bluuebunny/crossref_metadata_2025 huggingface dataset:
Gate Tunable In‐ and Out‐of‐Plane Spin–Orbit Coupling and Spin‐Splitting Anisotropy at LaAlO3/SrTiO3 (110) Interface
Authors: Gopinadhan Kalon , Annadi Anil , Kim Younghyun , Srivastava Amar , Kumar Brijesh , Chen Jingsheng , Coey J. Michael D. , Ariando  , Venkatesan Thirumalai
Published: June 2015

Manipulating spin–orbit coupling (SOC) is important for devices such as spin–orbit torque‐based memory and its understanding is necessary to answer several fundamental open questions in triplet state superconductivity, topological insulators, and Majorana fermions. Here spin splitting of 25 meV is reported at the LaAlO3/SrTiO3 (110) interface for in‐plane spins at a current density of 1.4 × 104 A cm−2, which is large compared to that found in semiconductor heterostructures or the LaAlO3/SrTiO3 (100) interface, and in addition it is anisotropic. The anisotropy arises from the difference in electron effective mass along the [001] and [1–10] directions. Our study predicts a spin‐splitting energy >1000 meV at a current density of 107 A cm−2, which is enormous compared to metallic systems and will be an ideal spin‐polarized source. In addition to the in‐plane effect, there is an unexpected gate‐tunable out‐of‐plane SOC at the LaAlO3/SrTiO3 (110) interface when the spins lie out‐of‐plane due to broken symmetry in the plane of the interface. It is demonstrated that this can be manipulated by varying the LaAlO3 thickness showing that this interface can be engineered for spin–orbit torque devices.
Degradation mechanism analysis of Ba0.5Sr0.5Co0.8Fe0.2O3‐δ membranes at intermediate‐low temperatures
Authors: Liu Yan , Zhu Xuefeng , Yang Weishen
Published: June 2015

The degradation of the permeation flux of Ba0.5Sr0.5Co0.8Fe0.2O3‐δ membranes has typically been attributed to the phase transformation of the material at intermediate temperatures. In this study, the effect of the interfacial oxygen exchange steps was considered to give an overall view of the degradation mechanism. The changes in the interfacial exchange resistances, bulk resistance, and morphologies of the membranes were investigated via physical characterizations and a permeation model. The interfacial oxygen exchange resistances increased more quickly with time than bulk resistance. Meanwhile, BaSO4 particles were detected on both surfaces of the membranes, and their contents reached maximum at 650°C. However, after the membrane surfaces were coated by Sm0.5Sr0.5CoO3‐δ porous layers, the interfacial oxygen exchange resistances kept constant and the degradation rates were slowed down. The degradation was predominated by the increase of interfacial oxygen exchange resistances induced by the enrichment of BaSO4 particles on membrane surfaces. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3879–3888, 2015
A new bubbling extraction tower: Toward liquid–liquid solvent extraction at large aqueous‐to‐oil phase ratios
Authors: Huang Kun , Liu Jie , Wu Huaizhi , Liu Huizhou
Published: June 2015

Enrichment and recovery of valuable components in industrial waste waters by traditional liquid–liquid solvent extraction is not economic due to extremely low concentrations of those targets. Large‐phase‐ratio extraction exhibits potential advantages for recovery of small quantities of target components from large volume of aqueous solutions. A novel bubbling extraction tower is proposed toward performing solvent extraction at large aqueous‐to‐oil phase ratios in this work. Organic extractants were covered onto surface of gas bubbles to form a layer of organic liquid membrane and the dispersed organic phase in tower could be small enough. The target components are extracted from aqueous feed solution onto the surface of the bubbles, and the enrichment ratios could be extremely high. We develop a feasible methodology to calculate tower height and operation phase ratios of the bubbling extraction tower, which is essential for future industrial scale‐up. Experimental results in pilot test are highly consistent with calculations. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3889–3897, 2015
Intergenerational changes in knee height among Maya mothers and their adult daughters from Merida, Mexico
Authors: Azcorra Hugo , RodrÍguez Luis , Varela‐Silva Maria Inês , Datta Banik Sudip , Dickinson Federico
Published: June 2015

Objectives

To analyze differences in knee height (KH) between adult Maya mothers and daughters in Merida City, Mexico, and determine if these differences are associated with their childhood socioeconomic conditions.

Methods

From September 2011 to January 2014, we measured KH and collected data on childhood conditions (place of birth, type of drinking water, family size, and fathers' occupation) from a sample of 180 Maya mother‐daughter dyads. Mean KH intergenerational difference was calculated and compared for each category of socioeconomic variables and a multiple regression model was used to assess the association between childhood conditions and KH difference.

Results

A relative increase of 1.05 cm (SD = 2.3 cm) or 0.45 standard deviations (effect size of difference) was observed in KH between generations. Place of birth was significantly associated with KH. With three other variables statistically adjusted for, the intergenerational KH difference was 1.5 cm greater when mothers were born outside Merida but daughters were born in the city. Piped water consumption by mother‐daughter dyads was associated with 1.5 cm of increase in KH difference compared with dyads who consumed well water (P = 0.058).

Conclusions

The relative increase in KH between mothers and daughters represents a portion of the expected change in growth in a group that has experienced few substantial improvements in their living conditions. Some improvements in childhood living conditions resulting from the intergenerational transition from rural to urban environments seem to be linked to a modest, but statistically significant intergenerational increase in KH among Maya women in Merida. Am. J. Hum. Biol. 27:792–797, 2015. © 2015 Wiley Periodicals, Inc.
Inside the 8p23.1 duplication syndrome; eight microduplications of likely or uncertain clinical significance
Authors: Barber John C. K. , Rosenfeld Jill A. , Graham John M. , Kramer Nancy , Lachlan Katherine L. , Bateman Mark S. , Collinson Morag N. , Stadheim Barbro Fossøy , Turner Claire L. S. , Gauthier Jacqueline N. , Reimschisel Tyler E. , Qureshi Athar M. , Dabir Tabib A. , Humphreys Mervyn W. , Marble Michael , Huang Taosheng , Beal Sarah J. , Massiah Joanne , Taylor Emma‐Jane , Wynn Sarah L.
Published: June 2015

The 8p23.1 duplication syndrome (8p23.1 DS) is a recurrent genomic condition with an estimated prevalence of 1 in 58,000. The core 3.68 Mb duplication contains 32 genes of which five are currently candidates for the phenotypic features. Here we describe four patients and five families with eight microduplications of 8p23.1 ranging from 187 to 1082 kb in size and one atypical duplication of 4 Mb. These indicate that a minimal region of overlap (MRO) in medial 8p23.1 can give rise to features of 8p23.1 DS including developmental delay, dysmorphism, macrocephaly and otitis media, but not congenital heart disease (CHD). This MRO spans 776 kb (chr8:10,167,881–10,943,836 hg19) and contains SOX7 and seven of the other 32 core 8p23.1 DS genes. In centromeric 8p23.1, microduplications including GATA4 can give rise to non‐syndromic CHD but the clinical significance of two smaller centromeric microduplications without GATA4 was uncertain due to severe neurological profiles not usually found in 8p23.1 DS. The clinical significance of three further 8p23.1 microduplications was uncertain due to additional genetic factors without which the probands might not have come to medical attention. Variable expressivity was indicated by the almost entirely unaffected parents in all five families and the mildly affected sibling in one. Intronic interruptions of six genes by microduplication breakpoint intervals had no apparent additional clinical consequences. Our results suggest that 8p23.1 DS is an oligogenetic condition largely caused by the duplication and interactions of the SOX7 and GATA4 transcription factors. © 2015 Wiley Periodicals, Inc.
A Total Synthesis of Prunustatin A
Authors: Usuki Yoshinosuke , Ogawa Hikaru , Yoshida Ken‐ichi , Inaoka Tomokazu , Iio Hideo
Published: June 2015

A total synthesis of prunustatin A, a GRP78 molecular chaperone down‐regulator, has been achieved. The key step in the synthesis is an intramolecular transesterification of the β‐keto ester alcohol intermediate to construct the 15‐membered tetralactone core of the natural product.
Dosing of sublingual immunotherapy for allergic rhinitis: evidence‐based review with recommendations
Authors: Leatherman Bryan D. , Khalid Ayesha , Lee Stella , McMains Kevin , Peltier Jacques , Platt Michael P. , Stachler Robert J. , Toskala Elina , Tropper Guy , Venkatraman Giri , Lin Sandra Y.
Published: June 2015

Background

Since the mid 1980s, the clinical use of sublingual immunotherapy (SLIT) has dramatically increased. However, 1 of the primary barriers to providing SLIT is lack of a published dosing recommendations. The purpose of this work is to provide a range of effective SLIT dosing based upon a rigorous review of the existing evidence base. An appendix with SLIT dosing recommendations is also included.

Methods

A comprehensive search of the past 25 years of the medical literature using PubMed was performed for specific antigens. Inclusion criteria for articles included: randomized, placebo‐controlled studies of SLIT, studies with clinical allergic rhinitis outcomes, and dosing units available to determine the micrograms per month of major allergen administered. The extracted data was used to compile a range of effective SLIT dosing for individual antigens.

Results

Seventy‐five articles met the inclusion criteria, providing a range of effective dosing for some allergens. There was commonly a wide range in doses for particular antigens between the individual studies. For some antigens, there was significant overlap in dosage amount between studies showing efficacy and lack of efficacy. Clinical trials meeting inclusion criteria are not available for many allergens.

Conclusion

This study provided a comprehensive review of the published sublingual dosing ranges for specific antigens. The review provided a range of effective sublingual doses for some allergens, whereas for other allergens there was insufficient published data to determine specific doses. Recommendations for SLIT dosing were produced based on the data revealed in the review and expert opinion.
Management of the orbit during endoscopic sinonasal tumor surgery
Authors: Christianson Brandon , Perez Carlos , Harrow Brian , Batra Pete S.
Published: June 2015

Background

The primary aims of the study were to report preoperative imaging characteristics and intraoperative management of the orbit during endoscopic resection of benign and malignant sinonasal tumors.

Methods

This study was a case series at an academic tertiary care center. Retrospective chart review and prospective imaging assessment was performed on 159 cases treated between July 2009 and December 2012.

Results

A total of 41 patients met predetermined inclusion criteria. Squamous cell carcinoma (17.1%) and inverted papilloma (31.7%) were the most common malignant and benign histology, respectively. Preoperative computed tomography (CT) scanning most commonly demonstrated erosion of the lamina papyracea (80.5%), whereas magnetic resonance imaging (MRI) most commonly illustrated loss of fat plane between tumor and extraocular muscle (53.1%). Endoscopic procedures to address the orbital interface included lamina papyracea resection (85.4%), dacryocystorhinostomy (26.8%), periorbita resection (26.8%), optic nerve decompression (7.3%), and orbital exenteration (2.4%). Oculoplastic surgery involvement was required in 31.7% of cases. Orbital complications included epiphora in 3 (7.3%) and diplopia in 2 (5.1%) patients. Postoperatively, no recurrences were noted in the benign group, whereas 6 (28.6%) recurrences were noted in 21 patients in the malignant group treated with intent to cure. Two patients died of disease due to distant metastases from mucosal melanoma and squamous cell carcinoma.

Conclusion

This represents the largest series to date on endoscopic management of the orbit in benign and malignant sinonasal tumors. A majority of these cases can be managed by a purely endoscopic approach with low complication and recurrence rates, although a subset still require adjunct open approaches for successful tumor extirpation.
Identification of Onodi cell and new classification of sphenoid sinus for endoscopic sinus surgery
Authors: Wada Kota , Moriyama Hiroshi , Edamatsu Hideo , Hama Takanori , Arai Chiaki , Kojima Hiromi , Otori Nobuyoshi , Yanagi Kiyoshi
Published: June 2015

Background

There is no effective classification method for the opening of the sphenoid sinus. The objective of this study was to examine the effectiveness of identification of the Onodi cell and classification of the sphenoid sinus using sagittal computed tomography (CT) for sphenoidotomy.

Methods

CT images of the sinuses of surgical patients (n = 261; 522 sides) were studied. Using sagittal CT, the relationships between the lateral side of the anterior wall of the sphenoid sinus and the optic nerve, and between the middle of the anterior wall of the sphenoid sinus and the skull base or pituitary gland were studied. Images were classified as demonstrating skull base (without the Onodi cell), optic canal, sella, or infra‐sella (all with the Onodi cell) type.

Results

Two hundred and fifty‐eight sides (49.2%) were of the skull‐base type, 181 (34.7%) were of the optic‐canal type, 58 (11.1%) were of the sella type, and 26 (5.0%) were of the infra‐sella type; ie, the Onodi cell was present in 50.8% of sides. The width of the anterior wall of the sphenoid sinus became narrower as it shifted from the skull‐base type to the infra‐sella type.

Conclusion

Classification of the anterior wall of the sphenoid sinus based on the Onodi cell allows 3‐dimensional assessment of the shape of the sphenoid sinus. We believe that the sphenoid sinus can be opened safely by full preoperative assessment of the anterior wall type, the position of the superior turbinate, and the position of the ostium of the sphenoid sinus.
DNA‐Encoded Tuning of Geometric and Plasmonic Properties of Nanoparticles Growing from Gold Nanorod Seeds
Authors: Song Tingjie , Tang Longhua , Tan Li Huey , Wang Xiaojing , Satyavolu Nitya Sai Reddy , Xing Hang , Wang Zidong , Li Jinghong , Liang Haojun , Lu Yi
Published: June 2015

Systematically controlling the morphology of nanoparticles, especially those growing from gold nanorod (AuNR) seeds, are underexplored; however, the AuNR and its related morphologies have shown promises in many applications. Herein we report the use of programmable DNA sequences to control AuNR overgrowth, resulting in gold nanoparticles varying from nanodumbbell to nanooctahedron, as well as shapes in between, with high yield and reproducibility. Kinetic studies revealed two representative pathways for the shape control evolving into distinct nanostructures. Furthermore, the geometric and plasmonic properties of the gold nanoparticles could be precisely controlled by adjusting the base compositions of DNA sequences or by introducing phosphorothioate modifications in the DNA. As a result, the surface plasmon resonance (SPR) peaks of the nanoparticles can be fine‐tuned in a wide range, from visible to second near‐infrared (NIR‐II) region beyond 1000 nm.
Sub‐Picosecond Singlet Exciton Fission in Cyano‐Substituted Diaryltetracenes
Authors: Margulies Eric A. , Wu Yi‐Lin , Gawel Przemyslaw , Miller Stephen A. , Shoer Leah E. , Schaller Richard D. , Diederich François , Wasielewski Michael R.
Published: June 2015

Thin films of 5,11‐dicyano‐6,12‐diphenyltetracene (TcCN) have been studied for their ability to undergo singlet exciton fission (SF). Functionalization of tetracene with cyano substituents yields a more stable chromophore with favorable energetics for exoergic SF (2E(T1)−E(S1)=−0.17 eV), where S1 and T1 are singlet and triplet excitons, respectively. As a result of tuning the triplet‐state energy, SF is faster in TcCN relative to the corresponding endoergic process in tetracene. SF proceeds with two time constants in the film samples (τ=0.8±0.2 ps and τ=23±3 ps), which is attributed to structural disorder within the film giving rise to one population with a favorable interchromophore geometry, which undergoes rapid SF, and a second population in which the initially formed singlet exciton must diffuse to a site at which this favorable geometry exists. A triplet yield analysis using transient absorption spectra indicates the formation of 1.6±0.3 triplets per initial excited state.
The Chemical Basis of Fungal Bioluminescence
Authors: Purtov Konstantin V. , Petushkov Valentin N. , Baranov Mikhail S. , Mineev Konstantin S. , Rodionova Natalja S. , Kaskova Zinaida M. , Tsarkova Aleksandra S. , Petunin Alexei I. , Bondar Vladimir S. , Rodicheva Emma K. , Medvedeva Svetlana E. , Oba Yuichi , Oba Yumiko , Arseniev Alexander S. , Lukyanov Sergey , Gitelson Josef I. , Yampolsky Ilia V.
Published: June 2015

Many species of fungi naturally produce light, a phenomenon known as bioluminescence, however, the fungal substrates used in the chemical reactions that produce light have not been reported. We identified the fungal compound luciferin 3‐hydroxyhispidin, which is biosynthesized by oxidation of the precursor hispidin, a known fungal and plant secondary metabolite. The fungal luciferin does not share structural similarity with the other eight known luciferins. Furthermore, it was shown that 3‐hydroxyhispidin leads to bioluminescence in extracts from four diverse genera of luminous fungi, thus suggesting a common biochemical mechanism for fungal bioluminescence.
A Fluorescent Adenosine Analogue as a Substrate for an A‐to‐I RNA Editing Enzyme
Authors: Mizrahi Rena A. , Shin Dongwon , Sinkeldam Renatus W. , Phelps Kelly J. , Fin Andrea , Tantillo Dean J. , Tor Yitzhak , Beal Peter A.
Published: June 2015

Adenosine to inosine RNA editing catalyzed by ADAR enzymes is common in humans, and altered editing is associated with disease. Experiments using substrate RNAs with adenosine analogues at editing sites are useful for defining features of the ADAR reaction mechanism. The reactivity of ADAR2 was evaluated with RNA containing the emissive adenosine analogue thieno[3,4‐d]‐6‐aminopyrimidine (thA). This nucleoside was incorporated into a mimic of the glutamate receptor B (GluR B) mRNA R/G editing site. We found that thA is recognized by AMV reverse transcriptase as A, and is deaminated rapidly by human ADAR2 to give thI. Importantly, ADAR reaction progress can be monitored by following the deamination‐induced change in fluorescence of the thA‐modified RNA. The observed high thA reactivity adds to our understanding of the structural features that are necessary for an efficient hADAR2 reaction. Furthermore, the new fluorescent assay is expected to accelerate mechanistic studies of ADARs.
Catalyst‐Switchable Regiocontrol in the Direct Arylation of Remote CH Groups in Pyrazolo[1,5‐a]pyrimidines
Authors: Bedford Robin B. , Durrant Steven J. , Montgomery Michelle
Published: June 2015

The regiodivergent palladium‐catalyzed CH arylation of pyrazolo[1,5‐a]pyrimidine has been achieved, wherein the switch in regioselectivity between positions C3 and C7 is under complete catalyst control. A phosphine‐containing palladium catalyst promotes the direct arylation at the most acidic position (C7), whereas a phosphine‐free catalyst targets the most electron‐rich position (C3).
Majority‐Rules‐Type Helical Poly(quinoxaline‐2,3‐diyl)s as Highly Efficient Chirality‐Amplification Systems for Asymmetric Catalysis
Authors: Ke Yuan‐Zhen , Nagata Yuuya , Yamada Tetsuya , Suginome Michinori
Published: June 2015

A highly efficient majority‐rules effect of poly(quinoxaline‐2,3‐diyl)s (PQXs) bearing 2‐butoxymethyl chiral side chains at the 6‐ and 7‐positions was established and attributed to large ΔGh values (0.22–0.41 kJ mol−1), which are defined as the energy difference between P‐ and M‐helical conformations per chiral unit. A PQX copolymer prepared from a monomer derived from (R)‐2‐octanol (23 % ee) and a monomer bearing a PPh2 group adopted a single‐handed helical structure (>99 %) and could be used as a highly enantioselective chiral ligand in palladium‐catalyzed asymmetric reactions (products formed with up to 94 % ee), in which the enantioselectivity could be switched by solvent‐dependent inversion of the helical PQX backbone.
A pH‐Responsive MRI Agent that Can Be Activated Beyond the Tissue Magnetization Transfer Window
Authors: Wang Xiaojing , Wu Yunkou , Soesbe Todd C. , Yu Jing , Zhao Piyu , Kiefer Garry E. , Sherry A. Dean
Published: June 2015

A terbium‐based complex that displays a water exchange CEST resonance well outside the normal magnetization transfer (MT) frequency range of tissues provides a direct readout of pH values by MRI. Deprotonation of the phenolic proton in this complex results in a frequency shift of 56 ppm in a bound water molecule exchange peak between pH 5 and 8. This allows direct imaging of pH without prior knowledge of the agent concentration and with essentially no interference from the tissue MT signal.
Reversal of a Single Base‐Pair Step Controls Guanine Photo‐Oxidation by an Intercalating Ruthenium(II) Dipyridophenazine Complex
Authors: Keane Páraic M. , Poynton Fergus E. , Hall James P. , Sazanovich Igor V. , Towrie Michael , Gunnlaugsson Thorfinnur , Quinn Susan J. , Cardin Christine J. , Kelly John M.
Published: June 2015

Small changes in DNA sequence can often have major biological effects. Here the rates and yields of guanine photo‐oxidation by Λ‐[Ru(TAP)2(dppz)]2+ have been compared in 5′‐{CCGGATCCGG}2 and 5′‐{CCGGTACCGG}2 using pico/nanosecond transient visible and time‐resolved IR (TRIR) spectroscopy. The inefficiency of electron transfer in the TA sequence is consistent with the 5′‐TA‐3′ versus 5′‐AT‐3′ binding preference predicted by X‐ray crystallography. The TRIR spectra also reveal the differences in binding sites in the two oligonucleotides.
CoOOH Nanosheets with High Mass Activity for Water Oxidation
Authors: Huang Junheng , Chen Junting , Yao Tao , He Jingfu , Jiang Shan , Sun Zhihu , Liu Qinghua , Cheng Weiren , Hu Fengchun , Jiang Yong , Pan Zhiyun , Wei Shiqiang
Published: June 2015

Endowing transition‐metal oxide electrocatalysts with high water oxidation activity is greatly desired for production of clean and sustainable chemical fuels. Here, we present an atomically thin cobalt oxyhydroxide (γ‐CoOOH) nanosheet as an efficient electrocatalyst for water oxidation. The 1.4 nm thick γ‐CoOOH nanosheet electrocatalyst can effectively oxidize water with extraordinarily large mass activities of 66.6 A g−1, 20 times higher than that of γ‐CoOOH bulk and 2.4 times higher than that of the benchmarking IrO2 electrocatalyst. Experimental characterizations and first‐principles calculations provide solid evidence to the half‐metallic nature of the as‐prepared nanosheets with local structure distortion of the surface CoO6−x octahedron. This greatly enhances the electrophilicity of H2O and facilitates the interfacial electron transfer between Co ions and adsorbed ‐OOH species to form O2, resulting in the high electrocatalytic activity of layered CoOOH for water oxidation.
Strukturelle Aufklärung der Bispezifität von A‐Domänen als Basis für die Aktivierung nicht‐natürlicher Aminosäuren
Authors: Kaljunen Heidi , Schiefelbein Stephan H. H. , Stummer Daniela , Kozak Sandra , Meijers Rob , Christiansen Guntram , Rentmeister Andrea
Published: June 2015

Viele biologisch aktive, bakterielle Sekundärmetabolite werden durch modulare Enzymkomplexe, die sogenannten nicht‐ribosomalen Peptidsynthetasen, hergestellt. Die Substratauswahl erfolgt durch eine Adenylierungsdomäne (A‐Domäne), die die entsprechende Aminosäure mit hoher Selektivität aktiviert. Die kürzlich entdeckte A‐Domäne der Anabaenopeptin‐Synthetase aus Planktothrix agardhii (ApnA A1) ist in der Lage, zwei chemisch sehr unterschiedliche Aminosäuren (Arg und Tyr) umzusetzen. Wir zeigen hier anhand von Kristallstrukturen dieser A‐Domäne, wie sich diese beiden Substrate an die Bindungstasche des Enzyms anpassen. Die Analyse der Bindungstasche führte zur Identifizierung von drei Resten, die für die Substraterkennung essentiell sind. Durch systematischen Austausch dieser Reste konnten wir Enzymvarianten generieren, die monospezifisch waren oder Tryptophan spezifisch aktivierten. Die nicht‐natürliche Aminosäure 4‐Azidophenylalanin konnte ebenfalls effizient durch eine A‐Domänenvariante aktiviert werden, sodass die Produktion von diversifizierten nicht‐ribosomalen Peptiden für die bioorthogonale Markierung in greifbare Nähe rückt.
Synthesis and Intracellular Redox Cycling of Natural Quinones and Their Analogues and Identification of Indoleamine‐2,3‐dioxygenase (IDO) as Potential Target for Anticancer Activity
Authors: Blunt Christopher E. , Torcuk Canan , Liu Yang , Lewis William , Siegel David , Ross David , Moody Christopher J.
Published: June 2015

Natural quinones, often linked with cellular oxidation processes, exhibit pronounced biological activity. In particular, the structurally unique isothiazolonaphthoquinone aulosirazole, isolated from blue‐green alga, possesses selective antitumor cytotoxicity, although its mechanism of action is unknown. The first synthesis of aulosirazole uses a route centered upon a late‐stage regioselective Diels–Alder reaction. The structurally related natural product pronqodine A, an inhibitor of prostaglandin release, and analogues thereof, were also prepared for comparison. Biological evaluation of the compounds identified one potential target as the immunoregulatory enzyme indoleamine‐2,3‐dioxygenase (IDO). The isothiazoloquinones are also efficient substrates for the human quinone reductase NQO1, and undergo intracellular NQO1‐dependent redox cycling resulting in the generation of reactive oxygen species, and at lower doses have the potential to alter the ratio of intracellular oxidized to reduced pyridine nucleotides.
Formation of the Δ18,19 Double Bond and Bis(spiroacetal) in Salinomycin Is Atypically Catalyzed by SlnM, a Methyltransferase‐like Enzyme
Authors: Jiang Chunyan , Qi Zhen , Kang Qianjin , Liu Jing , Jiang Ming , Bai Linquan
Published: June 2015

Salinomycin is a widely used polyether coccidiostat and was recently found to have antitumor activities. However, the mechanism of its biosynthesis remained largely speculative until now. Reported herein is the identification of an unprecedented function of SlnM, homologous to O‐methyltransferases, by correlating its activity with the formation of the Δ18,19 double bond and bis(spiroacetal). Detailed in vivo and in vitro investigations revealed that SlnM, using positively charged S‐adenosylmethionine (SAM) or sinefungin as the cofactor, catalyzed the spirocyclization‐coupled dehydration of C19 in a highly atypical fashion to yield salinomycin.
Selective Michael Reaction Controlled by Supersilyl Protecting Group
Authors: Izumiseki Atsuto , Yamamoto Hisashi
Published: June 2015

Selective Michael reaction of organolithium reagents to supersilyl methacrylate is reported. The method was able to control a single and double Michael addition. The successful termination of the process using the supersilyl protecting group allows for the controlled, chemoselective, and diastereoselective Michael reaction.
A Synthetic DNA‐Binding Domain Guides Distinct Chromatin‐Modifying Small Molecules to Activate an Identical Gene Network
Authors: Han Le , Pandian Ganesh N. , Chandran Anandhakumar , Sato Shinsuke , Taniguchi Junichi , Kashiwazaki Gengo , Sawatani Yoshito , Hashiya Kaori , Bando Toshikazu , Xu Yufang , Qian Xuhong , Sugiyama Hiroshi
Published: June 2015

Synthetic dual‐function ligands targeting specific DNA sequences and histone‐modifying enzymes were applied to achieve regulatory control over multi‐gene networks in living cells. Unlike the broad array of targeting small molecules for histone deacetylases (HDACs), few modulators are known for histone acetyltransferases (HATs), which play a central role in transcriptional control. As a novel chemical approach to induce selective HAT‐regulated genes, we conjugated a DNA‐binding domain (DBD) “I” to N‐(4‐chloro‐3‐trifluoromethyl‐phenyl)‐2‐ethoxy‐benzamide (CTB), an artificial HAT activator. In vitro enzyme activity assays and microarray studies were used to demonstrate that distinct functional small molecules could be transformed to have identical bioactivity when conjugated with a targeting DBD. This proof‐of‐concept synthetic strategy validates the switchable functions of HDACs and HATs in gene regulation and provides a molecular basis for developing versatile bioactive ligands.
A Photoresponsive Smart Covalent Organic Framework
Authors: Huang Ning , Ding Xuesong , Kim Jangbae , Ihee Hyotcherl , Jiang Donglin
Published: June 2015

Ordered π‐columnar structures found in covalent organic frameworks (COFs) render them attractive as smart materials. However, external‐stimuli‐responsive COFs have not been explored. Here we report the design and synthesis of a photoresponsive COF with anthracene units as the photoresponsive π‐building blocks. The COF is switchable upon photoirradiation to yield a concavo‐convex polygon skeleton through the interlayer [4π+4π] cycloaddition of anthracene units stacked in the π‐columns. This cycloaddition reaction is thermally reversible; heating resets the anthracene layers and regenerates the COF. These external‐stimuli‐induced structural transformations are accompanied by profound changes in properties, including gas adsorption, π‐electronic function, and luminescence. The results suggest that COFs are useful for designing smart porous materials with properties that are controllable by external stimuli.
Redox‐Controlled Exchange Bias in a Supramolecular Chain of Fe4 Single‐Molecule Magnets
Authors: Nava Andrea , Rigamonti Luca , Zangrando Ennio , Sessoli Roberta , Wernsdorfer Wolfgang , Cornia Andrea
Published: June 2015

Tetrairon(III) single‐molecule magnets [Fe4(pPy)2(dpm)6] (1) (H3pPy=2‐(hydroxymethyl)‐2‐(pyridin‐4‐yl)propane‐1,3‐diol, Hdpm=dipivaloylmethane) have been deliberately organized into supramolecular chains by reaction with RuIIRuII or RuIIRuIII paddlewheel complexes. The products [Fe4(pPy)2(dpm)6][Ru2(OAc)4](BF4)x with x=0 (2 a) or x=1 (2 b) differ in the electron count on the paramagnetic diruthenium bridges and display hysteresis loops of substantially different shape. Owing to their large easy‐plane anisotropy, the s=1 diruthenium(II,II) units in 2 a act as effective seff=0 spins and lead to negligible intrachain communication. By contrast, the mixed‐valent bridges (s=3/2, seff=1/2) in 2 b introduce a significant exchange bias, with concomitant enhancement of the remnant magnetization. Our results suggest the possibility to use electron transfer to tune intermolecular communication in redox‐responsive arrays of SMMs.
Coordination Assembly of Discoid Nanoparticles
Authors: Hirai Kenji , Yeom Bongjun , Chang Shu‐Hao , Chi Hang , Mansfield John F. , Lee Byeongdu , Lee Sungsik , Uher Ctirad , Kotov Nicholas A.
Published: June 2015

Supramolecular chemistry utilizes coordination bonds to assemble molecular building blocks into a variety of sophisticated constructs. However, traditional coordination assemblies are based on organic compounds that have limited ability to transport charge. Herein, we describe coordination assembly of anisotropic FeS2 pyrite nanoparticles (NPs) that can facilitate charge transport. Zn2+ ions form supramolecular complexes with carboxylate end‐groups on NP surface, leading to multiparticle sheets with liquid‐crystal‐like organization. Conductivity and Hall carrier mobility of the p‐type layered semiconductor films with Zn2+ coordination bridging exceed those known for coordination compounds, some by several orders of magnitude. The nanoscale porosity of the assembled sheets combined with fast hole transport leads to high electrocatalytic activity of the NP films. The coordination assembly of NPs embraces the versatility of several types of building blocks and opens a new design space for self‐organized materials combining nanoscale and supramolecular structural motifs.
Hierarchical Nacre Mimetics with Synergistic Mechanical Properties by Control of Molecular Interactions in Self‐Healing Polymers
Authors: Zhu Baolei , Jasinski Nils , Benitez Alejandro , Noack Manuel , Park Daesung , Goldmann Anja S. , Barner‐Kowollik Christopher , Walther Andreas
Published: June 2015

Designing the reversible interactions of biopolymers remains a grand challenge for an integral mimicry of mechanically superior biological composites. Yet, they are the key to synergistic combinations of stiffness and toughness by providing sacrificial bonds with hidden length scales. To address this challenge, dynamic polymers were designed with low glass‐transition temperature Tg and bonded by quadruple hydrogen‐bonding motifs, and subsequently assembled with high‐aspect‐ratio synthetic nanoclays to generate nacre‐mimetic films. The high dynamics and self‐healing of the polymers render transparent films with a near‐perfectly aligned structure. Varying the polymer composition allows molecular control over the mechanical properties up to very stiff and very strong films (E≈45 GPa, σUTS≈270 MPa). Stable crack propagation and multiple toughening mechanisms occur in situations of balanced dynamics, enabling synergistic combinations of stiffness and toughness. Excellent gas barrier properties complement the multifunctional property profile.
Formation of Discrete Ladders and a Macroporous Xerogel Film by the Zipperlike Dimerization of Meso–Meso‐Linked Zinc(II) Porphyrin Arrays with Di(pyrid‐3‐yl)acetylene
Authors: Kose Kohei , Motoyanagi Jin , Kusukawa Takahiro , Osuka Atsuhiro , Tsuda Akihiko
Published: June 2015

Metal porphyrins assemble to form a supramolecular architecture with a characteristic structure and characteristic properties and functions upon complexation with appropriate ligands. However, there are few applications of these assembly processes to the construction of polymeric porphyrin arrays with useful functionalities. In this study, we found that meso–meso‐linked ZnII porphyrin arrays underwent zipperlike dimerization upon complexation with di(pyrid‐3‐yl)acetylene (DPA) in chloroform to form discrete double‐stranded porphyrin ladders. Similarly, the assembly of poly(zinc(II) porphyrinylene) with DPA gave a thermoresponsive gel, whose three‐dimensional network structure was so strong that a macroporous xerogel film was obtained.
Identification of tert‐Butyl Cations in Zeolite H‐ZSM‐5: Evidence from NMR Spectroscopy and DFT Calculations
Authors: Dai Weili , Wang Chuanming , Yi Xianfeng , Zheng Anmin , Li Landong , Wu Guangjun , Guan Naijia , Xie Zaiku , Dyballa Michael , Hunger Michael
Published: June 2015

Experimental evidence for the presence of tert‐butyl cations, which are important intermediates in acid‐catalyzed heterogeneous reactions, on solid acids has still not been provided to date. By combining density functional theory (DFT) calculations with 1H/13C magic‐angle‐spinning NMR spectroscopy, the tert‐butyl cation was successfully identified on zeolite H‐ZSM‐5 upon conversion of isobutene by capturing this intermediate with ammonia.
Selective Monoarylation of Primary Amines Using the Pd‐PEPPSI‐IPentCl Precatalyst
Authors: Sharif Sepideh , Rucker Richard P. , Chandrasoma Nalin , Mitchell David , Rodriguez Michael J. , Froese Robert D. J. , Organ Michael G.
Published: June 2015

A single set of reaction conditions for the palladium‐catalyzed amination of a wide variety of (hetero)aryl halides using primary alkyl amines has been developed. By combining the exceptionally high reactivity of the Pd‐PEPPSI‐IPentCl catalyst (PEPPSI=pyridine enhanced precatalyst preparation, stabilization, and initiation) with the soluble and nonaggressive sodium salt of BHT (BHT=2,6‐di‐tert‐butyl‐hydroxytoluene), both six‐ and five‐membered (hetero)aryl halides undergo efficient and selective amination.
Octahedral and Cubic Gold Nanoframes with Platinum Framework
Authors: Ham Songyi , Jang Hee‐Jeong , Song Yookyung , Shuford Kevin L. , Park Sungho
Published: June 2015

Herein, we report a general synthetic pathway to various shapes of three‐dimensional (3D) gold nanoframes (NFs) embedded with a Pt skeleton for structural rigidity. The synthetic route comprises three steps: site‐specific (edge and vertex) deposition of Pt, etching of inner Au, and regrowth of Au on the Pt framework. Site‐specific reduction of Pt on Au nanoparticles (NPs) led to the high‐quality of 3D Au NFs with good structural rigidity, which allowed the detailed characterization of the corresponding 3D metal NFs. The synthetic method described here will open new avenues toward many new kinds of 3D metal NFs.
Processing and properties of biodegradable compounds based on aliphatic polyesters
Authors: Nobile Maria Rossella , Cerruti Pierfrancesco , Malinconico Mario , Pantani Roberto
Published: June 2015

Two aliphatic biodegradable polyesters, Poly(butylene succinate) and Poly(lactic acid), are selected together with two inorganic fillers, talc and TiO2, to obtain biodegradable compounds for replacing polystyrene in the production of disposable plastic cups and plates. The rheological behavior of the pure polymers and the compounds is investigated, the mechanical properties of the compounds are determined in terms of modulus and elongation at break, the heat distortion temperature of the compounds is measured and compared to those of pure PBS and PS. Finally, the biodegradation of the compounds is also investigated. The processability and the final properties, in terms of elastic modulus and heat distortion temperature, make these compounds interesting for the production of disposable plates and cups for hot food and beverages, also considering that the elongation at break is significant. Furthermore, the results of biodegradation tests in composting conditions show that the presence of TiO2 induces a lag time and lower values of biodegradation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42481.
A Modest Proposal to Universalize the Insanity Defense and Replace Prisons and Punishment with Treatment and Education
Authors: Gilligan James
Published: June 2015

The insanity defense is based on the assumptions that with the exception of the insane, everyone possesses free will and the ability to distinguish right from wrong. These assumptions are incompatible with the deterministic premises on which psychoanalysis, psychology, psychiatry and all other behavioral and natural sciences are based, and with the epistemological premises on which all of the modern sciences are based. Criminal law is based on answering moral questions as to how evil a given defendant's mind was and how much punishment he deserves. But even if we could gain the knowledge we would need in order to answer those philosophic questions (which we cannot, since philosophy cannot produce knowledge), the answers would give us no help in answering the only questions that are relevant to the goal of reducing the incidence of violence and increasing the safety and well‐being of the people: namely, the empirical, scientific questions, “what are the causes of violence, and how can we prevent it?” The modern prison system was a well‐meaning experiment in social engineering that has failed, because it is based on fallacious assumptions. For example, we know by now that punishing people in order to achieve a moral goal, justice, does not prevent violence, it stimulates it. That is among the reasons that prisons need to be abolished and replaced with a new approach based on proven methods of preventing violence, namely, safe, secure, home‐like residential colleges and therapeutic communities. Copyright © 2015 John Wiley & Sons, Ltd.
History, Murder and the Fear of Death
Authors: Doctor Ronald
Published: June 2015

The account of the crime is nearly always a cover up story. Murder occurs concretely in most cases when it has been committed many times previously in daydreams, nightmares and sometimes in unconscious phantasy that has never become conscious. Before the deed, conscious efforts – sometimes unconscious ones, too – are designed and devoted to keeping the murder encapsulation from action. Then something takes place internally that breaks loose the murderousness from it's cordoned off status, so that the whole of the energies of the individual becomes devoted to enacting the murderous deed. In the death constellation there is a psychically traumatic and indigestible experience to do with death. Only with a life threatening trigger, displayed as the fear of death, did they enact their murderousness. Violence is thus a communication about the patient's belief systems about themselves, about their relationships with others and about their origins. Copyright © 2015 John Wiley & Sons, Ltd.
Determination of Secondary Follicle Characteristics, Density, Activity, and Hoxc13 Expression Pattern of Hexi Cashmere Goats Breed
Authors: He Yanyu , Luo Yuzhu , Cheng Lixiang , Wang Jiqing , Liu Xiu , Shao Bin , Cui Yan
Published: June 2015

This experiment was conducted to identify some aspects of secondary follicle (SF) characteristics of Hexi cashmere goats at five different growing stages in one year in order and discover the expression pattern of Hoxc13 in a SF cycling to provide morphological basis for studying the growth of cashmere. Ten cashmere goats of one‐year old (5 males, 5 females) were included in this study. The density and activity of SF were observed and measured by making paraffin sections, the ultra‐structural features of SF were studied under transmission electron microscopy (TEM) by making ultra‐thin sections, and the expression of Hoxc13 was investigated through the immunohistochemistry method. The average diameter of SF had the smallest value in the anagen stage, and significant difference (P < 0.05) was found between the anagen stage and other stages. The density of SF increased gradually through the different growing stages, and significant difference was found between the anagen and procatagen stages (P < 0.05). With an increase in time (months), the percentage of SF activity increased, and significant difference in the percentage of SF activity was found between the telogen and anagen stages (P < 0.05). At the telogen stage, the layers of connective tissue sheath (CTS) of SF were unclear, hemidesmosomes between the outer root sheath (ORS) and basement membrane disappeared, and dead cells were found at the top of the SF. The rudiments of new SF were found in the proanagen stage, CTS was thickened, and the cells of ORS were stretched out like fingers. At the anagen stage, the structure of SF was integral, and the inner root sheath (IRS) consisted of three concentric layers (Helen, Huxley, and Cuticle layers). The cells of Huxley's layer degenerated gradually, and pseudopodia were formed on the cells of ORS in the procatagen stage. At the catagen stage, the ORS was separated from the IRS, and IRS disappeared. Huxley's layer was absent in the inactive SF while, the ORS was present in the active SF. Hoxc 13 was expressed in the epidermis and sebaceous gland o, ORS, IRS, hair shaft of SF in the skin. Hoxc13 was expressed weakly during procatagen, catagen, and telogen stage, while with an increase in proanagen and anagen stage, significant difference was found between them. These findings demonstrated the ultra‐structural features of SF could provide the useful activity criteria, and Hoxc13 associated with the SF activity. Anat Rec, 298:1796–1803, 2015. © 2015 Wiley Periodicals, Inc.
“Their God is their belly”: Moravian missionaries at the Weipa Mission (1898–1932), Cape York Peninsula
Authors: Morrison Michael , McNaughton Darlene , Keating Claire
Published: June 2015

The Weipa Mission (1898–1932) on Cape York Peninsula (north‐eastern Australia) was one of seven Australian missions designed and staffed by the Moravian Church during the nineteenth and early twentieth centuries. We present findings of archaeological and historical research that illustrate key aspects of the settlement's development and operations. Moravian missionaries at Weipa aimed to create a built landscape that reshaped Aboriginal social, cultural and economic relations, with particular emphasis on children through the use of a dormitory system. However, their efforts were mediated by the open spatial and social boundaries of the settlement, which enabled Aboriginal people to make choices about the nature and extent to which they engaged with the mission. Adopting a political economy approach, we show that this openness emerged through complex social relationships between missionaries and Aboriginal people. While missionaries required access to children and adults, they lacked the ability (or will) to maintain a resident population through force, with limited financial resources also hampering their activities. Instead, Aboriginal people came and went from the settlement, with some establishing and maintaining social relationships with missionaries to access economic and social benefits. We argue that these social relationships led to the development of the settlement as a more open domain.
Interprofessional anatomy education in the United Kingdom and Ireland: Perspectives from students and teachers
Authors: Smith Claire F. , Hall Samuel , Border Scott , Adds Philip J. , Finn Gabrielle M.
Published: June 2015

There is increasing recognition of multiprofessional learning in anatomy and its role in medical and healthcare professions. This study utilized two components to investigate anatomy interprofessional education (AIPE) in the United Kingdom and Ireland. First, a survey involving qualitative and quantitative components asked Heads of Anatomy to report on their institutions’ uptake of AIPE. Second, a series of case studies explored the experiences of students by using evaluation forms and an in‐depth analysis of thematic concepts to understand the learners’ perspectives on designing and delivering AIPE. Out of the 13 institutions that took part in the survey, eight did not offer an AIPE program. Between the remaining five institutions that deliver AIPE programs, 10 different modules are offered with the majority involving healthcare professions. The AIPE component is rated highly by students. The themes from the case studies highlight how valuable AIPE is from the student perspective both in terms of engaging them in anatomy as well as in the broader skills of teamwork and communication. The case studies also revealed how AIPE can be engaging for groups of students who might not have previously had access to cadaveric anatomy, for example, engineers and archeologists. The results of this study have implications for curriculum design in medicine and healthcare but also for further engagement of professional groups from non‐healthcare backgrounds. Anat Sci Educ 8:360–370. © 2015 American Association of Anatomists.