bluuebunny/crossref_metadata_2025 huggingface dataset:
Extraction Length Determination in Patterned Luminescent Sol–Gel Films
Authors: Devys Lucie , Dantelle Géraldine , Revaux Amélie , Kubytskyi Viacheslav , Paget Daniel , Benisty Henri , Gacoin Thierry
Published: November 2013

Optimization of light emitting devices when light is trapped within the dielectric structures opens the question of the management of light propagation and of control of the directionality of extracted light. These phenomena are closely connected to the so‐called extraction length of light propagating within the device, a parameter that is poorly discussed when considering the design and architecture of devices. In this work, a straightforward method for the measurement of the extraction length in the case of luminescent sol–gel films patterned with a 2D photonic bandgap structure is presented. Quantitative information usually obtained by spectro‐angular measurements can be retrieved from simpler standard spectrometry, allowing discussion of the influence of pattern depth, which determines the extraction by the photonic structure as compared to other uncontrolled pathways such as diffusion from defects in the film coating. These assessments provide a quick and safe method for the quantitative evaluation of light extraction strategies toward a rational design of light emitting devices with optimized properties.
Mature results of MM‐011: A phase I/II trial of liposomal doxorubicin, vincristine, dexamethasone, and lenalidomide combination therapy followed by lenalidomide maintenance for relapsed/refractory multiple myeloma
Authors: Lazaryan Aleksandr , Hussein Mohamad A. , Reu Frederic J. , Faiman Beth , Habecker Becky , Ann Karam Mary , Reed Janice , Hamilton Kimberly , Waksman Joel , Bruening Kellie , Srkalovic Gordan , Andresen Steven , Kalaycio Matthew , Sweetenham John W. , Sobecks Ronald , Dean Robert , Knight Robert , Zeldis Jerome B. , Baz Rachid
Published: November 2013

A previous interim report of MM‐011, the first study that combined lenalidomide with anthracycline‐based chemotherapy followed by lenalidomide maintenance for relapsed and/or refractory multiple myeloma (RRMM), showed promising safety and activity. We report the long‐term outcomes of all 76 treated patients with follow‐up ≥5 years. This single‐center phase I/II study administered lenalidomide (10 mg on days 1–21 of every 28‐day cycle), intravenous liposomal doxorubicin (40 mg/m2 on day 1), dexamethasone (40 mg on days 1–4), and intravenous vincristine (2 mg on day 1). After 4–6 planned induction cycles, lenalidomide maintenance therapy was given at the last tolerated dose until progression, with or without 50 mg prednisone every other day. The median number of previous therapies was 3 (range, 1–7); 49 (64.5%) patients had refractory disease. Forty‐three (56.6%) patients received maintenance therapy. Grade 3/4 adverse events occurred during induction and maintenance therapy in 48.7% and 25.6% of patients, respectively. Four (5.3%) treatment‐related deaths occurred during induction. Responses were seen in 53.0% (at least partial response) and 71.2% (at least minor response) of patients. Overall, median progression‐free survival and overall survival were 10.5 and 19.0 months, respectively; in patients with refractory disease these values were 7.5 and 11.3 months, respectively. Lenalidomide with anthracycline‐based chemotherapy followed by maintenance lenalidomide provided durable control in patients with RRMM (ClinicalTrials.gov number, NCT00091624). Am. J. Hematol. 89:349–354, 2014. © 2013 Wiley Periodicals, Inc.
Bortezomib, melphalan, prednisone (VMP) versus melphalan, prednisone, thalidomide (MPT) in elderly newly diagnosed multiple myeloma patients: A retrospective case‐matched study
Authors: Morabito Fortunato , Bringhen Sara , Larocca Alessandra , Wijermans Pierre , Victoria Mateos Maria , Gimsing Peter , Mazzone Carla , Gottardi Daniela , Omedè Paola , Zweegman Sonja , José Lahuerta Juan , Zambello Renato , Musto Pellegrino , Magarotto Valeria , Schaafsma Martijn , Oriol Albert , Juliusson Gunnar , Cerrato Chiara , Catalano Lucio , Gentile Massimo , Isabel Turel Ana , Marina Liberati Anna , Cavalli Maide , Rossi Davide , Passera Roberto , Rosso Stefano , Beksac Meral , Cavo Michele , Waage Anders , San Miguel Jesus , Boccadoro Mario , Sonneveld Pieter , Palumbo Antonio , Offidani Massimo
Published: November 2013

Novel agents in combination with melphalan and prednisone (MP) significantly improved progression‐free survival (PFS) and overall survival (OS) in multiple myeloma (MM). Randomized trials comparing MP plus bortezomib (VMP) versus MP plus thalidomide (MPT) are lacking. Nine hundred and fifty‐six elderly (>65 years) newly diagnosed MM patients from six European randomized trials were retrospectively analyzed and matched for age, albumin, and beta2‐microglobulin at diagnosis, 296 patients were selected from the VMP groups, and 294 from MPT. Complete response rate was 21% in the VMP patients and 13% in the MPT patients (P = 0.007). After a median follow‐up of 34 months (range, 1–92), VMP significantly prolonged both PFS (median 32.5 vs. 22.9 months, HR 0.65; 95% CI 0.52–0.82;P < 0.001) and OS (median 79.7 vs. 45.1 months, HR 0.44; 95% CI 0.32–0.59;P < 0.001) in comparison with MPT. The benefit in terms of OS of the VMP group was quite similar among patients with different risk factors defined by sex, ISS, ECOG performance status, or serum creatinine but not among patients ≥75 years. Multivariate analysis confirmed that VMP was an independent predictor of longer PFS and OS. In a control‐case matched analysis, PFS and OS were prolonged in patients who received VMP in comparison with those treated with MPT. Am. J. Hematol. 89:355–362, 2014. © 2013 Wiley Periodicals, Inc.
17p13.1 microdeletion: Genetic and clinical findings in a new patient with epilepsy and comparison with literature
Authors: Giordano Lucio , Palestra Filippo , Giuffrida Maria Grazia , Molinaro Anna , Iodice Alessandro , Bernardini Laura , La Boria Paola , Accorsi Patrizia , Novelli Antonio
Published: November 2013

Array comparative genomic hybridization is now a powerful tool to investigate patients with multiple congenital abnormalities and intellectual/motor impairment, and genomic imbalances are identified in a growing number of children with intellectual disability. Deletions in the 17p13.1 region have been reported in patients with dysmorphic features and developmental delay but a consistent phenotype has yet to emerge. Here, we report on the diagnosis of a 17p13.1 microdeletion of 829 kb in an 8‐year‐old girl presenting with profound cognitive disability, psychomotor delay, facial dysmorphisms, and refractory epilepsy. This deletion comprises 44 genes, including 8 OMIM morbid genes. We discuss genetic, clinical, and epileptic features comparing our patient with those previously reported in the literature. © 2013 Wiley Periodicals, Inc.
1p34.3 deletion involving GRIK3: Further clinical implication of GRIK family glutamate receptors in the pathogenesis of developmental delay
Authors: Takenouchi Toshiki , Hashida Noriko , Torii Chiharu , Kosaki Rika , Takahashi Takao , Kosaki Kenjiro
Published: November 2013

A growing body of evidence suggests an association between microdeletion/microduplication and schizophrenia/intellectual disability. Abnormal neurogenesis and neurotransmission have been implicated in the pathogenesis of these neuropsychiatric and neurodevelopmental disorders. The kainate/AMPA‐type ionotropic glutamate receptor (GRIK = glutamate receptor, ionotropic, kainate) plays a critical role in synaptic potentiation, which is an essential process for learning and memory. Among the five known GRIK family members, haploinsufficiency of GRIK1, GRIK2, and GRIK4 are known to cause developmental delay, whereas the roles of GRIK3 and GRIK5 remain unknown. Herein, we report on a girl who presented with a severe developmental delay predominantly affecting her language and fine motor skills. She had a 2.6‐Mb microdeletion in 1p34.3 involving GRIK3, which encodes a principal subunit of the kainate‐type ionotropic glutamate receptor. Given its strong expression pattern in the central nervous system and the biological function of GRIK3 in presynaptic neurotransmission, the haploinsufficiency of GRIK3 is likely to be responsible for the severe developmental delay in the proposita. A review of genetic alterations and the phenotypic effects of all the GRIK family members support this hypothesis. The current observation of a microdeletion involving GRIK3, a kainate‐type ionotropic glutamate receptor subunit, and the neurodevelopmental manifestation in the absence of major dysmorphism provides further clinical implication of the possible role of GRIK family glutamate receptors in the pathogenesis of developmental delay. © 2013 Wiley Periodicals, Inc.
Differential effects of unusual climatic stress on capuchin (Cebus capucinus) and howler monkey (Alouatta palliata) populations on Barro Colorado Island, Panama
Authors: Milton Katharine , Giacalone Jacalyn
Published: November 2013

Though the harmful effects anthropogenic disturbances pose to wild primates are well appreciated, comparatively little is known about the effects of natural disturbances. From December 2010 to January 2011, different mortality patterns were observed for two primate species, capuchins and howler monkeys, on Barro Colorado Island (BCI), Panama. Unusually high rainfall in 2010 was associated with census and cadaver data indicating the rapid loss of >70% of the capuchin population in late 2010 to early 2011. In contrast, over this same period, no decline was documented for howler monkeys and cadaver data for howlers was unexceptional. The high mortality experienced by the capuchin population was unexpected and its extent was not fully appreciated until the event was largely over. Explanations proposed for it included effects of hypothermia, disease or a shortage of some essential nutrient(s). Of these, the dietary explanation seems most probable. BCI capuchins depend most heavily on arthropod foods in December, when few higher quality ripe fruits are available. The unprecedented high rainfall in December 2010 is hypothesized to have largely eliminated the arthropod peak expected on BCI each December. A lack of protein‐rich arthropods, when coupled with the climatic and nutritional stress capuchins generally experience at this time of year, appears to have precipitated the rapid die‐off of most of the island's capuchin population. As howler monkeys obtain dietary protein primarily from leaves, a shortage of edible arthropods would not affect howler numbers. Comparison of our 2010 data with similar data on earlier primate/mammalian mortality events reported for BCI and for Corcovado, Costa Rica indicates that our understanding of the effects of natural disturbances on wild primate populations is not profound. We suggest that more research be devoted to this increasingly timely topic, so important to conservation policy. Am. J. Primatol. © 2013 Wiley Periodicals, Inc.
Kinship and similarity in residency status structure female social networks in black‐and‐white colobus monkeys (colobus vellerosus)
Authors: Wikberg Eva C. , Ting Nelson , Sicotte Pascale
Published: November 2013

Kinship shapes female social networks in many primate populations in which females remain in their natal group to breed. In contrast, it is unclear to which extent kinship affects the social networks in populations with female dispersal. FemaleColobus vellerosusshow routine facultative dispersal (i.e., some females remain philopatric and others disperse). This dispersal pattern allowed us to evaluate if facultative dispersed females form social networks shaped by an attraction to kin, to social partners with a high resource holding potential, or to similar social partners in terms of maturational stage, dominance rank, and residency status. During 2008 and 2009, we collected behavioral data via focal andad libitumsampling of 61 females residing in eight groups at Boabeng‐Fiema, Ghana. We determined kinship based on partial pedigrees and genotypes at 17 short tandem repeat loci. Kinship influenced coalition and affiliation networks in three groups consisting of long‐term resident females with access to a relatively high number of female kin. In contrast, similar residency status was more important than kinship in structuring the affiliation network in one of two groups that contained recent female immigrants. In populations with female dispersal, the occurrence of kin structured social networks may not only depend on the kin composition of groups but also on how long the female kin have resided together. We found no consistent support for females biasing affiliation toward partners with high resource holding potential, possibly due to low levels of contest competition and small inter‐individual differences in resource holding potential. Am J Phys Anthropol 153:365–376, 2014. © 2013 Wiley Periodicals, Inc.
Cooperative Tandem Catalysis by an Organometallic Complex and a Metalloenzyme
Authors: Denard Carl A. , Huang Hua , Bartlett Mark J. , Lu Lu , Tan Yichen , Zhao Huimin , Hartwig John F.
Published: November 2013

Although chemical and enzymatic catalysts have been combined, reactions in which an organometallic catalyst and a metalloenzyme work cooperatively to create products, which cannot be generated with either catalyst alone or in comparable yields by sequential reactions of the two catalysts, have not been reported. Such reactions are challenging to achieve, in part because the milieu in which these catalysts operate are typically different. Herein, two classes of catalysts are demonstrated to react cooperatively in the same system. Combination of a metathesis catalyst and a P450 enzyme lead to a dynamic equilibration of alkenes and a selective epoxidation of the cross‐metathesis products. These results show the potential of combining the two classes of catalysts for synthetic transformations.
Chiral Silver Phosphate Catalyzed Transformation of ortho‐Alkynylaryl Ketones into 1H‐Isochromene Derivatives through an Intramolecular‐Cyclization/Enantioselective‐Reduction Sequence
Authors: Terada Masahiro , Li Feng , Toda Yasunori
Published: November 2013

The transformation of ortho‐alkynylaryl ketones through a cyclization/enantioselective‐reduction sequence in the presence of a chiral silver phosphate catalyst afforded 1H‐isochromene derivatives in high yield with fairly good to high enantioselectivity. An asymmetric synthesis of the 9‐oxabicyclo[3.3.1]nona‐2,6‐diene framework, which has been found in some biologically active molecules, is presented as a demonstration of the synthetic utility of this method.
Kontrolle der Form verdunstender Tropfen über die Ionenstärke: Bildung anisometrischer SiO2‐Suprapartikel
Authors: Sperling Marcel , Velev Orlin D. , Gradzielski Michael
Published: November 2013

Anisometrische SiO2‐Suprapartikel werden durch einfache Verdunstung einer Dispersion von pyrogenem Siliciumdioxid in Wassertropfen auf einer superhydrophoben Oberfläche erhalten. Die Form der Suprapartikel wird unmittelbar durch die Salzkonzentration (NaCl) kontrolliert. Oberhalb einer Grenzkonzentration werden die Partikel anisometrisch, wie durch Lichtmikroskopie quantifiziert wurde. Das Verfahren kann leicht auf Suprapartikel mit anderen kolloidalen Komponenten übertragen werden.
Synthesis of Complex and Diverse Compounds through Ring Distortion of Abietic Acid
Authors: Rafferty Ryan J. , Hicklin Robert W. , Maloof Katherine A. , Hergenrother Paul J.
Published: November 2013

Many compound screening collections are populated by members that possess a low degree of structural complexity. In an effort to generate compounds that are both complex and diverse, we have developed a strategy that uses natural products as a starting point for complex molecule synthesis. Herein we apply this complexity‐to‐diversity approach to abietic acid, an abundant natural product used commercially in paints, varnishes, and lacquers. From abietic acid we synthesize a collection of complex (as assessed by fraction of sp3‐hybridized carbons and number of stereogenic centers) and diverse (as assessed by Tanimoto analysis) small molecules. The 84 compounds constructed herein, and those created through similar efforts, should find utility in a variety of biological screens.
Non‐Pyrolytic, Large‐Scale Synthesis of Trichalcogenasumanene: A Two‐Step Approach
Authors: Li Xuexiang , Zhu Yongtao , Shao Jiafeng , Wang Baolin , Zhang Shangxi , Shao Yongliang , Jin Xiaojie , Yao Xiaojun , Fang Ran , Shao Xiangfeng
Published: November 2013

Trichalcogenasumanenes were synthesized on a multigram scale through a two‐step approach that takes advantage of non‐pyrolytic cyclization and solventless ring contraction. Solid‐state structure and photophysical investigations demonstrate that these compounds are promising candidates for electronic materials.
“Metal‐Free” Catalytic Oxygen Reduction Reaction on Heteroatom‐Doped Graphene is Caused by Trace Metal Impurities
Authors: Wang Lu , Ambrosi Adriano , Pumera Martin
Published: November 2013

The oxygen reduction reaction (ORR) is of high industrial importance. There is a large body of literature showing that metal‐based catalytic nanoparticles (e.g. Co, Mn, Fe or hybrid Mn/Co‐based nanoparticles) supported on graphene act as efficient catalysts for the ORR. A significant research effort is also directed to the so‐called “metal‐free” oxygen reduction reaction on heteroatom‐doped graphene surfaces. While such studies of the ORR on nonmetallic heteroatom‐doped graphene are advertised as “metal‐free” there is typically no sufficient effort to characterize the doped materials to verify that they are indeed free of any trace metal. Here we argue that the claimed “metal‐free” electrocatalysis of the oxygen reduction reaction on heteroatom‐doped graphene is caused by metallic impurities present within the graphene materials.
Insights into the Metalation of Benzene and Toluene by Schlosser’s Base: A Superbasic Cluster Comprising PhK, PhLi, and tBuOLi
Authors: Unkelbach Christian , O'Shea Donal F. , Strohmann Carsten
Published: November 2013

The metalation of benzene by Schlosser’s base (nBuLi/tBuOK) occurs smoothly in THF at low temperatures to afford a discrete mixed‐metal Li2K4 cluster that contains phenyl anions and tert‐butoxide. The aggregate itself exhibits superbasic behavior by metalating toluene. The delocalized benzyl anion obtained this way π bonds to potassium counterions, thereby creating a 2D coordination polymer.
Recoding the Genetic Code with Selenocysteine
Authors: Bröcker Markus J. , Ho Joanne M. L. , Church George M. , Söll Dieter , O'Donoghue Patrick
Published: November 2013

Selenocysteine (Sec) is naturally incorporated into proteins by recoding the stop codon UGA. Sec is not hardwired to UGA, as the Sec insertion machinery was found to be able to site‐specifically incorporate Sec directed by 58 of the 64 codons. For 15 sense codons, complete conversion of the codon meaning from canonical amino acid (AA) to Sec was observed along with a tenfold increase in selenoprotein yield compared to Sec insertion at the three stop codons. This high‐fidelity sense‐codon recoding mechanism was demonstrated for Escherichia coli formate dehydrogenase and recombinant human thioredoxin reductase and confirmed by independent biochemical and biophysical methods. Although Sec insertion at UGA is known to compete against protein termination, it is surprising that the Sec machinery has the ability to outcompete abundant aminoacyl‐tRNAs in decoding sense codons. The findings have implications for the process of translation and the information storage capacity of the biological cell.
Immobilization of lipase with alginate hydrogel beads and the lipase‐catalyzed kinetic resolution of α‐phenyl ethanol
Authors: Zhang Shuang , Shang Wenting , Yang Xiaoxi , Zhang Xiaogang , Huang Yunqian , Zhang Shujuan , Chen Jiawei
Published: November 2013

The immobilization of enzymes is one of the key issues in both the field of enzymatic research and industrialization. In this article, we report a facile method for immobilizing Candida antarctica lipase B in an alginate carrier. In the presence of calcium cations, an enzyme–alginate suspension was crosslinked to form beads with a porous structure at room temperature, and the enzymes were well dispersed in the beads. The chiral resolution of α‐phenyl ethanol in the organic phase was tested by the enzyme–alginate beads. The effects of the reaction parameters, such as the enzyme concentration, temperature, and molar ratio of the substrate to the solvent, on the resolution behavior are discussed. Reuse cycle experiments for the chiral resolution of α‐phenyl ethanol demonstrated that the activity of the enzyme–alginate beads was maintained without marked deactivation up to five repeated cycles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40178.
Reinforcement of maleated polyethylene/ground tire rubber thermoplastic elastomers using talc and wood flour
Authors: Ramezani Kakroodi Adel , Rodrigue Denis
Published: November 2013

Maleated polyethylene (MAPE)/Ground tire rubber (GTR) thermoplastic elastomer with 50 vol % GTR was reinforced by incorporation of talc powder and wood flour. Scanning electron microscopy (SEM) reveals that maleated polyethylene (MAPE) has good compatibility with wood flour, but the adhesion with talc particles is weak. Tensile moduli of MAPE/GTR increase more significantly after inclusion of talc particles compared to wood flour. Prediction of the tensile modulus of hybrid MAPE/GTR/particle composites is successfully performed using a combination of Kerner and Halpin‐Tsai models. Elastic moduli are shown to depend strongly on both aspect ratio and level of particle dispersion in the matrix. Measurement of compression sets shows that elastic recovery of the compounds decreases after addition of solid particles. Samples having better particles/matrix compatibility show higher elastic recovery. Thermogravimetric analysis shows that inclusion of wood flour decreases thermal stability of compounds. Density and hardness of MAPE/GTR are also shown to increase after inclusion of particulate reinforcements. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40195.
Gold Nanorods with Phase‐Changing Polymer Corona for Remotely Near‐Infrared‐Triggered Drug Release
Authors: Liu Ji , Detrembleur Christophe , Grignard Bruno , De Pauw‐Gillet Marie‐Claire , Mornet Stéphane , Treguer‐Delapierre Mona , Petit Yannick , Jérôme Christine , Duguet Etienne
Published: November 2013

Herein, we report a new drug‐delivery system (DDS) that is comprised of a near‐infrared (NIR)‐light‐sensitive gold‐nanorod (GNR) core and a phase‐changing poly(ε‐caprolactone)‐b‐poly(ethylene glycol) polymer corona (GNR@PCL‐b‐PEG). The underlying mechanism of the drug‐loading and triggered‐release behaviors involves the entrapment of drug payloads among the PCL crystallites and a heat‐induced phase change, respectively. A low premature release of the pre‐loaded doxorubicin was observed in PBS buffer (pH 7.4) at 37 °C (<10 % of the entire payload after 48 h). However, release could be activated within 30 min by conventional heating at 50 °C, above the Tm of the crystalline PCL domain (43.5 °C), with about 60 % release over the subsequent 42 h at 37 °C. The NIR‐induced heating of an aqueous suspension of GNR@PCL‐b‐PEG under NIR irradiation (802 nm) was investigated in terms of the irradiation period, power, and concentration‐dependent heating behavior, as well as the NIR‐induced shape‐transformation of the GNR cores. Remotely NIR‐triggered release was also explored upon NIR irradiation for 30 min and about 70 % release was achieved in the following 42 h at 37 °C, with a mild warming (<4 °C) of the surroundings. The cytotoxicity of GNR@PCL‐b‐PEG against the mouse fibroblastic‐like L929 cell‐line was assessed by MTS assay and good compatibility was confirmed with a cell viability of over 90 % after incubation for 72 h. The cellular uptake of GNR@PCL‐b‐PEG by melanoma MEL‐5 cells was also confirmed, with an averaged uptake of 1250(±110) particles cell−1 after incubation for 12 h (50 μg mL−1). This GNR@PCL‐b‐PEG DDS is aimed at addressing the different requirements for therapeutic treatments and is envisaged to provide new insights into DDS targeting for remotely triggered release by NIR activation.
Well‐Defined Flowerlike NdOCl Nanostructures: Nonaqueous Sol–Gel Synthesis, Nanoscale Characterization and Their Magnetic and Photoluminescence Properties
Authors: Li Xinghua , Deng Xia , Zhu Hao , Feng Juan , Peng Yong , Bai Jintao , Zheng Xinliang , Fan Haibo , Wang Mingzi , Chen Haowei
Published: November 2013

A facile nonaqueous solution route for the fabrication of NdOCl nanostructures based on a ligand‐exchange protocol and further thermal decomposition in organic medium, using only chloride salt as the neodymium source, is reported and the formation mechanism is proposed. The morphology, crystal structure, and chemical compositions of the sample were characterized at the nanoscale. XRD results and selected‐area electron diffraction patterns show that the sample is purely tetragonal NdOCl without any other impurity phases. TEM results show that the NdOCl nanostructures have a well‐defined flowerlike shape, which looks like a chrysanthemum just about to bloom. Magnetization measurements reveal that the NdOCl nanoflowers show room‐temperature ferromagnetism. The photoluminescence properties were also studied. These results are significant for fundamental research and promising applications of rare‐earth‐based nanostructures.
Influence of tropical cyclone ‘AILA’ on atmospheric surface layer turbulence and fluxes at Ranchi during its landfall
Authors: Murthy B. S. , Latha R. , Kumar Manoj
Published: November 2013

Surface layer turbulent fluxes and normalized wind spectra at Ranchi, India during the landfall of severe cyclonic storm ‘AILA’ are compared with the fair weather spectra. Spectral peaks are shifted to lower frequencies as AILA crosses the coast. Dominant eddy sizes after the landfall are observed to be much higher than those before the landfall especially for u component. Spectral energy during the passage of synoptic disturbance in the vicinity is lesser than that of Kaimal's spectrum owing to mismatch of empirical constant over tropics. Mean vertical velocity is positive (negative) before (after) the landfall, indicating dominance of updrafts (downdrafts).
Fluorescent analogs of trypsin inhibitor SFTI‐1 isolated from sunflower seeds—synthesis and applications
Authors: Lesner Adam , Karna Natalia , Psurski Mateusz , Łęgowska Anna , Wysocka Magdalena , Guzow Katarzyna , Sieradzan Adam , Sieńczyk Marcin , Trzonkowski Piotr , Pikuła Michał , Zieliński Maciej , Kosikowska Paulina , Łukajtis Rałał , Łęgowska Monika , Dębowski Dawid , Wiczk Wiesław , Rolka Krzysztof
Published: November 2013

This article describes the synthesis and enzymatic study of newly synthesized analogs of trypsin inhibitors SFTI‐1 that were fluorescent labeled on their N‐terminal amino groups. Two fluorescent derivatives of benzoxazole (3‐[2‐(4‐diphenylaminophenyl)benzoxazol‐5‐yl]‐l‐alanine–[(4NPh2)Ph]Box‐Ala and 3‐[2‐(2',4',5'‐trimethoxyphenyl)benzoxazol‐5‐yl]‐l‐alanine–[2,4,5‐(OMe)3Ph]Box‐Ala) were used as efficient fluorescent labels. The compounds obtained preserved their inhibitory activity and were efficient inhibitors of bovine trypsin or chymotrypsin. Nevertheless, their association inhibition constants were one or two orders of magnitude lower than those determined for unlabeled monocyclic SFTI‐1 or [Phe5]SFTI‐1, respectively. The conjugates obtained were found to be proteolytically stable in the presence of cognate enzymes. Applying such fluorescent peptides, we were able to investigate enzyme‐inhibitor complex formation using fluorescent techniques. We found that such compounds were rapidly internalized by the fibroblast or cancer cells with no cytotoxic effects. © 2013 Wiley Periodicals, Inc. Biopolymers (Pept Sci) 102: 124–135, 2014.
Natural orifice transluminal endoscopic surgery for intra-abdominal emergency conditions
Authors: Bingener J , Ibrahim-zada I
Published: November 2013

Background

Patient benefits from natural orifice transluminal endoscopic surgery (NOTES) are of interest in acute-care surgery. This review provides an overview of the historical development of NOTES procedures, and addresses their current uses and limitations for intra-abdominal emergency conditions.

Methods

A PubMed search was carried out for articles describing NOTES approaches for appendicectomy, percutaneous gastrostomy, hollow viscus perforation and pancreatic necrosectomy. Pertinent articles were reviewed and data on available outcomes synthesized.

Results

Emergency conditions in surgery tax the patient's cardiovascular and respiratory systems, and fluid and electrolyte balance. The operative intervention itself leads to an inflammatory response and blood loss, thus adding to the physiological stress. NOTES provides a minimally invasive alternative access to the peritoneal cavity, avoiding abdominal wall incisions. A clear advantage to the patient is evident with the implementation of an endoscopic approach to deal with inadvertently displaced percutaneous endoscopic gastrostomy tubes and perforated gastroduodenal ulcer. The NOTES approach appears less invasive for patients with infected pancreatic necrosis, in whom it allows surgical debridement and avoidance of open necrosectomy. Transvaginal appendicectomy is the second most frequently performed NOTES procedure after cholecystectomy. The NOTES concept has provided a change in perspective for intramural and transmural endoscopic approaches to iatrogenic perforations during endoscopy.

Conclusion

NOTES approaches have been implemented in clinical practice over the past decade. Selected techniques offer reduced invasiveness for patients with intra-abdominal emergencies, and may improve outcomes. Steady future development and adoption of NOTES are likely to follow as technology improves and surgeons become comfortable with the approaches.
Damage control surgery for abdominal emergencies
Authors: Weber D G , Bendinelli C , Balogh Z J
Published: November 2013

Background

Damage control surgery is a management sequence initiated to reduce the risk of death in severely injured patients presenting with physiological derangement. Damage control principles have emerged as an approach in non-trauma abdominal emergencies in order to reduce mortality compared with primary definitive surgery.

Methods

A PubMed/MEDLINE literature review was conducted of data available over the past decade (up to August 2013) to gain information on current understanding of damage control surgery for abdominal surgical emergencies. Future directions for research are discussed.

Results

Damage control surgery facilitates a strategy for life-saving intervention for critically ill patients by abbreviated laparotomy with subsequent reoperation for delayed definitive repair after physiological resuscitation. The six-phase strategy (including damage control resuscitation in phase 0) is similar to that for severely injured patients, although non-trauma indications include shock from uncontrolled haemorrhage or sepsis. Minimal evidence exists to validate the benefit of damage control surgery in general surgical abdominal emergencies. The collective published experience over the past decade is limited to 16 studies including a total of 455 (range 3–99) patients, of which the majority are retrospective case series. However, the concept has widespread acceptance by emergency surgeons, and appears a logical extension from pathophysiological principles in trauma to haemorrhage and sepsis. The benefits of this strategy depend on careful patient selection. Damage control surgery has been performed for a wide range of indications, but most frequently for uncontrolled bleeding during elective surgery, haemorrhage from complicated gastroduodenal ulcer disease, generalized peritonitis, acute mesenteric ischaemia and other sources of intra-abdominal sepsis.

Conclusion

Damage control surgery is employed in a wide range of abdominal emergencies and is an increasingly recognized life-saving tactic in emergency surgery performed on physiologically deranged patients.
Unlocked Nucleic Acids with a Pyrene‐Modified Uracil: Synthesis, Hybridization Studies, Fluorescent Properties and i‐Motif Stability
Authors: Perlíková Pavla , Karlsen Kasper K. , Pedersen Erik B. , Wengel Jesper
Published: November 2013

The synthesis of two new phosphoramidite building blocks for the incorporation of 5‐(pyren‐1‐yl)uracilyl unlocked nucleic acid (UNA) monomers into oligonucleotides has been developed. Monomers containing a pyrene‐modified nucleobase component were found to destabilize an i‐motif structure at pH 5.2, both under molecular crowding and noncrowding conditions. The presence of the pyrene‐modified UNA monomers in DNA strands led to decreases in the thermal stabilities of DNA*/DNA and DNA*/RNA duplexes, but these duplexes' thermal stabilities were better than those of duplexes containing unmodified UNA monomers. Pyrene‐modified UNA monomers incorporated in bulges were able to stabilize DNA*/DNA duplexes due to intercalation of the pyrene moiety into the duplexes. Steady‐state fluorescence emission studies of oligonucleotides containing pyrene‐modified UNA monomers revealed decreases in fluorescence intensities upon hybridization to DNA or RNA. Efficient quenching of fluorescence of pyrene‐modified UNA monomers was observed after formation of i‐motif structures at pH 5.2. The stabilizing/destabilizing effect of pyrene‐modified nucleic acids might be useful for designing antisense oligonucleotides and hybridization probes.
D–π–A Structured ZnII‐Porphyrin Dyes with Thiophene Moiety for Highly Efficient Dye‐Sensitized Solar Cells
Authors: Kang Sung Ho , Kang Min Soo , Choi In Taek , Hong Ji Yeoun , Ju Myung Jong , Kim Hwan Kyu
Published: November 2013

Herein, we design and synthesize a new D–π–A zinc porphyrin, enveloped with a long alkyl thiophene unit (Th‐ZnP‐CNCOOH, TP), for dye‐sensitized solar cells. The long alkyl‐substituted thiophene unit is incorporated into the porphyrin dye to red‐shift its absorption wavelength. The effects of the alkyl thiophene moiety at the meso‐position of the zinc porphyrin on the optical, electrochemical, and photovoltaic properties of the material are investigated. Dye‐sensitized solar cells (DSSCs) prepared using the new dye, co‐adsorbed with a simply structured organic co‐adsorbent (HC‐A4), are fabricated. The obtained TP/HC‐A4‐sensitized DSSCs exhibit a remarkable enhancement in both short‐circuit current (JSC) and open‐circuit voltage (VOC), relative to the corresponding single‐dye DSSCs, which can be attributed to a combination of the light‐harvesting effect from their complementary absorption behavior and the slow charge‐recombination process. The device based on TP/HC‐A4 co‐sensitization yields: JSC=14.4 mA cm−2, VOC=0.62 V, a fill factor FF=0.75 and an efficiency η=6.7 %. This performance is superior to those of devices containing either TP (η=2.4 %) or HC‐A4 (η=2.8 %), fabricated under the same conditions. The present study indicates that the prevention of dye aggregation, as well as complementary absorption spectra of the porphyrin dyes using co‐sensitizers, are key to improving the device performance.
Climbing the Activity Volcano: Core–Shell Ru@Pt Electrocatalysts for Oxygen Reduction
Authors: Jackson Ariel , Viswanathan Venkatasubramanian , Forman Arnold J. , Larsen Ask H. , Nørskov Jens K. , Jaramillo Thomas F.
Published: November 2013

We outline a systematic approach to develop active catalyst materials for an electrochemical reaction. The strategy allows one to tune binding energies of oxygen reaction intermediates on a catalyst surface by taking advantage of two effects: weakening oxygen binding energies by means of thin‐film overlayers, and strengthening oxygen binding energies through nanoscale effects. By engineering a core–shell nanoparticle morphology with the appropriate dimensions, that is, the thickness of the overlayer and the size of the nanoparticle, bonding properties can be modified to improve the catalytic activity of the core–shell system. We demonstrate the application of this strategy for oxygen reduction by identifying Ru@Pt as a candidate material using density functional theory calculations, and then use these calculations to guide the synthesis of active Ru@Pt core–shell catalysts. The Ru@Pt particles, synthesized using a wet chemical method, exhibit ∼2 times higher specific activity (based on electrochemical active surface area) than state‐of‐the‐art Pt/C from TKK.
Chiral Hypervalent Iodine Reagents: Synthesis and Reactivity
Authors: Parra Alejandro , Reboredo Silvia
Published: November 2013

Chiral hypervalent iodine chemistry has been steadily increasing in importance in recent years. This review catalogues enantioselective transformations triggered by chiral hypervalent iodine(III/V) reagents, in stoichiometric or catalytic quantities, highlighting the different reactivities in terms of yield and enantioselectivity. Moreover, the synthesis of the most remarkable and successful catalysts has been illustrated in detail.
Microwave‐Assisted, Rhodium(III)‐Catalyzed N‐Annulation Reactions of Aryl and α,β‐Unsaturated Ketones with Alkynes
Authors: Lee Hyejeong , Sim Yong‐Kyun , Park Jung‐Woo , Jun Chul‐Ho
Published: November 2013

New RhIII‐catalyzed, one‐pot N‐annulation reactions of aryl and α,β‐unsaturated ketones with alkynes in the presence of ammonium acetate have been developed. Under microwave irradiation conditions, the processes lead to rapid formation of the respective isoquinoline and pyridine derivatives with efficiencies that are strongly dependent on the steric nature of the aryl ring and enone substituents. By employing this protocol, a variety of isoquinoline and pyridine derivatives were prepared in high yields. In addition, a new one‐pot approach to the synthesis of pyridines, involving four‐component reactions of ketones, formaldehyde, NH4OAc, and alkynes, has been uncovered. This process takes place through a route involving initial aldol condensation of the ketone with formaldehyde to generate a branched α,β‐unsaturated ketone that then undergoes RhIII‐catalyzed N‐annulation with NH4OAc and the alkyne.
Toward the peri‐Pentacene Framework
Authors: Zöphel Lukas , Berger Reinhard , Gao Peng , Enkelmann Volker , Baumgarten Martin , Wagner Manfred , Müllen Klaus
Published: November 2013

Based on modern pyrene chemistry, a new route toward the synthesis of the peri‐pentacene framework was developed. Firstly, the tetraketo form as stable precursor was targeted, because the fully aromatic peri‐pentacene is predicted to suffer from high instability and reactivity. Therefore, a recently developed 4,5,9,10‐tetrafunctionalization of pyrene was utilized to build up a planar and a dragonfly‐shaped derivative in five steps, which only differ in the two outer bonds between the peripheral benzene rings. The planar tetraketone could only be dissolved in strong acids upon protonation, which limited the use of analytical methods. In contrast, the dragonfly‐shaped form showed excellent organosolubility. In‐depth investigation by NMR spectroscopy revealed co‐existence of atropo‐isomers in solution. The optical and electronic properties were analyzed by UV/Vis spectroscopy and cyclic voltammetry. To approach aromatic conjugation, stepwise reduction in solution by using tetrabutylammonium borohydride was carried out. Reduced species were studied by ESR and UV/Vis spectroscopy, as well as by MALDI‐TOF MS, confirming the formation of the radical anion.
Triisopropylsilylethynyl‐Functionalized Graphene‐Like Fragment Semiconductors: Synthesis, Crystal Packing, and Density Functional Theory Calculations
Authors: Zhang Lei , Fonari Alexandr , Zhang Yue , Zhao Guangyao , Coropceanu Veaceslav , Hu Wenping , Parkin Sean , Brédas Jean‐Luc , Briseno Alejandro L.
Published: November 2013

Tri‐isopropylsilylethynyl (TIPS)‐functionalized polycyclic aromatic hydrocarbon (PAH) molecules incorporate structural components of graphene nanoribbons and represent a family of model molecules that form organic crystal semiconductors for electronic devices. Here, we report a series of TIPS‐functionalized PAHs and discuss their electronic properties and crystal packing features. We observe that these soluble compounds easily form one‐dimensional (1 D) packing arrangements and allow a direct evolution of the π stacking by varying the geometric shape. We find that the aspect ratio between length and width plays an important role on crystal packing. Our result indicates that when the PAH molecules have zigzag edges, these can provide enough volume for the molecules to rotate and reorient, alleviating the unfavorable electrostatic interactions found in perfectly cofacial π–π stacking. Density functional theory calculations were carried out to provide insights into how the molecular geometric shape influences the electronic structure and transport properties. The calculations indicate that, among the compounds studied here, “brick‐layer” stacks provide the highest hole mobility.
Primary Amines by Transfer Hydrogenative Reductive Amination of Ketones by Using Cyclometalated IrIII Catalysts
Authors: Talwar Dinesh , Salguero Noemí Poyatos , Robertson Craig M. , Xiao Jianliang
Published: November 2013

Cyclometalated iridium complexes are found to be versatile catalysts for the direct reductive amination (DRA) of carbonyls to give primary amines under transfer‐hydrogenation conditions with ammonium formate as both the nitrogen and hydrogen source. These complexes are easy to synthesise and their ligands can be easily tuned. The activity and chemoselectivity of the catalyst towards primary amines is excellent, with a substrate to catalyst ratio (S/C) of 1000 being feasible. Both aromatic and aliphatic primary amines were obtained in high yields. Moreover, a first example of homogeneously catalysed transfer‐hydrogenative DRA has been realised for β‐keto ethers, leading to the corresponding β‐amino ethers. In addition, non‐natural α‐amino acids could also be obtained in excellent yields with this method.
Tetraphenylethylene Conjugated with a Specific Peptide as a Fluorescence Turn‐On Bioprobe for the Highly Specific Detection and Tracing of Tumor Markers in Live Cancer Cells
Authors: Huang Yanyan , Hu Fang , Zhao Rui , Zhang Guanxin , Yang Hua , Zhang Deqing
Published: November 2013

Smart molecular probes and flexible methods are attracting remarkable interest for the visualization of cancer‐related biological and chemical events. In this work, a new fluorescence turn‐on probe with dual‐recognition characteristics for the specific imaging of cancer cells is reported. This new bioprobe is rationally designed by linking tetraphenylethylene (TPE), an aggregation‐induced emission (AIE) fluorophore, with the small peptide IHGHHIISVG (referred to as AP2H), a targeting ligand to the broad‐spectrum cancer‐related protein LAPTM4B. The binding of the probe TPE‐AP2H with the target, both in solution and at the cellular level, switches on the fluorescence of TPE because of the inhibition of internal rotations within the TPE framework. Accordingly, this bioprobe allows the real‐time monitoring and subcellular localization of LAPTM4B in cancer cells, with a very high target‐to‐background ratio for the imaging. Furthermore, brighter fluorescence images are detected after incubation of TPE‐AP2H with tumor cells at lower pH values. Thus, this new bioprobe is more advantageous because it can simultaneously target the LAPTM4B protein and sense the characteristic low‐pH environment of tumor cells. In addition, TPE‐AP2H displays high photostability and low cytotoxicity. Therefore, this new bioprobe is promising for the more accurate and reliable imaging of tumor markers in live cancer cells.
An approach to model three‐phase flow coupling during steam chamber rise
Authors: Murtaza Muhammad , He Zhongxue , Dehghanpour Hassan
Published: November 2013

During steam assisted gravity drainage (SAGD) process, a steam chamber forms due to continuous steam injection. This chamber first moves upward to the top of the reservoir and then spreads sideways. The upward chamber displacement is one of the key factors for optimising the steam injection rate. It is necessary to determine the accurate chamber rise velocity for predicting the oil recovery rate. Recent experiments show that oil flow is coupled to water flow during three‐phase gravity drainage in water‐wet systems. In this paper, we argue that this type of flow coupling can be significant in SAGD operations. We extend Butler's [Butler, J. Can. Petrol. Technol. 1987, 26, 70] and Gotawala and Gates [Gotawala and Gates, Can. J. Chem. Eng. 2008, 86, 1011] analytic models for the rise of interfering steam chambers to account for three‐phase flow and flow coupling. We also show the importance of flow coupling by solving a simple numerical example. We observe that by including three‐phase drainage and the flow coupling at the steam finger edge, the vertical rise velocity of a steam chamber increases. Moreover, the rise velocity is very sensitive to the coupling term introduced in the new models. Even a small value of the coupling term increases the rise velocity significantly. Furthermore, we compare the model predictions with the values measured in six fields.
Addition of N‐Acetyl Cysteine to Carvedilol Decreases the Incidence of Acute Renal Injury After Cardiac Surgery
Authors: Ozaydin Mehmet , Peker Tulay , Akcay Selahaddin , Uysal Bayram A. , Yucel Habil , Icli Atilla , Erdogan Dogan , Varol Ercan , Dogan Abdullah , Okutan Huseyin
Published: November 2013

Background

Oxidative stress and inflammation during cardiac surgery may be associated with acute renal injury (ARI). N‐acetyl cysteine (NAC) and carvedilol have antioxidant and anti‐inflammatory properties.

Hypothesis

A combination of carvedilol and NAC should decrease the incidence of ARI more than metoprolol or carvedilol.

Methods

Patients undergoing cardiac surgery were randomized to metoprolol, carvedilol, or carvedilol plus NAC. End points were occurrence of ARI and change in preoperative to postoperative peak creatinine levels.

Results

ARI incidence was lower in the carvedilol plus NAC group compared with the metoprolol (21.0% vs 42.1%; P = 0.002) or carvedilol (21.0% vs 38.6%; P = 0.006) groups, but was similar between the metoprolol and carvedilol groups (P = 0.62). Preoperative and postoperative day 1 creatinine levels were similar among the metoprolol (1.02 [0.9–1.2] and 1.2 [0.92–1.45]) the carvedilol (1.0 [0.88–1.08] and 1.2 [0.9–1.5]) and the carvedilol plus NAC groups (1.06 [0.9–1.18] and 1.1 [1.0–1.21] mg/dL; all P values >0.05). Postoperative day 3, day 5, and peak creatinine levels were lower in the carvedilol plus NAC group (1.11 [1.0–1.23], 1.14 [1.0–1.25] and 1.15 [1.0–1.25]) as compared with the metoprolol (1.4 [1.3–1.49], 1.3 [1.0–1.54] and 1.3 [1.0–1.54]) or carvedilol groups (1.2 [1.0–1.52], 1.25 [1.0–1.52] and 1.25 [1.0–1.55] mg/dL; all P values <0.05), but were similar between the metoprolol and carvedilol groups (all P values >0.05).

Conclusions

Combined carvedilol and NAC decreased ARI incidence as compared with carvedilol or metoprolol. No difference was detected between carvedilol and metoprolol.