bluuebunny/crossref_metadata_2025 huggingface dataset:
Copper/P(tBu)3‐Mediated Regiospecific Synthesis of Fused Furans and Naphthofurans
Authors: Naveen Togati , Deb Arghya , Maiti Debabrata
Published: December 2016

A novel [3+2] cycloaddition between a variety of cyclic ketones and diverse olefins or alkynes can be effectively promoted by copper in combination with the tri‐tert‐butylphosphine [P(tBu)3] ligand. This protocol exhibits excellent selectivity and provides an exemplary set of fused heterocycles in good to excellent yields. Present strategy also represents an extremely simple and atom‐economic way to construct substituted fused furans and naphthofurans from readily available starting materials under mild reaction conditions. The utility of the method is further demonstrated by the synthesis of chiral furans from (R)‐(−)‐carvone and (S)‐(+)‐carvone. A plausible mechanism involving the oxidative radical cyclization has been suggested based on experimental observations.
N‐Heterocyclic Carbene Stabilized Boryl Radicals
Authors: Silva Valverde Miguel F. , Schweyen Peter , Gisinger Daria , Bannenberg Thomas , Freytag Matthias , Kleeberg Christian , Tamm Matthias
Published: December 2016

The reaction of the 2‐(trimethylsilyl)imidazolium triflate 9 with diarylboron halides (4‐R‐C6H4)2BX (R=H, X=Br; R=CH3, X=Cl; R=CF3, X=Cl) afforded the NHC‐stabilized borenium cations 10 a–c. Cyclic voltammetry revealed a linear correlation between the Hammett parameter σp of the para substituent and the half‐wave potential. Chemical reduction with decamethylcobaltocene, [(C5Me5)2Co], furnished the corresponding radicals 11 a–c; their characterization by EPR spectroscopy confirmed the paramagnetic character of 11 a–c, with large hyperfine coupling constants to the boron isotopes 11B and 10B, while delocalization of the unpaired electron into the NHC is negligible. DFT calculations of the percentage of spin density distribution between the carbene (NHC) and the boryl fragments (BR2) revealed for 11 a–c a spin density ratio (BR2/NHC) of ca. 9:1, which underlines their distinct boryl radical character. The molecular structure of the most stable species 11 c was established by X‐ray diffraction analysis.
Working with Siblings of Children with Autism: A Solution‐focused Approach
Authors: Turns Brie , Eddy Brandon Paul , Jordan Sara Smock
Published: December 2016

The literature on how autism spectrum disorders (ASD) impact the family unit primarily focuses on the negative experiences of parents and neurotypical (NT) siblings. This unintentional focus may impact the therapist's ability to identify strengths within the family unit and further perpetuate the misconception that ASD is only a ‘problem.’ This paper reviews NT siblings’ experiences of living with an ASD sibling. A solution‐focused brief therapy framework is used in order to alter the covert message that an ASD diagnosis is a ‘problem’ for the families. Recommendations are provided to assist family therapists in focusing on the positive experiences reported by the NT sibling in ASD families, especially the relationship with his or her diagnosed sibling and primary caregivers.
Family Therapy for Adolescents: A Research‐informed Perspective
Authors: Carr Alan
Published: December 2016

Specific research‐informed models of family therapy have been developed for a range of adolescent problems. These include Brief Strategic Family Therapy (BSFT), Functional Family Therapy (FFT), Multisystemic Therapy (MST), Multidimensional Family Therapy (MDFT), and Multidimensional Treatment Foster care (MTFC) for conduct disorder and drug misuse; family‐focused cognitive behaviour therapy for anxiety disorders and depression; Attachment‐based Family Therapy (ABFT) for depression; family‐focused therapy as an adjunct to pharmacological therapy for bipolar disorder; ABFT, youth‐nominated support team, and Dialectical Behaviour Therapy (DBT) combined with Multifamily Therapy for self‐harm; the Maudsley model of family therapy for eating disorders; and psychoeducational family theory for psychosis. All of these approaches aim to reduce individual and familial risk factors which exacerbate adolescent problems, and enhance protective factors which promote resilience and recovery from psychological difficulties.
Dielectric properties of potassium carbonate‐impregnated cempedak peel for microwave‐assisted activation
Authors: Alias N. , Zaini M.A.A. , Kamaruddin M.J. , You K.Y.
Published: December 2016

This study was aimed to evaluate the dielectric properties of cempedak peel (Artocarpus chempeden, A. integer) impregnated with potassium carbonate. The materials were characterized by moisture content, elemental composition and thermal profile. The dielectric properties were examined using open‐ended coaxial probe method at microwave frequencies and different temperatures. Results show that the dielectric properties changed with frequency, temperature, potassium carbonate impregnation ratio, moisture content and carbon content. Cempedak peel exhibits a better microwave absorber at 25 °C because of higher tan δ than char and impregnated samples. Char displayed a higher tan δ at 35 °C probably because of high carbon content (63.7%). Moisture content and carbon content have to be taken into account in microwave‐assisted activation of cempedak peel. Potassium carbonate can act as microwave absorber to enhance the efficiency of microwave heating for low loss material. Copyright © 2016 Curtin University of Technology and John Wiley & Sons, Ltd.
Effects of Growth on Muscle, Tendon, and Aponeurosis Tissues in Rabbit Shank Musculature
Authors: Böl Markus , Leichsenring Kay , Siebert Tobias
Published: December 2016

There exist several studies using morphological analyses of skeletal muscles to obtain a better understanding of muscle structure. The structural information obtained are primarily determined from single muscle components using individual animals of discrete ages. Further, little is known about changing dimensions of the aponeurosis, which is an important load‐transferring interface in muscle mechanics. Thus, the aim of the present study was to determine how the muscle, tendon, and particularly the aponeurosis geometry of the rabbit shank musculature (M. soleus, M. extensor digitorum longus, and M. plantaris) change during growth. In doing so, morphological studies on muscles of eighty‐nine female rabbits aged between 18 and 108 days were conducted. We found an almost linear increase over time in all of the geometrical parameters observed. The aponeurosis of the muscles exhibited lower growth rates in width than in length. The distal and proximal aponeurosis areas were nearly identical. The ratio of aponeurosis area to the physiological cross‐sectional area was 2.54, 2.54, and 1.88 for M. soleus, M. extensor digitorum longus, and M. plantaris, respectively. M. extensor digitorum longus and M. soleus exhibited a nearly similar tendon‐muscle fascicle length ratio during growth, increasing from 2.86 to 5.30 and 3.48 to 6.16, respectively. Interestingly, the tendon‐muscle fascicle length ratio of the M. plantaris started initially with a much higher value (∼8) and increased to ∼18. Taken together, these results provide insight into the structure of the muscle‐tendon complex and thus, a general understanding of muscle growth. Anat Rec, 300:1123–1136, 2017. © 2016 Wiley Periodicals, Inc.
Arbitrary Pole Placement by Constant Output Feedback for Linear Time Invariant Systems
Authors: Kiritsis Konstadinos H.
Published: December 2016

In this paper, the pole placement problem by constant output feedback for linear time invariant systems is investigated. In particular, is proven that, for the class of linear time invariant systems with m inputs, p outputs, and McMillan degree n, the condition (m + p) > n is necessary for the solution of the arbitrary pole placement problem by constant output feedback.
Extreme Intertropical Convergence Zone shifts over Southern Maritime Continent
Authors: Freitas Ana Carolina Vasques , Aímola Luis , Ambrizzi Tércio , de Oliveira Cristiano Prestrelo
Published: December 2016

This study investigated the Intertropical Convergence Zone (ITCZ) extreme shifts in the Southern Maritime Continent (SMC) region in austral spring during the period 1979–2015. The results have shown that the ITCZ Southern Boundary (SB) presents great correlations with a meridional Sea Surface Temperature (SST) gradient and Indian Ocean Dipole (IOD) events. However, besides these local forcing, the extreme ITCZ shifts are also influenced by El Niño‐Southern Oscillation (ENSO) events and an associated zonal SST gradient. The extreme shifts are due mainly to the combination of changes in Walker Circulation (WC) in the Pacific and Indian Ocean (IO) and local SST anomalies. Therefore, during ITCZ southward extreme shifts, the WC is stronger leading to the strengthening of the northwest equatorial winds in the IO, which pumps moist air and boosts the diabatic heating in the SMC due to the local positive SST anomalies present in this region. Otherwise, during northward extreme shifts, the WC is weaker, not allowing the performance of the northwest equatorial winds in the IO, which associated with the local negative SST anomalies, leads to drier conditions in the SMC region. Another interesting result found here is that a strong meridional or zonal index not necessarily implies a larger shift. The combination of very strong ENSO and IOD events can lead to greater ITCZ SB shifts. Besides, the ITCZ SB shifts can act as a bridge linking IOD and ENSO.
Tragwerk in neuem Kleid
Authors: Seiler Josef
Published: December 2016

Ein in den 70er‐Jahren des vergangenen Jahrhunderts entstandenes ikonografisches Gebäude in Sichtbetonbauweise der Architekten Götz und Bätzner unter Mitwirkung der Ingenieurgruppe Bauen wurde dem Nutzer zur Last. Hohe Energie‐ und Unterhaltskosten, geringe Nutzerakzeptanz und Defizite bei der Betriebsorganisation infolge baulicher Zwänge führten zu Gedankenspielen, das Gebäude durch einen Neubau zu ersetzen. Im Zuge dieser Überlegungen wurde auch untersucht, inwieweit eine Revitalisierung des Gebäudes mit der vorhandenen Substanz realisierungsfähig ist. Dabei wurden nicht ausschließlich rein merkantile Aspekte betrachtet, sondern auch differenzierte Überlegungen zur Nachhaltigkeit angestellt. Der Entschluss, die Rohbaukonstruktion zu erhalten und das Gebäude zu revitalisieren, führte zu einem modernen Gebäude mit Wohlfühlcharakter, das aber auch den Anforderungen an zeitgemäße Arbeitsplatzkonzepte gerecht wird.
Die neue Orgel der Konstantin‐Basilika in Trier
Authors: Peter Boris , Pfaff Klaus
Published: December 2016

Für einen europaweit ausgeschriebenen und namhaft besetzten Architekturwettbewerb eine ungewöhnliche Aufgabe: Eine gewaltige Orgel von ca. 450 m3 Gesamtvolumen und ca. 32 t Gewicht sollte möglichst unauffällig in das monumentale Bestandsbauwerk des UNESCO‐Weltkulturerbes, der Konstantin‐Basilika in Trier, integriert werden. Die Eingriffe in die historische Bausubstanz sollten so gering wie möglich ausfallen.

Der Entwurf der Architekten Auer Weber aus Stuttgart in Zusammenarbeit mit Knippers Helbig Advanced Engineering besticht durch die Reduktion auf ein absolutes Minimum, ohne zusätzlichen Zierrat im fast selbstverständlichen Einklang mit dem beeindruckenden denkmalgeschützten Kirchenraum. Getragen wird die beachtliche Last der neuen Orgel und des stählernen Traggerüsts alleine vom historischen Bestandsbauwerk.
Teaching children with autism to follow gaze shift: A brief report on three cases
Authors: Gunby Kristin V. , Rapp John T. , Bottoni Melissa M. , Marchese Nancy , Wu Benjamin
Published: December 2016

This study evaluated the extent to which prompting and reinforcement increased three participants' correct selections of items following a therapist's gaze shift using a non‐concurrent multiple baseline design for two participants and an ABCD design for one participant. Results show that each participant learned to discriminate an adult's gaze direction to make a correct selection and each participant's responding generalized to selections with non‐reinforcing stimuli. Two participants also displayed the skill during probe sessions with their parents; however, the third participant required tangible reinforcement for correct selections to demonstrate the skill with a parent.
An ultrasensitive electrochemiluminescent sensor based on a pencil graphite electrode modified with CdS nanorods for detection of chlorogenic acid in honeysuckle
Authors: Zheng Ruijuan , Zhong Jianhai , Zhao Chenhao , Lang Xiaoling , Hu Zhibiao , Luo Jiangshui
Published: December 2016

In this paper, a novel and ultrasensitive electrochemiluminescent sensor employing a solvothermal‐synthesized CdS nanorod‐modified pencil graphite electrode (CdS/PGE) for the determination of chlorogenic acid (CA) is fabricated. In the first step, the PGE surface is modified using CdS nanorods. In the next step, the developed electrode is used to detect CA using a electrochemiluminescent (ECL) technique, in which potassium persulfate (K2S2O8) served as a co‐reactant. The possible ECL mechanism is investigated, and the influences of pH and cyclic voltammetric scanning rate on the signal response are studied. The ECL intensity decreases quantitatively in relation to the concentration of the target molecule. Under optimized conditions, the linear correlation between the quenched ECL intensity and the logarithm of CA concentration is observed in the range from 2 × 10−9 to 8 × 10−7 mol L−1 with a limit of detection of 1 × 10−9 mol L−1. This proposed method is applied to the analysis of CA in honeysuckle flower, giving recoveries of 99‐107%. The experimental results demonstrate that this ECL sensor shows good stability and reproducibility.
Surgical anatomy, radiological features, and molecular biology of the lumbar intervertebral discs
Authors: Ghannam Malik , Jumah Fareed , Mansour Shaden , Samara Amjad , Alkhdour Saja , Alzuabi Muayad A. , Aker Loai , Adeeb Nimer , Massengale Justin , Oskouian Rod J. , Tubbs R. Shane
Published: December 2016

The intervertebral disc (IVD) is a joint unique in structure and functions. Lying between adjacent vertebrae, it provides both the primary support and the elasticity required for the spine to move stably. Various aspects of the IVD have long been studied by researchers seeking a better understanding of its dynamics, aging, and subsequent disorders. In this article, we review the surgical anatomy, imaging modalities, and molecular biology of the lumbar IVD. Clin. Anat. 30:251–266, 2017. © 2017 Wiley Periodicals, Inc.
Efficacy, immunogenicity, and safety of the HPV‐16/18 AS04‐adjuvanted vaccine in Chinese women aged 18–25 years: event‐triggered analysis of a randomized controlled trial
Authors: Zhu Feng‐cai , Hu Shang‐Ying , Hong Ying , Hu Yue‐Mei , Zhang Xun , Zhang Yi‐Ju , Pan Qin‐Jing , Zhang Wen‐Hua , Zhao Fang‐Hui , Zhang Cheng‐Fu , Yang Xiaoping , Yu Jia‐Xi , Zhu Jiahong , Zhu Yejiang , Chen Feng , Zhang Qian , Wang Hong , Wang Changrong , Bi Jun , Xue Shiyin , Shen Lingling , Zhang Yan‐Shu , He Yunkun , Tang Haiwen , Karkada Naveen , Suryakiran Pemmaraju , Bi Dan , Struyf Frank
Published: December 2016

We previously reported the results of a phase II/III, double‐blind, randomized controlled study in Chinese women (NCT00779766) showing a 94.2% (95% confidence interval: 62.7–99.9) HPV‐16/18 AS04‐adjuvanted vaccine efficacy (VE) against cervical intraepithelial neoplasia grade 1 or higher (CIN1+) and/or 6‐month (M) persistent infection (PI) with a mean follow‐up of <2 years, and immunogenicity until 7 months post‐dose 1. Here, we report efficacy and safety results from an event‐triggered analysis with ~3 years longer follow‐up, and immunogenicity until M24. Healthy 18–25‐year‐old women (N = 6051) were randomized (1:1) to receive three doses of HPV‐16/18 vaccine or Al(OH)3 (control) at M0, 1, 6. VE against HPV‐16/18‐associated CIN2+, and cross‐protective VE against infections with nonvaccine oncogenic HPV types, immunogenicity, and safety were assessed. In the according‐to‐protocol efficacy cohort, in initially seronegative/DNA‐negative women (vaccine group: N = 2524; control group: N = 2535), VE against HPV‐16/18‐associated CIN2+ was 87.3% (5.3–99.7); VE against incident infection or against 6‐month persistent infection associated with HPV‐31/33/45 was 50.1% (34.3–62.3) or 52.6% (24.5–70.9), respectively. At least, 99.6% of HPV‐16/18‐vaccines remained seropositive for anti‐HPV‐16/18 antibodies; anti‐HPV‐16 and ‐18 geometric mean titers were 1271.1 EU/mL (1135.8–1422.6) and 710.0 EU/ml (628.6–801.9), respectively. Serious adverse events were infrequent (1.7% vaccine group [N = 3026]; 2.5% control group [N = 3026]). Of the 1595 reported pregnancies, nine had congenital anomalies (five live infants, three elective terminations, one stillbirth) that were unlikely vaccination‐related (blinded data). VE against HPV‐16/18‐associated CIN2+ was demonstrated and evidence of cross‐protective VE against oncogenic HPV types was shown. The vaccine was immunogenic and had an acceptable safety profile.
Whole‐exome sequencing predicted cancer epitope trees of 23 early cervical cancers in Chinese women
Authors: Li Xia , Huang Hailiang , Guan Yanfang , Gong Yuhua , He Cheng‐Yi , Yi Xin , Qi Ming , Chen Zhi‐Ying
Published: December 2016

Emerging evidence suggest that the heterogeneity of cancer limits the efficacy of immunotherapy. To search for optimal therapeutic targets for enhancing the efficacy, we used whole‐exome sequencing data of 23 early cervical tumors from Chinese women to investigate the hierarchical structure of the somatic mutations and the neo‐epitopes. The putative neo‐epitopes were predicted based on the mutant peptides’ strong binding with major histocompatibility complex class I molecules. We found that each tumor carried an average of 117 mutations and 61 putative neo‐epitopes. Each patient displayed a unique phylogenetic tree in which almost all subclones harbored neo‐epitopes, highlighting the importance of individual neo‐epitope tree in determination of immunotherapeutic targets. The alterations in FBXW7 and PIK3CA, or other members of the significantly altered ubiquitin‐mediated proteolysis and extracellular matrix receptor interaction related pathways, were proposed as the earliest changes triggering the malignant progression. The neo‐epitopes involved in these pathways, and located at the top of the hierarchy tree, might become the optimal candidates for therapeutic targets, possessing the potential to mediate T‐cell killing of the descendant cells. These findings expanded our understanding in early stage of cervical carcinogenesis and offered an important approach to assist optimizing the immunotherapeutic target selection.
How Diverse Is This Community? Sense of Community, Ethnic Prejudice and Perceived Ethnic Heterogeneity
Authors: Mannarini Terri , Talò Cosimo , Rochira Alessia
Published: December 2016

In this paper, the relationship between territorial sense of community (SoC), perceived ethnic heterogeneity within the community and ethnic prejudice was analyzed. Specifically, the moderating role of perceived ethnic heterogeneity within the community on the SoC–prejudice relationship was tested in a sample of residents (N = 603) of the Salento region, Italy. Results showed that the relationship between SoC and prejudice was moderated by perceived contextual heterogeneity. For blatant and subtle prejudice, when perceived ethnic heterogeneity was low, SoC was negatively associated with prejudice. In the case of modern prejudice, SoC was positively associated with prejudice when perceived ethnic heterogeneity was high. Copyright © 2016 John Wiley & Sons, Ltd.
Managing infected cardiovascular implantable electronic devices
Authors: Manolis A. S. , Melita H.
Published: December 2016

The number of cardiac implantable electronic device (CIED) implants is growing; unfortunately, the rate of device infections is also rising, outpacing the increase in device implantation and paralleling the complexity of current CIEDs and CIED recipients, incurring high morbidity and mortality, long hospital stays, and increased financial cost. For either pocket or lead infection, percutaneous complete removal of the infected device and lead system combined with prolonged antibiotic treatment is the standard approach to patient management. A variety of mechanical and/or laser‐assisted techniques and tools are employed with high success rates in experienced centers. Surgery is reserved for cases with very large vegetations, need for other concomitant cardiac surgery or for failed or complicated percutaneous approach. Following removal of an infected CIED, the need for reimplantation of a new device is individualized, although the timing is variable, mainly based on the absence of signs of continued infection. In general, CIED‐related infective endocarditis and the presence of comorbid conditions are associated with increased mortality. These and other important relevant issues of contemporary management of patients with infected CIEDs are herein reviewed.

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Remote monitoring of patients with CIEDs following the updated recommendations—Easing or adding to postimplant responsibilities?
Authors: Varma N.
Published: December 2016

Follow‐up of patients with cardiac implantable electronic devices is challenging due to both their increasing volume and technical complexity coupled to increasing clinical complexity of recipient patients. Remote monitoring (RM) offers an opportunity to resolve some of these difficulties by improving clinic efficiencies and providing a mechanism for device monitoring and patient management. Recent recommendations advocate for RM to be standard of care for this purpose. Several randomized clinical trials and registries have demonstrated that RM may reduce in‐hospital visit numbers, time required for patient follow‐up, physician and nurse time, and hospital and social costs. Furthermore, patient retention and adherence to follow‐up schedule are significantly improved by RM. Continuous wireless monitoring of data stored in the device memory with automatic alerts allows early detection of device malfunctions and of events, such as atrial fibrillation, ventricular arrhythmias, and heart failure suitable for clinical intervention. Early reaction may improve patient outcome. RM is easy to use and patients showed a high level of acceptance and satisfaction. Implementing RM in daily practice may require changes in clinic workflow. New organizational models promote significant efficiencies regarding physician and nursing time. Data management techniques are under development. Despite these demonstrable advantages of RM, adoption still remains modest, even in health care systems incentivized to use this follow‐up method.

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Extensive cutaneous metastases of pancreatic adenocarcinoma: a case report and review of the literature
Authors: Kotsantis Ioannis , Economopoulou Panagiota , Dritsakos Konstantinos , Oikonomopoulos Nikolaos , Bakogeorgos Marios , Rapti Cleopatra , Kentepozidis Nikolaos
Published: December 2016

Key Clinical Message

Herein, we present the case of a patient with pancreatic cancer and nonumbilical cutaneous metastasis. Patients with pancreatic adenocarcinomas can develop extensive cutaneous metastases involving not only abdominal skin but also other unusual sites such as the scrotum.
Interfacial Architectures Derived by Lithium Difluoro(bisoxalato) Phosphate for Lithium‐Rich Cathodes with Superior Cycling Stability and Rate Capability
Authors: Han Jung‐Gu , Park Inbok , Cha Jiho , Park Suhyeon , Park Sewon , Myeong Seungjun , Cho Woograe , Kim Sung‐Soo , Hong Sung You , Cho Jaephil , Choi Nam‐Soon
Published: December 2016

The front cover artwork is provided by the group of Nam‐Soon Choi at Ulsan National Institution Science Technology, Republic of Korea. The image shows lithium difluoro(bisoxalato) phosphate as an oxidizable additive for in‐situ formation of a stable artificial solid electrolyte interphase layer on the Li‐rich cathode. Read the full text of the Article at 10.1002/celc.201600297.
Rhodium‐Catalyzed Synthesis and Optical Properties of Silicon‐Bridged Arylpyridines
Authors: Shintani Ryo , Misawa Nana , Takano Ryo , Nozaki Kyoko
Published: December 2016

A convergent and regioselective synthesis of silicon‐bridged 4‐arylpyridines has been developed through a rhodium‐catalyzed [2+2+2] cycloaddition of silicon‐containing diynes with nitriles. The absorption and emission properties of these compounds have been examined and could be tuned by varying the substituent on the benzene ring, as well as through the protonation or alkylation of the nitrogen atom on the pyridine ring. A catalytic asymmetric synthesis of silicon‐centered axially chiral spirocyclic derivatives has also been achieved with high enantioselectivity by using a newly modified MeO‐MOP (MeO‐MOP=2‐(diphenylphosphino)‐2′‐methoxy‐1,1′‐binaphthyl) derivative as the chiral ligand. These spirocyclic compounds were found to be CPL‐active (CPL=circularly polarized luminescence), representing the first CPL‐active compounds based on the chirality at silicon.
Intramolecular Diaza‐Diels–Alder Protocol: A New Diastereoselective and Modular One‐Step Synthesis of Constrained Polycyclic Frameworks
Authors: Srinivasulu Vunnam , Reddy Amarnath , Mazitschek Ralph , Lukens Amanda K. , Wirth Dyann F. , Li Liang , Naumov Panče , O'Connor Matthew John , Al‐Tel Taleb H.
Published: December 2016

Phenotype‐based screening of diverse compound collections generated by privileged substructure‐based diversity‐oriented synthesis (pDOS) is considered one of the prominent approaches in the discovery of novel drug leads. However, one key challenge that remains is the development of efficient and modular synthetic routes toward the facile access of privileged small‐molecule libraries with skeletal and stereochemical complexity and drug‐like properties. In this regard, a novel and diverse one‐pot procedure for the diastereoselective synthesis of privileged polycyclic benzopyrans and benzoxepines is described herein. These unexplored chemotypes were accessed by utilizing an acid‐mediated diaza‐Diels–Alder reaction of 2‐allyloxy‐ and/or homoallyloxy benzaldehyde with 2‐aminoazine building blocks. Profiling of representative analogues against blood‐stage Plasmodium falciparum parasites identified three lead candidates with low micromolar antimalarial activity.
Homogeneous and Heterogeneous Anion Sensing by a Molecular Cobalt–Vanadium Oxide
Authors: Heiland Magdalena , Seliverstov Andrey , Schwarz Benjamin , Anjass Montaha H. , Streb Carsten
Published: December 2016

Spectroscopic anion sensing is a vital non‐invasive tool in chemistry and biology. Here, a molecular cobalt–vanadium‐oxide cluster was shown to be capable of selectively binding and detecting various mono‐anions in solution and immobilized on a solid support. The cluster anion [Co(X)V4O12]3− (X=mono‐anion, for example, halide, pseudohalide, carboxylate, etc.) was formed spontaneously upon anion addition by self‐assembly in solution. The cluster showed distinct spectral changes upon anion binding that could be followed spectroscopically and visually owing to a significant change of the solution color. DFT computations showed that the anion binding observed experimentally was correlated to the relative cluster stabilities. Competitive‐binding studies showed that selective anion binding was possible from a mixture of anions. Immobilization of the anion sensor on silica strips provided access to single‐use dip‐stick sensors for the facile detection of anions in solution. The system presented enables the development of homogeneous or heterogeneous molecular anion sensors with possible applications in chemistry, bio‐medical scenarios, and under harsh environmental conditions.
Divergent Iron‐Catalyzed Coupling of O‐Acyloximes with Silyl Enol Ethers
Authors: Yang Hai‐Bin , Selander Nicklas
Published: December 2016

An iron‐catalyzed coupling reaction of O‐acyloximes and O‐benzoyl amidoximes with silyl enol ethers is reported. The protocol provides access to functionalized pyrroles, 1,6‐ketonitriles, pyrrolines and imidazolines via carbon‐centered radicals generated from an initially formed iminyl radical. The intramolecular cyclization and ring‐opening processes of the iminyl radical take place preferentially over reactions that proceed through a 1,3‐hydrogen transfer, providing insights into iron‐catalyzed reactions with oxime derivatives. The cheap and environmentally friendly iron catalyst, the broad substrate scope and the functional group compatibility make this protocol useful for synthesis of valuable nitrogen‐containing products.
Design, Synthesis and Insecticidal Evaluation of Anthranilic Diamides Containing Optically Pure Amino Acid Moiety
Authors: Zhou Shaa , Zhou Sha , Hua Xuewen , Wei Wei , Xie Yongtao , Chen Minggui , Meng Xiangde , Liu Ming , Xiong Lixia , Yang Na , Wang Baolei , Li Zhengming
Published: December 2016

Two series of N‐pyridylpyrazolecarboxamide derivatives were designed and synthesized by introducing D‐alanine acid esters and D‐serine acid esters into the skelecton of chlorantraniliprole. The obtained structures were characterized by 1H NMR, 13C NMR, elemental analysis and specific optical rotation analysis. Preliminary bioassays indicated that some compounds displayed excellent insecticidal activities against Mythimna separate and Plutella xylostella in comparison with chlorantraniliprole. In particular, IIq showed excellent insecticidal activity against Plutella xylostella with a mortality rate of 90% at 0.01 mg·L−1. A 3D‐QSAR (CoMSIA) study was performed in order to disclose the insecticidal structure‐activity relationship and indicate the future work. The CoMSIA study demonstrated that large substitutes and electron deficient groups at the 3‐position of pyrazole ring are favorable, the same as a small group near the ester groups of amino acid.
Praseodymium Oxide Modified CeO2/Al2O3 Catalyst for Selective Catalytic Reduction of NO by NH3
Authors: Jin Qijie , Shen Yuesong , Zhu Shemin
Published: December 2016

A series of CeO2/Al2O3 catalysts was modified with praseodymium oxide using an extrusion method. The catalytic activities of the obtained catalysts were measured for the selective catalytic reduction of NO with NH3 to screen suitable addition of praseodymium oxide. These samples were characterized by XRD, N2‐BET, NH3‐TPD, NO‐TPD, Py‐IR, H2‐TPR, Raman spectra and XPS, respectively. Results showed the optimal catalyst with the Pr/Ce molar ratio of 0.10 exhibited more than 90% NO conversion in a wide temperature range of 290–425°C under GHSV of 5000 h−1. The number of Lewis acid sites and the chemisorbed oxygen concentration of the catalysts would increase with the Pr incorporation, which was favorable for the excellent catalytic performance. In addition, the Pr incorporation inhibited growth of the Al2O3 crystal particles and led to the lattice expansion of CeO2, which increased catalytic activity. The results implied that the higher chemisorbed oxygen concentrations and the more Lewis acid sites were conductive to obtain the excellent SCR activity.
Novel Fluorescent Chemosensor for Detection of F− Anions Based on a Single Functionalized Pillar[5]arene Iron(III) Complex
Authors: Zhang Youming , Su Junxia , Li Qiao , Li Wenting , Liang Guoyan , Li Hui , Ma Haixia , Lin Qi , Yao Hong , Wei Taibao
Published: December 2016

Novel fluorescent chemosensor with good selectivity for F− anion was designed and synthesized. The sensor has a bearing on a single functionalized pillar[5]arene and Fe3+ metal complex (PN‐Fe), which showed prominent fluorescent response for F− anion over other common anions (Cl−, Br−, I−, AcO−, HSO4−, H2PO4−, ClO4−, CN− and SCN−). These results were evaluated by fluorescent method. The detection limit of PN‐Fe to F− was calculated to be 2.50×10−7 mol/L. Moreover, the sensor PN‐Fe3+ might serve as a recyclable component in sensing materials.
Photodynamic Therapy Activities of 10‐(4‐Formylphenyl)‐5,15‐bis(pentafluorophenyl)corrole and Its Gallium Complex
Authors: Cheng Fan , Huang Liting , Wang Huahua , Liu Yunjun , Kandhadi Jaipal , Wang Hui , Ji Liangnian , Liu Haiyang
Published: December 2016

10‐(4‐Formylphenyl)‐5,15‐bis(pentafluorophenyl)corrole 1 and its gallium complex 1‐Ga were used to investigate their photocytotoxicity in liver cancer (BEL‐7402), lung cancer (A549) and cervical cancer (Siha, Hela) cell lines. Among all the tested tumor cells, Siha tumor cells were the most sensitive to photodynamic therapy (PDT) treatment by 1 and 1‐Ga. PDT IC50 of 1 and 1‐Ga toward Siha tumor cell reaches 1.3 and 0.8 µmol/L respectively, which is 10‐fold higher than that of cisplatin. 1 and 1‐Ga might pass across the tumor cell membrane smoothly without the help of carrier protein, and mainly localized in the cytoplasm of tumor cell. After PDT treatment, the intracellular reactive oxygen species (ROS) level increased and the mitochondrial membrane potential decreased significantly, which would finally result in the apoptosis of tumor cells.
Descending projections from the basal forebrain to the orexin neurons in mice
Authors: Agostinelli Lindsay J. , Ferrari Loris L. , Mahoney Carrie E. , Mochizuki Takatoshi , Lowell Bradford B. , Arrigoni Elda , Scammell Thomas E.
Published: December 2016

The orexin (hypocretin) neurons play an essential role in promoting arousal, and loss of the orexin neurons results in narcolepsy, a condition characterized by chronic sleepiness and cataplexy. The orexin neurons excite wake‐promoting neurons in the basal forebrain (BF), and a reciprocal projection from the BF back to the orexin neurons may help promote arousal and motivation. The BF contains at least three different cell types (cholinergic, glutamatergic, and γ‐aminobutyric acid (GABA)ergic neurons) across its different regions (medial septum, diagonal band, magnocellular preoptic area, and substantia innominata). Given the neurochemical and anatomical heterogeneity of the BF, we mapped the pattern of BF projections to the orexin neurons across multiple BF regions and neuronal types. We performed conditional anterograde tracing using mice that express Cre recombinase only in neurons producing acetylcholine, glutamate, or GABA. We found that the orexin neurons are heavily apposed by axon terminals of glutamatergic and GABAergic neurons of the substantia innominata (SI) and magnocellular preoptic area, but there was no innervation by the cholinergic neurons. Channelrhodopsin‐assisted circuit mapping (CRACM) demonstrated that glutamatergic SI neurons frequently form functional synapses with the orexin neurons, but, surprisingly, functional synapses from SI GABAergic neurons were rare. Considering their strong reciprocal connections, BF and orexin neurons likely work in concert to promote arousal, motivation, and other behaviors. J. Comp. Neurol. 525:1668–1684, 2017. © 2016 Wiley Periodicals, Inc.
Decomposition of Imidazolium‐Based Ionic Liquids in Contact with Lithium Metal
Authors: Schmitz Paulo , Jakelski Rene , Pyschik Marcelina , Jalkanen Kirsi , Nowak Sascha , Winter Martin , Bieker Peter
Published: December 2016

Ionic liquids (ILs) are considered to be suitable electrolyte components for lithium‐metal batteries. Imidazolium cation based ILs were previously found to be applicable for battery systems with a lithium‐metal negative electrode. However, herein it is shown that, in contrast to the well‐known IL N‐butyl‐N‐methylpyrrolidinium bis[(trifluoromethyl)sulfonyl]imide ([Pyr14][TFSI]), 1‐ethyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C2MIm][TFSI]) and 1‐butyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C4MIm][TFSI]) are chemically unstable versus metallic lithium. A lithium‐metal sheet was immersed in pure imidazolium‐based IL samples and aged at 60 °C for 28 days. Afterwards, the aged IL samples were investigated to deduce possible decomposition products of the imidazolium cation. The chemical instability of the ILs in contact with lithium metal and a possible decomposition starting point are shown for the first time. Furthermore, the investigated imidazolium‐based ILs can be utilized for lithium‐metal batteries through the addition of the solid–electrolyte interphase (SEI) film‐forming additive fluoroethylene carbonate.
One‐Pot Anchoring of Pd Nanoparticles on Nitrogen‐Doped Carbon through Dopamine Self‐Polymerization and Activity in the Electrocatalytic Methanol Oxidation Reaction
Authors: Li Xin , Niu Xiangheng , Zhang Wenchi , He Yanfang , Pan Jianming , Yan Yongsheng , Qiu Fengxian
Published: December 2016

Exploration of advanced electrocatalysts to promote the sluggish methanol oxidation reaction (MOR) is of vital importance for developing high efficiency and low‐cost direct methanol fuel cells. Highly dispersed palladium nanoparticles (Pd NPs) anchored on a nitrogen‐doped carbon support were fabricated using a facile one‐pot dopamine self‐polymerization mediated redox strategy, in which dopamine not only acted as a moderate reductant to induce the formation of Pd NPs during self‐polymerization but was also the precursor of the nitrogen‐doped carbon support for Pd. The synthesized hybrid features the following characteristics: 1) High dispersity of Pd NPs, which exposed a high abundance of active surfaces and sites for heterogeneous electrocatalysis; 2) metal‐support interactions, which may affect the surface chemistry and electron distribution of active Pd NPs; 3) the Pd NPs were partially imbedded or encapsulated into the support, thus reducing the possible agglomeration of Pd NPs during cyclic measurements. The electrocatalyst with such favorable features provided higher mass activity (2.2 times that of commercial Pd/C) and better durability (reduced loss of activity during simulated frequent startup–shutdown operations) for the MOR in alkaline media.
Comprehensive Mass Cytometry Analysis of Cell Cycle, Activation, and Coinhibitory Receptors Expression in CD4 T Cells from Healthy and HIV‐Infected Individuals
Authors: Corneau Aurélien , Cosma Antonio , Even Sophie , Katlama Christine , Le Grand Roger , Frachet Véronique , Blanc Catherine , Autran Brigitte
Published: December 2016

Rationale

Mass cytometry allows large multiplex analysis of cell cycle stages together with differentiation, activation, and exhaustion markers, allowing further assessment of the quiescence status of resting CD4 T cells.

Methods

Peripheral blood CD4 T lymphocytes from 8 individuals, 4 healthy donors, and 4 HIV‐infected on antiretroviral treatment (T) were stained with the same 26 monoclonal antibodies and dyes targeting surface and intracellular markers of differentiation, activation, exhaustion, and cell cycle stages. Samples were run on a CYTOF‐2.

Results

Patterns of naïve [TN] CD4 T cells strongly differed from all other memory subsets central‐memory (CM), transitional‐memory (TM), effector‐memory (EM), and terminally differentiated RA‐expressing (TEMRA) subsets, while stem‐cell memory (SCM) and T follicular‐helper cells (TfH) were close to CM and TM cells with the highest percentages in cell cycle. EM and TEMRA were the most altered by HIV infection, with an increased frequency of activated and cycling cells. Activation markers and coinhibitory receptor expression differed among cell cycle stages, with HLA‐DR fitting better than CD25 or CD38 with cycle, and opposite PD‐1 gradients along differentiation and cell cycle. “Resting” DR‐CD25‐ CD4+ T cells contained similar amounts of cells in G1 than the activated DR ± CD25± ones but three fold lower cells in S‐G2‐M.

Conclusion

This broad multiplex mass cytometry analysis demonstrates some subsets of the so‐called “resting” CD25‐DR‐ CD4+ T cells contain noticeable amounts of cells into cycle or expressing coinhibitory receptors, opening new avenues for a redefinition of resting peripheral blood CD4 T cells harboring the HIV reservoirs. © 2016 International Clinical Cytometry Society
Limits on carbon sequestration in arid blue carbon ecosystems
Authors: Schile Lisa M. , Kauffman J. Boone , Crooks Stephen , Fourqurean James W. , Glavan Jane , Megonigal J. Patrick
Published: December 2016

Coastal ecosystems produce and sequester significant amounts of carbon (“blue carbon”), which has been well documented in humid and semi‐humid regions of temperate and tropical climates but less so in arid regions where mangroves, marshes, and seagrasses exist near the limit of their tolerance for extreme temperature and salinity. To better understand these unique systems, we measured whole‐ecosystem carbon stocks in 58 sites across the United Arab Emirates (UAE) in natural and planted mangroves, salt marshes, seagrass beds, microbial mats, and coastal sabkha (inter‐ and supratidal unvegetated salt flats). Natural mangroves held significantly more carbon in above‐ and belowground biomass than other vegetated ecosystems. Planted mangrove carbon stocks increased with age, but there were large differences for sites of similar age. Soil carbon varied widely across sites (2–367 Mg C/ha), with ecosystem averages that ranged from 49 to 156 Mg C/ha. For the first time, microbial mats were documented to contain soil carbon pools comparable to vascular plant‐dominated ecosystems, and could arguably be recognized as a unique blue carbon ecosystem. Total ecosystem carbon stocks ranged widely from 2 to 515 Mg C/ha (seagrass bed and mangrove, respectively). Seagrass beds had the lowest carbon stock per unit area, but the largest stock per total area due to their large spatial coverage. Compared to similar ecosystems globally, mangroves and marshes in the UAE have lower plant and soil carbon stocks; however, the difference in soil stocks is far larger than with plant stocks. This incongruent difference between stocks is likely due to poor carbon preservation under conditions of weakly reduced soils (200–350 mV), coarse‐grained sediments, and active shoreline migration. This work represents the first attempt to produce a country‐wide coastal ecosystem carbon accounting using a uniform sampling protocol, and was motivated by specific policy goals identified by the Abu Dhabi Global Environmental Data Initiative. These carbon stock data supported two objectives: to quantify carbon stocks and infer sequestration capacity in arid blue carbon ecosystems, and to explore the potential to incorporate blue carbon science into national reporting and planning documents.
Functional community structure of African monodominant Gilbertiodendron dewevrei forest influenced by local environmental filtering
Authors: Kearsley Elizabeth , Verbeeck Hans , Hufkens Koen , Van de Perre Frederik , Doetterl Sebastian , Baert Geert , Beeckman Hans , Boeckx Pascal , Huygens Dries
Published: December 2016

Monodominant patches of forest dominated by Gilbertiodendron dewevrei are commonly found in central African tropical forests, alongside forests with high species diversity. Although these forests are generally found sparsely distributed along rivers, their occurrence is not thought to be (clearly) driven by edaphic conditions but rather by trait combinations of G. dewevrei that aid in achieving monodominance. Functional community structure between these monodominant and mixed forests has, however, not yet been compared. Additionally, little is known about nondominant species in the monodominant forest community. These two topics are addressed in this study. We investigate the functional community structure of 10 one‐hectare plots of monodominant and mixed forests in a central region of the Congo basin, in DR Congo. Thirteen leaf and wood traits are measured, covering 95% (basal area weighted) of all species present in the plots, including leaf nutrient contents, leaf isotopic compositions, specific leaf area, wood density, and vessel anatomy. The trait‐based assessment of G. dewevrei shows an ensemble of traits related to water use and transport that could be favorable for its location near forest rivers. Moreover, indications have been found for N and P limitations in the monodominant forest, possibly related to ectomycorrhizal associations formed with G. dewevrei. Reduced leaf N and P contents are found at the community level for the monodominant forest and for different nondominant groups, as compared to those in the mixed forest. In summary, this work shows that environmental filtering does prevail in the monodominant G. dewevrei forest, leading to lower functional diversity in this forest type, with the dominant species showing beneficial traits related to its common riverine locations and with reduced soil N and P availability found in this environment, both coregulating the tree community assembly.
Habitat–performance relationships of a large mammal on a predator‐free island dominated by humans
Authors: Allen Andrew M. , Dorey Augusta , Malmsten Jonas , Edenius Lars , Ericsson Göran , Singh Navinder J.
Published: December 2016

The demographic consequences of changes in habitat use driven by human modification of landscape, and/or changes in climate, are important for any species. We investigated habitat–performance relationships in a declining island population of a large mammal, the moose (Alces alces), in an environment that is predator‐free but dominated by humans. We used a combination of demographic data, knowledge of habitat selection, and multiannual movement data of female moose (n = 17) to understand how space use patterns affect fecundity and calf survival. The calving rate was 0.64 and was similar to calving rates reported in other populations. Calf survival was 0.22 (annually) and 0.32 (postsummer), which are particularly low compared to other populations where postsummer survival is typically above 0.7. Home ranges were mainly composed of arable land (>40%), and selection for arable land was higher in winter than in summer, which contrasts with previous studies. Females that spent more time in broadleaf forest in the summer prior to the rut had higher fecundity rates, while more time spent in arable land resulted in lower fecundity rates. Females that spent more time in thicket/scrubland habitats during winter had lower calf survival, while females that had higher use of mixed forests tended to have higher calf survival. The dominance, and subsequent use, of suboptimal foraging habitats may lead to poor body condition of females at parturition, which may lower calf body weights and affect the mother's ability to lactate. In addition, our results indicated that the growing season has advanced significantly in recent decades, which may be causing a mismatch between parturition and optimal resource availability. These effects may exacerbate the female's ability to meet the energetic demands of lactation. Therefore, the observed low calf survival appears to be caused by a combination of factors related to current land use and may also be due to changing vegetation phenology. These results have important implications for the management of species in human‐dominated landscapes in the face of climate change, and for an increased understanding of how species may adapt to future land use and climate change.