bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractRibonucleic 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

AbstractSupramolekulare 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

AbstractIn 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

AbstractCarbon 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

Abstractp53 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

AbstractWe 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

AbstractSingle‐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

ABSTRACTThe 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

ABSTRACTThe 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

ABSTRACTThis 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.
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

AbstractIn 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

AbstractThis 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.
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

Abstract

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

Abstract

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

AbstractBackgroundProlonged deficiency in self‐care strategies puts counsellors and psychotherapists at risk of burnout and compassion fatigue.AimTo measure associations between self‐compassion, compassion fatigue, well‐being and burnout in student counsellors and student cognitive behavioural psychotherapists.MethodA 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.ParticipantsA mixed sample of student counsellors and student cognitive behavioural psychotherapists (n = 54) in their final year of study.ResultsThis 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 practiceCompassion 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

AbstractThe 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

AbstractIt 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

AbstractA 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.