bluuebunny/crossref_metadata_2025 huggingface dataset:
Twinning‐, Polytypism‐, and Polarity‐Induced Morphological Modulation in Nonplanar Nanostructures with van der Waals Epitaxy
Authors: Utama Muhammad Iqbal Bakti , de la Mata Maria , Magen Cesar , Arbiol Jordi , Xiong Qihua
Published: October 2012

Twinning, polytypism, and polarity are important aspects in nanostructural growth since their presence can affect various properties of the as‐grown products. The morphology of nanostructures grown via van der Waals epitaxy is shown to be strongly influenced by the twinning density and the presence of polytypism within the nanostructures, while the growth direction is driven by the compound polarity. With ZnTe as the model material, vertically aligned nanorods are successfully produced with variable cross‐section and branched crystals (tripods and tetrapods) on only a single type of substrate. Van der Waals epitaxy contributes by relaxing the lattice‐mismatch requirements for epitaxial growth and by enabling a variety of crystal planes in the initial stages of the growth to be interfaced to the substrate, regardless of the polarity of the epitaxial material. These results may provide more flexibility in tuning rationally the morphology of epitaxial nanostructures into other shapes with higher complexity by routine adjustment of growth environment.
Rhodium‐Catalyzed Oxidative ortho‐Acylation of Aryl Ketone O‐Methyl Oximes with Aryl and Alkyl Aldehydes
Authors: Yang Yaxi , Zhou Bing , Li Yuanchao
Published: October 2012

The rhodium‐catalyzed oxidative ortho‐acylation of aryl ketone O‐methyl oximes with aryl and alkyl aldehydes via CH bond activation is described. The cross‐coupling reaction exhibits high functional group tolerance and regioselectivity under relatively mild conditions and constitutes a versatile route to a diverse library of diaryl ketones, which are difficult to obtain by the classical Friedel–Crafts acylation. Moreover, this reaction proceeds via an unprecedented Rh‐catalyzed oxidative ortho‐acylation of aryl ketone O‐methyl oximes with highly electron‐deficient aryl aldehydes followed by a direct addition of the second ortho CH bond to aldehydes in a one‐pot reaction, to generate two CC bonds simultaneously.
Unintended effects of orphan product designation for rare neurological diseases
Authors: Murphy Sinéad M. , Puwanant Araya , Griggs Robert C. ,   the Consortium for Clinical Investigations of Neurological Channelopathies (CINCH) and Inherited Neuropathies Consortium (INC) Consortia of the Rare Disease Clinical Research Network
Published: October 2012

Since the introduction of the Orphan Drug Act in 1983, designed to promote development of treatments for rare diseases, at least 378 orphan drugs have been approved. Incentives include financial support, tax credits, and perhaps most importantly, extended market exclusivity. These incentives have encouraged industry interest and accelerated research on rare diseases, allowing patients with orphan diseases access to treatments. However, extended market exclusivity has been associated with unacceptably high drug costs, both for newly developed drugs and for drugs that were previously widely available. We suggest that a paradoxical effect of orphan product exclusivity can be reduced patient access to existing drugs. In addition, the costs of each new drug are arguably unsustainable for patients and for the American health care system. Of all the specialties, neurology has the third highest number of orphan product designations, and neurological diseases account for at least one‐fifth of rare diseases. Citing the use of tetrabenazine for chorea in Huntington disease, adrenocorticotropic hormone for infantile spasms, and enzyme replacement therapy with alglucosidase alpha for Pompe disease, we highlight these paradoxical effects. ANN NEUROL 2012;72:481–490
Auditory cortical function during verbal episodic memory encoding in Alzheimer's disease
Authors: Dhanjal Novraj S. , Warren Jane E. , Patel Maneesh C. , Wise Richard J. S.
Published: October 2012

Objective

Episodic memory encoding of a verbal message depends upon initial registration, which requires sustained auditory attention followed by deep semantic processing of the message. Motivated by previous data demonstrating modulation of auditory cortical activity during sustained attention to auditory stimuli, we investigated the response of the human auditory cortex during encoding of sentences to episodic memory. Subsequently, we investigated this response in patients with mild cognitive impairment (MCI) and probable Alzheimer's disease (pAD).

Methods

Using functional magnetic resonance imaging, 31 healthy participants were studied. The response in 18 MCI and 18 pAD patients was then determined, and compared to 18 matched healthy controls. Subjects heard factual sentences, and subsequent retrieval performance indicated successful registration and episodic encoding.

Results

The healthy subjects demonstrated that suppression of auditory cortical responses was related to greater success in encoding heard sentences; and that this was also associated with greater activity in the semantic system. In contrast, there was reduced auditory cortical suppression in patients with MCI, and absence of suppression in pAD. Administration of a central cholinesterase inhibitor (ChI) partially restored the suppression in patients with pAD, and this was associated with an improvement in verbal memory.

Interpretation

Verbal episodic memory impairment in AD is associated with altered auditory cortical function, reversible with a ChI. Although these results may indicate the direct influence of pathology in auditory cortex, they are also likely to indicate a partially reversible impairment of feedback from neocortical systems responsible for sustained attention and semantic processing. ANN NEUROL 2013;73:294–302
Implication of double‐stranded RNA signaling in the etiology of autoimmune myasthenia gravis
Authors: Cufi Perrine , Dragin Nadine , Weiss Julia Miriam , Martinez‐Martinez Pilar , De Baets Marc H. , Roussin Régine , Fadel Elie , Berrih‐Aknin Sonia , Le Panse Rozen
Published: October 2012

Objective

Myasthenia gravis (MG) is an autoimmune disease mediated mainly by anti–acetylcholine receptor (AChR) antibodies. The thymus plays a primary role in MG pathogenesis. As we recently showed an inflammatory and antiviral signature in MG thymuses, we investigated whether pathogen‐sensing molecules could contribute to an anti‐AChR response.

Methods

We studied the effects of toll‐like receptor agonists on the expression of α‐AChR and various tissue‐specific antigens (TSAs) in human thymic epithelial cell (TEC) cultures. As polyinosinic–polycytidylic acid (poly[I:C]), which mimics double‐stranded RNA (dsRNA), stimulated specifically α‐AChR expression, the signaling pathways involved were investigated. In parallel, we analyzed the expression of dsRNA‐signaling components in the thymus of MG patients, and the relevance of our data was investigated in vivo in poly(I:C)‐injected mice.

Results

We demonstrate that dsRNA signaling induced by poly(I:C) specifically triggers the overexpression of α‐AChR in TECs and not of other TSAs. A poly(I:C) effect was also observed on MG TECs. This induction is mediated through toll‐like receptor 3 (TLR3) and protein kinase R (PKR), and by the release of interferon (IFN)‐β. In parallel, human MG thymuses also display an overexpression of TLR3, PKR, and IFN‐β. In addition, poly(I:C) injections specifically increase thymic expression of α‐AChR in wild‐type mice, but not in IFN‐I receptor knockout mice. These injections also lead to an anti‐AChR autoimmune response characterized by a significant production of serum anti‐AChR antibodies and a specific proliferation of B cells.

Interpretation

Because anti‐AChR antibodies are highly specific for MG and are pathogenic, dsRNA‐signaling activation could contribute to the etiology of MG. ANN NEUROL 2013;73:281–293
Nanoplasmonic smooth silica versus porous calcium carbonate bead biosensors for detection of biomarkers
Authors: Yashchenok A.M. , Borisova D. , Parakhonskiy B.V. , Masic A. , Pinchasik B. , Möhwald H. , Skirtach A.G.
Published: October 2012

Nanoplasmonic biosensors based on gold nanoparticle functionalized smooth silica and porous calcium carbonate particles are presented. It is identified in this comparative study the role of porosity for adsorbing gold nanoparticles and subsequent detection of biomarkers. That is further applied in this study for detection of biomarkers. Detection of glucose – a biomarker of diabetes is studied together with that of bovine serum albumin – a very relevant bio‐molecule. Raman scattering is used for label‐free detection of molecules in the sub‐µM–mM range detection capabilities, which covers the range corresponding to healthy and diseased persons. Implications of current study for detection and identification of biomarkers are discussed.
Preparation and properties of three novel poly(phosphazene‐aryl amide)s containing cyclotriphosphazene structures
Authors: Zhao Zhengping , Guo Qiang , Li Xia , Sun Jinliang , Nie Zhijun , Luo Weili
Published: October 2012

1,1,3,5‐tetraphenoxy‐3,5‐bis(4‐aminoanilino)cyclotriphosphazene, 1,1,3,5‐tetraphenoxy‐3,5‐bis[4‐(4‐aminophenysulfone)anilino)]cyclotriphosphazene, and 1,1,3,5‐tetraphenoxy‐3,5‐bis(N,N′‐ethanediamine)cyclotriphosphazene were synthesized in two steps from the p‐Phenylenediamine, 4,4′‐diaminodiphenylsulfone, and ethylenediamine via nucleophilic substitution and catalytic reduction with hexachlorocyclotriphosphazene. Three novel aromatic polyamides such as poly(cyclotriphosphazene‐p‐phenylene amide), poly(cyclotriphosphazene‐p‐sulfuryl amide), and poly(cyclotriphosphazene‐ethyl amide) were synthesized from these diamines by direct polycondensation reaction with terephthaloyl chloride and pyridine in N‐methyl pyrrolidone, respectively. The chemical structures of the diamine monomers and three novel poly(cyclotriphosphazene‐aryl amide)s were characterized by Fourier Transform Infrared, (1H and 31P) Nuclear Magnetic Resonance, and Elemental Analysis. The thermal properties of the polyamides were determined by Differential Scanning Calorimetry and Thermogravimetric Analysis (TGA). The crystallization behaviors of the polyamides were studied by Wide‐ray X‐ray diffraction, and the morphology of the pyrolysis residues were observed by Scanning Electron Microscope. The three poly(cyclotriphosphazene‐aryl amide)s with amorphous structure would exhibit an enhanced solubility in polar aprotic solvents and a superior thermal stability with initial decomposition temperature being at about 198–259°C. TGA curves of the poly(cyclotriphosphazene‐aryl amide)s exhibit mainly three thermal decomposition steps, and the poly(cyclotriphosphazene‐p‐phenylene amide) presents the highest solid residue rate 62.6% heated to 600°C. In the morphology analysis of the poly(cyclotriphosphazene‐aryl amide) solid residues, organophosphorus gelatum forms in the surface layer were observed. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013
Functional near‐infrared spectroscopy for the assessment of overt reading
Authors: Safi Dima , Lassonde Maryse , Nguyen Dang Khoa , Vannasing Phetsamone , Tremblay Julie , Florea Olivia , Morin‐Moncet Olivier , Lefrançois Mélanie , Béland Renée
Published: October 2012

Functional near‐infrared spectroscopy (fNIRS) has become increasingly established as a promising technique for monitoring functional brain activity. To our knowledge, no study has yet usedfNIRSto investigate overt reading of irregular words and nonwords with a full coverage of the cerebral regions involved in reading processes. The aim of our study was to design and validate a protocol usingfNIRSfor the assessment of overt reading. Twelve healthy French‐speaking adults underwent one session offNIRSrecording while performing an overt reading of 13 blocks of irregular words and nonwords. Reading blocks were separated by baseline periods during which participants were instructed to fixate a cross. Sources (n = 55) and detectors (n = 16) were placed bilaterally over frontal, temporal, parietal, and occipital regions. Two wavelengths were used: 690 nm, more sensitive to deoxyhemoglobin (HbR) concentration changes, and 830 nm, more sensitive to oxyhemoglobin (HbO) concentration changes. For all participants, total hemoglobin (HbT) concentrations (HbO + HbR) were significantly higher than baseline for both irregular word and nonword reading in the inferior frontal gyri, the middle and superior temporal gyri, and the occipital cortices bilaterally. In the temporal gyri, although the difference was not significant, [HbT] values were higher in the left hemisphere. In the bilateral inferior frontal gyri, higher [HbT] values were found in nonword than in irregular word reading. This activation could be related to the grapheme‐to‐phoneme conversion characterizing the phonological pathway of reading. Our findings confirm thatfNIRSis an appropriate technique to assess the neural correlates of overt reading.
Comparable clinical safety and efficacy of biodegradable versus durable polymer paclitaxel eluting stents despite shorter dual antiplatelet therapy: Insights from a multicenter, propensity score‐matched registry
Authors: Buszman Piotr P. , Orlik Bartlomiej , Trela Blazej , Milewski Krzysztof , Kozlowski Michal , Pruski Maciej , Drzewiecki Janusz , Peppas Athanasios , Granada Juan F. , Kaluza Greg L. , Buszman Pawel E.
Published: October 2012

Background

The biodegradable polymer drug‐eluting stents have been proposed as an alternative to durable polymer DES, theoretically improving vessel healing and reducing the need for prolonged double anti platelet therapy (DAPT), however clinical significance of this technology is under debate. Therefore, we sought to compare the clinical outcomes of two Paclitaxel eluting stents (PES) containing different polymer‐based eluting matrices.

Methods

In this multicenter registry of 392 consecutive patients who underwent PCI between June 2006 and September 2008, we included patients with stable angina or NSTE‐ACS displaying at least one significant lesion (>50% diameter stenosis) in native coronary arteries.

Results

Biodegradable polymer PES (BP‐PES, LUC Chopin2, Balton, Poland) was implanted in 206 patients, whereas durable polymer PES (DP‐PES, Taxus, Boston Scientific, USA) was implanted in 186 patients. There were no significant differences in baseline characteristics between groups with the exception of increased diabetes and number of lesions for BP‐PES. In risk‐unadjusted analysis at 1‐year follow‐up, there were no significant differences in TLR (BP‐PES: 8.4% vs. DP‐PES: 6%; P = 0.36), TVR (BP‐PES: 11.1% vs. DP‐PES: 8.4%; P = 0.36) and incidence of stent thromboses (BP‐PES: 2.15% vs. DP‐PES: 3.4%; P = 0.42) between groups. There was also no difference in MACCE between groups (17.6% vs. 14.4%, P = 0.49). The mean dual antiplatelet therapy (DAPT) compliance at 1 year was 77% for BP‐PES versus 92% for DP‐PES (P = 0.03). Kaplan–Meier analysis showed a significantly higher long‐term stroke free survival in BP‐PES (P = 0.04). After adjustment, this was sustained with an additional tendency toward higher MI free survival for BP‐PES (P = 0.059).

Conclusions

In this observational analysis, BP‐PES were comparable to DP‐PES, with regard to incidence of repeated revascularizations, stent thromboses and MACCE despite earlier DAPT discontinuation. © 2012 Wiley Periodicals, Inc.
Synthesis and Characterization of Reversible Chemosensory Polymers: Modulation of Sensitivity through the Attachment of Novel Imidazole Pendants
Authors: Satapathy Rudrakanta , Padhy Harihara , Wu Yen‐Hsing , Lin Hong‐Cheu
Published: October 2012

Three novel electron donor–acceptor conjugated polymers (P1–P3) bearing various imidazole pendants have been synthesized. Their excellent photophysical and electrochemical properties make them suitable transduction materials for chemosensing applications. Indeed, polymers P1–P3 have been found to show remarkable sensing capabilities towards H+ and Fe2+ in semi‐aqueous solutions. Upon titration with H+, polymers P1 and P2 showed hypsochromic shifts of their absorptions and photoluminescence (PL) maxima with enhanced fluorescence intensities. However, P3 showed diminished absorption and fluorescence intensities under similar conditions due to static quenching. The anomalous behavior of P3 compared with P1 and P2 has been clarified in terms of electronic distributions through computational analysis. Furthermore, P3 (KSV=1.03×107) showed a superior sensing ability towards Fe2+ compared with P1 (KSV=2.01×106) and P2 (KSV=4.12×106) due to its improved molecular wire effect. Correspondingly, the fluorescence lifetime of P3 was greatly decreased (almost 11‐fold) compared to those of polymers P1 (4.6‐fold) and P2 (6.2‐fold) in the presence of Fe2+. By means of a fluorescence on‐off‐on approach, chemosensing reversibilities in protonation–deprotonation and metallation–demetallation have been achieved by employing triethylamine (TEA) and the disodium salt of ethylenediaminetetraacetic acid (Na2‐EDTA)/phenanthroline, respectively, as suitable counter ligands. 1H NMR titrations have revealed the unique behavior of P3 compared with P1 and P2. To the best of our knowledge, there have been no previous reports of Fe2+ sensors based on single imidazole receptors conjugated to a main‐chain polymer showing such a diverse sensitivity pattern depending on their attached substituents.
Hollow‐Core Magnetic Colloidal Nanocrystal Clusters with Ligand‐Exchanged Surface Modification as Delivery Vehicles for Targeted and Stimuli‐Responsive Drug Release
Authors: Li Dian , Tang Jing , Guo Jia , Wang Shilong , Chaudhary Deeptangshu , Wang Changchun
Published: October 2012

The fabrication of hierarchical magnetic nanomaterials with well‐defined structure, high magnetic response, excellent colloidal stability, and biocompatibility is highly sought after for drug‐delivery systems. Herein, a new kind of hollow‐core magnetic colloidal nanocrystal cluster (HMCNC) with porous shell and tunable hollow chamber is synthesized by a one‐pot solvothermal process. Its novelty lies in the “tunability” of the hollow chamber and of the pore structure within the shell through controlled feeding of sodium citrate and water, respectively. Furthermore, by using the ligand‐exchange method, folate‐modified poly(acrylic acid) was immobilized on the surface of HMCNCs to create folate‐targeted HMCNCs (folate‐HMCNCs), which endowed them with excellent colloidal stability, pH sensitivity, and, more importantly, folate receptor‐targeting ability. These assemblages exhibited excellent colloidal stability in plasma solution. Doxorubicin (DOX), as a model anticancer agent, was loaded within the hollow core of these folate‐HMCNCs (folate‐HMCNCs‐DOX), and drug‐release experiments proved that the folate‐HMCNCs‐DOX demonstrated pH‐dependent release behavior. The folate‐HMCNCs‐DOX assemblages also exhibited higher potent cytotoxicity to HeLa cells than free doxorubicin. Moreover, folate‐HMCNCs‐DOX showed rapid cell uptake apart from the enhanced cytotoxicity to HeLa cells. Experimental results confirmed that the synthesized folate‐HMCNCs are smart nanovehicles as a result of their improved folate receptor‐targeting abilities and also because of their combined pH‐ and magnetic‐stimuli response for applications in drug delivery.
Synthesis and Characterization of Pd@MxCu1−x (M=Au, Pd, and Pt) Nanocages with Porous Walls and a Yolk–Shell Structure through Galvanic Replacement Reactions
Authors: Xie Shuifen , Jin Mingshang , Tao Jing , Wang Yucai , Xie Zhaoxiong , Zhu Yimei , Xia Younan
Published: October 2012

This paper describes the synthesis of Pd@MxCu1−x (M=Au, Pd, and Pt) nanocages with a yolk–shell structure through galvanic replacement reactions that involve Pd@Cu core–shell nanocubes as sacrificial templates and ethylene glycol as the solvent. Compared with the most commonly used templates based on Ag, Cu offers a much lower reduction potential (0.34 versus 0.80 V), making the galvanic reaction more easily to conduct, even at room temperature. Our structural and compositional characterizations indicated that the products were hollow inside, and each one of them contained porous M–Cu alloy walls and a Pd cube in the interior. For the Pd@AuxCu1−x yolk–shell nanocages, they displayed broad extinction peaks extending from the visible to the near‐IR region. Our mechanistic study revealed that the dissolution of the Cu shell preferred to start from the slightly truncated corners and then progressed toward the interior, because the Cu {100} side faces were protected by a surface capping layer of hexadecylamine. This galvanic approach can also be extended to generating other hollow metal nanostructures by using different combinations of Cu nanostructures and salt precursors.
Enzymes for Detergents
Authors: Rähse Wilfried
Published: October 2012

Die hohe Leistung moderner Waschmittel bei bereits 30 – 60 °C ist nur durch den Einsatz von spezifischen Enzymen und abgestimmten Enzymmischungen möglich. Die verschiedenen Enzyme docken am Schmutz an und hydrolysieren die festsitzenden Proteine, Polysaccharide und Fette. Tenside spülen die resultierenden Bruchstücke in die Waschflotte. Die Herstellung der Enzyme erfolgt mit Mikroorganismen in 40‐ bis 125‐m3‐Fermentern. Ins Fermentermedium sekretierte Enzyme werden nach Beendigung der Fermentation von den Mikroorganismen abgetrennt, konzentriert und konfektioniert. Hierbei dient die Enzymlösung als Granulationsflüssigkeit. Zur Gewährleistung der Produktsicherheit ist ein spezielles Coating notwendig. Das Produktdesign wird von der Gentechnik (Leistung) und der Gestaltung der Partikel (Handhabung) bestimmt.
Wide bandwidth and high precision power supply noise detector by using dual peak detection sample and hold circuits
Authors: Wey I‐Chyn , Peng Chien‐Chang , Chow Hwang‐Cherng
Published: October 2012

In this paper, we proposed a high‐performance, high‐precision power supply noise (PSN) detector by using dual peak detection sample and hold circuits with source follower. By using dual peak detection sample and hold circuits, we can avoid PSN missing detection and therefore avoid massive PSN detection error. We also added one dummy switch to cancel the charge injection effect and to improve the PSN detection accuracy. In the proposed design, we applied one PMOS type charging circuit to enhance the operation frequency of differential amplifier, which can widen both the PSN detection bandwidth and the detection range. As a result, in the proposed PSN detection circuit, the PSN detection bandwidth can be raised from 1 GHz to 2 GHz with the PSN detection error lowered to ±3%. Moreover, the PSN detection range is widened from 10%–50%VDD to 5%–65%VDD as compared with the state‐of‐the‐art design. Copyright © 2012 John Wiley & Sons, Ltd.
Domain specific genetic mosaic system in the Drosophila eye
Authors: Tare Meghana , Puli Oorvashi Roy , Moran Michael T. , Kango‐Singh Madhuri , Singh Amit
Published: October 2012

Genetic mosaic approach is commonly used in the Drosophila eye by completely abolishing or misexpressing a gene within a subset of cells to unravel its role during development. Classical genetic mosaic approach involves random clone generation in all developing fields. Consequently, a large sample size needs to be screened to generate and analyze clones in specific domains of the developing eye. To address domain specific functions of genes during axial patterning, we have developed a system for generating mosaic clones by combining Gal4/UAS and flippase (FLP)/FRT system which will allow generation of loss‐of‐function as well as gain‐of‐function clones on the dorsal and ventral eye margins. We used the bifid‐Gal4 driver to drive expression of UAS‐FLP. This reagent can have multiple applications in (i) studying spatio‐temporal function of a gene during dorso‐ventral (DV) axis specification in the eye, (ii) analyzing genetic epistasis of genes involved in DV patterning, and (iii) conducting genome wide screens in a domain specific manner. genesis 51:68–74, 2013. © 2012 Wiley Periodicals, Inc.
TB or not TB: The role of immunodiagnosis
Authors: Lange Christoph , Sester Martina
Published: October 2012

The evaluation of delayed‐type hypersensitivity immune responses by the tuberculin skin test and, more recently, by ex vivo IFN‐γ release assays (IGRAs) form the basis for the risk assessment for the development of tuberculosis (TB) in close contacts of infective index patients and in immunocompromised hosts. In contrast, immunodiagnosis has little value for the diagnosis of active TB so far. A report in this issue of the European Journal of Immunology [Eur J Immunol 2012. 42: 2844–2850] provides new insight into the phenotypic characteristics and selective recruitment of Ag‐specific T cells to the site of the infection, as analyzed by flow cytometry, which may provide new opportunities for the immune‐based diagnosis of TB in the future.
Wrestling with the repertoire: The promise and perils of next generation sequencing for antigen receptors
Authors: Baum Paul D. , Venturi Vanessa , Price David A.
Published: October 2012

Next generation sequencing technologies are revolutionizing the study of immune repertoires. These methods provide a previously unimaginable amount of sequence data, unfortunately accompanied by numerous challenges associated with error correction and interpretation that remain to be solved. For antigen receptors, these challenges will require dedicated solutions beyond those developed for genome sequencing, which may differ depending on the sequencing technology used and the purpose of the experiment. Many investigators are developing such methods, based on different sequencing platforms, but critical details of protocol and performance are proprietary. The field will move forward when these methods are shared and standardized, and when the accuracy, sensitivity and reproducibility of various sequencing, and analytic methods are evaluated using standardized samples in comparative experiments.
High‐Yielding Synthesis of β‐Octaalkyl‐meso‐(bromophenyl)‐Substituted Porphyrins and X‐ray Study of Axial Complexes of Their Zinc Complexes with THF and 1,4‐Dioxane
Authors: Mikhalitsyna Elena A. , Tyurin Vladimir S. , Nefedov Sergey E. , Syrbu Sergey A. , Semeikin Aleksandr S. , Koifman Oskar I. , Beletskaya Irina P.
Published: October 2012

New 5‐(4‐bromophenyl)‐3,7,12,13,17,18‐hexamethyl‐2,8‐dipentyl‐ and 5,15‐bis(4‐bromophenyl)‐2,8,12,18‐tetramethyl‐2,8,12,18‐tetrapentylporphyrins (H2P‐1 and H2P‐2) and their zinc metal complexes (ZnP‐1 and ZnP‐2, respectively) were synthesized in high yields by condensation of β‐tetraalkyl‐substituted dipyrromethanes with 2‐formyl‐3,4‐dialkylpyrroles or 4‐bromobenzaldehyde and subsequent metallation. X‐ray analysis data showed the formation of axial complexes of ZnP‐1 and ZnP‐2 with the solvent molecules of THF and dioxane in the solid state. Coordination of ZnP‐1 with dioxane led to polymer multidecker structures.
Near‐infrared spectroscopy for analysis of oil content and fatty acid profile in almond flour
Authors: Fernández‐Cuesta Álvaro , Fernández‐Martínez José M. , Socias i Company Rafel , Velasco Leonardo
Published: October 2012

Almond kernels show large variability for oil content and fatty acid profile. The objective of this research was to evaluate the potential of near infrared (NIR) reflectance spectroscopy (NIRS) for the analysis of these traits in almond flour. Ground kernels of 181 accessions collected in 2009 were used for developing calibration equations for oil content and concentrations of individual fatty acids. Calibration equations were developed using second derivative transformation and modified partial least squares regression. They were validated with samples from 179 accessions collected in 2010. The accuracy of calibration equations was measured through the coefficient of determination (r2) in external validation and the ratio of the SD in the validation set to the standard error of prediction (RPD). Both r2 and RPD were high for oil content (r2 = 0.99; RPD = 9.24) and concentrations of oleic (r2 = 0.97; RPD = 5.37) and linoleic acids (r2 = 0.98; RPD = 7.35), revealing that calibration equations for these traits are highly accurate. Conversely, the accuracy of the calibration equations for palmitic (r2 = 0.54; RPD = 1.41) and stearic acids (r2 = 0.52; RPD = 1.44) was too low for allowing their application in practice. NIRS discrimination of oil content and concentrations of oleic and linoleic acids was mainly based on the spectral region from 2240 to 2380 nm.

Practical applications: NIRS is a high‐throughput analytical technique that allows fast measurement of several traits in a single analysis without using chemical reagents. We evaluated the feasibility of analyzing oil content and concentrations of palmitic, stearic, oleic, and linoleic acids in almond flour using fruits collected during 2 years from a world germplasm collection. The fruits collected in 2009 were used for NIRS calibration, whereas the fruits collected in 2010 were used for validation. NIRS equations were highly accurate for measuring oil content and concentrations of oleic and linoleic acids, which are important traits defining the quality of almond flour for specific uses in the food industry. These results have applications both in the research laboratory and the food industry, where NIRS is becoming a widely used technique for quality control.
Synthesis and Copper(I)‐Driven Disaggregation of a Zinc‐Complexed Phthalocyanine Bearing Four Lateral Coordinating Rings
Authors: Martynov Alexander G. , Gorbunova Yulia G. , Nefedov Sergey E. , Tsivadze Aslan Y. , Sauvage Jean‐Pierre
Published: October 2012

A new zinc phthalocyaninate, bearing four flexible phenanthroline‐containing 30‐membered rings was synthesized by template condensation of a macrocyclic phthalonitrile. The resulting phthalocyanine was an insoluble aggregate. However, in the presence of CuI ions, the formation of a soluble complex was observed. UV/Vis and DOSY NMR spectroscopic studies showed a monomolecular state for this species in solution. 1H‐1H ROESY demonstrated that the macrocyclic substituents adopt a folded conformation, giving the complex a globular shape. The folding originates from stacking interactions between the phthalocyanine core and peripheral copper(I)–phenanthroline complexes.
NHC‐Ligand Effectiveness in the Fluorine‐Free Hiyama Reaction of Aryl Halides
Authors: Peñafiel Itziar , Pastor Isidro M. , Yus Miguel
Published: October 2012

1‐Benzyl‐3‐(2‐hydroxy‐2‐phenylethyl)imidazolium chloride (5), which is a precursor of an N‐heterocyclic carbene ligand, in combination with palladium acetate, has been employed as an effective catalyst for the fluorine‐free Hiyama reaction. A systematic study of the catalytic mixture, by a 32 factorial design, has revealed that both the amount of palladium and the Pd/NHC precursor ratio are important factors for obtaining good yields of the coupling products, indicating an interaction between them. The best catalytic system involves mixing 0.1 mol‐% palladium acetate in a 1:5 ratio (Pd/salt 5), which allows the effective coupling of a range of aryl bromides and chlorides with trimethoxy(phenyl)silane. The Hiyama reactions are carried out in NaOH solution (50 % H2O w/w), at 120 °C under microwave irradiation during 60 min.
Tsuji–Trost N‐Allylation with Allylic Acetates by Using a Cellulose–Palladium Catalyst
Authors: Vaddula Buchi Reddy , Saha Amit , Varma Rajender S. , Leazer John
Published: October 2012

Allylic amines were synthesized by a simple procedure using a biodegradable and easily recyclable heterogeneous cellulose–Pd catalyst through N‐allylation of primary and secondary amines. The scope of this protocol includes aliphatic and benzylamines with substituted and unsubstituted allyl acetates and culminates in high yield syntheses. The highlights of the protocol include a ligand‐free reaction, simple workup, and catalyst recyclability.
Investigation of Electrochemical Properties of Metalloporphyrin Species at the Liquid/Liquid Interface by Switching Substitutes on the Porphyrin Ring
Authors: Lu Xiaoquan , Gu Wenting , Sun Ruiping , Liu Xiuhui
Published: October 2012

In order to investigate the electrochemical properties of porphyrin complexes species in biological systems, metalloporphyrin with different substitutes was applied to observe the process of heterogeneous electron transfer (ET) at the interface between two immiscible electrolyte solutions (ITIES) by scanning electrochemical microscopy (SECM). Experimental results demonstrated that the process of electron transfer was affected dramatically by the presence of different substitutes. Our results also show that the rate constant follows BulterVolmer kinetics where the rate increases with increasing force at the low driving force, and Marcus inverted region kinetics at the high driving force where the rate decreases.
Biosensor with Protective Membrane for the Detection of DNA Damage and Antioxidant Properties of Fruit Juices
Authors: Ziyatdinova Guzel , Labuda Jan
Published: October 2012

With the purpose to prepare a DNA biosensor protected with an outer‐sphere membrane against high molecular weight interferences, a carbon film electrode was layer‐by‐layer modified with dsDNA and chitosan. Using cyclic and square‐wave voltammetry and impedance spectroscopy, the oxidative damage of DNA by the hydroxyl and superoxide anion radicals was detected which consists of opening of the helix structure followed by deep DNA chain degradation. The biosensor has been applied to the detection of the antioxidant effect of apple and orange juices. The investigation of the novel biosensor with a protective membrane represents a significant contribution to the field of DNA biosensors utilization.
Train‐the‐Trainer: Implementation of Cognitive Behavioural Guided Self‐Help for Recurrent Binge Eating in a Naturalistic Setting
Authors: Zandberg Laurie J. , Wilson G. Terence
Published: October 2012

Objective

The present study evaluated the feasibility and acceptability of cognitive behavioural guided self‐help (CBTgsh) for recurrent binge eating using the train‐the‐trainer implementation strategy.

Method

After receiving expert‐led training in CBTgsh, a master's‐level graduate student in clinical psychology subsequently trained and supervised less experienced graduate students to implement the treatment in an open clinical trial. Participants were 38 treatment‐seeking students at a university counselling centre with recurrent binge eating, featuring cases of bulimia nervosa, binge eating disorder, or eating disorder not otherwise specified.

Results

Intent‐to‐treat (ITT) analyses revealed 42.1% abstinence from binge eating at post‐treatment and 47.4% at one‐month follow‐up. Participants reported significant pretreatment to post‐treatment reductions on measures of specific eating disorder psychopathology, general psychopathology, and functional impairment and high levels of treatment acceptability.

Conclusions

These results provide ‘proof‐of‐concept’ for the train‐the‐trainer implementation strategy and add to the evidence supporting the feasibility and effectiveness of CBTgsh in routine clinical care. Copyright © 2012 John Wiley & Sons, Ltd and Eating Disorders Association.
Primary intestinal‐like adenocarcinoma of major salivary glands: 2 instances of previously undocumented phenotype
Authors: Gillenwater Ann M. , Frank Steven J. , Fatani Hanadi , El–Naggar Adel K.
Published: October 2012

Background

Primary intestinal‐like adenocarcinoma of the major salivary glands has not previously been reported.

Methods

The clinical and radiological findings of 2 patients with primary submandibular and sublingual tumors are presented. Histopathologic and immunohistochemical examinations of tumor sections were performed. Metastatic workup for distant occult primary was carried out.

Results

The light‐optic and the immunomarkers revealed intestinal‐like adenocarcinoma consistent with upper respiratory tract origin. Metastatic workup of both patients was negative for primary gastro‐intestinal primary.

Conclusion

Primary intestinal‐like adenocarcinoma can develop in major salivary glands and should be considered in the differential diagnosis. © 2012 Wiley Periodicals, Inc. Head Neck, 2012
Natural killer cells in liver disease
Authors: Tian Zhigang , Chen Yongyan , Gao Bin
Published: October 2012

Natural killer (NK) cells are enriched in lymphocytes within the liver and have unique phenotypic features and functional properties, including tumor necrosis factor–related apoptosis-inducing ligand–-dependent cytotoxicity and specific cytokine profiles. As a key component of innate immunity in the liver, NK cells perform critical roles in host defense against pathogens and tumors through their natural cytotoxicity and cytokine production, and they also act as regulatory cells by engaging in reciprocal interactions with other types of liver cells through cell-to-cell contact and the production of cytokines. Accumulating evidence from the last decade suggests that NK cells play an important role in controlling viral hepatitis, liver fibrosis, and liver tumorigenesis, but also contribute to the pathogenesis of liver injury and inflammation. The characterization of intrahepatic NK cell functions has not only helped us to better understand the pathogenesis of liver disease, but has also revealed new therapeutic targets for managing this disease.
Sclerostin antibody treatment improves bone mass, bone strength, and bone defect regeneration in rats with type 2 diabetes mellitus
Authors: Hamann Christine , Rauner Martina , Höhna Yvonne , Bernhardt Ricardo , Mettelsiefen Jan , Goettsch Claudia , Günther Klaus-Peter , Stolina Marina , Han Chun-Ya , Asuncion Franklin J , Ominsky Michael S , Hofbauer Lorenz C
Published: October 2012

Type 2 diabetes mellitus results in increased risk of fracture and delayed fracture healing. ZDF fa/fa rats are an established model of type 2 diabetes mellitus with low bone mass and delayed bone healing. We tested whether a sclerostin-neutralizing antibody (Scl-AbVI) would reverse the skeletal deficits of diabetic ZDF rats. Femoral defects of 3 mm were created in 11-week-old diabetic ZDF fa/fa and nondiabetic ZDF +/+ rats and stabilized by an internal plate. Saline or 25 mg/kg Scl-AbVI was administered subcutaneously (s.c.) twice weekly for 12 weeks (n = 9–10/group). Bone mass and strength were assessed using pQCT, micro–computed tomography (µCT), and biomechanical testing. Bone histomorphometry was used to assess bone formation, and the filling of the bone defect was analyzed by µCT. Diabetic rats displayed lower spinal and femoral bone mass compared to nondiabetic rats, and Scl-AbVI treatment significantly enhanced bone mass of the femur and the spine of diabetic rats (p < 0.0001). Scl-AbVI also reversed the deficit in bone strength in the diabetic rats, with 65% and 89% increases in maximum load at the femoral shaft and neck, respectively (p < 0.0001). The lower bone mass in diabetic rats was associated with a 65% decrease in vertebral bone formation rate, which Scl-AbVI increased by sixfold, consistent with a pronounced anabolic effect. Nondiabetic rats filled 57% of the femoral defect, whereas diabetic rats filled only 21% (p < 0.05). Scl-AbVI treatment increased defect regeneration by 47% and 74%, respectively (p < 0.05). Sclerostin antibody treatment reverses the adverse effects of type 2 diabetes mellitus on bone mass and strength, and improves bone defect regeneration in rats. © 2013 American Society for Bone and Mineral Research.
Quantifying load-induced solute transport and solute-matrix interaction within the osteocyte lacunar-canalicular system
Authors: Wang Bin , Zhou Xiaozhou , Price Christopher , Li Wen , Pan Jun , Wang Liyun
Published: October 2012

Osteocytes, the most abundant cells in bone, are essential in maintaining tissue homeostasis and orchestrating bone's mechanical adaptation. Osteocytes depend upon load-induced convection within the lacunar-canalicular system (LCS) to maintain viability and to sense their mechanical environment. Using the fluorescence recovery after photobleaching (FRAP) imaging approach, we previously quantified the convection of a small tracer (sodium fluorescein, 376 Da) in the murine tibial LCS under intermittent cyclic loading. In the present study, we first expanded the investigation of solute transport using a larger tracer (parvalbumin, 12.3 kDa), which is comparable in size to some signaling proteins secreted by osteocytes. Murine tibiae were subjected to sequential FRAP tests under rest-inserted cyclic loading while the loading magnitude (0, 2.8, or 4.8 N) and frequency (0.5, 1, or 2 Hz) were varied. The characteristic transport rate k and the transport enhancement relative to diffusion (k/k0) were measured under each loading condition, from which the peak solute velocity in the LCS was derived using our LCS transport model. Both the transport enhancement and solute velocity increased with loading magnitude and decreased with loading frequency. Furthermore, the solute-matrix interaction, quantified in terms of the reflection coefficient through the osteocytic pericellular matrix (PCM), was measured and theoretically modeled. The reflection coefficient of parvalbumin (σ = 0.084) was derived from the differential fluid and solute velocities within loaded bone. Using a newly developed PCM sieving model, the PCM's fiber configurations accounting for the measured interactions were obtained for the first time. The present study provided not only new data on the micro-fluidic environment experienced by osteocytes in situ but also a powerful quantitative tool for future study of the PCM, the critical interface that controls both outside-in and inside-out signaling in osteocytes during normal bone adaptation and in pathological conditions. © 2013 American Society for Bone and Mineral Research.
Sclerostin antibody inhibits skeletal deterioration due to reduced mechanical loading
Authors: Spatz Jordan M , Ellman Rachel , Cloutier Alison M , Louis Leeann , van Vliet Miranda , Suva Larry J , Dwyer Denise , Stolina Marina , Ke Hua Zhu , Bouxsein Mary L
Published: October 2012

Sclerostin, a product of the SOST gene produced mainly by osteocytes, is a potent negative regulator of bone formation that appears to be responsive to mechanical loading, with SOST expression increasing following mechanical unloading. We tested the ability of a murine sclerostin antibody (SclAbII) to prevent bone loss in adult mice subjected to hindlimb unloading (HLU) via tail suspension for 21 days. Mice (n = 11–17/group) were assigned to control (CON, normal weight bearing) or HLU and injected with either SclAbII (subcutaneously, 25 mg/kg) or vehicle (VEH) twice weekly. SclAbII completely inhibited the bone deterioration due to disuse, and induced bone formation such that bone properties in HLU-SclAbII were at or above values of CON-VEH mice. For example, hindlimb bone mineral density (BMD) decreased –9.2% ± 1.0% in HLU-VEH, whereas it increased 4.2% ± 0.7%, 13.1% ± 1.0%, and 30.6% ± 3.0% in CON-VEH, HLU-SclAbII, and CON-SclAbII, respectively (p < 0.0001). Trabecular bone volume, assessed by micro–computed tomography (µCT) imaging of the distal femur, was lower in HLU-VEH versus CON-VEH (p < 0.05), and was 2- to 3-fold higher in SclAbII groups versus VEH (p < 0.001). Midshaft femoral strength, assessed by three-point bending, and distal femoral strength, assessed by micro–finite element analysis (µFEA), were significantly higher in SclAbII versus VEH-groups in both loading conditions. Serum sclerostin was higher in HLU-VEH (134 ± 5 pg/mL) compared to CON-VEH (116 ± 6 pg/mL, p < 0.05). Serum osteocalcin was decreased by hindlimb suspension and increased by SclAbII treatment. Interestingly, the anabolic effects of sclerostin inhibition on some bone outcomes appeared to be enhanced by normal mechanical loading. Altogether, these results confirm the ability of SclAbII to abrogate disuse-induced bone loss and demonstrate that sclerostin antibody treatment increases bone mass by increasing bone formation in both normally loaded and underloaded environments. © 2013 American Society for Bone and Mineral Research.
Revealing noncovalent interactions in quantum crystallography: Taurine revisited
Authors: Yang Jack , Waller Mark P.
Published: October 2012

The charge density distribution in taurine (2‐aminoethane‐sulfonic acid) is further studied with the molecular orbital occupation number refinement scheme. The recently proposed NCIPLOT scheme (Johnson et al., J. Am. Chem. Soc. 2010, 132, 6498) is applied to visualize the noncovalent interactions from experimentally refined charge densities. Herein, we demonstrate the evolution of the reduced density gradient isosurface during the charge density refinement process. © 2012 Wiley Periodicals, Inc.
Block‐adaptive quantum mechanics: An adaptive divide‐and‐conquer approach to interactive quantum chemistry
Authors: Bosson Maël , Grudinin Sergei , Redon Stephane
Published: October 2012

We present a novel Block‐Adaptive Quantum Mechanics (BAQM) approach to interactive quantum chemistry. Although quantum chemistry models are known to be computationally demanding, we achieve interactive rates by focusing computational resources on the most active parts of the system. BAQM is based on a divide‐and‐conquer technique and constrains some nucleus positions and some electronic degrees of freedom on the fly to simplify the simulation. As a result, each time step may be performed significantly faster, which in turn may accelerate attraction to the neighboring local minima. By applying our approach to the nonself‐consistent Atom Superposition and Electron Delocalization Molecular Orbital theory, we demonstrate interactive rates and efficient virtual prototyping for systems containing more than a thousand of atoms on a standard desktop computer. © 2012 Wiley Periodicals, Inc.
Conventional strain energies of azetidine and phosphetane: Can density functional theory yield reliable results?
Authors: Smith Shelley A. , Hand Karen E. , Love Melissa L. , Hill Glake , Magers David H.
Published: October 2012

The conventional strain energies for azetidine and phosphetane are determined within the isodesmic, homodesmotic, and hyperhomodesmotic models. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies and zero‐point vibrational energies are computed for all pertinent molecular systems using self‐consistent field theory, second‐order perturbation theory, and density functional theory and using the correlation consistent basis sets cc‐pVDZ, cc‐pVTZ, and cc‐pVQZ. Single point fourth‐order perturbation theory, CCSD, and CCSD(T) calculations using the cc‐pVTZ and the cc‐pVQZ basis sets are computed using the MP2/cc‐pVTZ and MP2/cc‐pVQZ optimized geometries, respectively, to ascertain the contribution of higher order correlation effects and to determine if the quadruple‐zeta valence basis set is needed when higher order correlation is included. In the density functional theory study, eight different functionals are used including B3LYP, wB97XD, and M06‐2X to determine if any functional can yield results similar to those obtained at the CCSD(T) level. © 2012 Wiley Periodicals, Inc.
Catalytic Oxidation of Indigo Carmine in the Presence of Silver Nanoparticles: Application to Groundwater Analysis
Authors: Sahraei R. , Cheraghi J. , Hushmandfar R. , Abbasi S. , Mortazavi S. S. , Noorizadeh H. , Farmany A.
Published: October 2012

The oxidation of indigo carmine by potassium hexacyanoferrate(III) is catalyzed by trace of silver nanoparticle (AgNP). The reaction is followed UV‐Vis absorption spectrophotometrically by measuring the change in the absorption spectra (λmax 612 nm). The catalytic oxidation reaction is used for the quantification of indigo carmine. The calibration graph was linear in the concentration range 50 nM—1.8 μM of indigo carmine. The variables affecting the method have been optimized. The method is applied to the determination of indigo carmine in groundwater samples with the satisfactory results.