bluuebunny/crossref_metadata_2025_split huggingface dataset:
Intravascular ultrasound analysis of nonstented adjacent segments in diffuse in‐stent restenosis treated with radiation therapy with a rhenium‐188–filled balloon
Authors: Hong Myeong‐Ki , Park Seong‐Wook , Moon Dae‐Hyuk , Oh Seung‐Jun , Lee Cheol Whan , Kim Young‐Hak , Lee Jae‐Whan , Song Jong‐Min , Kang Duk‐Hyun , Song Jae‐Kwan , Kim Jae‐Joong , Park Seung‐Jung 
Published: March 2003

AbstractThe effects of β‐radiation therapy on nonstented adjacent segments in in‐stent restenosis have not been sufficiently evaluated. β‐radiation therapy for in‐stent restenosis was performed with a 188Re‐MAG3–filled balloon. We evaluated the effects of β‐radiation therapy on nonstented adjacent segments in in‐stent restenosis by intravascular ultrasound (IVUS) analysis in 50 patients who received radiation therapy vs. 9 control patients. The changes (Δ = follow‐up − postintervention) of the external elastic membrane (EEM), the lumen, and other IVUS variables were compared between the segments that received radiation therapy and the control segments. The significant differences between the two groups were as follows: Δ EEM area was 0.3 mm2 in the radiation vs. −1.0 mm2 in the control (P = 0.005) and Δ lumen area was 0.2 mm2 vs. −1.3 mm2, respectively (P < 0.001). In conclusion, compared with the changes of vessel shrinkage in the control group, significant vessel enlargement occurred in the nonstented adjacent segments that received radiation therapy. Cathet Cardiovasc Intervent 2003;58:428–433. © 2003 Wiley‐Liss, Inc.
Safety and efficacy of a novel device for treatment of thrombotic and atherosclerotic lesions in native coronary arteries and saphenous vein grafts: Results from the multicenter X‐sizer for treatment of thrombus and atherosclerosis in coronary applications trial (X‐TRACT) study
Authors: Stone Gregg W. , Cox David A. , Low Reginald , Cates Christopher U. , Satler Lowell , Bailey Steven R. , Kuntz Richard E. , Lansky Alexandra J. 
Published: March 2003

AbstractIntervention in thrombotic lesions and diseased saphenous vein grafts frequently results in thromboembolic complications, including no‐reflow, distal branch occlusion, periprocedural MI, and death. The utility of a novel thromboatherectomy device, the X‐Sizer, was tested in 50 consecutive patients at nine U.S. centers. A total of 61 lesions were treated in 31 vein grafts and 19 native coronary arteries; thrombus was present in 78% of lesions, and TIMI 0–1 flow in 21%. TIMI 3 flow improved from 57% at baseline to 94% postprocedure. No patient developed visible distal thromboemboli, side‐branch occlusion, or reduced antegrade flow. Thirty‐day events included one death (2.0%), Q‐ or non–Q‐wave MI in 4.0%, TVR in 6.0%, and any MACE in 6.0%. We conclude that the use of the X‐Sizer prior to percutaneous intervention is safe in high‐risk vein grafts and thrombotic lesions and results in a low rate of adverse events compared to historical controls. Cathet Cardiovasc Intervent 2003;58:419–427. © 2003 Wiley‐Liss, Inc.
Partial least squares for discrimination
Authors: Barker Matthew , Rayens William 
Published: March 2003

AbstractPartial least squares (PLS) was not originally designed as a tool for statistical discrimination. In spite of this, applied scientists routinely use PLS for classification and there is substantial empirical evidence to suggest that it performs well in that role. The interesting question is: why can a procedure that is principally designed for overdetermined regression problems locate and emphasize group structure? Using PLS in this manner has heurestic support owing to the relationship between PLS and canonical correlation analysis (CCA) and the relationship, in turn, between CCA and linear discriminant analysis (LDA). This paper replaces the heuristics with a formal statistical explanation. As a consequence, it will become clear that PLS is to be preferred over PCA when discrimination is the goal and dimension reduction is needed. Copyright © 2003 John Wiley & Sons, Ltd.
Resolution of two‐way data from spectroscopic monitoring of reaction or process systems by parallel vector analysis (PVA) and window factor analysis (WFA): inspection of the effect of mass balance, methods and simulations
Authors: Jiang Jian‐Hui , Šašić Slobodan , Yu Ru‐Qin , Ozaki Yukihiro 
Published: March 2003

AbstractThe effect of mass balance on the analysis of two‐way data of reaction or process systems is investigated. It is shown that the rank‐deficient species‐related bilinear model can be converted to a full‐rank reaction‐related bilinear model, and in general situations the chemical rank for a system is the number of reactions plus one. Two slightly modified procedures are thus suggested to extract the spectral subspaces essential for resolution and to ascertain the number of reactions in different time domains. Based on the reaction‐related bilinear model, a procedure of window factor analysis (WFA) is implemented for resolving the extent curves of reactions. A new two‐way resolution approach, parallel vector analysis (PVA), is also developed. The idea of PVA is to construct a set of subspaces comprising only one common (spectral) component and then find a vector that is in parallel with a series of vectors coming from different subspaces. With suitably constructed subspaces the PVA procedure offers a versatile avenue to approach the unique resolution of spectral profiles. A four‐component system which comprises four different processes or reactions is simulated. Results obtained reveal that favorable resolution is achieved for the spectral and concentration profiles by the suggested procedures of WFA and PVA. Copyright © 2003 John Wiley & Sons, Ltd.
DFT Study of the NMR Properties of Xenon in Covalent Compounds and van der Waals Complexes—Implications for the Use of 129Xe as a Molecular Probe
Authors: Bagno Alessandro , Saielli Giacomo 
Published: March 2003

AbstractThe NMR properties (chemical shift and spin–spin coupling constants) of 129Xe in covalent compounds and weakly bound complexes have been investigated by DFT methods including relativistic effects. For covalent species, a good agreement between experimental and calculated results is achieved without scalar relativistic effects, but their inclusion (with a triple‐ζ, double‐polarization basis set) leads to some improvement in the quality of the correlation. The spin–orbit coupling term has a significant effect on the shielding constant, but makes a small contribution to the chemical shift. Coupling constants contain substantial contributions from the Fermi contact and paramagnetic spin–orbit terms; unlike light nuclei the spin–dipole term is also large, whereas the diamagnetic spin–orbit term is negligible. For van der Waals dimers, the dependence of the xenon chemical shift and anisotropy is calculated as a function of the distance. Small (<1 Hz) but non‐negligible through‐space coupling constants between 129Xe and 13C or 1H are predicted. Much larger couplings, of the order of few Hz, are calculated between xenon and 17O in a model silicate residue.
Theoretical Study of the [2+3] Cycloaddition of Nitrones to Nitriles—Influence of Nitrile Substituent, Solvent and Lewis Acid Coordination
Authors: Wagner Gabriele 
Published: March 2003

AbstractThe [2+3] cycloaddition of nitrone PhCHN(Me)O to nitriles RCN (R=Me, Ph, CF3) was studied using quantum chemical calculations at the HF/6‐31G* and B3LYP/6‐31G* level of theory. With MeCN and PhCN, the reaction occurs through a concerted mechanism and leads selectively to Δ4‐1,2,4‐oxadiazolines rather than Δ2‐1,2,5‐oxadiazolines. Electron withdrawing substituents such as CF3 at the nitrile provoke a non‐synchronous bond formation, with the CO bond being established on an earlier stage than the CN bond. Additionally, the reaction becomes thermodynamically and kinetically more favourable. In the reaction of adducts of MeCN with BH3 or BF3 as model Lewis acids, the mechanism was found to change from fully concerted in the case of free MeCN towards a two‐step reaction in the presence of BF3, in which CO bond formation occurs first. The BH3‐mediated reaction occupies an intermediate stage where ring formation occurs in one‐step but non‐simultaneously, similar to the reaction of CF3CN. Interaction of the Lewis acid with the nitrile in the course of the reaction facilitates the cycloaddition by stabilizing transition states, intermediate and product rather than by activating the nitrile. The solvent influences the organic reaction mainly by lowering the energy of the reagents, thus leading to a higher activation barrier in a more polar solvent. In the Lewis acid mediated reaction, in contrast, the intermediate is strongly stabilised by a polar solvent and with that the synchronicity of the reaction changes in favour of a two‐step mechanism.
Palladium‐Catalyzed Cascade Reaction of α,β‐Unsaturated Sulfones with Aryl Iodides
Authors: Mauleón Pablo , Núñez Angel A. , Alonso Inés , Carretero Juan C. 
Published: March 2003

AbstractUnlike traditionally used acyclic 1,2‐disubstituted alkenes, the reaction of α,β‐unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)2 as catalyst, Ag2CO3 as base in DMF at 120 0C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9‐phenylsulfonyl‐9,10‐dihydrophenanthrene. The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic CH activation processes can compete with the usually fast syn β‐hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium‐catalyzed cascade arylation of α,β‐unsaturated sulfones has proved to be wide with regard to substitution at the β‐position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the CC bond (trans or cis). Moreover, although less favored than in the case of the arylation of α,β‐unsaturated sulfones, similarly substituted 9,10‐dihydrophenanthrenes have also been obtained in the case of α,β‐unsaturated phosphine oxides and α,β‐unsaturated phosphonate esters. A Pd0–PdII–PdIV mechanistic pathway involving the successive formation of highly electrophilic σ‐alkylpalladium intermediates and palladacycles is proposed for this multicomponent arylation.
Quantitative Comparison of Kinetic Stabilities of Metallomacrocycle‐Based Rotaxanes
Authors: Chang Sung‐Youn , Jang Hye‐Young , Jeong Kyu‐Sung 
Published: March 2003

AbstractFour mononuclear metallomacrocycles with identical cavities but different transition metals (OsVI, PdII, PtII, and ReI) were prepared. With these metallomacrocycles, the corresponding rotaxanes 2‐Os, 2‐Pd, 2‐Pt, and 2‐Re were self‐assembled by hydrogen‐bonding interactions. The kinetic stabilities of the rotaxanes were determined quantitatively and compared with each other by 1H NMR spectroscopic techniques, including two‐dimensional exchange spectroscopy (2D‐EXSY) experiments. The activation free energies (ΔG≠) for the exchange between the rotaxanes 2‐Os, 2‐Pd and 2‐Pt and their free components were determined to be 15.5, 16.0, and 16.4 kcal mol−1, respectively. These magnitudes imply that the rotaxanes 2‐Os, 2‐Pd and 2‐Pt are kinetically labile at room temperature and exist only as equilibrium mixtures with free components in solution. In contrast, the rotaxane 2‐Re is kinetically stable enough to be isolated in pure form by silica gel chromatography under ordinary laboratory conditions. However, at higher temperatures (>60 °C) 2‐Re was slowly disassembled into its components until the equilibrium was established. The rate constants were measured at three different temperatures, and the Eyring plot yielded the activation enthalpy ΔH≠=35 kcal mol−1 and the activation entropy ΔS≠=27 eu for the disassembly of the rotaxane 2‐Re in Cl2CDCDCl2. These thermodynamic parameters gave the activation free energy ΔG$\rm{^{\ne }_{off}}$=27.1 kcal mol−1 at 25 °C. Consequently, 2‐Re is one example of a novel metallomacrocycle‐based rotaxane that contains a coordination bond with enough strength to allow both for isolation in pure form around room temperature and for self‐assembly at higher temperatures.
The Structure of Lipid A of the Lipopolysaccharide from Burkholderia caryophylli with a 4‐Amino‐4‐deoxy‐L‐arabinopyranose 1‐Phosphate Residue Exclusively in Glycosidic Linkage
Authors: Molinaro Antonio , Lindner Buko , De Castro Cristina , Nolting Birte , Silipo Alba , Lanzetta Rosa , Parrilli Michelangelo , Holst Otto 
Published: March 2003

AbstractFrom the lipopolysaccharides (LPSs) of the plant‐pathogenic bacterium Burkholderia caryophylli, the complete structure of lipid A has been characterized. For the first time, a 4‐amino‐4‐deoxy‐L‐arabinopyranose 1‐phosphate residue was proven to be exclusively linked to the reducing end of lipid A from a wild‐type LPS. The LPSs of B. caryophylli were degraded by mild acetate buffer hydrolysis at pH 4.4. The obtained lipid A was analyzed as such, and also after de‐O‐acylation or dephosphorylation. The structure of lipid A was identified mainly by means of matrix‐assisted laser desorption/ionisation mass spectrometry, and by various 1D and 2D 1H and 13C NMR spectroscopic measurements.
Shape‐Controlled Bridged Silsesquioxanes: Hollow Tubes and Spheres
Authors: Moreau Joël J. E. , Vellutini Luc , Wong Chi Man Michel , Bied Catherine 
Published: March 2003

AbstractA new approach for the morphological control of bridged silsesquioxanes has been achieved by the hydrolysis of silylated organic molecules bearing urea groups. The urea groups are responsible for the auto‐association of the molecules through intermolecular hydrogen‐bonding interactions. The self‐assembly leads to supramolecular architectures that have the ability to direct the organization of hybrid silicas under controlled hydrolysis. The hydrolysis of the chiral diureido derivatives of trans‐(1,2)‐diaminocyclohexane 1 under basic conditions has been examined. The solid‐state NMR spectra (29Si and 13C) showed the hybrid nature of these materials with wholly preserved SiC covalent bonds throughout the silicate network. Hybrid silicas with hollow tubular morphologies were obtained by the hydrolysis of the enantiomerically pure compounds, (R,R)‐1 or (S,S)‐1, whereas the corresponding racemic mixture, rac‐1, led to a hybrid with ball‐like structures. The tubular shape is likely to result from a combination of two phenomena: the auto‐association abilities and a self‐templating structuration of the hybrid materials by the organic crystalline precursor. Electronic microscopy techniques (SEM and TEM) gave evidence for the self‐templating pathway. The formation of the ball‐like structures occurs through a usual nucleation growth phenomenon owing to a higher solubility of the corresponding crystals in the same medium.
Synthesis, Structure, and Properties of Novel Open‐Cage Fullerenes Having Heteroatom(s) on the Rim of the Orifice
Authors: Murata Yasujiro , Murata Michihisa , Komatsu Koichi 
Published: March 2003

AbstractA thermal liquid‐phase reaction of fullerene C60 with 3‐(2‐pyridyl)‐5,6‐diphenyl‐1,2,4‐triazine afforded aza‐open‐cage fullerene derivative 5 having an eight‐membered‐ring orifice on the fullerene cage. Compound 5 was found to undergo oxidative ring‐enlargement reactions with singlet oxygen under photo‐irradiation to give azadioxo‐open‐cage fullerene derivatives 9 and 10, which have a 12‐membered‐ring orifice, in addition to a small amount of azadioxa‐open‐cage fullerene derivative 11, which has a 10‐membered‐ring orifice. A thermal reaction of 9 with elemental sulfur in the presence of tetrakis(dimethylamino)ethylene resulted in further ring‐enlargement to give azadioxothia‐open‐cage fullerene derivative 15, which has a 13‐membered‐ring orifice. The structures of 5 and 15 were determined by X‐ray crystallography, while those of 9, 10, and 11 were confirmed by the agreement of observed 13C NMR spectra with those obtained by DFT‐GIAO calculations. These reactions were rationalized based on the results of molecular orbital calculations. Following electrochemical measurements, compounds 9 and 10, which have two carbonyl groups on the rim of the orifice, were found to be more readily reduced than C60 itself (the first reduction potential was found to be 0.2 V lower than that of C60), while the first reduction potentials of other open‐cage fullerene derivatives, 5, 11, and 15, were nearly the same as that of C60.
The Experimental Electron Density Distribution in the Complex of (E)‐1,2‐Bis(4‐pyridyl)ethylene with 1,4‐Diiodotetrafluorobenzene at 90 K
Authors: Bianchi Riccardo , Forni Alessandra , Pilati Tullio 
Published: March 2003

AbstractThe experimental electron density of the donor–acceptor complex of (E)‐1,2‐bis(4‐pyridyl)ethylene (bpe) with 1,4‐diiodotetrafluorobenzene (F4DIB) at 90 K has been determined with the aspherical atom formalism and analyzed by means of the topological theory of molecular structure. The bpe and F4DIB molecules are connected by intermolecular I⋅⋅⋅N bonds into infinite 1D chains. F⋅⋅⋅H bonds link these chains together to form the crystal assembly. The topological analysis reveals that the CI bond is of the “closed shell” type. Its bond‐critical properties run parallel to those found in metal–metal and metal–ligand bonds of organometallic compounds. The integrated net charges show that the I⋅⋅⋅N halogen bond has an essentially electrostatic nature. F⋅⋅⋅F, F⋅⋅⋅C, and C⋅⋅⋅C intermolecular interactions, for which a bond path was found, contribute to reinforce the crystal structure.
Decreased immunoreactivity for p27 protein in patients with early‐stage breast carcinoma is correlated with HER‐2/neu overexpression and with benefit from one course of perioperative chemotherapy in patients with negative lymph node status
Authors: Spataro Vito J. , Litman Heather , Viale Giuseppe , Maffini Fausto , Masullo Michele , Golouh Rastko , Martinez‐Tello Francisco J. , Grigolato Piergioranni , Shilkin Keith B. , Gusterson Barry A. , Castiglione‐Gertsch Monica , Price Karen , Lindtner Jurii , Cortés‐Funes Hernan , Simoncini Edda , Byrne Michael J. , Collins John , Gelber Richard D. , Coates Alan S. , Goldhirsch Aron 
Published: March 2003

AbstractBACKGROUNDThe objective of this study was to clarify the prognostic and predictive value of immunoreactivity for the cyclin‐dependent kinase inhibitor p27(Kip1) in patients with early‐stage breast carcinoma and to investigate its relation with clinicopathologic features and other markers.METHODSImmunoreactivity for p27 protein was analyzed on tumor slides from 461 patients who were enrolled in the International Breast Cancer Study Group (IBCSG) Trial V (median follow‐up, 13 years), including 198 patients with lymph node negative disease and 263 patients with lymph node positive disease. Tumors with < 50% immunoreactive neoplastic cells were considered low expressors. Immunoreactivity for p27 was correlated with several clinicopathologic characteristics. Disease free survival (DFS) and overall survival were analyzed according to p27 immunoreactivity and treatment group.RESULTSIn the lymph node negative population, decreased p27 immunoreactivity was associated with higher tumor grade (P = 0.001) and HER‐2/neu overexpression (P = 0.04). In the lymph node positive population, low p27 expression was associated with higher tumor grade (P = 0.01), low expression of thymidylate synthase (P = 0.001), and higher Ki‐67 expression (P = 0.007). DFS was not significantly different according to p27 status in either lymph node negative patients (10‐year DFS: low p27 expression, 53% ± 5%; high p27 expression, 55% ± 5%) or in lymph node positive patients (10 year DFS: low p27 expression, 33% ± 4%; high p27 expression, 32% ± 4%). However, in the lymph node negative population, the benefit of one course of perioperative chemotherapy with cyclophosphamide, methotrexate, and 5‐fluorouracil was confined exclusively to patients with tumors that showed reduced p27 immunoreactivity (P = 0.03; test for interaction).CONCLUSIONSThis analysis indicates that p27 immunoreactivity has little if any prognostic value in patients with early‐stage breast carcinoma. However, these findings suggest that, in patients with breast carcinoma who have negative lymph node status, reduced p27 immunoreactivity is associated with HER‐2/neu overexpression and may be predictive of a benefit from the early administration of adjuvant chemotherapy. Cancer 2003;97:1591–600. © 2003 American Cancer Society.DOI 10.1002/cncr.11224
Patient satisfaction with treatment decisions for clinically localized prostate carcinoma. Results from the Prostate Cancer Outcomes Study
Authors: Hoffman Richard M. , Hunt William C. , Gilliland Frank D. , Stephenson Robert A. , Potosky Arnold L. 
Published: March 2003

AbstractBACKGROUNDMen with early‐stage prostate carcinoma can choose aggressive treatment or conservative management. The authors used data from a population‐based cohort of men with clinically localized prostate carcinoma to describe satisfaction with treatment decisions 24 months after diagnosis and to examine the association of demographic, socioeconomic, and clinical characteristics with treatment satisfaction.METHODSThe authors evaluated 2365 men with clinically localized prostate carcinoma, diagnosed between October 1994 and October 1995, in one of six Surveillance, Epidemiology, and End Results tumor registries and who were available for 24 month follow‐up. Medical record review and patient‐completed surveys provided demographic, socioeconomic, and clinical data and measured treatment satisfaction. Logistic regression analyses were used to identify factors associated with satisfaction.RESULTSOverall, 59.2% of subjects were delighted or very pleased with their treatment selection. The perception of being cancer free (66.4%), maintaining urinary (64.2%) and bowel (60.5%) control and normal erectile function (65.9%), having good general health (71.3%), and preserving social relationships (68.1%) were significantly associated with being satisfied (P < 0.05). Men receiving no active treatment were less satisfied (50.5%, P < 0.001) than actively treated men, and Hispanic men were less satisfied than non‐Hispanic white men after undergoing radical prostatectomy (50.1% vs. 58.0%, P = 0.05) or androgen deprivation (29.7% vs. 71.8%, P < 0.02).CONCLUSIONSThe majority of men were satisfied with their treatment selection for clinically localized prostate carcinoma. Receiving an active treatment, believing oneself to be free of cancer, avoiding treatment complications, and having good overall health and social support were positively associated with satisfaction. Cancer 2003;97:1653–62. © 2003 American Cancer Society.DOI 10.1002/cncr.11233