bluuebunny/crossref_metadata_2025 huggingface dataset:
An integrated structural cell biology to unravel the vesicle and membrane coat formation mechanism at the inner nuclear envelope
Authors: Hagen Christoph , Zeev‐Ben‐Mordehai Tzviya , Dent Kyle , Grange Michael , Bosse Jens B. , Vasishtan Daven , Siebert C. Alistair , Kaufmann Rainer , Celeski Juliana , Whittle Cathy , Schermelleh Lothar , Klupp Barbara , Schneider Gerd , Antonin Wolfram , Enquist Lynn , Mettenleiter Thomas C , Grünewald Kay
Published: December 2016

Our group uses electron cryo microscopy (cryoEM) / tomography (cryoET) and combines these with complementary techniques to understand biological processes mechanistically. The power of such an integrated structural biology approach to cell biology at the macromolecular level will be exemplified along the group's analyses of crucial steps in the molecular interactions between viruses and their host cells . The main emphasis will be on understanding mechanisms of membrane modulation in vesicle formation at the inner nuclear envelope in cargo egress from the nucleus [1,2].

Although nucleo‐cytoplasmic transport is typically mediated through nuclear pore complexes, herpesvirus capsids exit the nucleus via a unique vesicular pathway. Vesicular nucleo‐cytoplasmic transport might also be a general cellular mechanism for translocation of large cargoes across the nuclear envelope. Cargo is recruited, enveloped at the inner nuclear membrane (INM), and delivered by membrane fusion at the outer nuclear membrane. To understand the structural underpinning for this trafficking, we investigated nuclear egress of progeny herpesvirus capsids where capsid envelopment is mediated by two viral proteins (pUL31 and pUL34), forming the nuclear egress complex (NEC). Using a multi‐modal imaging approach, we visualized the NEC
in situ
forming coated vesicles of defined size. Cellular electron cryo‐tomography revealed a protein layer showing two distinct hexagonal lattices at its membrane‐proximal and membrane‐ distant faces, respectively. NEC coat architecture was determined by combining this information with integrative modeling using small‐angle X‐ray scattering data. The molecular arrangement of the NEC establishes the basic mechanism for budding and scission of tailored vesicles at the INM. We further solved the crystal structure of the pseudorabies virus NEC. Fitting of the NEC crystal structure into the cryoEM‐derived hexagonal lattice found
in situ
, provided details on the molecular basis of NEC coat formation and inner nuclear membrane remodeling. Altogether, this multimodal imaging study exemplified the power of an integrated structural cell biology approach to reveal novel mechanistic insights by combining
in‐situ
data with information on the isolated macromolecules mediating the respective biological process of interest.
Unique Reactivity of α‐Substituted Electron‐Deficient Allenes using Sulfinate Salts as Lewis Base Organocatalysts
Authors: Martzel Thomas , Lohier Jean‐François , Gaumont Annie‐Claude , Brière Jean‐François , Perrio Stéphane
Published: December 2016

The efficient sulfinate‐catalyzed intermolecular addition reaction of α‐substituted allenyl sulfones and allenoates with Michael acceptors is highlighted. The sequence proceeds under mild conditions to provide a scalable and efficient access to versatile functionalized alkynes, displaying a quaternary stereocentre at the propargylic position. This work enriches the diversity of Lewis base organocatalysts in the field of allene chemistry, in addition to the well‐established phosphine and amine catalysts.

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Tertiary Amine‐Catalyzed Difluoromethylthiolation of Morita–Baylis–Hillman Carbonates of Isatins with Zard's Trifluoromethylthiolation Reagent
Authors: Fan Xing , Yang Haibin , Shi Min
Published: December 2016

In this paper, we report that a novel tertiary amine‐catalyzed [3+2] annulation between Morita–Baylis–Hillman (MBH) carbonates derived from isatins with thiocarbonyl fluoride (F2C=S) in situ generated from Zard's reagent proceeds smoothly under mild conditions, affording difluoromethylthiolated spirocyclic oxindoles in good to excellent yields. Moreover, the asymmetric variant could be realized with a modified Cinchona alkaloid, giving the desired cyclic adducts in good to excellent yields with good enantioselectivities.

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Diastereoselective Intramolecular Aldol‐Type Trapping of Zwitterionic Intermediates by Ketones for the Synthesis of Spiro[chroman‐4,3′‐oxindole] Derivatives
Authors: Jia Shikun , Lei Yubing , Song Longlong , Krishna Reddy A. Gopi , Xing Dong , Hu Wenhao
Published: December 2016

A simple, mild and efficient rhodium‐catalyzed aromatic C–H functionalization of α‐phenoxy ketones by 3‐diazooxindoles for the synthesis of the spiro[chroman‐4,3′‐oxindole] ring system is described. A series of functionalized spiro[chroman‐4,3′‐oxindole] derivatives bearing two adjacent quaternary carbon centers have been attained in a highly diastereoselective manner with very good yields. Control experiments suggested the possibility of an intramolecular aldol‐type trapping of zwitterionic intermediates after the C–H functionalization. Furthermore, the applicability of this method has been tested by a gram‐scale synthesis. A facile treatment with base enabled the access to both syn‐ and anti‐diastereomers via isomerization.

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Connecting the quantum and classical worlds
Authors: Drossel Barbara
Published: December 2016

By considering (non‐relativistic) quantum mechanics as it is done in practice in particular in condensed‐matter physics, it is argued that a deterministic, unitary time evolution within a chosen Hilbert space always has a limited scope, leaving a lot of room for embedding the quantum‐classical transition into our current theories without recurring to difficult‐to‐accept interpretations of quantum mechanics. Nonunitary projections to initial and final states, the breaking of time‐reversal symmetry, a change of Hilbert space, and the introduction of classical concepts such as external potentials or localized atomic nuclei are widespread in quantum mechanical calculations. Furthermore, quantum systems require classical environments that enable the symmetry breaking that is necessary for creating the atomic configurations of molecules and crystals. This paper argues that such classical environments are provided by finite‐temperature macroscopic systems in which the range of quantum correlations and entanglement is limited. This leads to classical behavior on larger scales, and to collapse‐like events in all dynamical processes that become coupled to the thermalized degrees of freedom.

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One‐Step Annulative π‐Extension of Alkynes with Dibenzosiloles or Dibenzogermoles by Palladium/o‐chloranil Catalysis
Authors: Ozaki Kyohei , Murai Keiichiro , Matsuoka Wataru , Kawasumi Katsuaki , Ito Hideto , Itami Kenichiro
Published: December 2016

Reliable and short synthetic routes to polycyclic aromatic hydrocarbons and nanographenes are important in materials science. Herein, we report an efficient one‐step annulative π‐extension reaction of alkynes that provides access to diarylphenanthrenes and related nanographene precursors. In the presence of a cationic palladium/o‐chloranil catalyst system and dibenzosiloles or dibenzogermoles as π‐extending agents, a variety of diarylacetylenes are transformed successfully into 9,10‐diarylphenanthrenes in a single step with good functional‐group tolerance. Furthermore, double π‐extension reactions of 1,4‐bis(phenylethynyl)benzene and diphenyl‐1,3‐butadiyne are demonstrated, affording oligoarylene products, which show potential for application in the synthesis of larger polycyclic aromatic hydrocarbons and nanographenes.
Ribonucleotides and RNA Promote Peptide Chain Growth
Authors: Griesser Helmut , Tremmel Peter , Kervio Eric , Pfeffer Camilla , Steiner Ulrich E. , Richert Clemens
Published: December 2016

All known forms of life use RNA‐mediated polypeptide synthesis to produce the proteins encoded in their genes. Because the principal parts of the translational machinery consist of RNA, it is likely that peptide synthesis was achieved early in the prebiotic evolution of an RNA‐dominated molecular world. How RNA attracted amino acids and then induced peptide formation in the absence of enzymes has been unclear. Herein, we show that covalent capture of an amino acid as a phosphoramidate favors peptide formation. Peptide coupling is a robust process that occurs with different condensation agents. Kinetics show that covalent capture can accelerate chain growth over oligomerization of the free amino acid by at least one order of magnitude, so that there is no need for enzymatic catalysis for peptide synthesis to begin. Peptide chain growth was also observed on phosphate‐terminated RNA strands. Peptide coupling promoted by ribonucleotides or ribonucleotide residues may have been an important transitional form of peptide synthesis that set in when amino acids were first captured by RNA.
Native Top‐Down Mass Spectrometry of TAR RNA in Complexes with a Wild‐Type tat Peptide for Binding Site Mapping
Authors: Schneeberger Eva‐Maria , Breuker Kathrin
Published: December 2016

Ribonucleic acids (RNA) frequently associate with proteins in many biological processes to form more or less stable complex structures. The characterization of RNA–protein complex structures and binding interfaces by nuclear magnetic resonance (NMR) spectroscopy, X‐ray crystallography, or strategies based on chemical crosslinking, however, can be quite challenging. Herein, we have explored the use of an alternative method, native top‐down mass spectrometry (MS), for probing of complex stoichiometry and protein binding sites at the single‐residue level of RNA. Our data show that the electrostatic interactions between HIV‐1 TAR RNA and a peptide comprising the arginine‐rich binding region of tat protein are sufficiently strong in the gas phase to survive phosphodiester backbone cleavage of RNA by collisionally activated dissociation (CAD), thus allowing its use for probing tat binding sites in TAR RNA by top‐down MS. Moreover, the MS data reveal time‐dependent 1:2 and 1:1 stoichiometries of the TAR–tat complexes and suggest structural rearrangements of TAR RNA induced by binding of tat peptide.
Halogenverbrückte supramolekulare Kapseln im Festkörper, in Lösung und in der Gasphase
Authors: Dumele Oliver , Schreib Benedikt , Warzok Ulrike , Trapp Nils , Schalley Christoph A. , Diederich François
Published: December 2016

Supramolekulare Kapseln wurden durch neutrale Halogenbrücken (XBs) aufgebaut und im Festkörper, in Lösung sowie in der Gasphase untersucht. Die Geometrie der hoch organisierten Kapseln wird durch eine Röntgenkristallstruktur belegt, die den Aufbau aus zwei XB‐Hemisphären zeigt, die geometrisch durch H‐Brücken zu acht MeOH‐Molekülen verfestigt sind und zwei Benzol‐Gäste einschließen. Aufgrund von Desolvatationseffekten in protischen Lösungsmitteln führen Änderungen des XB‐Donors zu einer effektiveren Erhöhung der Assoziationskonstante als Änderungen des XB‐Akzeptors. Dies wird am Beispiel einer Tetrachinuclidin‐XB‐Akzeptorhemisphäre gezeigt. Mit einem Tetra(iodethinyl)‐XB‐Donor und einem Tetralutidin‐XB‐Akzeptor wird eine Assoziationskonstante in deuteriertem Benzol/Aceton/Methanol 70:30:1 bei 283 K von Ka=(2.11±0.39)×105 m−1 (ΔG=(−6.9±0.1) kcal mol−1) erreicht. Die Stabilität der XB‐Kapsel in der Gasphase wurde durch ESI‐MS bestätigt. Innerhalb der verlängerten Iodethinyl‐Kapsel wurde eine neue Gastbindungsstelle beobachtet.
Lithium Dihydropyridine Dehydrogenation Catalysis: A Group 1 Approach to the Cyclization of Diamine Boranes
Authors: McLellan Ross , Kennedy Alan R. , Orr Samantha A. , Robertson Stuart D. , Mulvey Robert E.
Published: December 2016

In reactions restricted previously to a ruthenium catalyst, a 1‐lithium‐2‐alkyl‐1,2‐dihydropyridine complex is shown to be a competitive alternative dehydrogenation catalyst for the transformation of diamine boranes into cyclic 1,3,2‐diazaborolidines, which can in turn be smoothly arylated in good yields. This study established the conditions and solvent dependence of the catalysis through NMR monitoring, with mechanistic insight provided by NMR (including DOSY) experiments and X‐ray crystallographic studies of several model lithio intermediates.
CO2 Capture from Ambient Air by Crystallization with a Guanidine Sorbent
Authors: Seipp Charles A. , Williams Neil J. , Kidder Michelle K. , Custelcean Radu
Published: December 2016

Carbon capture and storage is an important strategy for stabilizing the increasing concentration of atmospheric CO2 and the global temperature. A possible approach toward reversing this trend and decreasing the atmospheric CO2 concentration is to remove the CO2 directly from air (direct air capture). Herein we report a simple aqueous guanidine sorbent that captures CO2 from ambient air and binds it as a crystalline carbonate salt by guanidinium hydrogen bonding. The resulting solid has very low aqueous solubility (Ksp=1.0(4)×10−8), which facilitates its separation from solution by filtration. The bound CO2 can be released by relatively mild heating of the crystals at 80–120 °C, which regenerates the guanidine sorbent quantitatively. Thus, this crystallization‐based approach to CO2 separation from air requires minimal energy and chemical input, and offers the prospect for low‐cost direct air capture technologies.
The Mechanism of p53 Rescue by SUSP4
Authors: Kim Do‐Hyoung , Lee Chewook , Lee Si‐Hyung , Kim Kyung‐Tae , Han Joan J. , Cha Eun‐Ji , Lim Ji‐Eun , Cho Ye‐Jin , Hong Seung‐Hee , Han Kyou‐Hoon
Published: December 2016

p53 is an important tumor‐suppressor protein deactivation of which by mdm2 results in cancers. A SUMO‐specific protease 4 (SUSP4) was shown to rescue p53 from mdm2‐mediated deactivation, but the mechanism is unknown. The discovery by NMR spectroscopy of a “p53 rescue motif” in SUSP4 that disrupts p53‐mdm2 binding is presented. This 29‐residue motif is pre‐populated with two transient helices connected by a hydrophobic linker. The helix at the C‐terminus binds to the well‐known p53‐binding pocket in mdm2 whereas the N‐terminal helix serves as an affinity enhancer. The hydrophobic linker binds to a previously unidentified hydrophobic crevice in mdm2. Overall, SUSP4 appears to use two synergizing modules, the p53 rescue motif described here and a globular‐structured SUMO‐binding catalytic domain, to stabilize p53. A p53 rescue motif peptide exhibits an anti‐tumor activity in cancer cell lines expressing wild‐type p53. A pre‐structures motif in the intrinsically disordered proteins is thus important for target recognition.
Radical Desulfur‐Fragmentation and Reconstruction of Enol Triflates: Facile Access to α‐Trifluoromethyl Ketones
Authors: Su Xiaolong , Huang Honggui , Yuan Yaofeng , Li Yi
Published: December 2016

We report an efficient oxidative radical desulfur‐fragmentation and reconstruction of enol triflates for the synthesis of α‐CF3 ketones. Preliminary mechanistic studies disclosed that oxidative fragmentation to release a CF3 radical from the triflyl group of enol triflate and subsequent addition of the CF3 radical to another enol triflate form the desired α‐CF3 ketones. This method provides a new approach to α‐CF3 ketones, featuring the utilization of catalytic amount of oxidants, broad substrate scope, and potential to control the regioselectivity.
Structure and Isotope Effects of the β‐H Agostic (α‐Diimine)Nickel Cation as a Polymerization Intermediate
Authors: Xu Hongwei , White Paul B. , Hu Chunhua , Diao Tianning
Published: December 2016

Single‐crystal X‐ray characterization of cationic (α‐diimine)Ni‐ethyl and isopropyl β‐agostic complexes, which are key intermediates in olefin polymerization and oligomerization, are presented. The sharp Ni‐Cα‐Cβ angles (75.0(3)° and 74.57(18)°) and short Cα−Cβ distances (1.468(7) and 1.487(5) Å) provide unambiguous evidence for a β‐agostic interaction. An inverse equilibrium isotope effect (EIE) for ligand coordination upon cleavage of the agostic bond highlights the weaker bond strength of Ni−H relative to the C−H bond. An Eyring plot for β‐hydride elimination–olefin rotation–reinsertion is constructed from variable‐temperature NMR spectra with 13C‐labeled agostic complexes. The enthalpy of activation (ΔH≠) for β‐H elimination is 13.2 kcal mol−1. These results offer important mechanistic insight into two critical steps in polymerization: ligand association upon cleavage of the β‐agostic bonds and chain‐migration via β‐H elimination.
Sexual Dimorphism and Population Affinity in the Human Zygomatic Structure—Comparing Surface to Outline Data
Authors: Schlager Stefan , Rüdell Alexandra
Published: December 2016

The human zygomatic structure, consisting of the zygomatic bone and the zygomatic process of the temporal bone, is an essential part of the masticatory apparatus and has been shown to reflect population history and sexual dimorphism to varying degrees. In this study, we analyzed the predictive value of the outlines vs. the complete surface shape of the zygomatic bone in a sample of 98 Chinese (50 ♀, 48 ♂) and 96 Germans (49 ♀, 47 ♂). We first applied a surface registration process based on statistical shape modeling. A dense set of 1,480 pseudo‐landmarks was then sampled automatically from the surface of the pooled mean shape and three curves were digitized manually along the outlines of the zygomatic bone. Both sets of pseudo‐landmarks were automatically transferred to all specimens. Analysis of sex and population affinity showed both factors to be independently significant, but the interaction between them was not. Population affinity could be predicted quite accurately with correct classification of 97.9% using the surface data and 93.3% with the curve data. Sexual dimorphism was less distinct with 89.2% correct sex determination when using surface information compared with 77.8% when using the curve data. Population‐related shape differences were captured primarily in the outlines, while sexual dimorphism is distributed more uniformly throughout the entire surface of the zygomatic structure. Anat Rec, 300:226–237, 2017. © 2016 Wiley Periodicals, Inc.
Biomechanical Evaluation of Different Musculoskeletal Arrangements inPsittacosaurusand Implications for Cranial Function
Authors: Taylor Adam C. , Lautenschlager Stephan , Qi Zhao , Rayfield Emily J.
Published: December 2016

The masseter muscle complex is a unique feature of extant mammals and their advanced cynodont precursors, originating from the zygomatic arch and inserting onto the lateral surface of the dentary. This muscle complex is absent in sauropsids, with the exception of the neomorphic m. pseudomasseter complex that is unique to psittaciform birds (parrots and cockatiels). The anterior position and anterodorsally inclined line of action of both muscle groups increases leverage of the jaw and is thought to contribute to increased bite force, particularly in psittaciforms. A corollary is that in mammals at least, the masseter places increased load on the zygomatic arch, which may be withstood by soft tissue temporal fascia. Recently the existence of a m. pseudomasster (mPSM) and m. adductor mandibulae externus ventralis (mAMEV) has been proposed in the ornithischian dinosaurPsittacosaurus. Here we use computed tomography, digital restoration of skull anatomy and adductor musculature and computational biomechanics to test how the presence of anterodorsally inclined muscle loads influences stress, strain, deformation and estimated bite forces in the skull ofPsittacosaurus. We find that the m. pseudomasseter and m. amev increases bite force with an associated increase in cranial stress and deformation. There is, however, limited osteological evidence for the existence of these two additional muscles in the psittacosaur skull and geometric morphometric informed sensitivity analysis of our finite element models shows that bite position has a greater effect on loading‐induced deformation than muscle loading or material property variation. Anat Rec, 300:49–61, 2017. © 2016 Wiley Periodicals, Inc.
Evolution of the Jugal/Zygomatic Bones
Authors: Dechow Paul C. , Wang Qian
Published: December 2016

This issue of the Anatomical Record is the second of a two‐volume set on the zygoma (also called the cheek bone, the zygomatic bone, the malar, or the jugal, the latter term being used in vertebrates other than mammals). The zygoma is an important component of the craniofacial skeleton, in which the zygoma is a connection between the midfacial and the cranial skeletons; has a functional role as the origin of one of the masticatory muscles, the masseter muscle, and several facial muscles; has been considered as an essential buttress of the facial skeleton for resisting masticatory forces; and has importance for determining phylogenetic relationships. In humans, the zygoma is also of aesthetic significance for facial appearance, and its restoration following trauma has resulted in a large clinical literature. In this second half of the special issue on the zygoma, a series of papers discuss studies related to evolution of the zygoma and related parts of the craniofacial skeleton throughout the vertebrates, and in particular in human evolution. There are also a series of articles discussing variation of the zygoma in modern humans. This article is an overview in which we discuss the primary findings of these studies and some of their implications. Anat Rec, 300:12–15, 2017. © 2016 Wiley Periodicals, Inc.
Goodreads: A social network site for book readers
Authors: Thelwall Mike , Kousha Kayvan
Published: December 2016

Goodreads is an Amazon‐owned book‐based social web site for members to share books, read, review books, rate books, and connect with other readers. Goodreads has tens of millions of book reviews, recommendations, and ratings that may help librarians and readers to select relevant books. This article describes a first investigation of the properties of Goodreads users, using a random sample of 50,000 members. The results suggest that about three quarters of members with a public profile are female, and that there is little difference between male and female users in patterns of behavior, except for females registering more books and rating them less positively. Goodreads librarians and super‐users engage extensively with most features of the site. The absence of strong correlations between book‐based and social usage statistics (e.g., numbers of friends, followers, books, reviews, and ratings) suggests that members choose their own individual balance of social and book activities and rarely ignore one at the expense of the other. Goodreads is therefore neither primarily a book‐based website nor primarily a social network site but is a genuine hybrid, social navigation site.
Analysis of change in users' assessment of search results over time
Authors: Zhitomirsky‐Geffet Maayan , Bar‐Ilan Judit , Levene Mark
Published: December 2016

We present the first systematic study of the influence of time on user judgements for rankings and relevance grades of web search engine results. The goal of this study is to evaluate the change in user assessment of search results and explore how users' judgements change. To this end, we conducted a large‐scale user study with 86 participants who evaluated 2 different queries and 4 diverse result sets twice with an interval of 2 months. To analyze the results we investigate whether 2 types of patterns of user behavior from the theory of categorical thinking hold for the case of evaluation of search results: (a) coarseness and (b) locality. To quantify these patterns we devised 2 new measures of change in user judgements and distinguish between local (when users swap between close ranks and relevance values) and nonlocal changes. Two types of judgements were considered in this study: (a) relevance on a 4‐point scale, and (b) ranking on a 10‐point scale without ties. We found that users tend to change their judgements of the results over time in about 50% of cases for relevance and in 85% of cases for ranking. However, the majority of these changes were local.
Search task features in work tasks of varying types and complexity
Authors: Saastamoinen Miamaria , Järvelin Kalervo
Published: December 2016

Information searching in practice seldom is an end in itself. In work, work task (WT) performance forms the context, which information searching should serve. Therefore, information retrieval (IR) systems development/evaluation should take the WT context into account. The present paper analyzes how WT features: task complexity and task types, affect information searching in authentic work: the types of information needs, search processes, and search media. We collected data on 22 information professionals in authentic work situations in three organization types: city administration, universities, and companies. The data comprise 286 WTs and 420 search tasks (STs). The data include transaction logs, video recordings, daily questionnaires, interviews. and observation. The data were analyzed quantitatively. Even if the participants used a range of search media, most STs were simple throughout the data, and up to 42% of WTs did not include searching. WT's effects on STs are not straightforward: different WT types react differently to WT complexity. Due to the simplicity of authentic searching, the WT/ST types in interactive IR experiments should be reconsidered.
Graphitic C3N4 Decorated with CoP Co‐catalyst: Enhanced and Stable Photocatalytic H2 Evolution Activity from Water under Visible‐light Irradiation
Authors: Zhao Hui , Jiang Pingping , Cai Wen
Published: December 2016

In this work, graphitic C3N4 decorated with a CoP co‐catalyst (g‐C3N4/CoP) is reported for photocatalytic H2 evolution reaction based on two‐step hydrothermal and phosphidation method. The structure of g‐C3N4/CoP is well confirmed by XRD, FTIR, TEM, XPS, and UV/Vis diffuse reflection spectra techniques. When the weight percentage of CoP loading is 3.4 wt % (g‐C3N4/CoP‐3.4 %), the highest H2 evolution amount of 8.4×102 μmol g−1 is obtained, which is 1.1×103 times than that over pure g‐C3N4. This value also is comparable with that of g‐C3N4 loaded by the same amount of Pt. In cycling experiments, g‐C3N4/CoP‐3.4 % shows a stable photocatalytic activity. In addition, g‐C3N4/CoP‐3.4 % is an efficient photocatalyst for H2 evolution under irradiation with natural solar light. Based on comparative photoluminescence emission spectra, photoelectrochemical I–t curves, EIS Nyquist plots, and polarization curves between g‐C3N4/CoP‐3.4 % and pure g‐C3N4, it is concluded that the presence of the CoP co‐catalyst accelerates the separation and transfer of photogenerated electrons of g‐C3N4, thus resulting in improved photocatalytic activity in the H2 evolution reaction.
More Relaxed Non‐Quadratic Stabilization Conditions Using Ts Open Loop System and Control Law Properties
Authors: Vafamand Navid , Shasadeghi Mokhtar
Published: December 2016

This paper proposes more relaxed stabilization conditions based on a non‐quadratic Lyapunov function (NQLF) and parallel distributed compensator (PDC) controller. The conditions are derived in terms of linear matrix inequalities (LMIs) by introducing three slack matrices based on the properties of TS membership functions, an open loop system and a PDC controller. These slack matrices are utilized to decouple the LMI variables from the TS system and the input matrices. Therefore, the proposed approach greatly reduces the number of LMI conditions and improves feasibility by providing more degrees of freedom compared to recently published studies. Moreover, local stability and stabilization conditions are considered to handle the time derivatives of membership functions appearing in the stabilization synthesis of the TS closed‐loop system with PDC controller. Finally, several examples are presented to demonstrate the advantages of the proposed approaches.
Auditory script location does not affect acquisition and maintenance of vocal initiations by children with autism
Authors: Gallant Emily E. , Reeve Sharon A. , Brothers Kevin J. , Reeve Kenneth F.
Published: December 2016

The present study evaluated whether two different locations of auditory scripts, relative to target discriminative stimuli, affected acquisition and maintenance of initiations of vocal interactions by four boys with autism or pervasive developmental disorder not otherwise specified. An alternating‐treatments design with an initial baseline was used. Button‐activated recording devices used to play the scripts were placed either on target stimuli or held behind the participants' heads to initiate interactions about a variety of toys. After scripts and the devices were faded, the frequency of initiations emitted was greater for two participants during the device‐visible condition, greater for another participant during the device‐not‐visible condition, and no difference as a function of auditory script location for the fourth participant. These results suggest that fading an auditory script played behind a child's head may be equally as effective for establishing stimulus control by target items as fading an auditory script initially attached to items.
Cost analysis of laparoscopic lavage compared with sigmoid resection for perforated diverticulitis in the Ladies trial
Authors: Vennix S , van Dieren S , Opmeer B C , Lange J F , Bemelman W A
Published: December 2016

Background

Laparoscopic peritoneal lavage is an alternative to sigmoid resection in selected patients presenting with purulent peritonitis from perforated diverticulitis. Although recent trials have lacked superiority for lavage in terms of morbidity, mortality was not compromised, and beneficial secondary outcomes were shown. These included shorter duration of surgery, less stoma formation and less surgical reintervention (including stoma reversal) for laparoscopic lavage versus sigmoid resection respectively. The cost analysis of laparoscopic lavage for perforated diverticulitis in the Ladies RCT was assessed in the present study.

Methods

This study involved an economic evaluation of the randomized LOLA (LaparOscopic LAvage) arm of the Ladies trial (comparing laparoscopic lavage with sigmoid resection in patients with purulent peritonitis due to perforated diverticulitis). The actual resource use per individual patient was documented prospectively and analysed (according to intention-to-treat) for up to 1 year after randomization.

Results

Eighty-eight patients were randomized to either laparoscopic lavage (46) or sigmoid resection (42). The total medical costs for lavage were lower (mean difference € − 3512, 95 per cent bias-corrected and accelerated c.i. −16 020 to 8149). Surgical reintervention increased costs in the lavage group, whereas stoma reversal increased costs in the sigmoid resection group. Differences in favour of laparoscopy were robust when costs were varied by ±20 per cent in a sensitivity analysis (mean cost difference € − 2509 to −4438).

Conclusion

Laparoscopic lavage for perforated diverticulitis is more cost-effective than sigmoid resection.
Network meta-analysis of the effect of preoperative carbohydrate loading on recovery after elective surgery
Authors: Amer M A , Smith M D , Herbison G P , Plank L D , McCall J L
Published: December 2016

Background

Three meta-analyses have summarized the effects of preoperative carbohydrate administration on postoperative outcomes in adult patients undergoing elective surgery. However, these studies could not account for the different doses of carbohydrate administered and the different controls used. Multiple-treatments meta-analysis allows robust synthesis of all available evidence in these situations.

Methods

Article databases were searched systematically for RCTs comparing preoperative carbohydrate administration with water, a placebo drink, or fasting. A four-treatment multiple-treatments meta-analysis was performed comparing two carbohydrate dose groups (low, 10–44 g; high, 45 g or more) with two control groups (fasting; water or placebo). Primary outcomes were length of hospital stay and postoperative complication rate. Secondary outcomes included postoperative insulin resistance, vomiting and fatigue.

Results

Some 43 trials involving 3110 participants were included. Compared with fasting, preoperative low-dose and high-dose carbohydrate administration decreased postoperative length of stay by 0·4 (95 per cent c.i. 0·03 to 0·7) and 0·2 (0·04 to 0·4) days respectively. There was no significant decrease in length of stay compared with water or placebo. There was no statistically significant difference in the postoperative complication rate, or in most of the secondary outcomes, between carbohydrate and control groups.

Conclusion

Carbohydrate loading before elective surgery conferred a small reduction in length of postoperative hospital stay compared with fasting, and no benefit in comparison with water or placebo.
Measuring relationships between self‐compassion, compassion fatigue, burnout and well‐being in student counsellors and student cognitive behavioural psychotherapists: a quantitative survey
Authors: Beaumont Elaine , Durkin Mark , Hollins Martin Caroline J. , Carson Jerome
Published: December 2016

Background

Prolonged deficiency in self‐care strategies puts counsellors and psychotherapists at risk of burnout and compassion fatigue.

Aim

To measure associations between self‐compassion, compassion fatigue, well‐being and burnout in student counsellors and student cognitive behavioural psychotherapists.

Method

A quantitative survey using four validated data collection instruments: (1) Professional Quality of Life Scale; (2) Self‐Compassion Scale; (3) short Warwick and Edinburgh Mental Well‐being Scale; (4) Compassion For Others scale, was used to measure relationships between self‐compassion, compassion fatigue, well‐being and burnout.

Participants

A mixed sample of student counsellors and student cognitive behavioural psychotherapists (n = 54) in their final year of study.

Results

This preliminary study shows that student counsellors and student cognitive behavioural psychotherapists who reported high on measures of self‐compassion and well‐being also reported less compassion fatigue and burnout.

Implications for practice

Compassion fatigue and burnout are found in many modern‐day, highly stressful healthcare professions. The practice of self‐compassion could help student practitioners manage these symptoms and subsequently improve their professional quality of life.
Integrin‐Targeting Fluorescent Proteins: Exploration of RGD Insertion Sites
Authors: Sonntag Michael H. , Schill Jurgen , Brunsveld Luc
Published: December 2016

The potential of the fluorescent protein scaffold to control peptide sequence functionality is illustrated by an exploration of fluorescent proteins as novel probes for targeting integrins. A library of fluorescent mCitrine proteins with RGD motifs incorporated at several positions in loops within the protein main chain was generated and characterized. Amino acid mutations to RGD as well as RGD insertions were evaluated: both led to constructs with typical mCitrine fluorescent properties. Screening experiments against four human integrin receptors revealed two strong‐binding constructs and two selective integrin binders. The effect of the site of RGD incorporation illustrates the importance of the protein scaffold on RGD sequence functionality, leading to fluorescent protein constructs with the potential for selective integrin targeting.
Boosting Oxidative Desulfurization of Model and Real Gasoline over Phosphotungstic Acid Encapsulated in Metal–Organic Frameworks: The Window Size Matters
Authors: Wang Xu‐Sheng , Li Lan , Liang Jun , Huang Yuan‐Biao , Cao Rong
Published: December 2016

It is desirable to develop new materials that can efficiently lower sulfur content in fossil fuels, such as gasoline and diesel oil. Polyoxometallic acids supported on metal–organic frameworks (MOFs) are an important class of heterogeneous catalysts for oxidative desulfurization. However, there has been no comprehensive study on the correlation between desulfurization activity and the window size of MOFs. A series of robust MOFs, which include MIL‐100(Fe), UiO‐66, and ZIF‐8, with different window sizes were exploited as hosts to encapsulate phosphotungstic acid by the “bottle around the ship” method and utilized for the ultra‐deep oxidative desulfurization (ODS) of model and real gasoline. Compared with UiO‐66 and ZIF‐8, which have very small window sizes, mesoporous MIL‐100(Fe), which has a large window size, exhibited the best catalytic performance in the ODS of refractory sulfur compounds (benzothiophene, dibenzothiophene, and 4,6‐dimethyl‐dibenzothiophene) and in recycling experiments. The correlations between the desulfurization activity and the window size of the corresponding MOFs could provide insights for the design of new porous catalysts for ODS and other size‐selective catalysis reactions in the future.
Oxidative Desulfurization of Model Diesel Using a Fenton‐Like Catalyst in the Ionic Liquid [Dmim]BF4
Authors: Wang Shunan , Li Pengcheng , Hao Lingwan , Deng Changliang , Ren Wanzhong , Lü Hongying
Published: December 2016

A Fenton‐like catalyst prepared from tetrabutylammonium chloride and ferric trichloride was characterized by Fourier transform infrared, UV‐vis and Raman spectroscopy. The catalyst (C4H9)4NFeCl4 (TBAFeCl4) in an extraction and catalytic oxidative desulfurization (ECODS) system containing H2O2 and the ionic liquid (IL) 1‐decyl‐3‐methylimidazolium tetrafluoroborate ([Dmim]BF4) exhibited high catalytic activity for the removal of dibenzothiophene (DBT) in model diesel. Desulfurization with the Fenton‐like catalyst TBAFeCl4 in ECODS involves the structural distortion of DBT via polarization of the IL and its subsequent oxidation. The catalytic system could be recycled multiple times without significant decrease in desulfurization activity due to the high stability of the system.
The Lipid A from Rhodopseudomonas palustris Strain BisA53 LPS Possesses a Unique Structure and Low Immunostimulant Properties
Authors: Di Lorenzo Flaviana , Palmigiano Angelo , Albitar‐Nehme Sami , Sturiale Luisa , Duda Katarzyna A. , Gully Djamel , Lanzetta Rosa , Giraud Eric , Garozzo Domenico , Bernardini Maria Lina , Molinaro Antonio , Silipo Alba
Published: December 2016

The search for novel lipid A analogues from any biological source that can act as antagonists, displaying inhibitory activity towards the production of pro‐inflammatory cytokines, or as immunomodulators in mammals, is a very topical issue. To this aim, the structure and immunological properties of the lipopolysaccharide lipid A from the purple nonsulfur bacterium Rhodopseudomonas palustris strain BisA53 have been determined. This lipid A displays a unique structural feature, with a non‐phosphorylated skeleton made up of the tetrasaccharide Manp‐α‐(1→4)‐GlcpN3N‐β‐1→6‐GlcpN3N‐α‐(1→1)‐α‐GalpA, and four primary amide‐linked 14:0(3‐OH) and, as secondary O‐acyl substituents, a 16:0 and the very long‐chain fatty acid 26:0(25‐OAc), appended on the GlcpN3N units. This lipid A architecture is definitely rare, so far identified only in the genus Bradyrhizobium. Immunological tests on both murine bone‐marrow‐derived and human monocyte‐derived macrophages revealed an extremely low immunostimulant capability of this LPS lipid A.
First Example of Nonlinear Optical Materials Based on Nanoconjugates of Sandwich Phthalocyanines with Quantum Dots
Authors: Oluwole David O. , Yagodin Alexey V. , Mkhize Nhlakanipho C. , Sekhosana Kutloano E. , Martynov Alexander G. , Gorbunova Yulia G. , Tsivadze Aslan Yu. , Nyokong Tebello
Published: December 2016

We report original, selective, and efficient approaches to novel nonlinear optical (NLO) materials, namely homoleptic double‐ and triple‐decker europium(III) complexes2and3with the A3B‐type phthalocyanine ligand (2,3‐bis[2′‐(2′′‐hydroxyethoxy)ethoxy]‐9,10,16,17,23,24‐hexa‐n‐butoxyphthalocyanine1) bearing two anchoring diethyleneglycol chains terminated with OH groups. Their covalently linked nanoconjugates with mercaptosuccinic acid‐capped ternary CdSeTe/CdTeS/ZnSeS quantum dots are prepared in the presence of an ethyl(dimethylaminopropyl)carbodiimide activating agent. Optical limiting (OL) properties of the obtained low‐symmetry complexes and their conjugates with quantum dots (QDs) are measured for the first time by the open‐aperture Z‐scan technique (532 nm laser and pulse rate of 10 ns). For comparison, symmetrical double‐ and triple‐decker EuIIIocta‐n‐butoxyphthalocyaninates5and6and their mixtures with trioctylphosphine oxide‐capped QDs are also synthesized and studied. It is revealed that both lowering of molecular symmetry and expansion of the π‐electron system upon moving from double‐ to triple‐decker complexes significantly improves the OL characteristics, making the low‐symmetry triple‐decker complex3the most efficient optical limiter in the studied family of sandwich complexes, affording 50 % lowering of light transmittance below 0.5 J cm−2input fluence. Conjugation (both covalent and noncovalent) with QDs affords further enhancement of the OL properties of both double‐ and triple‐decker complexes. Altogether, the obtained results contribute to the development of novel nonlinear optical materials for future nanoelectronic and optical device applications.
Inorganic and Organometallic Molecular Wires for Single‐Molecule Devices
Authors: Tanaka Yuya , Kiguchi Manabu , Akita Munetaka
Published: December 2016

Recent developments of single‐molecule conductance measurements allow us to understand fundamental conducting properties of molecular wires. While a wide variety of organic molecular wires have been studied so far, inorganic and organometallic molecular wires have received much less attention. However, molecular wires with transition‐metal atoms show interesting features and functions distinct from those of organic wires. These properties originate mainly from metal–ligand dπ–pπ interactions and metal–metal d–d interactions. Thanks to the rich combination of metal atoms and supporting ligands, frontier orbital energies of the molecular wires can be finely tuned to lead to highly conducting molecular wires. Moreover, the unique electronic structures of metal complexes are susceptible to subtle environmental changes, leading to potential functional molecular devices. This article reviews recent advances in the single‐molecule conductance study of inorganic and organometallic molecular wires.
Single‐Site Osmium Catalysts on MgO: Reactivity and Catalysis of CO Oxidation
Authors: Yang Dong , Zhang Shengjie , Xu Pinghong , Browning Nigel D. , Dixon David A. , Gates Bruce C.
Published: December 2016

MgO‐supported osmium dioxo species, described as Os(=O)2{−Osupport}1 or 2 (the brackets denote O atoms of the MgO surface), formed from Os3(CO)12 via supported Os(CO)2, and characterized by spectroscopy, microscopy, and theory, react with ethylene at 298 K to form osmium glycol species or with CO to give osmium mono‐ and di‐carbonyls. Os(=O)2{−Osupport}1 or 2 is the precursor of a CO oxidation catalyst characterized by a turnover frequency of 4.0×10−3 (molecules of CO)/(Os atom×s) at 473 K; the active species are inferred to be osmium monocarbonyls. The structures and frequencies calculated at the level of density functional theory with the B3LYP functional bolster the experimental results and facilitate structural assignments. The lowest‐energy structures have various osmium oxidation and spin states. The results demonstrate not only new chemistry of the supported single‐site catalysts but also their complexity and the value of complementary techniques used in concert to unravel the chemistry.
Intrinsic Thermodynamics and Structures of 2,4‐ and 3,4‐Substituted Fluorinated Benzenesulfonamides Binding to Carbonic Anhydrases
Authors: Zubrienė Asta , Smirnov Alexey , Dudutienė Virginija , Timm David D. , Matulienė Jurgita , Michailovienė Vilma , Zakšauskas Audrius , Manakova Elena , Gražulis Saulius , Matulis Daumantas
Published: December 2016

The goal of rational drug design is to understand structure–thermodynamics correlations in order to predict the chemical structure of a drug that would exhibit excellent affinity and selectivity for a target protein. In this study we explored the contribution of added functionalities of benzenesulfonamide inhibitors to the intrinsic binding affinity, enthalpy, and entropy for recombinant human carbonic anhydrases (CA) CA I, CA II, CA VII, CA IX, CA XII, and CA XIII. The binding enthalpies of compounds possessing similar chemical structures and affinities were found to be very different, spanning a range from −90 to +10 kJ mol−1, and are compensated by a similar opposing entropy contribution. The intrinsic parameters of binding were determined by subtracting the linked protonation reactions. The sulfonamide group pKa values of the compounds were measured spectrophotometrically, and the protonation enthalpies were measured by isothermal titration calorimetry (ITC). Herein we describe the development of meta‐ or ortho‐substituted fluorinated benzenesulfonamides toward the highly potent compound 10 h, which exhibits an observed dissociation constant value of 43 pm and an intrinsic dissociation constant value of 1.1 pm toward CA IX, an anticancer target that is highly overexpressed in various tumors. Fluorescence thermal shift assays, ITC, and X‐ray crystallography were all applied in this work.
Reinventing Design Principles for Developing Low‐Viscosity Carbon Dioxide‐Binding Organic Liquids for Flue Gas Clean Up
Authors: Malhotra Deepika , Koech Phillip K. , Heldebrant David J. , Cantu David C. , Zheng Feng , Glezakou Vassiliki‐Alexandra , Rousseau Roger
Published: December 2016

Anthropogenic CO2 emissions from point sources (e.g., coal fired‐power plants) account for the majority of the greenhouse gases in the atmosphere. Water‐lean solvent systems such as CO2‐binding organic liquids (CO2BOLs) are being developed to reduce the energy requirement for CO2 capture. Many water‐lean solvents such as CO2BOLs are currently limited by the high viscosities of concentrated electrolyte solvents, thus many of these solvents have yet to move toward commercialization. Conventional standard trial‐and‐error approaches for viscosity reduction, while effective, are time consuming and economically expensive. We rethink the metrics and design principles of low‐viscosity CO2‐capture solvents using a combined synthesis and computational modeling approach. We critically study the effects of viscosity reducing factors such as orientation of hydrogen bonding, introduction of higher degrees of freedom, and cation or anion charge solvation, and assess whether or how each factor affects viscosity of CO2BOL CO2 capture solvents. Ultimately, we found that hydrogen bond orientation and strength is the predominant factor influencing the viscosity in CO2BOL solvents. With this knowledge, a new CO2BOL variant, 1‐MEIPADM‐2‐BOL, was synthesized and tested, resulting in a solvent that is approximately 60 % less viscous at 25 mol % CO2 loading than our base compound 1‐IPADM‐2‐BOL. The insights gained from the current study redefine the fundamental concepts and understanding of what influences viscosity in concentrated organic CO2‐capture solvents.