bluuebunny/crossref_metadata_2025_split huggingface dataset:
A New Heptanuclear Dendritic Ruthenium(II) Complex Featuring Photoinduced Energy Transfer Across High‐Energy Subunits
Authors: Puntoriero Fausto , Serroni Scolastica , Galletta Maurilio , Juris Alberto , Licciardello Antonino , Chiorboli Claudio , Campagna Sebastiano , Scandola Franco 
Published: January 2005

AbstractThe new heptanuclear ruthenium(II) dendron, [Cl2Ru{(μ‐2,3‐dpp)Ru[(μ‐2,3‐dpp)Ru(bpy)2]2}2](PF6)12 (1; 2,3‐dpp=2,3‐bis(2′‐pyridyl)pyrazine; bpy=2,2′‐bipyridine), was prepared by means of the “complexes as ligands/complexes as metals” synthetic strategy, and its absorption spectrum, redox behavior, and luminescence properties were investigated. Compound 1 is a multicomponent species, which contains three different types of chromophores (namely, the {Cl2Ru(μ‐2,3‐dpp)2} core, the {Ru(μ‐2,3‐dpp)3}2+ intermediate, and the {(bpy)2Ru(μ‐2,3‐dpp)}2+ peripheral subunits) and several redox‐active sites. The new species exhibits very intense absorption bands in the UV region (ε value in the 105–106 M−1 cm−1 range) as a result of spin‐allowed ligand‐centered (LC) transitions, and intense bands in the visible region (ε value in the 104–105 M−1 cm−1 range) as a result of the various spin‐allowed metal‐to‐ligand charge‐transfer (MLCT) transitions. The redox investigation (accomplished by cyclic and differential pulse voltammetry) indicates that 1 undergoes a series of reversible metal‐centered oxidation and ligand‐centered reduction processes within the potential window investigated (+1.90/−1.40 V vs. the standard calomel electrode, SCE). The assignment of each absorption band and redox process to specific subunits of 1 was achieved by comparison with the properties of smaller multinuclear species of the same family, namely [Cl2Ru{(μ‐2,3‐dpp)Ru(bpy)2}2]4+ (2), [(bpy)2Ru(μ‐2,3‐dpp)Ru(bpy)2]4+ (4), and [Ru{(μ‐2,3‐dpp)Ru(bpy)2}3]4+ (5). The title compound exhibits luminescence both at room temperature in acetonitrile fluid solution and at 77 K in butyronitrile rigid matrix. The emission is attributed to the triplet MLCT (3MLCT) state involving the core {Cl2Ru(μ‐2,3‐dpp)2} subunit. Interestingly, the 3MLCT levels involving the peripheral {(bpy)2Ru(μ‐2,3‐dpp)}2+ subunits are deactivated by energy transfer to the emitting level, in spite of the presence of interposed high‐energy {Ru(μ‐2,3‐dpp)3}2+ components, which, in other dendrimers, acted as “isolating” subunits toward energy‐transfer processes. Ultrafast experiments on 1 and on the parent species 2 and 5 allowed us to rationalize this behavior and highlight that a sequential two‐step electron‐transfer process can be held responsible for the efficient overall energy transfer, which offers a way to overcome a limitation in antenna metal dendrimers.
The cytological spectrum of chronic pancreatitis
Authors: Stelow Edward B. , Bardales Ricardo H. , Lai Rebecca , Mallery Shawn , Linzie Bradley M. , Crary Gretchen S. , Stanley Michael W. 
Published: January 2005

AbstractChronic pancreatitis (CP) refers to a spectrum of changes generally seen after repeated injury that ranges histologically from mild fibrosis to extensive fibroinflammatory replacement of acinar tissue with accumulation of calcific debris. Because CP can share clinical and radiological features with malignancy, it often is sampled by fine‐needle aspiration (FNA). The cytology files at Hennepin County Medical Center (HCMC) were searched for 20 consecutive cases of CP sampled by FNA. Clinical data and cytological findings were recorded. A spectrum of cytological findings typifies aspirates of CP. In most cases, mixed inflammation with debris and calcific material is present. Often, ductal cells are present and at most show mild atypia but generally appear organized. Often, fibrotic acinar tissue also is present while definitive islets are identified only rarely. Although these cytological findings were consistent with CP, 3 of 17 patients with follow‐up were found to have pancreatic ductal adenocarcinoma. Diagn. Cytopathol. 2005;32:65–69. © 2005 Wiley‐Liss, Inc.
Bilateral primary lymphoma of the breast: A case report initially diagnosed by FNAC
Authors: Maounis N. , Ellina E. , Papadaki Th. , Ioannides G. , Kiale K. , Finokaliotis N. , Blana AiK. 
Published: January 2005

AbstractPrimary lymphoma of the breast (PLB) is a rare disease, representing 0.04–0.5% of all malignant breast neoplasms. We present a patient with bilateral breast involvement by a high‐grade diffuse large B‐cell lymphoma, which was diagnosed initially by fine‐needle aspiration cytology (FNAC). Mammography revealed a diffuse increase in density of the right breast and a large solitary mass on the left breast, suggestive of an inflammatory carcinoma. The patient underwent FNAC and the diagnosis of a non‐Hodgkin's lymphoma (NHL) was suggested. Physical examination revealed palpable bilateral axillary lymph nodes but no evidence of concurrent widespread disease. The patient underwent complete staging evaluation. The only positive findings were an elevated lactate dehydrogenase (LDH) and evidence of axillary lymphadenopathy on CT. Excisional biopsy was performed on the left breast. The morphological and immunohistochemical analysis confirmed the diagnosis of a high‐grade diffuse large B‐cell lymphoma with an immunophenotype suggestive of a germinal center cell origin. Diagn. Cytopathol. 2005;32:114–118. © 2005 Wiley‐Liss, Inc.
Differential expression of cdk inhibitors p16, p21cip1, p27kip1, and cyclin E in cervical cytological smears prepared by the ThinPrep method
Authors: Moore Grace D. , Lear Sheron C. , Wills‐Frank Lisa A. , Martin Alvin W. , Snyder James W. , Helm C. William 
Published: January 2005

AbstractOur objective was to correlate p16, p21cip1, p27kip1, and cyclin E protein expression with the degree of dysplasia on ThinPrep Papanicolaou (Pap) smears using a modified immunoperoxidase staining. Smears read as normal, atypical squamous cells of undetermined significance (ASC‐US), low‐grade squamous intraepithelial lesion (LSIL), or high‐grade SIL (HSIL) were identified and tested for high‐risk human papillomavirus (HR‐HPV). Additional smears were processed for immunoperoxidase for p16, p21cip1, p27kip1, and cyclin E. Thirty‐four smears were satisfactory for study. The p16 was positive in all nine HSIL, in four of nine LSIL, and in one of seven ASC‐US. The p27kip1 was positive in all nine HSIL, in eight of nine LSIL, and in one of seven ASC‐US. The p21cip1 was positive in all nine HSIL, in one of nine LSIL, and in one of seven ASC‐US. Cyclin E was positive in seven of nine HSIL and in one of nine LSIL and in none of the ASC‐US smears. Normal smears were negative for all the antigens. There was poor correlation of protein expression and HR‐HPV infection. We concluded that p16, p21cip1, p27kip1, and cyclin E can be demonstrated on Pap smears and they are expressed differentially in dysplastic cells, with highest expression in HSIL. The p21cip1 and cyclin E showed the greatest correlation with HSIL. Diagn. Cytopathol. 2005;32:82–87. © 2005 Wiley‐Liss, Inc.
A cost‐effectiveness analysis of four management strategies in the determination and follow‐up of atypical squamous cells of undetermined significance
Authors: Hughes Alice A. , Glazner Judith , Barton Phoebe , Shlay Judith C. 
Published: January 2005

AbstractAtypical squamous cells of undetermined significance (ASC‐US) are the most common abnormal cytological result on Papanicolaou (Pap) smear. We analyzed four management strategies in a hypothetical cohort of women divided by age group: (1) immediate colposcopy, (2) repeat cytology after an ASC‐US Pap smear result, (3) conventional Pap with reflex human papillomavirus (HPV) testing, and (4) liquid‐based cytology with reflex HPV testing. Parameter variables were collected from previously published data. Strategies that included reflex HPV testing had the lowest overall costs for all age groups combined. Repeat Pap smears had the highest number of true positive results throughout all stages but also had the uppermost number of missed cancers and highest costs. Immediate colposcopy had the second highest overall costs and detected fewer true positive results than liquid‐based cytology. Younger women (aged 18–24 yr) consistently had higher total costs for all strategies investigated. Using the incremental cost‐effectiveness (CE) ratio, the immediate colposcopy strategy was more costly and less effective than liquid‐based cytology and, therefore, was dominated. The incremental CE ratio was lowest for liquid‐based cytology compared with conventional cytology and liquid‐based cytology with reflex HPV testing was the most cost‐effective strategy. Diagn. Cytopathol. 2005;32:125–132. © 2005 Wiley‐Liss, Inc.
Generalized wall functions and their application for simulation of turbulent flows
Authors: Utyuzhnikov S. V. 
Published: January 2005

AbstractGeneralized wall functions in application to high‐Reynolds‐number turbulence models are derived. The wall functions are based on transfer of a boundary condition from a wall to some intermediate boundary near the wall (usually the first nearest to a wall mesh point but that is not obligatory). The boundary conditions on the intermediate boundary are of Robin‐type and represented in a differential form. The wall functions are obtained in an analytical easy‐to‐implement form, taking into account source terms such as pressure gradient, and do not include free parameters. The log‐profile assumption is not used in this approach. Although the generalized wall functions are obtained for the k–ε model, generalization to other turbulence models is straightforward. The general approach suggested can be applied for studying high‐temperature regimes with variable laminar viscosity and density. Copyright © 2005 John Wiley & Sons, Ltd.
Crystallographic analysis of thermochromic, unsolvated tetramesityldisilene at 173 K and 295 K
Authors: Shepherd Brian D. , Campana Charles F. , West Robert 
Published: January 2005

AbstractX‐ray crystal structure determinations of tetramesityldisilene (1) at 295 K, where it is bright orange, and at 173 K, where it is pale yellow, were experimentally equivalent. The thermochromism of 1, therefore, is not due to changes in conformation; a vibrational origin is considered. The crystal structure of unsolvated 1 differs substantially from that of the toluene solvate (1·C7H8) because of different crystal packing of the two forms. These two solid‐state structures are compared with those of four other disilenes.
Asymmetric synthesis of tertiary alcohols from α‐halo boronic esters
Authors: Matteson Donald S. , Hurst Gerald D. 
Published: January 2005

AbstractReaction of pinanediol boronates with (1,1‐dichloroethyl)lithium generated in situ at −78°C followed by rearrangement of the resulting borate complex 2S in the presence of zinc chloride at 25°C has resulted in chirally biased insertion of the 1‐chloroethyl group into the carbon–boron bond. (s)‐Pinanediol phenylboronate (7) produced (s)‐pinanediol (1S)‐(1‐chloro‐1‐phenylethyl)boronate (8S) in 92% DE. Nonstererospecific reaction with ethylmagnesium bromide to form (s)‐pinanediol (1S)‐(1‐phenyl‐1‐methylpropyl)boronate (5S) reduced the DE to 88%. Peroxidic deboronation yielded (R)‐(+)‐2‐phenyl‐2‐butanol (6R) (84% EE). (s)‐Pinanediol ethylboronate (4) with (1,1‐dichloroethyl)lithium showed the opposite chiral preference, yielding (s)‐pinanediol (1R)‐(1‐chloro‐1‐methylpropyl)boronate (3R) (89% DE), which was converted by phenylmagnesium bromide followed by hydrogen peroxide to 6R (76% EE). Diastereoselections were small in reactions of (1,1‐dichloroethyl)‐lithium with n‐alkylboronates 9a and 13 and with cyclohexylboronate 9c. The 13 was converted to the enantiomer of the insect pheromone frontalin (17) (21% EE). Good diastereoselections were found with α‐substituted alkylboronates 9b and 18, but the configurations of the products could not be determined. (s)‐Pinanediol (1,1‐dichloroethyl)boronate (1) reacts with Grignard reagents via an intermediate borate 2R with negligible diastereoselection.
π‐Complexes of p‐block elements: (η6‐Mesitylene)tin(II) chloride tetrachloroaluminate(III), a coordination polymer
Authors: Schmidbaur Hubert , Probst Thomas , Steigelmann Oliver , Müller Gerhard 
Published: January 2005

Abstract(η6‐1,3,5‐Trimethylbenzene)tin(II) chloride tetrachloroaluminate(III), (η6‐1,3,5‐C6H3Me3)SnCl (AlCl4), has been obtained from the reaction of anhydrous SnCl2 and AlCl3 in the molar ratio 1 : 2 in excess mesitylene as a solvent. The compound crystallizes in monoclinic needles, space group P21/n, containing a coordination polymer with planar four‐membered rings Sn‐Cl‐Sn‐Cl as the fundamental structural units. Each tin(II) atom of these rings is η6‐bonded to a mesitylene ring, with the metal approximately centered over the aromatic hydrocarbon at a distance of 2.71 Å. Each of the tin(II) atoms is further connected to two tetrachloroaluminate counter ions, one of these monodentate and one bidentate. Through this mono/bidentate contacts a one‐dimensional coordination polymer is generated with crystallographic centers of inversion in the middle of the Sn(Cl)2Sn and Sn(AlCl4)2Sn rings. The structure is similar to that of the analogous benzene complex, but not identical owing to a different connectivity pattern. Also, the arene‐Sn(II) distance is much shorter in the mesitylene complex (2.71 Å) than in the benzene complex (2.90 Å), indicating that the trimethylbenzene molecule is a much better donor than benzene.
1‐Phosphinodiazaphosphene: Synthesis, crystal structure, and bonding properties
Authors: Altmeyer Oliver , Niecke Edgar , Nieger Martin , Busch Thilo , Schoeller Wolfgang W. , Stalke Dietmar 
Published: January 2005

AbstractThe iminophosphane, tBu2PPNNR2 (RSiMe3), produced by base‐catalyzed elimination of ClSiMe3 from the corresponding phosphane, possesses an unusually long PN bond (162 pm), which is in accord with quantum chemical calculations.
The preparation and characterization of binary phosphorus–selenium rings
Authors: Pilkington Mark J. , Slawin Alexandra M. Z. , Williams David J. , Wood Paul T. , Woollins J. Derek 
Published: January 2005

AbstractDepending on the ratio of reactants, reaction of (PPh)5 (1) with grey selenium gives (PhPSe2)2 (2), (PhP)3Se2 (3), (PhP)4Se (4), and (PhP)3Se3 (5). The compounds have been characterized by multielement NMR, mass spectrometry, microanalyses, and, in the case of 4, X‐ray crystallography. 4 consists of a puckered 5‐membered ring with all four phenyl substituents axial; the average P–P and P–Se bond lengths are 2.194 and 2.271 Å respectively.
Synthesis of mesocyclic and macrocyclic polythioethers using the cesium dithiolate technique
Authors: Setzer William N. , Afshar Shahrara , Burns Norman L. , Ferrante Lucille A. , Hester Amy M. , Meehan Edward J. , Grant Gregory J. , Isaac Saju M. , Laudeman Christopher P. , Lewis Charles M. , VanDerveer Donald G. 
Published: January 2005

AbstractThe mesocyclic trithioethers, 1,4,7‐trithiacyclodecane, 1,4,7‐trithiacycloundecane, 1,4,8‐trithiacycloundecane, and 1,5,9‐trithiacyclododecane; the mesocyclic trithioether ketones, 1,4,7‐trithiacyclodecan‐9‐one; 1,4,8‐trithiacycloundecan‐6‐one, and 1,5,9‐trithiacyclododecan‐3‐one; and the mesocyclic trithioether alcohols, 1,4,7‐trithiacyclodecan‐9‐ol, 1,4,8‐trithiacycloundecan‐6‐ol, and 1,5,9‐trithiacyclododecan‐3‐ol, have been synthesized using the cesium dithiolate technique. In some cases, the corresponding macrocyclic hexathioether was isolated from the reaction mixture in addition to the mesocyclic trithioether; 1,4,7,11,14,17‐hexathiacycloeicosane, 1,4,7,11,14,17‐hexathiacycloeicosan‐9,19‐dione, 1,4,7,12,15,18‐hexathiacyclodocosane, and 1,5,9,13,17,21‐hexathiacyclotetracosane. Single‐crystal X‐ray structures have been determined for 1,5,9‐trithiacyclododecan‐3‐ol and 1,4,7,12,15,18‐hexathiacyclodocosane. For 1,5,9‐trithiacyclododecane‐3‐ol, the compound crystallizes in the monoclinic space group, C2/c, with a = 10.5926(9) Å, b = 15.582(2) Å, c = 13.6015(8) Å, β = 98.186(6)0, Z = 8, and R = 0.038. The macrocycle, 1,4,7,12,15,18‐hexathiacyclodocosane, crystallizes in the orthorhombic space group, Pbca, with a = 21.406(5) Å, b = 9.810(2) Å, c = 10.225(2) Å, Z = 4, and R = 0.020.
Convenient synthesis of 1‐alkoxy‐1,2‐dihydrophosphinine 1‐oxides by ring enlargement
Authors: Keglevich GyöRgy , Brlik JáNos , Janke Frank , Tőke László 
Published: January 2005

AbstractThe addition of dichlorocarbene to the double bond of 1‐alkoxy‐dihydrophosphole oxides and subsequent thermolysis of the adduct so obtained affords mixtures of the two double bond isomers of alkoxy‐dihydrophosphinine oxides, if the latter step is carried out in the presence of triethylamine. Experimental data support the involvement of a cationic intermediate during the opening of the cyclopropane ring. A simplified procedure for the preparation of the starting dihydrophospholes is also presented.
Synthesis and crystal structures of the triphenylstannyl esters of N‐phthaloyl‐glycine and ‐leucine
Authors: Ng Seik Weng , Das V. G. Kumar , Pelizzi Giancarlo , Vitali Francesca 
Published: January 2005

AbstractTriphenyltin N‐phthaloylglycinate crystallizes from ethanol as a bridged, cyclic hexamer (rhombohedral R3 space group, a = 19.928(3) Å, α = 116.47(2)0; Z = 6) and triphenyltin N‐phthaloylleucinate as a monomeric molecule (orthorhombic Pbca space group, a = 18.032(6), b = 26.992(7), c = 11.705(4) Å; Z = 8).
arachno‐Diazapentaboranes
Authors: Küpper Stefan , Englert Ullrich , Paetzold Peter 
Published: January 2005

AbstractThe reaction of appropriate amounts of BH3 with diazadiboretidines (RBNtBu)2 (1a–e; R = Et, Pr, Bu, tBu, tBu(Me3Si)N) transforms them into cyclic diazapentaboranes either of the type [RB(H2)BRNtBuBHNtBu] (2a–c), of the type [HB(H2)BRNtBuBHNtBu] (3a–d), or of the type [HB(H2)BHNtBuBHNtBu] (4), or into an acyclic product RBHNtBuBHNtBuBHR (2e). The structure of 3c is characterized by a planar N2B3 ring skeleton with an unsymmetrical double‐hydrogen bridge.
Steric aspects of selectivity of organophosphorus extractants
Authors: Kabachnik M. I. 
Published: January 2005

AbstractThis paper is devoted to the steric aspects of the efficiency and selectivity of extractants in the process of extraction of metal cations from acidic aqueous solution into a nonpolar phase. The extraction of uranium, plutonium, americium, and europium by tertiary carbamoylmethyl phosphine oxides and polydiphenylphosphinylmethyl benzenes have been studied. The separation factors of uranium and plutonium from americium are measured. Tertiary carbamoylmethyl phosphine oxides and diphenylphosphinylmethyl benzenes of the ortho type are characterized by unusually high separation factors. The diphenylphosphinylmethyl derivatives of benzene of the meta type do not possess a high selectivity in the process of separation of uranium and plutonium from americium, but are more efficient in extraction of americium.
Investigations of a highly crowded phosphino‐substituted biphenyl: A precursor for a λ3, λ5‐diphosphaphenanthrene
Authors: Van Den Winkel Yvar , Van Der Laarse Jeroen , De Kanter Frans J. J. , Van Der Does Thomas , Bickelhaupt Friedrich , Smeets Wilberth J. J. , Spek Anthony L. 
Published: January 2005

AbstractThe synthesis of 2,2′‐bis(bis(dimethylamino)‐phosphino)‐3,3′5,5′‐tetra‐tert‐butylbiphennyl (5) is described. It was extensively studied by 1H, 13C, and 31P NMR spectroscopy. Furthermore, the X‐ray analysis of 5 is reported. Crystals of 5 are tetragonal, space group P¯421c, a = b = 24.770 (3) Å, c = 12.658 (4) Å, Z = 8. The surprising reaction of 5 with proton acids leading to the formation of various phosphorus containing five‐ and six‐membered ring compounds is discussed. On reaction of one of the six‐membered ring compounds (9) with magnesium in THF, a λ3, λ5‐diphosphaphenanthrene (19) was obtained.
A phosphoranide (10‐P‐4) anion coordinating to transition metals, as a Lewis base and a π‐acceptor
Authors: Chopra Suman K. , Martin J. C. 
Published: January 2005

AbstractThe reaction of 10‐P‐5 hydridophosphorane 6 with KH provides the 10‐P‐4 potassium phosphoranide anion 7a. Anion 7a reacts with CpFe(CO)2I and BrAu(PEt3) to replace the halide with the phosphoranide as a monodentate ligand forming 8 and 9. The X‐ray structure of 8 shows that the equatorial—Fe(CO)2Cp ligand of 8 makes the apical PO bonds (1.824 Å) longer than the PO bonds (1.80 Å) of the phosphoranide oxide anion 10. The PO bonds (1.75 Å) of 6, with an equatorial proton ligand, are still shorter. This provides evidence that the—Fe(CO)2Cp ligand is not only a sigma‐acceptor Lewis acid ligand, but also a pi‐donor that transfers electrons into the OPO three‐center bond's anti‐bonding orbital to increase its P—O bond lengths. It is a better pi‐donor than the O− pi‐donor of phosphoranide oxide 10.
Unusual formation of a λ 6P‐tetrafluorophosphate involving intramolecular donor–acceptor interaction; x‐ray crystal structure analysis and temperature‐dependent NMR‐spectra
Authors: Kaukorat Thomas , Jones Peter G. , Schmutzler Reinhard 
Published: January 2005

AbstractThe N,N,N′‐trimethylethylenediaminetetrafluorophosphate, 4, was formed in the unusual reaction of N,N,N′‐trimethyl‐N′‐trimethylsilylethylenediamine, 1, with the NP‐bonded tetrafluorophosphoranes, dimethylaminotetrafluorophosphorane, 2, or morpholinotetrafluorophosphorane, 3. There was no evidence for the cleavage of a PF bond in the tetrafluorophosphoranes (with formation of Me3SiF); instead, the SiN compounds, R2NSiMe3 (R2 = Me2 or O(CH2CH2)2) were formed. The 19F and 31P NMR spectra of 4 at room temperature indicated dynamic behavior. The X‐ray crystal structure analysis of 4 revealed the presence of a five‐membered ring, formally as a result of intramolecular donor–acceptor interaction (PN = 196.5 pm) between the nitrogen atom of the Me2N group and phosphorus.
The synthesis of P‐chiral optically pure phosphorothioates, phosphorotrithioates, phosphoroselenothioates, methanephosphonothioates, and methylphenylphosphinothioates
Authors: KrzyżZanowska BożZenna , Stec Wojciech J. 
Published: January 2005

AbstractEnantiomers of representative alkyl esters of phosphorothioic (7), phosphorodithioic (6), phosphorotrithioic (11), phosphoroselenothioic (9), methanephosphonothioic (28), methanephosphonodithioic (25), and methylphenylphosphinothioic (31) acids were prepared from corresponding pure diastereoisomers of N‐[R(+)‐ or S(‐)‐α‐methylbenzyl] phosphamidochalcogenates (e.g. 2, 3, 12, 17, 23, 26, and 30) via PN → PX conversion, which has been proved to proceed with full retention of configuration at phosphorus.
Peculiarities of pπpπ conjugation in aminosubstituted phosphaalkenes
Authors: Chernega Alexander N. , Ruban Alexander V. , Romanenko Vladislav D. , Markovski Leonid N. , Korkin Anatoly A. , Antipin Mikhail Yu. , Struchkov Yuri T. 
Published: January 2005

AbstractEffets of pπpπ conjugation in phosphaalkenes have been considered by taking into account the results of X‐ray structural studies and ab initio quantum‐chemical calculations. The structural consequences of the conjugation depend to a certain extent on the character of the substituent and the place of its attachment to the double PC bond. Depending on the location of the substituent, bond polarization may strengthen or weaken (compensate for) the conjugation effects. A high contribution of the s‐character of the lone electron pair of the P atom is an essential feature of the electron structure of a phosphaalkene.