bluuebunny/crossref_metadata_2025_split huggingface dataset:
Effect of cyclosporin A treatment on the enteropathy of graft‐versus‐host reaction in the rat: A quantitative study of intestinal morphology, epithelial cell kinetics and mucosal immune activity
Authors: Cummins AG , Munro GH , Miller HRP , Ferguson A 
Published: July 2007

SummaryMucosal graft‐versus‐host reaction (GvHR) of the small intestine exemplifies an immunologically mediated enteropathy that is associated with expansion of mucosal mast cells (MMC). Quantitative measures of intestinal morphology, epithelial cell kinetics and mucosal immune activity were used to assess the effect of the immunosuppressive agent, cyclosporin A (CyA), in ameliorating this enteropathy and on increased activity of MMC in the jejunum. GvHR was induced in two groups of PVGU × PVGC rats by irradiation (4·50 Gy) and intravenqus injection of PVGC spleen cells (150 × 106). One group remained untreated, while a second group of eight rats was treated with a 50 mg/kg dose of CyA subcutaneously given daily for the first 3 days and then every second day, and which had commenced the day before induction of GvHR. On day 14, all animals were killed. Treatment with CyA prevented intestinal crypt hyperplasia but did not affect villus length, and normalized the crypt cell production rate (CCPR) from 38 to 15 cells/crypt/h (P<0·0001). CyA reduced the number of MMC and jejunal content of the MMC associated protease, rat mucosal mast cell protease II (RMCPII). Mean serum RMCPII concentration was reduced from 302 (s.d. = 112) in GvHR animals to 10 (s.d. = 6) ng/mL in GvHR/CyA‐treated rats (P<0·0001). We conclude that CyA ameliorates the enteropathy of GvHR and depresses the activation of MMC, as evident by the strongly depressed serum RMCPII concentration.
Genetically‐restricted effector molecules released by human lymphocytes in response to early pregnancy factor
Authors: Rolfe Barbara , Quinn Kathryn , Athanasas Stavrosia , Cavanagh Alice , Morton Halle 
Published: July 2007

SummaryThe binding of early pregnancy factor (EPF) to lymphocytes stimulates the release of soluble effector molecules. Studies in mice have shown that it is these factors rather than EPF as such which are inhibitory in the T cell‐dependent reactions, the adoptive transfer of contact sensitivity and the rosette inhibition test. Two factors have been identified: mEPF‐S1 (Mr ∼15 000) is major histocompatibility complex (MHC)‐restricted while mEPF‐S2 (Mr ∼55 000) is restricted to a locus (or loci) outside the MHC. In the present paper, evidence is presented which shows that EPF also induces the release of soluble mediators from human lymphocytes. With the rosette inhibition test two factors have been detected, both of similar size and genetic restriction to those described previously in the mouse. One factor, designated hEPF‐S1 (Mr 14‐18 000), is human lymphocyte antigen (HLA)‐restricted and the other, hEPF‐S2 (Mr 50‐60 000), appears to be restricted to a locus (or loci) outside the HLA complex.
Immunolocalization of collagenase in neoplastic epithelial cells
Authors: Whitelock JM , O'Grady RL , Lyons JG 
Published: July 2007

SummaryThe distribution of interstitial collagenase in a rat mammary carcinoma model system has been studied by immunocytochemistry. Rabbit antibodies were raised against collagenase from neoplastic epithelial cells which were derived from an anaplastic, invasive, rat mammary carcinoma (BC1). Specificity of the antibodies was determined by Western blot analysis which showed reactivity with the inactive procollagenase from conditioned culture medium of BC1 cells as well as with purified, active BC1 collagenase. Anti‐BC1 collagenase antibodies did not recognize BC1 collagenase entrapped by the inhibitor, rat α‐2‐macroglobulin (α2M), or collagenase derived from TPA‐stimulated human fibroblasts. Anti‐human fibroblast collagenase antibodies did not recognize BC1 collagenase, suggesting that the human‐mesenchymal and rat‐epithelial enzymes are immunologically distinct molecules.Collagenase was immunolocalized intracellularly in BC1 cells cultured in the presence of monensin. Neither BC1 collagenase, α2M nor enzyme‐inhibitor complexes were demonstrated in or around invading tumours by immunostaining of tissue sections of rat mammary carcinomas.
Transfection of genes for human cell surface antigens identified by monoclonal antibodies
Authors: Cole SR , Kriek GW , Hope RM , Ashman LK 
Published: July 2007

SummarySix murine L cell lines expressing five different human cell surface antigens have been prepared by DNA‐mediated gene transfer. Ltk− cells were transfected with calcium phosphate co‐precipitates of human genomic DNA and a plasmid containing the Herpes simplex thymidine kinase gene. After HAT selection, transfectants expressing specific cell surface antigens were identified by in situ immune resetting using monoclonal antibodies. In this way, transfected cell lines expressing the CD9 antigen, the CD31 antigen (two lines), a unique platelet antigen, an X‐linked antigen (R1), and a previously unreported monocyte antigen 11D1 were prepared. These cell lines have proved useful in the definitive assignment of monoclonal antibodies to specific CD groups. In addition, they provide a source of mRNA for use in expression cloning of the genes for these antigens.
Reduced immunostaining for c‐kit receptors in mucosal mast cells in inflammatory bowel disease
Authors: Farhadi Ashkan , Keshavarzian Ali , Fields Jeremy Z , Jakate Shriram , Shaikh Maliha , Banan Ali 
Published: July 2007

AbstractBackground and Aim:  The deleterious effects of stress in inflammatory bowel disease (IBD) have been attributed to activation of the brain–gut axis (BGA) and its end effectors, mast cells (MC). We previously showed that cold pressor stress test (CPT) results in increased activation and degranulation (but not increased proliferation) of mucosal MC, mitochondrial damage to epithelial cells and mucosal protein oxidation in both healthy controls and IBD patients. These changes are more marked in IBD patients. This increased activation of MC in IBD could be due to (i) greater activation of the BGA or (ii) inherited or acquired abnormalities in mucosal MC. In the current study we investigated the latter possibility.Methods:  To assess the effects of stress on mucosal MC in patients with IBD, seven controls and 15 subjects with inactive IBD underwent 5 consecutive days of CPT to activate the BGA. Endoscopic mucosal biopsies of the distal sigmoid colon were taken during unprepared sigmoidoscopy before the first CPT and after the last CPT, and formalin‐fixed samples were stained for both MC granules (MCg) and for the c‐kit receptor, which is present on MC membranes (MCm). Mast cell degranulation was assessed using electron microscopy.Results:  Mast cell granule staining suggested that IBD subjects do not have a significantly different number of MC compared with controls, either before or after stress. Mast cell membrane staining, in contrast, suggested that MC c‐kit immunostaining was significantly reduced – at both baseline (P = 0.01) and post stress (P = 0.04) samples – in IBD patients compared to controls. MC c‐kit immunostaining was independent of stress‐induced MC degranulation. There was no significant change in MC number as a result of the stress intervention using either staining method in both groups.Conclusion:  These data support our previous report that the size of the mucosal MC population in patients with inactive IBD is not altered by disease or by stress, yet MC in IBD are different (fewer c‐kit receptors) and respond differently (greater activation) than MC in control subjects. It remains to be seen whether this abnormality is an inherited or acquired one and to identify its role and mechanism in tissue injury in the pathogenesis of IBD.
Surgical management of endometriosis
Authors: Kenney Nicholas , English James 
Published: July 2007

Key content

Advances in laparoscopic surgery have made the surgical management of endometriosis an effective treatment that offers advantages over medical therapy.
The majority of gynaecologists readily perform laparoscopic ablation of superficial disease. Excision of deeper disease and management of rectovaginal disease require more expertise and should be managed in tertiary centres.
Hysterectomy should not be necessary in the majority of cases. Although some women may benefit, extrauterine disease should also be excised.
Evidence suggests that laparoscopic uterine nerve ablation (LUNA) has no effect on long‐term symptoms.
There is no consensus as to the optimal surgical approach for rectal disease. A multicentre, randomised controlled trial is urgently required to resolve the issue.

Learning objectives

To understand the role of surgery in the management of endometriosis.
To be aware of the best available evidence so that the optimal approach can be used when performing surgery.
To be aware of the preoperative care of women with advanced disease and when to refer them for further management.

Ethical issues

What should be regarded as an acceptable complication rate for women undergoing surgery for advanced endometriosis?
What level of training should gynaecologists reach if they are to be judged competent in the surgical management of endometriosis?
Given that the surgical management of endometriosis is a developing skill, where is the boundary between accepted and acceptable practice?

Please cite this article as: Kenney N, English J. Surgical management of endometriosis. The Obstetrician & Gynaecologist 2007;9:147–152.
Bis(azidomethyl) oxetane/hydroxyl‐terminated polybutadiene/bis(azidomethyl) oxetane triblock copolymer: Synthesis and characterization
Authors: Reddy T. S. , Nair J. K. , Satpute R. S. , Wagh R. M. , Sikder A. K. , Venugopalan S. 
Published: July 2007

AbstractA copolymer consisting of bis(azidomethyl) oxetane and hydroxyl‐terminated polybutadiene was synthesized with different monomer ratios via an activated monomer mechanism. The copolymer thus obtained was characterized with Fourier transform infrared, 1H‐NMR, molecular weight, and polydispersity measurements. Rhe‐ological and thermal studies were also carried out. The mechanical properties of the gum stock obtained through curing with toluene diisocyanate and crosslinking with pyrogallol at about 50°C were also determined. This was an attempt to combine the useful properties of hydroxyl‐terminated polybutadiene (a nonenergetic binder providing excellent mechanical properties) and poly[bis(azidomethyl) oxetane] (an energetic binder). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007
Diastereoselective Synthesis of 4‐Hydroperoxy‐3,5‐cyclohexadienones in the Photooxygenation of Hydroxyethyl‐Substituted Phenols
Authors: Prein Michael , Maurer Michael , Peters Eva Maria , Peters Karl , von Schnering Hans Georg , Adam Waldemar 
Published: July 2007

AbstractThree of the four possible isomeric para‐substituted hydroxyethyl‐methylphenols were prepared from readily available starting materials and submitted to photooxygenation. In the case of 3‐hydroxy‐α,6‐dimethylbenzenemethanol (1 a) and 2‐hydroxy‐α,5‐dimethylbenzene‐methanol (1 b) the corresponding 4‐hydroperoxy‐3,5‐cyclohexadienones were obtained as oxy‐functionalized products (⩾90%, d.r. 85:15 and 75:15). The stereochemistry of the products was assigned after reduction to the corresponding p‐quinols. The ready cleavage of the initial oxygenated product, which can be observed at low temperature as a single diastereomer, prevented rigorous assignment of the π‐facial selectivity of the singlet oxygen attack for the derivative 4‐hydroxy‐α,2‐dimethylbenzenemethanol (1 c). The present stereochemical results indicate that the hydroxyl group directing effect, that is, coordination of the incoming singlet oxygen dienophile with the hydroxyl group, is also operating in the photooxygenation of the chiral phenols 1 a‐c. However, in the case of the derivative 1 b, hydrogen bonding in the starting material leads to an opposite stereochemical outcome. This conclusion is further substantiated by solvent effects and the fact that the methyl ether 1 d of alcohol 1 c displays a significant lower diastereoselectivity.
Synthesis of a Fullerene[60] Cryptate and Systematic Langmuir‐Blodgett and Thin‐Film Investigations of Amphiphilic Fullerene Derivatives
Authors: Jonas Ulrich , Cardullo Francesca , Belik Pavel , Diederich François , Gügel Andreas , Harth Eva , Herrmann Andreas , Isaacs Lyle , Müllen Klaus , Ringsdorf Helmut , Thilgen Carlo , Uhlmann Peter , Vasella Andrea , Waldraff Christian A. A. , Walter Michael 
Published: July 2007

AbstractThe synthesis of the first fullerene cryptate 7 with a sodium ion bound to a benzo[2.2.2]cryptand covalently attached to a methanofullerene[60] is described. The amphiphilic properties of 7 as well as of a variety of other covalent fullerene derivatives with polar functional groups and the ability of these compounds to form Langmuir monolayers at the air‐water interface were investigated in a systematic study. Among these derivatives are Diels‐Alder adducts of C60 and methanofullerenes, four of which are fullerene C‐glycosides. The films at the water surface were characterized by their surface pressure versus molecular area isotherms, compression and expansion cycles, and optical light microscopy. UV/Vis spectroscopy and small‐angle X‐ray diffraction (SAXS) were employed for LB film characterization on solid substrates. Parameters influencing the spreading and monolayer character include (a) polarity, (b) balance of hydrophobicity to hydrophilicity, (c) size and bulkiness of the polar groups attached to the fullerene, and (d) presence of aromatic residues in these groups.
Asymmetric Synthesis of Carboranyl Amino Acids with Potential use in BNCT
Authors: Sjöberg Stefan , Hawthorne M. Frederick , Wilmouth Serge , Lindström Peter 
Published: July 2007

AbstractTwo α‐amino acids containing the 1,2‐dicarba‐closo‐dodecaborane (12) cage, namely, 5‐(1,2‐dicarba‐closo‐dodecaboran (12)‐1‐yl)‐2‐aminopentanoic acid (1) and 5‐(2‐methyl‐1,2‐dicarba‐closo‐dodecaboran (12)‐1‐yl)‐2‐aminopentanoic acid (2), were prepared by asymmetric synthesis (e.p. > 98%) by using the chiral glycine equivalent, imidazolidinone 3, introduced by Seebach, and Oppolzer's camphor‐derived sultam derivative 4. The dextrorotatory enantiomers (sodium D line in methanol) of the amino acids 1 and 2 were both shown to have (S) configuration.
Semiconductor‐Catalysed Photoaddition of Olefins and Enol Ethers to 1,2‐Diazenes: A New Route to Allylhydrazines
Authors: Künneth Ronald , Feldmer Christian , Knoch Falk , Kisch Horst 
Published: July 2007

AbstractSuspensions of zinc or cadmium sulfide powders in a protic solvent catalyse the linear addition of enol ethers and olefins to 1,2‐diaryl‐ and 1‐aryl‐2‐alkyl‐1,2‐diazenes, producing allylhydrazine derivatives. Relative quantum yields decrease sharply when the 1,2‐diazene is more difficult to reduce, while their relationship to the oxidation potential of the enol ether/olefin is complicated. Reduction to 1,2‐diarylhydrazine and concomitant dehydrodimerization of the enol ether occurs as a side reaction. It is favoured by increasing light intensity and becomes the major reaction path when platinized (5 mol%) photocatalysts are employed. It is proposed that the photogenerated electron‐hole pair in a proton‐coupled electron transfer reduces the diazene to a hydrazyl radical and oxidizes the olefin/enol ether to a radical cation. The allylic radical obtained from the latter by deprotonation then undergoes CN coupling with the hydrazyl radical to afford the allylhydrazine. Diarylhydrazine formation occurs by disproportionation of the hydrazyl radical or by a successive proton‐coupled reduction. Thus photoaddition can be classified as a 1 e−/1 h+ process while 2e−/2h+ are necessary for the reduction.
Magnetic and Structural Studies of Copper–Lanthanoid Complexes; the Synthesis and Structures of New Cu3Ln Complexes of 6‐chloro‐2‐Pyridone (Ln = Gd, Dy and Er) and Magnetic Studies on Cu2Gd2, Cu4Gd2 and Cu3Gd Complexes
Authors: Benelli Cristiano , Blake Alexander J. , Milne Paul E. Y. , Rawson Jeremy M. , Winpenny Richard E. P. 
Published: July 2007

AbstractThe synthesis and structural characterisation of three copper–lanthanoid complexes are reported. The compounds, of general formula [Cu3M(chp)8(NO3)(S)] [M = Gd, S = H2O in 2; M = Dy, S = H2O in 3; M = Er, S = (H2O)0.5(MeOH)0.5 in 4; chp = anion of 6‐chloro‐2‐pyridone], are made by reaction of [Cu2(chp)4] (1) with the hydrated lanthanoid nitrate salt in methanol. Structural studies reveal the three copper atoms lie in an approximate hemisphere about a central lanthanoid atom. Magnetic studies on 2 and two further Cu–Gd complexes show ferromagnetic coupling between the 3d and 4f metals. Consideration of these results along with magnetic data previously reported for Cu–Gd compounds leads to a correlation between the magnitude of this exchange coupling and the exponential of the Cu…Gd distance. This is the first magneto‐structural correlation reported for mixed d‐block/f‐block metal complexes.
The Role of Porphyrin‐to‐Porphyrin Linkage Topology in the Extensive Modulation of the Absorptive and Emissive Properties of a Series of Ethynyl‐ and Butadiynyl‐Bridged Bis‐ and Tris(porphinato)zinc Chromophores
Authors: Lin Victor S.‐Y. , Therien Michael J. 
Published: July 2007

AbstractA new method for the regulation of the photophysical properties of highly conjugated porphyrin arrays is described. The absorptive and emissive signatures of such supramolecular structures can be modulated to an impressive degree by regulation of: i) the extent of the steric interactions that define the barrier to rotation about the conjugated bridge between the porphyrin chromophores, and ii) the magnitude of ground state chromophore–chromophore electronic communication within the supermolecule. The power of this approach is illustrated by the straightforward synthesis as well as the electronic and emission spectra of eight different porphyrin arrays in which (5,10,15,20‐tetraphenylporphinato)zinc(11) and (10,20‐diphenylporphinato)zinc(11) complexes are joined by ethyne or butadiyne groups. The points of connectivity of these bridges between the chromophoric building blocks are systematically varied to produce a series of supramolecular structures with meso‐to‐meso, meso‐to‐β, or β‐to‐β linkage topologies. These variations allow excellent control of the ground‐ and excited‐state characteristics of the arrays in the series by regulating the degree of both excitonic and electronic porphyrin‐to‐porphyrin coupling. Our approach shows the precision with which photophysical properties can be engineered in appropriately designed supramolecular systems.
Ruthenium‐Catalyzedcis‐Dihydroxylation of Alkenes: Scope and Limitations
Authors: Shing Tony K. M. , Tam Eric K. W. , Tai Vincent W.‐F. , Chung Ivan H. F. , Jiang Qin 
Published: July 2007

AbstractOxidative ruthenium catalysis (0.07 molequiv RuCl3·(H2o)3, 1.5 molequiv NaIO4, EtOAc/CH3CH3CN/H2O 3:3:1), beyond the usual CC bond cleavage to give dicarbonyls, has been shown tosyn‐dihydroxylate a wide range of alkenes (except for strained bicyclic alkenes, sterically hindered trisubstituted alkenes, and most tetrasubstituted alkenes) to give vicinal diols rapidly (within minutes) and efficiently. The minor products are the usual oxidative fission products, namely, ketones and aldehydes or carboxylic acids, and sometimes ketols. Longer reaction times lower the yields of most diols, probably owing to oxidative glycol cleavage. Reactions with substrates containing one or more electron‐with‐drawing groups in conjugation with or adjacent to the alkene moiety are generally slower but give better yields. The diastereoselectivity of the present “flash” dihydroxylation,antito the existing α‐stereogenic center, with cycloalkenes is excellent whereas that with acyclic alkenes is moderate to poor. Sodium metaperiodate is still the best co‐oxidant for the catalytic reaction. Aqueous acetonitrile (approximately 86%) as an alternative solvent system was found to give better yields of 1,2‐diols than the original solvent system in some cases.
Solvent Effect on the NMR Chemical Shieldings in Water Calculated by a Combination of Molecular Dynamics and Density Functional Theory
Authors: Malkin Vladimir G. , Malkina Olga L. , Steinebrunner Gerold , Huber Hanspeter 
Published: July 2007

AbstractThe solvent effect on the NMR chemical shielding in liquid water is calculated from a combination of molecular dynamics simulations and quantum chemical calculations for protons and 17O. The simulations are performed with three different potentials, ab initio as well as empirical ones, to study the influence of the force field. From the liquid configurations obtained in these simulations, molecules are randomly chosen together with neighbouring molecules to give clusters of water typical for the liquid at the selected temperature and density. Different cluster sizes are studied. The clusters are treated as supermolecules in quantum chemical calculations of chemical shifts by sum‐over‐states density functional perturbation theory with individual gauge for localised orbitals. The influence of the quantum chemical method is studied with an ab initio coupled Hartree‐Fock gauge including atomic orbitals calculations with different basis sets for a selected cluster. An average over clusters yields the chemical shielding in the liquid at the selected temperature and density. The calculated values for the gas–liquid shift, which are in best agreement with experiment, are –3.2 ppm (exp. –4.26 ppm) for the proton and –37.6 ppm (exp. –36.1 ppm) for 17O, but the results depend strongly on the chosen interatomic potential.
Versatile Synthesis of Enantiomerically Pure 2‐Alkoxy‐1‐Ethynylcyclopropanes and their Application in the Synthesis of Enantiomerically Pure Bicyclo‐[3.3.0]oct‐1‐en‐3‐ones
Authors: Bräse Stefan , Schömenauer Sten , McGaffin Gregory , Stolle Andreas , de Meijere Armin 
Published: July 2007

AbstractA variety of chiral, nonracemic 2‐alkoxy‐1‐alkynylcyclopropanes 7 were synthesized in good to very good yields from enantiomerically pure glycidol derivatives (glycidol tosylate, epichlorohydrin) by boron trifluoride promoted addition of lithium trimethylsilylacetylide followed by protection of the secondary hydroxyl group and finally a diastereoselective γ‐elimination. The 2‐ethoxy derivative (S,R)‐7 b was deprotonated with n‐butyllithium, and the resulting 1‐lithio‐2‐ethoxy derivative (S,R)‐20 functionalized by treatment with oxygen followed by tosyl chloride. Protodesilylation and catalytic hydrogenation smoothly furnished 1‐ethenylcyclopropyl sulfonates, which underwent a clean Pd0‐catalyzed SN2′‐type substitution with dimethyl propargylsodiummalonate to give the (E)‐configurated enyne (R,E)‐26 with a methylenecyclopropane end group. A diastereoselective Pauson–Khand reaction completed the sequence to give the enantiomerically pure spirocyclopropaneannelated bicyclo[3.3.0]octane derivative 31.
Porphyrin Synthesis by the “3+1” Approach: New Applications for an Old Methodology
Authors: Lash Timothy D. 
Published: July 2007

AbstractAcid‐catalyzed condensation of tripyrranes with pyrrole‐2,5‐dicarboxaldehydes, followed by oxidation with an electron‐deficient quinone, affords porphyrin products in excellent yields. This previously little used methodology has now been exploited in the synthesis of novel porphyrin structures, including tetrapyrrolic compounds with fused aromatic rings. By utilizing other aromatic or unsaturated dialdehydes, the “3+1” approach also allows the synthesis of new aromatic porphyrinoid systems, including benzene‐ and pyridine‐containing macrocycles and carbaporphyrins.