bluuebunny/crossref_metadata_2025 huggingface dataset:
An Extended State Observer Based Fractional Order Sliding‐Mode Control for a Novel Electro‐Hydraulic Servo System with Iso‐Actuation Balancing and Positioning
Authors: Gao Qiang , Hou Yuanlong , Liu Jingbao , Hou Runming , Lv Mingming , Wang Li , Wang Chao
Published: September 2018

An extended state observer based fractional order sliding‐mode control (ESO‐FOSMC) is proposed in this study, with consideration of the strong nonlinear characteristics of a new electro‐hydraulic servo system with iso‐actuation balancing and positioning. By adopting the fractional order calculus theory, a fractional order proportional–integral–derivative (PID)‐based sliding mode surface was designed, which has the ability to obtain an equivalent positioning control with fractional order kinetic characteristics. By introducing the integral term into the sliding mode surface, it was found to be beneficial in reducing the steady‐state errors, as well as improving the precision of the control system. Also, by using the fractional order calculus to replace the integral calculus, the form of the convergence is improved; the system transfer of energy is slowed down; and the chattering of the system is greatly weakened. The extended state observer was designed to observe the real‐time disturbances, and also to generate the compensation control commands which are added to the FOSMC to achieve the dynamic compensation. By means of numerical simulations, the dynamic and static characteristics of the sliding mode control system were compared with those of the FOSMC and ESO‐FOSMC. The experimental results show that the ESO‐FOSMC system could effectively restrain the external disturbances and achieve higher control precision, as well as better control quantity without chattering. The semi‐physical simulations based experimental tests also demonstrated that the proposed ESO‐FOSMC outperformed the FOSMC in terms of system robustness and control precision, which could have a stable control of the gun system quickly and accurately.
Ratiometric fluorescence detection of Cu2+ based on carbon dots/bovine serum albumin–Au nanoclusters
Authors: Yang Li , Zeng Mulan , Du Yue , Wang Li , Peng Bingxian
Published: September 2018

A ratiometric fluorescence sensor for Cu2+ detection was developed by employing carbon dots (CDs) as the reference fluorophore, and bovine serum albumin (BSA)–Au nanoclusters (AuNCs) both as specific recognition element and as response signal. The CDs were prepared by heating an acetic acid solution of chitosan at 180°C. The proposed nanoprobe was prepared by simply mixing the CDs and BSA–AuNCs. Here, the CDs were associated with BSA–AuNCs to form CDs/BSA–AuNCs nanoprobes based on electrostatic interaction and hydrogen bonds. In the hybrid fluorescent CDs/BSA–AuNCs nanoprobe, the emission of BSA–AuNCs at 640 nm was quenched by Cu2+, whereas the emission of CDs at 424 nm was maintained. The fluorescence changes of I640/I424 had good linearity with Cu2+ concentration in the range 1.5–600 nM, and the detection limit of the nanoprobe was 0.5 nM for Cu2+ detection, almost 4 × 104 times lower than the maximum allowable amount of Cu2+ in drinking water. The proposed method for detecting Cu2+ also had high selectivity and feasibility.
Developing clarity on the coaching‐counselling conundrum: Implications for counsellors and psychotherapists
Authors: Grant Anthony M. , Green Robert M.
Published: September 2018

Coaching, as a methodology for facilitating intentional positive change, has apparently become a permanent fixture in contemporary Western society. However, it would seem that counsellors and psychotherapists, despite been seen as having expertise in helping people deal with emotional difficulties and life challenges, have been relatively slow in positioning themselves in the coaching market. This has left other, possibly less qualified individuals to address the ubiquitous human need for goal attainment, self‐discovery and personal development. To develop clarity on the coaching‐counselling conundrum we firstly discuss the distinctions between coaching and counselling/psychotherapy, and we emphasise some key differences between the counsellor–client relationship and the coach–coachee relationship. We outline a tripartite metatypology of coaching (skills, performance and developmental coaching) and we use this to further make links between coaching and counselling. To address the question whether coaching is somehow less “valid” than counselling we then present an overview of the current evidence‐base for coaching and conclude with some key points for counsellors making a transition to coaching practice.
Optimal positioning of self‐expanding valves before deployment decreases paravalvular regurgitation following transcatheter aortic valve replacement
Authors: Dadu Razvan T. , Xu Jiaqiong , Rehman Hasan , von Ballmoos Moritz Wyler , Barker Colin M. , Reyes Manuel , Ramchandani Mahesh , Reul Ross M. , Reardon Michael J. , Kleiman Neal S.
Published: September 2018

Objectives

To evaluate the association between measurements performed during Medtronic CoreValve (MCV) deployment and paravalvular leak (PVL).

Background

The MCV can be recaptured and repositioned, allowing the TAVR operator to implant at a more favorable position. The association between angiographic measurements of MCV position while the valve is recapturable and PVL post deployment has not been investigated.

Methods

493 patients undergoing TAVR with MCV (January 2011–July 2017) were included. PVL was defined as intraprocedural aortic regurgitation that was judged clinically to require balloon postdilation. Depth of the valve at the left coronary cusp (LCC) and noncoronary cusp (NCC) were measured when the valve was 80% deployed. An optimal cutoff value for the ratio LCC/NCC for PVL was identified in 40 patients. Using this cutoff value, the association between LCC/NCC and PVL was then validated in 453 patients.

Results

The median LCC/NCC was 1.51 (interquartile range 1.06–1.89).The optimal cutoff value for LCC/NCC was 1.48 (93% sensitivity, 77% specificity, AUC0.85). In the validation group 112 (24.7%) patients had PVL. For LCC/NCC ≥ 1.48, the incidence of PVL was lower compared to LCC/NCC < 1.48 (9.58% vs. 41.78%, P < 0.0001). LCC/NCC of 1.48 had a sensitivity of 79.5% and specificity of 63.6% for PVL (AUC0.72). In a multivariate model, LCC/NCC < 1.48 independently predicted PVL (OR = 6.67, 95% CI 3.96–11.23, P < 0.0001).

Conclusion

Positioning the MCV such that the LCC/NCC is ≥1.48 may result in less PVL.
Aminotriazole Mn(I) Complexes as Effective Catalysts for Transfer Hydrogenation of Ketones
Authors: Martínez‐Ferraté Oriol , Werlé Christophe , Franciò Giancarlo , Leitner Walter
Published: September 2018

A catalytic system based on complexes comprising abundant and cheap manganese together with readily available aminotriazole ligands is reported. The new Mn(I) complexes are catalytically competent in transfer hydrogenation of ketones with 2‐propanol as hydrogen source. The reaction proceeds under mild conditions at 80 °C for 20 h with 3 % of catalyst loading using either KOtBu or NaOH as base. Good to excellent yields were obtained for a wide substrate scope with broad functional group tolerance. The obtained results by varying the substitution pattern of the ligand are consistent with an out‐sphere mechanism for the H‐transfer.
Fructosylation of Hydroxytyrosol by the β‐Fructofuranosidase from Xanthophyllomyces dendrorhous: Insights into the Molecular Basis of the Enzyme Specificity
Authors: Míguez Noa , Ramírez‐Escudero Mercedes , Gimeno‐Pérez María , Poveda Ana , Jiménez‐Barbero Jesús , Ballesteros Antonio O. , Fernández‐Lobato María , Sanz‐Aparicio Julia , Plou Francisco J.
Published: September 2018

This work investigates the ability of the β‐fructofuranosidase pXd‐INV from the yeast Xanthophyllomyces dendrorhous to glycosylate the olive biophenol hydroxytyrosol (HT). Two fructosylated derivatives (Fru‐HT1 and Fru‐HT2) were synthesized. Under the best conditions (300 mg/mL sucrose, 25 mg/mL HT), the maximum yield was 45.6 %. MS and 2D‐NMR analyses showed that the major product (Fru‐HT1) was fructosylated at the primary OH of HT. The structure of the complexes with the substrates and the product analyzed by crystallography led to the understanding of the molecular determinants regulating the enzymatic mechanism. Product‐soaked crystals revealed that the minor derivative (Fru‐HT2) was fructosylated at the phenolic p‐OH group. The two binding modes for HT at pXd‐INV active site are governed almost exclusively by packing to Trp105 (Fru‐HT1) and polar interactions with the loop Glu334‐Asn342 (Fru‐HT2), respectively. Specific mutagenesis at these residues was accomplished to tune the enzyme regiospecificity. One of the studied mutants (N342Q) was notably more specific for the fructosylation at the phenolic OH than the wild‐type.
Gold‐Clip‐Assisted Self‐Assembly and Proton‐Coupled Expansion–Contraction of a Cofacial FeIII–Porphyrin Cage
Authors: Wang Yuanyuan , Ang Pau Lin , Wong Chun‐Yuen , Yip John H. K.
Published: September 2018

A molecular cage {Au8(μ‐PAnP)4[Fe(H2O)2(TPyP)]2(OTf)2}(OTf)8 (1) composed of two cofacial FeIII‐porphyrin can be self‐assembled from the gold clip [Au2(PAnP)Cl2] and Fe3+(H2O)2(TPyP)+ (PAnP=9,10‐bis(diphenylphosphino)anthracene, TPyP=meso‐tetra(4‐pyridyl)porphyrinato). The height of the cage is 8.579(3) Å. The addition of a base to a solution of the cage leads to a contracted and twisted cage {[Au8(μ‐PAnP)4[Fe2(μ‐O)(TPyP)2]}(OTf)8 (2), which has a height of ≈4.4 Å and porphyrin–porphyrin torsional angle of ≈20°. The contracted cage can be synthesized independently from the gold clip and Fe2(μ‐O)(TPyP)2. The spectroscopy and crystal structure of an unclipped analog of the contracted cage, {[AuPPh3)8[Fe2(μ‐O)(TPyP)2]}(OTf)8 (3), supports the DFT‐calculated structure of 2. NMR and UV/Vis titrations show that the expansion‐untwisting and contraction‐twisting of the cage is reversible.
The relationship between household income and patient‐reported symptom distress and quality of life in children with advanced cancer: A report from the PediQUEST study
Authors: Ilowite Maya F. , Al‐Sayegh Hasan , Ma Clement , Dussel Veronica , Rosenberg Abby R. , Feudtner Chris , Kang Tammy I. , Wolfe Joanne , Bona Kira
Published: September 2018

Background

Children with advanced cancer experience high symptom distress, which negatively impacts their health‐related quality of life (HRQOL). To the authors’ knowledge, the relationship between income and symptom distress and HRQOL is not well described.

Methods

The Pediatric Quality of Life and Symptoms Technology (PediQUEST) multisite clinical trial evaluated an electronic patient‐reported outcome system to describe symptom distress and HRQOL in children with advanced cancer via repeated surveys. The authors performed a secondary analysis of PediQUEST data for those children with available parent‐reported household income (dichotomized at 200% of the Federal Poverty Level and categorized as low income [<$50,000/year] or high income [≥$50,000/year]). The prevalence of the 5 most commonly reported physical and psychological symptoms was compared between groups. Multivariable generalized estimating equation models were used to test the association between household income and symptom distress and HRQOL.

Results

A total of 78 children were included in the analyses: 56 (72%) in the high‐income group and 22 (28%) in the low‐income group. Low‐income children were more likely to report pain than high‐income children (64% vs 42%; P=.02). In multivariable models, children from low‐income families demonstrated a uniform trend toward higher total (βlow‐high=3.1; 95% confidence interval [95% CI], −0.08 to 6.2 [P=.06]), physical (β=3.8; 95% CI, −0.4 to 8.0 [P=.09]), and psychological (β=3.46; 95% CI, −1.91 to 8.84 [P=.21]) symptom distress compared with children from high‐income families. Low income was associated with a uniform trend toward lower total (β=−7.9; 95% CI, −14.8, to −1.1 [P=.03]), physical (β=−11.2; 95% CI, −21.2 to −1.2 [P=.04]), emotional (β=−5.8; 95% CI, −13.6 to 2.0 [P=.15]), social (β=−2.52; 95% CI, −9.27 to 4.24 [P=.47]), and school (β=−9.8; 95% CI, −17.8 to −1.8 [P=.03]) HRQOL.

Conclusions

In this cohort of children with advanced cancer, children from low‐income families were found to experience higher symptom burden and worse QOL.
Research on image de‐disturbing algorithm based on dark channel prior and anisotropic Gaussian filtering
Authors: Du Hongchun
Published: September 2018

In order to solve the problem of serious degradation of images collected outdoors in dense fog weather, a defogging algorithm for dense fog images was proposed. The fog‐day imaging physical model was simplified; the concept of fog concentration factor was proposed. The single image de‐hazing algorithm based on dark channel priors solves the problem of estimating the transmittance of fog and sky scenes. The image recovered by the algorithm is clear and natural. The algorithm has high computational complexity. It takes a long time to meet real‐time requirements. The principle of anisotropic Gaussian filtering is introduced. It combines with the dark channel. The value of the fog concentration coefficient is obtained by estimating the visibility value of a single fog image. It is then combined with an anisotropic Gaussian filter of the image to estimate the atmospheric light value. Defogging of the fog image is performed by using the repair function. It is necessary to perform effective de‐hazing processing on smog images. Experiments show that the improved algorithm can greatly reduce the complexity of the algorithm while ensuring the defogging effect of the original algorithm.
Clusters of the Ionic Liquid 1‐Hydroxyethyl‐3‐methylimidazolium Picrate: From Theoretical Prediction in the Gas Phase to Experimental Evidence in the Solid State
Authors: Panja Sumit K. , Haddad Boumediene , Kiefer Johannes
Published: September 2018

Interonic interactions determine the macroscopic properties of ionic liquids (ILs). Hence, unravelling the relationships between the microscopic and macroscopic scales is key for rational design. Combining density functional theory (DFT) calculations of isolated ion pairs and vibrational spectroscopy of the condensed phase (fluid or solid) has become a very common approach. In the present work, we make a step towards understanding how the physicochemical effects in small gas phase clusters of a hydroxyl functionalized imidazolium‐picrate IL relate with the molecular structure and interactions of the corresponding solid material taking 1‐hydroxyethyl‐3‐methylimidazolium picrate, C2OHmimPic, as an example. In the isolated ion pair, strong alkyl‐OH⋅⋅⋅Pic hydrogen bonding interactions are found rather than the commonly observed hydrogen bonding interactions at the slightly acidic C(2)−H site of the imidazolium ring. However, this part of the cation plays an important role when clusters of ion pairs in the gas phase and inside a crystal lattice are considered. For example, in the dimeric ion‐pair cluster, one centre (O*) with two interaction sites (C(2)−H−O* and alkyl OH‐Pic) is observed. This configuration is suggested by single crystal X‐ray diffraction (XRD), vibrational spectroscopy, and the dispersion‐corrected DFT calculations. Hence, the study provides evidence for the appearance of theoretical gas phase clusters in an actual solidified ionic liquid. This ion pair dimer formation may be a general behavior of hydroxyl functionalized imidazolium ILs, but further research is needed to draw a final conclusion. Moreover, the Raman spectra confirm the exclusive gauche conformation of the hyroxyl functionalized alkyl chain.
Demographic Composition of Select Oncologic New Molecular Entities Approved by the FDA Between 2008 and 2017
Authors: Ramamoorthy Anuradha , Knepper Todd C. , Merenda Christine , Mendoza Martin , McLeod Howard L. , Bull Jonca , Zhang Lei , Pacanowski Michael
Published: September 2018

Race, ethnicity, sex, and age are demographic factors that can influence drug exposure and/or response, and can consequently affect treatment outcome. We evaluated demographic subgroup enrollment patterns in new therapeutic products approved by the US Food and Drug Administration (FDA) for the treatment of select cancers—breast, colorectal, lung, and prostate—that have comparative differences in morbidity and/or mortality among some demographic subgroups. In submissions of products approved between 2008 and 2013, participants (n = 22,481) were white (80%), from outside the United States (74%), between 17 and 64 years old (59%), and men (56% and 53%, including and excluding sex‐specific indications, respectively). In pivotal trials of products approved between2014 and 2017, participants (n = 3,612) were white (71%), between 17 and 64 years old (61%), and men (48% and 63%, including and excluding sex‐specific indications, respectively). The US‐relevant minority populations were under‐represented. A broader representation of patient subgroups in clinical trials may contribute to better understanding of exposure and/or response variability, and consequently help personalize drug therapy.
Social responsibility: Experts’ viewpoints on adoption of the ISO 26000 standard
Authors: Balzarova Michaela , Castka Pavel
Published: September 2018

The ISO 26000 guidance standard for social responsibility represents an important instrument in managing social responsibility in organizations. However, studies of the adoption of ISO 26000 have been conceptual so far, and little is known about future adoption patterns. In this study, we provide insights into the type of adopting organization, geographical adoption and adoption challenges at the firm level, as well as discussing the importance of ISO 26000 in the context of other voluntary standards for social responsibility. We gathered the data from experts who developed ISO 26000. We have also identified differences, especially related to adoption of ISO 26000 in the developing world and to specific challenges of firm level adoption. By drawing parallels with existing literature on voluntary standards, managers and policy makers will understand the areas of overlap with existing standards as well as challenges specific to ISO 26000.
Favorable effect of mycorrhizae on biomass production efficiency exceeds their carbon cost in a fertilization experiment
Authors: Verlinden Melanie S. , Ven Arne , Verbruggen Erik , Janssens Ivan A. , Wallander Håkan , Vicca Sara
Published: September 2018

Biomass production efficiency (BPE), the ratio of biomass production to photosynthesis, varies greatly among ecosystems and typically increases with increasing nutrient availability. Reduced carbon partitioning to mycorrhizal fungi (i.e., per unit photosynthesis) is the hypothesized underlying mechanism, as mycorrhizal abundance and plant dependence on these symbionts typically decrease with increasing nutrient availability. In a mesocosm experiment with Zea mays, we investigated the effect of nitrogen (N) and phosphorus (P) addition and of mycorrhizal inoculation on BPE. Photosynthesis and respiration were measured at mesocosm scale and at leaf scale. The growth of arbuscular mycorrhizal fungi (AMF) was assessed with ingrowth bags while also making use of the difference in δ13C between C4 plants and C3 soil. Mesocosms without AMF, that is, with pasteurized soil, were used to further explore the role of AMF. Plant growth, photosynthesis, and BPE were positively affected by P, but not by N addition. AMF biomass also was slightly higher under P addition, but carbon partitioning to AMF was significantly lower than without P addition. Interestingly, in the absence of AMF, plants that did not receive P died prematurely. Our study confirmed the hypothesis that BPE increases with increasing nutrient availability, and that carbon partitioning to AMF plays a key role in this nutrient effect. The comparison of inoculated vs. pasteurized mesocosms further suggested a lower carbon cost of nutrient uptake via AMF than via other mechanisms under nutrient rich conditions.
Coupled High Spin CoII Ions Linked by Symmetrical Double Hydrogen Bonds: Role of a Slowly Relaxing CuII Impurity in Interrupting the CoII–CoII Exchange Interaction
Authors: Pérez Ana L. , Kemmerer Axel , Rey Marilin A. , Dalosto Sergio D. , Ramos Carlos A. , Passeggi Mario C. G. , Rizzi Alberto C. , Brondino Carlos D.
Published: September 2018

CoII and CuII ions are two paramagnetic transition metal ions showing different relaxation rates (ν), with νCoII >> νCuII. To measure the isotropic exchange constant (J) between high spin CoII ions and between CuII ions and high spin CoII ions, we performed magnetic and EPR measurements complemented with computational calculations on pure trans‐diaqua‐bis(picolinato‐N,O)‐cobalt(II) dihydrate (1), on the CuII ion doped compound of 1 (2), and on the CuII ion doped compound in a ZnII matrix isomorphous to 1. The temperature dependence of the CuII EPR resonance lines of 2 induced by the fast relaxing CoII ion host as well as the evaluation of the temperature‐independent CoII–CoII and CuII–CoII isotropic exchange interaction are analyzed. We determined an antiferromagnetic interaction [JCo–Co = –1.07(1) cm–1] associated with a double symmetrical hydrogen bond bridge and another one [|J|Co–Cu = 0.0015(2) cm–1] associated with a double but asymmetrical hydrogen bond bridge, which are in line with the values obtained from computational calculations. This work shows that EPR spectroscopy can advantageously be used to evaluate weak exchange interactions between distinct metal ions with different relaxation rates by using the fact that those metal–metal interactions that broaden the EPR resonance line, which are described by matrices with a trace of zero, are averaged out at high temperatures.
Application of Molecular Dynamics to the Investigation of Metalloproteins Involved in Metal Homeostasis
Authors: Sala Davide , Musiani Francesco , Rosato Antonio
Published: September 2018

Available estimates indicate that 30–40 % of all proteins need at least one metal ion to perform their biological function. Therefore, they are called metalloproteins. The correct biosynthesis of metalloproteins requires living organisms to be able to cope with issues such as the limited bioavailability or the potential cytotoxicity of several essential metals. Thus, organisms have developed complex machineries that guarantee the proper intracellular concentration and distribution among compartments of each metal, i.e. metal homeostasis. To understand how the different proteins responsible for metal homeostasis carry out their function, it is necessary to investigate their three‐dimensional (3D) structure and mobility at the atomic level. Nuclear magnetic resonance spectroscopy is one of the main experimental techniques providing this information. Computer simulations of molecular dynamics (MD) complement experimental information by showing how the 3D structure fluctuates over time and as a function of environmental conditions, with the possibility of exploring a wider range of timescales and conditions than usually amenable to experiment. Here we review numerous applications of MD for the investigation of the structure and dynamics of metalloproteins, and we also mention some technical aspects related to the parametrization of metals in commonly used force fields.
Hybridization of CsPbBr3 Perovskite Nanocrystals with Polymer Nanofiber to Improve their Luminescence Stability
Authors: Li Qing‐Feng , Wang Jin‐Tao , Tian Boshi , Kong Suna , Wang Ting , Wang Zhenling
Published: September 2018

All‐inorganic cesium lead halide perovskite nanocrystals (IPNCs) exhibit exceptional optical properties but the low chemical and structural stability has restricted their long‐term applications. According to previous studies, hybridization of IPNCs with other matrix materials provides an efficient method for improving their optical stability. Here, we develop a new strategy to synthesize a chemically and structurally stable CsPbBr3 perovskite material using polymer nanofiber as the protective layer. It is found that CsPbBr3 nanocrystals grow spontaneously inside the polymer nanofiber. Furthermore, the crystal structure and grain size remain substantially unchanged for two months due to the presence of the polymer layer, resulting in a decrease in luminescence quenching. We expect that the results obtained in this work could open new possibilities for the design and development of air‐stable CsPbBr3 by hybridization with polymer nanofibers.
Preparation and Self‐Assembly of a 2:1 Polyoxometalate‐Fullerene C60 Shape Amphiphile
Authors: Zhou Shengju , Wang Lin , Yuan Zaiwu , Chen Mengjun , Zhang Geping , Li Hongguang
Published: September 2018

An organic‐inorganic hybrid (5) is synthesized where two Dawson polyoxometalate (POM) moieties are linked to one fullerene C60 unit. In a POM‐friendly solvent such as DMSO, DMF and CH3CN, 5 forms small vesicles below 100 nm at a concentration of 37.3 mg mL–1. When the concentration decreases to 9.0 mg mL–1, detection of aggregates becomes difficult. However, supramolecular structures with diverse morphologies can be induced upon the addition of H2O or toluene. In DMSO/H2O and DMF/H2O systems, plates form, which break to debris and small vesicles at high volume percentage of H2O. In CH3CN/H2O mixtures, solid spheres form, which fail to further evolve into other self‐assembled structures. In DMSO‐based binary mixtures, the type of poor solvent has a big influence on the aggregation behavior of 5, and replacing H2O with toluene transfers the aggregates from plates to multilamellar and multicellular vesicles. In contrast, in CH3CN‐based systems, the influence of the type of poor solvent is quite limited. Although the morphologies of the aggregates change a lot, their magnetic properties remain unchanged as confirmed by electron spin‐resonance measurements.
Homoleptic Silver Complexes of the Cages P4Se3 and As4S3
Authors: Weis Philippe , Hettich Clarissa , Kratzert Daniel , Krossing Ingo
Published: September 2018

By reacting P4Se3 and As4S3 with Ag[Al(ORF)4] {–RF = –C(CF3)3 or –hfip [= –C(H)(CF3)2]} in suitable solvents, Ag(P4Se3)[Al(Ohfip)4] (1), Ag(P4Se3)2[Al(ORF)4] (2), Ag(P4Se3)3[Al(ORF)4] (3), Ag2(As4S3)3[Al(ORF)4]2 (4) and Ag(As4S3)2[Al(ORF)4] (5) were synthesized and characterized by SC‐XRD, Mass spectrometry, Raman spectroscopy as well as solution NMR spectroscopy. When using stronger coordinating anions, only P4Se3 forms an isolable complex yielding 1 featuring a [Ag2(P4Se3)2]2+ core capped by anions acting as the first example of P4Se3 coordinating through selenium atoms. Upon using the weakly coordinating anion [Al{OC(CF3)3}4]–, the dimeric complexes 2 and 4 are accessible in dichloromethane or ortho‐difluorobenzene (o‐dfb), respectively. Complex 2 shows isolated [Ag2(P4Se3)4(CH2Cl2)2]2+ dications with a [Ag2(P4Se3)2]2+ core similar to 1. Complex 4 shows isolated [Ag2(As4S3)3]2+ dications featuring a weak argentophilic contact. All of these complexes include solvent molecules or anions in the coordination sphere of the metal. When switching to the polar yet non‐coordinating solvent SO2, the coordination spheres are filled with additional ligands and compounds 3 and 5 form. Complex 3 shows condensed [Ag(P4Se3)3]+ units yielding a one dimensional chain and represents the first homoleptic metal(P4Se3) complex. Complex 5 shows a similar paddle wheel structure as in 4 with interconnecting As4S3 ligands and is the first known example of a homoleptic metal(As4S3) complex.
FeII Complexes with Triple N1,N2‐Triazole Bridge Schiff Base Ligand: Antiferromagnetic Dimer vs. Spin Conversion Trimer
Authors: Li Ai‐Min , Hochdörffer Tim , Wolny Juliusz A. , Schünemann Volker , Rentschler Eva
Published: September 2018

Based on the p‐tolyl functionalized Schiff base 1,2,4‐triazole ligand 4‐(p‐tolylidene‐amino)‐4H‐1,2,4‐triazole (toltrz), a series of three triazole‐bridged FeII complexes have been prepared. The compounds represent a range of dinuclear and trinuclear species, with µ2‐N1,N2‐triazole bridges linking the FeII centers. Mössbauer spectroscopy and magnetic susceptibility measurements reveal a gradual single‐step spin crossover (SCO) behavior for the trimeric compound 3 on the central FeII site. Single‐crystal X‐ray diffraction at 120 K confirms that the central FeII site undergoes a HS to LS transition while the peripheral FeII remain in HS state (HS = high spin; LS = low spin). Compounds 1 and 2 are isostructures with different terminal ligand XCN (X = S, Se), these two compounds stay in high spin state over the whole temperature range but display weak antiferromagnetic exchange coupling.
Isolation and Crystallographic Identification of Photoactive PtII Tris‐ and Bis(N‐methylbenzimidazole‐NHC) Complexes
Authors: Wang Zhe , Jiang Lu , Ng Chee Koon , Song Xiaolu , Hor T. S. Andy , Zhao Jin
Published: September 2018

Tri‐NHC PtII complexes, [Pt(LC)3Cl]Cl, 1 and [Pt(LC)2(LCN)](BF4)2, 3 [L = 1‐(N‐methylbenzimidazol‐2‐yl)‐3‐benzylimidazol‐2‐ylidene] and the analogous di‐NHC complex [Pt(LC)(LCN)Cl]Cl, 2 have been isolated and crystallographically identified. The N‐benzimidazole NHC ligand L acts either as a monodentate carbene C‐donor or a C^N chelating hybrid, denoted as LC and LCN, respectively. Mixed coordination modes are found in both 2 and 3. Complexes 1–3 exhibit deep blue to green emission in solution and/or in solid state.
Heterogeneous Organocatalysts Based on a Triazine‐Triazole Silane Ligand
Authors: Cruz Paula , Pérez Yolanda , del Hierro Isabel
Published: September 2018

Robust and non‐air‐sensitive metal‐free triazine‐triazole heterogeneous organocatalysts were prepared. The synthetic procedure involved the co‐condensation of a bridged tris silane precursor with tetraethyl orthosilicate (TEOS) in the presence of cetyltrimethylammonium bromide (CTAB). In addition, the silane precursor was anchored post‐synthesis onto mesoporous silica nanoparticles and used to stabilize magnetic nanoparticles. The organocatalysts were characterized by X‐ray diffraction (XRD), X‐ray fluorescence (XRF), N2 adsorption‐desorption, transmission electron microscopy (TEM), solid‐state nuclear magnetic resonance spectroscopy (CP‐MAS‐NMR), Fourier‐transform infrared spectroscopy (FT‐IR), and UV/Vis diffuse reflectance spectroscopy (DRUV/Vis). All materials, recoverable and recyclable, possess good catalytic activity in Knoevenagel condensation and in the one‐pot three‐component reaction for the synthesis of 2‐amino‐chromene derivatives under mild conditions.
Photoactive Molecular‐Based Devices, Machines and Materials: Recent Advances
Authors: Baroncini Massimo , Canton Martina , Casimiro Lorenzo , Corra Stefano , Groppi Jessica , La Rosa Marcello , Silvi Serena , Credi Alberto
Published: September 2018

Molecular and supramolecular‐based systems and materials that can perform predetermined functions in response to light stimulation have been extensively studied in the past three decades. Their investigation continues to be a highly stimulating topic of chemical research, not only because of the inherent scientific value related to a bottom‐up approach to functional nanostructures, but also for the prospective applications in diverse fields of technology and medicine. Light is an important tool in this context, as it can be conveniently used both for supplying energy to the system and for probing its states and transformations. In this microreview we recall some basic aspects of light‐induced processes in (supra)molecular assemblies, and discuss their exploitation to implement novel functionalities with nanostructured devices, machines and materials. To this aim we illustrate a few examples from our own recent work, which are meant to illustrate the trends of current research in the field.
Advances in the Asymmetric Synthesis of Bridged and Fused Bicyclic Acetals
Authors: Bera Smritilekha , Chatterjee Bhaskar , Mondal Dhananjoy
Published: September 2018

Fused and bridged bicyclic acetals are important structural motifs found in a diverse array of biologically active molecules. These conformationally rigid but stable structural segments are established within natural and unnatural compounds with biological importance. The structural and biological features of the molecules containing the fused and bridged ring systems have triggered a profound impact in the layout of newer synthetic methodologies and other designed entities. The interest in the development of efficient strategies to construct bicyclic scaffolds with fused and bridged bicyclic acetals in a stereocontrolled manner is substantial and challenging in the community of synthetic chemistry. The purpose of this review is to shed some light on the intriguing chemistry involved in the synthesis of conformationally constrained bridged and fused bicyclic acetals and its exploitation towards the synthesis of complex natural and unnatural molecules of biological and synthetic interest.
Enantiomerically Pure 5,13‐Dicyano‐9‐oxa[7]helicene: Synthesis and Study
Authors: Gupta Riddhi , Cabreros Trevor A. , Muller Gilles , Bedekar Ashutosh V.
Published: September 2018

Optically pure dicyano oxa[7]helicenes and helicene‐like molecules have been prepared and investigated for their optical behavior. The isomers of the intermediate 4,4′‐biphenanthrene‐3,3′‐diol were resolved by physically separating their 1‐menthyl carbonate derivatives. In this work a mild method was developed to cleave ArOMe in presence of a cyano group. The optical rotation of atropisomeric diol, helicenes‐like compounds and the oxa[7]helicenes was observed to be in increasing order, while the molecules also showed good response to circularly polarized luminescence.
Gold(I)‐Catalyzed and Nucleophile‐Guided Ligand‐Directed Divergent Synthesis
Authors: Lee Yen‐Chun , Knauer Lena , Louven Kathrin , Golz Christopher , Strohmann Carsten , Waldmann Herbert , Kumar Kamal
Published: September 2018

Transition metal catalysts can mediate a plethora of skeleton rearrangements of a range of substrates to construct complex small molecules. Yet, their potential to transform common substrates into distinct molecular scaffolds has not been fully explored to deliver biologically relevant small molecules. Gold(I)‐catalyzed transformations of enynes are amongst the most intriguing rearrangements and provide opportunities to access a range of diverse scaffolds efficiently. In ligand‐directed divergent synthesis (LDS), variation of ligands in metal complexes determines the fate of substrates during their transformation into distinct scaffolds. For instance, variation of ligands for the gold(I) catalysts helps to transform oxindole derived 1,6‐enynes into several distinct molecular frameworks. In this report, we present how ligand variation in gold(I) catalysts, nucleophile‐additives and alkyl and alkynyl substitutions on the 1,6‐enynes as well as replacement of the oxindole ring with a different privileged ring‐system (PRS) influence the LDS approach to access a wider chemical space. Based on the experimental results, we propose several mechanistic pathways in gold(I)‐catalyzed cycloisomerizations and cascade reactions of 1,6‐enyne substrates leading to structurally distinct chemotypes.
Benzisothiazol‐3‐ones through a Metal‐Free Intramolecular N–S Bond Formation
Authors: Yang Ke , Zhang Hao , Niu Ben , Tang Tiandi , Ge Haibo
Published: September 2018

The highly efficient synthesis of benzoisothiazol‐3‐ones from thiobenzamides has been described with good functional group compatibility and excellent yields. This work represents the first example of selectfluor‐promoted N–S bond formation processes. This method provides a facile approach to access various important bioactive benzoisothiazol‐3‐ones.
Ruthenium‐Alkylidene Complexes with Sterically Rigid Fluorinated NHC Ligands
Authors: Masoud Salekh M. , Akmalov Timur R. , Palagin Konstantin A. , Dolgushin Fedor M. , Nefedov Sergey E. , Osipov Sergey N.
Published: September 2018

An efficient procedure for the preparation of novel olefin metathesis catalysts of Grubbs‐Hoveyda type bearing sterically rigid NHC ligands has been developed. A preliminary evaluation of their catalytic activity has been performed on representative olefin metathesis reactions, such as RCM of malonates as well as self‐metathesis of allylbenzene. As result, it was found that along with excellent robustness, new complexes demonstrate remarkable activity in metathesis of allylbenzene, outperforming commercially available Grubbs‐Hoveyda catalyst in terms of yield and regioselectivity.
Cyclization of β‐Chlorovinyl Thiohydrazones into Pyridazines: A Mechanistic Study
Authors: Komendantova Anna S. , Fakhrutdinov Artem N. , Menchikov Leonid G. , Sukhorukov Alexey Yu. , Zavarzin Igor V. , Volkova Yulia A.
Published: September 2018

Extensive experimental and theoretical investigations on the isomerization and heterocyclizations of β‐chlorovinyl thiohydrazones derived from oxamic acid thiohydrazides and β‐chlorovinyl aldehydes were performed to elucidate the reaction mechanism of pyridazine formation. We showed that model β‐chlorovinyl thiohydrazone undergoes multiple isomerization reactions in solution induced by thione–thiol tautomerism and Z/E‐isomerization at the C=N bond. Mechanistic rationalization along with computational studies demonstrated that pyridazine is predominantly generated from the Z‐thiol isomers by 6π‐electrocyclization of the thiohydrazone‐derived 2,3‐diazatriene intermediate. The autocatalytic character of cyclization accelerated by the formation of acid was demonstrated by means of 1H NMR monitoring.
Pd/Zn(OTf)2 Co‐Catalyzed Asymmetric Hydrogenation of Imines under Normal Pressure of Hydrogen
Authors: Gao Yang , Yang Fan , Pu Dongdong , Laishram Ronibala Devi , Fan Ruifeng , Shen Guoli , Zhang Xuexin , Chen Jingchao , Fan Baomin
Published: September 2018

An efficient method for the asymmetric hydrogenation of cyclic and acyclic N‐sulfonylimines co‐catalyzed by Pd/Zn(OTf)2 using hydrogen gas under ambient pressure was developed. The methodology offers an easy access to generate chiral sulfonylamines in good yields and excellent enantioselectivities.
Stereochemistry of the Levy Reaction
Authors: Kröger Lukas , Wünsch Bernhard
Published: September 2018

The one‐pot three‐component Levy reaction was used to prepare tetracyclic pyrrolo[3,4‐b]carbazoles6–8.cis,cis,cis‐Configured products6b–8bbearing an ester moiety were isolated for the first time. Epimerization studies showed that thecis,cis,cis‐configured diastereomers6b–8bare the kinetically controlled less stable products, which are formed first. The stereochemistry is nicely explained by theendo‐stereoselectivity of the Diels–Alder reaction. High temperature, prolonged reaction times, polar solvents, bases and high concentration of acids led to epimerization at 4‐position to provide the thermodynamically favoredcis,cis,trans‐configured diastereomers6a–8a. It is postulated that epimerization occurred via the enol12or the corresponding enolate.
Understanding and coping with immigration detention: Social identity as cure and curse
Authors: Kellezi Blerina , Bowe Mhairi , Wakefield Juliet R.H. , McNamara Niamh , Bosworth Mary
Published: September 2018

Over 29,000 foreign nationals are detained yearly in British Immigration Removal Centres for undefined periods. This study investigated the role played by social identities in the way detainees are affected by, make sense of, and deal with detention. An opportunity sample of 40 detainees was interviewed on topics including support, identity, and well‐being, and data were analysed using theoretical thematic analysis. Participants struggled with loss of social networks, loss of rights, loss of agency, and joining a stigmatised group. Social identities guided exchange of support, aided meaning‐making, and mitigated distrust, serving as ‘Social Cures’. However, shared identities could also be sources of burden, ostracism, and distress, serving as ‘Social Curses’. Inability to maintain existing identities or create new ones fuelled feelings of isolation. Participants also reported rejection/avoidance of social identities to maximise their benefits. This study is the first to apply the Social Identity Approach to the experience of immigration detention.
Assessment of the mutagenic potential of para‐chloroaniline and aniline in the liver, spleen, and bone marrow of Big Blue® rats with micronuclei analysis in peripheral blood
Authors: Koenig Claire M. , Beevers Carol , Pant Kamala , Young Robert R.
Published: September 2018

Splenic tumors have been reported in rat cancer bioassays with para‐chloroaniline (PCA) and aniline. Development of these tumors is hypothesized to be due to hematotoxicity via the formation of methemoglobin (MetHb) and not direct DNA reactivity. To evaluate the mode of action (MOA) for tumor formation a transgenic rodent (TGR) in vivo gene mutation assay in Big Blue® TgF344 rats was performed with parallel micronuclei analysis in peripheral blood. Male rats were gavaged daily for 28 d to 0.5, 15, and 60 mg/kg PCA and 100 mg/kg aniline, the base molecular structure of PCA. On test day 10, the 60 mg/kg PCA dose was reduced to 30 mg/kg due to toxicity. On test day 4 and 29 peripheral blood micronucleus analysis was performed and on test day 29 clinical chemistry, hematology, and MetHb measurements were taken. At study termination, on test day 31, spleen, bone marrow, and liver (control tissue) were analyzed for cII transgene mutant frequency (MF). Repeat gavage exposure to PCA and aniline for 28 d did not produce an increase in cII transgene MF in analyzed tissues. An increase in micronuclei was seen at both time points at ≥15 mg/kg PCA and 100 mg/kg aniline. At the same dose levels, significant reductions in red blood cells, increases in absolute reticulocytes (ABRET), and increased levels of MetHb were observed. Together these results support that generation of micronuclei and tumorigenicity following exposure to PCA and aniline is due to compensatory mechanisms (e.g. increased cellular turnover) and not direct DNA reactivity. Environ. Mol. Mutagen. 59:785–797, 2018. © 2018 Wiley Periodicals, Inc.
Role of N‐Propyl‐N‐Methyl Pyrrolidinium bis(trifluoromethanesulfonyl)imide as an Electrolyte Additive in Sodium Battery Electrochemistry
Authors: Manohar C. V. , Forsyth Maria , MacFarlane Douglas R. , Mitra Sagar
Published: September 2018

Electrolyte compatibility with sodium metal and known sodium‐ion battery cathodes is of intense interest recently. In this work, electrolytes including an ionic liquid (IL) additive are formulated and shown to enhance the properties of the well‐known Na3V2(PO4)3/C (NVP/C) cathode. NVP/C composite material was synthesized by a carbothermal reduction process and studied in cells containing either organic electrolyte (1 M NaClO4 in PC) or organic electrolyte with added [C3mpyr][NTf2] IL. In an electrolyte containing 5 wt % [C3mpyr][NTf2] IL, the cathode material exhibited a stable capacity of 107.0±0.7 mAh g−1 after 50 cycles at a C/2 rate; in contrast, the capacity obtained with the organic electrolyte was only 85±1 mAh g−1 after 50 similar cycles. In situ impedance spectroscopy revealed that the electrode‐electrolyte charge‐transfer resistance is lower in the organic electrolyte with IL. Consistent with this finding, XPS, SEM, EDX and TEM results indicate that the interfacial layer formed on the surface of the NVP/C cathode material in the presence of the IL is more compact than that formed in the organic electrolyte, and that reaction between cathode and electrolyte is suppressed by the IL.
Anticancer, antithrombotic, antityrosinase, and anti‐α‐glucosidase activities of selected wild and commercial mushrooms from Pakistan
Authors: Sharif Sumaira , Atta Asia , Huma Tayyaba , Shah Asad Ali , Afzal Gulnaz , Rashid Saira , Shahid Muhammad , Mustafa Ghulam
Published: September 2018

Mushrooms have been accepted as nutraceutical foods because of their high nutritional and functional values. They have also gained interest due to their medicinal properties, economic importance, and organoleptic merit. In this study, wild Ganoderma lucidum and four commercial mushrooms, that is, Pleurotus ostreatus, Volvariella volvacea, Hericium erinaceus, and Lentinus edodes from Pakistan were screened for their biological activities such as anticancer, antityrosinase, anti‐α‐glucosidase, and antithrombotic activities from their methanol, ethanol, and water extracts. Enzyme inhibition assay showed that selected mushrooms are potent inhibitors with %age inhibition ranging from 19.00% to 80.91%, and 32.85% to 83.38% for tyrosinase and α‐glucosidase, respectively. The best tyrosinase inhibition was shown by P. ostreatus whereas L. edodes was found best as α‐glucosidase inhibitor. These mushrooms were tested against cancer cell lines including HT‐29 colon and H‐1299 lungs carcinoma cell lines. G. lucidum showed 29% and 24% viability of cells against HT‐29 and H‐1299 cell lines, respectively. This antiproliferative effect was in dose‐dependent manner, and the maximum inhibition was observed at 200 μg/ml. Mushrooms extracts were also found effective against clot lysis. The percentage of clot lysis was in the range of 27%–29%. The research would provide knowledge to the people of Pakistan about the importance of locally available commercial mushrooms and wild mushrooms for health improvement and prevention against different kinds of diseases.
Validation of Risk Score in Predicting Early Readmissions in Decompensated Cirrhotic Patients: A Model Based on the Administrative Database
Authors: Mumtaz Khalid , Issak Abdulfatah , Porter Kyle , Kelly Sean , Hanje James , Michaels Anthony J. , Conteh Lanla F. , El‐Hinnawi Ashraf , Black Sylvester M. , Abougergi Marwan S.
Published: September 2018

Early readmission in patients with decompensated liver cirrhosis leads to an enormous burden on health care use. A retrospective cohort study using the 2013 and 2014 Nationwide Readmission Database (NRD) was conducted. Patients with a diagnoses of cirrhosis and at least one feature of decompensation were included. The primary outcome was to develop a validated risk model for early readmission. Secondary outcomes were to study the 30‐day all‐cause readmission rate and the most common reasons for readmission. A multivariable logistic regression model was fit to identify predictors of readmissions. Finally, a risk model, the Mumtaz readmission risk score, was developed for prediction of 30‐day readmission based on the 2013 NRD and validated on the 2014 NRD. A total of 123,011 patients were included. The 30‐day readmission rate was 27%, with 79.6% of patients readmitted with liver‐related diagnoses. Age <65 years; Medicare or Medicaid insurance; nonalcoholic etiology of cirrhosis; ≥3 Elixhauser score; presence of hepatic encephalopathy, ascites, variceal bleeding, hepatocellular carcinoma, paracentesis, or hemodialysis; and discharge against medical advice were independent predictors of 30‐day readmission. This validated model enabled patients with decompensated cirrhosis to be stratified into groups with low (<20%), medium, (20%‐30%), and high (>30%) risk of 30‐day readmissions. Conclusion: One third of patients with decompensated cirrhosis are readmitted within 30 days of discharge. The use of a simple risk scoring model with high generalizability, based on demographics, clinical features, and interventions, can bring refinement to the prediction of 30‐day readmission in high‐risk patients; the Mumtaz readmission risk score highlights the need for targeted interventions in order to decrease rates of readmission within this population.