bluuebunny/crossref_metadata_2025 huggingface dataset:
Incidence of stroke in patients with d‐transposition of the great arteries that undergo balloon atrial septostomy in the University Healthsystem Consortium Clinical Data Base/Resource Manager
Authors: Applegate Stacey E. , Lim D. Scott
Published: January 2010

Objectives:

The aim of this study was to investigate the incidence of stoke in pediatric patients undergoing a balloon atrial septostomy (BAS).

Background:

Newborn infants with d‐transposition of the great arteries (dTGA) can be compromised from significant hypoxemia due to inadequate mixing at the atrial level. BAS can be lifesaving by improving the intra‐atrial mixing. BAS, although life‐saving, is associated with risks including arrhythmias, infection, bleeding, stroke, or death. Recent studies have conflicting conclusions demonstrating the risk of BAS and brain injury using magnetic resonance imaging. However, these studies did not demonstrate the clinical significance of brain injury through physical manifestations of stroke.

Methods:

The University HealthSystem Consortium Clinical Data Base/Resource Manager (UHC CDB/RM) consists of 103 Academic Medical Centers, and affiliated institutions. The CDB/RM was queried using billing codes upon discharge from the consortium hospitals from 2004 to 2008.

Results:

In total, the UHC CDB/RM contained information on 1,295 neonatal patients (group 1) who were discharged with a diagnosis of dTGA, of which 440 had a BAS during the same hospitalization. In group 1, 18 had a coded diagnosis of stroke and only six of these 18 had a BAS. In group 2 (pediatric patients with dTGA), 952 patients were discharged with a diagnosis of dTGA, of which 37 had BAS. Pediatric patients (19 of 952) had a stroke and none of them had a BAS.

Conclusions:

In over 2,000 cases of dTGA reported in the CDB/RM over a 4‐year period, BAS was not associated with an increased risk of clinical stroke either in the neonatal period or in follow‐up hospitalizations. © 2009 Wiley‐Liss, Inc.
Decreasing operators' radiation exposure during coronary procedures
Authors: Behan Miles , Haworth Peter , Colley Paul , Brittain Michael , Hince Andrew , Clarke Michael , Ghuran Azad , Saha Mrinal , Hildick‐Smith David
Published: January 2010

Aim: Transradial coronary procedures are associated with decreased vascular access site complications and other benefits compared to the femoral approach. There is some concern however about high‐recorded radiation doses for interventional cardiologists using the transradial route. We therefore designed and investigated the effect of a transradial radiation protection board (TRPB) on operator radiation exposure during coronary procedures. Methods and Results: One hundred and six patients were randomly assigned by time period to undergo radial coronary procedures either with or without a TRPB. This is a grooved arm board with a detachable 0.5‐mm lead equivalent shield designed to rest between the patient's arm and side. Individual case‐specific radiation exposures were measured using electronic personal dosimeter worn on the left outer pocket of the lead apron at chest level. The TRPB was used in addition to standard lead apron and thyroid shielding, below‐table leaded flaps, and leaded glass. Operator radiation exposure was significantly decreased in the TRPB group overall: 28 [18–65] μSV versus 19.5 [10.5–35] μSV, P = 0.003. There were no significant differences in procedure duration, total fluoroscopy dose, or contrast load between the two groups. Conclusion: Identification of methods to reduce operator radiation dose is important. The use of the TRPB can significantly reduce radiation exposure to radial operators. © 2010 Wiley‐Liss, Inc.
Failure of the Amplatzer ductal occluder II
Authors: Beck Carsten , Laser Kai Thorsten , Haas Nikolaus A.
Published: January 2010

Since March 2008, the new Amplatzer duct occluder II (ADO II) has been used clinically for PDA closure in Europe. We report an interesting case of a 2½‐year‐old girl with a 3‐mm conical shape PDA (type A PDA) who underwent uneventful implantation of 3/4 ADO II with complete closure by angiography and echocardiographic control at the end of the procedure. To our surprise, echocardiography 24 hr later revealed a moderate secondary shunt due to kinking of the aortic retention disk of the device with the central waist and the pulmonary retention disk still in correct position. The persistent shunt was closed 1 year later in the cath lab with a 9/6 Nit‐Occlud device. To our knowledge, this is the first reported late complication directly related to the device. © 2010 Wiley‐Liss, Inc.
Optimization of drug‐eluting balloon use for safety and efficacy: Evaluation of the 2nd generation paclitaxel‐eluting DIOR‐balloon in porcine coronary arteries
Authors: Pósa Anikó , Nyolczas Noemi , Hemetsberger Rayyan , Pavo Noemi , Petnehazy Örs , Petrasi Zsolt , Sangiorgi Giuseppe , Gyöngyösi Mariann
Published: January 2010

Objectives: The aim of this preclinical study was to optimize the use of drug‐eluting balloon (DEB) DIOR2nd
generation by measurements of tissue and plasma paclitaxel concentrations in porcine coronary artery overstretch and prove efficacy in inhibition of neointimal growth without complementary use of stent. Background: The usually recommended DEB 60 sec inflation time causes prolonged ischemia and arterial injury. Methods: Tissue, plasma, and balloon surface concentrations of paclitaxel were measured in pigs 45 min and 12 hr after balloon inflation times of 15, 20, 30, 45, and 60 sec. Extent of neointimal hyperplasia was compared using DIOR2nd
generation or noncoated balloon at two‐week follow‐up. Paclitaxel was replaced by fluorescent paclitaxel derivative in DEB and DES to demonstrate the distribution of the drug in arterial wall. Results: DIOR2nd
generation DEB provided 29 ± 3 μM/L, 52 ± 6 μM/L, 196 ± 44 μM/L, 202 ± 36 μM/L, and 184 ± 59 μM/L paclitaxel to the vessel wall after 15, 20, 30, 45, and 60 sec of dilation, reaching plateau at 30 sec inflation time. Paclitaxel penetrated up to 2 mm tissue deepness. Measurable plasma paclitaxel level (45 ± 28 ng/mL) was found only after 60 sec balloon inflation time. At follow‐up, the dilated arterial segment neointimal area and maximal neointimal thickness were significantly smaller with DIOR vs. uncoated balloon use. Fluorescence images of DIOR showed a homogenous distribution of the drug on the vessel, in contrast with DES. Conclusion: Using the DIOR2nd
generation DEB, a maximal balloon inflation time of 30–45 sec is optimal, reducing effectively the neointimal hyperplasia. © 2010 Wiley‐Liss, Inc.
Predictors of embolization during protected renal artery angioplasty and stenting: Role of antiplatelet therapy
Authors: Kanjwal Khalil , Cooper Christopher J. , Virmani Renu , Haller Steven , Shapiro Joseph I. , Burket Mark W. , Steffes Michael , Brewster Pamela , Zhang Haifeng , Colyer William R.
Published: January 2010

Objective: The objective of this study was to identify the predictors of distal embolization (DE) during protected renal artery angioplasty and stenting. Background: DE may contribute to worsening renal function after renal artery stenting. The factors associated with DE, rates of platelet‐rich emboli, and treatments that may prevent DE during renal stenting have not been evaluated. Methods: The current study evaluated patients randomized to receive an embolic protection device (EPD) in the RESIST trial. Forty‐two patients were identified for inclusion in this study. These patients were further randomized to abcizimab (N = 22) or placebo (N = 20). Modification in Diet in Renal Disease glomerular filtration rate (GFR) was used as the primary measure of renal function. Creatinine was measured by a modified Jaffe reaction using the IDMS‐traceable assay. The primary endpoint was capture of platelet rich emboli in the angioguard basket. Results: DE occurred in 15/42 (35%) of the patients and platelet rich DE in 10 (24%) of the patients who received an EPD. Of the angiographic characteristics only lesion length was significantly higher in patients with DE (16 ± 7 mm vs. 10 ± 5 mm, P = 0.04). Preprocedural abciximab reduced DE from 42 to 8% (P = 0.02). The rate of platelet rich emboli was 50% with neither abciximab nor a thienopyridine, 36% with thienopyridine only, 15% abciximab only, and 0% in patients who received both a thienopyridine and abciximab. Only Abciximab use was associated with improved renal function at 1‐month, thienopyridine was not. Angiographic characteristics including percent stenosis, minimal luminal diameter (MLD), reference diameter, change in MLD, contrast volume, and procedure time were not predictors of DE during renal stenting. Conclusion: Capture of DE and specifically platelet DE are common during protected renal stenting using a filter‐type EPD. Abciximab use, and potentially combined thienopyridine and abciximab use, decreased the rate of platelet rich DE; however, only abciximab improved renal function at 1‐month. © 2010 Wiley‐Liss, Inc.
Race, ethnicity, and socioeconomic status influence the survival of patients with hepatocellular carcinoma in the United States
Authors: Artinyan Avo , Mailey Brian , Sanchez‐Luege Nicelio , Khalili Joshua , Sun Can‐Lan , Bhatia Smita , Wagman Lawrence D. , Nissen Nicholas , Colquhoun Steven D. , Kim Joseph
Published: January 2010

BACKGROUND:

Racial, ethnic, and socioeconomic disparities in the survival of patients with hepatocellular carcinoma (HCC) continue to exist. The authors of this report hypothesized that these differences result from inequities in access to care and in response to therapy.

METHODS:

Patients with HCC (n = 20,920) were identified from the Surveillance, Epidemiology, and End Results (SEER) database, and patients who underwent liver transplantation for HCC (n = 4735) were identified from the United Network for Organ Sharing (UNOS) database. Clinical and pathologic factors were compared after patients were stratified by race and ethnicity.

RESULTS:

The survival of patients with HCC improved over time for all racial, ethnic, and income groups (P < .001). Black and low income individuals had the poorest long‐term survival (P < .001). On multivariate analysis, black race was predictive of the poorest survival (hazard ratio [HR], 1.15; 95% confidence interval [CI], 1.09‐1.22; P < .001), whereas Asian race was associated with the best survival (HR, 0.87; 95% CI, 0.83‐0.91; P < .001). After liver transplantation, black patients had the worst graft survival and overall survival (median survival [MS], 30.5 months and 39.7 months, respectively; P < .001), whereas Hispanics had the best survival (MS, 83.4 months and 86.6 months, respectively; P < .001). In a multivariate analysis of transplantation patients, race and ethnicity were associated significantly with outcome.

CONCLUSIONS:

Significant racial and ethnic disparities in the outcome of patients with HCC persist despite the receipt of comparable treatment. The authors concluded that further investigations are warranted to identify the reasons for the stark disparity in outcomes between black patients and Hispanic patients after liver transplantation for HCC. Cancer 2010. © 2010 American Cancer Society.
Prostate cancer treatment for economically disadvantaged men
Authors: Parsons J. Kellogg , Kwan Lorna , Connor Sarah E. , Miller David C. , Litwin Mark S.
Published: January 2010

BACKGROUND.

The authors compared the types of treatments prostate cancer patients received from county hospitals and private providers as part of a statewide public assistance program.

METHODS.

This was a cohort study of 559 men enrolled in a state‐funded program for low‐income patients known as Improving Access, Counseling, and Treatment for Californians With Prostate Cancer (IMPACT). Multinomial regression was used to compare types of treatments patients received from different providers.

RESULTS.

Between 2001 and 2006, 315 (56%) participants received treatment from county hospitals and 244 (44%) from private providers. There were no significant between‐group differences with respect to age (P = .22), enrollment year (P = .49), Charlson comorbidity index (P = .47), Gleason sum (P = .33), clinical T stage (P = .36), prostate‐specific antigen (P = .39), or D'Amico risk criteria (P = .45). Participants treated by private providers were more likely than those treated in county hospitals to be white (35% vs 10%, P < .01) and less likely to undergo surgery (29% vs 54%, P < .01). Multinomial regression analyses showed that participants treated by private providers were nearly 2½ times more likely than those treated by public providers to receive radiotherapy (odds ratio [OR], 2.36; 95% confidence interval [CI], 1.37‐4.07) and >4½ times more likely to receive primary androgen deprivation (OR, 4.71; 95% CI, 2.15‐10.36) than surgery.

CONCLUSIONS.

In this economically disadvantaged cohort, prostate cancer treatments differed significantly between county hospitals and private providers. These data reveal substantial variations in treatment patterns between different types of healthcare institutions that—given the implications for health policy and quality of care—merit further scrutiny. Cancer 2010. © 2010 American Cancer Society.
High‐performance hybrid information service architecture
Authors: Aktas Mehmet S. , Pierce Marlon
Published: January 2010

We introduce a distributed high‐performance Information Service Architecture, which forms a metadata replica hosting system to manage both highly dynamic small‐scale metadata and relatively large static metadata associated with Grid/Web Services. We present an empirical evaluation of the proposed architecture and investigate its practical usefulness. The results demonstrate that the proposed system achieves high performance and fault tolerance with negligible processing overheads. The results also indicate that efficient decentralized hybrid Information Service Architectures can be built by utilizing publish‐subscribe‐based messaging schemes. Copyright © 2010 John Wiley & Sons, Ltd.
Hydrogen Evolution on Single‐Crystal Copper and Silver: A Theoretical Study
Authors: Santos Elizabeth , Pötting Kay , Lundin Angelica , Quaino Paola , Schmickler Wolfgang
Published: January 2010

Hydrogen evolution on single‐crystal copper and silver is investigated by a combination of density functional theory and a theory developed in our own group. At short times, the reaction rate is determined by the transfer of the first proton to the electrode surface. In accord with experiment, we find for both metals that this reaction proceeds faster on the (111) surfaces than on the (100) ones. The main cause is the lower, that is, more favourable, adsorption energy on the former surfaces. On both silver surfaces, the second step is electrochemical desorption. The same mechanism is likely to operate on copper.
A Promising Approach to the Synthesis of 3D Nanoporous Graphitic Carbon as a Unique Electrocatalyst Support for Methanol Oxidation
Authors: Tiwari Jitendra N. , Tiwari Rajanish N. , Chang Yun‐Min , Lin Kun‐Lin
Published: January 2010

A 3D nanoporous graphitic carbon (g‐C) material is synthesized by using an adamantane (C10H16) flame, and utilized to support a Pt50–Ru50 alloy catalyst. The physico‐chemical properties of the Pt50–Ru50/3D nanoporous g‐C electrode are examined by a range of spectroscopy techniques as well as Brunauer–Emmett–Teller surface area analysis. Cyclic voltammetry measurements are used for electrochemical characterization of the Pt50–Ru50/3D nanoporous g‐C electrode. The electrochemical investigations show that the supported Pt50–Ru50 has excellent activity and stability towards methanol electro‐oxidation. Good CO tolerance is also shown, and considered to be due to the presence of Ru nanoparticles. It is proposed that Ru is able to promote the oxidation of strongly adsorbed CO on Pt by supplying an oxygen source: Ru(OH)ad. Moreover, the presence of 3D nanopores in the g‐C support may also contribute to the observed higher current density by virtue of the easy transport of methanol and the oxidation products through these nanopores.
Inadequacies of absolute threshold levels for diagnosing prediabetes
Authors: Bergman Michael
Published: January 2010

Prediabetes comprising Impaired Fasting Glucose (IFG) and Impaired Glucose Tolerance (IGT) represents an intermediate stage of altered glucose metabolism between normal glucose levels and type 2 diabetes mellitus and is associated with an increased risk for the development of diabetes and cardiovascular disease. There is considerable evidence that glucose levels lower than those meeting the current definition of prediabetes may also be associated with similar risks particularly in high‐risk individuals. Prediabetes is often unrecognized and therefore constitutes a major public health concern suggesting the need for earlier intervention than is currently recommended. Copyright © 2010 John Wiley & Sons, Ltd.
Unexpectedly high rates of obesity and dysglycemia among villagers in Cameroon
Authors: Napoli Nicola , Mottini Giovanni , Arigliani Michele , Creta Antonio , Giua Renato , Incammisa Antonino , Carotti Simone , Sihom François , Yimagou Isaac , Alombah Richard , Mbanya Jean Claude , Pozzilli Paolo
Published: January 2010

Our survey in Cameroon recorded obesity and dysglycemia in inhabitants, which are similar to those reported elsewhere in the region. Typically these metabolic disturbances are attributed to the adoption of a new urban lifestyle including diminished physical activity and an altered (‘Western’) diet. Unexpectedly we found that, like urban populations, our rural population had high rates of metabolic disturbances, despite living in villages and being physically active and consuming traditional diet that is high in plant sources of food and low in meat. From our preliminary study, we raise the possibility that the environmental elements that are driving the pandemic of obesity and diabetes in sub‐Saharan Africa are far more complex than heretofore appreciated. Copyright © 2010 John Wiley & Sons, Ltd.
In vitro‐induced Th17 cells fail to induce inflammation in vivo and show an impaired migration into inflamed sites
Authors: Janke Marko , Peine Michael , Nass Alexia , Morawietz Lars , Hamann Alf , Scheffold Alexander
Published: January 2010

Recently, IL‐17 produced by Th17 cells was described as pro‐inflammatory cytokine with an eminent role in autoimmune diseases, e.g. rheumatoid arthritis. A lack of IL‐17 leads to amelioration of collagen‐induced arthritis. IL‐17 induction in naïve CD4+ T cells depends on IL‐6 and TGF‐β and is enhanced by IL‐23. The in vivo inflammatory potential of in vitro‐primed Th17 cells however, remains unclear. Here, we show that, although IL‐17 neutralisation results in amelioration of murine OVA‐induced arthritis, in vitro‐primed Th17 cells cannot exacerbate arthritic symptoms after adoptive transfer. Furthermore, Th17 cells cannot induce an inflammatory delayed type hypersensitivity reaction because they fail to migrate into inflamed sites, possibly due to the lack of CXCR3 expression. Also, re‐isolated Th17 cells acquired IFN‐γ expression, indicating instability of the Th17 phenotype. Taken together, the data show that IL‐6, TGF‐β and IL‐23 might not provide sufficient signals to induce “fully qualified” Th17 cells.
Involvement of CD8+ T cells in protective immunity against murine blood‐stage infection with Plasmodium yoelii 17XL strain
Authors: Imai Takashi , Shen Jianying , Chou Bin , Duan Xuefeng , Tu Liping , Tetsutani Kohhei , Moriya Chikako , Ishida Hidekazu , Hamano Shinjiro , Shimokawa Chikako , Hisaeda Hajime , Himeno Kunisuke
Published: January 2010

When developing malaria vaccines, the most crucial step is to elucidate the mechanisms involved in protective immunity against the parasites. We found that CD8+ T cells contribute to protective immunity against infection with blood‐stage parasites of Plasmodium yoelii. Infection of C57BL/6 mice with P. yoelii 17XL was lethal, while all mice infected with a low‐virulence strain of the parasite 17XNL acquired complete resistance against re‐infection with P. yoelii 17XL. However, the host mice transferred with CD8+ T cells from mice primed only with P. yoelii 17XNL failed to acquire protective immunity. On the other hand, the irradiated host mice were completely resistant to P. yoelii 17XL infection, showing no grade of parasitemia when adoptively transferred with CD8+ T cells from immune mice that survived infection with both P. yoelii XNL and, subsequently, P. yoelii 17XL. These protective CD8+ T cells from immune WT mice had the potential to generate IFN‐γ, perforin (PFN) and granzyme B. When mice deficient in IFN‐γ were used as donor mice for CD8+ T cells, protective immunity in the host mice was fully abrogated, and the immunity was profoundly attenuated in PFN‐deficient mice. Thus, CD8+ T cells producing IFN‐γ and PFN appear to be involved in protective immunity against infection with blood‐stage malaria.
CCL20/CCR6 blockade enhances immunity to RSV by impairing recruitment of DC
Authors: Kallal Lara E. , Schaller Matthew A. , Lindell Dennis M. , Lira Sergio A. , Lukacs Nicholas W.
Published: January 2010

Chemokines are important mediators of the immune response to pathogens, but can also promote chronic inflammatory states. Chemokine receptor 6 (CCR6) is found on immature DC and effector/memory T cells, and binds a single ligand, CCL20, with high affinity. Here, we investigated the role of CCL20 and CCR6 in a pulmonary viral infection caused by RSV, a ubiquitous virus that can cause severe pulmonary complications. Neutralization of CCL20 during RSV infection significantly reduced lung pathology and favored a Th1 effector response. CCR6‐deficient animals recapitulated this phenotype, and additionally showed enhanced viral clearance when compared with WT mice. No differences were observed in migration of T cells to the lungs of CCR6−/− animals; however, a significant reduction was observed in numbers of conventional DC (cDC), but not plasmacytoid DC, in CCR6−/− mice. A pathogenic phenotype could be reconstituted in CCR6−/− mice by supplying cDC into the airway, indicating that mere number of cDC dictates the adverse response. Our data suggest that blockade of the CCL20/CCR6 pathway provides an environment whereby the attenuated recruitment of cDC alters the balance of innate immune cells and mediates the efficient antiviral response to RSV.
Uptake of apoptotic DC converts immature DC into tolerogenic DC that induce differentiation of Foxp3+ Treg
Authors: Kushwah Rahul , Wu Jing , Oliver Jordan R. , Jiang George , Zhang Jinyi , Siminovitch Katherine A. , Hu Jim
Published: January 2010

DC apoptosis has been observed in patients with cancer and sepsis, and defects in DC apoptosis have been implicated in the development of autoimmune diseases. However, the mechanisms of how DC apoptosis affects immune responses, are unclear. In this study, we showed that immature viable DC have the ability to uptake apoptotic DC as well as necrotic DC without it being recognized as an inflammatory event by immature viable DC. However, the specific uptake of apoptotic DC converted immature viable DC into tolerogenic DC, which were resistant to LPS‐induced maturation. These tolerogenic DC secreted increased levels of TGF‐β1, which induced differentiation of naïve T cells into Foxp3+ Treg. Furthermore, induction of Treg differentiation only occurred upon uptake of apoptotic DC and not apoptotic splenocytes by viable DC, indicating that it is specifically the uptake of apoptotic DC that gives viable immature DC the potential to induce Foxp3+ Treg. Taken together, these findings identify uptake of apoptotic DC by viable immature DC as an immunologically tolerogenic event.
Differential phosphorylation of functional tyrosines in CD19 modulates B‐lymphocyte activation
Authors: Ishiura Nobuko , Nakashima Hiroko , Watanabe Rei , Kuwano Yoshihiro , Adachi Takahiro , Takahashi Yoshimasa , Tsubata Takeshi , Okochi Hitoshi , Tamaki Kunihiko , Tedder Thomas F. , Fujimoto Manabu
Published: January 2010

CD19 is a B‐cell transmembrane molecule that is critical for B‐cell activation. CD19 serves as a scaffold protein for key signal transduction molecules including Lyn, PI3K, and Vav, by providing docking sites for these molecules via phosphorylation of CD19‐Y513, CD19‐Y482, and CD19‐Y391. We investigated the process of CD19 tyrosine phophorylation during B‐cell activation using Ab specific for each of these phosphorylated tyrosines. BCR engagement induced differential tyrosine phosphorylation, as CD19‐Y513 phophorylation occurred first, and CD19‐Y482 phosphorylation was delayed and transient. Different BCR isotypes exhibited distinct patterns of CD19 phosphorylation: IgG‐BCR ligation resulted in faster phosphorylation of CD19‐Y513 and more intense phosphorylation of CD19‐Y391 than IgM‐BCR ligation. This affected CD19‐mediated downstream pathways involving Vav, PI3K, and Akt. Additionally, the phosphorylation profile of CD19 differed distinctly according to its plasma membrane location. CD19 phosphorylated at Y513 was almost exclusively located within lipid rafts, whereas phosphorylated Y482 and Y391 were found both inside and outside of the rafts. Furthermore, the phosphorylation of all three tyrosines was remarkably enhanced and prolonged following the simultaneous stimulation of BCR and CD40. Thus, variations in phosphorylation patterns may contribute to the complexity of CD19‐regulated signal transduction.
Controllable Synthesis of Cu2O Microcrystals via a Complexant‐Assisted Synthetic Route
Authors: Zhang Wanqun , Shi Lei , Tang Kaibin , Dou Shumei
Published: January 2010

A novel method using Cu(AC)2·H2O and dimethylglyoxime as reagents has been successfully developed for the controllable synthesis of Cu2O microcrystals with distinctive morphologies, including porous hollow microspheres, octahedral microcages, and microcrystals with truncated corners and edges and octahedral microcrystals. These structures can be fine‐tuned by varying reaction temperature, reaction time, and concentration. The products were characterized by X‐ray diffraction, field emission scanning electron microscopy, X‐ray photoelectron spectra, and UV/Vis diffuse reflectance spectra. This is the first report of the preparation of the novel microcage structure of Cu2O through a simple solution‐based route. By investigating the intermediate products which resemble the final crystal structures, a possible growth mechanism is proposed. Moreover, the investigations showed that the various 3D architectures of the as‐made products exhibit different abilities to catalytically degrade rhodamine‐B. Our work shows that octahedral Cu2O crystals with entirely {111} faces are photocatalytically more active than octahedral microcrystals with truncated corners and edges, suggesting the {111} faces of Cu2O nanostructures are catalytically more active than the {100} and {110} faces. Due to dual effect of the cavity structure and the {111} surfaces, the octahedral microcages with truncated corners and edges exhibit a higher extent of the photodecomposition reaction. As a result of very slow photocorrosion rate of the Cu2O microcrystal, it is expected that these microcrystals with different surfaces may find more applications in photocatalysis.
β‐Diketiminate Zinc Complexes for the Hydroamination of Alkynes
Authors: Biyikal Mustafa , Löhnwitz Karolin , Meyer Nils , Dochnahl Maximilian , Roesky Peter W. , Blechert Siegfried
Published: January 2010

A series of electronically and sterically modified β‐diketiminate methylzinc complexes [{N,N′‐bis(2,6‐diisopropylphenyl)‐β‐diketiminato}methylzinc] (1), [{N,N′‐bis(2‐isopropylphenyl)‐β‐diketiminato}methylzinc] (2), [{N,N′‐bis(2,4,6‐trimethylphenyl)‐β‐diketiminato}methylzinc] (3), [{N,N′‐bis(4‐methoxyphenyl)‐β‐diketiminato}methylzinc] (4), a bis(β‐diketiminato)zinc compound [bis{N,N′‐bis(4‐methoxyphenyl)‐β‐diketiminato}zinc] (5), and a β‐diketiminate bis(trimethylsilylamido)zinc complex [{2‐(1‐cyclohexylimidazolidine‐2‐ylidene)‐1‐methylethylidene‐(2,6‐diisopropylphenyl)aminato}bis(trimethysilylamido)zinc] (6) were prepared and structurally characterized by single‐crystal X‐ray diffraction. All methylzinc compounds exhibit a trigonal‐planar coordinated zinc atom, with the exception of polymeric compound4, in which intermolecular coordination of the OMe group to the zinc atom additionally takes place. All zinc complexes were investigated as catalysts in the intramolecular hydroamination of nonactivated alkynes and show high catalytic activity in the presence of the cocatalyst [PhNMe2H][SO3CF3]. The zinc complex1shows the highest catalytic activityin most of the cyclization reactions. In this context, it waspossible to isolate the intermediate, which was formed bythe reaction of the precatalyst1and the cocatalyst [PhNMe2H][SO3CF3]. The resulting zinc catalyst [{N,N′‐bis(2,6‐diisopropylphenyl)‐β‐diketiminato}(trifluoromethanesulfonate)zinc]·thf (7) was structurally characterized by single‐crystal X‐ray diffraction. The zinc complex7show the same catalytic activity in the hydroamination when an equimolar mixture of the precatalyst1and the cocatalyst was used. It is supposed that the high steric bulk of the precatalyst1protects the Lewis acid zinc center from polar functional groups but allows interactions for the cyclization process.
Mechanistic Studies on the Copper‐Catalyzed Hydrosilylation of Ketones (Eur. J. Inorg. Chem. 4/2010)
Authors: Issenhuth Jean‐Thomas , Notter François‐Paul , Dagorne Samuel , Dedieu Alain , Bellemin‐Laponnaz Stéphane
Published: January 2010

The cover picture shows the Aiguille du Midi, Mont Blanc massif, France. The mechanism of the copper‐catalyzed hydrosilylation of ketones has been determined by experimental mechanistic investigations and computational studies. The insertion of the ketone into the Cu–H bond was found to have a lower activation barrier than the reaction of the copper alkoxy intermediate with the silane that regenerates the Cu–H bond along with the silyl ether product, as shown in the picture. Details are discussed in the article by A. Dedieu, S. Bellemin‐Laponnaz et al. on p. 529 ff.
Phytomining of plant enzymes for biotechnological use of fats and oils
Authors: Jach Guido , Soezer Nursen , Schullehner Katrin , Lalla Bernhard , Welters Peter , Mueller Andreas
Published: January 2010

Human history is closely linked to the use of plants as valuable sources for nutrition, commodities and energy as well as a multitude of raw materials, such as fats, oils and natural polymers like cellulose or starch. However, only recently, plants have become a cornerstone of sustainable industry by exploiting lead structures and biosynthetic pathways for the modification of renewable resources. The chemical industry already uses plant oils as renewable feedstock. Unsaturated fatty acids are well‐suited raw materials for the production of polymers, plasticizers and lubricants. Doubtlessly, the wealth of plant biosynthetic pathways makes them an attractive source of fascinating new enzymes for fat and oil modification and new biotechnological applications. The use of plant enzymes and compounds in industrial biotechnology offers new means to address energy savings and increases in efficiency and sustainability. Discovery and evaluation of suitable enzymes can be done via phytomining, an iterative approach unlocking the huge potential of plant biodiversity while aiming to increase the efficiency of current production processes, e.g. by complementing microbial production lines with a suitable gene, or implementing completely new and innovative fermentation processes. This article reflects potential biotechnological and industrial uses of (plant) oils and enzymes as well as the use of the phytomining platform to gain required enzymatic functions from plants.
Cross‐metathesis with acrylonitrile and applications to fatty acid derivatives
Authors: Bruneau Christian , Fischmeister Cédric , Miao Xiaowei , Malacea Raluca , Dixneuf Pierre H.
Published: January 2010

In this minireview, we report on the state of the art concerning the cross‐metathesis of acrylonitrile with olefins. A special focus is given to catalytic conditions that are suitable for medium‐size and long‐chain aliphatic model substrates. The recent applications of this metathesis reaction to fatty acid derivatives to generate fatty nitriles and bifunctional products are considered. They represent very attractive transformations for the access to N‐containing monomers and functional intermediates for the chemical industry from renewable raw materials.
Asymmetric bolaamphiphiles from vernonia oil designed for drug delivery
Authors: Grinberg Sarina , Kipnis Noa , Linder Charles , Kolot Victoria , Heldman Eliahu
Published: January 2010

Throughout the ages, fats, oils and their chemical derivatives have been used in a variety of medical applications, but currently they are becoming important as components in drug delivery systems. Liposomes (vesicles from phospholipids) are among the lipid‐based delivery systems that have been most extensively studied. However, targeting of liposomes to specific tissues is still problematic, and attempts to overcome these limitations include developments in nano‐sized monolayer vesicles made of bolaamphiphiles (compounds containing two hydrophilic headgroups at each end of an alkyl chain). This paper describes bolaamphiphile synthesis and characterization of the nano‐sized vesicles formed from the bolaamphiphiles with potential application for targeted drug delivery to the brain. The starting material for the synthesis is vernonia oil (or its fatty acids or methyl esters), which is a naturally epoxidized triacylglycerol obtained from the seeds ofVernonia galamensis. The targeting mechanism is based on the hydrolysis of the amphiphile's headgroup by an enzyme abundant in the target tissue, with subsequent release of the encapsulated drug at the target site. Preliminary experiments in mice demonstrated that the marker FITC‐dextran, which normally does not penetrate the blood brain barrier, is delivered into the brain when encapsulated in these vesicles.
Oxidation of a tensidic alcohol to its corresponding carboxylic acid via Au catalysts
Authors: Heidkamp Katharina , Decker Nadine , Martens Kerstin , Prüße Ulf , Vorlop Klaus‐Dieter , Franke Oliver , Stankowiak Achim
Published: January 2010

The oxidation of the fatty‐alcohol ethoxylate GENAPOL LA 050 to its corresponding ether carboxylic acid using supported Au catalysts under mild aerobic conditions in aqueous alkaline solution was investigated. Screening of different metal oxide supports and several preparation methods yielded an assortment of highly selective catalysts with varying activities. AEROXIDE® TiO2 P25 turned out to be the most suitable support and deposition‐precipitation with urea emerged as the best‐suited preparation method. Further experiments with this catalyst displayed the dependency of the catalytic activity on reaction parameters such as temperature, pressure and reactant/catalyst ratio. The long‐term stability study of this particular catalyst in repeated batches revealed catalyst deactivation by Au particle agglomeration due to intermediate Au leaching under the reaction conditions.
Protein engineering and discovery of lipases
Authors: Kourist Robert , Brundiek Henrike , Bornscheuer Uwe T.
Published: January 2010

Lipases are widely used in the modification of fats and oils with applications in the production of structured triacylglycerols, selective isolation or incorporation of specific fatty acids, and in oleochemistry for the synthesis of emollient esters and sugar fatty acid esters. Despite the numerous examples for the effective use of lipases, the biocatalysts often need to be optimized to show the desired specificities, stability, operational properties, etc. Beside rather classical methods such as variation of the solvent system or carrier for immobilization, the use of protein engineering methods to modify the protein on a molecular level is an important tool for the creation of tailor‐designed enzymes. Protein design is also complemented with the efficient isolation of novel lipases from the metagenome. This article covers concepts and examples for the discovery of novel lipases and their variants by protein engineering and metagenome techniques.
Nickel(II) adsorption mechanism from aqueous solution by a new adsorbent—Waste acorn of Quercus ithaburensis
Authors: Malkoc Emine , Nuhoglu Yasar
Published: January 2010

This article presents the data for the effect of adsorbent dose, initial metal concentration, solution pH, agitating rate, and temperature on the adsorption of nickel(II) on waste of acorn. Batch adsorption studies have been carried out. Adsorption equilibrium was approached within 30–60 min. The nature of the possible adsorbent and metal ion interactions were examined by the FTIR technique. The maximum nickel(II) adsorption is noted at pH 5.0. The experimental isotherm data were analyzed using the Langmuir, Freundlich, and Temkin equations. The equilibrium data fit well the Langmuir isotherm. The adsorption capacity (Qo) calculated from Langmuir isotherm was 9.42 mg g−1 at initial pH of 5.0 at 60°C. The adsorption of nickel(II) on waste of acorn increased from 7.68 to 9.1 mg g−1 when temperature was increased from 25 to 60°C at an initial concentration of 200 mg L−1. The adsorption of nickel(II) ions increased with increasing temperature indicating endothermic nature of the adsorption process. Various thermodynamic parameters, such as ΔG°, ΔH°, and ΔS° have been calculated. The thermodynamics of nickel(II) ion onto waste of acorn system indicates spontaneous and endothermic nature of the process. The pseudo first‐ and second‐order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data were fitted by the second‐order kinetic model, which indicates that chemical sorption is the rate limiting step, inside of mass transfer. © 2010 American Institute of Chemical Engineers Environ Prog, 2010
Coastal foredune topography as a control on secondary airflow regimes under offshore winds
Authors: Lynch Kevin , Jackson Derek W. T. , Cooper J. Andrew G.
Published: January 2010

Aeolian sediment transport under offshore winds is usually discounted from sediment budget considerations of coastal dunes. Results presented here indicate however, that depending on wind orientation and foredune morphology, positive contributions to the sediment budget can arise from offshore winds. Lee‐side airflow patterns, seaward of the foredune crest, under offshore winds were studied at three sites of varying foredune geometry along Magilligan Strand, Northern Ireland. Ultrasonic anemometers recorded 1 Hz wind velocity data at 1° intervals. Descriptive statistics and wind rose diagrams were used in the analysis of these data. Under perpendicularly offshore winds each site exhibited a different type of lee‐side airflow pattern. A tall (11·4 m), sharp‐crested foredune produced flow separation with a recirculation cell. A lower (6·6 m), more rounded, foredune crest exhibited lee‐side flow that remained attached but was deflected parallel to the crest, while flow over a low incipient foredune crest resulted in attached flow with no deflection in the lee. The morphology of the lee slopes best explained these airflow adjustments. More obliquely offshore winds were also found to affect the secondary airflow patterns, with a smooth transition from flow separation to flow attachment as the incident angle decreased. At higher wind velocities this smooth transition was replaced with a more abrupt switch between the secondary airflow types. This threshold was located at similar approach angles to those recorded for desert dunes (90° +/− 20°). These findings have significant implications for the post‐storm recovery and long‐term evolution of beach‐dune systems where the predominant winds are offshore, and offer an explanation for the presence of many beach‐dune systems in lee‐coast locations. Copyright © 2010 John Wiley & Sons, Ltd.
The distribution and residence time of suspended sediment stored within the channel margins of a gravel‐bed bedrock river
Authors: Skalak Katherine , Pizzuto James
Published: January 2010

Previously undocumented deposits are described that store suspended sediment in gravel‐bedded rivers, termed ‘fine‐grained channel margin’ (FGCM) deposits. FGCM deposits consist of sand, silt, clay, and organic matter that accumulate behind large woody debris (LWD) along the margins of the wetted perimeter of the single‐thread, gravel‐bed South River in Virginia. These deposits store a total mass equivalent to 17% to 43% of the annual suspended sediment load. Radiocarbon, 210Pb and 137C dating indicate that sediment in FGCM deposits ranges in age from 1 to more than 60 years. Reservoir theory suggests an average turnover time of 1·75 years and an annual exchange with the water column of a mass of sediment equivalent to 10% to 25% of the annual sediment load. The distribution of ages in the deposits can be fitted by a power function, suggesting that sediment stored in the deposits has a wide variety of transit times. Most sediment in storage is reworked quickly, but a small portion may remain in place for many decades. The presence of FGCM deposits indicates that suspended sediment is not simply transported downstream in gravel‐bed rivers in agricultural watersheds: significant storage can occur over decadal timescales. South River has a history of mercury contamination and identifying sediment sources and sinks is critical for documenting the extent of contamination and for developing remediation plans. FGCM deposits should be considered in future sediment budget and sediment transport modeling studies of gravel‐bed rivers in agricultural watersheds. Copyright © 2010 John Wiley & Sons, Ltd.
Backshore coarsening processes triggered by wave‐induced sand transport: the critical role of storm events
Authors: Udo Keiko , Mano Akira
Published: January 2010

Spatial backshore processes were investigated through field observations of topography and median sand grain size at a sandy beach facing the Pacific Ocean in Japan. A comparison of the backshore profile and cross‐shore distribution of the median sand grain size in 1999 and 2004 revealed an unusual sedimentary process in which sand was coarsened in a depositional area in the 5‐year period, although sediment is generally coarsened in erosional areas. In support of these observations, monthly spatial field analyses carried out in 2004 demonstrated a remarkable backshore coarsening process triggered by sedimentation in the seaward part of the backshore during a storm event. In order to elucidate mechanisms involved in the backshore coarsening process, thresholds of movable sand grain size under wave and wind actions (a uniform parameter for both these cases) in the onshore and offshore directions were estimated using wave, tide, and wind data. The cross‐shore distributions of the estimated thresholds provided reasonable values and demonstrated a coarsening mechanism involving the intermediate zone around the shoreline under alternating wave and wind actions as a result of which coarse sand was transported toward the seaward part of the backshore by large waves during storms and then toward the landward part by strong onshore winds. The 5‐year backshore coarsening is most certainly explained by repetition of short‐term coarsening mechanisms caused by wave‐induced sand transport occurring from the nearshore to the intermediate zone. Copyright © 2010 John Wiley & Sons, Ltd
Constraining Holocene sea levels using U‐Th ages of phreatic overgrowths on speleothems from coastal caves in Mallorca (Western Mediterranean)
Authors: Tuccimei Paola , Soligo Michele , Ginés Joaquin , Ginés Angel , Fornós Joan , Kramers Jan , Villa Igor Maria
Published: January 2010

Phreatic overgrowths on speleothems (POS) are carbonate formations deposited at the water table of caves in unique karstic coastal settings having morphologies that can be directly related to sea level at the time of formation. The U‐Th ages of calcite and aragonite overgrowths collected from the modern water table in coastal caves on Mallorca (Cova de Cala Varques A and Cova des Pas de Vallgornera) were determined using high‐precision MC‐ICPMS techniques. U‐Th ages indicate that phreatic carbonate deposition occurred between ca 2·8 and at least 0·6 ka BP and are in accord with an archeologically estimated age of 3·7–3·0 ka BP for a drowned prehistoric construction at a depth of 1 m below current sea level in a cave from the same area. Speleothem δ13C and δ18O and chemical composition of cave pools provide supportive evidence that POS reflect mixing between seawater and brackish water table. Copyright © 2010 John Wiley & Sons, Ltd.
Large‐scale sediment bodies and superimposed bedforms on the continental shelf close to the Strait of Gibraltar: interplay of complex oceanographic conditions and physiographic constraints
Authors: Lobo F. J. , Maldonado A. , Noormets R.
Published: January 2010

A previously unknown field of large‐scale sedimentary bodies has been mapped and studied on the continental shelf off the Cape Trafalgar near the Strait of Gibraltar with particular emphasis on the relationship between large‐scale sediment bodies and the superimposed bedforms. This study is based on a grid of 975 km of high‐resolution seismic profiles collected at water depths ranging between 15 and 60 m.

High variability of large‐scale sedimentary bodies is attributed to the complex interaction of hydrodynamic agents. The most prominent sedimentary features are sand banks and ridges that indicate long‐term southwest and southward‐directed sediment transport patterns, possibly due to the interplay of two dominant current systems flowing southward and westward. These sediment bodies evolve laterally to distinct external geometries, such as sand shoals in shallow water and sand sheets in the vicinity of larger sand banks that indicate moderate current velocities. In addition, pre‐existing physiography is considered to play a role in the generation of certain sediment bodies, developed over inclined surfaces or confined laterally by elevations.

Relationships between superimposed bedforms (mostly very large dunes) and underlying sediment bodies vary across the study area. Most superimposed bedforms occur over the complex mosaic of sediment banks and sheets, suggesting the interaction of several high‐energy currents with different directions, such as tidal and/or wind‐driven currents. Copyright © 2010 John Wiley & Sons, Ltd.