bluuebunny/crossref_metadata_2025 huggingface dataset:
In situ enhancement of surfactin biosynthesis in Bacillus subtilis using novel artificial inducible promoters
Authors: Jiao Song , Li Xu , Yu Huimin , Yang Huan , Li Xue , Shen Zhongyao
Published: October 2016

Surfactin‐family lipopeptides are green biosurfactants with substantial industrial potential. The major problem prohibiting surfactin use is the low titer of the wild producer, Bacillus subtilis. Using transcriptomic analysis, four strong promoters, PgroE, Pcdd, PrplK, and PsspE, were identified and cloned from the genome of B. subtilis THY‐7, a novel surfactin producer that has been identified from soil with a 0.55 g/L surfactin titer. An optimal promoter, PgroE, was selected to replace the native THY‐7 surfactin synthase (SrfA) promoter through single‐cross homologous recombination; however, the resulting engineered strain containing the PgroE substitution did not synthesize surfactin. The sucrose‐inducible promoters PsacB and PsacP were then substituted in place of PsrfA, and the resulting engineered strains produced 1.09 and 0.22 g/L surfactin, respectively. An artificial, sucrose‐inducible Pg1 promoter was produced through fusion of the PgroE and PsacB ribonucleic antiterminator (RAT), and the engineered strain containing the Pg1‐substitution produced a surfactin titer of 1.44 g/L. An artificial IPTG‐inducible promoter, Pg2, was constructed from a PgroE‐lacO fusion and then substituted for the chromosomal PsrfA locus, and the surfactin titer of the resulting THY‐7/Pg2‐srfA increased to 5.98 g/L. The driving capacity of Pg2 was further improved by the inclusion of two point mutations in the −35 and −10 regions to produce the novel promoter Pg3. Pg3 exhibited super‐strong activity as measured by lacZ reporter gene overexpression (approximately 3000 U). The Pg3‐substitution strain THY‐7/Pg3‐srfA produced up to 9.74 g/L surfactin in a 5 L fermentor. The maximum productivity was 0.30 g/L/h, and the greatest yield reached 0.14 g surfactin/g sucrose. Biotechnol. Bioeng. 2017;114: 832–842. © 2016 Wiley Periodicals, Inc.
Meta-analysis of the use of surgical sealants for suture-hole bleeding in arterial anastomoses
Authors: Rogers A C , Turley L P , Cross K S , McMonagle M P
Published: October 2016

Background

Suture-hole bleeding in arterial anastomoses prolongs operating time and increases blood loss, particularly with the use of prosthetic grafts. Surgical sealants (such as fibrin) may be used as haemostatic adjuncts in vascular surgery. This is a systematic review and meta-analysis of published studies that investigated the utility of surgical sealants in arterial-to-prosthetic graft anastomoses.

Methods

A systematic review was undertaken of papers published until January 2015 on Embase, MEDLINE, PubMed, PubMed Central and Cochrane databases that analysed the use of surgical sealants as haemostatic adjuncts after arterial anastomoses. RCTs were included, with study endpoints of time to haemostasis or haemostasis at 5 min. Secondary outcomes included treatment failure, mean difference in estimated blood loss and duration of surgery. Sensitivity and subgroup analyses were performed, as well as funnel plot analysis for publication bias.

Results

A total of 2513 citations were reviewed; 19 RCTs comprising 1560 patients were ultimately included in the analysis. The majority of studies compared fibrin sealant with control haemostatic measures. Pooled analysis suggested that surgical sealants reduced the time to haemostasis (mean difference 243·26 (95 per cent c.i. 183·99 to 302·53) s; P < 0·001), improved haemostasis at 5 min (odds ratio 4·50, 95 per cent c.i. 2·59 to 7·81; P < 0·001), and were associated with less treatment failure, blood loss and shorter duration of surgery.

Conclusion

Surgical sealants appear to reduce suture-hole bleeding significantly in vascular prosthetic graft anastomoses compared with standard haemostatic measures.
Chirality Switching in the Crystallization of 1‐(4‐Chlorophenyl)ethylamine with Binaphthoic Acid by Ketimine Formation
Authors: Jin Ying‐Ji , Choi Yunseo , Chen Qian , Shirbhate Mukesh Eknath , Huang Haofei , Kim Youngmee , Kim Sung‐Jin , Jun Moo‐Jin , Koo Eon Cheol , Kim Kwan Mook
Published: October 2016

Axially chiral binaphthoic acid (BNA) was studied as a resolving agent for a stereoselective crystallization of 1‐(4‐chlorophenyl)ethylamine (CPEA). The diastereomeric pair of (R)‐BNA/(S)‐CPEA crystallizes in methylene chloride, on the other hand, the pair of (S)‐BNA/(S)‐CPEA crystallizes in acetone. The switch of the solubility of the diastereomeric pair is due to the imine formation with acetone. The very low solubility of the BNA/imine pair appears to be responsible for the fast and complete imine formation. The crystal structure of the BNA part in both crystals of the diastereomers maintains a same feature. Asymmetric chiral channels and pockets composed by intermolecular packing of BNA molecules appear in the crystal structures, and the robustness of them seem to contribute to the recognition of the chirality of CPEA with high selectivity.
Evaluation of Long‐Range Transport Potential of Selected Brominated Flame Retardants with Measured 1‐Octanol–Air Partition Coefficients
Authors: Lee Hyun‐Jeoung , Kwon Jung‐Hwan
Published: October 2016

Various alternative flame retardants are used in many countries since polybrominated diphenyl ethers (PBDEs) were classified as persistent organic pollutants (POPs). However, difficulties in the evaluation of the long‐range transport potential (LRTP) of the alternatives are related to the lack of information on their physicochemical properties, which govern their environmental fates and transport. Based on the simulation of LRTP using OECD POV and LRTP Screening Tool, five alternative brominated flame retardants (BFRs) (hexabromobenzene [HBB], 2,3,4,5,6‐pentabromotoluene [PBT], 2,3,4,5,6‐pentabromoethylbenzene [PBEB], 2‐ethylhexyl 2,3,4,5‐tetrabromobenzoate [TBB], and 1,2,4,5‐tetrabromo‐3,6‐dimethylbenzene [TBX]), and 3 PBDEs (BDE‐28, BDE‐47, and BDE‐99) were chosen to perform a refined assessment. This was done using an experimentally measured 1‐octanol–air partition coefficient (KOA) for the calculation of the air–water partition coefficient (KAW) required for the model. The four selected alternative BFRs (HBB, PBT, PBEB, TBX) have KOA values close to the in silico estimation used in the screening evaluation. On the other hand, the measured KOA value for TBB was two orders of magnitude lower than the estimated value used in the screening simulation. The refined simulation showed that characteristic travel distance (CTD) and transfer efficiency (TE) for HBB, PBT, PBEB, and TBX were greater than those for BDE‐28, whereas CTD and TE for TBB were lower than those for BDE‐28. This suggested that TBB has a lower LRTP than BDE‐28, considering the refined partition coefficients.
Synthesis and Characterization of Carbazole Core‐based Small Molecular‐Hole‐transporting Materials for Red Phosphorescent OLEDs
Authors: Fan Jin Guo , Kim Mi Jin , Nguyen Quynh Pham Bao , Braveenth Ramanaskanda , Ko Haye Min , Han Ji‐Hun , Kim Gyeong Woo , Kwon Jang Hyuk , Chai Kyu Yun
Published: October 2016

A series of carbazole core‐based hole‐transporting materials (HTMs) have been synthesized using Buchwald–Hartwig amination reaction. HTMs 7a and 7b exhibited high thermal decomposition temperatures of 400 and 380°C, respectively, without any crystalline features. Among the designed HTMs 7a–c, the device performance based on HTM 7a is the best and identical with that of the typical hole‐transporting N,N′‐di(1‐naphthyl)‐N,N′‐diphenyl‐(1,1′‐biphenyl)‐4,4′‐diamine (NPB) material.
Recent analytical methods for atmospheric polycyclic aromatic hydrocarbons and their derivatives
Authors: Hayakawa Kazuichi , Tang Ning , Toriba Akira
Published: October 2016

Polycyclic aromatic hydrocarbons (PAHs) and nitropolycyclic aromatic hydrocarbons (NPAHs) are ubiquitous environmental pollutants. Moreover, some oxidative metabolites of these pollutants, such as hydroxylated and epoxide PAHs, cause endocrine disruption or produce reactive oxygen species. These compounds have become a large concern from the viewpoint of particulate matter (PM2.5) pollution. This report deals with recent studies concerning analytical methods for PAHs, NPAHs and related compounds in atmospheric and biological samples.
Homoharringtonine combined with aclarubicin and cytarabine synergistically induces apoptosis in t(8;21) leukemia cells and triggers caspase‐3‐mediated cleavage of the AML1‐ETO oncoprotein
Authors: Cao Jiang , Feng Hao , Ding Ning‐Ning , Wu Qing‐yun , Chen Chong , Niu Ming‐Shan , Chen Wei , Qiu Ting‐Ting , Zhu Hong‐Hu , Xu Kai‐Lin
Published: October 2016

Homoharringtonine combined with aclarubicin and cytarabine (HAA) is a highly effective treatment for acute myeloid leukemia (AML), especially for t(8;21) AML. However, the underlying mechanisms by which HAA kills t(8;21) AML cells remain unclear. In this study, SKNO‐1 and Kasumi‐1 cells with t(8;21) were used. Compared with individual or pairwise administration of homoharringtonine, aclarubicin, or cytarabine, HAA showed the strongest inhibition of growth and induction of apoptosis in SKNO‐1 and Kasumi‐1 cells. HAA caused cleavage of the AML1‐ETO (AE) oncoprotein to form truncated AE (ΔAE). Pretreatment with the caspase‐3 inhibitor caspase‐3 inhibitor Q‐DEVD‐OPh (QDO) not only suppressed HAA‐induced apoptosis but also abrogated the cleavage of AE and generation of ΔAE. These results suggest that HAA synergistically induces apoptosis in t(8;21) leukemia cells and triggers caspase‐3‐mediated cleavage of the AML1‐ETO oncoprotein, thus providing direct evidence for the strong activity of HAA toward t(8;21) AML.
Minding the gaps: Using narrative accounts to explore people's experiences of using North Staffs MIND's Adult Counselling Service
Authors: Beaumont Elaine , Hickey Anthony Joseph , McAndrew Sue , Goldman Stacey , Warne Tony
Published: October 2016

Introduction

In the UK, almost 50% of illness diagnosed among working age adults is mental distress, with depression and chronic anxiety cited as the two most prevalent psychological illnesses. However, only 24% of those who experience anxiety and depression, consistent with diagnoses, receive National Health Service (NHS) interventions. Effective mental health care is predicated on understanding the lived experiences of those using services in order to provide sensitively attuned therapy. An understanding of the process of counselling and what makes it effective will only be achieved through hearing the voices of service users. However, with regard to counselling, the literature foregrounding the perspectives of those using services remains sparse.

Method

This study reports on a qualitative research project, the aim of which was to explore the experiences of people who have used North Staffs MIND’s Adult Counselling Service in order to elicit the strengths of and/or opportunities for improving the service. Twelve participants, five males and seven females, were interviewed on a one‐to‐one basis and six themes were identified; Mindful of the Gap; Easing Like Sunday Morning; Magic Moments; Love is in the Air; Lighting up a Future and Following up the Changes: Spreading the Word.

Results

Findings suggest the participants in this study found the service beneficial, with therapeutic interventions being tailor‐made to meet the person's needs, and one which ensures a safe environment and compassionate care for those in distress.
Ivy League's executive director reveals how balance can bring athletic, academic success
Authors: McCarthy Claudine
Published: October 2016

Long before other colleges realized the connection between time demands and student‐athletes' success and well‐being, The Ivy League was way ahead of the game.
Structural Basis for Phospholyase Activity of a Class III Transaminase Homologue
Authors: Cuetos Anibal , Steffen‐Munsberg Fabian , Mangas Sanchez Juan , Frese Amina , Bornscheuer Uwe T. , Höhne Matthias , Grogan Gideon
Published: October 2016

Pyridoxal‐phosphate (PLP)‐dependent enzymes catalyse a remarkable diversity of chemical reactions in nature. A1RDF1 from Arthrobacter aurescens TC1 is a fold type I, PLP‐dependent enzyme in the class III transaminase (TA) subgroup. Despite sharing 28 % sequence identity with its closest structural homologues, including β‐alanine:pyruvate and γ‐aminobutyrate:α‐ketoglutarate TAs, A1RDF1 displayed no TA activity. Activity screening revealed that the enzyme possesses phospholyase (E.C. 4.2.3.2) activity towards O‐phosphoethanolamine (PEtN), an activity described previously for vertebrate enzymes such as human AGXT2L1, enzymes for which no structure has yet been reported. In order to shed light on the distinctive features of PLP‐dependent phospholyases, structures of A1RDF1 in complex with PLP (internal aldimine) and PLP⋅PEtN (external aldimine) were determined, revealing the basis of substrate binding and the structural factors that distinguish the enzyme from class III homologues that display TA activity.
Predictors of emotional and physical dating violence in a sample of serious juvenile offenders
Authors: Sweeten Gary , Larson Matthew , Piquero Alex R.
Published: October 2016

Aim

We estimate group‐based dating violence trajectories and identify the adolescent risk factors that explain membership in each trajectory group.

Method

Using longitudinal data from the Pathways to Desistance Study, which follows a sample of 1354 serious juvenile offenders from Philadelphia, Pennsylvania and Phoenix, Arizona between mid‐adolescence and early adulthood, we estimate group‐based trajectory models of both emotional dating violence and physical dating violence over a span of five years in young adulthood. We then estimate multinomial logistic regression models to identify theoretically motivated risk factors that predict membership in these groups.

Results

We identified three developmental patterns of emotional dating violence: none (33%), low‐level (59%) and high‐level decreasing (8%). The best‐fitting model for physical dating violence also had three groups: none (73%), low‐level (24%) and high‐level (3%). Race/ethnicity, family and psychosocial variables were among the strongest predictors of both emotional and physical dating violence. In addition, delinquency history variables predicted emotional dating violence and relationship variables predicted physical dating violence.

Conclusions

Dating violence is quite prevalent in young adulthood among serious juvenile offenders. Numerous predictors distinguish between chronic dating violence perpetrators and other groups. These may suggest points of intervention for reducing future violence. Copyright © 2016 John Wiley & Sons, Ltd.
Comparison of acute expansion of bioresorbable vascular scaffolds versus metallic drug‐eluting stents in different degrees of calcification: An optical coherence tomography study
Authors: Ming Fam Jiang , van Der Sijde Johannes N , Karanasos Antonios , Felix Cordula , Diletti Roberto , van Mieghem Nicolas , de Jaegere Peter , Zijlstra Felix , Jan van Geuns Robert , Regar Evelyn
Published: October 2016

Objectives

The acute expansion of bioresorbable vascular scaffolds (BRS) and drug‐eluting stents (DES) in lesions with different extent of calcification was compared by Optical Coherence Tomography (OCT).

Background

The acute mechanical performance of polymeric BRS in calcified lesions is poorly understood.

Methods

Acute device performance in lesions treated with either BRS(N = 50) or DES (N = 50) was compared using Optical Coherence Tomography (OCT). According to angiographic degree of calcification the lesions were divided in three groups: no/mild, moderate and heavy calcification. Device performance was assessed with the following parameters by OCT: mean scaffold area, eccentricity index (EI), symmetry index (SI) and percentage incomplete strut apposition (ISA).

Results

One hundred lesions from 85 patients (BRS/DES; 37/48) were analyzed. Scaffold area and SI were similar between BRS and DES groups in the three calcification subgroups. Compared to DES, EI in BRS was marginally lower in the no/mild calcification group (0.86 ± 0.03 versus 0.88 ± 0.03, p = 0.018) but was similar in the moderate and heavy calcification groups. Compared to DES, percentage ISA struts in BRS was similar in the no/mild calcification group and was significantly lower in the moderate and heavy calcification groups (2.96 ± 2.36 versus 6.78 ± 4.61%, p = 0.002 and 1.82 ± 2.40 versus 8.89 ± 8.25%, p = 0.025 respectively).

Conclusions

With adequate lesion preparation, implantation of BRS in a population reflective of clinical practice, resulted in a similar luminal gain compared to DES as measured by OCT, regardless of the degree of angiographic calcification, while acute malapposition is lower with BRS in moderately and heavily calcified lesions. The clinical significance of our findings warrants further evaluation in future studies. © 2016 Wiley Periodicals, Inc.
Functional salivary reservoir in maxillary complete denture – technique redefined
Authors: Joseph Angel Mary , Joseph Suja , Mathew Nicholas , Koshy Ashwin Thomas
Published: October 2016

Key Clinical Message

Complete dentures are poorly tolerated in patients with xerostomia. A salivary reservoir can be incorporated into a denture that provides slow, sustained, and continuous release of salivary substitute. This article describes a simple, cost‐effective, and innovative technique of fabrication and designing of functional maxillary salivary reservoir complete denture.
A case of gingival cancer with pulmonary metastases that developed complete atrioventricular block and ventricular fibrillation as a result of myocardial metastases
Authors: Yoneda Taro , Kase Kazumasa , Amino Yoshiaki , Ogawa Naohiko , Watanabe Satoshi , Hara Johsuke , Abo Miki , Sone Takashi , Kimura Hideharu , Kasahara Kazuo
Published: October 2016

Key Clinical Message

We present a rare case of gingival cancer with pulmonary metastases that developed life‐threatening complete atrioventricular block and ventricular fibrillation as a result of myocardial metastases. This case suggests that implantable cardioverter defibrillators significantly improve the quality of life in these patients and maintain their performance status.
Operating the blues
Authors: Chatzis Andrew C. , Kanakis Meletios A. , Sofianidou Joanne , Tsoutsinos Alexandros J.
Published: October 2016

Key Clinical Message

A 63‐year‐old man bearing most signs and symptoms (facial pigmentation, degenerative arthritis, and dark urine) pertinent to his known history of alkaptonuria underwent aortic valve replacement for critical aortic stenosis. Although rare, aortic stenosis is the most common cardiac manifestation of alkaptonuric ochronosis.
N‐Substituted Azacalixphyrins: Synthesis, Properties, and Self‐Assembly
Authors: Chen Zhongrui , Haddoub Rose , Mahé Jérôme , Marchand Gabriel , Jacquemin Denis , Andeme Edzang Judicaelle , Canard Gabriel , Ferry Daniel , Grauby Olivier , Ranguis Alain , Siri Olivier
Published: October 2016

Pre‐ and postintroduction of substituents with respect to the macrocyclization step leads to previously unknown N‐substituted azacalixphyrins. The stepwise synthetic approach has been studied in detail to highlight the key role of the N‐substituents of the precursors and/or intermediates in terms of reactivity. Based on a combined experimental and theoretical investigation, the relationship between the properties of the macrocycles and their degree of substitution is rationalized. Depending on the nature of the N‐substituents, the formation of supramolecular ribbon‐like structures could also be observed, as demonstrated by combined TEM, SEM, AFM, and FTIR experiments.
Torsional and Electronic Factors Control the C−H⋅⋅⋅O Interaction
Authors: Driver Russell W. , Claridge Timothy D. W. , Scheiner Steve , Smith Martin D.
Published: October 2016

The precise role of non‐conventional hydrogen bonds such as the C−H⋅⋅⋅O interaction in influencing the conformation of small molecules remains unresolved. Here we survey a series of β‐turn mimetics using X‐ray crystallography and NMR spectroscopy in conjunction with quantum calculation, and conclude that favourable torsional and electronic effects are important for the population of states with conformationally influential C−H⋅⋅⋅O interactions. Our results also highlight the challenge in attempting to deconvolute a myriad of interdependent noncovalent interactions in order to focus on the contribution of a single one. Within a small molecule that is designed to resemble the complexity of the environment within peptides and proteins, the interplay of different steric burdens, hydrogen‐acceptor/‐donor properties and rotational profiles illustrate why unambiguous conclusions based solely on NMR chemical shift data are extremely challenging to rationalize.
Mechanistic Investigation of Molybdate‐Catalysed Transfer Hydrodeoxygenation
Authors: Larsen Daniel B. , Petersen Allan R. , Dethlefsen Johannes R. , Teshome Ayele , Fristrup Peter
Published: October 2016

The molybdate‐catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the transfer HDO of five para‐substituted benzylic alcohols was carried out. Density‐functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH2OH at 175 °C. Under these conditions, PhCH2OH underwent disproportionation to yield benzaldehyde, toluene, and significant amounts of bibenzyl. Isotopic‐labelling experiments (using PhCH2OD and PhCD2OH) showed that incorporation of deuterium into the resultant toluene originated from the α position of benzyl alcohol, which is in line with the mechanism suggested by the DFT study.
The Role of Reduced Graphite Oxide in Transition Metal Oxide Nanocomposites Used as Li Anode Material: An Operando Study on CoFe2O4/rGO
Authors: Permien Stefan , Indris Sylvio , Neubüser Gero , Fiedler Andy , Kienle Lorenz , Zander Stefan , Doyle Stephen , Richter Björn , Bensch Wolfgang
Published: October 2016

A composite consisting of CoFe2O4 spinel nanoparticles and reduced graphite oxide (rGO) is studied as an anode material during Li uptake and release by applying synchrotron operando X‐ray diffraction (XRD) and operando X‐ray absorption spectroscopy (XAS), yielding a comprehensive picture of the reaction mechanisms. In the early stages of Li uptake, a monoxide is formed as an intermediate phase containing Fe2+ and Co2+ ions; this observation is in contrast to reaction pathways proposed in the literature. In the fully discharged state, metallic Co and Fe nanoparticles are embedded in an amorphous Li2O matrix. During charge, metallic Co and Fe are oxidized simultaneously to Co2+ and Fe3+, respectively, thus enabling a high and stable capacity to be achieved. Here, evidence is presented that the rGO acts as a support for the nanoparticles and prevents the particles from contact loss. The operando investigations are complemented by TEM, Raman spectroscopy, galvanostatic cycling, and cyclic voltammetry.
Biogenic Manganese‐Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi‐Copper Oxidase, MnxEFG
Authors: Tao Lizhi , Simonov Alexandr N. , Romano Christine A. , Butterfield Cristina N. , Fekete Monika , Tebo Bradley M. , Bond Alan M. , Spiccia Leone , Martin Lisandra L. , Casey William H.
Published: October 2016

In a natural geochemical cycle, manganese‐oxide minerals (MnOx) are principally formed through a microbial process, where a putative multicopper oxidase MnxG plays an essential role. Recent success in isolating the approximately 230 kDa, enzymatically active MnxEFG protein complex, has advanced our understanding of biogenic MnOx mineralization. Here, the kinetics of MnOx formation catalyzed by MnxEFG are examined using a quartz crystal microbalance (QCM), and the first electrochemical characterization of the MnxEFG complex is reported using Fourier transformed alternating current voltammetry. The voltammetric studies undertaken using near‐neutral solutions (pH 7.8) establish the apparent reversible potentials for the Type 2 Cu sites in MnxEFG immobilized on a carboxy‐terminated monolayer to be in the range 0.36–0.40 V versus a normal hydrogen electrode. Oxidative priming of the MnxEFG protein complex substantially enhances the enzymatic activity, as found by in situ electrochemical QCM analysis. The biogeochemical significance of this enzyme is clear, although the role of an oxidative priming of catalytic activity might be either an evolutionary advantage or an ancient relic of primordial existence.
Reinterpretation of Dynamic Vibrational Spectroscopy to Determine the Molecular Structure and Dynamics of Ferrocene
Authors: Best Stephen P. , Wang Feng , Islam M. Tauhidul , Islam Shawkat , Appadoo Dominique , Trevorah Ryan M. , Chantler Christopher T.
Published: October 2016

Molecular distortion of dynamic molecules gives a clear signature in the vibrational spectra, which can be modeled to give estimates of the energy barrier and the sensitivity of the frequencies of the vibrational modes to the reaction coordinate. The reaction coordinate method (RCM) utilizes ab initio‐calculated spectra of the molecule in its ground and transition states together with their relative energies to predict the temperature dependence of the vibrational spectra. DFT‐calculated spectra of the eclipsed (D5h) and staggered (D5d) forms of ferrocene (Fc), and its deuterated analogue, within RCM explain the IR spectra of Fc in gas (350 K), solution (300 K), solid solution (7–300 K), and solid (7–300 K) states. In each case the D5h rotamer is lowest in energy but with the barrier to interconversion between rotamers higher for solution‐phase samples (ca. 6 kJ mol−1) than for the gas‐phase species (1–3 kJ mol−1). The generality of the approach is demonstrated with application to tricarbonyl(η4‐norbornadiene)iron(0), Fe(NBD)(CO)3. The temperature‐dependent coalescence of the ν(CO) bands of Fe(NBD)(CO)3 is well explained by the RCM without recourse to NMR‐like rapid exchange. The RCM establishes a clear link between the calculated ground and transition states of dynamic molecules and the temperature‐dependence of their vibrational spectra.
Amphiphilic Diblock Co‐polymers Bearing a Cysteine Junction Group: Synthesis, Encapsulation of Inorganic Nanoparticles, and Near‐Infrared Photoresponsive Properties
Authors: Geng Yi , Wang Zhi‐Fei , Lin Bao‐Ping , Yang Hong
Published: October 2016

Encapsulation of inorganic nanoparticles (NPs) in the interfaces of amphiphilic vesicles is a challenging task. The traditional strategy is to use amphiphilic triblock co‐polymers, which possess two outer blocks for building the walls and coronas of the vesicles, and one middle NP binding block for localizing NPs at the vesicle interfaces. In this manuscript, we describe the design and synthesis of an amphiphilic diblock co‐polymer, that is, PEG‐SH‐b‐PS (PEG=poly(ethylene glycol), PS=polystyrene) bearing a cysteine junction with one free pendant thiol group at the center point between the hydrophilic poly(ethylene glycol) block and the hydrophobic polystyrene block. The amphiphilicity‐driven self‐assembly in aqueous solution of the pure linear diblock co‐polymer PEG‐SH‐b‐PS and the corresponding amphiphilic PEG‐SH‐b‐PS/gold NPs (GNPs) nanocomposites is examined. From TEM observations of the self‐assembled samples containing the conjugated GNPs, it can be concluded that most of the GNPs are dispersed at the interfaces of the formed vesicles. In addition, near‐infrared (NIR)‐absorbing copper monosulfide (CuS) NPs are also encapsulated into the PEG‐SH‐b‐PS vesicles. Due to the photothermal heating effect of the CuS NPs, the corresponding PEG‐SH‐b‐PS/CuSNPs vesicles can disassemble and release the embedded cargos under NIR illumination, which endows this nanocomposite material with potential in biomedical applications, such as cancer imaging, photothermal therapy, and drug delivery.
A DFT Mechanistic Study on Ethylene Tri‐ and Tetramerization with Cr/PNP Catalysts: Single versus Double Insertion Pathways
Authors: Britovsek George J. P. , McGuinness David S.
Published: October 2016

The mechanism of ethylene trimerization and tetramerization with a chromium–diphosphinoamine (Cr–PNP) catalyst system has been studied by theoretical (DFT) methods. Two representative ligands have been explored, namely Ph2PN(Me)PPh2 and (o‐MeC6H4)2PN(Me)P(o‐MeC6H4)2. Calculations on the former ligand reveal how a combination of single and double ethylene insertion mechanisms may lead to 1‐hexene, 1‐octene and the major side products (cyclopentanes and n‐alkanes). For the latter ligand, introduction of o‐alkyl substitution leads to a more sterically congested active species, which suppresses the available pathways for tetramerization and side product formation. Hence, the high selectivity of o‐aryl substituted PNP ligands for trimerization can be rationalized.
Structures, Lewis Acidities, Electrophilicities, and Protecting Group Abilities of Phenylfluorenylium and Tritylium Ions
Authors: Follet Elsa , Mayer Peter , Berionni Guillaume
Published: October 2016

The isolation, characterization, and the first X‐ray structures of a fluorenylium ion and its Lewis adducts with nitrogen‐ and phosphorus‐centered Lewis bases are reported. Kinetics of the reactions of a series of fluorenylium ions with reference π‐, σ‐, and n‐nucleophiles of various sizes and nucleophilicities allowed the interplay between electronic and structural parameters on the electrophilicities of these planarized tertiary carbenium ions to be elucidated. Structure–reactivity correlations and extensive comparisons of their reactivities with those of di‐ and triarylcarbenium ions are described. Quantitative determination of the electrofugalities of fluorenylium ions revealed to which extent they are complementing tritylium ions as protecting groups and how their tuning is possible. Determination of the equilibrium constants of the Lewis adducts formation between pyridines of calibrated Lewis basicities and phenylfluorenylium and tritylium ions allowed the determination of their Lewis acidities and to showcase the potential of these carbon‐centered Lewis acids in catalysis.
Supramolecular Virus‐Like Nanorods by Coassembly of a Triblock Polypeptide and Reversible Coordination Polymers
Authors: Hernandez‐Garcia Armando , Velders Aldrik H. , Stuart Martien A. Cohen , de Vries Renko , van Lent Jan W. M. , Wang Junyou
Published: October 2016

We investigate a new case of a self‐assembly‐stimulated self‐assembly in which a triblock polypeptide is combined with a anionic coordination polymer of a dipicolinic acid bis‐ligand, and d‐ or f‐ block metal ions like ZnII or EuIII. The polypeptide not only has a silk‐like domain that can fold and stack, but also a C‐terminal cationic sequence by which it can interact with the supramolecular (coordination) polyanion. In the presence of all three ingredients (polypeptide, bis‐ligand, and metal ions), we observe the initiation and slow growth of well‐defined metal‐containing nanorods of up to 150 nm in length, proving that self‐assembly of the polypeptide is triggered by the self‐assembly of the coordination polyelectrolyte and vice versa. The particles, which have a striking resemblance to rod‐like viruses, are stable up to 1.2 m NaCl, and can be made fluorescent when lanthanides like EuIII are used, showing the potential to exploit functional properties and applications of virus‐like supramolecular structures.
Monomeric Cinchona Alkaloid‐Based Catalysts for Highly Enantioselective Bromolactonisation of Alkynes
Authors: Wilking Michael , Daniliuc Constantin G. , Hennecke Ulrich
Published: October 2016

The cinchona alkaloid dimer (DHQD)2PHAL has been shown to be a broadly applicable catalyst for asymmetric halogenations. However, this catalyst does not have to be dimeric and a class of monomeric quinidine and quinine‐derived catalysts was prepared, often showing superior selectivity in bromolactonisations of terminal alkynoic acids. Mechanistic investigations show that these organocatalysts act as host molecules that can bind carboxylic acid‐based substrates as guests with substantial binding constants. Based on these findings, it is proposed that this class of catalysts is bifunctional in nature activating the halogenating agent as well as the nucleophile in electrophilic halogenation reactions.
Encapsulation and Enhanced Luminescence Properties of IrIII Complexes within a Hexameric Self‐Assembled Capsule
Authors: Horiuchi Shinnosuke , Tanaka Hirotaka , Sakuda Eri , Arikawa Yasuhiro , Umakoshi Keisuke
Published: October 2016

Encapsulation and luminescence studies of [Ir(ppy)2(bpy)]Cl (ppy=2‐phenylpyridinate, bpy=2,2′‐bipyridine) within a hexameric resorcinarene capsule are reported. One IrIII complex cation was encapsulated within the capsule, as demonstrated by NMR and dynamic light scattering (DLS) studies. The emission color of the IrIII complex was drastically changed from orange to yellow by encapsulation, in contrast with the lack of significant changes in the absorption spectrum. The hexameric capsule effectively hampers the non‐radiative pathway to increase both the luminescence quantum yield and the exited state lifetime. The luminescent properties of the encapsulated IrIII complex depend on the ratio of IrIII complex to the resorcinarene monomer as well as the concentration of resorcinarene monomer owing to the reversible process of self‐assembly of the hexameric capsule. Quenching experiments revealed that the IrIII complex in the capsule was effectively separated from quenchers.
C(sp3)−H Functionalizations Promoted by the Gold Carbene Generated from Vinylidenecyclopropanes
Authors: Li De‐Yao , Fang Wei , Wei Yin , Shi Min
Published: October 2016

The gold carbene generated from vinylidenecyclopropanes (VDCPs) can smoothly perform a C(sp3)−H bond insertion reaction, stereoselectively affording the intramolecular C(sp3)−H bond functionalized product, benzoxepine, with syn‐configuration in moderate to good yields under mild conditions. The KIE investigation on this bond functionalization partially revealed that the carbene insertion step might be rate‐determining. Using a chiral gold(I) catalyst, the first example on the asymmetric variant of gold carbene insertion into C(sp3)−H bond has been disclosed, giving the desired products with excellent results.
Ni3 versus Ni30: A Truncated Octahedron Metal–Organic Cage Constructed with [Ni5(CN)4]6+ Squares and Tripodal Tris‐tacn Ligands That are Large and Flexible
Authors: Zhang Zongyao , Zheng Kunyi , Xia Tianlong , Xu Lijin , Cao Rui
Published: October 2016

Reactions of trinickel complex of tripodal tris‐tacn ligand N(CH2‐m‐C6H4‐CH2tacn)3 (L, tacn=1,4,7‐triazacyclononane) in acetonitrile–methanol solution with and without phosphate led to two complexes of distinct nuclearities, [(NiIICl)3(CH3OH)3(HPO4)L](PF6) (Ni3, 1) and [(NiII5(CN)4(H2O)8Cl)6L8]Cl30 (Ni30, 2). Ligand L takes upward and downward conformation in the structure of 1 and 2, respectively. It is proposed that phosphate directs the upward conformation of Ni3L to form 1. In the absence of phosphate, Ni3L assembles with cyanide ions, which are formed by Ni‐catalyzed C−CN bond cleavage of acetonitrile, to give a nano‐sized Ni30 cage. Complex 2 represents a discrete truncated octahedron cage assembled with [Ni5(CN)4]6+ squares and large and flexible triangular ligands, which is scarcely observed for self‐assembled metal‐organic cages. The magnetic properties of 1 and 2 were examined, showing intriguing magnetic properties.
ChemInform Abstract: Crystal Structure, 7Li NMR, and Structural Relationship of Two Rare‐Earth Metal Richer Polar Intermetallics: La15Ge9Li1.50(16) and La7Ge3.
Authors: Nam Gnu , Jo Hongil , Ok Kang Min , Kim Jongsik , You Tae‐Soo
Published: October 2016

Small single crystals of La15Ge9Li1.50 (I) and La7Ge3 (II) are obtained by solid state reaction of a 15:9:2 (7:3) molar mixture of the elements (Nb ampoule in evacuated silica tubes, 1080 °C, 5 h).
ChemInform Abstract: One Dimensional Group 12 Metal Undecafluoridoditantalates.
Authors: Tavcar Gasper , Goreshnik Evgeny
Published: October 2016

Single crystals of Cd(Ta2F11)2 and Hg(Ta2F11)2 are grown from solutions of CdF2 or HgF2 and TaF5 in anhydrous HF (crystallization vessel, 28 K temperature gradient, quantitative yield).
ChemInform Abstract: Lead Flux Crystal Growth of Ce2Ru12P7.
Authors: Niehaus Oliver , Hoffmann Rolf‐Dieter , Poettgen Rainer
Published: October 2016

Crystals of the title phosphide are prepared by reaction of the elements in a Pb flux (620 K for 1 d and 1070 K for 1 d).
ChemInform Abstract: Versatile Route to Benzoannulated Medium‐Ring Carbocycles via Aryne Insertion into Cyclic 1,3‐Diketones: Application to a Synthesis of Radermachol.
Authors: Samineni Ramesh , Srihari Pabbaraja , Mehta Goverdhan
Published: October 2016

The facile procedure allows the synthesis of benzoannulated 7‐ and 8‐membered carbocycles including the Radermachol precursor (IX) from in situ generated arynes and cyclic 1,3‐diketones.
ChemInform Abstract: Triflic Acid‐Catalyzed Enynes Cyclization: A New Strategy Beyond Electrophilic π‐Activation.
Authors: Yu Zhunzhun , Liu Lu , Zhang Junliang
Published: October 2016

A new and efficient strategy for enynes cyclization catalyzed by triflic acid is disclosed.
ChemInform Abstract: Functionalization of Quinolines Through Copper‐Catalyzed Regioselective Halogenation Reaction.
Authors: Sahoo Harekrishna , Ramakrishna Isai , Baidya Mahiuddin
Published: October 2016

A protocol for a copper‐catalyzed chelation‐controlled halogenation of quinolines is presented.
ChemInform Abstract: Mild C—H/C—C Activation by Z‐Selective Cobalt Catalysis.
Authors: Zell Daniel , Bu Qingqing , Feldt Milica , Ackermann Lutz
Published: October 2016

The cobalt‐catalyzed reaction of indoles (I) with vinylcyclopropanes (II) leads to desired 2‐functionalized indoles with moderate to high Z‐selectivity.
ChemInform Abstract: Catalyst‐Free Insertion of Sulfoxonium Ylides into Aryl Thiols. A Direct Preparation of β‐Keto Thioethers.
Authors: Dias Rafael M. P. , Burtoloso Antonio C. B.
Published: October 2016

The presented method is an useful alternative to traditional thioether syntheses that may employ metal catalysts in combination with diazo compounds or toxic and hardly accessible haloketones.
ChemInform Abstract: Facile and Green Chemistry Access to 5‐Aryl‐1,2,4‐triazolidine‐3‐thiones in Aqueous Medium.
Authors: Ramesh Rathinam , Lalitha Appaswami
Published: October 2016

A rapid, facile approach is disclosed for the one‐pot, cyclocondensation of aromatic aldehydes with thiosemicarbazides in aqueous ethanol as green solvent leading to aryltriazolidine‐thiones in good yields.
ChemInform Abstract: Redox‐Divergent Hydrogen‐Retentive or Hydrogen‐Releasing Synthesis of 3,4‐Dihydroisoquinolines or Isoquinolines.
Authors: He Ke‐Han , Zhang Wei‐Dong , Yang Ming‐Yu , Tang Kai‐Li , Qu Mengnan , Ding You‐Song , Li Yang
Published: October 2016

The Ru‐catalyzed chemoselective annulation of arylimines (I) to give isoquinolines (II) is developed.
ChemInform Abstract: Chiral Phosphoric Acid‐Catalyzed Enantioselective Formal [3 + 2] Cycloaddition of Azomethine Imines with Enecarbamates.
Authors: Wang Yang , Wang Qian , Zhu Jieping
Published: October 2016

A series of isoquinoline‐fused pyrazolidines containing 2 or 3 contiguous stereocenters is obtained with complete regio‐ and diastereoselectivity and excellent enantioselectivity.
ChemInform Abstract: A Convenient Domino Ferrier Rearrangement‐Intramolecular Cyclization for the Synthesis of Novel Benzopyran‐Fused Pyranoquinolines.
Authors: Moshapo Paseka T. , Sokamisa Mokela , Mmutlane Edwin M. , Mampa Richard M. , Kinfe Henok H.
Published: October 2016

A one‐pot three‐component cyclocondensation sequence involving the Ferrier and Povarov‐like reactions is presented to synthesize novel pentacyclic N‐heterocycles.
ChemInform Abstract: Synthesis of 6‐Trichloromethylphenanthridines by Transition Metal‐Free Radical Cyclization of 2‐Isocyanobiphenyls.
Authors: Zhou Yuhan , Wu Changpeng , Dong Xiaoliang , Qu Jingping
Published: October 2016

Further transformation of the products to 6‐functionalized phenanthridines is demonstrated.
ChemInform Abstract: Catalytic Asymmetric Synthesis of Phosphoryl‐1,4‐dihydropyridazines via an Enantioselective Allylic Alkylation/1,3‐Dipolar Cycloaddition/Rearrangement Reaction Sequence.
Authors: Du Fei , Yin Liyang , Ning Yanqiang , Peng Yungui
Published: October 2016

A novel methodology for the highly enantioselective synthesis of pharmaceutically important phosphorylated pyridazine derivatives is developed.
ChemInform Abstract: Synthetic Methods of CuS Nanoparticles and Their Applications for Imaging and Cancer Therapy
Authors: Wang Lu
Published: October 2016

Review: 152 refs.
ChemInform Abstract: Characterization of Gold Catalysts
Authors: Villa Alberto , Dimitratos Nikolaos , Chan‐Thaw Carine E. , Hammond Ceri , Veith Gabriel M. , Wang Di , Manzoli Maela , Prati Laura , Hutchings Graham J.
Published: October 2016

Review: 364 refs.
ChemInform Abstract: Transition Metal Complexes of Bidentate and Tridentate Ligands: From Optoelectronic Studies to Supramolecular Assemblies
Authors: Pal Amlan K.
Published: October 2016

Review: 57 refs.
ChemInform Abstract: Synthetic Applications of Proton‐Coupled Electron Transfer
Authors: Gentry Emily C. , Knowles Robert R.
Published: October 2016

Review: 47 refs.
ChemInform Abstract: Tetrazolethiones: Synthesis and S‐Functionalization Reactions (Microreview)
Authors: Il'inykh Elena S. , Kim Dmitry G.
Published: October 2016

Review: [18 refs.
ChemInform Abstract: Oxidative Cleavage of Furans
Authors: Merino Pedro
Published: October 2016

Review: 853 refs.
ChemInform Abstract: Chemistry of Cyclic Imides: An Overview on the Past, Present and Future
Authors: Kavitha Kankanala , Shanthi Praveena Koduru Sri , Venkat Shivaji Ramarao Edupuganti Veera , Sreenivasa Murthy Nandula Yadagiri , Pal Sarbani
Published: October 2016

Review: data on synthesis and reactions of cyclic imides mainly from 1980 to the end f 2015
ChemInform Abstract: Design and Engineering of Artificial Oxygen‐Activating Metalloenzymes
Authors: Nastri Flavia , Chino Marco , Maglio Ornella , Bhagi‐Damodaran Ambika , Lu Yi , Lombardi Angela
Published: October 2016

Review: 335 refs.
ChemInform Abstract: Natural Products at Work: Structural Insights into Inhibition of the Bacterial Membrane Protein MraY
Authors: Koppermann Stefan , Ducho Christian
Published: October 2016

Review: 15 refs.
ChemInform Abstract: Perovskite Materials for Light‐Emitting Diodes and Lasers
Authors: Veldhuis Sjoerd A. , Boix Pablo P. , Yantara Natalia , Li Mingjie , Sum Tze Chien , Mathews Nripan , Mhaisalkar Subodh G.
Published: October 2016

Review: 152 refs.
ChemInform Abstract: Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium‐Ion Storage
Authors: Chen Gen , Yan Litao , Luo Hongmei , Guo Shaojun
Published: October 2016

Review: [149 refs.
ChemInform Abstract: Taming Hazardous Chemistry by Continuous Flow Technology
Authors: Movsisyan M. , Delbeke E. I. P. , Berton J. K. E. T. , Battilocchio C. , Ley S. V. , Stevens C. V.
Published: October 2016

Review: 193 refs.
ChemInform Abstract: Perspectives for Hyperpolarization in Compact NMR
Authors: Halse Meghan E.
Published: October 2016

Review: 95 refs.
Neonikotinoide schaden Honigbienen
Authors: Wessler Ignaz
Published: October 2016

Schon länger stehen Neonikotinoide im Verdacht, eine mögliche Ursache für das seit Jahren zu beobachtende Bienensterben zu sein [4]. Nun wurde ein neuer Mechanismus entdeckt, nach dem die Insektizide über den Futtersaft der Bienen auf die Larven wirken.
Evaluation of ash‐free coal for chemical looping combustion ‐ part II: Thermogravimetric multi‐cycle performance
Authors: Shabani Azar , Rahman Moshfiqur , Pudasainee Deepak , Samanta Arunkumar , Sarkar Partha , Gupta Rajender
Published: October 2016

In this paper, performance of AFC in CLC during multi‐cycle thermogravimetric (TG) experiments was investigated. The close to stoichiometric CuO/AFC ratio of 30 is selected for the consecutive reduction and re‐oxidation cyclic experiments. The reactivity of the first cycle was higher than the consecutive cycles due to the fresh CuO in the first cycle. The thermal behaviours, such as mass change in the consecutive cycles, were almost similar and there was no residual ash deposition after each cycle. Furthermore, reduction and oxidation processes were performed with different isothermal times. After 1 h the combustion was incomplete but a longer combustion period (3 h) leads to almost complete combustion. Moreover, fresh samples and solid residues were analyzed by several advanced analytical techniques including XRD, SEM, and BET. XRD analysis of the residue of CuO/AFC showed the presence of CuO at the end of the cycles; CuO and SiO2 in residues from CuO/BL raw coal (parent coal of AFC) were shown in XRD results. At the higher temperatures (900 °C) the sintering effect and increased agglomeration were observed after each cycle. Total pore volume and average pore radius of the material decreased, however, the CLC performances at 900 °C did not reduce. The multi‐cycle experiments showed AFC as a promising candidate for CLC.
How do you write and present research well? Answers to the 20 questions
Authors: Patience Gregory S. , Boffito Daria C. , Patience Paul A.
Published: October 2016

At the beginning of this series on how to write and present research,[1,2] we repeated Whitesides's[3] message that working in the laboratory, modelling, designing, and troubleshooting constitute only part of the research effort. Discovery, development, analysis, and reviewing literature is work which is incomplete until you publish it and others cite it.[4] Our questions address specifically how to write and present with greater clarity, which is only one element in the process and includes: (a) acknowledging that you should write and present better; (b) deciding that you want to improve; (c) identify means to achieve this goal—courses and books, for example; (d) dedicating time to practice; (e) finding a coach or some way to get feedback on how you are doing; and (f) implementing what you learn in all written and oral communication. Writing and presenting are indispensable skills for researchers, but for many of us, formal instruction on communication ended in high school or the first year of university. However, universities are now implementing soft skill workshops as part of the offering to new graduate students. Funding agencies recognize the importance of these skills and now require programs in grant proposals (NSERC CREATE, European RECHIND). These resources are most effective when students recognize that they need to improve their skills and also want to improve them. Great musicians, athletes, and Go players practice continually. Furthermore, they have coaches to give them feedback and help them develop strategies. Writing is as complex as these activities and, like with them, we can improve at it continually.[5,6]