bluuebunny/crossref_metadata_2025 huggingface dataset:
Enhancing the Water Stability of Al‐MIL‐101‐NH2 via Postsynthetic Modification
Authors: Wittmann Thomas , Siegel Renée , Reimer Nele , Milius Wolfgang , Stock Norbert , Senker Jürgen
Published: October 2014

The resistance of metal–organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al‐MIL‐101‐NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long‐term stability of Al‐MIL‐101‐URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al‐MIL‐101‐URPh decomposed at least 12‐times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2O sorption measurements, powder X‐ray diffraction, thermogravimetric and chemical analysis as well as solid‐state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m2 g−1 for Al‐MIL‐101‐URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity‐dependent uptake of Al‐MIL‐101‐URPh is slowed and occurs at higher relative humidity values. In combination with 1H‐27Al D‐HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.
Carboranes Tuning the Phosphorescence of Iridium Tetrazolate Complexes
Authors: Shi Chao , Tu Deshuang , Yu Qi , Liang Hua , Liu Yahong , Li Zhihong , Yan Hong , Zhao Qiang , Huang Wei
Published: October 2014

New iridium tetrazolate complexes containing o‐, m‐, or p‐carboranyl substitution in different positions of a phenylpyridine ligand have been prepared. The carborane isomers and the effect of their substitution position in the tuning of optical properties have been examined. The neutral complexes with the carboranyl substituent on the phenyl ring in meta position relative to the metal exhibit redshifted emission bands in contrast to blueshifts for those with carboranyl in para position. All cationic complexes display evidently blueshifted dual‐peak emission compared with the carborane‐free complex (c‐TZ) with a broad single‐peak emission. Introduction of carborane leads to a blueshift over 70 nm relative to c‐TZ. Carboranes also significantly improve phosphorescence efficiency (ΦP) and lifetime (τ), that is, ΦP=0.64 versus 0.21 (c‐TZ) and τ=880 ns versus 241 ns (c‐TZ). The unique hydrophilic nido‐carborane‐based IrIII complex nido‐o‐1 shows the largest phosphorescence efficiency (abs ΦP=0.57) among known water‐soluble iridium complexes, long emission lifetime (τ=4.38 μs), as well as varying emission efficiency and lifetime with O2 content in aqueous solution. Therefore, nido‐o‐1 has been used as an excellent oxygen‐sensitive phosphor for intracellular O2 sensing and hypoxia imaging.
A Combined Experimental and Theoretical Study on the Isomers of 2,3,4,5‐Tetracarba‐nido‐Hexaborane(6) Derivatives and Their Photophysical Properties
Authors: Braunschweig Holger , Ghosh Sundargopal , Jimenez‐Halla J. Oscar C. , Klein Johannes H. , Lambert Christoph , Radacki Krzysztof , Steffen Andreas , Vargas Alfredo , Wahler Johannes
Published: October 2014

Building upon our ongoing studies on the high‐yield synthetic route to 2,3,4,5‐tetracarba‐1,6‐nido hexaborane derivative 5, we continue to explore the chemistry of this system to isolate a range of perphenylated C4B2‐type carborane isomers. As a result, the photolysis of 5 for an elongated period yielded 6, which exhibits an intense luminescence upon excitation with a UV lamp (λex=366 nm). In contrast, the conversion of 5 under thermal conditions (microwave heating) generated the isomer 7, which does not show any luminescence. The structural disparity among the three isomers 5–7 is the position of the butadiene moiety with respect to the C4B2‐carborane cage as deduced from single‐crystal X‐ray diffraction analyses. In an attempt to generate the classical structural motif of 5, an equimolar amount of KOtBu was added to a THF solution of 5, which immediately provided the boratacyclopentadiene derivative 8 in good yield. The observed rearrangement reactions were further investigated by quantum chemical calculations to suggest a plausible reaction pathway. According to the DFT calculations, the energetically favored reaction mechanism most likely involves tricyclic transition states and classical intermediate structures. In addition, the fluorescence emission properties of 6 were investigated in solution as well as in the solid state.
Enantioselective Synthesis of Chiral Isotopomers of 1‐Alkanols by a ZACA–Cu‐Catalyzed Cross‐Coupling Protocol
Authors: Xu Shiqing , Oda Akimichi , Negishi Ei‐ichi
Published: October 2014

Chiral compounds arising from the replacement of hydrogen atoms by deuterium are very important in organic chemistry and biochemistry. Some of these chiral compounds have a non‐measurable specific rotation, owing to very small differences between the isotopomeric groups, and exhibit cryptochirality. This particular class of compounds is difficult to synthesize and characterize. Herein, we present a catalytic and highly enantioselective conversion of terminal alkenes to various β and more remote chiral isotopomers of 1‐alkanols, with ≥99 % enantiomeric excess (ee), by the Zr‐catalyzed asymmetric carboalumination of alkenes (ZACA) and Cu‐catalyzed cross‐coupling reactions. ZACA‐in situ iodinolysis of allyl alcohol and ZACA‐in situ oxidation of TBS‐protected ω‐alkene‐1‐ols protocols were applied to the synthesis of both (R)‐ and (S)‐difunctional intermediates with 80–90 % ee. These intermediates were readily purified to provide enantiomerically pure (≥99 % ee) compounds by lipase‐catalyzed acetylation. These functionally rich intermediates serve as very useful synthons for the construction of various chiral isotopomers of 1‐alkanols in excellent enantiomeric purity (≥99 % ee) by introducing deuterium‐labeled groups by Cu‐catalyzed cross‐coupling reactions without epimerization.
Copper/Palladium‐Cocatalyzed Aerobic Synthesis of Bisaryl Ketones from Olefins via C‐C Double Bonds Cleavage
Authors: Gu Lijun , Liu Jiyan , Zhang Hongtao
Published: November 2014

A novel palladium/copper‐catalyzed aerobic synthesis of bisaryl ketones from 1,2‐diarylalkenes via C‐C double bonds cleavage has been described. This reaction constitutes a new transformation from 1,2‐diarylalkenes into bisaryl ketones, providing a unifying, simple and environmentally friendly complement to the available methods.
Stochastic dynamic models and Chebyshev splines
Authors: Fan Ruzong , Zhu Bin , Wang Yuedong
Published: November 2014

In this article, we establish a connection between a stochastic dynamic model (SDM) driven by a linear stochastic differential equation (SDE) and a Chebyshev spline, which enables researchers to borrow strength across fields both theoretically and numerically. We construct a differential operator for the penalty function and develop a reproducing kernel Hilbert space (RKHS) induced by the SDM and the Chebyshev spline. The general form of the linear SDE allows us to extend the well‐known connection between an integrated Brownian motion and a polynomial spline to a connection between more complex diffusion processes and Chebyshev splines. One interesting special case is connection between an integrated Ornstein–Uhlenbeck process and an exponential spline. We use two real data sets to illustrate the integrated Ornstein–Uhlenbeck process model and exponential spline model and show their estimates are almost identical.The Canadian Journal of Statistics42: 610–634; 2014 © 2014 Statistical Society of Canada
Synthetic 1‐Deoxynojirimycin N‐Substituted Peptides Offer Prolonged Disruption to N‐Linked Glycan Processing
Authors: Aguilar Aimé López , Escribano Jaime , Wentworth Paul , Butters Terry D.
Published: October 2014

A panel of 1‐deoxynojirimycin (DNJ) N‐linked peptides were synthesized. Their IC50 values were measured in vitro against α‐glucosidases I and II and were found to be in the micromolar range for both isozymes, and better than that of the iminosugar NB‐DNJ (miglustat, 3) against α‐glucosidase II. Cell‐based studies revealed that although the free iminosugar 3 is most effective at disrupting N‐linked glycan processing for short‐term incubations (one day), when the cell‐based studies were extended to three days, the DNJ N‐linked tetrapeptide KDEL, which is an endoplasmic reticulum (ER)‐retaining sequence, performed far better than 3. In low inhibitor washout studies, NB‐DNJ inhibition was decreased to zero after 24 h, but DNJ–KDEL retained 13 % activity. This method offers a general approach for targeting drugs to the ER and prolonging their activity. Moreover, it is modular, so as new iminosugars of increased potency are discovered, they can be added to this template for targeting.
Analysis of thyroid malignant pathologic findings identified during 3 rounds of screening (1997‐2008) of a cohort of children and adolescents from Belarus exposed to radioiodines after the Chernobyl accident
Authors: Zablotska Lydia B. , Nadyrov Eldar A. , Rozhko Alexander V. , Gong Zhihong , Polyanskaya Olga N. , McConnell Robert J. , O'Kane Patrick , Brenner Alina V. , Little Mark P , Ostroumova Evgenia , Bouville Andre , Drozdovitch Vladimir , Minenko Viktor , Demidchik Yuri , Nerovnya Alexander , Yauseyenka Vassilina , Savasteeva Irina , Nikonovich Sergey , Mabuchi Kiyohiko , Hatch Maureen
Published: October 2014

BACKGROUND

Recent studies of children and adolescents who were exposed to radioactive iodine‐131 (I‐131) after the 1986 Chernobyl nuclear accident in Ukraine exhibited a significant dose‐related increase in the risk of thyroid cancer, but the association of radiation doses with tumor histologic and morphologic features is not clear.

METHODS

A cohort of 11,664 individuals in Belarus who were aged ≤18 years at the time of the accident underwent 3 cycles of thyroid screening during 1997 to 2008. I‐131 thyroid doses were estimated from individual thyroid activity measurements taken within 2 months after the accident and from dosimetric questionnaire data. Demographic, clinical, and tumor pathologic characteristics of the patients with thyroid cancer were analyzed using 1‐way analysis of variance, chi‐square tests or Fisher exact tests, and logistic regression.

RESULTS

In total, 158 thyroid cancers were identified as a result of screening. The majority of patients had T1a and T1b tumors (93.7%), with many positive regional lymph nodes (N1; 60.6%) but few distant metastases (M1; <1%). Higher I‐131 doses were associated with higher frequency of solid and diffuse sclerosing variants of thyroid cancer (P < .01) and histologic features of cancer aggressiveness, such as lymphatic vessel invasion, intrathyroidal infiltration, and multifocality (all P < .03). Latency was not correlated with radiation dose. Fifty‐two patients with self‐reported thyroid cancers which were diagnosed before 1997 were younger at the time of the accident and had a higher percentage of solid variant cancers compared with patients who had screening‐detected thyroid cancers (all P < .0001).

CONCLUSIONS

I‐131 thyroid radiation doses were associated with a significantly greater frequency of solid and diffuse sclerosing variants of thyroid cancer and various features of tumor aggressiveness. Cancer 2015;121:457–466. © 2014 American Cancer Society.
Dynamic Potential‐Dependent Electron Transport Pathway Shifts in Anode Biofilms of Geobacter sulfurreducens
Authors: Yoho Rachel A. , Popat Sudeep C. , Torres César I.
Published: October 2014

Biofilms of the anode‐respiring bacterium Geobacter sulfurreducens (G. sulfurreducens) demonstrate dynamic potential‐dependent changes between two electron transport pathways that are used selectively depending on the anode potential. Electrochemical impedance spectroscopy (EIS) measurements suggest that these pathways (both n=1), with midpoint potentials of −0.155 (±0.005) and −0.095 (±0.003) V versus standard hydrogen electrode, are not additive within the biofilm, but are preferentially used depending on the anode potential. Potential step voltammetry and cyclic voltammetry (CV) confirmed rapid changes between the two pathways in minutes when the anode potential is changed. We confirm that the electrochemical response observed in a slow‐scan‐rate CV (∼1 mV s−1) is often composed of at least the two pathways characterized. Thus, beyond understanding the electron transport pathways in G. sulfurreducens, this study also has implications on the interpretation of previously collected and future potential‐dependent datasets.
3 D Single‐Walled Carbon Nanotube/Graphene Aerogels as Pt‐Free Transparent Counter Electrodes for High Efficiency Dye‐Sensitized Solar Cells
Authors: Ma Jie , Li Cheng , Yu Fei , Chen Junhong
Published: October 2014

3D single‐walled carbon nanotube (SWCNT)/graphene aerogel (NGS) was synthesized and used as an alternative to platinized fluorine‐doped tin oxide (FTO) in dye‐sensitized solar cells (DSSCs). An island‐like structure formed on the FTO using the spin‐coating method, leading to a transmittance (49.86 % at 671 nm). The resulting NGS‐based counter electrodes (CEs) exhibited excellent power conversion efficiency (PCE) (8.31 %) compared to Pt (7.56 %). Surprisingly, PCE increased to 9.64 % under assisted by a mirror; The excellent performance of DSSCs can be attributed to the high electrical conductivity and good electrocatalytic activity induced by the SWCNTs and the excellent catalytic properties of graphene, coupled with the 3D structure with a larger surface area and good surface hydrophilicity for increased electrolyte‐electrode interactions and electrolyte/reactant diffusion. Hence, our results demonstrate that 3D‐NGS materials have considerable potential for DSSC‐related applications and merit further investigation.
Three‐dimensional image cytometer based on widefield structured light microscopy and high‐speed remote depth scanning
Authors: Choi Heejin , Wadduwage Dushan N. , Tu Ting Yuan , Matsudaira Paul , So Peter T. C.
Published: October 2014

A high throughput 3D image cytometer have been developed that improves imaging speed by an order of magnitude over current technologies. This imaging speed improvement was realized by combining several key components. First, a depth‐resolved image can be rapidly generated using a structured light reconstruction algorithm that requires only two wide field images, one with uniform illumination and the other with structured illumination. Second, depth scanning is implemented using the high speed remote depth scanning. Finally, the large field of view, high NA objective lens and the high pixelation, high frame rate sCMOS camera enable high resolution, high sensitivity imaging of a large cell population. This system can image at 800 cell/sec in 3D at submicron resolution corresponding to imaging 1 million cells in 20 min. The statistical accuracy of this instrument is verified by quantitatively measuring rare cell populations with ratio ranging from 1:1 to 1:105. © 2014 International Society for Advancement of Cytometry
Middle cerebral artery territory infarct due to Cryptococcus infectionstitle
Authors: Cachia David , Singh Charanjeet , Tetzlaff Michael T. , Penas‐Prado Marta
Published: October 2014

Cryptococcal meningitis is the most common manifestation of cryptococcosis and is caused by the encapsulated yeast organism Cryptococcus neoformans. It occurs most commonly in patients with impaired cell‐mediated immunity such as in HIV infection; patients with hematological malignancies; patients post solid‐organ transplantation; on chronic steroids or immunosuppressants. Clinically, stroke can arise as a complication of cryptococcal meningitis. While cerebrospinal fluid (CSF) examination is usually not indicated for evaluation of stroke patients, demonstration of cryptococcal yeast forms in CSF is valuable in guiding appropriate therapy in arterial stroke caused by Cryptococci. Herein, we describe the CSF and radiologic correlation in a female patient who presented with disseminated cryptococcosis, cryptococcal meninigitis and a middle cerebral artery infarct. Diagn. Cytopathol. 2015;43:632–634. © 2014 Wiley Periodicals, Inc.
Perspective on cells: Evolution of cytopathology and the University of Pennsylvania, Philadelphia PA
Authors: Jhala Nirag , Gupta Prabodh K.
Published: October 2014

This document briefly captures the development of cytopathology at the Hospital of the University of Pennsylvania (HUP) in Philadelphia PA; the first medical school and the teaching hospital in the Country. Literature suggests that cells from malignancy have been described since early 1830s. While earlier accounts are not available, in the year 1895, 9th edition of the book written by Professor of Pathology, Dr. Tyson of the University of Pennsylvania describes urothelial cell morphology. It is also noted that both gynecologic as well as non‐gynecologic cytopathology is routinely being practiced at this Institution since 1949. Following the administrative consolidation of the department of pathology and laboratory medicine, a separate section of cytopathology within the department was established. Growing academic and clinical enterprises of HUP have resulted in establishment of Ruth and Raymond Perelman Center for Advanced Medicine (PeCAM) in the year 2010. Currently, the section has seven full time cytopathologists. It has patented a cart for onsite cytopathology interpretation, offers state of the art cytopathology services including onsite interpretation and reporting, point of care specimen triaging, molecular cytopathology testing as well as hosts telecytopathology systems within the Health System and training program. Diagn. Cytopathol. 2015;43:169–173. © 2014 Wiley Periodicals, Inc.
Metastatic medullary thyroid carcinoma to the breast in a patient with combined medullary and papillary carcinoma of thyroid—A case report
Authors: Alath Preetha , Shafi Ahmed Inamdar Naquib , Al‐Jassar Aisha , Hussein Sundus , Amir Thasneem , Al‐Waheeb Salah , Al‐Abdulghani Rana , George Sara Shirly , Kapila Kusum
Published: October 2014

We report the fine‐needle aspiration cytology of a case of medullary thyroid carcinoma (MTC) metastatic to the breast in a 66‐year old female within two years of diagnosis of the thyroid tumor. The aspirate of the breast metastases revealed a plasmacytoid population of cells in loose clusters and singly with mild to moderate pleomorphism. Nuclear groves and occasional intranuclear cytoplasmic inclusions were seen. The cells stained positive for calcitonin and negative for thyroglobulin. Use of immunocytochemical methods proved useful to diagnose metastasis which was essential in planning treatment. Cases of metastatic MTC to the breast diagnosed on fine‐needle aspirates reported in the literature are reviewed. Diagn. Cytopathol. 2015;43:343–348. © 2014 Wiley Periodicals, Inc.
Suspicious sonographic and cytological findings in patients with subacute thyroiditis: Two case reports
Authors: Park Ha Kyoung , Kim Dong Wook , Lee Yoo Jin , Ha Tae Kwun , Kim Do Hun , Bae Sang Kyun , Jung Soo Jin
Published: October 2014

We here report on two cases of suspicious cytological findings upon ultrasound (US)‐guided fine‐needle aspiration (US‐FNA) in patients with subacute thyroiditis (SAT). A 46‐year‐old woman who underwent US‐FNA for a suspicious thyroid nodule in the right lobe at a local clinic was referred to our hospital for surgical treatment. Based on the cytology results, total thyroidectomy was performed. The histopathology findings confirmed the presence of SAT in the right lobe and absence of thyroid malignancy. A 40‐year‐old woman with a thyroid nodule in the left lobe with suspicious cytological findings upon US‐FNA was referred to our hospital for surgical treatment. However, neck US revealed typical sonographic findings of SAT. On follow‐up US 3 months later, near complete disappearance of the typical sonographic findings of SAT was observed, while a hypoechoic solid thyroid nodule in the left upper lobe was clearly visualized. Accordingly, US‐FNA was performed for the hypoechoic thyroid nodule. Papillary thyroid carcinoma was suspected on the basis of the cytology findings; histopathologically, SAT was confirmed in both thyroid lobes and a papillary thyroid carcinoma was confirmed in the left lobe. Diagn. Cytopathol. 2015;43:399–402. © 2014 Wiley Periodicals, Inc.
Cover Image
Authors: Itou Junji , Akiyama Ryutaro , Pehoski Steve , Yu Xiaodan , Kawakami Hiroko , Kawakami Yasuhiko
Published: October 2014

Background: The zebrafish heart regenerates after various severe injuries. Common processes of heart regeneration are cardiomyocyte proliferation, activation of epicardial tissue, and neovascularization. In order to further characterize heart regeneration processes, we introduced milder injuries and compared responses to those induced by ventricular apex resection, a widely used injury method. We used scratching of the ventricular surface and puncturing of the ventricle with a fine tungsten needle as injury‐inducing techniques. Results: Scratching the ventricular surface induced subtle cardiomyocyte proliferation and responses of the epicardium. Endothelial cell accumulation was limited to the surface of the heart. Ventricular puncture induced cardiomyocyte proliferation, endocardial and epicardial activation, and neo‐vascularization, similar to the resection method. However, the degree of the responses was milder, correlating with milder injury. Sham operation induced epicardial aldh1a2 expression but not tbx18 and WT1. Conclusions: Puncturing the ventricle induces responses equivalent to resection at milder degrees in a shorter time frame and can be used as a simple injury model. Scratching the ventricle did not induce heart regeneration and can be used for studying wound responses to epicardium. Developmental Dynamics 243:1477–1486, 2014. © 2014 Wiley Periodicals, Inc.
Shrub spatial organization and partitioning of evaporation and transpiration in arid environments
Authors: Zhu Jianting , Sun Dongmin , Young Michael H. , Caldwell Todd G. , Pan Feng
Published: October 2014

Evapotranspiration (ET) dominates water fluxes in arid and semiarid ecosystems. The partitioning of ET into transpiration (T) and evaporation (E) has drawn increasing attention, particularly with respect to quantifying the control of shrub cover on water budget studies. The main objective of this study was to simulate the effects of shrub coverage spatial patterns on water partitioning into T and E and its relation to the simulation cell sizes. Correlation lengths of spatially distributed shrub cover in fine resolution grid cells were used to distinguish spatial patterns (i.e. patchiness) of shrub distributions. We then aggregated the fine resolution grid cells into larger cells of various hierarchies, calculated the potential T of each large cell as a portion of potential ET in the aggregated cell, and simulated the partitioning of actual ET into T and E. Results illustrated that simulated T increases with aggregated cell size, while E rate and total E do not change significantly (i.e. T/ET increases with aggregated cell size). The spatial distribution of shrub pattern influences the partitioning of ET: T increases with decreasing correlation length of shrub spatial pattern. Significant differences in T/ET are linked to the different correlation lengths, as a result of the highly non‐linear relationship between potential T and % shrub cover, which indirectly take into account subsurface lateral flows in the root zone. Copyright © 2014 John Wiley & Sons, Ltd.
Role of the Isolable Hydride Intermediate in the Hydrosilylation of Carbonyl Compounds Catalyzed by the High‐Valent Mono‐Oxido–Rhenium(V) Complex
Authors: Huang Liangfang , Zhang Yu , Wei Haiyan
Published: October 2014

The hydrosilylation of carbonyl compounds catalyzed by high‐valent mono‐oxido–rhenium(V) complex [Re(O)Cl3(PPh3)2] (1) and its hydride [Re(O)(H)Cl2(PPh3)2] (1H) was theoretically investigated using density functional theory. Our calculations indicated that the most energetically favorable process for 1‐catalyzed hydrosilylation was the “ionic mechanistic pathway”. The catalytic cycle is initiated by carbonyl substrate nucleophilic attacks on the η1‐silane rhenium adduct, which results in the heterolytic cleavage of the Si–H bond and generation of a siloxy carbenium ion paired with an anionic rhenium hydride, [ReOCl3(H)(PPh3)]–[Me3SiOCHPh]+. The ionic mechanistic pathway is more favorable than the σ‐bond metathesis pathway that involves the generation of rhenium hydride (23.8 versus 31.5 kcal mol–1). Therefore, our results indicated that an undetected η1‐silane rhenium adduct was the real intermediate rather than the isolable hydride intermediate 1H in the hydrosilylation catalyzed by 1.
Synthesis, Structures, and Reactivity of Copper(I) Complexes Supported by a Rigid Dinucleating Ligand
Authors: Bheemaraju Amarnath , Beattie Jeffrey W. , Danylyuk Yury , Rochford Jonathan , Groysman Stanislav
Published: October 2014

Herein, we report the diverse CuI chemistry of a dinucleating ligand L that features two iminopyridine chelates bridged by a 1,8‐diaminoxanthene linker {L = (1E,1′E)‐N,N′‐(2,7‐di‐tert‐butyl‐9,9‐dimethyl‐9H‐xanthene‐4,5‐diyl)bis[1‐(pyridin‐2‐yl)methanimine]}. The ligand L leads to the formation of discrete bimetallic species, or metallopolymers, as a result of syn‐parallel or anti‐parallel mutual disposition of the chelating units. The reaction of L with [Cu(NCMe)4]+ forms the discrete bimetallic complexes [Cu2(L)(NCMe)2]2+ (1) or [Cu2(L)2]2+ (2), depending on the solvent and the ligand‐to‐metal ratio. In contrast, the reaction of L with CuX (X = Cl, Br) forms the metallopolymers [Cu2(L)(Br)2]n (3) and {[Cu3(L)2Cl2][CuCl2]}n (4). The compounds were characterized by X‐ray crystallography, NMR spectroscopy, mass spectrometry, electrochemistry, and DFT calculations. The reaction of compound 1 with O2 in CH2Cl2 was found to lead to a mixture of CuII products of which tetrametallic [Cu4(L)4(OH)3(Cl)]4+ and [Cu4(L)2(OH)4]4+ were identified by X‐ray crystallography.
Synthetic Strategies for Variably Substituted Ruthenium–Imidazophenanthrolinium Complexes
Authors: Petermann Lydia , Staehle Robert , Pilz T. David , Sorsche Dieter , Görls Helmar , Rau Sven
Published: October 2014

The synthesis of several symmetric and asymmetric substituted imidazophenanthrolinium ligands and their corresponding ruthenium polypyridyl complexes was achieved by applying a newly designed synthetic concept. By testing different moieties, the advantages and limits of the synthetic approach could be defined. The substitution pattern on the imidazolium moiety has no significant influence on the structural aspects of the imidazophenanthrolinium backbone or on the photophysical properties of the ruthenium compounds. Given that imidazolium salts act as precursors for N‐heterocyclic carbenes, the reported results provide the basis for the design of highly efficient oligonuclear photocatalysts.
Switching the Macrocycle Conformation from Nonplanar to Planar in Cobalt(II) and Copper(II) β‐Tetra‐2′‐thienyl‐meso‐tetraphenylporphyrin Cocrystallates with C60
Authors: Bhyrappa Puttaiah , Sarangi Ujwal K. , Varghese Babu
Published: October 2014

Crystal structures of cobalt(II) and copper(II) complexes of 2,3,12,13‐tetra‐2′‐thienyl‐5,10,15,20‐tetraphenylporphyrin/C60 cocrystallates were determined by single‐crystal XRD analysis. The crystal structures of the two cocrystallates, MTPP(2′‐thienyl)4·C60·(toluene)2 (M = CoII and CuII; TPP = tetraphenylporphyrin), compounds 1 and 2, respectively, are isomorphous and reveal a one‐dimensional (1D) supramolecular structure. In these cocrystallates, the macrocycle is almost planar within ±0.08 Å, as evidenced by comparing the value of ΔCb (the average deviation of the β‐pyrrole carbon from the porphyrin ring mean plane) with those for the nonplanar parent structures, CoTPP(2′‐thienyl)4 [±0.710(5) Å] and CuTPP(2′‐thienyl)4 [±0.546(2) Å]. This difference has been ascribed to intermolecular interactions and/or crystal packing forces.
Chiral Squaramide‐Catalyzed Sulfa‐Michael/Aldol Cascade for the Asymmetric Synthesis of Spirocyclic Tetrahydrothiophene Chromanone Derivatives
Authors: Zhao Bo‐Liang , Liu Lei , Du Da‐Ming
Published: October 2014

A bifunctional squaramide‐catalyzed sulfa‐Michael/aldol cascade reaction between benzylidenechroman‐4‐ones and 1,4‐dithiane‐2,5‐diol with a low catalyst loading has been developed. This reaction constitutes a facile asymmetric synthesis of chiral spirocyclic tetrahydrothiophene chromanone derivatives with three contiguous stereocenters in high to excellent yields (up to 99 %) and with high enantioselectivities (up to 92 % ee). Additionally, a remarkable temperature effect on reaction efficiency was observed and gram‐scale syntheses were found to proceed smoothly with the same efficiency as smaller scale reactions.
Synthesis of Galactoclusters by Metal‐Free Thiol “Click Chemistry” and Their Binding Affinities for Pseudomonas aeruginosa Lectin LecA
Authors: Ligeour Caroline , Dupin Lucie , Marra Alberto , Vergoten Gérard , Meyer Albert , Dondoni Alessandro , Souteyrand Eliane , Vasseur Jean‐Jacques , Chevolot Yann , Morvan François
Published: October 2014

Mannose‐centered galactoclusters specific for lectin I of Pseudomonas aeruginosa (LecA) were synthesised by a combination of phosphoramidite chemistry and metal‐free thiol click chemistry (i.e., thiol addition to acrylamide or nucleophilic displacement of bromine in a bromoacetamide group by a thiol function). These thiol click reactions were performed with microwave assistance in the presence of Et3N and with use of a reducing agent to avoid disulfide formation. Nine tetravalent galactoclusters containing different linkers (aliphatic, oligoethyleneglycol or aromatic) were synthesised with a DNA tag. Their binding to LecA was monitored in a DNA‐based glycoarray and compared with that of a galactocluster synthesised by copper‐catalyzed azide–alkyne cycloaddition. The results indicated stronger binding of all galactoclusters relative to the monovalent galactoside but slightly weaker binding than that shown by the galactocluster incorporating a triazole ring, due to a favourable interaction of the latter with proline 51 of LecA.
Highly Efficient Synthesis of Allenes from Trimethylaluminum Reagent and Propargyl Acetates Mediated by a Palladium Catalyst
Authors: Li Qing‐Han , Jeng Jung‐Yuan , Gau Han‐Mou
Published: October 2014

A series of propargyl acetates were prepared and used as propargyl electrophiles for coupling reactions with trimethylaluminum. The simple catalytic system of palladium(II) acetate (1 mol‐%) and tri(o‐tolyl)phosphine (2 mol‐%) worked efficiently for a wide variety of aromatic and aliphatic propargyl acetates, producing the substituted allenes in good to excellent yields of up to 94 % in tetrahydrofuran. The process was simple and easily performed, and it provides an efficient method for the synthesis of substituted allene derivatives. On the basis of the experimental results, a possible catalytic cycle has been proposed.
A Palladium Catalyst Supported on Carbon‐Coated Cobalt Nanoparticles – Preparation of Palladium‐Free Biaryls by Suzuki–Miyaura Reactions in Ethanol
Authors: Derible Antoine , Diebold Carine , Dentzer Joseph , Gadiou Roger , Becht Jean‐Michel , Le Drian Claude
Published: October 2014

The preparation of a heterogeneous Pd catalyst supported on carbon‐coated magnetic nanoparticles (NPs) bearing 4‐(diphenylphosphinomethyl)phenyl groups is discussed. These NPs were initially prepared by chemical vapour deposition (CVD) of carbon on preformed Co NPs; however, the particles prepared in one step by reducing flame synthesis were more appropriate for functionalization. The Pd catalyst was then prepared by three simple steps. We show that Suzuki–Miyaura couplings can be efficiently performed in the presence of very low amounts of supported Pd, usually 50 μequiv. Finally, the Pd leaching was very low: in most cases only 1 μequiv. of Pd is found in the reaction medium (which amounts to less than 1 ppm of the product). Compared to other catalysts supported on magnetic particles, this catalyst is very simple to prepare even in large quantities and is easy to recover completely owing to the high magnetic saturation of the Co nucleus. To the best of our knowledge, it is the simplest and the most‐active Pd catalyst supported on carbon‐coated Co nanoparticles for Suzuki–Miyaura reactions. The reusability of the catalyst was also ascertained.
High‐Temperature Synthesis of Amides from Alcohols or Aldehydes by Using Flow Chemistry
Authors: Ambreen Nida , Wirth Thomas
Published: October 2014

An efficient conversion of aliphatic and aromatic alcohols or aldehydes into the corresponding primary amides was successfully achieved by using flow chemistry. Excellent yields were obtained in very short reaction times, and thus this method offers an efficient alternative to traditional methods for amide formation.
A High Sensitivity Electrochemical Sensor Based on Fe3+‐Ion Molecularly Imprinted Film for the Detection of T‐2 Toxin
Authors: Gao Xing , Cao Wenying , Chen Miaomiao , Xiong Huayu , Zhang Xiuhua , Wang Shengfu
Published: October 2014

The excellent detection sensitivity in various matrices of T‐2 toxin (T‐2), which has cytotoxic and immunosuppressive effects in DNA and RNA synthesis, is a highly desirable characteristic. A sensitive molecularly imprinted electrochemical sensor was constructed for the selective detection of T‐2. In this study, iron ions (Fe3+) were introduced to increase the chelation of the metal ions and templates for preparing molecularly imprinted polymers (MIPs). With the increased chelation of the metal ions and templates, the selectivity and sensitivity of the MIPs were effectively improved. The imprinted sensor was successfully employed to detect T‐2 in cereals and human serum samples.
Counting of Escherichia coli by a microflow cytometer based on a photonic–microfluidic integrated device
Authors: Guo Tianyi , Wei Yin , Xu Changqing , Watts Benjamin R. , Zhang Zhiyi , Fang Qiyin , Zhang Haiying , Selvaganapathy P. Ravi , Deen M. Jamal
Published: October 2014

Counting of Escherichia coli DH5α‐cell suspensions in PBS is performed using a microflow cytometer based on a photonic–microfluidic integrated device. Side‐scattered light signals are used to count the E. coli cells. A detection efficiency of 92% is achieved when compared with the expected count from a hemocytometer. The detection efficiency is correlated to the ratio of sample to sheath flow rates. It is demonstrated that E. coli can be easily distinguished from beads of similar sizes (2–4 μm) as their scattering intensities are different.
Volumetric measurement of human red blood cells by MOSFET‐based microfluidic gate
Authors: Guo Jinhong , Ai Ye , Cheng Yuanbing , Li Chang Ming , Kang Yuejun , Wang Zhiming
Published: October 2014

In this paper, we present a MOSFET‐based (metal oxide semiconductor field‐effect transistor) microfluidic gate to characterize the translocation of red blood cells (RBCs) through a gate. In the microfluidic system, the bias voltage modulated by the particles or biological cells is connected to the gate of MOSFET. The particles or cells can be detected by monitoring the MOSFET drain current instead of DC/AC‐gating method across the electronic gate. Polystyrene particles with various standard sizes are utilized to calibrate the proposed device. Furthermore, RBCs from both adults and newborn blood sample are used to characterize the performance of the device in distinguishing the two types of RBCs. As compared to conventional DC/AC current modulation method, the proposed device demonstrates a higher sensitivity and is capable of being a promising platform for bioassay analysis.
A wavelet‐nearest neighbor model for short‐term load forecasting
Authors: Sudheer Gopinathan , Suseelatha Annamareddy
Published: October 2014

Load forecasts of short lead times ranging from an hour to a day ahead are essential for improving the economic efficiency and reliability of power systems. This paper proposes a hybrid model based on the wavelet transform (WT) and the weighted nearest neighbor (WNN) techniques to predict the day ahead electrical load. The WT is used to decompose the load series into deterministic series and fluctuation series that reflect the changing dynamics of data. The two subseries are then separately forecast using appropriately fitted WNN models. The final forecast is obtained by composing the predicted results of each subseries. The hourly electrical load of California and Spanish energy markets are taken as experimental data and the mean absolute percentage error (MAPE), Weekly MAPE (WMAPE) and Monthly MAPE (MMAPE) are computed to evaluate the forecasting performance of the next‐day load forecasts. The forecasting efficiency of the proposed model is evaluated using db2, db4, db5 and bior 3.1 wavelets. The results demonstrate the forecasting accuracy of the proposed hybrid model.
Expanded Graphite–Epoxy–Flexible Silica Composite Bipolar Plates for PEM Fuel Cells
Authors: Dursun B. , Yaren F. , Unveroglu B. , Yazici S. , Dundar F.
Published: October 2014

Silica impregnated expanded graphite–epoxy composites are developed as bipolar plates for proton exchange membrane (PEM) fuel cells. These composite plates were prepared by solution impregnation, followed by compression molding and curing. Mechanical properties, electrical conductivities, corrosion resistance, and contact angles were determined as a function of impregnated content. The plates show high flexural strength with 5% methyltrimethoxysilane (MTMS) addition (20 MPa) and in‐plane conductivity of 131 S cm−1 that meet the DOE target (>100 S cm−1). Corrosion current values as low as 1.09 μA cm−2 were obtained. The contact angle was found to be 80°. Power density of 1 W cm−2 was achieved with custom made expanded graphite–polymer composite plates. High efficiency values were obtained at low current regions.
Hyalinizing clear cell carcinoma of the head and neck: Case series and update
Authors: Albergotti W. Greer , Bilodeau Elizabeth A. , Byrd J. Kenneth , Mims Mark M. , Lee Stella , Kim Seungwon
Published: October 2014

Background

Hyalinizing clear cell carcinoma (HCCC) is a rare neoplasm of salivary gland origin which is low‐grade in nature. In this series, we report on 9 cases of HCCC and update the literature.

Methods

A comprehensive literature search was performed. Our institutional database was queried for cases of HCCC. Pathology reports and slides were reviewed. Data was extracted, including demographics, staging, primary treatment, histopathologic findings, recurrence, and disease status. Statistical analysis was performed using a Pearson's chi‐square test.

Results

One hundred thirty‐six total cases were included for analysis. The overall recurrence rate was 19.8%. Necrosis was associated with risk of recurrence (p = .003). Positive margins and lymph node status were associated with risk of recurrence. Prognosis was good with only 3 of 82 patients reported dying with disease.

Conclusion

HCCC has an overall good prognosis with potential for aggressive behavior. The presence of necrosis, locoregional disease, or positive margins is associated with risk for recurrence. © 2015 Wiley Periodicals, Inc. Head Neck 38: 426–433, 2016
Influence of genetic background and oxidative stress response on risk of mandibular osteoradionecrosis after radiotherapy of head and neck cancer
Authors: Danielsson Daniel , Brehwens Karl , Halle Martin , Marczyk Michal , Sollazzo Alice , Polanska Joanna , Munck–Wikland Eva , Wojcik Andrzej , Haghdoost Siamak
Published: October 2014

Background

Osteoradionecrosis (ORN) of the mandible is a severe complication of head and neck radiotherapy (RT) treatment, where the impact of individual radiosensitivity has been a suggested explanation.

Methods

A cohort of patients with stage II/III ORN was compared to matched controls. Blood was collected and irradiated in vitro to study the capacity to handle radiation‐induced oxidative stress. Patients were also genotyped for 8 single‐nucleotide polymorphisms (SNPs) in genes involved in the oxidative stress response.

Results

A difference in 8‐oxo‐7,8‐dihydro‐2′‐deoxyguanosine (8‐oxo‐dG) levels was found between the patient cohorts (p = 0.01). The SNP rs1695 in glutathione s‐transferase p1 (GSTP1) was also found to be more frequent in the patients with ORN (p = .02). Multivariate analysis of the clinical and biological factors revealed concomitant brachytherapy plus the 2 biomarkers to be significant factors which influense risk of mandibular osteoradionecrosis after radiotherapy of head and neck cancer.

Conclusion

The current study indicates that oxidative stress response contributes to individual radiosensitivity and healthy tissue damage caused by RT and may be predicted by biomarker analysis. © 2015 Wiley Periodicals, Inc. Head Neck 38: 387–393, 2016
Assessment of the change in cetuximab‐induced antibody‐dependent cellular cytotoxicity activity of natural killer cells by steroid
Authors: Kumai Takumi , Oikawa Kensuke , Aoki Naoko , Kimura Shoji , Harabuchi Yasuaki , Kobayashi Hiroya
Published: October 2014

Background

Epidermal growth factor receptor (EGFR)‐targeted therapy has been widely accepted as a promising treatment for solid tumors. Steroid treatment is used to prevent adverse effect of anti‐EGFR antibody; however, influence of steroids in the antitumor activity of targeted antibody remains poorly understood. Herein, we demonstrated the impact of steroids in induced antibody‐dependent cellular cytotoxicity (ADCC) activity of natural killer (NK) cells by cetuximab.

Methods

Various numbers of NK cells from healthy donors were co‐cultured with tumor and/or cetuximab with or without dexamethasone. After incubation, NK cells, ADCC activity, survival, and activation markers expression were determined.

Results

Clinical concentration of dexamethasone treatment clearly inhibited cetuximab‐induced ADCC activity of NK cells against head and neck squamous cell carcinoma (HNSCC) and colon cancer. Dexamethasone decreased the activation marker CD69 expression on NK cells.

Conclusion

This is the first report that shows the negative affect of steroids in cancer treatment using therapeutic antibody. Attention needs to be paid for using steroids in tumor treatment. © 2015 Wiley Periodicals, Inc. Head Neck 38: 410–416, 2016
Intraoperative hypertensive crisis due to a catecholamine‐secreting esthesioneuroblastoma
Authors: Salmasi Vafi , Schiavi Adam , Binder Zev A. , Ruzevick Jacob , Orr Brent A. , Burger Peter C. , Ball Douglas W. , Blitz Ari M. , Koch Wayne M. , Ishii Masaru , Gallia Gary L.
Published: October 2014

Background

Although uncommon, esthesioneuroblastomas may produce clinically significant amounts of catecholamines.

Methods

We report a patient with a catecholamine‐secreting esthesioneuroblastoma who developed an intraoperative hypertensive crisis.

Results

A patient with a history of hypertension was referred to our skull base center for management of a residual esthesioneuroblastoma. A staged endonasal endoscopic approach was planned. At the conclusion of the first stage, a hypertensive crisis occurred. Workup revealed elevated levels of serum and urinary catecholamines. The patient was treated with alpha adrenoceptor blockade before the second stage. Serum catecholamine levels after this second stage were normal. On immunohistochemical analysis, the tumor cells were found to be positive for tyrosine hydroxylase, the rate limiting enzyme in catecholamine synthesis, and achaete‐scute homologue 1, a transcription factor essential in the development of olfactory and sympathetic neurons.

Conclusion

Catecholamine production should be considered in the differential of unexpected extreme hypertension during surgical resection of esthesioneuroblastoma. © 2015 Wiley Periodicals, Inc. Head Neck 37: E74–E80, 2015
CT finding of ectopic pituitary adenoma: Case report and review of literature
Authors: Wu Xiaofeng , Wen Ming
Published: October 2014

Background

Ectopic pituitary adenoma was first described by Erdheim in 1909, about 100 cases have been reported in literature, to the best of our knowledge, an ectopic pituitary adenoma located in the parapharyngeal space has not been reported thus far.

Method

A 59‐year‐old woman presenting with a neck lump, which was painlessness and growing, was without any neurological disorders or endocrine disorders. Auxiliary examinations included ultrasound, electronic nasopharyngolaryngoscopy, endocrine assessment, CT, and CT angiography.

Results

A CT scan showed a soft tissue density mass with clear boundary involving the carotid sheath area. The contrast‐enhanced CT scan showed heterogeneous density. Tissues around the mass were pushed and displaced. CT angiography showed the mass was hypervascular and supported by the right internal carotid artery and branches of the external carotid artery. The tumor underwent a total removal and was confirmed as an adenoma with pituitary cells by histopathologic examinations, and postoperative recovery went well.

Conclusion

It is rarely seen that a pituitary adenoma is ectopic to the parapharyngeal space. Diagnosis is difficult and mainly depends on the postoperative pathological examination. © 2015 Wiley Periodicals, Inc. Head Neck 37: E120–E124, 2015
Demonstration of nasopharyngeal surgery with a single port operator‐controlled flexible endoscope system
Authors: Schuler Patrick J. , Hoffmann Thomas K. , Duvvuri Uma , Rotter Nicole , Greve Jens , Scheithauer Marc O.
Published: October 2014

Background

Nasopharyngeal surgery is commonly performed with a rigid endoscope using a transnasal or transoral approach. Here, we demonstrate a flexible single port computer‐assisted endoscopic system enabling easy transoral access to the nasopharynx.

Methods

Transoral nasopharyngeal surgery was performed in human cadavers (n = 8) using the Flex System (Medrobotics, Raynham, MA). Learning curves were evaluated based on the time necessary for reaching the Eustachian tube. Mock surgical procedures were performed with compatible flexible instruments.

Results

Nasopharyngeal surgery is feasible with the Flex System with a nontraumatic approach. The inbuilt HD digital camera enables high‐quality visualization of the nasopharynx. The design of the flexible compatible tools adequately meets the requirements for surgical procedures in the nasopharynx.

Conclusion

The single port operator‐controlled flexible endoscope system is a feasible way to approach the nasopharynx for surgical manipulation. Further clinical studies as well as development of supplemental tools are in progress. © 2015 Wiley Periodicals, Inc. Head Neck 38: 370–374, 2016
Repair of pharyngocutaneous fistula after total laryngectomy: A novel endoscopic approach
Authors: Fink Daniel S. , Peña Sarah , Hanby Duncan , Kunduk Melda , McWhorter Andrew J.
Published: October 2014

Background

Pharyngocutaneous fistula (PCF) is a common and challenging complication of laryngectomy. The purpose of this study was to evaluate the results of endoscopic repair of postlaryngectomy PCF.

Methods

Five patients who underwent salvage laryngectomy complicated by PCF underwent endoscopic repair at a regional medical center between 2006 and 2013. Data were compiled through a manual chart review and demographic data, adjuvant treatment, comorbidities, and clinical course were all recorded.

Results

Five patients underwent endoscopic repair of PCF. All patients had previously received radiation or chemoradiation therapy and underwent salvage total laryngectomy. The mean number of days to resumption of oral intake after endoscopic repair was 22 days. One patient required reoperation. No complications were noted.

Conclusion

Endoscopic suture repair can be an effective method for treating PCF with less morbidity than flap reconstruction or conservative wound management. © 2014 Wiley Periodicals, Inc. Head Neck 37: E81–E84, 2015