bluuebunny/crossref_metadata_2025 huggingface dataset:
Assessing the Europeanization of Bosnia and Herzegovina: A litmus test for the European Union
Authors: Brljavac Bedrudin
Published: December 2011

The concept of Europeanization has become very popular in studies of European integration and particularly in analyses on the post-communist countries undergoing extensive transformation on the road to European Union membership. Although the Europeanization process has been quite successful in the countries of Central and Eastern Europe (CEE), the same scenario has not played out in the western Balkans region. With the purpose of analysing the effectiveness and impact of the Europeanization process in the western Balkans, the main subject of the paper is Bosnia and Herzegovina’s EU-related reform processes. Although Bosnia has been undergoing thorough Europeanizing reforms since the late 1990s, when the country entered the Stabilization and Association Process (SAP), it is still an unstable and dysfunctional country. That makes it the perfect case for assessing the possible shortcomings of the Europeanization process. Thus far, most scholars have concluded that domestic political elites in Bosnia are the only party responsible for Bosnia’s political deadlock. However, this paper analyses the continued Bosnian deadlock from a different perspective, trying to figure out the degree of responsibility the European Union shares in the country’s Europeanization process. Although uncooperative Bosnian political elites are to a great extent responsible for the continued political and social status quo, EU leaders are not faultless either. In fact, so far European leaders have often appeared to be deeply divided, incoherent, and short-sighted in terms of Europeanization policies in Bosnia, thus further deepening the political deadlock in the country. Therefore, we can ask whether Bosnia represents a litmus test which the EU has failed.
Distribution and origin of organic matter in the Baltic Sea sediments dated with 210Pb and 137Cs
Authors: Szczepańska Aleksandra , Zaborska Agata , Maciejewska Anna , Kuliński Karol , Pempkowiak Janusz
Published: December 2011

Organic carbon deposited in marine sediments is an important part of the global carbon cycle. The knowledge concerning the role of shelf seas (including the Baltic Sea) in the carbon cycle has increased substantially, however organic carbon accumulation rates in the Baltic sediments still require clarification.

This paper describes methods used for assessing organic carbon and nitrogen accumulation rates in six sediment cores collected in the sediment accumulation areas in the Baltic Sea. Mass sediment accumulation rates were based on 210Pb method validated by 137Cs measurements. The organic carbon accumulation rates ranged from 18 to 75 g·C·m−2·yr−1. The C/N ratios and δ13C were used to access sedimentary organic matter provenance. The C/N ratios in the investigated cores vary in the range from 7.4 to 9.6, while δ13C ranged from −24.4‰ to −26.4‰. Results of the terrestrial organic matter contribution in the sedimentary organic matter were calculated basing on δ13C using the end member approach. Large proportion (41–73%) of the sedimentary organic carbon originates on land.

The obtained results indicate the Baltic Sea sediments as an important sink for organic carbon. Substantial fraction of the sedimentary load originates on land.
Paleogeography of the Early Badenian connection between the Vienna Basin and the Carpathian Foredeep
Authors: Brzobohatý Rostislav , Stráník Zdeněk
Published: December 2011

The paleogeographic reconstruction for an early Badenian connection of the Vienna Basin and the Carpathian Foredeep in the Mikulov area (Mikulov Gate) based on paleontological (otoliths) and geological (regional geology, tectonics) data has been provided. The ecologically homogenous deep water associations of otoliths in the most NW tip of the Vienna Basin (Sedlec HJ-2 Borehole) links up bathymetrically with nearly adequate otolith assemblages in the southernmost Moravian part of the foredeep. Ten meso- and bathypelagic teleost species have been identified in the Vienna Basin for the first time. Geological analyses proved inversion processes of recurrent nature along old faults of the NW-SE direction in the Dyje (Thaya) Depression. In the early Badenian the Mikulov Gate resulted from the sagging block of the Waschberg Zone. This marine channel was relatively deep (> 200m, as indicated by otoliths) and in all probability flooded an entire front of the nappes in this area.
Organ-Specific Cellular Requirements for In Vivo Dendritic Cell Generation
Authors: Miloud Tewfik , Fiegler Nathalie , Suffner Janine , Hämmerling Günter J. , Garbi Natalio
Published: December 2011

Bone marrow-derived dendritic cell (DC) precursors seed peripheral organs, where they encounter diverse cellular environments during their final differentiation into DCs. Flt3 ligand (Flt3-L) is critical for instructing DC generation throughout different organs. However, it remains unknown which cells produce Flt3-L and, importantly, which cellular source drives DC development in such a variety of organs. Using a novel BAC transgenic Flt3-L reporter mouse strain coexpressing enhanced GFP and luciferase, we show ubiquitous Flt3-L expression in organs and cell types. These results were further confirmed at the protein level. Although Flt3-L was produced by immune and nonimmune cells, the source required for development of the DC compartment clearly differed among organs. In lymphoid organs such as the spleen and bone marrow, Flt3-L production by hemopoietic cells was critical for generation of normal DC numbers. This was unexpected for the spleen because both immune and nonimmune cells equally contributed to the Flt3-L content in that organ. Thus, localized production rather than the total tissue content of Flt3-L in spleen dictated normal splenic DC development. No differences were observed in the number of DC precursors, suggesting that the immune source of Flt3-L promoted pre-cDC differentiation in spleen. In contrast, DC generation in the lung, kidney, and pancreas was mostly driven by nonhematopoietic cells producing Flt3-L, with little contribution by immune cells. These findings demonstrate a high degree of flexibility in Flt3-L–dependent DC generation to adapt this process to organ-specific cellular environments encountered by DC precursors during their final differentiation.
Expression of Helios in Peripherally Induced Foxp3+ Regulatory T Cells
Authors: Gottschalk Rachel A. , Corse Emily , Allison James P.
Published: December 2011

The transcription factor Helios has been reported to be a marker of regulatory T cells (Treg) of thymic origin, distinguishing them from Treg induced in the periphery (iTreg). In this study, we demonstrate Helios expression in Foxp3+ iTreg, both in vitro and in vivo. Following i.v. peptide injection, in vivo Helios expression in adoptively transferred TCR transgenic T cells was more rapid than Foxp3 induction but less stable at later time points without a second injection of peptide. Our in vitro data suggest that APC influence Helios expression in a manner distinct from stimuli required for Foxp3 induction. Thus, Helios expression in iTreg may reflect the context of stimulation during Foxp3 induction. In summary, the robust Helios expression we observe in iTreg precludes its use as a marker of thymic Treg.
Postoperative Outcomes of Familial Adrenal Pheochromocytoma1
Authors: Kagawa Chikara , Hibi Yatsuka , Uchida Hiroki , Noda Sumiyo , Idota Ai , Sato Shigenori , Hayashi Hironori , Kikumori Toyone , Imai Tsuneo , Kiuchi Tetsuya
Published: December 2011

There are no current guidelines for the management of familial pheochromocytoma (FP). We tried to determine the optimal management of patients with FP. Among 191 patients with pheochromocytoma who underwent surgical resection between 1979 and 2010, there were 18 FP (13 different kindreds; 11 females/7 males; mean age at initial operation: 38.7 years). The 18 FP cases comprised 10 with MEN2A, 2 with MEN2B, 4 with von Hippel-Lindau disease, and 2 with FP only, and all pheochromocytomas were of adrenal origin. The number of probands and family members was 9 and 9 respectively. Mean tumor size was 6.4 cm in diameter. Simultaneous bilateral adrenalectomy was performed in 6 patients, and unilateral adrenalectomy was performed as the initial surgery in 12 patients. A metachronous contralateral adrenalectomy was performed in 3 patients, 90, 236 and 312 months after the primary operation, respectively. None of the patients received partial adrenalectomy. Among another 9 patients with unilateral adrenalectomy, contralateral pheochromocytomas were suspected in 4 cases at the initial operation. However, none of these contralateral lesions developed severe symptoms or tumor enlargement during a median follow-up of 116 months. In the remaining 5 patients, pheochromocytoma did not develop in the contralateral adrenals over a median follow-up of 80.5 months. Bilateral lesions of adrenal pheochromocytoma in familial cases occurred in 78% of cases (14/18); 9 patients (including 4 with contralateral pheochromocytoma) did not require a contralateral adrenalectomy during a median follow-up of 119 months. No patients have suffered from Addisonian crisis. The ipsilateral adrenalectomy and follow-up of contralateral small pheochromocytoma is one of the management options to preserve adrenocortical function in FP patients.
Surgeon-performed Ultrasound-guided Needle Biopsy of the Thyroid: A Safe and Effective Diagnostic Procedure
Authors: Law Michael T , Taylor Martyn , Bennett Ian C
Published: December 2011

With the ready availability of good quality portable units, office-based ultrasound (US) is increasingly being utilized by endocrine surgeons in their daily practices, particularly in the management of thyroid patients. Ultrasound-guided fine needle aspiration biopsy (US-FNAB) of thyroid lesions is a useful interventional diagnostic technique which can be readily performed by endocrine surgeons as an office-based procedure offering significant convenience for the patient. A retrospective review of US-FNAB's performed in a single surgeon practice between 2006 and 2008 was undertaken particularly assessing the diagnostic outcomes and complication rates. Factors affecting FNAB outcome were tested using Chi-square test and significance defined as p < 0.05. A total of 128 FNABs were performed on 100 patients in the time period under review. Mean lesion size was 22 mm, and the majority were solid on US. US-FNAB had sensitivity of 85%, accuracy 75%. No complications were reported. A total of 14.8% of samples were reported as either malignant, atypical or with Hurthle cell findings. In this series of patients, 22% of cases proceeded to thyroidectomy, 46% of which yielded malignancy. The nondiagnostic rate was only 5.5%. Solid lesions < 2 cm were associated with higher nondiagnostic rate (p = 0.04). Surgeon-performed thyroid US-FNAB is a safe and effective procedure which compares favorably to radiologist-performed series and offers a convenient ‘one-stop’ process for patients. In this series, it was associated with a low nondiagnostic rate and a low complication rate. Surgeon-performed US-FNAB techniques can be easily acquired; however, structured training and appropriate credentialing are important for the maintenance of quality assurance standards.
Transoral Excision of a High Retropharyngeal Parathyroid
Authors: Neilan Ryan E , Truelson John , Holt Shelby
Published: December 2011

In patients with renal failure, hypocalcemia leads to multiglandular parathyroid growth and parathyroid hypersecretion. Parathyroidectomy has been shown to decrease cardiovascular events and mortality in these patients. One of the challenges of surgery for secondary hyperparathyroidism is the high reported incidence of supernumerary and ectopic glands. This in conjuction with reported low sensitivity of preoperative imaging studies in multigland disease and unclear criteria for intraoperative PTH in 2HPT may lead to incomplete parathyroidectomy and need for reoperation. We report a case of recurrent 2HPT from an ectopic supernumerary gland in the high retropharyngeal region found by CT imaging. Due to the patient's obesity, short neck and history of prior neck surgery, we elected to excise the gland transorally using intraoperative EUS.
Recurrent Graves' Disease after Successful Radioiodine Therapy Induced Hypothyroidism: A Rare Occurrence
Authors: PRK Bhargav , Amar V , Uday SK
Published: December 2011

One of the three principal therapies of Graves' disease is radioiodine treatment. Hypothyroidism is considered as a treatment end point of successful radioiodine treatment for Graves' disease. The radioiodine-induced hypothyroidism is mostly irreversible. Though, early recurrences can be due to treatment failure, inadequate radioiodine dose or rarely due to Marine-Lenhart syndrome. Here, we report a rare case of recurrent Graves' disease, 3 years after successful radioiodine therapy induced hypothyroidism in a 50-year-old lady.
Adrenal Incidentaloma: A Cautionary Tale of Three Cases of Adrenocortical Carcinoma Arising from Apparently Benign Incidentalomas
Authors: Armstrong Chris , Pasieka Janice L , Harvey Adrian
Published: December 2011

Unexpected incidental findings on cross-sectional imaging are becoming more commonplace in today's medical practice. These are likely due to ongoing improvements in the resolution of cross-sectional imaging and our increasing use of these tests combined with an aging population. In the case of the adrenal incidentalomas the majority of these represent benign nonfunctional adenomas and these are believed to have no malignant potential. On the contrary adrenocortical carcinoma (ACC) is an uncommon malignancy that carries a high mortality. Current biochemical and radiological follow-up investigations are expensive and are of limited benefit in the majority of cases of adrenal incidentalomas. This has created a dilemma for the proper diagnostic, clinical and radiologic follow-up as well as the triggers for surgical intervention. We present a series of three patients presenting with ACC that retrospectively arose from a small incidentally found adrenal lesion. Three patients were identified with ACC arising from an apparently benign adrenal incidentaloma. The average size of the original lesion was 1.6 cm whereas the average size of their adrenal tumor was 9.3 cm when they presented with ACC. Two of the three cases were found to develop functional tumors at the time of the diagnosis of ACC. Two of the three cases underwent surgical resection. The third patient was found to have metastatic disease at presentation and declined surgical intervention. We agree that current follow-up guidelines result in an increasing burden on our healthcare system; with expensive biochemical testing and imaging for what in most cases will prove to be a benign adenoma, these three cases have influenced our current strategies for follow-up. At the present time, we continue to follow the AAES/AACE guidelines. The development of improved methods of biochemical, radiologic and tissue diagnosis may help to improve our ability to recognize an ACC in this population at an earlier and potentially curable stage.
Intraoperative Monitoring of the Recurrent Laryngeal Nerve during Thyroidectomy: A Standardized Approach (Part 1)
Authors: Dralle Henning , Sitges-Serra Antonio , Angelos Peter , Poveda Manuel C Durán , Dionigi Gianlorenzo , Barczynski Marcin , Phelan Eimear , Randolph Gregory
Published: December 2011

One of the most feared complications in thyroid surgery is injury to the superior laryngeal nerve or recurrent laryngeal nerve. Neural identification during surgery is insufficient to assess nerve injury. Intraoperative nerve monitoring of the vagal nerve and recurrent laryngeal nerve during thyroid surgery is a new adjunct designed to allow better identification of nerves at risk and therefore reduce complications related to their injury. This new working tool does not substitute adequate surgical technique but merely provides the surgeon with an adjunct to routine visual identification and functional assessment. The use of nerve monitoring requires standardization of the monitoring procedure. Pursuant to this, we will discuss in two related articles the current state of the art standardized technique of nerve monitoring in thyroid surgery. The aim of part 1 is to provide a concise overview of nerve monitoring in thyroid surgery and its effectiveness. This will include a brief review of the surgical anatomy of the recurrent laryngeal nerve and the key landmarks used to identify the nerve during surgery. Part 2 will describe how to perform the standardized nerve monitoring in a step by step fashion during thyroid surgery which will diminish variable results and misleading information associated with a nonstandardized nerve monitoring procedure.
Biocompatible Poly(2‐hydroxyethyl methacrylate)‐b‐poly(L‐histidine) Hybrid Materials for pH‐Sensitive Intracellular Anticancer Drug Delivery
Authors: Johnson Renjith P. , Jeong Young‐Il , Choi Eunji , Chung Chung‐Wook , Kang Dae Hwan , Oh Sae‐Ock , Suh Hongsuk , Kim Il
Published: December 2011

A series of synthetic polymer bioconjugate hybrid materials consisting of poly(2‐hydroxyethyl methacrylate) (p(HEMA)) and poly(l‐histidine) (p(His)) are synthesized by combining atom transfer radical polymerization of HEMA with ring opening polymerization of benzyl‐N‐carboxy‐L‐histidine anhydride. The resulting biocompatible and membranolytic p(HEMA)25‐b‐p(His)n (n = 15, 25, 35, and 45) polymers are investigated for their use as pH‐sensitive drug‐carrier for tumor targeting. Doxorubicin (Dox) is encapsulated in nanosized micelles fabricated by a self‐assembly process and delivered under different pH conditions. Micelle size is characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM) observations. Dox release is investigated according to pH, demonstrating the release is sensitive to pH. Antitumor activity of the released Dox is assessed using the HCT 116 human colon carcinoma cell line. Dox released from the p(HEMA)‐b‐p(His) micelles remains biologically active and has the dose‐dependent capability to kill cancer cells at acidic pH. The p(HEMA)‐b‐p(His) hybrid materials are capable of self‐assembling into nanomicelles and effectively encapsulating the chemotherapeutic agent Dox, which allows them to serve as suitable carriers of drug molecules for tumor targeting.
Counting quantum fluctuations of particle density
Authors: Rammer J. , Shelankov A.
Published: December 2011

Methods of charge projectors using special gauge transformations for tagging particles are presented. Such engineering of a many‐body wave function allows extracting information regarding properties of a physical system beyond average values. The method is first used to establish under which circumstances the properties of particle currents can be understood as discrete transfers of particles from one region to another. Next, the method is extended to show that in a tunnel junction coupled to a two‐level system, the transmission of electrical noise causes decoherence and thereby a projective measurement of the two‐level system as encoded by the amount of tunnelled charge. Finally the method is extended to deal with the exceptional circumstance where a measurement on a system with a large number of particles gives macroscopically distinguishable outcomes that are unpredictable, the observed interference pattern of interfering BEC's.
Von “Kaffeeringen” lernen: geordnete Strukturen durch Selbstorganisation bei kontrollierter Verdunstung
Authors: Han Wei , Lin Zhiqun
Published: December 2011

Trocknende Lösungen sind nicht nur ein Modell für die Untersuchung des Verdunstungsvorgangs an sich, sondern sie lassen sich auch nutzen, um nichtflüchtige gelöste Stoffe zu komplexen geordneten Strukturen im Submikrometermaßstab und darüber zu aggregieren. Dieser Aufsatz behandelt aktuelle Fortschritte bei der Verdunstungsaggregation aus räumlich eingeschränkten Lösungen mit besonderem Augenmerk auf neuen präparativen Ansätzen zur Herstellung von Strukturen mit höchster Regelmäßigkeit aus Polymeren, Nanopartikeln und Biomaterialien über kontrollierte verdunstungsgetriebene strömungsunterstützte Selbstorganisation. Die Abscheidung kann über verschiedene Variablen kontrolliert werden. Schließlich wird ein Ausblick auf zukünftige Entwicklungen auf diesem faszinierenden Gebiet gegeben.
Synthesis, Structure, and Physical Properties of 5,7,14,16‐Tetraphenyl‐8:9,12:13‐bisbenzo‐hexatwistacene
Authors: Xiao Jinchong , Liu Shuwei , Liu Yi , Ji Li , Liu Xuewei , Zhang Hua , Sun Xiaowei , Zhang Qichun
Published: December 2011

A novel compound, 5,7,14,16‐tetraphenyl‐8:9,12:13‐bisbenzo‐hexatwistacene (TBH), has been successfully synthesized through a retro‐Diels–Alder reaction. Single‐crystal structure analysis indicated that TBH has a twisted configuration with a torsion angle of 27.34°. The HOMO–LUMO gap of TBH calculated from the difference between the half‐wave redox potentials (E1/2ox=+0.40 eV and E1/2red=−1.78 eV) is 2.18 eV, which is in good agreement with the band gap (2.19 eV) derived from the UV/Vis absorption data. In addition, organic light‐emitting devices using TBH as emitter have been fabricated. The results revealed that TBH is a promising red light‐emitting candidate for applications in organic light‐emitting diodes.
High‐Performance Organic Materials for Dye‐Sensitized Solar Cells: Triarylene‐Linked Dyads with a 4‐tert‐Butylphenylamine Donor
Authors: Chang Yuan Jay , Chou Po‐Ting , Lin Szu‐Yu , Watanabe Motonori , Liu Zhi‐Qian , Lin Ju‐Ling , Chen Kew‐Yu , Sun Shih‐Sheng , Liu Ching‐Yang , Chow Tahsin J.
Published: December 2011

A series of organic dyes were prepared that displayed remarkable solar‐to‐energy conversion efficiencies in dye‐sensitized solar cells (DSSCs). These dyes are composed of a 4‐tert‐butylphenylamine donor group (D), a cyanoacrylic‐acid acceptor group (A), and a phenylene‐thiophene‐phenylene (PSP) spacer group, forming a D‐π‐A system. A dye containing a bulky tert‐butylphenylene‐substituted carbazole (CB) donor group showed the highest performance, with an overall conversion efficiency of 6.70 %. The performance of the device was correlated to the structural features of the donor groups; that is, the presence of a tert‐butyl group can not only enhance the electron‐donating ability of the donor, but can also suppress intermolecular aggregation. A typical device made with the CB‐PSP dye afforded a maximum photon‐to‐current conversion efficiency (IPCE) of 80 % in the region 400–480 nm, a short‐circuit photocurrent density Jsc=14.63 mA cm−2, an open‐circuit photovoltage Voc=0.685 V, and a fill factor FF=0.67. When chenodeoxycholic acid (CDCA) was used as a co‐absorbent, the open‐circuit voltage of CB‐PSP was elevated significantly, yet the overall performance decreased by 16–18 %. This result indicated that the presence of 4‐tert‐butylphenyl substituents can effectively inhibit self‐aggregation, even without CDCA.
Local wavelet‐vaguelette‐based functional classification of gene expression data
Authors: Rincón Hidalgo Margarita M. , Ruiz‐Medina María Dolores
Published: December 2011

This paper focuses on the problem of functional statistical classification of gene expression curves. A local‐wavelet‐vaguelette‐based functional logistic regression approach is presented. This approach is specially suitable for the classification of non‐stationary singular (non‐differentiable) curves. The performance of the methodology proposed is illustrated by implementing it for the classification of yeast cell‐cycle temporal gene expression profiles. A simulation study is also carried out for comparison with other functional classification methodologies.
A length‐based hierarchical model of brown trout (Salmo trutta fario) growth and production
Authors: Lecomte Jean‐Baptiste , Laplanche Christophe
Published: December 2011

We present a hierarchical Bayesian model (HBM) to estimate the growth parameters, production, and production over biomass ratio (P/B) of resident brown trout (Salmo trutta fario) populations. The data which are required to run the model are removal sampling and air temperature data which are conveniently gathered by freshwater biologists. The model is the combination of eight submodels: abundance, weight, biomass, growth, growth rate, time of emergence, water temperature, and production. Abundance is modeled as a mixture of Gaussian cohorts; cohorts centers and standard deviations are related by a von Bertalanffy growth function; time of emergence and growth rate are functions of water temperature; water temperature is predicted from air temperature; biomass, production, andP/Bare subsequently computed. We illustrate the capabilities of the model by investigating the growth and production of a brown trout population (Neste d'Oueil, Pyrénées, France) by using data collected in the field from 2005 to 2010.
Interactions of Multicationic Bis(guanidiniocarbonylpyrrole) Receptors with Double‐Stranded Nucleic Acids: Syntheses, Binding Studies, and Atomic Force Microscopy Imaging
Authors: Klemm Karsten , Radić Stojković Marijana , Horvat Gordan , Tomišić Vladislav , Piantanida Ivo , Schmuck Carsten
Published: December 2011

Compounds1–3, composed of two guanidiniocarbonylpyrrole moieties linked by oligoamide bridges and differing in number and type of basic groups, were prepared. The sites and degree of protonation of1–3depend strongly on the pH value. The interactions of these compounds with several double‐stranded (ds) DNA and dsRNA were investigated by means of UV/Vis and CD spectroscopy as well as isothermal titration microcalorimetry (ITC). These studies revealed that the binding of1–3to the polynucleotides is driven by three factors, the presence of aliphatic amino groups, the protonation state of the compounds, and the steric properties of the polynucleotide binding site, that is, the shape and structure of their grooves. The results obtained by all applied methods consistently indicated that receptors1–3bind to the minor groove of DNA, but, by contrast, to the major groove of RNA. Additionally, it was shown by atomic force microscopy (AFM) imaging that upon interaction of compound2with calf thymus (ct) DNA induced aggregation of the DNA occurs, leading to pronounced changes in its secondary structure.
On the Cl⋅⋅⋅N Halogen Bond: A Rotational Study of CF3Cl⋅⋅⋅NH3
Authors: Feng Gang , Evangelisti Luca , Gasparini Nicola , Caminati Walther
Published: December 2011

The rotational spectra of six isotopologues (CF335Cl⋅⋅⋅14NH3, CF337Cl⋅⋅⋅14NH3, CF335Cl⋅⋅⋅15NH3, CF337Cl⋅⋅⋅15NH3, CF335Cl⋅⋅⋅14ND3 and CF337Cl⋅⋅⋅14ND3) of the CF3Cl⋅⋅⋅NH3 adduct have been investigated and analyzed by pulsed jet Fourier transform microwave spectroscopy. Rotational, centrifugal distortion and quadrupole (35Cl, 37Cl, 14N) coupling constants have been precisely obtained. The two subunits of the complex are held together via a Cl⋅⋅⋅N halogen bond interaction. Information on the internal dynamics and on the dissociation energy of the complex is provided.
Coordination Polymers Based on [Cp*Fe(η5‐P5)]: Solid‐State Structure and MAS NMR Studies
Authors: Dielmann Fabian , Schindler Andrea , Scheuermayer Sabine , Bai Junfeng , Merkle Roger , Zabel Manfred , Virovets Alexander V. , Peresypkina Eugenia V. , Brunklaus Gunther , Eckert Hellmut , Scheer Manfred
Published: December 2011

Slow diffusion reactions of the pentaphosphaferrocene [Cp*Fe(η5‐P5)] (Cp*=η5‐C5Me5 (1)) with CuX (X=Cl, Br, I) in different stoichiometric ratios and solvent mixtures result in the formation of one‐ and two‐dimensional polymeric compounds 2–6 with molecular formula [{Cu(μ‐X)}{Cp*Fe(μ3,η5:η1:η1‐P5)}]n (X=Cl (2 a), I (2′c)), [{Cu(μ‐I)}{Cp*Fe(μ3,η5:η1:η1‐P5)}]n (3), [{CuX}{Cp*Fe(μ4,η5:η1:η1:η1‐P5)}]n (X=Cl (4 a), Br (4 b), I (4 c), Br (4′b), I (4′c)), [{Cu3(μ‐I)2(μ3‐I)}{Cp*Fe(μ5,η5:η1:η1:η1:η1‐P5)}]n (5) and [{Cu4(μ‐X)4(CH3CN)}{Cp*Fe(μ7,η5:η2:η1:η1:η1:η1:η1‐P5)}]n (X=Cl (6 a), Br (6 b)), respectively. The polymeric compounds have been characterised by single‐crystal X‐ray diffraction analyses and, for selected examples, by magic angle spinning (MAS) NMR spectroscopy. The solid‐state structures demonstrate the versatile coordination modes of the cyclo‐P5 ligand of 1, extending from two to five coordinating phosphorus atoms in either σ or σ‐and‐π fashion. In compounds 2 a, 2′c and 3, two phosphorus atoms of 1 coordinate to copper atoms in a 1,2 coordination mode (2 a, 2′c) and an unprecedented 1,3 coordination mode (3) to form one‐dimensional polymers. Compounds 4 a–c, 4′b, 4′c and 5 represent two‐dimensional coordination polymers. In compounds 4, three phosphorus atoms coordinate to copper atoms in a 1,2,4 coordination mode, whereas in 5 the cyclo‐P5 ligand binds in an unprecedented 1,2,3,4 coordination mode. The crystal structures of 6 a,b display a tilted tube, in which all P atoms of the cyclo‐P5 ligand are coordinated to copper atoms in σ‐ and π‐bonding modes.
Synthesis and Anti‐tumor Evaluation of B‐ring Modified Caged Xanthone Analogues of Gambogic Acid
Authors: Li Xiang , Zhang Xiaojin , Wang Xiaojian , Li Nianguang , Lin Changjun , Gao Yuan , Yu Zhuoqin , Guo Qinglong , You Qidong
Published: December 2011

Gambogic acid (GA, 1), the most prominent member of Garcinia natural products, has been reported to be a promising anti‐tumor agent. Previous studies have suggested that the planar B ring and the unique 4‐oxa‐tricyclo[4.3.1.03,7]dec‐2‐one caged motif were essential for anti‐tumor activity. To further explore the structure‐activity relationship (SAR) of caged Garcinia xanthones, two new series of B‐ring modified caged GA analogues 13a–13e and 15a–15e were synthesized utilizing a Claisen/Diel‐Alder cascade reaction. Subsequently, these compounds were evaluated for their in vitro anti‐tumor activities against A549, MCF‐7, SMMC‐7721 and BGC‐823 cancer cell lines by MTT assay. Among them, 13b–13e exhibited micromolar inhibition against several cancer cell lines, being approximately 2–4 fold less potent in comparison to GA. SAR analysis revealed that the peripheral gem‐dimethyl groups are essential for maintaining anti‐tumor activity and substituent group on C1 position of B‐ring has a significant effect on potency, while modifications at C‐2, C‐3 and C‐4 positions are relatively tolerated. These findings will enhance our understanding of the SAR of Garcinia xanthones and lead to the development of simplified analogues as potential anti‐tumor agents.
Asymmetric Synthesis of Both Enantiomers of Disparlure
Authors: Wang Zhigang , Zheng Jianfeng , Huang Peiqiang
Published: December 2011

Starting from propargyl alcohol (12), and on the basis of Zhou's modified Sharpless asymmetric epoxidation, the sex pheromone of the Gypsy moth, disparlure (+)‐8 and its enantiomer (−)‐8 have been synthesized, each in six steps, with overall yields of 29% for (+)‐8 and 27% for (−)‐8 (ee>98%). The use of the sequential coupling tactic renders the method flexible, which is applicable to the synthesis of other cis‐epoxy pheromones.
Experimente alternativ dokumentieren
Authors: Groß Katharina , Reiners Christiane S.
Published: December 2011

Seit vielen Jahren, insbesondere seit der Veröffentlichung der PISA Ergebnisse, wird von Lehrerinnen und Lehrern ein bewussterer und differenzierterer Umgang mit der Heterogenität von Lerngruppen im (Chemie‐) Unterricht gefordert. In den Blick geraten zahlreiche Differenzierungsmöglichkeiten, die versuchen, den individuellen Schüler entsprechend seiner entwicklungs‐ und lernpsychologischen Voraussetzungen in seinem Lernen optimal zu fördern. Voraussetzung für die Entwicklung und Implementierung geeigneter Differenzierungsmaßnahmen ist die Fähigkeit der Lehrenden, die Lernfähigkeiten und ‐schwierigkeiten der Lernenden diagnostizieren zu können. Demnach ist die ganzheitliche Diagnose ein wesentlicher Bestandteil der Lehrerkompetenz. Neben dem Regelunterricht (formales Lernen) bieten auch außerschulische Aktivitäten (informelles bzw. nicht‐formales Lernen, wie z. B. Wettbewerbe, Schülerexperimentiertage u. ä.) für die Lehrenden die Möglichkeit, Diagnosefähigkeiten zu entwickeln und geeignete Differenzierungsmaßnahmen zu erproben und zu evaluieren. Der vorliegende Beitrag beschreibt ein Projekt, dessen kurzfristiges Ziel es ist, alternative Formen für die Dokumentation von Experimenten als Differenzierungsmaßnahmen zu erproben. Langfristig zielt das Projekt darauf ab, diese Differenzierungsmaßnahmen auch im Hinblick auf ihre Eignung als Diagnoseinstrument zu hinterfragen und damit einen Beitrag zur Förderung der diagnostischen Kompetenz in der Lehrerbildung zu leisten.
Evaluation of Two Low‐Cost–High‐Performance Adsorbent Materials in the Waste‐to‐Product Approach for the Removal of Pesticides from Drinking Water
Authors: Thuy Pham Thi , Anh Nguyen Viet , van der Bruggen Bart
Published: December 2011

This study evaluates the performance of two low cost and high performance adsorption materials, i.e., activated carbon produced from two natural waste products: Bamboo and coconut shell, in the removal of three pesticides from drinking water sources. Due to the fact that bamboo and coconut shell are abundant and inexpensive materials in many parts of the world, they respond to the “low‐cost” aspect. The adsorption capacities of two local adsorbents have been compared with commercial activated carbon to explore their potential to respond to the “high quality” aspect. Two pesticides were selected, namely dieldrin and chlorpyrifos, because they are commonly used in agriculture activities, and may remain in high concentrations in surface water used as drinking water sources. The results indicate that the adsorption of pesticides on activated carbons is influenced by physico‐chemical properties of the activated carbon and the pesticides such as the presence of an aromatic ring, and their molar mass. The activated carbon produced from bamboo can be employed as low‐cost and high performance adsorbent, alternative to commercial activated carbon for the removal of pesticides during drinking water production. The performance of activated carbon from bamboo was better due to its relatively large macroporosity and planar surface. The effect of adsorbent and pesticide characteristics on the performance was derived from batch experiments in which the adsorption behavior was studied on the basis of Freundlich isotherms.
Selective Agonists for Dopamine/Neurotensin Receptor Heterodimers
Authors: Koschatzky Susanne , Gmeiner Peter
Published: December 2011

The neuromodulatory peptide neurotensin has been described to functionally interact with dopaminergic pathways of the human brain. We employed radioligand binding studies to investigate the physical interaction between co‐expressed dopamine D2L or D3 and neurotensin NTS1 or NTS2 receptors. Substantial cross‐inhibitory effects of both receptor subtypes NTS1 and NTS2 on the agonist binding of D2L or D3 were detected in the presence of neurotensin. To identify ligand‐specific modulation and subtype‐dependent differences, the novel dopamine receptor agonists 5 and 6 bearing the 7‐OH‐DPAT pharmacophore were synthesized. Exceptional ligand specificity was observed for D3–NTS2 co‐expression, which gave a 20‐fold decrease in affinity for biphenylcarboxamide 5 in the presence of neurotensin. Comparing the binding properties of dopaminergic compounds in the presence of neurotensin, dopamine receptor subtype‐selective profiles of the cross‐inhibitory effect of neurotensin were observed.
Spontaneous Ionization of N‐Alkylphenothiazine Molecules Adsorbed in Channel‐Type Zeolites: Effects of Alkyl Chain Length and Confinement on Electron Transfer
Authors: Carré Sonia , Luchez Florence , Moissette Alain , Poizat Olivier , Batonneau‐Gener Isabelle
Published: December 2011

The mere mixing of N‐alkylphenothiazines with three channel‐type acid zeolites with various structures (ferrierite, H‐MFI, and mordenite) induces the spontaneous ionization of the heterocyclic molecule in high yield upon adsorption. The diffuse reflectance UV–visible absorption and Raman scattering spectra show that the accessibility of the highly polarizing acid sites is not indispensable to induce the spontaneous ionization process. Due to their particularly low ionization potential values (6.7 eV), the adsorption of the molecules on the external surface or in the inner volume is the key parameter to generate the radical cation. However, the ionization yield and charge stabilization are intimately correlated to the possibility of the zeolites accommodating molecules inside their channels. Moreover, the higher electrostatic field gradient induced by high confinement is required to favor the second ionization and dication formation. The alkyl chain length plays a decisive role by either slowing down the diffusion process or blocking the molecule at the pore entry. Therefore, the efficiency of the ionization process that depends on the number of adsorbed molecules decreases significantly from phenothiazine to the N‐alkylphenothiazines. The spectral data demonstrate that deformation of the alkyl group is necessary to allow the diffusion of the molecules into the channels.
Copper Nanoparticle‐Catalyzed CarbonCarbon and CarbonHeteroatom Bond Formation with a Greener Perspective
Authors: Ranu Brindaban C. , Dey Raju , Chatterjee Tanmay , Ahammed Sabir
Published: December 2011

The carboncarbon and carbonheteroatom bond formations constitute the backbone of organic synthesis and have been widely used in the synthesis of natural products and useful compounds. Because of growing environmental concern, more attention has been focussed on the development of greener methods. Copper is environment‐friendly and comparatively inexpensive. Although the use of copper salts in catalysis has been known since the last century, this area of research has been less explored compared to other metals, such as palladium, magnesium, and zinc. This review highlights the general features of nanoparticles as catalysts with particular reference to copper and the recent developments in the copper(0) nanoparticle‐catalyzed C(aryl)C(aryl/alkynyl), C(aryl)N, C(aryl)O, C(aryl)S, and C(aryl)Se bond formations and related reactions. The mechanisms of the reactions have been outlined and discussed with respect to the active catalytic species and possible intermediates. The scope, limitations, and green aspects of the reactions have also been highlighted. The convenient methods of preparation of copper nanoparticles and their characterization are described.
Tris(allylammonium) Hexabromobismuthate(III) – Crystal Structure, Phase Transitions and Thermal, Dielectric, Vibrational and 1H NMR Properties Over a Range of Temperatures
Authors: Płowaś Iwona , Białońska Agata , Bator Grażyna , Jakubas Ryszard , Medycki Wojciech , Baran Jan
Published: December 2011

A novel inorganic‐organic hybrid compound, allylammonium hexabromobismuthate(III), (C3H5NH3)3BiBr6 (ABB), was synthesised and its structure determined by means of single‐crystal X‐ray diffraction studies at four temperatures (280, 230, 170 and 100 K). At 100 K, the compound crystallises in the monoclinic space group, C2/c. Its crystal structure consists of discrete BiBr63– anions and three inequivalent allylammonium (C3H5NH3)+ cations. Four solid‐solid structural phase transitions for ABB were detectable by means of DSC and dilatometric techniques: continuous (I↔II) at 272/272 K (upon heating/cooling), discontinuous (II↔III) at 218/215, discontinuous (III↔IV) at 205/204 K and discontinuous (IV↔V) at 146/144 K. The ferroelastic domain structure was observed over one intermediate phase (III) below 215 K. The electric properties of ABB have been measured over a wide temperature range (105–310 K). Low frequency relaxation processes with dielectric increments Δϵ1 ≈ 0.9 and Δϵ2 ≈ 0.05 were observed within phases II and V, respectively. Temperature‐dependent vibrational properties of ABB in the frequency region 3500–500 cm–1 and the molecular motions of its allylammonium cations were studied by means of proton magnetic resonance. The mechanisms of the phase transitions in the title compound are discussed.
Synthesis and Reactivity of Ester‐Functionalized 5‐Membered RhI‐κ2‐C,O‐Chelates and Their Relevance in Rh(cod)‐Mediated Carbene Polymerization
Authors: Finger Markus , Lutz Martin , Reek Joost N. H. , de Bruin Bas
Published: December 2011

The previous mechanistic studies of the Rh‐mediated polymerization of carbenes suggests the involvement of organometallic compounds that have been derived from Rh(diene) species that contain a five‐membered chelate ring of the type Rh{κ2‐C,O‐[–CH(COOR)–CH(Pol)–C(OR)=O–]} (Pol = polymer chain), which are characterized by the coordination of the β‐ester group of the growing polymer chain to the metal. Herein we present our efforts to characterize the possibly related RhI(cod){κ2‐C,O‐[–CH(COOR)–CHR′–C(OR)=O–]} (cod = 1,5‐cyclooctadiene) species. These structures can be generated by means of olefin exchange with an allyl complex and with the concomitant release of the corresponding 1,3‐diene, which is derived from the allyl ligand. The product is unstable and further reacts by means of a bimolecular C–H activation process to form a related dinuclear complex [(cod)Rh(μ‐{–CH(COOR)–CH–C(OR)=O–})2Rh(cod)], in which the carbon dianion of the dimethyl or diethyl succinate bridges two Rh(cod) moieties. The complex was synthesized in an independent way and was structurally characterized. We investigated the importance of these complexes in carbene polymerization.
Ligand Effect on Cobalt(II)‐Catalyzed Asymmetric Cyclopropanation with Diazosulfones – Approaching High Stereoselectivity through Modular Design of D2‐Symmetric Chiral Porphyrins
Authors: Zhu Shifa , Cui Xin , Zhang X. Peter
Published: December 2011

A significant ligand effect study has been summarized for asymmetric cyclopropanation with diazosulfones catalyzed by CoII complexes of a series of D2‐symmetric chiral porphyrins. The structure of the ligands was shown to play an important role in both the reactivity and the stereoselectivity of the reactions. Fine‐tuning of the porphyrin ligand environments led to the development of an efficient CoII‐based catalytic system for cyclopropanation of styrene with diazosulfones in high diastereoselectivity and enantioselectivity.
Real Space Structure Factor for Different Quasicrystals
Authors: Wolny Janusz , Kozakowski Bartlomiej , Kuczera Pawel , Strzalka Radoslaw , Wnek Anna
Published: December 2011

The statistical approach to the description of aperiodic structures using the concept of the so called Average Unit Cell (AUC) is presented. The use of this method is shown for 1D, 2D, and 3D structures. We start with the presentation of the basic ideas for 1D simple sinusoidal modulation (1q) and the Fibonacci chain (a 1D model of a quasicrystalline structure). Up to now the AUC concept has been most thoroughly studied for 2D decagonal quasicrystals. The idea of structure factor derivation for the decorated Penrose tiling, a quasilattice for the description of decagonal quasicrystals, is presented. Two examples of structure refinement of decagonal phases from the Al‐Ni‐Co system are discussed. The potential of the cluster description of decagonal structures is also presented. The AUC construction and structure factor derivation is shown for the 3D Amman–Kramer–Neri tiling, which is a model quasilattice for the description of icosahedral phases. The AUC concept can also be extended to structures with singular‐continuous Fourier spectrum. An example for the 1D Thue–Morse sequence is studied.
David V. Tiedeman: Statistician, Scholar, and Sage
Authors: OLSON SANDRA K. , ROBERTS VALERIE F.
Published: December 2011

David V. Tiedeman, a major contributor to vocational guidance, was interviewed about influences on his initial career choice, significant others, his major contributions, and perspectives on his career. Also interviewed was Anna Miller‐Tiedeman, his collaborator and wife.
Credentialing Career Counselors
Authors: SMITH ROBERT L. , KARPATI FRANK S.
Published: December 2011

The credentialing of career counselors is an important step in ensuring quality service to individuals entering the work environment for the first time as well as individuals making midlife career changes. With over 50 million jobs changing in the next two decades, the need for credentialed career counselors is expected to multiply.
On the Perceived Non‐Utility of Research in Counseling
Authors: HEPPNER P. PAUL , ANDERSON WAYNE P.
Published: December 2011

Additional observations about the perceived non‐utility of research are offered in terms of relevance and rigor, practicum training, practitioners' work environments, and efficiency of information exchange.
Some Thoughts I Can't Help Thinking
Authors: HOWARD GEORGE S.
Published: December 2011

Specific reactions to the Heppner and Anderson, Keeney and Morris, and Gelso articles are offered. Also, some general thoughts on counseling research are provided.
Reaction to Gunnison's Article on the Similarities Between Erickson and Rogers
Authors: ROGERS CARL R.
Published: December 2011

Rogers and Erickson had no direct contact with each other's work. Whatever similarities exist developed independently. Rogers stresses his reliance on an intuitive relationship to the client's inner core and discusses the basis for this intuition. He also relies on a fundamental directional tendency which exists in every person. He trusts the client to choose his or her own goals. In these respects he sees some similarities between himself and Erickson, confirming Gunnison's points and going beyond them.
A Model for Job Development Services
Authors: BURLEW LARRY D.
Published: December 2011

A model for the skill of job development is presented. The model should be useful to employment, rehabilitation, and career counselors.
Group Facilitator Supervision Through a One‐Way Mirror
Authors: WALKER JIMMY R. , ALPHONSE ANNA , COHEN ELON
Published: December 2011

A model for group facilitator supervision using a one‐way mirror for unobtrusive observations and interventions is presented. Methodology adapted from selected family therapies was applied in a group counseling class in order to achieve live supervision.
Effects of Pressure and Legal Guideline Clarity on Counselor Decision Making in Legal and Ethical Conflict Situations
Authors: HINKELDEY NANCY S. , SPOKANE ARNOLD R.
Published: December 2011

Seventy‐two randomly selected American Mental Health Counselor Association members completed a mailed questionnaire containing four ethical conflict vignettes in written analogue form. Two levels of pressure (high and low) and legal guideline clarity (clear and unclear) were incorporated into the descriptions of the conflict situations. Participants indicated the likelihood of each of five Likert‐scaled response options designed specifically for the conflict situation in question. These options corresponded to five decision styles postulated by Janis and Mann (1977) (unconflicted adherence, unconflicted change, defensive avoidance, hypervigilance, and vigilance). The 2 × 2 analyses of variance with repeated measures of these likelihood responses revealed significant main effects for pressure and for legal guideline clarity for responses to conflict and significant interaction effects (pressure × clarity). In general, pressure tended to increase unconflicted change and hypervigilance and to decrease unconflicted adherence. Clarity of legal guidelines had few effects on decision responses. Consistent with Janis and Mann's theory, results showed that decision making was affected negatively by pressure but that participants relied little on legal guidelines in making responses to ethical conflict dilemmas.