bluuebunny/crossref_metadata_2025 huggingface dataset:
Autonomous Chemical Sensing Interface for Universal Cell Phone Readout
Authors: Comina Germán , Suska Anke , Filippini Daniel
Published: June 2015

Exploiting the ubiquity of cell phones for quantitative chemical sensing imposes strong demands on interfacing devices. They should be autonomous, disposable, and integrate all necessary calibration and actuation elements. In addition, a single design should couple universally to a variety of cell phones, and operate in their default configuration. Here, we demonstrate such a concept and its implementation as a quantitative glucose meter that integrates finger pumps, unidirectional valves, calibration references, and focusing optics on a disposable device configured for universal video acquisition.
Step‐by‐Step Growth of Complex Oxide Microstructures
Authors: Datskos Panos , Cullen David A. , Sharma Jaswinder
Published: June 2015

The synthesis of complex and hybrid oxide microstructures is of fundamental interest and practical applications. However, the design and synthesis of such structures is a challenging task. A solution‐phase process to synthesize complex silica and silica–titania hybrid microstructures was developed by exploiting the emulsion‐droplet‐based step‐by‐step growth featuring shape control. The strategy is robust and can be extended to the preparation of complex hybrid structures consisting of two or more materials, with each having its own shape.
Bridging the Gap between Bisylides and Methandiides: Isolation, Reactivity, and Electronic Structure of an Yldiide
Authors: Scherpf Thorsten , Wirth Regina , Molitor Sebastian , Feichtner Kai‐Stephan , Gessner Viktoria H.
Published: June 2015

Bisylides and methandiides are two unique families of carbon bases that have found a variety of applications in recent years. Metalated ylides (yldiides) are the link between these types of compounds. Yet, only little is known about their properties, reactivities, and particularly their electronic structure. Here, we report the preparation of the metalated ylide [Ph3P‐C‐SO2Tol]− (1) with different alkali metal counterions. The compounds have been studied by X‐ray diffraction analysis and NMR spectroscopy and the first structures of a sodium and potassium yldiide are presented. The electronic structure of 1 was explored by DFT calculations confirming its relation with other divalent carbon species. Reactivity studies demonstrate the strong nucleophilicity of the yldiide and its capability to act both as a σ‐ and π‐donor.
Oxidative Decarboxylation of Short‐Chain Fatty Acids to 1‐Alkenes
Authors: Dennig Alexander , Kuhn Miriam , Tassoti Sebastian , Thiessenhusen Anja , Gilch Stefan , Bülter Thomas , Haas Thomas , Hall Mélanie , Faber Kurt
Published: June 2015

The enzymatic oxidative decarboxylation of linear short‐chain fatty acids (C4:0–C9:0) employing the P450 monooxygenase OleT, O2 as the oxidant, and NAD(P)H as the electron donor gave the corresponding terminal C3 to C8 alkenes with product titers of up to 0.93 g L−1 and TTNs of >2000. Key to this process was the construction of an efficient electron‐transfer chain employing putidaredoxin CamAB in combination with NAD(P)H recycling at the expense of glucose, formate, or phosphite. This system allows for the biocatalytic production of industrially important 1‐alkenes, such as propene and 1‐octene, from renewable resources for the first time.
l‐Proline‐functionalized Fe3O4 nanoparticles as a novel magnetic chiral catalyst for the direct asymmetric Mannich reaction
Authors: Safaei‐Ghomi Javad , Zahedi Safura
Published: June 2015

l‐Proline has been successfully anchored on the surface of magnetic nanoparticles and characterized using powder X‐ray diffraction, scanning electron microscopy, vibrating sample magnetometry and Fourier transform infrared spectroscopy. These nanoparticles as a chiral catalyst have been employed to promote the direct asymmetric Mannich reaction. The corresponding products are obtained in high yields with high level of diastereoselectivity (up to 99:1 dr) in the presence of Fe3O4– l‐proline. Also this heterogeneous catalyst can be recovered easily and reused many times without significant loss of its catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.
Thermal and electrical conductivity of melt mixed polycarbonate hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets
Authors: Wegrzyn Marcin , Ortega Amaya , Benedito Adolfo , Gimenez Enrique
Published: June 2015

In this work, we present thermoplastic nanocomposites of polycarbonate (PC) matrix with hybrid nanofillers system formed by a melt‐mixing approach. Various concentrations of multi‐walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were mixed in to PC and the melt was homogenized. The nanocomposites were compression molded and characterized by different techniques. Torque dependence on the nanofiller composition increased with the presence of carbon nanotubes. The synergy of carbon nanotubes and GnP showed exponential increase of thermal conductivity, which was compared to logarithmic increase for nanocomposite with no MWCNT. Decrease of Shore A hardness at elevated loads present for all investigated nanocomposites was correlated with the expected low homogeneity caused by a low shear during melt‐mixing. Mathematical model was used to calculate elastic modulus from Shore A tests results. Vicat softening temperature (VST) showed opposite pattern for hybrid nanocomposites and for PC‐MWCNT increasing in the latter case. Electrical conductivity boost was explained by the collective effect of high nanofiller loads and synergy of MWCNT and GnP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42536.
Preparation and characterization of P(AN‐co‐VA‐co‐DEMA) fibers coated with multiwalled carbon nanotubes by electrostatic interactions
Authors: Yang Cheng‐Ran , Zhang Yu‐Mei , Wang Biao
Published: June 2015

P(AN‐co‐VA‐co‐DEMA) terpolymers were synthesized by aqueous precipitation copolymerization of acrylonitrile (AN), vinyl acetate (VA), and 2‐dimethylamino ethyl methacrylate (DEMA) with an Na2S2O5–NaClO3 redox initiating system and fibers from these terpolymers were thus prepared by a wet spinning method. Functionalized multiwalled carbon nanotube (F‐MWNT) networks were created on the surface of P(AN‐co‐VA‐co‐DEMA) fibers by a simple dipping method. The morphology and interfacial interactions of the obtained F‐MWNTs‐coated fibers were characterized by scanning electron microscope, Raman spectroscopy, and Fourier transform infrared spectroscopy. The results showed that F‐MWNTs were assembled on the fibers and the density of F‐MWNTs can be controlled by adjusting the F‐MWNTs content in the dipping solution. The assembly process was driven by electrostatic interactions between the negative charges on the nanotube sidewalls and the positive charges of the fibers. The F‐MWNTs‐coated fibers had a good conductivity. The volume resistivity of the fibers coated with 1.18 wt % F‐MWNTs reached 0.27 Ω·cm, while the original mechanical properties were preserved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42545.
Definition of Forensic Psychotherapy and its Aims
Authors: Welldon Estela
Published: June 2015

In this paper the author shall try to illuminate the advantages of using a psychoanalytical model in our understanding of the forensic patient. There is the problem that sometimes the judicial and psychoanalytic approaches appear to be incompatible, though both are inherently intertwined with societal mores through the nature of anti‐social, delinquent actions usually associated with such cases. Many of the ideas at the root of this paper are from Karl Menninger, with whom the author trained in the early 1960s. Copyright © 2015 John Wiley & Sons, Ltd.
The Inpatient Treatment of Personality‐disordered Offenders: Multidisciplinary Successes and Tensions
Authors: Taylor Celia
Published: June 2015

The “Dangerous and Severe Personality Disorder” (DSPD) program of pilot treatment units was established following the high profile double homicide of a mother and one of her two daughters: the very kind of stranger killing that, although in fact extremely rare, the public identifies with most fearfully. This paper describes one of the medium secure DSPD services in terms of the nature of the patients’ difficulties, and the treatment model that was established to address the dual task of reducing the risks they pose to the public and improving psychological health. The impact upon staff and upon teams working with such a disturbed and dangerous group of men is explored. Copyright © 2015 John Wiley & Sons, Ltd.
Spatial Expression of Otolith Matrix Protein‐1 and Otolin‐1 in Normally and Kinetotically Swimming Fish
Authors: Weigele Jochen , Franz‐Odendaal Tamara A. , Hilbig Reinhard
Published: June 2015

Kinetosis (motion sickness) has been repeatedly shown to affect some fish of a given clutch following the transition from 1g to microgravity or from hypergravity to 1g. This susceptibility to kinetosis may be correlated with irregular inner ear otolith growth. Otoliths are mainly composed of calcium carbonate and matrix proteins, which play an important role in the process of otolith mineralization. Here, we examine the morphology of otoliths and the expression pattern of the major otolith proteins OMP‐1 and otolin‐1 in a series of hypergravity experiments. In the utricle, OMP‐1 is present in centripetal (medial) and centrifugal (lateral) regions of the meshwork area. In the saccule, OMP‐1 was expressed within a dorsal and a ventral narrow band of the meshwork area opposite to the periphery of the sulcus acusticus. In normal animals, the spatial expression pattern of OMP‐1 reaches more posteriorly in the centrifugal aspect and is considerably broader in the centripetal portion of the utricle compared to kinetotic animals. However, otolin‐1 was not expressed in the utricule. In the saccule, no differences were observed for either gene when comparing normal and kinetotically behaving fish. The difference in the utricular OMP‐1 expression pattern between normally and kinetotically swimming fish indicates a different otolith morphology and thus a different geometry of the otoliths resting on the corresponding sensory maculae. As the utricle is the endorgan responsible for sensing gravity, the aberrant morphology of the utricular otoliths, based on OMP‐1 expression, likely leads to the observed kinetotic behavior. Anat Rec, 298:1765–1773, 2015. © 2015 Wiley Periodicals, Inc.
A Mechanochromic Luminescent Dye Exhibiting On/Off Switching by Crystalline–Amorphous Transitions
Authors: Imoto Hiroaki , Kizaki Kohei , Naka Kensuke
Published: June 2015

A mechanochromic luminescent dye based on a simple aminomaleimide skeleton was readily synthesized in a one‐pot process. It exhibited an on/off mechanochromic luminescent switching property dependent on external stimuli, unlike a traditional mechanochromic color change. The green emission was turned on by grinding in a mortar and turned off by heating or treatment with dichloromethane. In the crystalline state, two molecules were stacked by cofacial π–π interactions, which caused concentration self‐quenching. The crystalline‐to‐amorphous transition induced by grinding removed cofacial π–π stacking, which led to intensive emission. Crystallizing processes recovered the cofacial π–π stacking, resulting in elimination of the emission. Theoretical calculations and X‐ray diffraction analyses revealed that the dye molecule was distorted in the crystalline state; thus even a mechanical stimulus caused the crystalline‐to‐amorphous transition.
A Domino Oxidation/Arylation/Protodecarboxylation Reaction of Salicylaldehydes: Expanded Access to meta‐Arylphenols
Authors: Luo Junfei , Preciado Sara , Araromi Solomon Olatokunbo , Larrosa Igor
Published: June 2015

A method that allows salicylaldehydes to be efficiently transformed into meta‐arylated phenol derivatives through a cascade oxidation/arylation/protodecarboxylation sequence is presented. We demonstrate that the aldehyde functional group can be used as a convenient removable directing group to control site selectivity in C−H activation. Aldehydes are easily introduced into the starting materials and the group is readily cleaved after the C−H functionalization event.
The adjoint sensitivity of heavy rainfall to initial conditions in debris flow areas in China
Authors: Zhou Feifan , Cui Xiaopeng
Published: June 2015

By studying three heavy rainfall events that were accompanied by debris flows in southwestern China, we find that 24‐h accumulated rainfall is most sensitive to the initial temperature. The sensitivities to wind, surface pressure, and specific humidity are generally smaller. Moreover, the upper levels of the atmosphere are identified as the sensitive levels, and the sensitive areas are the areas with heavy rainfall. These results suggest that local temperature perturbations in the upper levels are a signal of short‐term heavy rainfall in southwestern China. A validation experiment is carried out to justify the sensitivity results. The possible reasons are discussed and analyzed.
A climatology of low‐level jets in the mid‐latitudes and polar regions of the Northern Hemisphere
Authors: Tuononen M. , Sinclair V. A. , Vihma T.
Published: June 2015

A wintertime climatology of the occurrence and characteristics of low‐level jets (LLJs) in the Northern Hemisphere mid‐latitudes and polar regions was developed. A LLJ detection algorithm was applied to 11 years of Arctic system reanalysis data. The highest occurrence of LLJs was associated with strong gradients in topography and with the sea‐ice edge. Sea areas fully covered with sea ice also favoured the occurrence of LLJs, however, these areas, including the central Arctic, had fewer LLJs than along the sea‐ice edge. LLJs also occurred frequently in the seldom studied Sea of Okhotsk area.
High‐level production of Arthrobacter aurescens CYC705 nitrilase in Escherichia coli for biosynthesis of iminodiacetic acid
Authors: Su Erzheng , Lu Chao , Ma Xiaoqiang , Cai Wenwen , Zhu Shujing
Published: June 2015

Nitrilase from Arthrobacter aurescens CYC705 can hydrolyze the iminodiacetonitrile to iminodiacetic acid (IDA) efficiently, and its high‐level production in Escherichia coli has not been established. In the present work, the production of this nitrilase expressed in E. coli BL21(DE3) with a recombinant plasmid pET28a‐cyc705 was optimized. Various culture conditions and process parameters including medium components and concentrations, inducer types and concentrations, inducing temperature and time were systematically examined in a shake flask. After optimization, the OD600, nitrilase activity, and productivity were obviously improved and achieved to 40.91 ± 1.341, 98.12 ± 1.248 U/mL, and 2,230 ± 28.36 U L−1 H−1, respectively, about 2.1‐, 30‐, and 33‐fold increases as compared with those in the primary medium. Furthermore, four different fermentation strategies were adopted to scale up cultivation of the recombinant E. coli BL21(DE3)/pET28a‐cyc705 in a 3.7‐L fermenter. Substituting the peanut powder with fish peptone and accompanying with 1.0% glycerol feeding could significantly reduce the bubble production and shorten the fermentation time, which resulted in a nitrilase productivity of 4,653 ± 38.16 U L−1 H−1 that was about two times higher than that in a shake flask. The high‐level production of A. aurescens CYC705 nitrilase established in this study will meet the need of industrial biosynthesis of IDA.
Exploring the Generalization Process from Past Behavior to Predicting Future Behavior
Authors: Harris Lasana , Lee Victoria K. , Thompson Elizabeth H. , Kranton Rachel
Published: June 2015

Substantial evidence in social psychology documents that traits predict behavior. Research in behavioral economics establishes prior behavioral information—the actual behavior of another person in the past—influences future decision making, suggestive of the role of traits in guiding future behavior, but agnostic to the specific psychological mechanism. Yet the entire generalization process from past behavior to predicting future behavior has not been fully explored. Additionally, previous paradigms do not adequately dissociate prediction from explanation, and provide participants with trait information, or rely on participants to generate the appropriate trait. Here, we combine literature and experimental approaches in social psychology and behavioral economics to explore the generalization process from prior behavior that guides future decisions. Across three studies utilizing consequential economic game paradigms and online questionnaires, an initial group of participants (employees) played a time estimation game and a charity donations game before a second group of participants (employers) viewed the behavior of the first group, then decided whether to invest in employees in a trust game and rock guessing game. Although participants infer trait warmth and competence from the behavioral information in the first two games, estimates of normative behavior predicted investment decisions on the warmth‐relevant games better than trait inferences. These results dissociate generalizations guided by warmth and competence behavioral information, and question the extent to which traits always serve as heuristics to predict behavior. Copyright © 2015 John Wiley & Sons, Ltd.
Suppression of Arabidopsis flowering by near‐null magnetic field is affected by light
Authors: Xu Chunxiao , Li Yue , Yu Yang , Zhang Yuxia , Wei Shufeng
Published: June 2015

We previously reported that a near‐null magnetic field suppressed Arabidopsis flowering in white light, which might be related to the function modification of cryptochrome (CRY). To further demonstrate that the effect of near‐null magnetic field on Arabidopsis flowering is associated with CRY, Arabidopsis wild type and CRY mutant plants were grown in the near‐null magnetic field under blue or red light with different light cycle and photosynthetic photon flux density. We found that Arabidopsis flowering was significantly suppressed by near‐null magnetic field in blue light with lower intensity (10 µmol/m2/s) and shorter cycle (12 h period: 6 h light/6 h dark). However, flowering time of CRY1/CRY2 mutants did not show any difference between plants grown in near‐null magnetic field and in local geomagnetic field under detected light conditions. In red light, no significant difference was shown in Arabidopsis flowering between plants in near‐null magnetic field and local geomagnetic field under detected light cycles and intensities. These results suggest that changes of blue light cycle and intensity alter the effect of near‐null magnetic field on Arabidopsis flowering, which is mediated by CRY. Bioelectromagnetics. 36:476–479, 2015. © 2015 Wiley Periodicals, Inc.
Re‐programming CHO cell metabolism using miR‐23 tips the balance towards a highly productive phenotype
Authors: Kelly Paul S. , Breen Laura , Gallagher Clair , Kelly Shane , Henry Michael , Lao Nga T. , Meleady Paula , O'Gorman Donal , Clynes Martin , Barron Niall
Published: June 2015

microRNA engineering of CHO cells has already proved successful in enhancing various industrially relevant phenotypes and producing various recombinant products. A single miRNA's ability to interact with multiple mRNA targets allows their regulatory capacity to extend to processes such as cellular metabolism. Various metabolic states have previously been associated with particular CHO cell phenotypes such as glycolytic or oxidative metabolism accommodating growth and productivity, respectively. miR‐23 has previously been demonstrated to play a role in glutamate metabolism resulting in enhanced oxidative phosphorylation through the TCA cycle. Re‐programming cellular bioenergetics through miR‐23 could tip the balance, forcing mammalian production cells to be more productive by favoring metabolic channelling into oxidative metabolism. CHO clones depleted of miR‐23 using a miR‐sponge decoy demonstrated an average ∼three‐fold enhanced specific productivity with no impact on cell growth. Using a cell respirometer, mitochondrial activity was found to be enhanced by ∼30% at Complex I and II of the electron transport system. Additionally, label‐free proteomic analysis uncovered various potential novel targets of miR‐23 including LE™1 and IDH1, both implicated in oxidative metabolism and mitochondrial activity. These results demonstrate miRNA‐based engineering as a route to re‐programming cellular metabolism resulting in increased productivity, without affecting growth.
Tumour regression in the randomized Stockholm III Trial of radiotherapy regimens for rectal cancer
Authors: Pettersson D , Lörinc E , Holm T , Iversen H , Cedermark B , Glimelius B , Martling A
Published: June 2015

Background

The Stockholm III Trial randomized patients with primary operable rectal cancers to either short-course radiotherapy (RT) with immediate surgery (SRT), short-course RT with surgery delayed 4–8 weeks (SRT-delay) or long-course RT with surgery delayed 4–8 weeks. This preplanned interim analysis examined the pathological outcome of delaying surgery.

Methods

Patients randomized to the SRT and SRT-delay arms in the Stockholm III Trial between October 1998 and November 2010 were included, and data were collected in a prospective register. Additional data regarding tumour regression grade, according to Dworak, and circumferential margin were obtained by reassessment of histopathological slides.

Results

A total of 462 of 545 randomized patients had specimens available for reassessment. Patients randomized to SRT-delay had earlier ypT categories, and a higher rate of pathological complete responses (11·8 versus 1·7 per cent; P = 0·001) and Dworak grade 4 tumour regression (10·1 versus 1·7 per cent; P < 0·001) than patients randomized to SRT without delay. Positive circumferential resection margins were uncommon (6·3 per cent) and rates did not differ between the two treatment arms.

Conclusion

Short-course RT induces tumour downstaging if surgery is performed after an interval of 4–8 weeks.
Fast simultaneous LC/MS/MS determination of 10 active compounds in human serum for therapeutic drug monitoring in psychiatric medication
Authors: Sistik Pavel , Urinovska Romana , Brozmanova Hana , Kacirova Ivana , Silhan Petr , Lemr Karel
Published: June 2015

A UPLC/MS/MS method with simple protein precipitation has been validated for the fast simultaneous analysis of agomelatine, asenapine, amisulpride, iloperidone, zotepine, melperone, ziprasidone, vilazodone, aripiprazole and its metabolite dehydro‐aripiprazole in human serum. Alprenolol was applied as an internal standard. A BEH C18 (2.1 × 50 mm, 1.7 µm) column provided chromatographic separation of analytes using a binary mobile phase gradient (A, 2 mmol/L ammonium acetate, 0.1% formic acid in 5% acetonitrile, v/v/v; B, 2 mmol/L ammonium acetate, 0.1% formic acid in 95% acetonitrile, v/v/v). Mass spectrometric detection was performed in the positive electrospray ionization mode and ion suppression owing to matrix effects was evaluated. The validation criteria were determined: linearity, precision, accuracy, recovery, limit of detection, limit of quantification, reproducibility and matrix effect. The concentration range was as follows: 0.25–1000 ng/mL for agomelatine; 0.25–100 ng/mL for asenapine and iloperidone; 2.5–1000 ng/mL for amisulpride, aripiprazole, vilazodone and zotepine; 2.3–924.6 ng/mL for dehydroaripiprazole; 2.2–878.4 ng/mL for melperone; and 2.2–883.5 ng/mL for ziprasidone. Limits of quantitation below a therapeutic reference range were achieved for all analytes. Intra‐run precision of 0.4–5.5 %, inter‐run precision of 0.6–8.2% and overall recovery of 87.9–114.1% were obtained. The validated method was successfully implemented into routine practice for therapeutic drug monitoring in our hospital. Copyright © 2015 John Wiley & Sons, Ltd.
Evaluation of clinically relevant landmarks of the marginal mandibular branch of the facial nerve: A three‐dimensional study with application to avoiding facial nerve palsy
Authors: Davies Joel C. , Ravichandiran Mayoorendra , Agur Anne M. , Fattah Adel
Published: June 2015

Injury to the marginal mandibular branch of the facial nerve (MMN) during surgery often results in poor functional and cosmetic outcomes. A line two finger breadths or 2 cm inferior to the border of the mandible is commonly used in planning neck incisions to avoid injury to the MMN. The purpose was to compare the two finger breadth/2 cm landmarks in predicting MMN course, and their accuracy/reliability. Thirty‐one cadaveric specimens were scanned to obtain 3D surface topography (FARO® scanner). Four independent raters pinned the inferior border of the mandible and a two finger breadth line and 2cm line below. The location of each pin was digitized (Microscribe™). A preauricular flap was raised, and MMN branches were digitized and modelled (Geomagic®/Maya®) enabling quantification of the accuracy of these landmarks. The location of the two‐finger breadth line was variable, spanning 25–51 mm below the inferior border of the mandible (ICC = 0.10). The most inferior MMN branch did not pass below the two‐finger breadth line in any specimen, but a narrow clearance zone (≤5 mm) was found in two. In contrast, in 7/31 specimens, the most inferior MMN branch coursed below the 2 cm line and would be at risk of injury. It was concluded that an incision two finger breadths below the inferior border of the mandible could provide safer access than the 2 cm line. After an incision has been placed using the two finger‐breadth landmark, caution must be exercised during dissection as branches of the MMN may lie only a few millimeters superior to the incision. Clin. Anat. 29:151–156, 2016. © 2015 Wiley Periodicals, Inc.
Domestic minor sex trafficking: An emerging health crisis
Authors: Kaplan Dana , Kemp Kathleen
Published: June 2015

The commercial sexual exploitation of children (CSEC) occurs when a person induces a minor to engage in a sex act in exchange for remuneration in the form of money, food, shelter or another valued entity. Domestic minor sex trafficking (DMST) refers to the commercial sexual exploitation of children who live within U.S. borders. This term assists in differentiating these victims from those who have been trafficked from other countries into the United States or elsewhere specifically for the purpose of performing sexual acts (“international sex trafficking”).
Adaptive Internal Model Control of a High‐Purity Heat‐Integrated Air Separation Column
Authors: Fu Yao , Liu Xinggao
Published: June 2015

An internal model control scheme based on a second‐order internal model (SI‐IMC) is proposed for the heat‐integrated air separation column (HIASC). An adaptive internal model control (ASI‐IMC) scheme is further presented to make the model more accurate. The IMC scheme based on the first‐order model (F‐IMC) and the multi‐loop PID (M‐PID) scheme are also explored as the comparison basis of ASI‐IMC and SI‐IMC schemes. Comparative researches among these four control schemes are carried out in detail. The results indicate that ASI‐IMC presents the best performances among the four control schemes in both servo control and regulatory control, which proves the improvement of ASI‐IMC over the SI‐IMC and the superiority of ASI‐IMC for the high‐purity HIASC.
Gas‐Liquid Mass Transfer Rates and Impeller Power Consumptions for Industrial Vessel Design
Authors: Labík Libor , Moucha Tomáš , Kordač Michal , Rejl František J. , Valenz Lukáš
Published: June 2015

Volumetric mass transfer coefficients (kLa) and power input (P) are often the key parameters in the design of gas‐liquid contactors. However, due to the limitations of most measurement methods, there is a lack of reliable data for predicting kLa for non‐coalescent batches under high energy dissipation rates. Accurate kLa and P correlations are proposed. The reliability of the correlations is ensured by using experimental data from a wide range of process conditions conducted in multiple‐impeller vessels of both laboratory scale and pilot scale, and including both non‐coalescent and coalescent batches. Applying the proposed correlations, the scale‐up and optimization of industrial vessels can be performed more accurately.
Pt supported on Nanostructured NCNTs/RGO Composite Electrodes for Methanol Electrooxidation
Authors: Wang Pei , Kottakkat Tintula , Bron Michael
Published: June 2015

Composites consisting of N‐doped carbon nanotubes and reduced graphene oxide (NCNTs/RGO) are prepared directly on carbon cloth (CC) via H2‐assisted thermal reduction of graphene oxide (GO) followed by chemical vapor deposition of NCNTs to form NCNTs/RGO/CC. Pt nanoparticles are uniformly electrodeposited onto these nanostructured composite electrodes. The success of each preparation step is verified by Raman spectroscopy, X‐ray diffraction and scanning electron microscopy, respectively, indicating dense and homogeneous distribution of NCNTs and Pt. The resulting composite electrode exhibits enhanced mass specific activity for methanol oxidation in comparison to Pt‐NCNTs/CC (without RGO), as evaluated by cyclic voltammetry. The ratio of the forward to backward peak current values (if/ib) and the COad stripping voltammetry reveal high tolerance of Pt‐NCNTs/RGO/CC towards poisoning in comparison to Pt‐NCNTs/CC or literature reports, leading to an efficient methanol electrooxidation.
Improving the Lithium‐Storage Properties of Self‐Grown Nickel Oxide: A Back‐Up from TiO2 Nanoparticles
Authors: Balogun Muhammad‐Sadeeq , Qiu Weitao , Luo Yang , Huang Yongchao , Yang Hao , Li Mingyang , Yu Minghao , Liang Chaolun , Fang Pingping , Liu Peng , Tong Yexiang
Published: June 2015

After long electrochemical cycles, the continuous loss in the capacity of nickel oxide (NiO) hinders its practical application as anode material for lithium‐ion batteries. The need to improve the lithium‐storage performance of NiO becomes essential for the accomplishment of high‐performance lithium‐ion batteries. In this respect, a new form of 3D NiO, which comprises TiO2 nanoparticles, has been fabricated and used as anode for lithium‐ion storage. The as‐prepared 3D NiO–TiO2 nanocomposites achieved areal discharge capacities of 1.49 and 0.78 mAh cm−2 at current densities of 1.0 and 6.0 mA cm−2, respectively. The improvement in the lithium‐storage properties of the NiO/TiO2 nanocomposite is attributed to the TiO2 nanoparticles creating rational interfaces with the NiO, which incredibly supports the NiO surface and improves the structural stability.
Energy Transfer in a Hybrid IrIII Carbene–PtII Acetylide Assembly for Efficient Hydrogen Production
Authors: Yu Zhen‐Tao , Yuan Yong‐Jun , Chen Xin , Cai Jian‐Guang , Zou Zhi‐Gang
Published: June 2015

A new heterometallic supramolecular complex, consisting of an iridium carbene‐based unit appended to a platinum terpyridine acetylide unit, representing a new IrIII–PtII structural motif, was designed and developed to act as an active species for photocatalytic hydrogen production. The results also suggested that a light‐harvesting process is essential to realize the solar‐to‐fuel conversion in an artificial system as illustrated in the natural photosynthetic system.
Surface‐Functionalized Nanoparticles by Olefin Metathesis: A Chemoselective Approach for In Vivo Characterization of Atherosclerosis Plaque
Authors: Salinas Beatriz , Ruiz‐Cabello Jesús , Lechuga‐Vieco Ana V. , Benito Marina , Herranz Fernando
Published: June 2015

The use of click chemistry reactions for the functionalization of nanoparticles is particularly useful to modify the surface in a well‐defined manner and to enhance the targeting properties, thus facilitating clinical translation. Here it is demonstrated that olefin metathesis can be used for the chemoselective functionalization of iron oxide nanoparticles with three different examples. This approach enables, in one step, the synthesis and functionalization of different water‐stable magnetite‐based particles from oleic acid‐coated counterparts. The surface of the nanoparticles was completely characterized showing how the metathesis approach introduces a large number of hydrophilic molecules on their coating layer. As an example of the possible applications of these new nanocomposites, a focus was taken on atherosclerosis plaques. It is also demonstrated how the in vitro properties of one of the probes, particularly its Ca2+‐binding properties, mediate their final in vivo use; that is, the selective accumulation in atherosclerotic plaques. This opens promising new applications to detect possible microcalcifications associated with plaque vulnerability. The accumulation of the new imaging tracers is demonstrated by in vivo magnetic resonance imaging of carotids and aorta in the ApoE−/− mouse model and the results were confirmed by histology.
Fabrication of Efficient Hydrogenation Nanoreactors by Modifying the Freedom of Ultrasmall Platinum Nanoparticles within Yolk–Shell Nanospheres
Authors: Peng Juan , Lan Guojun , Guo Miao , Wei Xuming , Li Can , Yang Qihua
Published: June 2015

The synthesis of silica‐based yolk–shell nanospheres confined with ultrasmall platinum nanoparticles (Pt NPs) stabilized with poly(amidoamine), in which the interaction strength between Pt NPs and the support could be facilely tuned, is reported. By ingenious utilization of silica cores with different surface wettability (hydrophilic vs. ‐phobic) as the adsorbent, Pt NPs could be confined in different locations of the yolk–shell nanoreactor (core vs. hollow shell), and thus, exhibit different interaction strengths with the nanoreactor (strong vs. weak). It is interesting to find that the adsorbed Pt NPs are released from the core to the hollow interiors of the yolk–shell nanospheres when a superhydrophobic inner core material (SiO2Ph) is employed, which results in the preparation of an immobilized catalyst (Pt@SiO2Ph); this possesses the weakest interaction strength with the support and shows the highest catalytic activity (88 500 and 7080 h−1 for the hydrogenation of cyclohexene and nitrobenzene, respectively), due to its unaffected freedom of Pt NPs for retention of the intrinsic properties.
Recent Developments in Synthetic Carbohydrate‐Based Diagnostics, Vaccines, and Therapeutics
Authors: Fernández‐Tejada Alberto , Cañada F. Javier , Jiménez‐Barbero Jesús
Published: June 2015

Glycans are everywhere in biological systems, being involved in many cellular events with important implications for medical purposes. Building upon a detailed understanding of the functional roles of carbohydrates in molecular recognition processes and disease states, glycans are increasingly being considered as key players in pharmacological research. On the basis of the important progress recently made in glycochemistry, glycobiology, and glycomedicine, we provide a complete overview of successful applications and future perspectives of carbohydrates in the biopharmaceutical and medical fields. This review highlights the development of carbohydrate‐based diagnostics, exemplified by glycan imaging techniques and microarray platforms, synthetic oligosaccharide vaccines against infectious diseases (e.g., HIV) and cancer, and finally carbohydrate‐derived therapeutics, including glycomimetic drugs and glycoproteins.
Highly Segregated Lamello‐Columnar Mesophase Organizations and Fast Charge Carrier Mobility in New Discotic Donor–Acceptor Triads
Authors: Zhao Ke‐Qing , An Ling‐Ling , Zhang Xiao‐Bo , Yu Wen‐Hao , Hu Ping , Wang Bi‐Qin , Xu Jing , Zeng Qing‐Dao , Monobe Hirosato , Shimizu Yo , Heinrich Benoît , Donnio Bertrand
Published: June 2015

Four new donor–acceptor triads (D–A–D) based on discotic and arylene mesogens have been synthesized by using Sonogashira coupling and cyclization reactions. This family of triads consists of two side‐on pending triphenylene mesogens, acting as the electron‐donating groups (D), laterally connected through short lipophilic spacers to a central perylenediimide (PI), benzo[ghi]perylenediimide (BI), or coronenediimide (CI) molecular unit, respectively, playing the role of the electron acceptor (A). All D–A–D triads self‐organize to form a lamello‐columnar oblique mesophase, with a highly segregated donor–acceptor (D–A) heterojunction organization, consequent to efficient molecular self‐sorting. The structure consists in the regular alternation of two disrupted rows of triphenylene columns and a continuous row of diimine species. High‐resolution STM images demonstrate that PI‐TP2 forms stable 2D self‐assembly nanostructures with some various degrees of regularity, whereas the other triads do not self‐organize into ordered architectures. The electron‐transport mobility of CI‐TP2, measured by time‐of‐flight at 200 °C in the mesophase, is one order of magnitude higher than the hole mobility. By means of this specific molecular designing idea, we realized and demonstrated for the first time the so‐called p–n heterojunction at the molecular level in which the electron‐rich triphenylene columns act as the hole transient pathways, and the coronenediimide stacks form the electron‐transport channels.
A Nitro‐Functionalized Metal–Organic Framework as a Reaction‐Based Fluorescence Turn‐On Probe for Rapid and Selective H2S Detection
Authors: Nagarkar Sanjog S. , Desai Aamod V. , Ghosh Sujit K.
Published: June 2015

The toxic gas H2S has recently emerged as one of the important signaling molecules in biological systems. Thus understanding the production, distribution, and mode of action of H2S in biological system is important, but the fleeting and reactive nature of H2S makes it a daunting task. Herein we report a biocompatible, nitro‐functionalized metal–organic framework as reaction‐based fluorescence turn‐on probe for fast and selective H2S detection. The selective turn‐on performance of MOF remains unaffected even in presence of competing biomolecules.
Visible‐Light‐Driven Intermolecular [2+2] Cycloadditions between Coumarin‐3‐Carboxylates and Acrylamide Analogs
Authors: Liu Qiang , Zhu Fu‐Ping , Jin Xiao‐Ling , Wang Xiao‐Ju , Chen Han , Wu Li‐Zhu
Published: June 2015

This paper reports a room temperature visible‐light‐driven protocol for the intermolecular [2+2] cycloadditions between coumarin‐3‐carboxylates and acrylamides analogs by an energy‐transfer process. Using an iridium complex FIrPic as a photosensitizer and a 3 W blue LED as a light source, an array of cyclobutabenzocypyranones were prepared in moderate to excellent yields.
Fluorescent Pyrene‐Based Bis‐azole Compounds: Synthesis and Photophysical Analysis
Authors: Ibáñez Susana , Guerrero Antonio , Poyatos Macarena , Peris Eduardo
Published: June 2015

A rational synthetic procedure for the preparation of a series of pyrene‐based neutral and dicationic bis‐azole compounds is reported. The method allows the tailored design of pyrene‐based azoles with different substituents at the nitrogen atoms of the heterocycles, for which the relative conformation of the resulting bis‐azoles can be easily controlled. The bis‐azoliums were used for the preparation of the related diplatinum complexes by reaction with [{Pt(ppy)(μ‐Cl)2}2] (ppy=2‐phenylpyridinate). The X‐ray molecular structure of one of the resulting compounds, a diplatinum(II) bis(N‐heterocyclic carbene) complex, is described. Studies on the photophysical properties of all new species are described. The emission of the bis‐azole‐based compounds seems to be independent of their substitution patterns, which basically indicates that physical properties such as solubility, melting point, and viscosity can be fine‐tuned while maintaining the luminescence properties. Finally, the energies associated with the HOMO and LUMO levels suggest that this family provides versatility to match the energy levels of a wide range of host materials, which is important for the preparation of organic light‐emitting devices.
Silver‐Catalyzed Coupling of Two CH Groups and One‐Pot Synthesis of Tetrasubstituted Furans, Thiophenes, and Pyrroles
Authors: Mao Shuai , Zhu Xue‐Qing , Gao Ya‐Ru , Guo Dong‐Dong , Wang Yong‐Qiang
Published: June 2015

Silver‐catalyzed coupling of two CH groups to form 1,4‐diketones have been developed for the first time. The resultant ketones then undergo cyclization to synthesize tetrasubstituted furans, thiophenes, and pyrroles from benzyl ketone derivatives in a one‐pot reaction process. This highly‐efficient synthetic method, which utilizes air as the terminal oxidant and readily accessible starting materials, displays a wide substrate scope and broad functional‐group tolerance.
Highly Chemoselective Catalytic Coupling of Substituted Oxetanes and Carbon Dioxide
Authors: Rintjema Jeroen , Guo Wusheng , Martin Eddy , Escudero‐Adán Eduardo C. , Kleij Arjan W.
Published: June 2015

The chemoselective coupling of oxetanes and carbon dioxide to afford functional, heterocyclic organic compounds known as six‐membered cyclic carbonates remains a challenging topic. Here, an effective method for their synthesis relying on the use of Al catalysis is described. The catalytic reactions can be carried out with excellent selectivity for the cyclic carbonate product tolerating various (functional) groups present in the 2‐ and 3‐position(s) of the oxetane ring. The presented methodology is the first general approach towards the formation of six‐membered cyclic carbonates (6MCCs) through oxetane/CO2 coupling chemistry. Apart from a series of substituted six‐membered cyclic carbonates, also the unprecedented room‐temperature coupling of oxetanes and CO2 is disclosed giving, depending on the structural features of the substrate, a variety of five‐ and six‐membered heterocyclic products. A mechanistic rationale is presented for their formation and support for the intermediary presence of a carbonic acid derivative is given. The presented functional carbonates may hold great promise as building blocks in organic synthesis and the development of new, biodegradable polymers.
Synergistic Stereocontrol in the Enantioselective Ruthenium‐Catalyzed Sulfoxidation of Spirodithiolane‐Indolones
Authors: Zhong Fangrui , Pöthig Alexander , Bach Thorsten
Published: June 2015

A chiral ruthenium catalyst was developed for the enantioselective sulfoxidation of the title compounds. The catalyst combines two elements of chirality, a chiral pybox ligand and a chiral bicylic lactam unit, to which the ligand is attached. The latter unit was shown to improve significantly the performance of the catalyst by exposing one of the two enantiotopic sulfur atoms to the active site via hydrogen‐bond mediated coordination. Ten differently substituted substrates were converted into the respective sulfoxides in yields of 52–71 % and with ≥90 % ee.
Dipeptide‐Derived Multifunctional Quaternary Phosphonium Salt Catalyzed Asymmetric Cyclizations via a Tandem Michael Addition/SN2 Sequence
Authors: Cao Dongdong , Zhang Jiaxing , Wang Hongyu , Zhao Gang
Published: June 2015

A novel family of dipeptide‐based multifunctional quaternary phosphonium salts has been developed as chiral phase‐transfer catalysts, which feature ready accessibility and structure modularity, allowing easy fine‐tunings of activity. They demonstrated high efficiency in catalyzing the tandem asymmetric Michael addition/intramolecular SN2 reaction between 6 or 7‐substituted conjugate enones and malonates, providing synthetically important five or six‐membered carbocycles and heterocycles in good yields and with good to excellent enantioselectivities.
Metal–Organic Frameworks (MOFs) as Multivalent Materials: Size Control and Surface Functionalization by Monovalent Capping Ligands
Authors: Rijnaarts Timon , Mejia‐Ariza Raquel , Egberink Richard J. M. , van Roosmalen Wies , Huskens Jurriaan
Published: June 2015

Control over particle size and composition are pivotal to tune the properties of metal organic frameworks (MOFs), for example, for biomedical applications. Particle‐size control and functionalization of MIL‐88A were achieved by using stoichiometric replacement of a small fraction of the divalent fumarate by monovalent capping ligands. A fluorine‐capping ligand was used to quantify the surface coverage of capping ligand at the surface of MIL‐88A. Size control at the nanoscale was achieved by using a monovalent carboxylic acid‐functionalized poly(ethylene glycol) (PEG‐COOH) ligand at different concentrations. Finally, a biotin–carboxylic acid capping ligand was used to functionalize MIL‐88A to bind fluorescently labeled streptavidin as an example towards bioapplications.
Recent Advances in Stereoselective Drug Targeting
Authors: Zask Arie , Ellestad George A.
Published: June 2015

Reviewed here are some recent examples of medically important protein targets for which stereoselective drugs have been identified. These include heat shock protein 90 (Hsp90) inhibitors as anticancer agents; transient receptor potential vanilloid type 1 antagonists as new analgesics; stereospecific inhibition of human mutT homolog MTH1 for cancer treatment; the stereoselective binding of R‐ and S‐propranolol by the α1–acid glycoprotein transporter; metallohelical complexes that are nonpeptide α‐helical mimetics that enantioselectively target Aβ amyloid for the treatment of Alzheimer's disease; metallohelical assemblies with promising antimicrobial activity that enantioselectively target DNA of resistant bacteria; nonpeptide α‐helical metallohelices that target the DNA of cisplatin‐resistant cancer cells; diastereomeric selectivity of phenanthriplatin‐guanine adducts; and phenazine biosynthetic enzyme active sites that can host both enantiomers of a racemic ligand simultaneously. Chirality 27:589–597, 2015. © 2015 Wiley Periodicals, Inc.
Glycosaminoglycan and DNA Binding Induced Intra‐ and Intermolecular Exciton Coupling of the bis‐4‐Aminoquinoline Surfen
Authors: Zsila Ferenc
Published: June 2015

Despite the diverse biological activities of the glycosaminoglycan (GAG) antagonist surfen, the molecular details of its interaction with biomacromolecules remain poorly understood. Therefore, heparin and DNA binding properties of surfen were studied by circular dichroism (CD) and UV absorption spectroscopy methods. High‐affinity (Ka ~ 107 M‐1) association of surfen to the chiral heparin chain gives rise to a characteristic biphasic CD pattern due to the conformational twist of the aminoquinoline moieties around the central urea bridge. At higher drug loading, intermolecular stacking of surfen molecules alters the induced CD profile and also provokes strong UV hypochromism. In contrast to the right‐handed heparin template, binding of surfen to the left‐helicity chondroitin sulfate chains produces inverted CD pattern. Large UV hypochromism as well as polyphasic induced ellipticity bands indicate that surfen intercalates between the base pairs of calf‐thymus DNA. Extensive CD spectroscopic changes observed at higher drug binding ratios refer to cooperative binding interactions between the intercalated drug molecules. The inherent conformational flexibility of surfen demonstrated here for the first time is important in its binding to distinct macromolecular targets and should be considered for rational drug design of novel GAG antagonists. Chirality 27:605–612, 2015. © 2015 Wiley Periodicals, Inc.
Sorting Semiconducting Single‐Walled Carbon Nanotubes by Water‐Soluble Polyfluorene Assisted Electrophoresis and Its Application in Field‐effect Transistors
Authors: Zhu Haoyun , Wang Weizhi
Published: June 2015

We report a considerably promising method based on agarose gel electrophoresis (AGE) to separate single‐walled carbon nanotubes by adding a water‐soluble polyfluorene (w‐PFO) as surfactant into the agarose gel. In this effective method, the AGE/w‐PFO gel network will trap more semiconducting single‐walled carbon nanotubes (SWNTs) with the assistance of w‐PFO, for the strong interaction between w‐PFO and semiconducting species. The optical absorbance, photoluminescence emission and resonant Raman scattering characterization were used to verify the separation effect. The purity of separated semiconducting species is as high as (98±1)%. The demonstrated field effect transistors give the on/off ratio and mobility about 27000 and 10.2 cm2·V−1·s−1, respectively.