bluuebunny/crossref_metadata_2025 huggingface dataset:
CD4+ T regulatory cells are more resistant to DNA damage compared to CD4+ T effector cells as revealed by flow cytometric analysis
Authors: Winzler Claudia , Fantinato Margherita , Giordan Marco , Calore Elisabetta , Basso Giuseppe , Messina Chiara
Published: September 2011

A number of apoptotic stimuli produce a different response by CD4+ regulatory and effector lymphocytes. So far, little is known concerning the sensitivity of CD4+ regulatory T cells (Treg) to genotoxic agents. Observations from a mouse model suggest that Treg are more resistant to DNA damage compared to CD4+ T effector cells (Teff). By flow cytometry we analysed the apoptotic response to genotoxic stimuli in culture, comparing Treg and Teff. CD4+ regulatory lymphocytes appeared to be more resistant than CD4+ effector lymphocytes. Results of costaining experiments for CD45RA suggest that this dissimilarity is not related to the differentiation to a CD45RA negative phenotype. Further, neither the antiapoptotic protein Bcl‐2 nor Bcl‐xL were found to be expressed in greater amounts by Treg compared to Teff. The differential sensitivity of Treg and Teff to DNA‐damage inducing agents may be of clinical relevance in cancer therapy. © 2011 International Society for Advancement of Cytometry
ZAP‐70 and Bcl‐2 expression in B lymphoblastic leukemia cells and hematogones
Authors: Craig Fiona E. , Monaghan Sara A. , Surti Urvashi , Swerdlow Steven H.
Published: September 2011

Background:

Flow cytometric immunophenotyping has an established role in the diagnosis and monitoring of B‐lymphoblastic leukemia (B‐LL). However, the search continues for an optimal reagent set that can identify leukemic blasts with specificity, reproducibility, and sensitivity, at any point during the course of the disease and in every specimen type.

Methods:

This study evaluated the diagnostic utility of detecting the intracytoplasmic antigens zeta‐associated protein (ZAP‐70) and Bcl‐2 in the distinction between the leukemic blasts of B‐LL and hematogones.

Results:

In comparison with hematogones in reference specimens, significantly higher levels of Bcl‐2 were identified in 21 of 23 (91%) B‐LL. In particular, Bcl‐2 expression was consistently higher in leukemic blasts with bright intensity CD10 expression than the equivalent most immature (CD10 bright intensity) hematogones. As previously reported, Bcl‐2 expression was lower in B‐LL with BCR‐ABL1 gene rearrangement, but the fluorescence intensity of this group of specimens was still significantly higher than that seen for hematogones. In contrast, ZAP‐70 was expressed at significantly higher levels in only 7 of 23 (30%) B‐LL and demonstrated other findings that might limit clinical utility, including differences in the level of ZAP‐70 expression during therapy and between blasts in the peripheral blood and bone marrow.

Conclusions:

Bcl‐2 over‐expression provides a useful tool for the distinction between B‐LL and hematogones. In contrast, although further optimization of the ZAP‐70 assay might increase the sensitivity of detection, over‐expression of ZAP‐70 was identified in only a minority of B‐LL. © 2011 International Clinical Cytometry Society
Comparison of different antenna arrays for the BER reduction in indoor wireless communication
Authors: Ho Min‐Hui , Chiu Chien‐Ching , Liao Shu‐Han
Published: September 2011

In this paper, we use the ultra wideband antenna array combined with particle swarm optimization (PSO) to minimize the BER for indoor communication systems. Three types of antenna arrays, namely the circular shape, L shape, and Y shape arrays, are used in the transmitter and their corresponding BER on several paths in the indoor environment are calculated. On the basis of the topography of the antenna array and the BER formula, the array pattern synthesis problem can be reformulated into an optimization problem and solved by the PSO. The novelties of our approach is not only choosing BER as the object function instead of the sidelobe level of the antenna pattern, but also considering the antenna feed length effect of each array element. The particle swarm optimization algorithm is employed to optimize the excitation voltages and feed lengths for these antenna arrays to reduce the BER. The strong point of the PSO is that it can find the solution even if the performance index cannot be formulated by simple equations. By the obtained antenna patterns, we can know the route with the lowest BER; meanwhile, transmission power using this route can be reduced. Numerical results show that the synthesized antenna array pattern is effective in focusing maximum gain to the line‐of‐sight path for these antenna arrays. The synthesized array pattern also can mitigate severe multipath fading in complex propagation environments. As a result, the BER can be reduced substantially in indoor ultra wideband communication systems. The investigated results can help communication engineers improve their planning and design of indoor wireless communication.Copyright © 2011 John Wiley & Sons, Ltd.
Cytodiagnosis of congenital mesoblastic nephroma: A case report
Authors: Kulkarni Medha Pradeep , Gosavi Alka Vikas , Anvikar Arti Rameshrao , Ramteerthakar Nayan A. , Lanjewar Dhaneshwar N.
Published: September 2011

Mesoblastic nephroma (MN) is the most common renal tumor diagnosed in infancy. A case of congenital MN was diagnosed in a 6‐month old child by fine‐needle aspiration cytology. The smears were cellular and consisted of plump spindle cells arranged in clusters along with scattered naked nuclei in the background. Blastemal, epithelial, or glomeruloid structures were not seen. Considering the age and the cytomorphology, a diagnosis of cellular variant of MN was offered which was confirmed on histopathology. Unlike Wilms tumor, preoperative chemotherapy is not required for MN. Hence cytologic diagnosis is important. Diagn. Cytopathol. 2013. © 2011 Wiley Periodicals, Inc.
Nuclear characteristics of the endometrial cytology: Liquid‐based versus conventional preparation
Authors: Norimatsu Yoshiaki , Shigematsu Yumie , Sakamoto Shingo , Ohsaki Hiroyuki , Yanoh Kenji , Kawanishi Namiki , Kobayashi Tadao K.
Published: September 2011

The aim of this study was to assess the utility of liquid‐based cytologic preparation (LP) compared with conventional preparation (CP) for the assessment of nuclear findings in endometrial glandular and stromal breakdown (EGBD) which may be misdiagnosed as carcinoma in EGBD cases. The material consists of cytologic smears including 20 cases of proliferative endometrium (PE), 20 cases of EGBD, and 20 cases of endometrioid adenocarcinoma grade1 (G1) for which histopathological diagnosis was obtained by endometrial curettage at the JA Suzuka General Hospital. Nuclear findings were examined in PE cells, EGBD‐stromal cells, EGBD‐metaplastic cells, and G1 cells, respectively. It was examined about the following items; (1) nuclear shape; (2) A long/minor axis ratio in cell nuclei; (3) an area of cell nuclei; (4) overlapping nuclei. Results are as follows: (1) nuclear shape; as for the reniform shape of EGBD‐stromal cells and spindle shape of EGBD‐metaplastic cells, the ratio of the LP method was a higher value than the CP method. (2) The long axis and area of cell nuclei; LP in all groups was a recognizable tendency for nuclear shrinkage. (3) The long/minor axis ratio in cell nuclei; only EGBD‐metaplastic cells recognize a significant difference between CP and LP. (4) Overlapping nuclei; LP was a higher value in comparison with CP in the other groups except PE cells, and the degree of overlapping nuclei was enhanced about three times. Therefore, although a cell of LP has a shrinking tendency, (1) it is excellent that LP preserves a characteristic of nuclear shape than CP; (2) a cellular characteristic becomes clearer, because three‐dimensional architecture of LP is preserved of than CP. As for the standard preparation method for endometrial cytology samples, we considered that a concrete introduction of the LP method poses no problems. Diagn. Cytopathol. 2013. © 2011 Wiley Periodicals, Inc
Fungal contamination of Hanks solution
Authors: Henwood Anthony
Published: September 2011

Laboratory contamination of clinical specimens submitted for cytological examination is an on‐going threat that requires continuous vigilance and quality control. We recently were confronted with a suspected fungal infection in a bone aspirate that was found to derive from contaminated Hanks solution used in cytological preparation. Diff‐Quik staining of air‐dried cytocentrifuged preparations of Hanks fluid as well as any other suspect laboratory fluid is recommended as a routine quality control procedure. Diagn. Cytopathol. 2013. © 2011 Wiley Periodicals, Inc.
Regulation of spinal interneuron differentiation by the paracrine action of glycine
Authors: Côté Sebastien , Drapeau Pierre
Published: September 2011

Glycine and γ‐aminobutyric acid (GABA) are depolarizing during early development but the purpose is unclear. We tested the effect of altering glycine signaling in zebrafish embryos by overexpressing the potassium‐chloride co‐transporter type 2 (KCC2) to reverse the chloride gradient or by blocking glycine receptors with strychnine or by selectively knocking down the embryonic glycine receptor (GlyR KD). Using a variety of markers we observed in all three cases a reduction of all types of spinal interneuron populations examined, indicating that glycine modulates their overall differentiation rather than choice of cell fate. Other cell populations (motor, sensory, and glial cells) were unaffected. As glycine appeared to act preceding neural and synaptic development, we examined the bandoneon (beo) mutant in which glycine receptors are functional but not clustered at synapses. Neural populations in beo embryos appeared normal, suggesting a paracrine action of circulating glycine in promoting interneuron differentiation. © 2011 Wiley Periodicals, Inc. Develop Neurobiol 72: 208–214, 2012
Generation of mice with a conditional allele for the transforming growth factor beta3 gene
Authors: Doetschman Thomas , Georgieva Teodora , Li Hongqi , Reed Thomas D. , Grisham Christina , Friel Jacqueline , Estabrook Mark A. , Gard Connie , Sanford L.P. , Azhar Mohamad
Published: September 2011

The transforming growth factor beta (TGFβ) pathway is involved in embryonic development and several inherited and acquired human diseases. The gene for TGFβ3 (Tgfb3) encodes one of the three ligands for TGFβ receptors. It is widely expressed in the embryo and its mutation or misexpression is found in human diseases. Tgfb3−/− mice die at birth from cleft palate, precluding functional studies in adults. Here, we generated mice in which exon 6 of Tgfb3 was flanked with LoxP sites (Tgfb3flox/flox). The adult mice were normal and fertile. EIIa‐Cre‐mediated deletion of exon 6 in Tgfb3flox/flox mice efficiently generated Tgfb3 conditional knockout (Tgfb3cko/cko) mice which died at birth from the same cleft palate defect as Tgfb3−/− mice, indicating that the conditional and knockout alleles are functionally equivalent. This Tgfb3cko allele will now enable studies of TGFβ3 function in different cell or tissue types in embryonic development and during adulthood. genesis 50:59–66, 2012. © 2011 Wiley Periodicals, Inc.
Signaling and gene regulatory programs in plant vascular stem cells
Authors: Zhou Jing , Sebastian Jose , Lee Ji‐Young
Published: September 2011

A key question about the development of multicellular organisms is how they precisely control the complex pattern formation during their growth. For plants to grow for many years, a tight balance between pluripotent dividing cells and cells undergoing differentiation should be maintained within stem cell populations. In this process, cell–cell communication plays a central role by creating positional information for proper cell type patterning. Cell‐type specific gene regulatory networks govern differentiation of cells into particular cell types. In this review, we will provide a comprehensive overview of emerging key signaling and regulatory programs in the stem cell population that direct morphogenesis of plant vascular tissues. genesis 49:885–904, 2011. © 2011 Wiley Periodicals, Inc.
Are eating disorders a significant clinical issue in urban India? a survey among psychiatrists in Bangalore
Authors: Chandra Prabha S. , Abbas Sarvath , Palmer Robert
Published: September 2011

Objective:

It is believed that cultural changes such as urbanization and westernization can lead to increasing rates of eating disorders (EDs). A survey was conducted among psychiatrists in Bangalore, India to assess whether they were seeing more cases of ED in the last year.

Method:

Contact details of all psychiatrists in urban Bangalore were obtained from the directory of the local psychiatric society. These psychiatrists were contacted by telephone, email, or in person. A brief proforma was used to record information about the number and nature of eating disorders they had seen in their practice in the last one year.

Results:

Sixty‐six psychiatrists took part in the study. Thirty‐eight (56%) were in private practice and 28 (42%) in teaching hospitals. 45 (67%), reported having seen patients with eating disorders in the last year. The total number of cases seen was 74. Of these, 32 were diagnosed as anorexia nervosa (AN), 12 as bulimia nervosa (BN), and 30 as eating disorders not otherwise specified (EDNOS). Sixteen (23.5%) respondents were of the opinion that EDs were increasing in Bangalore, 18 (26.5%) felt the rates were stable and 28 (42%) were not sure.

Discussion:

Two‐thirds of psychiatrists reported seeing at least one case of ED indicating that EDs are not uncommon in urban India. Epidemiological studies of EDs in India are needed to provide better estimates of their prevalence. © 2011 by Wiley Periodicals, Inc. (Int Eat Disord 2012;)
A case of anorexia nervosa with disseminated intravascular coagulation syndrome
Authors: Haruta Izumi , Asakawa Akihiro , Ogiso Kazuma , Amitani Haruka , Amitani Marie , Tsai Minglun , Hamada Satoshi , Inui Akio
Published: September 2011

A 36‐year‐old Japanese woman with anorexia nervosa (AN) was admitted to our department because of severe emaciation. Although we were thorough in her clinical management and were careful to avoid precipitating refeeding syndrome, disseminated intravascular coagulation (DIC) developed 3 weeks after hospitalization. We treated her for DIC with sepsis using anticoagulants, protease inhibitors, antithrombin, and platelet concentrate transfusion. To treat her bacterial infection, we administered antimicrobial drugs and immunoglobulin. We began probiotic and prebiotic (synbiotics) treatment for bacterial translocation. We think that the prevention of sepsis via bacterial translocation is an important aspect of care for patients with severe AN in addition to the prevention of refeeding syndrome. © 2011 by Wiley Periodicals, Inc. (Int J Eat Disord 2012)
An examination of the food addiction construct in obese patients with binge eating disorder
Authors: Gearhardt Ashley N. , White Marney A. , Masheb Robin M. , Morgan Peter T. , Crosby Ross D. , Grilo Carlos M.
Published: September 2011

Objective:

This study examined the psychometric properties of the Yale food addiction scale (YFAS) in obese patients with binge eating disorder (BED) and explored its association with measures of eating disorder and associated psychopathology.

Method:

Eighty‐one obese treatment‐seeking BED patients were given the YFAS, structured interviews to assess psychiatric disorders and eating disorder psychopathology, and other pathology measures.

Results:

Confirmatory factor analysis revealed a one‐factor solution with an excellent fit. Classification of “food addiction” was met by 57% of BED patients. Patients classified as meeting YFAS “food addiction” criteria had significantly higher levels of depression, negative affect, emotion dysregulation, eating disorder psychopathology, and lower self‐esteem. YFAS scores were also significant predictors of binge eating frequency above and beyond other measures.

Discussion:

The subset of BED patients classified as having YFAS “food addiction” appear to represent a more disturbed variant characterized by greater eating disorder psychopathology and associated pathology. © 2011 by Wiley Periodicals, Inc. (Int J Eat Disord 2011)
Oleum and Sulfuric Acid as Reaction Media: Structural Features and Thermal Behavior of RE2[W2O3(SO4)6] (RE = Sm–Gd, Ho), RE2Nb2O2(SO4)3[H(SO4)2]2 (RE = Y, Ce–Nd, Sm–Er), Sm2Nb2O2(SO4)5(S2O7), and M2Nb4O5(SO4)8 (M = Bi, Eu)
Authors: Betke Ulf , Wickleder Mathias S.
Published: September 2011

The first examples of ternary sulfates containing refractory metals and trivalent ions of the rare‐earth group and bismuth were prepared by solvothermal synthesis from H2SO4/SO3 mixtures. The tungsten compounds RE2[W2O3(SO4)6] (RE = Sm–Gd, Ho) were obtained by the reaction of WOCl4 and RE2O3 in oleum (25 % SO3). They crystallize in the monoclinic space group C2/c and contain the unique [W2O3(SO4)6]6– anion. Thermal decomposition leads to the oxides RE2O(WO4)2. Tetragonal rare‐earth–niobium sulfates of the type RE2Nb2O2(SO4)3[H(SO4)2]2 (RE = Y, Ce–Nd, Sm–Er) (space group P$\bar {4}$21m) were synthesised from NbCl5 and RE2O3 in 100 % H2SO4. They contain [O3SO···H···OSO3]3– ions featuring a strong hydrogen bond and form a polymeric structure with niobium in an octahedral coordination and the rare‐earth ion is surrounded by eight [SO4] tetrahedra in the form of a square antiprism. The decomposition temperature of RE2Nb2O2(SO4)3[H(SO4)2]2 depends on the size of the respective rare‐earth ion with a maximum in thermal stability found for RE = Sm–Gd (≈550 °C). The reaction of NbCl5 and Sm(NO3)3·6H2O in oleum (25 % SO3) yielded Sm2Nb2O2(SO4)5(S2O7), which is a possible intermediate of the thermal decomposition of Sm2Nb2O2(SO4)3[H(SO4)2]2. It crystallizes in the monoclinic space group I2/a and contains 2∞[NbO(SO4)2/2(SO4)3/3] layers connected by 2∞[Sm(SO4)2/4(S2O7)2/4] units to a polymeric structure. Reaction of NbCl5 with (BiO)2CO3 or Eu2O3 in 95 % H2SO4 yielded M2Nb4O5(SO4)8 (M = Bi, Eu, monoclinic, space group C2/c). These compounds contain the unprecedented [M2Nb4O5]16+ cluster cation and decompose into MNbO4 and Nb2O5 on heating.
Waste rapeseed oil as a substrate for medium‐chain‐length polyhydroxyalkanoates production
Authors: Możejko Justyna , Przybyłek Grzegorz , Ciesielski Slawomir
Published: September 2011

Medium‐chain‐length polyhydroxyalkanoates (mcl‐PHAs) are biodegradable, biocompatible polyesters produced by many bacteria as intracellular storage compounds of energy and carbon. They have gained great attention as a new green alternative to petrochemical plastic such as polypropylene. The present study was focused on mcl‐PHA production by two Pseudomonas strains (Gl01 and Gl06). To make this process more economical, waste rapeseed oil was used as a carbon source. The levels of PHAs synthesized by Pseudomonas sp. Gl01 strain and Gl06 strain were 21.0%, and 19.3% of CDW, respectively. The polyester accumulation increased until nitrogen and oxygen were depleted from the medium. Reverse transcription real‐time PCR approach was applied to quantitatively evaluate phaC1, phaC2, and phaZ gene expression. A positive correlation was found between the cellular PHA content and the gene expression of the PHA synthases. The transcriptional analysis revealed that the phaC1 and phaZ genes could be co‐transcribed. The overexpressed phaC2 gene was only observed in the Gl06 strain. The monomeric composition of the obtained mcl‐PHA was dependent on the strain: 3‐hydroxyoctanoic acid (3HO) and 3‐hydroxydecanoic acid (3HD) were dominant in strain Gl01, whereas 3‐hydroxyhexanoic (3HHx) was present in significant amounts in strain Gl06.

Practical applications: This article presents the procedure of medium‐chain‐length polyhydroxyalkanoates (mcl‐PHAs) synthesis by the Pseudomonas Gl01 and Gl06 strains from waste rapeseed oil as a feedstock. Beside the microbial production of these environmentally friendly plastics, this approach also represents a new way of utilizing waste oils. The knowledge of the key enzymes involved in mcl‐PHAs accumulation is necessary in order to understand the mechanisms of their synthesis, and to use them effectively in biotechnological applications.
Valence Isomerization between Diazo Compounds and Diazirines
Authors: Korneev Sergei M.
Published: September 2011

Diazo compounds and diazirines have been separately studied in detail and are widely used in research and for applied purposes. Although the mutual isomerization of these compounds was discovered 50 years ago, it has still been only modestly investigated. Meanwhile, this type of mutual transformation has to be taken into account on every occasion when one of these compounds is used or investigated. This review discusses all main cases of mutual isomerization between diazo compounds and diazirines with the goal of providing an impulse for its rational application, as well as describing the isomerism.
Total Synthesis of (+)‐7,11‐Helianane and (+)‐5‐Chloro‐7,11‐helianane through Stereoselective Aromatic Claisen Rearrangement
Authors: Quartieri Francesca , Mesiano Laura Elisabetta , Borghi Daniela , Desperati Viviana , Gennari Cesare , Papeo Gianluca
Published: September 2011

The aromatic bisabolene sesquiterpene of marine origin (+)‐7,11‐helianane (1) and its moderately cytotoxic halogenated relative (+)‐5‐chloro‐7,11‐helianane (3) have been synthesized by a concise, stereoselective route. By capitalizing on a palladium‐catalyzed asymmetric allylic alkylation (Pd‐AAA) reaction, followed by a thermal (uncatalyzed) aromatic Claisen rearrangement, which allowed for the installation of the required benzylic stereocenter, the aforementioned natural products were secured in 80 % ee, with almost complete transfer of stereochemical information during the [3,3] sigmatropic process. The enantioselective total synthesis confirmed the recently proved (S) absolute configuration for (+)‐7,11‐helianane (1) and demonstrated the same configuration, for the first time, in the case of (+)‐5‐chloro‐7,11‐helianane (3).
Effect of Surfactant Structure on Carbon Nanotube Sidewall Adsorption
Authors: Di Crescenzo Antonello , Germani Raimondo , Del Canto Elisa , Giordani Silvia , Savelli Gianfranco , Fontana Antonella
Published: September 2011

One conventional and two related gemini surfactants have been used for the preparation of stable single‐walled carbon nanotube (SWNT) aqueous dispersions. The surfactants investigated are able to disperse SWNTs at surfactant/carbon nanotube weight ratios far lower than widely used conventional surfactants. The gemini surfactants investigated demonstrated the ability to solubilize a larger amount of SWNTs with respect to the related single‐tailed surfactant at concentrations far lower than their critical micellar concentrations. Their selectivity towards semiconducting SWNTs with large diameters was inferred from radial breathing mode Raman data.
Tetrathiaheterohelicene Phosphanes as Helical‐Shaped Chiral Ligands for Catalysis
Authors: Monteforte Marco , Cauteruccio Silvia , Maiorana Stefano , Benincori Tiziana , Forni Alessandra , Raimondi Laura , Graiff Claudia , Tiripicchio Antonio , Stephenson G. Richard , Licandro Emanuela
Published: September 2011

Tetrathia[7]helicene‐based phosphanes thiaheliphos (2a), nPr‐thiaheliphos (2b) and di‐nPr‐thiaheliphos (2c) have been prepared from the 2,13‐dilithio derivatives of thiahelicenes 1a–c by reaction with an excess of Ph2PCl. Protection of the air‐sensitive products as BH3 adducts, from which the phosphanes 2a–c are easily regenerated on heating with ethanol, is described. New rhodium(I) complexes 8 and 9 were obtained by reaction of 2c with [Rh(COD)2]+[BF4]– and [BARF]–,respectively, which were converted by oxidation into thechelating phosphane–phosphane oxide RhI complexes 10 and 11. The monophosphane 5 was similarly prepared, and reaction of the dilithio species with ClP(O)(OEt)2 gave the diphosphonate 17, which was characterized by X‐ray crystallography. Comparison of data from DFT calculations (B3LYP/SVP) on 2c, 8 and 10 and X‐ray data for 17 reveals a strong tension within the thiaheliphos ligands that is partially relaxed by increasing the Rh–P distances and the bite angle of the chelating ligand. Compound (P)‐(+)‐1c, obtained by chromatographic resolution, was transformed into optically pure (P)‐(+)‐2c, which was used in the asymmetric hydrogenation of itaconic acid ester and methyl 2‐acetamidoacrylate (product ees up to 40 %).
Regio‐ and Stereocontrolled Synthesis of (Z)‐α‐(Phenylseleno)sulfinyl and ‐sulfonyl Alkenes via Sulfenic Acids, and a Study of their Reactivity
Authors: Aversa Maria Chiara , Barattucci Anna , Bonaccorsi Paola , Temperini Andrea
Published: September 2011

A general procedure for the synthesis of α‐(phenylseleno)sulfinyl and ‐sulfonyl alkenes has been described. 1‐(Phenylseleno)ethenyl sulfoxides were prepared by the syn‐addition of in situ‐generated sulfenic acids on to the triple bond of suitably substituted (phenylseleno)acetylenes. 1‐(Phenylseleninyl)ethenyl sulfones were obtained by further oxidation of their sulfinyl analogues. The mild conditions of the sulfenic acid/(phenylseleno)alkyne syn‐addition and its stereospecificity and regioselectivity allowed us to obtain electron‐poor alkenes with a well defined stereochemistry and sensitive substituents at the double bond. Chiral (Z)‐1‐[(2,3,4,6‐tetra‐O‐acetyl‐β‐D‐glucopyranosyl)sulfinyl]‐1‐(phenylseleno)‐1‐hexene was also obtained via the enantiopure2,3,4,6‐tetra‐O‐acetylglucosulfenic acid. The reactivity of α‐(phenylseleninyl)sulfinyl and ‐sulfonyl alkenes has been evaluated in nucleophilic additions to the electron‐poor double bond, conducted with hard nucleophiles such as piperidine and phenol.
The Effect of the Cation π‐Surface Area on the 3D Organization and Catalytic Ability of Imidazolium‐Based Ionic Liquids
Authors: D'Anna Francesca , Marullo Salvatore , Vitale Paola , Noto Renato
Published: September 2011

The dichotomic nature of ionic liquids (ILs, simple solvents or supramolecular fluids) induced us to carry out a structural investigation of some mono‐ and dicationic ionic liquids using 1D and 2D NMR, resonance light scattering, and UV/Vis spectroscopy. Ionic liquids with different cation π‐surface areas were used, namely [bmim][NTf2], [Bzmim][NTf2], [Bzbim][NTf2], [p‐Xyl‐(bim)2][NTf2]2, and [m‐Xyl‐(bim)2][NTf2]2 [bmim = 1‐butyl‐3‐methylimidazolium, Bzmim = 1‐benzyl‐3‐methylimidazolium, Bzbim = 1‐benzyl‐3‐butylimidazolium, NTf2 = bis(trifluoromethansulfonyl)imide]. In order to verify to what extent the structural investigation, coupled with the determination of solvent parameters, could help to rationalize the effects of the solvent media on a given reaction, the thermally induced mononuclear rearrangement of heterocycles was studied. Variation of the cation structure has significant repercussions on the 3D structure of the ILs and on the effect they can exert on a given reaction.
Synthesis of Pyridin‐2(1H)‐one Derivatives: Temperature‐Dependent Selectivity
Authors: Chikhalikar Sandip , Bhawe Vijay , Jachak Madhukar , Ghagare Maruti
Published: September 2011

Two alternative methods for the synthesis of biologically important pyridin‐2(1H)‐one derivatives have been developed. The behavior of enamine 1 with aromatic amines in an aqueous solution of HCl resulted in the formation of substituted enamines 2a–f at ambient temperature. The obtained product enamines 2a–f, upon treatment with 2,2,6‐trimethyl‐4H‐1,3‐dioxin‐4‐one, generated pyridin‐2(1H)‐one derivatives 5a–f along with the unwanted side products 8a–f. However, the exclusive formation of pyridin‐2(1H)‐one derivatives 5a–f was achieved when starting from β‐enaminones 3a–f, which were synthesized successfully from enamine 1 and aromatic amines at elevated temperatures.
Amino Surface‐Functionalized Tris(calix[4]arene) Dendrons with Rigid C3‐Symmetric Propeller Cores
Authors: Gattuso Giuseppe , Grasso Giulia , Marino Nino , Notti Anna , Pappalardo Andrea , Pappalardo Sebastiano , Parisi Melchiorre F.
Published: September 2011

Dendrons composed of three functionalized cone calix[4]arene substructures covalently bound to rigid C3‐symmetric tris‐anilino cores through amide linkages have been obtained by a divergent synthetic protocol involving the coupling of p‐nitrocalix[4]arene butanoic acid 9 with tris(4‐aminophenyl)amine (TAPA), 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), and 2,4,6‐tris(4‐aminophenyl)‐s‐triazine (TAPT). Two different amidation procedures were used to generate the dodecanitro intermediates (through activation of acid 9 with PyBOP catalyst or transformation into its acid chloride). The final reduction to the title dodecaamino dendrons was smoothly carried out with H2 and Raney‐Ni catalyst.
Hyaluronan–Carbon Nanotube Derivatives: Synthesis, Conjugation with Model Drugs, and DOSY NMR Characterization
Authors: Marega Riccardo , Bergamin Massimo , Aroulmoji Vincent , Dinon Francesca , Prato Maurizio , Murano Erminio
Published: September 2011

Carbon nanotube (CNTs) derivatives are nowadays under thorough investigation as biomedically interesting materials. In this paper we describe a method for the preparation of water‐soluble CNTs by condensation of the carboxylic groups introduced onto the carbon framework and the primary amine moieties inserted in the naturally occurring biopolymer hyaluronan (HA). The covalent conjugation between CNTs and HA should merge the biocompatibility and further processability of the HA chains with the well‐known cellular penetration properties of the CNT derivatives to produce novel drug delivery platforms. In fact, thanks to the primary amino groups introduced in the HA chains, HA–CNT derivatives can be further covalently modified with model drugs like ibuprofen and methotrexate. We describe also the monitoring of all the CNT derivatization steps by diffusion‐ordered NMR spectroscopy (DOSY), a technique that allows fast and reliable characterization of these novel derivatives.
[5]Ferrocenophanene–Phosphane Ligands for Enantioselective Rh‐Catalyzed Conjugate Additions
Authors: Csizmadiová Jana , Mečiarová Mária , Rakovský Erik , Horváth Branislav , Šebesta Radovan
Published: September 2011

Ferrocenophanene–phosphane ligands with bridged cyclopentadienyl rings have been synthesized and characterized by spectroscopic methods. Rhodium complexes of these ligands can catalyze the Michael addition of phenylboronic acid to cyclic enones and lactones with good yields and an interesting level of stereoselectivity [up to a 95:5 enantiomeric ratio (er)]. In comparison, a ligand without a bridge between the cyclopentadienyl rings affords a product with a lower enantioselectivity (er = 78:22).
Bulk Heterojunction Solar Cells – Tuning of the HOMO and LUMO Energy Levels of Pyrrolic Squaraine Dyes
Authors: Beverina Luca , Drees Martin , Facchetti Antonio , Salamone Matteo , Ruffo Riccardo , Pagani Giorgio A.
Published: September 2011

The optimization of organic photovoltaic (OPV) devices requires, amongst several factors mainly related to thin‐film blend morphology, the capability to finely tune the characteristic energy levels of both the donor and the acceptor materials constituting the active layer. Squaraine compounds represent one of the most promising small molecule materials to be employed as the donor in the bulk heterojunction (BHJ) OPV configuration. In this study a series of arylhydrazone end‐capped symmetric squaraine compounds bearing electron‐withdrawing substituents on the aryl ring has been synthesized with the aim of increasing the device open circuit voltage by shifting the highest occupied molecular orbital (HOMO) energy level. These new semiconductors have been characterized by optical spectroscopy (UV/Vis absorption and IR transmittance) and electrochemical measurements (cyclic voltammetry and differential pulsed voltammetry). Our data enable the establishment of interesting structure–property relationships relating the nature, position and number of electron‐withdrawing substituents to the position of the donor HOMO and lowest unocupied molecular orbital (LUMO) levels. The low energy shift effect on the HOMO level with respect to the parent unsubstituted squaraine can be as high as 0.3 eV. The effect is so strong that the derivative bearing the strongest acceptor no longer behaves as a donor semiconductor. Preliminary results on OPV device preparation and characterization are also discussed.
Enantioselective Molecular Recognition of Chiral Organic Ammonium Ions and Amino Acids Using Cavitand–Salen‐Based Receptors
Authors: Amato Maria E. , Ballistreri Francesco P. , D'Agata Salvatore , Pappalardo Andrea , Tomaselli Gaetano A. , Toscano Rosa M. , Sfrazzetto Giuseppe Trusso
Published: September 2011

Two new receptors, a cavitand–salen (2) and a uranyl–cavitand–salen (3), for the selective molecular recognition of chiral ammonium ion pairs, where the amino acid is the countercation or counteranion of the ion pair, were designed and synthesized. UV/Vis measurements indicate the formation of 1:1 host–guest complexes with high association constants and good to excellent enantiomeric discriminations. NMR spectroscopic experiments confirmed cation–π interactions between the organic cations and the π‐electron‐rich cavity, leading to the stability of the complexes, as well as the coordination of the amino acid carboxylate anion to the uranyl metal center. Extraction experiments showed that a racemic mixture of (R,S)‐α‐methylbenzyltrimethylammonium iodides undergoes chiral resolution by 2 with high selectivity.
Naplephos through the Looking‐Glass: Chiral Bis(phosphanylamides) Based on β‐1,2‐D‐Glucodiamine and Their Application in Enantioselective Allylic Substitutions
Authors: Benessere Vincenzo , De Roma Antonella , Del Litto Raffaella , Lega Matteo , Ruffo Francesco
Published: September 2011

The straightforward design of a new library of chiral ligands (elpanphos) based on β‐1,2‐D‐glucodiamine is described, which represents the enantiomeric counterpart of the naplephos library. In this guise, two representative ligands have been successfully applied in the Pd‐catalyzed desymmetrization of meso‐cyclopent‐2‐ene‐1,4‐diol, which leads to the expected enantiomer within short times and with high ees in both traditional and unconventional solvents.
Effective Synthesis of ortho‐Substituted Trithiophenol Amines by Miyazaki–Newman–Kwart Rearrangement
Authors: Gjoka Blerina , Romano Francesco , Zonta Cristiano , Licini Giulia
Published: September 2011

An efficient synthesis of ortho‐substituted trithiophenol amines from commercially available salicaldehydes by Miyazaki–Newman–Kwart rearrangement/threefold reductive amination is reported. The rearrangement has been carried out on salicaldehyde‐O‐thiocarbamates using microwave induced heating, which furnishes a series of thiosalicaldehyde‐S‐carbamates in high yield. The thiocarbamate has three roles: it enables effective S–O rearrangement, acts as a protecting group during the threefold reductive amination and can be easily removed under reductive conditions. The three‐step synthesis has an overall yield ranging from 30–35 %, and it enables access to a series of increasingly important C3v symmetric ligands in a structurally systematic way.
Chiral analysis of amphetamines, methadone and metabolites in biological samples by electrodriven methods
Authors: Mandrioli Roberto , Mercolini Laura , Raggi Maria A.
Published: September 2011

Amphetamines and methadone are synthetic chiral drugs with a high potential for abuse. As such, several analytical methods have been developed for their enantioseparation and analysis in biological tissues, and some of these are based on electrodriven techniques. In this review, the most important and recent of these latter methods are reviewed and their main advantages and disadvantages are discussed. Particular attention is paid to the suitability of each method for the application to the biological matrix of interest: while all methods have been successfully applied for one or more biological tissues, to reach this goal they must overcome the sensitivity problem that is common to almost all capillary electrophoretic techniques. Most methods use one or more cyclodextrin derivatives as the chiral selector, thus the separation mechanism is not particularly complicated or unusual.
Enantiomeric separation of FMOC‐amino acids by nano‐LC and CEC using a new chiral stationary phase, cellulose tris(3‐chloro‐4‐methylphenylcarbamate)
Authors: Domínguez‐Vega Elena , Crego Antonio L. , Lomsadze Ketevan , Chankvetadze Bezhan , Marina Maria L.
Published: September 2011

A novel polysaccharide‐based chiral stationary phase (CSP), cellulose tris(3‐chloro‐4‐methylphenylcarbamate), also known as Sepapak‐2 or Lux Cellulose‐2, has been evaluated for the enantiomeric separation of FMOC derivatives of amino acids. After mobile‐phase optimization in nano liquid chromatography (nano‐LC) the column enabled the enantiomeric separation of 19 out of 23 amino acids tested, indicating the high chiral recognition power of this new CSP. Subsequently, a comparison of the driving force employed (pressure or voltage) was carried out comparing nano‐LC and CEC under the same conditions. Better peak efficiencies and resolution were observed by using CEC experiments, which enabled the chiral discrimination of 20 out of 23 amino acids tested. Finally, in order to show the potential of this new CSP, the determination of the content and the enantiomeric purity of the non‐protein amino acid citrulline in food supplements was performed. For that purpose, the method was optimized, evaluated and applied to different commercial samples.
Analysis of chiral amino acids in cerebrospinal fluid samples linked to different stages of Alzheimer disease
Authors: Samakashvili Shorena , Ibáñez Clara , Simó Carolina , Gil‐Bea Francisco J. , Winblad Bengt , Cedazo‐Mínguez Angel , Cifuentes Alejandro
Published: September 2011

Chiral micellar electrokinetic chromatography with laser‐induced fluorescence detection (chiral‐MEKC‐LIF) was used to investigate D‐ and L‐amino acid contents in cerebrospinal fluid (CSF) samples related to different Alzheimer disease (AD) stages. CSF samples were taken from (i) control subjects (S1 pool), (ii) subjects showing a mild cognitive impairment who remained stable (S2 pool), (iii) subjects showing an mild cognitive impairment that progressed to AD (S3 pool) and (iv) subjects diagnosed with AD (S4 pool). The optimized procedure only needed 10 μL of CSF and it included sample cleaning, derivatization with FITC and chiral‐MEKC‐LIF separation. Eighteen standard amino acids were baseline separated with efficiencies up to 703 000 plates/m, high sensitivity (LODs in the nM range) and good resolution (values ranging from 2.6 to 9.5). Using this method, L‐Arg, L‐Leu, L‐Gln, γ‐aminobutyric acid, L‐Ser, D‐Ser, L‐Ala, Gly, L‐Lys, L‐Glu and L‐Asp were detected in all the CSF samples. S3 and S4 samples (i.e. AD subjects) showed significant lower amounts of L‐Arg L‐Lys, L‐Glu and L‐Asp compared to the non‐AD S1 and S2 samples, showing in the S4 group the lowest amounts of L‐Arg L‐Lys, L‐Glu and L‐Asp. Moreover, γ‐aminobutyric acid was significantly higher in AD subjects with the highest amount also found for S4. No significant differences were observed for the rest of amino acids including D‐Ser. Based on the obtained chiral‐MEKC‐LIF data, it was possible to correctly classify all the samples into the four groups. These results demonstrate that the use of enantioselective procedures as the one developed in this work can provide some new light on the investigations of AD, including the discovery of new biomarkers related to different stages of AD.
Differences in the frequencies of K‐ras c12–13 genotypes by gender and pathologic phenotypes in colorectal tumors measured using the allele discrimination method
Authors: Chow Lihui , Lin Peng‐Chan , Chang Jeffrey S. , Chu Pei‐Yi , Lee Pao‐Kung , Chen Shan‐Na , Cheng Ying‐Min , Lee Jenq‐Chang , Chang Jang‐Yang , Liu Tsang‐Wu
Published: September 2011

The frequencies of different genotypes of the K‐ras oncogene in colorectal cancer (CRC) reveal complex relationships among gender, age, and tumor aggression, however, differences among these studies could also be attributed to a lack of standardization of the detection methods used. We developed the allele discrimination assay, which uses dual‐color real‐time polymerase chain reaction (qPCR) as a fast K‐ras genotyping method, and demonstrated higher sensitivity and specificity than DNA sequencing with formalin‐fixed paraffin tissues. The assay detected K‐ras mutations among 83 of 204 patients with CRC (40.7%); 20.6% of these mutations were G12D (GAT) mutations, 7.4% were G13D (GAC) and G12V (GTT), and 5.3% were other types. A higher proportion of females was observed overall in tumors with K‐ras mutations (60.2%, P = 0.01), codon 12 mutations (63.2%, P = 0.005), and transversions (69.6%, P = 0.02), which reflected the higher prevalence of females among the well‐ to moderately differentiated tumors (29% in males vs. 53% in females; interaction P = 0.03). The opposite was observed for poorly differentiated tumors (47% in males vs. 35% in females). No significant influence of age was found on the prevalence of K‐ras mutation. Males with pathological changes and females with poorly differentiated tumors displayed GAT as a less common genotype compared with most other prevalence studies. In conclusion, allele discrimination, with no additional amplification step, is a fast and reliable genotyping method for detecting K‐ras c12–13 mutations. Using this method, we demonstrate differences in the frequencies of K‐ras genotypes by gender and pathologic phenotypes of CRC. Environ. Mol. Mutagen., 2012. © 2011 Wiley‐Liss,Inc.
Chromodomain helicase DNA‐binding protein 2 affects the repair of X‐ray and UV‐Induced DNA damage
Authors: Rajagopalan Sangeetha , Nepa Justin , Venkatachalam Sundaresan
Published: September 2011

Eukaryotic cells have evolved a variety of parallel and redundant DNA damage response pathways that function in a coordinated fashion to prevent the fixation of DNA damage as mutations. Despite the wealth of knowledge on DNA damage signaling on downstream cellular events, the mechanisms of DNA damage recognition, DNA repair as well as DNA damage signaling in the context of chromatin is poorly understood. Chromodomain helicase DNA‐binding proteins (CHD) belong to a group of highly conserved chromatin remodeling proteins that are implicated in regulation of transcription. In an effort to understand the physiological role of one of the CHD members in a mammalian model system, we developed a mutant mouse model for the Chd2 gene. The Chd2 mutant mice are highly susceptible to spontaneous lymphoid tumor formation. In this study, we present evidence that the Chd2 mutant cells are defective in their ability to repair DNA damage induced by ionizing and ultraviolet radiation. Consistent with the role of Chd2 in regulating DNA damage responses, the Chd2 mutant cells are also sensitive to DNA damaging agents in clonogenic assays. In summary, our data suggest that the Chd2 protein is involved in regulating the DNA damage responses at the chromatin level. Environ. Mol. Mutagen. 2012. © 2011 Wiley Periodicals, Inc.
Performance analysis of UPQC with heterogeneous control during load power factor variation
Authors: Srinath S , Selvan M P
Published: September 2011

This paper deals with the analysis of a unified power quality conditioner (UPQC) with a new heterogeneous control applied to its active power filters (APF). This control, when applied to the APFs of UPQC, relieves completely the reactive power burden of the source and makes the input power factor unity. The proposed control, termed as heterogeneous control, utilizes sinusoidal pulse width modulation (SPWM) for series APF (SAPF) and hysteresis PWM for parallel APF (PAPF). No transformation is used in this control for generating the reference quantities for both voltage and current. The performance of UPQC with the proposed control is compared with other transformation less homogeneous control schemes which include hysteresis and SPWM for both APFs. The heterogeneous control performance is found superior in terms of complete reactive power support from the PAPF with reduced APF ratings. PSCAD/EMTDC simulation results are presented to show the effectiveness of the proposed control. Copyright © 2011 John Wiley & Sons, Ltd.
A novel approach for global voltage stability assessment of a power system incorporating static var compensator
Authors: Nagendra Palukuru , Halder nee Dey Sunita , Paul Subrata , Datta Tanaya
Published: September 2011

Voltage stability is a growing concern for the successful planning and operation of modern power systems. The prediction of voltage collapse point of the multibus power network through its two‐bus equivalent model is a hot topic of the research in the field of power system operation and control. This article presents a method to assess the voltage stability status of a power system incorporating the static var compensator (SVC) using a unique two‐bus π‐network equivalent model obtained with the optimal power flow solution of the actual system at different operating conditions. The novelty of the proposed methodology is that it considers the series and shunt parts of transmission losses lumped separately in equivalent series and shunt form to evaluate the π‐network equivalent two‐bus model. SVC firing angle model is integrated into optimal power flow program to investigate its effect on power system performance in terms of voltage stability assessed in the equivalent two‐bus domain. The simulation results for a practical power system (203‐bus Indian Eastern Grid) have shown that the proposed methodology is promising to assess voltage stability of any power system at any operating point in global scenario. Voltage stability margin augmentation with the application of SVC at the weakest bus is compared with the system having no compensation. In the proposed π‐network equivalent model, the generators have been modeled more accurately considering economic operation. Copyright © 2011 John Wiley & Sons, Ltd.
Cytogenetic polyclonality of breast carcinomas: Association with Clinico‐Pathological Characteristics and Outcome
Authors: Steinarsdottir Margret , Gudmundsson Ingi Hrafn , Jonasson Jon Gunnlaugur , Olafsdottir Elinborg J. , Eyfjörd Jorunn E. , Ögmundsdottir Helga M.
Published: September 2011

Routinely used prognostic factors fail to predict clinical outcome in a significant proportion of breast cancer patients, implying that they can not detect some important biological characteristics. Chromosomal changes have been described in breast carcinomas for many years but their significance is not clear. We compared chromosomal changes with clinico‐pathological characteristics and clinical outcome in 203 breast cancer patients with a follow‐up of 9–18 years. Combining data from classical cytogenetics and flow cytometry revealed chromosomal abnormalities in 142 cases (70%). Of these, 51 (35.9%) contained two or more cytogenetically abnormal clones. Polyclonality was significantly associated with poor breast‐cancer‐specific survival (P = 0.03) within 5 years, independent of tumor size, lymph node metastases, and hormone receptors. Specific changes were similar to those previously described, but a new finding was a significant association between del 3p12p21 and poor survival. Polyclonality was significantly associated with TP53‐mutations but not with a germline BRCA2 mutation. Less than one third of the polyclonal samples were identified by flow cytometry alone. Cytogenetic changes were detected in 17 out of 114 samples from non‐tumorous tissue (15%), two of them identical with a clone in the corresponding tumor. Several samples contained clearly unrelated clones within the tumor and outside, implying either multifocal origin or early divergence. In conclusion, the common deletion on Chromosome 3p12p21 was associated with poor clinical outcome. Chromosomal polyclonality is common in breast carcinomas and predicts poor survival. Polyclonality was poorly detected by one‐sample flow cytometry. Multiple sampling might improve the detection rate. © 2011 Wiley‐Liss, Inc.