bluuebunny/crossref_metadata_2025 huggingface dataset:
Recycling Application of Li–MnO2 Batteries as Rechargeable Lithium–Air Batteries
Authors: Hu Yuxiang , Zhang Tianran , Cheng Fangyi , Zhao Qing , Han Xiaopeng , Chen Jun
Published: February 2015

The ever‐increasing consumption of a huge quantity of lithium batteries, for example, Li–MnO2 cells, raises critical concern about their recycling. We demonstrate herein that decayed Li–MnO2 cells can be further utilized as rechargeable lithium–air cells with admitted oxygen. We further investigated the effects of lithiated manganese dioxide on the electrocatalytic properties of oxygen‐reduction and oxygen‐evolution reactions (ORR/OER). The catalytic activity was found to be correlated with the composition of LixMnO2 electrodes (0<x<1) generated in situ in aprotic Li–MnO2 cells owing to tuning of the Mn valence and electronic structure. In particular, modestly lithiated Li0.50MnO2 exhibited superior performance with enhanced round‐trip efficiency (ca. 76 %), high cycling ability (190 cycles), and high discharge capacity (10 823 mA h gcarbon−1). The results indicate that the use of depleted Li–MnO2 batteries can be prolonged by their application as rechargeable lithium–air batteries.
Developing Conjugated Polymers with High Electron Affinity by Replacing a CC Unit with a B←N Unit
Authors: Dou Chuandong , Ding Zicheng , Zhang Zijian , Xie Zhiyuan , Liu Jun , Wang Lixiang
Published: February 2015

The key parameters of conjugated polymers are lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) energy levels. Few approaches can simultaneously lower LUMO and HOMO energy levels of conjugated polymers to a large extent (>0.5 eV). Disclosed herein is a novel strategy to decrease both LUMO and HOMO energy levels of conjugated polymers by about 0.6 eV through replacement of a CC unit by a B←N unit. The replacement makes the resulting polymer transform from an electron donor into an electron acceptor, and is proven by fluorescence quenching experiments and the photovoltaic response. This work not only provides an effective approach to tune the LUMO/HOMO energy levels of conjugated polymers, but also uses organic boron chemistry as a new toolbox to develop conjugated polymers with high electron affinity for polymer optoelectronic devices.
Synthesis, crystal structures and characterization of late first row transition metal complexes derived from thiosemicarbazone hub: DNA binding/cleavage studies
Authors: Netalkar Priya P. , Netalkar Sandeep P. , Revankar Vidyanand K.
Published: February 2015

Air‐ and moisture‐stable coordination compounds of late first row transition metals, i.e. Co(III), Ni(II), Cu(II) and Zn(II), derived from the ligand (E)‐4‐(4‐chlorophenyl)‐1‐(1‐hydroxypropan‐2‐ylidene)thiosemicarbazide were prepared and successfully characterized using various spectro‐analytical techniques. The molecular structures of the ligand LH and complexes C1 and C2 were determined using single‐crystal X‐ray diffraction. The complexes C1 and C2 are stabilized by weak intermolecular CH⋅⋅⋅π stacking interactions: C1 between phenyl rings (C2–H21⋅⋅⋅C2) with a contact distance of 2.855 Å and C2 between phenyl ring and thione sulfur (C13⋅⋅⋅S1) with a contact distance of 3.366(6) Å. Complex C3 is found to be electrochemically active in the working potential range, showing a quasi‐reversible redox process. The interactions of all the compounds with calf thymus DNA were comprehensively investigated using electronic absorption spectroscopy, viscosity and thermal denaturation studies. Cleavage studies of Escherichia coli DNA were monitored using agarose gel electrophoresis. The results show that LH and complex C4 bind to calf thymus DNA through partial intercalation, while remaining complexes bind electrostatically. Further, C1, C2 and C4 complexes show better cleavage potential towards E. coli DNA. Copyright © 2015 John Wiley & Sons, Ltd.
Thermal and dielectric properties of polycarbonatediol polyurethane
Authors: Ortiz‐Serna Pilar , Carsí Marta , Redondo‐Foj Belén , Sanchis María Jesús , Culebras Mario , Gómez Clara María , Cantarero Andrés
Published: February 2015

The dielectric relaxation behavior of segmented polyurethane has been studied using Broad‐Band Dielectric Spectroscopy in the frequency domain, 10−2 to 108 Hz, and in the temperature range of −120 to 140°C. The spectra show three secondary processes (δ, γ, and β) followed by the α relaxation and conductive processes. The Havriliak‐Negami (HN) phenomenological equation was used in order to characterize all the processes. The δ, γ, and β relaxations are probably associated with (i) local motions of the main chain (ii) motions of the carbonate group in the soft phase and (iii) reorientational motions of water molecules. The microphase separated morphology associated with soft and hard domains is reflected in the dielectric spectra, at high temperatures, by the presence of the Maxwell‐Wagner‐Sillars (MWS) interfacial polarization process. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42007.
Designing crosslinked hyaluronic acid hydrogels with tunable mechanical properties for biomedical applications
Authors: Khanlari Anahita , Schulteis Jason E. , Suekama Tiffany C. , Detamore Michael S. , Gehrke Stevin H.
Published: February 2015

This study develops a simple copolymerization/crosslinking technique to control the swelling and mechanical properties of hyaluronic acid‐based hydrogels. Because of the widespread acceptance of poly(ethylene glycol) in biomedical applications, functionalized oligomers of ethylene glycol (EG) were used as comonomers to crosslink methacrylated hyaluronic acid (MHA). The swelling degree, shear and elastic moduli, and fracture properties (stress and strain) of the gels were investigated as a function of the crosslinking oligomer length and reactive group(s). It was hypothesized that acrylated oligomers would increase the crosslink density of the gels through formation of kinetic chains by reducing the steric hindrances that otherwise may limit efficient crosslinking of hyaluronic acid into gels. Specifically, after crosslinking 13 wt % MHA (47% degree of methacrylation) with 0.06 mol % of (EG)n‐diacrylate, the swelling ratio of the MHA gel decreased from 27 to 15 g/g and the shear modulus increased from 140 to 270 kPa as n increased from 1 to 13 units. The length and functionality (i.e., acrylate vs. methacrylate) of the oligomer controlled the crosslink density of the gels. The significant changes in the gel properties obtained with the addition of low levels of the PEG comonomer show that this method allows precise tuning of the physical properties of hyaluronic acid (HA) gels to achieve desired target values for biomedical applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42009.
Influence of plasticizer with different functional groups on thermoplastic starch
Authors: Niazi Muhammad B. K. , Zijlstra Mark , Broekhuis Antonius A.
Published: February 2015

Retrogradation of amorphous thermoplastic starch (TPS) films obtained by compression molding of spray dried modified potato starch was investigated. The aim was to investigate the influence of plasticizers with similar molecular weight but different functionality, i.e., isoleucine, asparagine and malic acid, on the properties of plasticized powder and TPS films. Combinations of malic acid with glycerol, urea, and maltodextrin were also evaluated. Except for isoleucine formulated starch, all samples were obtained as amorphous powders and films. Malic acid was identified as a strong antiretrogradation agent as it inhibited recrystallization of starch over the full range of humidity levels. Malic acid was also found to inhibit the retrogradation of formulations containing urea, glycerol and maltodextrin. The converse of the strong inhibition implied strong moisture absorption and high strain at break values, and low tensile strengths. Malic acid was also identified as a potential crosslinking agent to control swelling of starch‐based products. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42012.
γ Irradiation effects on optical, thermal, and mechanical properties of polysulfone/MWCNT nanocomposites in argon atmosphere
Authors: Ghosh Soumen Kumar , Chaki Tapan Kumar , Khastgir Dipak , Pinto Richard
Published: February 2015

Polymer‐based composites find use in many nuclear and space application for their ease of fabrication, tailor made properties and light weight. Certain polymers like PTFE, unfilled polyesters and polyamides are prone to degradation in presence of high energy radiation while polymers like epoxies, polyimides, and poly‐ether ether ketone have good stability to ionizing radiation. Incorporation of fillers like carbon nanotubes (CNTs) is likely to improve the radiation resistance of the polymers. In this work, polysulfone (PSU)‐based nanocomposites were fabricated using multiwalled carbon nanotube (MWCNT) by solution mixing process. The morphology of the PSU/ MWCNT nanocomposites films were studied using Field Emission Scanning Electron Microscopy (FESEM). The prepared films were subjected to γ radiation in an argon environment (to avoid the effect of air/oxygen). Different techniques were used to understand the radiation‐induced changes. Gel Permeation Chromatography (GPC) traces of neat PSU before and after exposure to radiation shows a decrease in molecular weight. Infrared spectroscopy shows changes in chemical structure. Differential Scanning Calorimetry (DSC) thermograms reveal dose‐related changes. For neat PSU, a decrease in Tg was observed with increase in dose. For PSU/ MWCNT nanocomposites, the increase in MWCNT content and dose (up to 1.5 MGy) increased the Tg. Thermo Gravimetric Analysis (TGA) showed a marginal decrease in thermal stability for pristine PSU as well as PSU/MWCNT nanocomposites with irradiation. Tensile strength increased with increasing MWCNT content but decreased with dose. Elongation at break decreased with MWCNT content as well as radiation dose. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42017.
Highly monodisperse, lanthanide‐containing polystyrene nanoparticles as potential standard reference materials for environmental “nano” fate analysis
Authors: Hughes Jonathan M. , Budd Peter M. , Grieve Andrew , Dutta Pranab , Tiede Karen , Lewis John
Published: February 2015

For the safe commercialization of nanoparticle technology, there is a need for reference materials that can be used in studies related to the environmental fate of nanoparticles. This work produced metal‐containing polystyrene nanoparticles with target parameters such as high monodispersity, tailorable size range (33–193 nm), and variable surface charge. In addition, the combination of organic and inorganic components made them detectable by all of the main analytical techniques routinely used in nanoparticle characterization, e.g., TEM, DCS, DLS, and ICP‐MS (the latter when interfaced to chromatographic instrumentation). The lanthanides Gd, Dy, and Nd were investigated as the inorganic component because of their high response when analyzed by ICP‐MS, and because of their low environmental abundance. Particles were prepared by emulsion polymerization using one of two stabilizers: the nonionic surfactant Pluronic F68 or the anionic surfactant sodium dodecyl sulfate © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42061.
Novel Antiviral Compounds against Gastroenteric Viral Infections
Authors: Mohamed Mosaad S. , Abd El‐Hameed Rania H. , Sayed Amira I. , Soror Sameh H.
Published: February 2015

Viral gastroenteritis is a serious viral infection which affects a large number of individuals around the world, most of them being children. The infection may occur due to different viruses, for example, coxsackievirus, adenovirus, and rotavirus. There is no available cure for such infections, and the treatment mainly depends on hospitalization and administration of nutritional supports. A new antiviral agent against gastroenteritis viral infection will be a breakthrough in healthcare. Pyrrole and pyrrolopyrimidine derivatives are well known for their biological activity as antibacterial, antifungal, and anticancer agents. These compounds also proved to possess antiviral activity. Here, we synthesized novel pyrrole and pyrrolopyrimidine compounds and examined their antiviral activity. We synthesized several new pyrrole, pyrrolo[2,3‐d]pyrimidine, and pyrrolo[3,2‐e][1,2,4]triazolo[1,5‐c]pyrimidine derivatives. The characterization of all synthesized compounds was based on microanalysis and spectral data. Moreover, we determined the non‐toxic doses of these compounds on BGM, Hep‐2, and MA‐104 cells. We tested all the synthesized compounds for their antiviral activities against coxsackievirus B4, adenovirus type 7, and rotavirus Wa strain. Several compounds exhibited significant activities as antiviral agents.
Treatment of Systemic Necrotizing Vasculitides in Patients Aged Sixty‐Five Years or Older: Results of a Multicenter, Open‐Label, Randomized Controlled Trial of Corticosteroid and Cyclophosphamide–Based Induction Therapy
Authors: Pagnoux Christian , Quéméneur Thomas , Ninet Jacques , Diot Elisabeth , Kyndt Xavier , de Wazières Benoît , Reny Jean‐Luc , Puéchal Xavier , le Berruyer Pierre‐Yves , Lidove Olivier , Vanhille Philippe , Godmer Pascal , Fain Olivier , Blockmans Daniel , Bienvenu Boris , Rollot Florence , Aït el Ghaz‐Poignant Séverine , Mahr Alfred , Cohen Pascal , Mouthon Luc , Perrodeau Elodie , Ravaud Philippe , Guillevin Loïc ,   for the French Vasculitis Study Group
Published: February 2015

Objective

To investigate a new therapeutic strategy, with rapid corticosteroid dose tapering and limited cyclophosphamide (CYC) exposure, for older patients with systemic necrotizing vasculitides (SNVs; polyarteritis nodosa [PAN], granulomatosis with polyangiitis [Wegnener's] [GPA], microscopic polyangiitis [MPA], or eosinophilic GPA [Churg‐Strauss] [EGPA]).

Methods

A multicenter, open‐label, randomized controlled trial comprising patients ≥65 years old and newly diagnosed as having SNV was conducted. The experimental treatment consisted of corticosteroids for ∼9 months and a maximum of six 500‐mg fixed‐dose intravenous (IV) CYC pulses, every 2–3 weeks, then maintenance azathioprine or methotrexate. The control treatment included ∼26 months of corticosteroids for all patients, combined with 500 mg/m2 IV CYC pulses, every 2–3 weeks until remission, then maintenance for all patients with GPA or MPA and for those with EGPA or PAN with a Five‐Factors Score (FFS) of ≥1. Randomization used a 1:1 ratio computer‐generated list and was performed centrally with sealed opaque envelopes. The primary outcome measure was ≥1 serious adverse event (SAE) occurring within 3 years of followup. Secondary outcome measures included remission and relapse rates.

Results

Among the 108 patients randomized, 4 were excluded (early consent withdrawal or protocol violation). Mean ± SD age at diagnosis was 75.2 ± 6.3 years. Analysis at 3 years included 53 patients (21 GPA, 21 MPA, 8 EGPA, and 3 PAN) in the experimental arm and 51 patients (15 GPA, 23 MPA, 6 EGPA, and 7 PAN) in the conventional arm. In total, 32 (60%) versus 40 (78%) had ≥1 SAE (P = 0.04), most frequently infections; 6 (11%) versus 7 (14%) failed to achieve remission (P = 0.71); 9 (17%) versus 12 (24%) died (P = 0.41); and 20 (44%) of 45 versus 12 (29%) of 41 survivors in remission experienced a relapse (P = 0.15).

Conclusion

For older SNV patients, an induction regimen limiting corticosteroid exposure and with fixed low‐dose IV CYC pulses reduces SAEs in comparison to conventional therapy, and does not affect the remission rate. Three‐year relapse rates remain high for both arms.
A new approach to the QS university ranking using the composite I‐distance indicator: Uncertainty and sensitivity analyses
Authors: Dobrota Marina , Bulajic Milica , Bornmann Lutz , Jeremic Veljko
Published: February 2015

Some major concerns of universities are to provide quality in higher education and enhance global competitiveness, thus ensuring a high global rank and an excellent performance evaluation. This article examines the Quacquarelli Symonds (QS) World University Ranking methodology, pointing to a drawback of using subjective, possibly biased, weightings to build a composite indicator (QS scores). We propose an alternative approach to creating QS scores, which is referred to as the composite I‐distance indicator (CIDI) methodology. The main contribution is the proposal of a composite indicator weights correction based on the CIDI methodology. It leads to the improved stability and reduced uncertainty of the QS ranking system. The CIDI methodology is also applicable to other university rankings by proposing a specific statistical approach to creating a composite indicator.
Liposomes Assembled from a Dual Drug‐tailed Phospholipid for Cancer Therapy
Authors: Fang Shuo , Niu Yuge , Zhu Wenjun , Zhang Yemin , Yu Liangli , Li Xinsong
Published: February 2015

We report a novel dual drug‐tailed phospholipid which can form liposomes as a combination of prodrug and drug carrier. An amphiphilic dual chlorambucil‐tailed phospholipid (DCTP) was synthesized by a straightforward esterification. With two chlorambucil molecules as hydrophobic tails and one glycerophosphatidylcholine molecule as a hydrophilic head, the DCTP, a phospholipid prodrug, undergoes assembly to form a liposome without any additives by the thin lipid film technique. The DCTP liposomes, as an effective carrier of chlorambucil, exhibited a very high loading capacity and excellent stability. The liposomes had higher cytotoxic effects to cancer cell lines than free DCTP and chlorambucil. The in vivo antitumor activity assessment indicated that the DCTP liposomes could inhibit the tumor growth effectively. This novel strategy of dual drug‐tailed phospholipid liposomes may be also applicable to other hydrophobic anticancer drugs which have great potential in cancer therapy.
Field to flight: A techno‐economic analysis of the corn stover to aviation biofuels supply chain
Authors: Bittner Amanda , Tyner Wallace E. , Zhao Xin
Published: February 2015

Aviation biofuels can help to reduce greenhouse gas (GHG) emissions in the United States, help to meet the Renewable Fuel Standard for cellulosic biofuels, and improve US energy security. Cellulosic biofuels carry a lot of risk, because conversion technology is expensive. As a result, incentives are needed to reduce the risk for private investors. Government can implement policies to reduce the risk in investment in aviation biofuels. The issue is deciding which policy will provide the most reduction in risk, while providing a lowest cost to the government. This analysis focuses on aviation biofuel production using fast pyrolysis from corn stover. Cost benefit analysis is used to calculate the net present value, internal rate of return, and benefit‐cost ratio for a plant. Uncertainty is added to fuel price and four technical variables: capital cost, final fuel yield, hydrogen cost, and feedstock cost using @Risk, a Palisade Corporation software. We look at the impact of two policies: reverse auction and capital subsidy. For the reverse auction and capital subsidy, we used contract lengths of 5, 10, and 15 years to see the impact a longer contract could have on probability of loss. Both policies reduced risk in investment of aviation biofuels. A reverse auction reduced risk of investment more. As the contract length increased, the probability of loss and coefficient of variation in net present value were reduced substantially. When fuel price increased stochastically and a contract length of 15 years was used, probability of loss was reduced to 18.4%.
Enhanced orange–red emission of SrZn2(PO4)2:Sm3+ via codoping Eu2+ as a sensitizer
Authors: Wang Zhijun , Lou Shuqin , Li Panlai
Published: February 2015

A series of Eu2+‐, Sm3+‐ and Eu2+/Sm3+‐doped SrZn2(PO4)2 samples were synthesized using a solid‐state reaction. SrZn2(PO4)2:Eu2+ presented a broad emission band due to 4f65d–4f7 transition of the Eu2+ ion. The spectra of SrZn2(PO4)2:Sm sintered in air and H2/N2 were identical in every aspect, except for a very small difference in intensity. A Eu2+–Sm3+ energy transfer scheme was proposed to realize the sensitization of Sm3+ ion emission by Eu2+ ions, and UV‐convertible Sm3+‐activated red phosphor was obtained in SrZn2(PO4)2:Eu2+, Sm3+. Copyright © 2015 John Wiley & Sons, Ltd.
Visible‐near‐infrared luminescent lanthanide ternary complexes based on beta‐diketonate using visible‐light excitation
Authors: Sun Lining , Qiu Yannan , Liu Tao , Feng Jing , Deng Wei , Shi Liyi
Published: February 2015

We used the synthesized dinaphthylmethane (Hdnm) ligand whose absorption extends to the visible‐light wavelength, to prepare a family of ternary lanthanide complexes, named as [Ln(dnm)3phen] (Ln = Sm, Nd, Yb, Er, Tm, Pr). The properties of these complexes were investigated by Fourier transform infrared (FT‐IR) spectroscopy, diffuse reflectance (DR) spectroscopy, thermogravimetric analyses, and excitation and emission spectroscopy. Generally, excitation with visible light is much more advantageous than UV excitation. Importantly, upon excitation with visible light (401–460 nm), the complexes show characteristic visible (Sm3+) as well as near‐infrared (Sm3+, Nd3+, Yb3+, Er3+, Tm3+, Pr3+) luminescence of the corresponding lanthanide ions, attributed to the energy transfer from the ligands to the lanthanide ions, an antenna effect. Now, using these near‐infrared luminescent lanthanide complexes, the luminescent spectral region from 800 to 1650 nm, can be covered completely, which is of particular interest for biomedical imaging applications, laser systems, and optical amplification applications. Copyright © 2015 John Wiley & Sons, Ltd.
Preparation of Ag/Au bimetallic nanostructures and their application in surface‐enhanced fluorescence
Authors: Dong Jun , Ye Yanyan , Zhang Wenhui , Ren Zebin , Huo Yiping , Zheng Hairong
Published: February 2015

An effective substrate for surface‐enhanced fluorescence, which consists of cluster Ag/Au bimetallic nanostructures on a copper surface, was synthesized via a multi‐stage galvanic replacement reaction of a Ag cluster in a chlorauric acid (HAuCl4) solution at room temperature. The fabricated silver/gold bimetallic cluster were found to yield large surface‐enhanced fluorescence (SEF) enhancement factors for rhodamine 6G probe molecules deposited on the substrate, and also the fluorescence efficiency is critically dependent on the period of nanostructure growth. With the help of proper control reaction conditions, such as the reaction time, and concentration of reaction solutions, the maximum fluorescence enhanced effect was obtained. Therefore, the bimetallic nanostructure substrate also can be adapted to studies in SEF, which will expand the application of SEF. Copyright © 2015 John Wiley & Sons, Ltd.
Sensitive detection of sodium cromoglycate with glutathione‐capped CdTe quantum dots as a novel fluorescence probe
Authors: Hao Chenxia , Liu Shaopu , Li Dan , Yang Jidong , He Youqiu
Published: February 2015

A sensitive and simple analytical strategy for the detection of sodium cromoglycate (SCG) has been established based on a readily detectable fluorescence quenching effect of SCG for glutathione‐capped (GSH‐capped) CdTe quantum dots (QDs). The fluorescence of GSH‐capped CdTe QDs could be efficiently quenched by SCG through electron transfer from GSH‐capped CdTe QDs to SCG. Under optimum conditions, the response was linearly proportional to the concentration of SCG between 0.6419 and 100 µg/mL, with a correlation coefficient (R) of 0.9964; the detection limit (3δ/K) was 0.1926 µg/mL. The optimum conditions and the influence of coexisting foreign substances on the reaction were also investigated. The very effective and simple method reported here has been successfully applied to the determination of SCG in synthetic and real samples. It is believed that the established approach could have good prospects for application in the fields of clinical diseases diagnosis and treatment. Copyright © 2015 John Wiley & Sons, Ltd.
Advances in inline quantification of co‐eluting proteins in chromatography: Process‐data‐based model calibration and application towards real‐life separation issues
Authors: Brestrich Nina , Sanden Adrian , Kraft Axel , McCann Karl , Bertolini Joseph , Hubbuch Jürgen
Published: February 2015

Pooling decisions in preparative liquid chromatography for protein purification are usually based on univariate UV absorption measurements that are not able to differentiate between product and co‐eluting contaminants. This can result in inconsistent pool purities or yields, if there is a batch‐to‐batch variability of the feedstock. To overcome this analytical bottleneck, a tool for selective inline quantification of co‐eluting model proteins using mid‐UV absorption spectra and Partial Least Squares Regression (PLS) was presented in a previous study and applied for real‐time pooling decisions. In this paper, a process‐data‐based method for the PLS model calibration will be introduced that allows the application of the tool towards chromatography steps of real‐life processes. The process‐data‐based calibration method uses recorded inline mid‐UV absorption spectra that are correlated with offline fraction analytics to calibrate PLS models. In order to generate average spectra from the inline data, a Visual Basic for Application macro was successfully developed. The process‐data‐based model calibration was established using a ternary model protein system. Afterwards, it was successfully demonstrated in two case studies that the calibration method is applicable towards real‐life separation issues. The calibrated PLS models allowed a successful quantification of the co‐eluting species in a cation‐exchange‐based aggregate and fraction removal during the purification of monoclonal antibodies and of co‐eluting serum proteins in an anion‐exchange‐based purification of Cohn supernatant I. Consequently, the presented process‐data‐based PLS model calibration in combination with the tool for selective inline quantification has a great potential for the monitoring of future chromatography steps and may contribute to manage batch‐to‐batch variability by real‐time pooling decisions. Biotechnol. Bioeng. 2015;112: 1406–1416. © 2015 Wiley Periodicals, Inc.
Tailor‐made TALEN system for highly efficient targeted gene replacement in the rice blast fungus
Authors: Arazoe Takayuki , Ogawa Tetsuo , Miyoshi Kennosuke , Yamato Tohru , Ohsato Shuichi , Sakuma Tetsushi , Yamamoto Takashi , Arie Tsutomu , Kuwata Shigeru
Published: February 2015

Genetic manipulation is key to unraveling gene functions and creating genetically modified strains of microbial organisms. Recently, engineered nucleases that can generate DNA double‐strand breaks (DSBs) at a specific site in the desired locus within genome are utilized in a rapidly developing genome editing technology via DSBs repair. However, the use of engineered nucleases in filamentous fungi has not been validated. In this study, we demonstrated that tailor‐made transcriptional activator‐like effector nucleases (TALENs) system, Platinum–Fungal TALENs (PtFg TALENs), could improve the efficiency of homologous recombination‐mediated targeted gene replacement by up to 100% in the rice blast fungus Pyricularia oryzae. This high‐efficiency PtFg TALEN has great potential for basic and applied biological applications in filamentous fungi. Biotechnol. Bioeng. 2015;112: 1335–1342. © 2015 Wiley Periodicals, Inc.
Oncoplastic and reconstructive breast surgery in the elderly
Authors: James R , McCulley S J , Macmillan R D
Published: February 2015

Background

The recommendations of the UK All Party Parliamentary Group on Breast Cancer (2013) have been endorsed recently by the UK Association of Breast Surgeons and are in line with the 2007 Cancer Reform Strategy, which states that treatment in older British women should be equivalent to that in younger patients unless precluded by co-morbidity or patient choice. Oncoplastic and reconstructive techniques are increasingly available to women with breast cancer. A review of the literature was carried out to investigate use of these techniques in older patients.

Methods

A MEDLINE search was conducted to identify studies relating to oncoplastic and reconstructive surgery in the elderly.

Results and conclusion

Nine studies were identified and included in the review. Older patients undergoing reconstruction, particularly autologous reconstruction, have outcomes that are at least as good as those achieved in younger patients, yet are far less likely to be offered these techniques. Issues influencing oncoplastic and reconstructive surgery in the elderly include: lack of standard pathways of care, concerns regarding higher operative risk, lack of evidence regarding outcomes, preconceptions regarding body image and lack of engagement with the decision-making process. A minority of older women are likely to accept reconstruction, but those who do are pleased with the results and experience good quality of life. There is now a range of safe oncoplastic and reconstructive options that could be considered as an alternative to standard mastectomy or wide local excision in older patients.
Randomized double-blind trial comparing the cosmetic outcome of cutting diathermy versus scalpel for skin incisions
Authors: Aird L N F , Bristol S G , Phang P T , Raval M J , Brown C J
Published: February 2015

Background

Controversy exists about whether cutting diathermy for skin incisions leads to a cosmetically inferior scar. Cosmetic outcomes were compared between skin incisions created with cutting diathermy versus scalpel. Wound infection rates and postoperative incisional pain were also compared.

Methods

This was a randomized double-blind trial comparing cutting diathermy and scalpel in patients undergoing bowel resection. Scar cosmesis was assessed at 6 months after surgery by a plastic surgeon and a research associate using the Vancouver Scar Scale (VSS) and the Patient and Observer Scar Assessment Scale (POSAS). Patients also used POSAS to self-evaluate their scars. Wound infections within 30 days were recorded, and incision pain scores were measured on the first 5 days after operation.

Results

A total of 66 patients were randomized to cutting diathermy (31) or scalpel (35). At 6 months, there was no significant difference between the diathermy and scalpel groups in mean(s.d.) VSS scores (4·9(2·6) versus 5·0(1·9); P = 0·837), mean POSAS total scores (19·2(8·0) versus 20·0(7·4); P = 0·684) or subjective POSAS total scores (20·2(12·1) versus 21·3(10·4); P = 0·725). Neither were there significant differences in wound infection rates between the groups (5 of 30 versus 5 of 32; P = 1·000). Pain scores on day 1 after operation were significantly lower in the diathermy group (mean 1·68 versus 3·13; P = 0·018), but were not significantly different on days 2–5.

Conclusion

Cutting diathermy is a cosmetically acceptable technique for abdominal skin incisions. There is no increased risk of wound infection, and diathermy may convey benefit in terms of early postoperative wound pain. Registration number: NCT01496404 (http://www.clinicaltrials.gov).
Sustainable Purchasing in Food Retailing: Interorganizational Relationship Management to Green Product Supply
Authors: Chkanikova Olga
Published: February 2015

Stakeholders’ demands for product sustainability redefine the focus of corporate purchasing strategies from the traditional concern with financial performance to considerations of ‘triple bottom line’ viability. This adds to the complexity of managing interorganizational relationships and poses a question regarding corporate ability to effectively leverage suppliers over environmental and social performance of supplied goods. Since it is not clear what type of purchasing relationship is more favorable for greening a product supply, the current paper aims to investigate how food retailers manage their relationships with suppliers in order to influence the environmental and social performance of procured goods and improve the availability of sustainably produced supply. The research is based on two case studies of Swedish supermarkets and supplementary semi‐structured interviews with Swedish, British and Danish supermarkets. The results of the study contribute to the existing body of academic knowledge in the field of sustainable supply chain management by developing a typology of sustainable purchasing relationships with detailed insights into the nature of collaborative practices, structure of incentives, sustainability ambition, and approaches to verification of compliance. The study has also revealed the dependence of sustainable purchasing relationships on the characteristics of the procurement context, namely the presence of well‐established sustainability certification schemes, perceived by purchaser's situation with availability of sustainability certified supply and purchaser's interpretation of the state of power dependence in relationships with suppliers. Copyright © 2015 John Wiley & Sons, Ltd and ERP Environment
Roles of MoS2 and Graphene as Cocatalysts in the Enhanced Visible‐Light Photocatalytic H2 Production Activity of Multiarmed CdS Nanorods
Authors: Lang Di , Shen Tingting , Xiang Quanjun
Published: February 2015

The incorporation of cocatalysts into semiconductors is proved to be an effective approach to improving the efficiency of the photocatalytic H2 production. Noble metals such as Pt have been widely used as cocatalysts and can significantly improve the performance of photocatalytic H2 production. However, owing to the high cost and low abundance, the use of Pt in practical applications is restricted. Herein, we report two well‐known 2 D layered materials, MoS2 and graphene, as highly active cocatalysts for H2 production in CdS‐based photocatalytic systems. The CdS–MoS2 and CdS‐MoS2–graphene nanocomposites were prepared by using a facile two‐step solvothermal method, and the morphologies of CdS and MoS2 can be well controlled. The as‐prepared binary CdS–MoS2 nanocomposite exhibits the enhanced visible‐light photocatalytic activity for H2 production in lactic acid aqueous solution compared with a CdS–graphene nanocomposite and a conventional platinized CdS photocatalyst. Moreover, the ternary CdS–MoS2–graphene nanocomposite achieves the highest visible‐light photocatalytic H2 production activity of 621.3 μmol h−1 and the apparent quantum efficiency of 54.4 % at λ=420 nm. The enhanced photocatalytic activity of the CdS–MoS2–graphene nanocomposite can be primarily attributed to the positive synergistic effect between graphene sheets and thin MoS2 nanoplates. The graphene sheets can accelerate the efficient electron transfer from CdS nanorods to the active edge sites of MoS2 nanoplates, and the nanosized MoS2 can facilitate the photogenerated electrons participating in the photocatalytic H2 production. The mechanisms for improving the photocatalytic performance of the MoS2‐ and/or graphene‐modified CdS nanocomposites were proposed by using the electrochemical analysis and photoluminescence measurement.
Mycotoxin Aptasensing Amplification by using Inherently Electroactive Graphene‐Oxide Nanoplatelet Labels
Authors: Loo Adeline Huiling , Bonanni Alessandra , Pumera Martin
Published: February 2015

We develop an electrochemical aptasensor for ochratoxin A (OTA) by utilizing graphene‐oxide nanoplatelets (GONPs) as electroactive labels. OTA aptamer (OTA‐apt), which serves as the recognition element, was first immobilized onto the electrode surface before the modified electrode underwent exposure to OTA. Subsequently, incubation with GONPs was performed and the nanoplatelets conjugated to the immobilized OTA‐apt through π–π interactions. The principle of detection lies in the ability of these nanoplatelets to be electrochemically reduced, thereby producing a well‐defined reduction peak that was then employed as the analytical signal. The fabricated aptasensor is capable of detecting OTA in the concentration range of 310 fM to 310 pM, with good selectivity against common interferences. The obtained results from this study have the potential to contribute towards the aim of developing a biosensor for OTA, with high selectivity and sensitivity.
Supramolecular Assembly of Achiral Alkynylplatinum(II) Complexes and Carboxylic β‐1,3‐Glucan into Different Helical Handedness Stabilized by Pt⋅⋅⋅Pt and/or π–π Interactions
Authors: Chung Clive Yik‐Sham , Tamaru Shun‐ichi , Shinkai Seiji , Yam Vivian Wing‐Wah
Published: February 2015

Two‐component ensembles of alkynylplatinum(II) terpyridine (tpy) complexes and carboxylic β‐1,3‐glucan (CurCOOH) have been investigated by using spectroscopic and microscopic techniques, as well as time‐dependent UV/Vis absorption and circular dichroism (CD) experiments. Microscopic images of [Pt(tpy){CCC6H4(CH2NMe3‐4)}](OTf)2 (1) have revealed spherical nanostructures, whereas helical fibrous structures of different lengths, depending on the concentration of complex 1 and CurCOOH, were observed. The helical assemblies have been found to show low‐energy metal‐metal‐to‐ligand charge transfer (MMLCT) absorption and triplet MMLCT (3MMLCT) emission, which are indicative of Pt⋅⋅⋅Pt and/or π–π interactions between the complex 1 molecules. Interestingly, the ensemble has been demonstrated to show different handedness and even a change in handedness over time under different experimental conditions. Low temperatures, low concentrations of CurCOOH, high concentrations of complex 1, or successive addition of CurCOOH into complex 1 solution favor the formation of right‐handed helical assemblies, whereas high temperatures, high concentrations of CurCOOH, low concentrations of complex 1, or single‐batch addition of CurCOOH into complex 1 solution result in a fast chiroptical inversion of the ensemble solution, giving rise to the left‐handed helical assemblies as the dominant species. The results have been rationalized by considering the competing kinetically and thermodynamically controlled assembly–elongation of the ensemble, which leads to the formation of right‐handed and left‐handed helical assemblies, respectively. The change in the handedness of the ensemble has been demonstrated to stem from the formation of two‐component assemblies with supramolecular interactions, in contrast to the template‐ induced chiral amplification commonly observed in other systems.
Palladium‐Catalyzed Annulation of 9‐Halophenanthrenes with Alkynes: Synthesis, Structural Analysis, and Properties of Acephenanthrylene‐Based Derivatives
Authors: Liu En‐Chih , Chen Min‐Kuan , Li Jen‐Yi , Wu Yao‐Ting
Published: February 2015

The palladium‐catalyzed annulation of 9‐bromo‐ and 9‐chlorophenanthrenes with alkynes gave 4,5‐disubstituted acephenanthrylenes in yields of 58–95 % (9 examples). Asymmetric alkynes, such as 1‐phenyl‐1‐propyne, 1‐phenyl‐1‐hexyne, and 1‐cyclopropyl‐2‐phenylethyne, regioselectively form (cyclo)alkyl‐substituted products, following the regular rule that governs the carbopalladation of alkynes. This synthetic protocol can also be utilized in annulations with several π‐extended bromoarenes, such as 7‐bromo[5]helicene, 5‐bromo[4]helicene, 9‐bromoanthracene, 3‐bromoperylene, and 3‐bromofluoranthene, to give the corresponding annulated products in moderate to good yields (51–86 %; 6 examples). Similarly, bromocorannulene produced highly curved 1,2‐disubstituted cyclopentacorannulenes. Reactions of 6,12‐dibromochrysene and 4,7‐dibromo[4]helicene with di(4‐tolyl)ethyne provided the twofold annulated products in moderate yields. 4,5‐Diphenylacephenanthrylene and 6,7‐diphenylbenzo[a]acephenanthrylene thus generated were converted into phenanthro[9,10‐e]acephenanthrylene and benzo[a]phenanthro[9,10‐e]acephenanthrylene, respectively, by oxidative cyclodehydrogenation. The structures of 4,5‐diphenylacephenanthrylene, 4,5‐diphenyldibenzo[a,l]acephenanthrylene, 1,2‐diarylcyclopentacorannulenes, and benzo[a]phenanthro[9,10‐e]acephenanthrylene were verified by X‐ray crystallography. The photophysical and electrochemical properties of the selected annulated products were investigated.
Long‐Lived Charge Carriers in Mn‐Doped CdS Quantum Dots for Photoelectrochemical Cytosensing
Authors: Wu Peng , Pan Jian‐Bing , Li Xiang‐Ling , Hou Xiandeng , Xu Jing‐Juan , Chen Hong‐Yuan
Published: February 2015

Photoelectrochemical (PEC) biosensing with semiconductor quantum dots (QDs) has received great attention because it integrates the advantages of both photo‐excitation and electrochemical detection. During the photon‐to‐electricity conversion in PEC processes, electron–hole (charge) separation competes with electron–hole recombination, and the net effect essentially determines the performance of PEC biosensors. Herein, we propose a new approach for slowing down electron–hole recombination to increase charge separation efficiency for PEC biosensor development. Through doping with Mn2+, a pair of d bands (4T1 and 6A1) is inserted between the conduction and valence bands of CdS QDs, which alters the electron–hole separation and recombination dynamics, allowing the generation of long‐lived charge carriers with ms‐scale lifetime that decay about 104–105‐fold more slowly than in the case of undoped QDs. Photocurrent tests indicated that Mn2+ doping resulted in an approximately 80 % increase in photocurrent generation compared with undoped CdS QDs. For application, the Mn‐doped CdS QDs were coated on the surface of a glassy carbon electrode and functionalized with a cell surface carbohydrate‐specific ligand (3‐aminophenylboronic acid). In this way, a sensitive cytosensor for K562 leukemia cells was constructed. Moreover, the sugar‐specific binding property of 3‐aminophenylboronic acid allowed the electrode to serve as a switch for the capture and release of cells. This has been further explored with a view to developing a reusable PEC cytosensing platform.
Conceptual Quantum Chemical Analysis of Bonding and Noncovalent Interactions in the Formation of Frustrated Lewis Pairs
Authors: Skara Gabriella , Pinter Balazs , Top Jens , Geerlings Paul , De Proft Frank , De Vleeschouwer Freija
Published: February 2015

The contributions of covalent and noncovalent interactions to the formation of classical adducts of bulky Lewis acids and bases and frustrated Lewis pairs (FLPs) were scrutinized by using various conceptual quantum chemical techniques. Significantly negative complexation energies were calculated for fourteen investigated Lewis pairs containing bases and acids with substituents of various sizes. A Ziegler–Rauk‐type energy decomposition analysis confirmed that two types of Lewis pairs can be distinguished on the basis of the nature of the primary interactions between reactants; dative‐bond formation and concomitant charge transfer from the Lewis base to the acid is the dominant and most stabilizing factor in the formation of Lewis acid–base adducts, whereas weak interactions are the main thermodynamic driving force (>50 %) for FLPs. Moreover, the ease and extent of structural deformation of the monomers appears to be a key component in the formation of the former type of Lewis pairs. A Natural Orbital for Chemical Valence (NOCV) analysis, which was used to visualize and quantify the charge transfer between the base and the acid, clearly showed the importance and lack of this type of interaction for adducts and FLPs, respectively. The Noncovalent Interaction (NCI) method revealed several kinds of weak interactions between the acid and base components, such as dispersion, π–π stacking, CH⋅⋅⋅π interaction, weak hydrogen bonding, halogen bonding, and weak acid–base interactions, whereas the Quantum Theory of Atoms in Molecules (QTAIM) provided further conceptual insight into strong acid–base interactions.
Pyrene‐Based Dyad and Triad Leading to a Reversible Chemical and Redox Optical and Magnetic Switch
Authors: Franco Carlos , Mas‐Torrent Marta , Caballero Antonio , Espinosa Arturo , Molina Pedro , Veciana Jaume , Rovira Concepció
Published: February 2015

Two new pyrene–polychlorotriphenylmethyl (PTM) dyads and triads have been synthesized and characterized by optical, magnetic, and electrochemical methods. The interplay between the different electronic states of the PTM moiety in the dyads and triads and the optical and magnetic properties of the molecules have been studied. The electronic spectra of the radicals 5. and 6. show the intramolecular charge‐transfer transition at around 700 nm due to the acceptor character of the PTM radical. In the diamagnetic protonated derivatives 3 and 4 the fluorescence due to the pyrene is maintained, whereas in the radicals 5. and 6. and the corresponding anions 5− and 6− there is a clear quenching of the fluorescence, which is more efficient in the case of radicals. The redox activity of PTM radicals that are easily reduced to the corresponding carbanion has been exploited to fabricate electrochemical switches with optical and magnetic response.
Boron‐Doped, Carbon‐Coated SnO2/Graphene Nanosheets for Enhanced Lithium Storage
Authors: Liu Yuxin , Liu Ping , Wu Dongqing , Huang Yanshan , Tang Yanping , Su Yuezeng , Zhang Fan , Feng Xinliang
Published: February 2015

Heteroatom doping is an effective method to adjust the electrochemical behavior of carbonaceous materials. In this work, boron‐doped, carbon‐coated SnO2/graphene hybrids (BCTGs) were fabricated by hydrothermal carbonization of sucrose in the presence of SnO2/graphene nanosheets and phenylboronic acid or boric acid as dopant source and subsequent thermal treatment. Owing to their unique 2D core–shell architecture and B‐doped carbon shells, BCTGs have enhanced conductivity and extra active sites for lithium storage. With phenylboronic acid as B source, the resulting hybrid shows outstanding electrochemical performance as the anode in lithium‐ion batteries with a highly stable capacity of 1165 mA h g−1 at 0.1 A g−1 after 360 cycles and an excellent rate capability of 600 mA h g−1 at 3.2 A g−1, and thus outperforms most of the previously reported SnO2‐based anode materials.
Anisotropic Expansion of an M2L4 Coordination Capsule: Host Capability and Frame Rearrangement
Authors: Yamashina Masahiro , Yuki Tsubasa , Sei Yoshihisa , Akita Munetaka , Yoshizawa Michito
Published: February 2015

Anisotropic expansion of a spherical M2L4 coordination capsule through the elongation of the ligand led to a new M2L′4 capsule. The expanded capsule provides an elliptical cavity encircled by polyaromatic frameworks with large openings and thereby can encapsulate elliptical fullerene C70 and monofunctionalized fullerene C60 in high yields. In addition, selective formation of a new M2L2L′2 capsule occurs by mixing the original M2L4 and expanded M2L′4 capsules in a 1:1 ratio upon addition of C60 or monofunctionalized C60 as a template molecule.
Chemistry of Stannylene‐Based Lewis Pairs: Dynamic Tin Coordination Switching Between Donor and Acceptor Character
Authors: Krebs Kilian M. , Freitag Sarah , Schubert Hartmut , Gerke Birgit , Pöttgen Rainer , Wesemann Lars
Published: February 2015

The coordination chemistry of cyclic stannylene‐based intramolecular Lewis pairs is presented. The P→Sn adducts were treated with [Ni(COD)2] and [Pd(PCy3)2] (COD=1,5‐cyclooctadiene, PCy3=tricyclohexylphosphine). In the isolated coordination compounds the stannylene moiety acts either as an acceptor or a donor ligand. Examples of a dynamic switch between these two coordination modes of the PSn ligand are illustrated and the structures in the solid state together with heteronuclear NMR spectroscopic findings are discussed. In the case of a Ni0 complex, 119Sn Mössbauer spectroscopy of the uncoordinated and coordinated phosphastannirane ligand is presented.