐co‐facial arrangements. Infinite chains of homo‐co‐facial π–π dimers are found in 1 b, 1 f and 1 g; in the latter the position of the CF3 group controls the slippage of the dimers in the chain. No π–π parallel arrangements were found in 1 e. Magnetic susceptibility measurements demonstrated strong antiferromagnetic interactions in 1 b (J=−264±4 cm−1) and 1 f (J=−134±1 cm−1), while weak intradimer ferromagnetic interactions were found in 1 g (J2=+21±1 and J1=−15±1 cm−1). Other derivatives exhibit typical weak antiferromagnetic exchange interactions in a range of −5 to −10 cm−1.
Self‐Assembled Nanomicelles as MRI Blood‐Pool Contrast Agent
Authors: Babič Andrej , Vorobiev Vassily , Xayaphoummine Céline , Lapicorey Gaëlle , Chauvin Anne‐Sophie , Helm Lothar , Allémann Eric
Published: November 2017

Gadolinium‐loaded nanomicelles show promise as future magnetic resonance imaging (MRI) contrast agents (CAs). Their increased size and high gadolinium (Gd) loading gives them an edge in proton relaxivity over smaller molecular Gd‐complexes. Their size and stealth properties are fundamental for their long blood residence time, opening the possibility for use as blood‐pool contrast agents. Using l‐tyrosine as a three‐functional scaffold we synthesized a nanostructure building block 8. The double C18 aliphatic chain on one side, Gd‐1,4,7,10‐tetraazacyclododecane‐1‐4‐7‐triacetic acid (Gd‐DO3A) with access to bulk water in the center and 2 kDa PEG on the hydrophilic side gave the amphiphilic properties required for the core–shell nanomicellar architecture. The self‐assembly into Gd‐loaded monodispersed 10–20 nm nanomicelles occurred spontaneously in water. These nanomicelles (Tyr‐MRI) display very high relaxivity at 29 mm−1 s−1 at low field strength and low cytotoxicity. Good contrast enhancement of the blood vessels and the heart together with prolonged circulation time in vivo, makes Tyr‐MRI an excellent candidate for a new supramolecular blood‐pool MRI CA.
Deltamides and Croconamides: Expanding the Range of Dual H‐bond Donors for Selective Anion Recognition
Authors: Zwicker Vincent E. , Yuen Karen K. Y. , Smith David G. , Ho Junming , Qin Lei , Turner Peter , Jolliffe Katrina A.
Published: November 2017

Dual H‐bond donors are widely used as recognition motifs in anion receptors. We report the synthesis of a library of dual H‐bond receptors, incorporating the deltic and croconic acid derivatives, termed deltamides and croconamides, respectively, and a comparison of their anion binding affinities (for monovalent species) and Brønsted acidities to those of the well‐established urea and squaramide dual H‐bond donor motifs. For dual H‐bonding cores with identical substituents, the trend in Brønsted acidity is croconamides>squaramides>deltamides>ureas, with the croconamides found to be 10–15 pKa units more acidic than the corresponding ureas. In contrast to the trends displayed by ureas, deltamides and squaramides, N,N′‐dialkyl croconamides displayed higher binding affinity to chloride than the N,N′‐diaryl derivatives, which was attributed to partial deprotonation of the N,N′‐diaryl derivatives at neutral pH. A number of differences in anion binding selectivity were observed upon comparison of the dual H‐bond cores. Whereas the squaramides display similar affinity for both chloride and acetate ions, the ureas have significantly higher affinity for acetate than chloride ions and the deltamides display higher affinity for dihydrogenphosphate ions than other oxoanions or halides. These inherent differences in binding affinity could be exploited in the design of anion receptors with improved ability to discriminate between monovalent anions.
Cobalt‐Catalyzed Asymmetric Allylation of Cyclic Ketimines
Authors: Wu Liang , Shao Qihang , Yang Guoqiang , Zhang Wanbin
Published: November 2017

A CoII/Box‐catalyzed [Box=bis(oxazoline)] enantioselective addition of potassium allyltrifluoroborate to cyclic ketimines was developed, providing the corresponding chiral α‐tertiary amines in high yields and with good enantioselectivity values. Alkoxycarbonyl‐ and alkyl‐substituted saccharin‐derived ketimines are suitable substrates for this allylation reaction. The product can be converted to complex molecules over several simple steps, including a precursor of MK‐0371, which is a kinesin spindle protein inhibitor. In addition, this catalytic system showed a strong positive nonlinear effect.
Conformational Bias by a Removable Silyl Group: Construction of Bicyclo[n.3.1]alkenes by Ring Closing Metathesis
Authors: Lin Minggui , Cai Pei‐Jun , Zeng Zhixiong , Lin Na , Shen Yang , Tang Bin , Li Fan , Chen Chen , Yu Zhi‐Xiang , Zhang Yandong
Published: November 2017

Herein, we report a novel strategy based on a conformationally controlled RCM by a removable silyl group, which allows the facile synthesis of various bicyclo[n.3.1]alkenes, especially a set of highly strained bicyclo[5.3.1]alkenes. Further derivatizations of the silyl group and the resultant double bond of bicyclo[5.3.1]undecene 2 f enabled a concise synthesis of A‐B‐C ring skeleton of taxol. Density functional theory (DFT) calculations suggest that the introduction of a bulky silyl group at C‐5 position of the 1,3‐dialkenylcyclohexanol substrates dramatically lowers the energy bias gap between diaxial conformers (to RCM) and diequatorial conformers (to cross metathesis), thereby favoring the expected RCM reaction to give the challenging bridged molecules.
Novel Gold and Silver Carbene Complexes Exert Antitumor Effects Triggering the Reactive Oxygen Species Dependent Intrinsic Apoptotic Pathway
Authors: Iacopetta Domenico , Mariconda Annaluisa , Saturnino Carmela , Caruso Anna , Palma Giuseppe , Ceramella Jessica , Muià Noemi , Perri Mariarita , Sinicropi Maria Stefania , Caroleo Maria Cristina , Longo Pasquale
Published: November 2017

Cisplatin and other platinum‐based drugs are well‐known valid anticancer drugs. However, during chemotherapy, the presence of numerous side effects and the onset of frequent phenomena of resistance has pushed many research groups to devise new metal‐based compounds holding improved anticancer properties and fewer undesired effects. Amongst the variety of synthesized compounds, significant antiproliferative effects have been obtained by employing organometallic compounds, particularly those based on silver and gold. With this in mind, we synthesized four compounds, two silver complexes and two gold complexes, with good inhibitory effects on the in vitro proliferation of breast and ovarian cancer‐cell models. The antitumor activity of the most active compound, that is, AuL4, was found to be ninefold higher than that of cisplatin, and this compound induced dramatic morphological changes in HeLa cells. AuL4 induced PARP‐1 cleavage, caspases 3/7 and 9 activation, mitochondria disruption, cytochrome c release in cancer‐cell cytoplasm, and the intracellular production of reactive oxygen species. Thus, AuL4 treatment caused cancer‐cell death by the intrinsic apoptotic pathway, whereas no cytotoxic effects were recorded upon treating non‐tumor cell lines. The reported outcomes may be an important contribution to the expanding knowledge of medicinal bio‐organometallic chemistry and enlarge the available anticancer toolbox, offering improved features, such as higher activity and/or selectivity, and opening the way to new discoveries and applications.
Magneto‐Conducting Core/Shell Nanoparticles for Biomedical Applications
Authors: Srinivasan Sumithra Y. , Paknikar Kishore M. , Gajbhiye Virendra , Bodas Dhananjay
Published: November 2017

Nanocomposites comprising magnetic nanoparticles and conducting polymers (MN‐CPs) are promising multifunctional nanomaterials that exhibit a unique combination of magnetism and electrical conductivity. Magnetic nanoparticles (MNPs) have a high surface area to volume ratio, excellent mechanical strength, and biocompatibility, whereas the conducting polymers are advantageous for their ease of synthesis, environmental stability, biocompatibility, and low cost. Therefore, the MN‐CP nanocomposites having synergistic qualities are being increasingly considered for almost all spheres of biomedical applications including biosensors, environmental remediation, drug delivery, as well as theranostics. In biosensors and purification applications, the magnetic affinity is useful for separation, and electrical transduction is utilized for signal transmission. MN‐CP nanocomposites are also promising in drug‐delivery applications as well since both external magnetic and electrical fields can be employed for targeted and stimuli responsive drug release. The MN‐CP nanocomposites are also potential near‐infrared (NIR) photothermal, magnetothermal, and MRI contrast agents and used for multimodal imaging in cancer diagnostics and therapeutics. MN‐CP nanocomposites are multitalented nanoparticles with unique attributes that make them advantageous over other conventional agents and other nanocomposite systems. The objective of the current review is to provide an overview of the unique properties of these nanocomposites, their synthetic strategies and their potential applications explored so far in the biomedical field.
Foreword to the special issue of the Cray User Group (CUG 2017)
Authors: Michael Scott , He Yun
Published: November 2017

The 10 best papers from 77 submissions to the Cray User Group (CUG) 2017 conference, held in Redmond, Washington, are presented in this issue. Several themes of the conference are highlighted in this group of articles, including the Knight's Landing Architecture, Optimization of I/O, and data analytics.
Effect of Solvents on the Behavior of Lithium and Superoxide Ions in Lithium–Oxygen Battery Electrolytes
Authors: Smirnov Vladimir S. , Kislenko Sergey A.
Published: November 2017

The molecular life of intermediates, namely, O2− and Li+, produced during the discharge of aprotic Li–O2 batteries was investigated by molecular dynamics simulation. This work is of potential interest in the development of new electrolytes for Li–air batteries. We present the results on the structure and stability of the Li+ and O2− solvation shells and the thermodynamics and kinetics of the ion‐association reaction in solvents such as dimethyl sulfoxide (DMSO), dimethoxyethane (DME), and acetonitrile (ACN). The residence time of solvent molecules in the Li+ solvation shell increases with the solvent donor number and is 100 times larger in DMSO than in ACN. In DMSO and DME, the Li+ ion diffuses with its solvation shell as a whole. On the contrary, in ACN it diffuses as a “bare” ion because of weak solvation. The rate constant for the association of the lithium ion with the superoxide anion in DMSO is two orders of magnitude slower than that in ACN due to fact that the free‐energy barrier is 2.5 times larger in DMSO than in ACN. In addition, we show that despite the strong dependence of the Li+ shell stability on donor number, the rate of association does not necessarily correlate with this solvent property.
Multiple mechanisms of early plant community assembly with stochasticity driving the process
Authors: Marteinsdóttir Bryndís , Svavarsdóttir Kristín , Thórhallsdóttir Thóra Ellen
Published: November 2017

Initial plant establishment is one of the most critical phases in ecosystem development, where an early suite of physical (environmental filtering), biological (seed limitation, species interactions) and stochastic factors may affect successional trajectories and rates. While functional traits are commonly used to study processes that influence plant community assembly in late successional communities, few studies have applied them to primary succession. The objective here was to determine the importance of these factors in shaping early plant community assembly on a glacial outwash plain, Skeiðarársandur, in SE Iceland using a trait based approach. We used data on vascular plant assemblages at two different spatial scales (community and neighborhood) sampled in 2005 and 2012, and compiled a dataset on seven functional traits linked to species dispersal abilities, establishment, and persistence for all species within these assemblages. Trait‐based null model analyses were used to determine the processes that influenced plant community assembly from the regional species pool into local communities, and to determine if the importance of these processes in community assembly was dependent on local environment or changed with time. On the community scale, for most traits, random processes dominated the assembly from the regional species pool. However, in some communities, there was evidence of non‐random assembly in relation to traits linked to species dispersal abilities, persistence, and establishment. On the neighborhood scale, assembly was mostly random. The relative importance of different processes varied spatially and temporally and the variation was linked to local soil conditions. While stochasticity dominated assembly patterns of our early successional communities, there was evidence of both seed limitation and environmental filtering. Our results indicated that as soil conditions improved, environmental constraints on assembly became weaker and the assembly became more dependent on species availability.
Thermally Induced Oxidation of [FeII(tacn)2](OTf)2 (tacn = 1,4,7‐triazacyclononane)
Authors: Li Jia , Banerjee Atanu , Preston Debra R. , Shay Brian J. , Adhikary Amitiva , Sevilla Michael D. , Loloee Reza , Staples Richard J. , Chavez Ferman A.
Published: November 2017

We previously reported the spin‐crossover (SC) properties of [FeII(tacn)2](OTf)2 (1) (tacn = 1,4,7‐triazacyclononane). Upon heating under dynamic vacuum, 1 undergoes oxidation to generate a low‐spin iron(III) complex. The oxidation of the iron center was found to be facilitated by initial oxidation of the ligand through loss of a H atom. The resulting complex was hypothesized to have the formulation [FeIII(tacn)(tacn‐H)](OTf)2 (2) where tacn‐H is N‐deprotonated tacn. The formulation was confirmed by ESI‐MS. The powder EPR spectrum of the oxidized product at 77 K reveals the formation of a low‐spin iron(III) species with rhombic spectrum (g = 1.98, 2.10, 2.19). We have indirectly detected H2 formation during the heating of 1 by reacting the headspace with HgO. Formation of water (1H NMR in anhydrous [D6]DMSO) and elemental mercury were observed. To further support this claim, we independently synthesized [FeIII(tacn)2](OTf)3 (3) and treated it with one equivalent of base yielding 2. The structures of 3 were characterized by X‐ray crystallography. Compound 2 also exhibits a low‐spin iron(III) rhombic signal (g = 1.97, 2.11, 2.23) in DMF at 77 K. Variable temperature magnetic susceptibility measurements indicate that 3 undergoes gradual spin increase from 2 to 400 K. DFT studies indicate that the deprotonated nitrogen in 2 forms a bond to iron(III) exhibiting double‐bond character (Fe–N, 1.807 Å).
Rising Stars in Science and Technology: Luminescent Lanthanide Materials
Authors: Bünzli Jean‐Claude G.
Published: November 2017

This essay draws attention to lanthanide luminescence by putting into perspective the sensitization process of f–f emission, the design of highly luminescent lanthanide‐based compounds, and upconversion nanoparticles. A brief overview of the recent advances in some applications, namely lighting, security inks and tags, as well as biological applications, is presented.
tBuLi‐Promoted Intermolecular Regioselective Nucleophilic Addition of Arenes to Diazo Compounds as N‐Terminal Electrophiles: Efficient Synthesis of Hydrazine Derivatives
Authors: Zhang Lu , Meng Xiang‐He , Liu Pei , Chen Jie , Zhao Yu‐Long
Published: November 2017

The tBuLi‐promoted intermolecular direct nucleophilic addition of arenes to diazo compounds as the N‐terminal electrophiles has been developed. This reaction proceeds in a completely regioselective manner and is an efficient method for the preparation of hydrazine derivatives in high to excellent yields. This transformation not only provides an efficient approach for aromatic C–N bond formation under transition‐metal‐free and oxidant‐free conditions but also represents a strategy for the 3‐amination of pyridines and the dearomatization of indoles.
Attempted [2]Catenane Synthesis via a Quasi[1]catenane by a Templated Backfolding Strategy
Authors: Steemers Luuk , Wanner Martin J. , van Leeuwen Bart R. C. , Hiemstra Henk , van Maarseveen Jan H.
Published: November 2017

A templated backfolding concept to construct a [2]catenane was attempted via a quasi[1]catenane showing an inverted spiro geometry. The template is covalently connected to the ketal‐connected semi‐perpendicular‐arranged linear precursors and spatially directs the sterically congested backfolding macrocyclizations that are required to give a quasi[1]catenane. So far, we are unable to hydrolyze the cyclic ketal to liberate the [2]catenane.
Determination of tetracyclines in human urine samples by capillary electrophoresis in combination with field amplified sample injection
Authors: Moreno‐González David , Krulišová Markéta , Gámiz‐Gracia Laura , García‐Campaña Ana M.
Published: November 2017

A sensitive method using CZE‐UV detection has been developed for the determination of five tetracycline antibiotics in human urine samples. To improve the sensitivity of the method, an on‐line preconcentration strategy, named field‐amplified sample injection, has been developed, based on the electrokinetic injection of the sample, which requires only a 1:100 dilution with sample solvent before injection. Under optimum conditions, sensitivity enhancement factors ranged from 450 to 800 for the studied compounds. The applicability of the proposed method was demonstrated by the determination of these antibiotics in spiked urine samples. The limits of quantification were lower than 0.8 mg/L and the precision (intra‐ and inter‐day), expressed as %RSD was below 14%. Recoveries ranged from 92.1 to 96.7%. Thus, the proposed procedure is a simple, fast and efficient strategy which could be used as therapeutic drug monitoring in human urine samples.