bluuebunny/crossref_metadata_2025 huggingface dataset:
Impact of ineffective oesophageal motility and wrap type on dysphagia after laparoscopic fundoplication
Authors: Broeders J A , Sportel I G , Jamieson G G , Nijjar R S , Granchi N , Myers J C , Thompson S K
Published: June 2011

Background

Laparoscopic 360° fundoplication is the most common operation for gastro-oesophageal reflux disease, but is associated with postoperative dysphagia in some patients. Patients with ineffective oesophageal motility may have a higher risk of developing postoperative dysphagia, but this remains unclear.

Methods

From 1991 to 2010, 2040 patients underwent primary laparoscopic fundoplication for gastro-oesophageal reflux disease and met the study inclusion criteria; 343 had a 90°, 498 a 180° and 1199 a 360° fundoplication. Primary peristalsis and distal contraction amplitude during oesophageal manometry were determined for 1354 patients. Postoperative dysphagia scores (range 0–45) were recorded at 3 and 12 months, then annually. Oesophageal dilatations and/or reoperations for dysphagia were recorded.

Results

Preoperative oesophageal motility did not influence postoperative dysphagia scores, the need for dilatation and/or reoperation up to 6 years. Three-month dysphagia scores were lower after 90° and 180° compared with 360° fundoplication (mean(s.e.m.) 8·0(0·6) and 9·8(0·5) respectively versus 11·9(0·4); P < 0·001 and P = 0·003), but these differences diminished after 6 years of follow-up. The incidence of dilatation and reoperation for dysphagia was lower after 90° (2·6 and 0·6 per cent respectively) and 180° (4·4 and 1·0 per cent) fundoplications than with a 360° wrap (9·8 and 6·8 per cent; both P < 0·001 versus 90° and 180° groups).

Conclusion

Tailoring the degree of fundoplication according to preoperative oesophageal motility by standard manometric parameters has no long-term impact on postoperative dysphagia. There is, however, a proportionate increase in short-term dysphagia scores with increasing degree of wrap, and a corresponding proportionate increase in dilatations and reoperations for dysphagia. These differences in dysphagia scores diminish with time.
Systematic review of intraperitoneal chemotherapy for gastric cancer
Authors: Matharu G , Tucker O , Alderson D
Published: June 2011

Background

Gastric cancer with peritoneal carcinomatosis has a poor prognosis. Intraperitoneal chemotherapy has been proposed as a treatment option. This systematic review examined recent literature to determine the role of intraperitoneal chemotherapy in gastric cancer.

Methods

Four electronic databases were searched between January 2004 and January 2010 for relevant studies. Defined outcomes of interest were treatment-related morbidity and mortality, long-term survival and sites of recurrence.

Results

Fourteen studies were identified involving 914 patients with gastric cancer, of whom 819 (89·6 per cent) received intraperitoneal chemotherapy. There were two randomized controlled trials, two case–control studies and ten observational studies. Methodological quality was rated as poor in 12 studies, with selection and observer bias apparent in most non-randomized cohorts. Studies were often small and varied in terms of intraperitoneal timing of chemotherapy, chemotherapeutic agents, treatment temperature, and the use of adjuvant therapies. In the better conducted studies, survival was longer in patients receiving intraperitoneal chemotherapy and surgery than in those having surgery alone.

Conclusion

There is limited good-quality evidence to determine the role of intraperitoneal chemotherapy in gastric cancer. Intraperitoneal chemotherapy in gastric cancer is worthy of further appraisal. However, the quality of trials must be improved, and studies must be conducted more uniformly to minimize bias and aid comparison between centres.
Nerve terminal distribution in the human tongue intrinsic muscles: An immunohistochemical study using midterm fetuses
Authors: Abe Shin‐Ichi , Kikuchi Ryusuke , Nakao Tadashi , Cho Baik Hwan , Murakami Gen , Ide Yoshinobu
Published: June 2011

Intrinsic tongue muscles, especially the transverse and vertical (T&V) muscles, regulate the shape of the tongue. However, little information is available on the nerve distribution pattern in human T&V muscles. Using S100 protein immunohistochemistry for paraffin‐embedded histology, we investigated semiserial sagittal or frontal sections of eight human fetal tongues (180–240 mm crown‐rump length: CRL). The height of the T&V muscle bundle showed a threefold difference between specimens with a small and a large CRL. Thus, the T&V muscles were still growing at the stages examined. In the intrinsic longitudinal muscles and all extrinsic tongue muscles, we observed the typical motor endplate band. In lower‐magnification views, the T&V muscles also appeared to carry the band in the lateral part of the tongue, where the genioglossus muscle fibers did not cross these muscles. However, in higher magnification views, the nerve terminal distribution in the T&V muscles showed a unique rule: the nerve terminal for the transverse muscle bundle was located distantly from that of the adjacent vertical muscle bundle. This pattern seemed to be established during the stages examined. To provide such “distantly separated nerve terminals,” thin nerve twigs took a highly curved course oblique to the T&V muscle bundles. We hypothesize that the unique nerve course and terminal distribution in the T&V muscles are a result of sorting to provide a good functional match between the nerve fiber and the muscle bundle. After sorting, the T&V muscle cells may initiate proliferation to increase the muscle bundle. Clin. Anat. 25:189–197, 2012. © 2011 Wiley‐Liss, Inc.
Lumbar shape characterization of the neural arch and vertebral body in spondylolysis: A comparative skeletal study
Authors: Masharawi Y.
Published: June 2011

The lumbar vertebral shape is an important causative factor in spondylolysis (SP). However, a complete characterization of this shape, that would shed light on its pathophysiology enhance its earlier diagnosis, is still missing. The aim of this study was to evaluate the shape distinctiveness of the lumbar (L1–L5) vertebral body (VB) and neural arch (isthmus, lamina, vertebral canal, spinous, and transverse processes) in SP. Using a three‐dimensional (3D) digitizer, the VB length, width, height, and sagittal wedging as well as the lengths of the isthmus, lamina spinous, and transverse processes of all lumbar vertebrae (L1–L5) were measured from 115 male skeletons with bilateral SP at L5 and compared with 120 normal ones. Compared with the normal group, the following results were indicated in SP [analysis of variance (ANOVA), P < 0.05]: the VB's are significantly longer at the superior surfaces of L1–L4 and inferior surfaces of L1–L3 (total mean difference = 7.61 mm and 3.94 mm, respectively), and wider at the superior surfaces of L1–L4 and inferior surfaces of L1–L5 (total mean difference = 10.06 mm and 12.90 mm, respectively); The L5 VB is significantly shorter posteriorly (mean difference = 3.05 mm) and more lordotic (+1° of dorsal wedging); L5 is manifested with longer lamina (mean difference = 1.85–2.18 mm), longer isthmus (mean difference = 3.24–4.69 mm), and longer and wider vertebral canal (mean differences = 3.64 mm and 1.13 mm, respectively); The L2–L5 spinous processes are significantly longer (total mean difference = 7.45 mm). Clinically, detecting the aforementioned unique lumbar vertebral morphometric features in individuals suffering from chronic low back pain may facilitate the early diagnosis of SP. Clin. Anat. 25:224–230, 2012. © 2011 Wiley‐Liss, Inc.
Topographical anatomy of central venous system in extremely low‐birth weight neonates less than 1000 grams and the effect of central venous catheter placement
Authors: Eifinger F. , Brisken K. , Roth B. , Koebke J.
Published: June 2011

Central venous catheterization is widely used in neonatology. Although ultrasonic guidance for central venous catheter placement is available, complications occur significantly more frequently in infants, especially neonates, than in adults. This study seeks to determine the characteristics, topographical conditions, regional relationships, and diameters of the venous structures of the upper extremity and the thoracic central venous system in extremely small preterm neonates (mean: 900 g). Nine formaldehyde‐fixed preterm stillborns were prepared (mean 27 2/7 weeks' gestational age). The anatomical preparation involved the complete thoracic wall, neck and shoulder region, and preparation of the upper extremities. It was shown that the course of the internal jugular vein can be influenced by rotation of the head. Maximum head rotation (80°) to the contralateral side leads the internal jugular vein to overlap the common carotid artery and sharpens the confluence angle of the internal jugular into the brachiocephalic vein. We propose that this has the potential to result in dislocation of the catheter. Less rotation of the head (<30°) is favorable as the internal jugular vein and common carotid artery run in parallel. Commonly used central venous catheters (2F‐4F) may not occlude the vascular lumen completely. Small central venous cannulation using a single‐orifice catheter through arm veins (1F) may also not occlude peripheral vessels of the upper extremity (cephalic and basilic veins). The right internal jugular vein has a straight course, appears suitable for central venous access and less hazardous, especially when using stiff catheters. The use of small straight wire guides is recommended. Clin. Anat. 24:711–716, 2011. © 2011 Wiley‐Liss, Inc.
Topography of the arteries supplying the masseter muscle: Using dissection and Sihler's method
Authors: Won Sung‐Yoon , Choi Da‐Yae , Kwak Hyun‐Ho , Kim Seong‐Taek , Kim Hee‐Jin , Hu Kyung‐Seok
Published: June 2011

Various surgical procedures require surgeons to have detailed knowledge of the course of blood vessels in the masseter muscle, such as masseter muscle flap formation, mandibular angle resection, parotidectomy, and mandibular ramus osteotomy. Without this knowledge serious complications can occur, endangering the lives of patients. Occasionally, during routine dissections we sometimes encounter an additional branch. The purpose of this study was to provide a comprehensive detailed anatomic description of the blood supply of the masseter muscle. This will provide critical information for various surgical procedures. Twenty‐five Korean cadavers were dissected and subjected to modified Sihler's method to reveal the branching patterns of the arteries surrounding the masseter muscle, and its intramuscular blood supply. The masseter can be supplied by seven branches from the external carotid artery. Among these, the masseteric branch from the deep temporal artery has not been described previously. This previously undescribed branch enters the medial surface of the masseter, turning medially around the anterior border of the ramus immediately after the branching point of the deep temporal artery. The branch originating from the transverse facial artery was the largest, and the branches originating from the external carotid artery and deep temporal artery were the smallest. Examination of intramuscular patterns revealed that the branches of the transverse facial artery were the most widely distributed. When considering arterial diameters and distribution areas, the branches of the transverse facial artery can be considered the main components of the seven branches supplying the masseter muscle. Clin. Anat. 25:308–313, 2012. © 2011 Wiley Periodicals, Inc.
Very late thrombosis in a bare metal stent
Authors: Qian Jie , Yang Yue‐Jin
Published: June 2011

Recent publications have emphasized the concept that restenosis of a bare metal stent (BMS) is not as clinically benign as previously believed. We present a case of very late stent thrombosis 9 years after implantation of a BMS is described. Optical coherence tomography shows plaque rupture in the stent. These findings suggest that the formation and progression of a neoatheroma over a previously healed intrastent vascular intima may represent a “new” mechanism for stent thrombosis. Evidence from the current case supports this hypothesis. © 2011 Wiley Periodicals, Inc.
Retrograde access via the popliteal artery to facilitate the re‐entry technique for recalcitrant superficial femoral artery Chronic total occlusions
Authors: Pappy Reji , Hennebry Thomas A. , Abu‐Fadel Mazen S.
Published: June 2011

Subintimal recanalization is beneficial in selected patients with peripheral chronic total occlusions (CTO). However, in complex cases, re‐entry into the true arterial lumen may prove to be unsuccessful with a conventional guidewire or a re‐entry catheter when using standard femoral artery access. Our case series describes these technical dilemmas along with strategies that can be utilized to overcome these challenges. © 2011 Wiley‐Liss, Inc.
Objective performance goals of safety and blood pressure efficacy for clinical trials of renal artery bare metal stents in hypertensive patients with atherosclerotic renal artery stenosis
Authors: Rocha‐Singh Krishna J. , Novack Victor , Pencina Michael , D'Agostino Ralph , Ansel Gary , Rosenfield Kenneth , Jaff Michael R.
Published: June 2011

Objective: To provide safety and performance goals for prospective single‐arm trials of bare metal renal artery stenting in patients with resistant hypertension associated with high grade atherosclerotic renal artery stenosis. Background: To date, there have been no US Pre‐Market Approval (PMA) bare metal renal stent device trials which have focused on improvement of blood pressure control as a primary effectiveness endpoint. Methods: Analysis of subject‐level data from three large industry sponsored pre‐market approval (PMA) trials was performed. Hypertensive patients (≥155 mmHg) with a ≥50% atherosclerotic renal artery stenosis were included. Thirty day and 9‐month systolic and diastolic blood pressure measurements, renal function and 9‐month duplex ultrasound assessment of renal artery patency were analyzed. Results: Initial data analysis of 600 patients from the 3 PMA trials identified 286 patients who met inclusion criteria. The mean baseline systolic blood pressure was 177.8 ± 19.3 mmHg with a mean 68.1% diameter renal artery stenosis. Nine months after successful stenting, the mean SBP was 156.7 ± 24.1 mmHg; the 9 month restenosis rate was 14.4%. Conclusion: Based on the statistical modeling of these data and a priori established performance criteria, the co‐primary endpoints of 9 month reduction in blood pressure and in‐stent restenosis are proposed. The reduction in blood pressure will be analyzed as a continuous variable and will be compared to this performance goal. © 2011 Wiley‐Liss, Inc.
The results of transcatheter closure of VSD using amplatzer® device and nit occlud® Lê coil
Authors: Chungsomprasong Paweena , Durongpisitkul Kritvikrom , Vijarnsorn Chodchanok , Soongswang Jarupim , Lê Trong Phi
Published: June 2011

Objective: We retrospectively reviewed the result of patients who underwent transcatheter closure of ventricular septal defect (VSD) using Amplatzer® Perimembranous or Amplatzer® muscular VSD device (the Amplatzer® group) and Nit Occlud® Lê VSD Coil (the Pfm group). Background: Perimembranous type (PmVSD) and doubly committed subarterial (DCSA) VSD were the major isolated congenital heart defects in Thai children. Transcatheter device closure technique for both types of VSD has emerged as an alternative treatment to surgery. Methods: Retrospectively, data was reviewed between 2003 and 2009. Results: 116 patients were enrolled. Device or coil was successfully implanted in 94%. Complete closure at 24 hr is slightly higher in the Amplatzer® group. The average size of VSD in the Amplatzer® group was larger than the Pfm group (P = 0.001). The Pfm coil was primarily deployed in DCSA VSD when compared with the Amplatzer® group (P < 0.01). At 6 months follow‐up the residual shunt was comparable (P = 0.054). There was only one transient AV block (AVB) in the Pfm group and 5 AVB in the Amplatzer® group. Four pacemakers were placed in the Amplatzer® group. Conclusions: Transcatheter closure of VSD in both Pm VSD and DCSA can be achieved by using either of the device. The Amplatzer® VSD device had the advantage of closure of larger defects with immediate less residual shunt but appeared to have a significant number of 3° AVB, which required pacemaker implantation. The Nit Occlud® Lê VSD Coil had the advantage of closure of both types of defects, in particular DCSA VSD with only small residual shunt. © 2011 Wiley Periodicals, Inc.
Mechanistic Studies of Pd‐Catalyzed Regioselective Aryl CH Bond Functionalization with Strained Alkenes: Origin of Regioselectivity
Authors: Chai David I. , Thansandote Praew , Lautens Mark
Published: June 2011

Mechanistic studies of a palladium‐catalyzed regioselective aryl CH functionalization of 2‐pyrrole phenyl iodide with norbornene are presented. Kinetic and spectroscopic analyses together with crystallographic data provide evidence for intermediates in a proposed stepwise mechanism. On the basis of the mechanistic studies, the origin of the regioselectivity is due to a ligand exchange between I− and HO− on the norbornyl palladium complex. These mechanistic studies also implicate that either alkoxide or water is responsible for the formation of the palladacycle, but a reversible ring‐opening–ring‐closing process of the palladacycle with HX can retard the rate of reaction of a key intermediate. The significant aspects of the proposed mechanism are discussed in detail.
Ligand Effects in the Formation of Tertiary Carbanions from Substituted Tertiary Aromatic Amides
Authors: Campbell Smith Alison , Donnard Morgan , Haywood Joanna , McPartlin Mary , Vincent Mark A. , Hillier Ian H. , Clayden Jonathan , Wheatley Andrew E. H.
Published: June 2011

Reaction of 2‐isopropyl‐(N,N‐diisopropyl)‐benzamide 5 with tBuLi in ether results in ortho deprotonation and the formation of a hemisolvate based on a tetranuclear dimer of (5‐Lio)2⋅Et2O. The solid‐state structure exhibits a dimer core in which the amide oxygen atoms fail to stabilize the metal ions but are instead available for interaction with two metalated monomers that reside peripheral to the core. Reaction of 5 with tBuLi in the presence of the tridentate Lewis base PMDTA (N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine) takes a different course. In spite of the tertiary aliphatic group at the 2‐position in 5, X‐ray crystallography revealed that a remarkable benzylic (lateral) deprotonation had occurred, giving the tertiary benzyllithium 5‐Lil⋅PMDTA. The solid‐state structure reveals that amide coordination and solvation by PMDTA combine to distance the Li+ ion from the deprotonated α‐C of the 2‐iPr group (3.859(4) Å), thus giving an essentially flat tertiary carbanion and a highly distorted aromatic system. DFT analysis suggests that the metal ion resides closer to the carbanion center in solution. In line with this, the same (benzylic) deprotonation is noted if the reaction is attempted in the presence of tridentate diglyme, with X‐ray crystallography revealing that the metal is now closer to the tertiary carbanion (2.497(4) Å). Electrophilic quenches of lithiated 5 have allowed, for the first time, the formation of quaternary benzylic substituents by lateral lithiation.
Asymmetric Cycloaddition of β,γ‐Unsaturated α‐Ketoesters with Electron‐Rich Alkenes Catalyzed by a Chiral Er(OTf)3/N,N′‐Dioxide Complex: Highly Enantioselective Synthesis of 3,4‐Dihydro‐2 H‐pyrans
Authors: Zhu Yin , Xie Mingsheng , Dong Shunxi , Zhao Xiaohu , Lin Lili , Liu Xiaohua , Feng Xiaoming
Published: June 2011

The asymmetric inverse‐electron‐demand hetero‐Diels–Alder (HDA) reactions of β,γ‐unsaturated α‐ketoesters with electron‐rich alkenes were investigated, with an N,N′‐dioxide/erbium(III) complex employed as the catalyst. Quantitative conversion of the β,γ‐unsaturated α‐ketoesters and excellent enantioselectivities (up to >99 % ee) and diastereoselectivities (up to >99:1 d.r.) were observed for a broad range of substrates by using a 0.5–0.05 mol % catalyst loading under mild reaction conditions. The reaction could be scaled up to the gram scale with the same results. In addition, this was the first application of Er(OTf)3 to the asymmetric inverse‐electron‐demand HDA reaction and it behaved as an efficient catalyst. Moreover, the synthetic utility of this methodology was demonstrated with the synthesis of key intermediates of some natural products.
Benzylidene Acetal Type Bridged Nucleic Acids: Changes in Properties Upon Cleavage of the Bridge Triggered by External Stimuli
Authors: Morihiro Kunihiko , Kodama Tetsuya , Obika Satoshi
Published: June 2011

Four classes of benzylidene acetal type bridged nucleic acids (BA‐BNAs) were designed with 2′,4′‐bridged structures that cleaved upon exposure to appropriate external stimuli. Cleavage of 6‐nitroveratrylidene and 2‐nitrobenzylidene acetal type BNA bridges occurred upon photoirradiation and subsequent treatment with thiol caused changes in secondary structure to afford 4′‐C‐hydroxymethyl RNA. Benzylidene and 4‐nitrobenzylidene acetal type BNA responded to acids and reducing agents, respectively, resulting in hydrolysis of the acetal‐bridged structure. Cleavage of the bridge removed sugar conformational restrictions and changed the duplex‐ and triplex‐forming properties of the BNA‐modified oligonucleotides. Moreover, oligonucleotides incorporating a single BA‐BNA modification had considerably improved stability toward 3′‐exonuclease, which was lost upon cleavage of the bridge. Thus, these new BNAs may be useful as therapeutic and detection tools by sensing various environments.
Highly Trifluoromethylated Platinum Compounds
Authors: Martínez‐Salvador Sonia , Forniés Juan , Martín Antonio , Menjón Babil
Published: June 2011

The homoleptic, square‐planar organoplatinum(II) compound [NBu4]2[Pt(CF3)4] (1) undergoes oxidative addition of CF3I under mild conditions to give rise to the octahedral organoplatinum(IV) complex [NBu4]2[Pt(CF3)5I] (2). This highly trifluoromethylated species reacts with Ag+ salts of weakly coordinating anions in Me2CO under a wet‐air stream to afford the aquo derivative [NBu4][Pt(CF3)5(OH2)] (4) in around 75 % yield. When the reaction of 2 with the same Ag+ salts is carried out in MeCN, the solvento compound [NBu4][Pt(CF3)5(NCMe)] (5) is obtained in around 80 % yield. The aquo ligand in 4 as well as the MeCN ligand in 5 are labile and can be cleanly replaced by neutral and anionic ligands to furnish a series of pentakis(trifluoromethyl)platinate(IV) compounds with formulae [NBu4][Pt(CF3)5(L)] (L=CO (6), pyridine (py; 7), tetrahydrothiophene (tht; 8)) and [NBu4]2[Pt(CF3)5X] (X=Cl (9), Br (10)). The unusual carbonyl–platinum(IV) derivative [NBu4][Pt(CF3)5(CO)] (6) is thermally stable and has a νCO of 2194 cm−1. The crystal structures of 2⋅CH2Cl2, 5, [PPh4][Pt(CF3)5(CO)] (6′), and 7 have been established by X‐ray diffraction methods. Compound 2 has shown itself to be a convenient entry to the chemistry of highly trifluoromethylated platinum compounds. To the best of our knowledge, compounds 2 and 4–10 are the organoelement compounds with the highest CF3 content to have been isolated and adequately characterized to date.
Columnar Benzoperylene‐Hexa‐ and Tetracarboxylic Imides and Esters: Synthesis, Mesophase Stabilisation and Observation of Charge‐Transfer Interactions between Electron‐Donating Esters and Electron‐Accepting Imides
Authors: Kelber Julien , Achard Marie‐France , Garreau‐de Bonneval Bénédicte , Bock Harald
Published: June 2011

Benzo[ghi]perylene 1,2,4,5,10,11‐hexacarboxylic trialkylimide and dialkylimido‐dialkyl ester derivatives, displaying a thermodynamically stable hexagonal columnar liquid‐crystalline phase at room temperature, have been obtained by the use of previously unexplored chiral racemic α‐branched alkylimide functions. One of the trialkylimides described here is the first room temperature columnar solely oligo‐alkylimide‐substituted arene, and thus constitutes a prototype case of self‐assembling organic acceptor materials. As the related hexacarboxylic hexaesters are found to exhibit only a weak tendency to form columnar mesophases, benzo[ghi]perylene 1,2,5,10‐tetracarboxylic tetraalkyl esters have been synthesized by regioselective oxidative Diels–Alder addition of maleic anhydride to 3,10‐dicyanoperylene, and a room temperature hexagonal columnar mesophase was obtained with branched alkyl chains. The acceptor‐type electronic properties of the tri‐ and diimides have been found to be considerably more pronounced than those of the hexa‐ and tetracarboxylic esters, and to approach those of the prototype acceptor material C60. The formation of bathochromically absorbing donor–acceptor complexes was observed with a di‐ or triimide as acceptor and a tetraester as donor, but not with a hexaester as donor. Exploiting the non‐negligible differences in reduction and oxidation potentials between all four types of materials, the minimum HOMO energy difference necessary for charge‐transfer‐complex formation has been determined to lie between 0.29 and 0.35 eV.
Efficient Epoxidation of Electron‐Deficient Alkenes with Hydrogen Peroxide Catalyzed by [γ‐PW10O38V2(μ‐OH)2]3−
Authors: Kamata Keigo , Sugahara Kosei , Yonehara Kazuhiro , Ishimoto Ryo , Mizuno Noritaka
Published: June 2011

A divanadium‐substituted phosphotungstate, [γ‐PW10O38V2(μ‐OH)2]3− (I), showed the highest catalytic activity for the H2O2‐based epoxidation of allyl acetate among vanadium and tungsten complexes with a turnover number of 210. In the presence of I, various kinds of electron‐deficient alkenes with acetate, ether, carbonyl, and chloro groups at the allylic positions could chemoselectively be oxidized to the corresponding epoxides in high yields with only an equimolar amount of H2O2 with respect to the substrates. Even acrylonitrile and methacrylonitrile could be epoxidized without formation of the corresponding amides. In addition, I could rapidly (≤10 min) catalyze epoxidation of various kinds of terminal, internal, and cyclic alkenes with H2O2 under the stoichiometric conditions. The mechanistic, spectroscopic, and kinetic studies showed that the I‐catalyzed epoxidation consists of the following three steps: 1) The reaction of I with H2O2 leads to reversible formation of a hydroperoxo species [γ‐PW10O38V2(μ‐OH)(μ‐OOH)]3− (II), 2) the successive dehydration of II forms an active oxygen species with a peroxo group [γ‐PW10O38V2(μ‐η2:η2‐O2)]3− (III), and 3) III reacts with alkene to form the corresponding epoxide. The kinetic studies showed that the present epoxidation proceeds via III. Catalytic activities of divanadium‐substituted polyoxotungstates for epoxidation with H2O2 were dependent on the different kinds of the heteroatoms (i.e., Si or P) in the catalyst and I was more active than [γ‐SiW10O38V2(μ‐OH)2]4−. On the basis of the kinetic, spectroscopic, and computational results, including those of [γ‐SiW10O38V2(μ‐OH)2]4−, the acidity of the hydroperoxo species in II would play an important role in the dehydration reactivity (i.e., k3). The largest k3 value of I leads to a significant increase in the catalytic activity of I under the more concentrated conditions.
Chemistry and applications of nanocrystalline cellulose and its derivatives: A nanotechnology perspective
Authors: Peng B. L. , Dhar N. , Liu H. L. , Tam K. C.
Published: June 2011

Nanocrystalline cellulose (NCC) is an emerging renewable nanomaterial that holds promise in many different applications, such as in personal care, chemicals, foods, pharmaceuticals, etc. By appropriate modification of NCC, various functional nanomaterials with outstanding properties, or significantly improved physical, chemical, biological, as well as electronic properties can be developed. The nanoparticles are stabilised in aqueous suspension by negative charges on the surface, which are produced during the acid hydrolysis process. NCC suspensions can form a chiral nematic ordered phase beyond a critical concentration, i.e. NCC suspensions transform from an isotropic to an anisotropic chiral nematic liquid crystalline phase. Due to its nanoscale dimension and intrinsic physicochemical properties, NCC is a promising renewable biomaterial that can be used as a reinforcing component in high performance nanocomposites. Many new nanocomposite materials with attractive properties were obtained by the physical incorporation of NCC into a natural or synthetic polymeric matrix. Simple chemical modification on NCC surface can improve its dispersability in different solvents and expand its utilisation in nano‐related applications, such as drug delivery, protein immobilisation, and inorganic reaction template. This review paper provides an overview on this emerging nanomaterial, focusing on the surface modification, properties and applications of NCC.
Evolutionary design of optimum distillation column sequence
Authors: Boozarjomehry Ramin Bozorgmehry , Laleh Ali Pourahmadi , Svrcek William Y.
Published: June 2011

Synthesis of the optimum distillation column sequence (DCS), which incorporates a huge search space composed of both conventional and complex arrangements, is a highly complicated combinatorial problem in the field of chemical process design and optimisation. In this study, a novel procedure for the synthesis of optimum DCS proposed by Boozarjomehry et al. [Boozarjomehry et al., Can. J. Chem. Eng. 87, 477–492 (2009)] is expanded to include the complex distillation arrangements. The method is based on evolutionary algorithms, and the total annual cost (TAC) is the main criterion used to screen alternatives. Efficient procedure has been proposed for encoding mechanism to include and classify various complex arrangements together with conventional distillation columns. All columns existing in each DCS alternative are designed using the most recommended short‐cut methods to estimate the TAC of the DCS. Four standard benchmark case studies are carried out to clearly demonstrate the excellent performance of the proposed method. The produced results for these problems indicate that the proposed method outperforms the other existing approaches in terms of flexibility, accuracy and comprehensiveness. © 2011 Canadian Society for Chemical Engineering
The CAPRA‐S score
Authors: Cooperberg Matthew R. , Hilton Joan F. , Carroll Peter R.
Published: June 2011

BACKGROUND:

The authors previously developed and validated the Cancer of the Prostate Risk Assessment (CAPRA) score to predict prostate cancer recurrence based on pretreatment clinical data. They aimed to develop a similar postsurgical score with improved accuracy via incorporation of pathologic data.

METHODS:

A total of 3837 prostatectomy patients in the Cancer of the Prostate Strategic Urologic Research Endeavor (CaPSURE™) national disease registry were analyzed. Cox regression was used to determine the predictive power of preoperative prostate‐specific antigen (PSA), pathologic Gleason score (pGS), surgical margins (SM), extracapsular extension (ECE), seminal vesicle invasion (SVI), and lymph node invasion (LNI). Points were assigned based on the relative weights of these variables in predicting recurrence. The new postsurgical score (CAPRA‐S) was tested and compared with a commonly cited nomogram with proportional hazards analysis, concordance (c) index, calibration plots, and decision‐curve analysis.

RESULTS:

Recurrence appeared in 16.8% of the men; actuarial progression‐free probability at 5 years was 78.0%. The CAPRA‐S was determined by adding up to 3 points for PSA, up to 3 points for pGS, 1 point each for ECE and LNI, and 2 points each for SM and SVI. The hazard ratio for each point increase in CAPRA‐S score was 1.54 (95% confidence interval, 1.49‐1.59), indicating a 2.4‐fold increase in risk for each 2‐point increase in score. The CAPRA‐S c‐index was 0.77, substantially higher than 0.66 for the pretreatment CAPRA score and comparable to 0.76 for the nomogram. The CAPRA‐S score performed better in both calibration and decision curve analyses.

CONCLUSIONS:

The CAPRA‐S offers good discriminatory accuracy, calibration, and ease of calculation for clinical and research settings. Cancer 2011;. © 2011 American Cancer Society.
Spectroscopy of Dibenzorubicene: Experimental Data for a Search in Interstellar Spectra
Authors: Rouillé Gaël , Steglich Mathias , Jäger Cornelia , Huisken Friedrich , Henning Thomas , Theumer Gabriele , Bauer Ingmar , Knölker Hans‐Joachim
Published: June 2011

We report on the characterization of dibenzo[cde,opq]rubicene (C30H14). The molecule was studied in solution at room temperature with absorption spectroscopy in the visible (vis) and ultraviolet (UV) wavelength ranges, and with emission spectroscopy. The infrared (IR), visible, ultraviolet, and vacuum ultraviolet (VUV) absorption spectra of a thin film were measured also at room temperature. In addition, the UV/vis absorption spectrum was measured at cryogenic temperatures using the matrix isolation spectroscopy technique. The interpretation of spectra was supported by theoretical calculations based on semiempirical and ab initio models, as well as on density functional theory. Finally, the results of the laboratory study were compared with interstellar spectra.
Experimental and Theoretical Investigation of Vibrational Spectra of Coordination Polymers Based on TCE‐TTF
Authors: Olejniczak Iwona , Łapiński Andrzej , Świetlik Roman , Olivier Jean , Golhen Stéphane , Ouahab Lahcène
Published: June 2011

The room‐temperature infrared and Raman spectra of a series of four isostructural polymeric salts of 2,3,6,7‐tetrakis(2‐cyanoethylthio)‐tetrathiafulvalene (TCE‐TTF) with paramagnetic (CoII, MnII) and diamagnetic (ZnII, CdII) ions, together with BF4− or ClO4− anions are reported. Infrared and Raman‐active modes are identified and assigned based on theoretical calculations for neutral and ionized TCE‐TTF using density functional theory (DFT) methods. It is confirmed that the TCE‐TTF molecules in all the materials investigated are fully ionized and interact in the crystal structure through cyanoethylthio groups. The vibrational modes related to the CC stretching vibrations of TCE‐TTF are analyzed assuming the occurrence of electron–molecular vibration coupling (EMV). The presence of the antisymmetric CC dimeric mode provides evidence that charge transfer takes place between TCE‐TTF molecules belonging to neighboring polymeric networks.
Cobalt Monolayer Islands on Ag(111) for ORR Catalysis
Authors: Loglio Francesca , Lastraioli Elisa , Bianchini Claudio , Fontanesi Claudio , Innocenti Massimo , Lavacchi Alessandro , Vizza Francesco , Foresti Maria Luisa
Published: June 2011

The design of a catalyst for one of the most important electrocatalytic reactions, the oxygen reduction reaction (ORR), was done following the most recent guidelines of theoretical studies on this topic. Aim of this work was to achieve a synergic effect of two different metals acting on different steps of the ORR. The catalytic activity of Ag, already known and characterized, was enhanced by the presence of a monolayer of cobalt subdivided into nanosized islands. To obtain such a controlled nanostructure, a novel method utilizing self‐assembled monolayers (SAMs) as templates was employed. In a recent study, we were able to perform a confined electrodeposition of cobalt onto Ag(111) in a template formed by selectively desorbing a short‐chain thiol (3‐mercaptopropionic acid, MPA) from binary SAMs using 1‐dodecanthiols (DDT). [32] This method allows for an excellent control of the morphology of the deposit by varying the molar ratio of the two thiols. Because cobalt does not deposit on silver at an underpotential, the alternative approach of surface limited redox replacement (SLRR) was used. This method, recently developed by Adžić et al.,13 consists of the use of a monolayer of a third metal, which can be deposited at an underpotential, as a template for the spontaneous deposition of a more noble metal. Herein, we choose zinc as template for the deposition of cobalt. Ag(111) crystals were covered by monolayer islands consisting of cobalt, with the surface atomic ratios ranging from 12 to 39 % for cobalt. The catalytic activity of such samples towards ORR was evaluated and the best improvement in activity was found to be that of the sample with a cobalt percentage of approximately 30 % with respect to the bare silver, which is in good agreement with theoretical hypotheses.
Macrophage and microglia ontogeny in the mouse visual system can be traced by the expression of Cathepsins B and D
Authors: Bejarano‐Escobar Ruth , Holguín‐Arévalo María Salud , Montero Juan Antonio , Francisco‐Morcillo Javier , Martín‐Partido Gervasio
Published: June 2011

Here, we show a detailed chronotopographical analysis of cathepsin B and D expression during development of the mouse visual system. Both proteases were detected in large rounded/ameboid cells usually located in close relationship with prominent sites of extensive physiological cell death. In concordance with their morphological features and topographical distribution, we demonstrate that expressing cells corresponded with macrophages and microglial precursors. We found that as microglial precursors differentiated the expression of both cathepsins was down‐regulated. Of interest, cathepsin B and D transcripts were never observed in degenerating cells. Our findings point to a role for cathepsin D and B in cell debris degradation after apoptotic processes rather than promoting cell death, as proposed for other developmental models. Additionally their pattern of expression suggests a role in the maturation of the microglial precursors. Developmental Dynamics 240:1841–1855, 2011. © 2011 Wiley‐Liss, Inc.
Revisiting the Zintl–Klemm Concept: A2AuBi (A = Li or Na)
Authors: Wang Fei , Miller Gordon J.
Published: June 2011

Alkali metal gold bismuthides, A2AuBi, are isoelectronic with alkali metal thallides, ATl = A2TlTl, and yet Na2AuBi adopts an orthorhombic structure with a 1‐D zigzag “ribbon” structural motif rather than the cubic double diamond structure type of NaTl as well as Li2AuBi. Using first principles quantum mechanical calculations applied to A2AuBi, hypothetical “A2HgPb,” and A2TlTl, and comprehensively decomposing the total energies into metallicity, ionicity, and covalency components to establish parallels with the qualitative Zintl–Klemm formalism, the factors determining the relative stability between the zigzag “ribbon” and the diamond network are examined. An interplay between volume‐dependent energy terms, i.e., metallicity or ionicity, and covalency among the electronegative components determines which structural motif is favored. In Na2AuBi, there are two factors stabilizing the zigzag “ribbon.” Au 5d states significantly interact with Bi 6p states, especially Au 5d with Bi 6pz to promote stronger Au–Bi covalent interactions than in the diamond network. This factor does not exist in Na2TlTl and “A2HgPb,” where Hg, Tl, and Pb 5d states are well localized. Secondly, the zigzag ribbons provide effective covalent interactions at larger volumes, as in Na2AuBi, while effective covalent interactions occur in the diamond network only at smaller volume, as in Li2AuBi.
Crystal Structure and Properties of Yb5Ni4Ge10
Authors: Peter Sebastian C. , Rayaprol Sudhindra , Francisco Melanie C. , Kanatzidis Mercouri G.
Published: June 2011

The new compound Yb5Ni4Ge10 was obtained as single crystals in high yield from reactions run in liquid indium. Single‐crystal X‐ray diffraction data showed that it crystallizes in the Sc5Co4Si10 structure type in the tetragonal space group P4/mbm. The structure is a three‐dimensional framework of [Ni4Ge10] atoms with voids filled by Yb atoms. The Ni and Ge atoms form pentagons, hexagons, and octagons along the ab one‐dimensional plane, which are interconnected along the c axis via Ni–Ge–Ni zigzag chains. Magnetic measurements reveal that Yb5Ni4Ge10 crystals show paramagnetic behavior with a lack of long‐range magnetic ordering down to 2 K. The magnetic susceptibility deviates from the Curie–Weiss law below 100 K, presumably because of crystal field effects from Yb3+ ions. In specific heat measurements, the compound exhibits non‐Fermi‐liquid‐like behavior at low temperatures.
Linear Synthesis of Chiral cycloSal‐Pronucleotides
Authors: Morales Edwuin Hander Rios , Román Cristina Arbelo , Thomann Jens Oliver , Meier Chris
Published: June 2011

CycloSal‐nucleosyl‐phosphate triesters are a known class of highly effective nucleotide prodrugs (pronucleotides) of antivirally active nucleoside analogues. Until recently, the synthesis of these compounds always gave diastereoisomeric mixtures. Then, a convergent route for the stereospecific synthesis of cycloSal‐triesters was described to give isomerically pure cycloSal‐prodrugs for the treatment of viral diseases. Here, the development of a stereoselective synthesis of these pronucleotides using various chiral auxiliaries is described. In contrast to pyrrolidine‐ or pyrrolidinone derivatives it was found that a thiazolidine derived from valinol fulfilled all three requirements to act as a suitable chiral moiety, allowing: (i) strong chirality transfer, (ii) the formation of separable diastereoisomeric intermediates, and (iii) a suitable leaving group that allows the introduction of the nucleoside analogue (e.g., d4T) in the final step under mild reaction conditions. The title compounds were obtained with very high diastereoisomeric excesses of more than 95 %.
Biaryl‐Bridged Salalen Ligands and Their Application in Titanium‐Catalyzed Asymmetric Epoxidation of Olefins with Aqueous H2O2
Authors: Xiong Donglu , Hu Xiaoxue , Wang Shoufeng , Miao Cheng‐Xia , Xia Chungu , Sun Wei
Published: June 2011

A series of biaryl‐bridged salalen ligands together with their titanium complexes have been designed and synthesized. The Ti complexes could serve as highly efficient catalysts for the asymmetric epoxidation of a wide range of olefins, giving the corresponding epoxides with high ee values.
Synthesis of Various Chiral 1,2,4‐Triazole‐Containing α‐Amino Acids from Aspartic or Glutamic Acids
Authors: Blayo Anne‐Laure , Brunel Frédéric , Martinez Jean , Fehrentz Jean‐Alain
Published: June 2011

Starting from N‐ and C‐protected aspartic or glutamic acids, new unnatural α‐amino acids containing 3,4,5‐trisubstituted 1,2,4‐triazole heterocycles on their side chains have been synthesized. Two points of diversity could easily be achieved on the heterocyclic moiety, which could easily be incorporated in peptide sequences to modify or improve their pharmacokinetic properties.
The motivation to diet in young women: Fear is stronger than hope
Authors: Dalley Simon E. , Buunk Abraham P.
Published: June 2011

This research examined the relative impact of a hoped‐for, thin body and a feared, overweight body on weight‐loss dieting (WLD) motivation. We hypothesised that the women most motivated to engage in WLD would report a higher similarity to, and a higher cognitive availability of, a feared, overweight body. In study 1, WLD motivation was operationalized as WLD intention and in study 2 as a food choice (chocolate bar versus low‐fat snack bar). As expected, those most similar to the feared body and who had a highly available overweight body had the greatest intention to engage in WLD, and were more likely to choose a low‐fat snack over a chocolate bar. The implications of our findings for future research as well as the development of eating pathology in college women are discussed. Copyright © 2011 John Wiley & Sons, Ltd.
On the meaningfulness of existence: When life salience boosts adherence to worldviews
Authors: van Tilburg Wijnand A. P. , Igou Eric R.
Published: June 2011

We investigated when and how life salience boosts adherence to worldviews. It was hypothesized that, similar to thoughts of mortality, thoughts about a meaningful existence increase adherence to worldviews. Study 1a, 1b, and 1c yielded support for the symmetric effects of life and mortality salience on existential thoughts and worldview adherence. Furthermore, study 2 showed that contemplating life's meaningfulness (versus meaninglessness) increased adherence to worldviews. Study 3 showed increased worldview adherence when contemplating life's meaningfulness (versus meaninglessness), and provided additional evidence that the effect on worldview adherence was mediated by the appraisals of life's meaningfulness. Finally, study 4 suggests that both reflecting on life and mortality leads to more worldview adherence under conditions of meaningful life appraisals. The findings are discussed with respect to research in existential psychology. Copyright © 2011 John Wiley & Sons, Ltd.
The impact of Gacaca tribunals in Rwanda: Psychosocial effects of participation in a truth and reconciliation process after a genocide
Authors: Rimé Bernard , Kanyangara Patrick , Yzerbyt Vincent , Paez Dario
Published: June 2011

Victims (N = 200) of the 1994 genocide in Rwanda and prisoners (N = 184) accused of genocidal acts reported their genocide‐related emotions and outgroup perceptions before and after their participation to Truth and Reconciliation Gacaca trials. So did control groups of victims (N = 195) and prisoners (N = 176) not yet exposed to Gacaca. The data supported Durkheim's model of social rituals as cultural tools for transforming emotions, reasserting norms, and enhancing cohesion. Specifically, participation entailed the general reactivation of resignation negative emotions, the enhancement of shame among prisoners, and the decrease of shame among victims, whereas the opposite pattern occurred for antagonist emotions. Participation also enhanced social integration by reducing perceived outgroup homogeneity, decreasing ingroup self‐categorization, and increasing positive stereotypes among both victim and prisoner participants. Moreover, the increase in genocide‐related emotions resulting from participation was associated to positive changes outcomes, suggesting that the increase of negative emotions is an important mechanism at work in collective events of this type. Enhancement of the perception of a positive emotional climate (solidarity and trust) was limited to perpetrator participants. Together, these findings show that Durkheim's model can be extended to restorative justice trials involving both victims and perpetrators. Copyright © 2011 John Wiley & Sons, Ltd.
Serine/threonine‐protein phosphatase 1 α levels are paralleling olfactory memory formation in the CD1 mouse
Authors: Winding Christiana , Sun Yanwei , Höger Harald , Bubna‐Littitz Hermann , Pollak Arnold , Schmidt Peter , Lubec Gert
Published: June 2011

Although olfactory discrimination has already been studied in several mouse strains, data on protein levels linked to olfactory memory are limited. Wild mouse strains Mus musculus musculus, Mus musculus domesticus and CD1 laboratory outbred mice were tested in a conditioned odor preference task and trained to discriminate between two odors, Rose and Lemon, by pairing one odor with a sugar reward. Six hours following the final test, mice were sacrificed and olfactory bulbs (OB) were taken for gel‐based proteomics analyses and immunoblotting. OB proteins were extracted, separated by 2‐DE and quantified using specific software (Proteomweaver). Odor‐trained mice showed a preference for the previously rewarded odor suggesting that conditioned odor preference occurred. In CD1 mice levels, one out of 482 protein spots was significantly increased in odor‐trained mice as compared with the control group; it was in‐gel digested by trypsin and chymotrypsin and analyzed by tandem mass spectrometry (nano‐ESI‐LC‐MS/MS). The spot was unambiguously identified as serine/threonine‐protein phosphatase PP1‐α catalytic subunit (PP‐1A) and differential levels observed in gel‐based proteomic studies were verified by immunoblotting. PP‐1A is a key signalling element in synaptic plasticity and memory processes and is herein shown to be paralleling olfactory discrimination representing olfactory memory.