bluuebunny/crossref_metadata_2025 huggingface dataset:
Problemas eclesiásticos de la Luisiana tras su cesión a España
Authors: Armillas Vicente José A.
Published: June 2012

En 1793 el papa Pío VI eregía la Diócesis de la Luisiana y Florida a instancia de la Corona española. La situación geoestratégica de la Florida, requería una política particular para afincar una población estable ante las reiteradas agresiones inglesas.
La polémica interna en la Iglesia Católica Argentina a la luz de la pastoral del obispo de Calahorra (1941-1942)
Authors: Ben-Dror Graciela
Published: June 2012

El artículo analiza el impacto de la pastoral de Fidel García, obispo de Calahorra (España) sobre algunos errores contemporáneos, entre los que destacaba el nazismo. Los demócrata cristianos argentinos y su periódico Orden Cristiano la utilizaron frente al monolitismo anticomunista de otra prensa católica, como El Pueblo.La A. estudia la polémica entre ellos.
El Beato del archivo histórico provincial de Zamora
Authors: Suárez González Ana
Published: June 2012

Los fragmentos 276 y 277 del A.H.P. de Zamora son los testigos de un nuevo códice del Comentario al Apocalipsis atribuido a Beato de Liébana. El Beato al que pertenecen, en escritura visigótica, puede datarse en la primera mitad del siglo X. El presente trabajo recoge el análisis externo e interno de ambas piezas y la edición de su texto, cotejado con el de los restantes ejemplares visigóticos, para situar el volumen al que remiten en el stemma de los beatos conocidos hasta la fecha.
La revisión del concordato de 1953: la reunión entre Casaroli y López Rodó (noviembre de 1973)
Authors: Martín de Santa Olalla Saludes Pablo
Published: June 2012

El Concilio Vaticano II constituyó un impulso decisivo para la transformación de la relación Iglesia-Estado en España. El Concordato de 1953, que era el marco jurídico que regulaba la relación entre el catolicismo y el Régimen de Franco, hubo de ser renegociado al haber quedado anacrónico. Ante una creciente tensión entre ambos poderes, la llegada al ministerio de Asuntos Exteriores de Laureano López Rodó hizo posible la celebración de un primer encuentro tras el fracaso del llamado Anteproyecto Casaroli-Garrigues en febrero de 1971.
1868 en la memoria carlista de 1931: dos revoluciones anticlericales y un paralelo
Authors: Moral Roncal Antonio Manuel
Published: June 2012

El presente artículo analiza la cuestión religiosa en 1868 y, especialmente, 1931 prestando atención central al papel que ésta tuvo como elemento de ruptura y factor movilizador de la reacción contrarrevolucionaria que el carlismo lideró en España durante la Segunda República.
Propiedades eclesiásticas en una ciudad aduanera: los jesuitas en Orduña, 1689-1767
Authors: Porres Marijuán Rosario
Published: June 2012

El colegio de los jesuitas de Orduña, uno de los más tardíos de todo el País Vasco, sigue en su fundación un patrón característico en los casos de mecenazgo indiano: benefactor oriundo, capital consolidado sobre el comercio y el servicio de la Corona, y diseño dirigido desde el otro lado del Atlántico, en este caso desde el Perú. El presente artículo aporta algunas claves sobre esas cuestiones, y ahonda en la formación del patrimonio que la Compañía de Jesús logró reunir en esta ciudad aduanera del Señorío de Vizcaya hasta el momento de la expulsión decretada por el rey Carlos III.
Review of KoreanLatibulus(Hymenoptera: Ichneumonidae: Cryptinae) and a key to the world species
Authors: Oh Seung-Ho , An Seung-Lak , Lee Jong-Wook
Published: June 2012

The Korean species of the genusLatibulusGistel (Hymenoptera: Ichneumonidae) are reviewed. Two new species and a key to nine species are presented:Latibulus argiolus(Rossi),Latibulus bilacunitusSheng and Xu,Latibulus flavopetiolusOh and Lee new species,Latibulus fulvusOh and Lee new species,Latibulus hokkaidensisLee and Oh,Latibulus lautus(Tosquinet),Latibulus liaoningensisShenget al.,Latibulus nigrinotum(Uchida), andLatibulus orientalisHorstmann. The genus is reported from Mongolia for the first time, based on the cocoon of an unidentified species.Polistes chinensis antennalisPérez andPolistes jadwigae jadwigaeDalla Torre (Hymenoptera: Vespidae) are reported as new host species for the genus andL. nigrinotum, respectively.
Quality control procedures at Euskalmet data center
Authors: Hernández R. , Maruri M. , Otxoa de Alda K. , Egaña J. , Gaztelumendi S.
Published: June 2012

Abstract. The Basque Country Mesonet measures more than 130 000 observations daily from its 85 Automatic Weather Stations (AWS). It becomes clear that automated software is an indispensable tool for quality assurance (QA) of this mesoscale surface observing network. This work describes a set of experimental semi-automatic quality control (QC) routines that is applied at Euskalmet data center. It has paid special attention to level validation design and associated flags, as well as to the system outputs, which are used by meteorologist and maintenance staff.
Circulating Tumor Cells and Extracellular Nucleic Acids in Breast Cancer
Authors: Ryu Dong Won , Lee Chung Han
Published: June 2012

Circulating tumor cells (CTCs) are defined as tumor cells circulating in the peripheral blood of patients, shed from either the primary tumor or from its metastases. The detection of circulating tumor cells (CTCs) in the peripheral blood of breast cancer patients may account for the different steps in the biologic progression of the disease. The detection of microscopic disease in patients with breast cancer is imperative to prognosis and can predict the efficacy of targeted treatments. In general, there are two main methods for their detection. These are based on cytometric and nucleic acid manipulation. Both methods generally require an enrichment step to increase sensitivity of the assay. This step is based on either detection of specific surface markers using immuno-selection and/or on morphological features, such as cell size or density. We review the methods of detecting CTCs, their prognostic implications, and opportunities to exploit the properties of CTCs to develop personalized therapy.
Degree of Agreement between Phadia EliA ENA and Euroimmun line Immunoassay; Comparison of Two Methods to Evaluate the Ability to Detect ENA Antibodies
Authors: Hwang Hyun Yong
Published: June 2012

Objectives
 The purpose of this study is to compare newly developed assay for identification of ENA antibody, Phadia EliA ENA with Euroimmun line immunoassay by analyzing the degree of agreement and the individual antibodies between two methods.

Methods
 A total of 82 patient samples were used. Indirect immunofluorescence assay using Hep-2 cell was performed to screen the antinuclear antibody (ANA). Euroimmun line immunoassay (LIA) and Phadia EliA ENA assay were tested to identify the antibodies against extractable nuclear antigens (ENAs). Kappa statistics was used to evaluate the degree of agreement.

Results
 Mean age of patients was 41.0 (8-79), and the M:F ratio was 21:61. ANA was positive in 74 samples, and negative were 8 samples. Kappa analysis of the 82 tested samples showed a moderate strength of agreement (κ = 0.521, P = 0.000). There were differences in the order of identified individual antibodies between two methods (Ro > La = RNP > Centromere > Sm > Scl-70 in Phadia EliA ENA, Ro > RNP > Sm>La > Scl-70 > Centromere=Jo-1 in Euroimmun LIA). Ro antibody was most frequently identified in Phadia EliA ENA negative-Euroimmun LIA positive specimens (Ro > RNP = Jo-1 > La = Sm = Centromere > Scl-70).

Conclusions
 A moderate strength of agreement was observed between the Phadia EliA ENA and the Euroimmun LIA. There seemed to be a significant difference in the ratio of individual antibodies, especially in the anti-Ro and Sm antibodies.
Clinical Outcome of Positive Margin of Postgastrectomy with Adenocarcinoma of Stomach
Authors: Yang Song-I , Lee Sang-Ho
Published: June 2012

Objectives
 Many investigators have recommended adequate resection margin and lymphadenectomy for radical curative resection. The aim of this study is to evaluate clinical characteristics of positive resection margin (proximal or distal) of postgastrectomy in advanced gastric cancer.

Methods
 We studied 17 patients with gastric cancer who were diagnosed positive resection margin by intraoperative frozen biopsy or permanent biopsy report from January 2005 to December 2007, retrospectively. Surgical margin monitored by endoscopy.

Results
 Distal gastrectomy was performed in 13 patients and total gastrectomy in 4. Gastrectomy with combined resection including splenectomy was performed in 3, distal pancreatectomy in 2, transverse colon segmental resection in 1, and cholecystectomy in 2. Positive Proximal margin was found in 12, positive distal margin in 3, and both in 2. Palliative chemotherapy was performed in 8 patients. Postoperative follow up endoscopy was established in only 8 patients. Malignant results from endoscopic biopsy in gastroenteric or esophagoenteric anastomotic line were proven in 2 patients during follow up. 9 patients were not performed follow-up endoscopy. Among total 17 patients, 2 patients are alive. Fifteen patients died of aggravation of disease in 13 and postoperative complication in 2.

Conclusions
 Although positive surgical margin in far advanced gastric cancer were found, it can consider that does not further resection to obtain microscopic clear anastomotic margin.
A Case of Henoch Schönlein Purpura with Gastrointestinal Bleeding Due to Jejunal Ulcer by Capsule Endoscopy
Authors: Lee Yong Kang , Oh Tak Keun , Choi Ara , Lee Ji Hoon , Kim Mi Na , Hong Sung Pil
Published: June 2012

Henoch-Schönlein purpura (HSP) is the most common form of systemic vasculitis in children. Palpable purpura, arthralgia, arthritis, abdominal pain and renal involvement are the major clinical manifestations. Gastrointestinal involvement is related with abdominal pain and bleeding. We described a 71 year-old female experienced acute exacerbation of HSP presented with gastrointestinal bleeding. She was hospitalized for hematemesis and diagnosed duodenitis by esophagogastroduonenoscopy (EGD). Duodenitis was improved at EGD checked in 7 days. She still complained of melena and abdominal pain. There were no abnormal findings at sigmoidoscopy. Jejunal ulcer and purpura were diagnosed by capsule endoscopy. Symptoms were relieved after administration of systemic steroid. But she needed renal replacement therapy for 3 months. Small bowel ulcer diagnosed by capsule endoscopy in patients with HSP was rarely described in Korean literature. This case suggests that capsule endoscopy have a role in diagnosis of small bowel ulcer and its severity in HSP with gastrointestinal symptom.
Your Genes, Your Health and Personalised Medicine
Authors: Michaelis R. C. , Sweet K. M.
Published: June 2012

We are fast approaching the era of personalised medicine, in which we will each be able to know our level of risk for many diseases, and medical treatments will be tailored to fit the individual, rather than treating all patients who have the same disorder in the same manner. This book is intended to help you understand how your genes influence your health.
Anatomy for Problem Solving in Sports Medicine
Authors: Harris Philip , Ranson Craig
Published: June 2012

The Authors of this book are an anatomist and a sports physiotherapist with wide experience who both teach sports injury related university courses. Because of its critical location in the body and its many components, diagnosing, managing and rehabilitating sport related back injury is extremely challenging and requires a detailed knowledge of the associated anatomy. In this book the general and specific structures of the back, including the cervical, thoracic and lumbo-sacral spine, are presented and illustrated as a basis for clinical practice. Since clinical signs and symptoms require correct interpretation for an accurate diagnosis and effective management, a special feature of this book is to include detailed case histories showing how knowledge of back anatomy can be used to arrive at a correct diagnosis. This book will therefore be of benefit to a wide range of professionals concerned with sports disorders and injuries.
Models for Delamination
Authors: König Manfred , D'Ottavio Michele
Published: June 2012

The chapter reviews some aspects of the broad and complex problem of delamination in composites. The focus is put on computational models for delamination predictions in the framework of a damage tolerance design. Both delamination initiation and its propagation under quasi‐static and cyclic loading are addressed, and their simulation by means of the Finite Element Method (FEM) is discussed. However, dynamic delamination propagation under impact loads, as well as the prediction of the effect of delamination on the ultimate failure, is not considered in this chapter.

Basically, two modeling approaches are reviewed, namely Linear Elastic Fracture Mechanics (LEFM) in the form of the Virtual Crack Closure Technique (VCCT) and Continuum Damage Mechanics (CDM) applied to interface problems, that is, Cohesive Zone Models. Both approaches have recently been implemented in commercially available FE software. A summary of the respective peculiarities and limitations is presented. The significance of 2D laminated plate/shell elements that ensure the capturing of relevant through‐thickness effects is emphasized.

The authors believe that a comprehensive knowledge of where obsolescence can strike and how to plan to manage obsolescence must be incorporated into the earliest stages of design.
Structural Design: Weight Estimation
Authors: Elham Ali
Published: June 2012

Weight estimation and calculation of aircraft structural and nonstructural weight is an important aspect of the aircraft design process. The estimation and calculation process is built on an aircraft weight breakdown method. The weight breakdown process is discussed based on several examples, with a focus on the structural weight breakdown principles. The weight estimation methods are categorized in four different classes. The low‐class methods are based on statistical data to estimate the structural weight while the high‐class methods use physics‐based calculations like beam theory and finite element modeling complemented with empirical methods to estimate the weight of the nonstructural parts. Statistical weight estimation methods are usually used in the early design stages when the knowledge of designers about the new aircraft is limited and the weight estimation process has to rely on previous experience. When the design matures there is an increasing understanding of the design and higher class weight estimation methods can be used. In the final design phase, weight estimation transfers into weight calculation.
Meshfree Methods
Authors: Li Shaofan , Ren Bo
Published: June 2012

In this chapter, we briefly discuss the basic concepts, methodology, applications, and the history of meshfree methods. In particular, we have discussed a few representatives of meshfree method, such as the smoothed particle hydrodynamics (SPH) and the reproducing kernel particle method (PKPM). The chapter is intended as a short introduction to meshfree methods, which may serve as starting reference point for anyone who may be interested in studying the method as well as applying the method to solve engineering problems.
Chromium: Biological Relevance
Authors: Lay Peter A. , Levina Aviva
Published: June 2012

Despite popular claims in nutritional literature, there is no definitive evidence that chromium (Cr) is an essential element for human or animal nutrition. No functional Cr‐containing biomolecules have been unambiguously characterized thus far, and no Cr deficiency disease is known. The use of Cr supplementation (commonly in the form of Cr(III) picolinate) has been proved to be inefficient in improving glucose metabolism in nondiabetic humans, but pharmacological doses of Cr(III) may assist in the treatment of diabetes and related diseases. While Cr(III) complexes are relatively nontoxic because of their poor bioavailability, the oxidized form, Cr(VI), is a proven human carcinogen and a significant environmental pollutant. There is mounting evidence that the antidiabetic activity of Cr(III) complexes is caused by the formation of high‐oxidation‐state (Cr(VI) or Cr(V)) species during the reactions with biological oxidants (e.g. H
2
O
2
or ClO
−
) in blood plasma, rather than by a specific Cr(III)‐containing biomolecule. This hypothesis explains the efficacy of Cr(III) in poorly controlled diabetes, which is linked to oxidative stress. The changing views on the biological role of Cr(III), combined with its rather weak and variable antidiabetic activity, as well as safety concerns over the likely formation of carcinogenic Cr(VI) as a Cr(III) metabolite, mean that the promotion of Cr(III) compounds as nutritional supplements or antidiabetics may need to be reassessed.
C
us
BA
Heavy‐Metal Efflux Complex of Escherichia Coli
Authors: Su Chih‐Chia , Long Feng , Yu Edward W
Published: June 2012

Gram‐negative bacteria, such as
Escherichia coli
, expel toxic chemicals via tripartite efflux pumps spanning both the inner and outer membranes. The three parts are: (i) a membrane fusion protein connecting (ii) a substrate‐binding inner membrane transporter to (iii) an outer membrane‐anchored channel in the periplasmic space. A crystallographic model of this tripartite efflux complex has been unavailable simply because co‐crystallization of different components of the system has proven to be extremely difficult. Previously, the crystal structures of both the inner membrane transporter CusA and membrane fusion protein CusB of the CusCBA tripartite efflux system from
E. coli
have been described. In addition, the co‐crystal structure of the CusBA adaptor‐transporter heavy‐metal efflux complex has been determined, revealing that the trimeric CusA efflux pump interacts with six CusB protein molecules at the upper half of the periplasmic domain. These six CusB protomers form a channel extending contiguously from the top of the pump. On the basis of the structural information, a three‐dimensional model of the CusCBA tripartite efflux assemblage was developed. This CusC3–CusB6–CusA3 model presents a 750 kDa efflux complex that spans the entire bacterial cell envelope of
E. coli
whose cellular role is to export Cu(I) and Ag(I) ions. Here, we summarize the structural information of these efflux proteins, and present the accumulated evidence that this efflux system utilizes methionine residues to bind and export Cu(I) and Ag(I).
Emerging Applications of Atomic Layer Deposition for Lithium‐Ion Battery Studies
Authors: Meng Xiangbo , Yang Xiao‐Qing , Sun Xueliang
Published: June 2012

Lithium‐ion batteries (LIBs) are used widely in today's consumer electronics and offer great potential for hybrid electric vehicles (HEVs), plug‐in HEVs, pure EVs, and also in smart grids as future energy‐storage devices. However, many challenges must be addressed before these future applications of LIBs are realized, such as the energy and power density of LIBs, their cycle and calendar life, safety characteristics, and costs. Recently, a technique called atomic layer deposition (ALD) attracted great interest as a novel tool and approach for resolving these issues. In this article, recent advances in using ALD for LIB studies are thoroughly reviewed, covering two technical routes: 1) ALD for designing and synthesizing new LIB components, i.e., anodes, cathodes, and solid electrolytes, and; 2) ALD used in modifying electrode properties via surface coating. This review will hopefully stimulate more extensive and insightful studies on using ALD for developing high‐performance LIBs.
Symmetric and Asymmetric Zeolitic Imidazolate Frameworks (ZIFs)/Polybenzimidazole (PBI) Nanocomposite Membranes for Hydrogen Purification at High Temperatures
Authors: Yang Tingxu , Shi Gui Min , Chung Tai‐Shung
Published: June 2012

High‐performance zeolitic imidazolate frameworks (ZIFs)/polybenzimidazole (PBI) nanocomposites are molecularly designed for hydrogen separation at high temperatures, and demonstrate it in a useful configuration as dual‐layer hollow fibers for the first time. By incorporating as‐synthesized nanoporous ZIF‐8 nanoparticles into the high thermal stability but extremely low permeability polybenzimidazole (PBI), the resultant mixed matrix membranes show an impressive enhancement in H2 permeability as high as a hundred times without any significant deduction in H2/CO2 selectivity. The 30/70 ZIF‐8/PBI dense membrane has a H2 permeability of 105.4 Barrer and a H2/CO2 selectivity of 12.3. This performance is far superior to ZIF‐7/PBI membranes and is the best ever reported data for H2‐selective polymeric materials in the literature. Meanwhile, defect‐free ZIF‐8‐PBI/Matrimid dual‐layer hollow fibers are successfully fabricated, without post‐annealing and coating, by optimizing ZIF‐8 nanoparticle loadings, spinning conditions, and solvent‐exchange procedures. Two types of hollow fibers targeted at either high H2/CO2 selectivity or high H2 permeance are developed: i) PZM10‐I B fibers with a medium H2 permeance of 64.5 GPU (2.16 ×10−8 mol m−2 s−1 Pa−1) at 180°C and a high H2/CO2 selectivity of 12.3, and, ii) PZM33‐I B fibers with a high H2 permeance of 202 GPU (6.77 ×10−8 mol m−2 s−1 Pa−1) at 180°C and a medium H2/CO2 selectivity of 7.7. This work not only molecularly designs novel nanocomposite materials for harsh industrial applications, such as syngas and hydrogen production, but also, for the first time, synergistically combines the strengths of both ZIF‐8 and PBI for energy‐related applications.
Titania‐Coated Metal Nanostructures
Authors: Seh Zhi Wei , Liu Shuhua , Han Ming‐Yong
Published: June 2012

The synergistic effect between metal and TiO2 nanoparticles brings about new, enhanced functionalities for a myriad of applications, ranging from labeling and sensing to catalysis and surface‐enhanced Raman scattering. Although extensive work has been done in the preparation of concentric TiO2‐coated metal nanostructures, current methods for the synthesis of noncentrosymmetric morphologies are still very limited. This Focus review summarizes the various methods used to prepare TiO2‐coated metal nanostructures, with a particular emphasis on noncentrosymmetric morphologies, their novel plasmonic properties, and their promising applications in the fields of catalysis and photocatalysis.
Improved rehandling strategies for the container retrieval process
Authors: Ünlüyurt Tonguç , Aydın Cenk
Published: June 2012

The breakdown of trade barriers among countries led to an enormous increase in the volume of international trade. Consequently, the amount of bulk cargo carried in containers and transported overseas exploded because of flexibility and reliability of this type of transportation. So, the efficiency in container terminals has emerged as a major problem. In this work, we deal with an operational problem in container terminals. We try to develop strategies to minimize the total time required to retrieve the containers from a bay in a predetermined sequence. The problem is solved optimally using a branch and bound‐based algorithm, and alternative heuristics that give near‐optimal solutions are proposed. Copyright © 2012 John Wiley & Sons, Ltd.
Simultaneous determination of vitexin and isovitexin in rat plasma after oral administration of Santalum album L. leaves extract by liquid chromatography tandem mass spectrometry
Authors: Yan Chong , Liu Hongju , Lin Li
Published: June 2012

An LC‐MS/MS method was developed for the simultaneous determination of vitexin and isovitexin in rat plasma, using puerarin as the internal standard (IS). Plasma samples extracted with protein precipitation procedure were separated on a Diamonsil® C18 column (150 × 4.6 mm, 5 µm) with a mobile phase composed of methanol and 0.1% formic acid (45:55, v/v). The detection was accomplished by multiple reaction monitoring mode in positive electrospray ionization source. The optimized mass transition ion‐pairs for quantitation were m/z 431.2 → 311.1 for vitexin and isovitexin, and m/z 415.1 → 295.1 for IS. The total run time was 7.5 min for each injection. The calibration curves were linear (r2 > 0.99) over the investigated concentration range (2.00–2000 ng/mL) and the lower limits of quantification were 2.00 ng/mL in rat plasma sample. The intra‐ and inter‐day relative standard deviations were no more than 14.9% and the relative errors were within the range of −3.2–2.1%. The extraction recoveries for both compounds were between 89.3 and 97.3%. The robust LC‐MS/MS method was further applied in the pharmacokinetic study in Sprague–Dawley rats after oral administration of Santalum album L. leaves extract at a dose of 116 mg/kg. Copyright © 2012 John Wiley & Sons, Ltd.
Quantification and pharmacokinetics of Taiwanin E methyl ether in rats by liquid chromatography–tandem mass spectrometry
Authors: Qiu Feng , Fu Shujun , Zhou Shujun , Yang Shihai , Yang Meihua
Published: June 2012

This study firstly describes the development of an accurate and sensitive high‐performance liquid chromatography–tandem mass spectrometry (LC‐MS/MS) assay for the quantification of Taiwanin E methyl ether (TEME) in rat plasma. The assay involved a simple liquid–liquid extraction step with ethyl acetate and a gradient elution using a mobile phase consisting of water containing 0.1% formic acid and acetonitrile containing 0.1% formic acid. Chromatographic separation was successfully achieved on an Agilent Zorbax‐C18 column (2.1 × 50 mm, 3.5 µm) with a flow rate of 0.40 mL/min. The multiple reaction monitoring was based on the transitions of m/z = 379.1 → 320.1 for TEME and 386.1 → 122.0 for buspirone (internal standard). The assay was validated to demonstrate the specificity, linearity, recovery, accuracy, precision and stability. The lower limit of quantification was 0.50 ng/mL in 50 μL of rat plasma. The developed and validated method was successfully applied to the quantification and pharmacokinetic study of TEME in rats after intravenous and oral administration of 1.45 mg/kg TEME. The oral absolute bioavailability of TEME was estimated to be 5.85 ± 1.41% with an elimination half‐life value of 2.61 ± 0.55 h, suggesting its poor absorption and/or strong metabolism in vivo. Copyright © 2012 John Wiley & Sons, Ltd.
Novel Phenyl‐1‐benzoxepinols from Butcher's Broom (Rusci rhizoma)
Authors: Barbič Matej , Schmidt Thomas J. , Jürgenliemk Guido
Published: June 2012

Two novel compounds, (3S)‐2,3‐dihydro‐3‐(4‐hydroxyphenyl)‐1‐benzoxepin‐8‐ol (1; ruscozepine A) and (3S)‐2,3‐dihydro‐3‐(4‐hydroxyphenyl)‐8‐methoxy‐1‐benzoxepin‐7‐ol (2; ruscozepine B) were isolated from butcher's broom (Rusci rhizoma) together with a biosynthetically possible phenylethanoid precursor, hydroxytyrosol (3). The structures were elucidated by spectroscopic methods such as 1D‐ and 2D‐NMR (COSY, HSQC, HMBC, ROESY), and HR‐EI‐MS experiments. The absolute configuration of the ruscozepines was determined by electronic circular dichroism.
Sesquiterpenes and Cyclopeptides from the Endophytic Fungus Trichoderma asperellumSamuels, Lieckf. & Nirenberg
Authors: Ding Gang , Chen Amanda Juan , Lan Jin , Zhang Hongwu , Chen Xiangdong , Liu Xingzhong , Zou Zhongmei
Published: June 2012

Trichodones A–C (1–3, resp.), three new sesquiterpenes, together with the two known cyclopeptides PF1022F and halobacillin (4 and 5, resp.), have been isolated from the crude extract of the endophytic fungus Trichoderma asperellum Samuels, Lieckf. & Nirenberg residing in the traditional Chinese medicinal plant Panax notoginseng (Burkill) F.H.Chen. The structures and configurations of compounds 1–3 were determined by NMR spectroscopy and mass spectrometry. The relative configuration for 1 was determined by analysis of its pertinent coupling constants and NOESY correlations, whereas the absolute configuration of 1 was established by CD spectroscopy. Compounds 4 and 5 displayed antibacterial activities against Enterococcus faecium (CGMCC 1.2025) with IC50 values of 7.30 and 5.24 μm, and against Staphylococcus aureus COL (CGMCC 1.2465) with IC50 values of 19.02 and 14.00 μM, respectively.
Anti‐Inflammatory and Anti‐Tumor‐Promoting Effects of 5‐Deprenyllupulonol C and Other Compounds from Hop (Humulus lupulus L.)
Authors: Akazawa Hiroyuki , Kohno Hideki , Tokuda Harukuni , Suzuki Nobutaka , Yasukawa Ken , Kimura Yumiko , Manosroi Aranya , Manosroi Jiradej , Akihisa Toshihiro
Published: June 2012

A new phloroglucinol derivative, 5‐deprenyllupulonol C (1), along with four other phloroglucinol derivatives, 2–5, five chalcones, 6–10, four flavanones, 11–14, two flavonol glycosides, 15 and 16, and five triterpenoids, 17–21, were isolated from the female inflorescence pellet extracts of hop (Humulus lupulus L.). Upon evaluation of these compounds against the EpsteinBarr virus early antigen (EBV‐EA) activation induced by 12‐O‐tetradecanoylphorbol 13‐acetate (TPA) in Raji cells, twelve compounds, i.e., 1–4, 11–14, 17–19, and 21, showed potent inhibitory effects on EBV‐EA induction, with IC50 values in the range of 215–393 mol ratio/32 pmol TPA. In addition, eleven compounds, i.e., 1–4, 6, 11, 12, 14, 17, 18, and 20, were found to inhibit TPA‐induced inflammation (1 μg/ear) in mice, with ID50 values in the range of 0.13–1.06 μmol per ear. Further, lupulone C (2) and 6‐prenylnaringenin (14) exhibited inhibitory effects on skin‐tumor promotion in an in vivo two‐stage mouse‐skin carcinogenesis test based on 7,12‐dimethylbenz[a]anthracene (DMBA) as initiator and with TPA as promoter.
Coproduction and Ecological Significance of Naphthoquinones in Carnivorous Sundews (Drosera)
Authors: Egan Paul A. , van der Kooy Frank
Published: June 2012

While the 1,4‐naphthoquinone derivatives 7‐methyljuglone (1) and plumbagin (2) possess a diverse and well documented array of biological activities, relatively little remains known about the functional significance of these compounds in planta and, in particular, their possible relation to carnivorous syndromes. In addition, the chemotaxonomic distribution of naphthoquinones (NQs) amongst species of Drosera L. is of phytopharmaceutical interest. Following the quantitative assessment of interspecific variation of 1 and 2 in 13 species and cultivars of Drosera, our findings demonstrate that these NQs are ubiquitously coproduced in, generally, species‐specific ratios, and that 1 appears negatively associated with the occurrence of pigmentation in sundews. The prospective antifeedant function of 1 was evaluated in relation to allocation in various organs and ontogenetic phases of D. capensis L., revealing that significantly higher levels were accumulated in young and reproductive organs, most likely for defensive purposes. Investigation into the relationship between the biosynthesis of NQs and carnivory showed that production of 1 is optimally induced and localized in leaves in response to capture of insect prey. As a whole, these findings reveal the clear importance of this secondary metabolite in ecological interactions as well as holding implication for future bioactivity studies on the genus.
Melanogenesis‐Inhibitory Saccharide Fatty Acid Esters and Other Constituents of the Fruits of Morinda citrifolia (Noni)
Authors: Akihisa Toshihiro , Tochizawa Shun , Takahashi Nami , Yamamoto Ayako , Zhang Jie , Kikuchi Takashi , Fukatsu Makoto , Tokuda Harukuni , Suzuki Nobutaka
Published: June 2012

Five new saccharide fatty acid esters, named nonioside P (3), nonioside Q (4), nonioside R (8), nonioside S (10), and nonioside T (14), and one new succinic acid ester, butyl 2‐hydroxysuccinate (=4‐butoxy‐3‐hydroxy‐4‐oxobutanoic acid) (31), were isolated, along with 26 known compounds, including eight saccharide fatty acid esters, 1, 2, 5, 6, 7, 9, 12, and 13, three hemiterpene glycosides, 15, 17, and 18, six iridoid glycosides, 21–25, and 27, and nine other compounds, 20, 28, 29, and 32–37, from a MeOH extract of the fruit of Morinda citrifolia (noni). Upon evaluation of these and five other glycosidic compounds, 11, 16, 19, 26, and 30, from M. citrifolia fruit extract for their inhibitory activities against melanogenesis in B16 melanoma cells induced with α‐melanocyte‐stimulating hormone (α‐MSH), most of the saccharide fatty acid esters, hemiterpene glycosides, and iridoid glycosides showed inhibitory effects with no or almost no toxicity to the cells. These compounds were further evaluated with respect to their cytotoxic activities against two human cancer cell lines (HL‐60 and AZ521) and their inhibitory effects on EpsteinBarr virus early antigen (EBV‐EA) activation induced with 12‐O‐tetradecanoylphorbol‐13‐acetate (TPA) in Raji cells.
Rational Co‐Immobilization of Bi‐Enzyme Cascades on Porous Supports and their Applications in Bio‐Redox Reactions with In Situ Recycling of Soluble Cofactors
Authors: Rocha‐Martín Javier , Rivas Blanca de las , Muñoz Rosario , Guisán José M , López‐Gallego Fernando
Published: June 2012

In bio‐redox cascade reactions that are immobilized on porous supports, mass‐transfer limitations may impede the effective concentration of the cofactor around the corresponding dehydrogenases. This main drawback has been addressed by the co‐immobilization of both the main and recycling dehydrogenases. Herein, we report tailor‐made co‐immobilization procedures to assemble three different bio‐redox orthogonal cascades in vitro (two selective reductions and one selective oxidation) with in situ cofactor‐regeneration. However, the co‐immobilization itself does not guarantee the success of the biotransformation because the same co‐immobilization chemistry may not be suitable for the two enzymes that are involved in the bio‐redox cascade. Therefore, our co‐immobilization system was optimized for each bi‐enzymatic cascade. In all cases, the optimized co‐immobilization procedure was more efficient in the biocatalytic cascade than if the two dehydrogenases were immobilized on two different carriers. In one specific case (one thermophilic cascade), the co‐immobilization of an optimal ratio of main/recycling dehydrogenases (1:5) on the same carrier resulted in a biocatalyst that was able to recycle NADH up to 9000 times per equivalent of substrate in 1 hour at 55 °C. Moreover, uniform distributions of both dehydrogenases across the porous surface also enhanced the recycling efficiency of the cofactor 1.5‐fold versus cascades in which the enzymes were not uniformly distributed across the same porous surface, presumably because of vicinal cooperation effects. Hence, this system for the co‐immobilization of bi‐enzymatic systems may be extended to other biocatalytic cascades, thereby opening a window for the optimization of other multi‐enzyme biotransformations in which cofactor‐recycling is necessary.
Thermodynamic Analysis of Nonoxidative Dehydroaromatization of Methane
Authors: Moghimpour Bijani P. , Sohrabi M. , Sahebdelfar S.
Published: June 2012

The thermodynamics of methane dehydroaromatization in the absence and presence of coke‐removing agents was studied using the Gibbs free energy minimization approach. Numerical results indicated that higher temperatures and lower pressures increase methane conversion as well as formation of olefins and aromatics but suppress that of paraffins. Higher H2/CH4 ratios enhance the selectivity of light hydrocarbons but reduce that of naphthalene. Benzene selectivity has a maximum at an H2/CH4 molar ratio of 0.26. Methane conversion exhibits a minimum at an H2O/CH4 molar ratio of 0.07. As the H2O/CH4 ratio increases, formations of heavier hydrocarbons decrease at the expense of CO, CO2, and hydrogen. These results may provide guidelines to improve the process performance.
Two‐Component Fibers/Gels and Vesicles Formed from Hetero‐Double‐Helices of Pseudoenantiomeric Ethynylhelicene Oligomers with Branched Side Chains
Authors: Saito Nozomi , Shigeno Masanori , Yamaguchi Masahiko
Published: June 2012

A methodology for the formation of fibers/gels and vesicles by molecular assembly and for controlling their properties is presented. Two‐component systems of pentamer (P)‐5 and tetramer (M)‐4 pseudoenantiomeric ethynylhelicenes with decyloxycarbonyl (D) and 4‐methyl‐2‐(2‐methylpropyl)‐1‐pentyloxycarbonyl (bD) side‐chains have been examined. Distinct aggregates were formed by changing the solvent for the three combinations of (P)‐bD‐5/(M)‐bD‐4, (P)‐D‐5/(M)‐bD‐4, and (P)‐D‐5/(M)‐D‐4. In toluene, (P)‐bD‐5/(M)‐bD‐4, (P)‐D‐5/(M)‐bD‐4, and (P)‐D‐5/(M)‐D‐4 all formed gels and fibrous assemblies were observed by AFM. The minimum gel‐forming concentration (MGC) decreased in the order (P)‐bD‐5/(M)‐bD‐4>(P)‐D‐5/(M)‐bD‐4>(P)‐D‐5/(M)‐D‐4. In diethyl ether, vesicular formation was observed by dynamic light scattering (DLS), AFM, and TEM, and the size of the vesicles decreased in the order (P)‐bD‐5/(M)‐bD‐4>(P)‐D‐5/(M)‐bD‐4>(P)‐D‐5/(M)‐D‐4. Both fiber/gel and vesicle formation were accompanied by enhanced CDs and redshifted UV/Vis absorption bands with a change in color to deep yellow. These are novel two‐component oligomeric systems that form assemblies of fibers/gels or vesicles depending on the solvent, and the structures and properties of the assemblies can be fine‐tuned by changing the combination of oligomers. In m‐difluorobenzene, a homogeneous solution was obtained with (P)‐D‐5/(M)‐bD‐4, which again exhibits enhanced CDs and redshifted UV/Vis absorptions. Vapor pressure osmometry analysis showed the formation of a bimolecular heteroaggregate. The study has indicated that pseudoenantiomeric oligomers form hetero‐double‐helices that hierarchically assemble to form fibers/gels and vesicles.
Fabrication Based on the Kirkendall Effect of Co3O4 Porous Nanocages with Extraordinarily High Capacity for Lithium Storage
Authors: Hu Lin , Yan Nan , Chen Qianwang , Zhang Ping , Zhong Hao , Zheng Xinrui , Li Yan , Hu Xianyi
Published: June 2012

Herein we report a novel facile strategy for the fabrication of Co3O4 porous nanocages based on the Kirkendall effect, which involves the thermal decomposition of Prussian blue analogue (PBA) Co3[Co(CN)6]2 truncated nanocubes at 400 °C. Owing to the volume loss and release of internally generated CO2 and NxOy in the process of interdiffusion, Co3O4 nanocages with porous shells and containing nanoparticles were finally obtained. When evaluated as electrode materials for lithium‐ion batteries, the as‐prepared Co3O4 porous nanocages displayed superior battery performance. Most importantly, capacities of up to 1465 mA h g−1 are attained after 50 cycles at a current density of 300 mA g−1. Moreover, this simple synthetic strategy is potentially competitive for scaling‐up industrial production.
Three Types of Induced Tryptophan Optical Activity Compared in Model Dipeptides: Theory and Experiment
Authors: Hudecová Jana , Horníček Jan , Buděšínský Miloš , Šebestík Jaroslav , Šafařík Martin , Zhang Ge , Keiderling Timothy A. , Bouř Petr
Published: June 2012

The tryptophan (Trp) aromatic residue in chiral matrices often exhibits a large optical activity and thus provides valuable structural information. However, it can also obscure spectral contributions from other peptide parts. To better understand the induced chirality, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and Raman optical activity (ROA) spectra of Trp‐containing cyclic dipeptides c‐(Trp‐X) (where X=Gly, Ala, Trp, Leu, nLeu, and Pro) are analyzed on the basis of experimental spectra and density functional theory (DFT) computations. The results provide valuable insight into the molecular conformational and spectroscopic behavior of Trp. Whereas the ECD is dominated by Trp π–π* transitions, VCD is dominated by the amide modes, well separated from minor Trp contributions. The ROA signal is the most complex. However, an ROA marker band at 1554 cm−1 indicates the local χ2 angle value in this residue, in accordance with previous theoretical predictions. The spectra and computations also indicate that the peptide ring is nonplanar, with a shallow potential so that the nonplanarity is primarily induced by the side chains. Dispersion‐corrected DFT calculations provide better results than plain DFT, but comparison with experiment suggests that they overestimate the stability of the folded conformers. Molecular dynamics simulations and NMR results also confirm a limited accuracy of the dispersion‐DFT model in nonaqueous solvents. Combination of chiral spectroscopies with theoretical analysis thus significantly enhances the information that can be obtained from the induced chirality of the Trp aromatic residue.
Multichromophoric Calix[4]arenes: Effect of Interchromophore Distances on Linear and Nonlinear Optical Properties
Authors: Andreu Raquel , Franco Santiago , Garín Javier , Romero Judith , Villacampa Belén , Blesa María Jesús , Orduna Jesús
Published: June 2012

Multichromophoric calix[4]arenes with two or four disperse red one (DR1) moieties linked to the lower rim have been synthesized. The second‐order nonlinear optical activity was measured by using the electric‐field‐induced second‐harmonic generation technique and there was a nearly linear increase of the μβ value with the number of chromophores in the molecule without affecting the charge‐transfer absorption wavelength. The effect that the number of DR1 units plays on the hyperpolarizability, the dipole moment, and the absorption maxima has been also studied by using quantum chemical calculations. It was found that it was necessary to synthesize multichromophores with distant chromophores to obtain large nonlinear optical responses.
Microwave‐Assisted Modular Fabrication of Nanoscale Luminescent Metal‐Organic Framework for Molecular Sensing
Authors: Yang Weiting , Feng Jing , Song Shuyan , Zhang Hongjie
Published: June 2012

Miniaturizing the size of metal‐organic framework (MOF) crystals to the nanometer scale is challenging, but it provides more advanced applications without changing the characteristic features itself. It is especially useful to investigate the correlation between the porous properties and the interfacial structures of nanocrystals. Using amino acids as capping agents, nanoscale Tb‐MOF‐76 is fabricated rapidly by means of microwave‐assisted methods. Both the modular effects of the amimo acids and the acid–base environment of the reaction medium have an important impact on the morphologies and dimensions of Tb‐MOF‐76. The structures of the samples are confirmed by powder X‐ray diffraction, and the morphologies are characterized by SEM. Photoluminescence studies reveal that these Tb‐MOF‐76 materials exhibit a green emission corresponding to the transition 5D4→7FJ of Tb3+ ions under UV‐light excitation, which is sensitive to small organic molecules in solution.
Cooperative and Diminutive Interplay Between Lithium and Dihydrogen Bonding in F3YLi…︁NCH…︁HMH and F3YLi…︁HMH…︁HCN Triads (Y=C, Si; M=Be, Mg)
Authors: Solimannejad Mohammad
Published: June 2012

The F3YLi…NCH…HMH and F3YLi…HMH…HCN triads (Y=C, Si; M=Be, and Mg) are connected by lithium and dihydrogen bonds. To understand the properties of the systems better, the corresponding dyads are also studied. Molecular geometries, binding energies, infrared spectra and NMR properties of monomers, dyads, and triads are investigated at the MP2/6‐311++G** computational level. Particular attention is paid to parameters, such as cooperative energies, and many‐body interaction energies. Triads with the HMH molecule located at the end of the chain, show energetic cooperativity ranging between −3.66 to −7.59 kJ mol‐1. When the HMH molecule is located in the middle, the obtained cluster is diminutive with an energetic effect between 3.49 to 5.17 kJ mol‐1. The electronic properties of the complexes are analyzed using parameters derived from the atoms in molecules (AIM) methodology.
Metal‐Free Photocatalytic Graphitic Carbon Nitride on p‐Type Chalcopyrite as a Composite Photocathode for Light‐Induced Hydrogen Evolution
Authors: Yang Florent , Lublow Michael , Orthmann Steven , Merschjann Christoph , Tyborski Tobias , Rusu Marin , Kubala Sven , Thomas Arne , Arrigo Rosa , Hävecker Michael , Schedel‐Niedrig Thomas
Published: June 2012

Recently, it has been shown that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible‐light irradiation in the presence of a sacrificial donor. We present herein the preparation and characterization of graphitic carbon nitride (g‐C3N4) films on p‐type semiconducting CuGaSe2 chalcopyrite thin‐film substrates by thermal condensation of a dicyandiamide precursor under inert‐gas conditions. Structural and surface morphological studies of the carbon nitride films suggest a high porosity of g‐C3N4 thin films consisting of a network of nanocrystallites. Photoelectrochemical investigations show light‐induced hydrogen evolution upon cathodic polarization for a wide range of proton concentrations in the aqueous electrolyte. Additionally, synchrotron radiation‐based photoelectron spectroscopy has been applied to study the surface/near‐surface chemical composition of the utilized g‐C3N4 film photocathodes. For the first time, it has been shown that g‐C3N4 films coated on p‐type CuGaSe2 thin films can be successfully applied as new photoelectrochemical composite photocathodes for light‐induced hydrogen evolution.
Temperature‐/Pressure‐Dependent Selective Separation of CO2 or Benzene in a Chiral Metal–Organic Framework Material
Authors: Tan Yan‐Xi , He Yan‐Ping , Zhang Jian
Published: June 2012

Presented here is a chiral microporous metal–organic framework material with a three‐fold interpenetrating diamond‐type structural topology and interesting properties for selective separation. The material has a high storage capacity for CO2 gas (4.23 mmol g−1 at 273 K and 1 bar) and shows fantastic temperature‐dependent selectivity for CO2 over N2. Moreover, this multifunctional material, which has a rich π system, can selectively adsorb benzene over cyclohexane at low pressure (0.05 bar) at 298 K.
Nth best relay selection with network coding in two‐way relay systems
Authors: Han Bin , Wang Wenbo , Zhao Zhongyuan , Peng Mugen
Published: June 2012

In this paper, we propose an Nth best relay selection (Nth‐RS) scheme for analog network coding in two‐way relay systems. In traditional two‐way single‐relay selection schemes, only the best one is selected to forward network‐coded signals. However, in practical applications, the best relay may be unavailable because of the scheduling or overload constraints. In this case, we investigate a more general scheme, where the Nth best but available relay is selected. To evaluate the transmission of reliability, the expression of outage probability in exponential–integral form and its asymptotic expression in closed form are presented. Moreover, the upper bound and lower bound of outage probability are also derived. The analysis reveals that the diversity order of Nth‐RS equals to (M − N + 1), where M is the number of relay nodes, and the results are verified by simulations. In order to improve system performance, transmit power between sources and relay is optimally allocated to minimize the upper bound of outage probability under total power constraint. Simulation results show that Nth‐RS scheme with proposed power allocation can achieve substantial improvement over equal power allocation scheme. Copyright © 2012 John Wiley & Sons, Ltd.