bluuebunny/crossref_metadata_2025 huggingface dataset:
Psychoanalytic perspectives on the treatment of an acute suicidal crisis
Authors: Maltsberger John T. , Weinberg Igor
Published: December 2005

The psychoanalytic understanding of suicide has greatly expanded in the past 30 years, and the older therapeutic approach has been modified. Although the turning of murder on the self inferred by Freud 90 years ago remains a cornerstone, current practice concentrates on the identification of a precipitating event, the escalation of intolerable painful affect that the patient cannot moderate, the self‐perception of helplessness, the evolution of hopelessness as a secondary affect, increasing fantasies of suicide as a means of escape, and ego regression (self‐deconstruction), leading progressively to suicide. Recent clinical research, advances in the study of cognition, and neurobiological studies have contributed to the reorientation and enrichment of the psychoanalytic perspective on suicide. The treatment of a university student who had fallen into a suicide crisis is discussed from the psychoanalytic point of view, and evidence for the efficacy of this treatment is reviewed. © 2005 Wiley Periodicals, Inc. J Clin Psychol: In Session 62: 223–234, 2006.
Structure of the PRYSPRY‐domain: Implications for autoinflammatory diseases
Authors: Grütter Christian , Briand Christophe , Capitani Guido , Mittl Peer R.E. , Papin Stephanie , Tschopp Jürg , Grütter Markus G.
Published: December 2005

We determined the first structure of PRYSPRY, a domain found in over 500 different proteins, involved in innate immune signaling, cytokine signaling suppression, development, cell growth and retroviral restriction. The fold encompasses a 7‐stranded and a 6‐stranded antiparallel β‐sheet, arranged in a β‐sandwich. In the crystal, PRYSPRY forms a dimer where the C‐terminus of an acceptor molecule binds to the concave surface of a donor molecule, which represents a putative interaction site. Mutations in the PRYSPRY domains of Pyrin, which are responsible for familial Mediterranean fever, map on the putative PRYSPRY interaction site.
Activation of naïve B lymphocytes via CD81, a pathogenetic mechanism for hepatitis C virus-associated B lymphocyte disorders
Authors: Rosa Domenico , Saletti Giulietta , De Gregorio Ennio , Zorat Francesca , Comar Consuelo , D'Oro Ugo , Nuti Sandra , Houghton Michael , Barnaba Vincenzo , Pozzato Gabriele , Abrignani Sergio
Published: December 2005

Infection with hepatitis C virus (HCV), a leading cause of chronic liver diseases, can associate with B lymphocyte proliferative disorders, such as mixed cryoglobulinemia and non-Hodgkin lymphoma. The major envelope protein of HCV (HCV-E2) binds, with high affinity CD81, a tetraspanin expressed on several cell types. Here, we show that engagement of CD81 on human B cells by a combination of HCV-E2 and an anti-CD81 mAb triggers the JNK pathway and leads to the preferential proliferation of the naïve (CD27-) B cell subset. In parallel, we have found that B lymphocytes from the great majority of chronic hepatitis C patients are activated and that naïve cells display a higher level of activation markers than memory (CD27+) B lymphocytes. Moreover, eradication of HCV infection by IFN therapy is associated with normalization of the activation-markers expression. We propose that CD81-mediated activation of B cellsin vitrorecapitulates the effects of HCV binding to B cell CD81in vivoand that polyclonal proliferation of naïve B lymphocytes is a key initiating factor for the development of the HCV-associated B lymphocyte disorders.
Differential autocrine modulation of atrial and ventricular potassium currents and of oxidative stress in diabetic rats
Authors: Shimoni Yakhin , Hunt Don , Chen Keyun , Emmett Teresa , Kargacin Gary
Published: December 2005

The autocrine modulation of cardiac K+ currents was compared in ventricular and atrial cells (V and A cells, respectively) from Type 1 diabetic rats. K+ currents were measured by using whole cell voltage clamp. ANG II was measured by ELISA and immunofluorescent labeling. Oxidative stress was assessed by immunofluorescent labeling with dihydroethidium, a measure of superoxide ions. In V cells, K+ currents are attenuated after activation of the renin-angiotensin system (RAS) and the resulting ANG II-mediated oxidative stress. In striking contrast, these currents are not attenuated in A cells. Inhibition of the angiotensin-converting enzyme (ACE) also has no effect, in contrast to current augmentation in V cells. ANG II levels are enhanced in V, but not in A, cells. However, the high basal ANG II levels in A cells suggest that in these cells, ANG II-mediated pathways are suppressed, rather than ANG II formation. Concordantly, superoxide ion levels are lower in diabetic A than in V cells. Several findings indicate that high atrial natriuretic peptide (ANP) levels in A cells inhibit RAS activation. In male diabetic V cells, in vitro ANP (300 nM–1 μM, >5 h) decreases oxidative stress and augments K+ currents, but not when excess ANG II is present. ANP has no effect on ventricular K+ currents when the RAS is not activated, as in control males, in diabetic males treated with ACE inhibitor and in diabetic females. In conclusion, the modulation of K+ currents and oxidative stress is significantly different in A and V cells in diabetic rat hearts. The evidence suggests that this is largely due to inhibition of RAS activation and/or action by ANP in A cells. These results may underlie chamber-specific arrhythmogenic mechanisms.
Atorvastatin-induced cardioprotection is mediated by increasing inducible nitric oxide synthase and consequent S-nitrosylation of cyclooxygenase-2
Authors: Atar Shaul , Ye Yumei , Lin Yu , Freeberg Sheldon Y. , Nishi Shawn P. , Rosanio Salvatore , Huang Ming-He , Uretsky Barry F. , Perez-Polo Jose R. , Birnbaum Yochai
Published: December 2005

We determined the effects of cyclooxygenase-1 (COX-1; SC-560), COX-2 (SC-58125), and inducible nitric oxide synthase (iNOS; 1400W) inhibitors on atorvastatin (ATV)-induced myocardial protection and whether iNOS mediates the ATV-induced increases in COX-2. Sprague-Dawley rats received 10 mg ATV·kg−1·day−1 added to drinking water or water alone for 3 days and received intravenous SC-58125, SC-560, 1400W, or vehicle alone. Anesthesia was induced with ketamine and xylazine and maintained with isoflurane. Fifteen minutes after intravenous injection rats underwent 30-min myocardial ischemia followed by 4-h reperfusion [infarct size (IS) protocol], or the hearts were explanted for biochemical analysis and immunoblotting. Left ventricular weight and area at risk (AR) were comparable among groups. ATV reduced IS to 12.7% (SD 3.1) of AR, a reduction of 64% vs. 35.1% (SD 7.6) in the sham-treated group ( P < 0.001). SC-58125 and 1400W attenuated the protective effect without affecting IS in the non-ATV-treated rats. ATV increased calcium-independent NOS (iNOS) [11.9 (SD 0.8) vs. 3.9 (SD 0.1) × 1,000 counts/min; P < 0.001] and COX-2 [46.7 (SD 1.1) vs. 6.5 (SD 1.4) pg/ml of 6-keto-PGF1α; P < 0.001] activity. Both SC-58125 and 1400W attenuated this increase. SC-58125 did not affect iNOS activity, whereas 1400W blocked iNOS activity. COX-2 was S-nitrosylated in ATV-treated but not sham-treated rats or rats pretreated with 1400W. COX-2 immunoprecipitated with iNOS but not with endothelial nitric oxide synthase. We conclude that ATV reduced IS by increasing the activity of iNOS and COX-2, iNOS is upstream to COX-2, and iNOS activates COX-2 by S-nitrosylation. These results are consistent with the hypothesis that preconditioning effects are mediated via PG.
CXCR3 surface expression in human airway epithelial cells: cell cycle dependence and effect on cell proliferation
Authors: Aksoy Mark O. , Yang Yi , Ji Rong , Reddy P. J. , Shahabuddin Syed , Litvin Judith , Rogers Thomas J. , Kelsen Steven G.
Published: December 2005

We recently demonstrated that human bronchial epithelial cells (HBEC) constitutively express the CXC chemokine receptor CXCR3, which when activated, induces directed cell migration. The present study in HBEC examined the relative expression of the CXCR3 splice variants CXCR3-A and -B, cell cycle dependence of CXCR3 expression, and the effects of the CXCR3 ligand, the interferon-γ-inducible CXC chemokine I-TAC/CXCL11, on DNA synthesis and cell proliferation. Both CXCR3-A and -B mRNA, assessed by real-time RT-PCR, were expressed in normal HBEC (NHBEC) and the HBEC line 16-HBE. However, CXCR3-B mRNA was 39- and 6-fold greater than CXCR3-A mRNA in NHBEC and 16-HBE, respectively. Although most HBEC (>80%) assessed by flow cytometry and immunofluorescence microscopy contained intracellular CXCR3, only a minority (<40%) expressed it on the cell surface. In this latter subset of cells, most (>75%) were in the S + G2/M phases of the cell cycle. Stimulation of CXCR3 with I-TAC enhanced thymidine incorporation and cell proliferation and increased p38 and ERK1/2 phosphorylation. These data indicate that 1) human airway epithelial cells primarily express CXCR3-B mRNA, 2) surface expression of CXCR3 is largely confined to the S + G2/M phases of the cell cycle, and 3) activation of CXCR3 induces DNA synthesis, cell proliferation, and activation of MAPK pathways. We speculate that activation of CXCR3 exerts a mitogenic effect in HBEC, which may be important during airway mucosal injury in obstructive airway diseases such as asthma and chronic obstructive pulmonary disease.
Enhancing Density-Based Data Reduction Using Entropy
Authors: Huang D. , Chow Tommy W. S.
Published: December 2005

Data reduction algorithms determine a small data subset from a given large data set. In this article, new types of data reduction criteria, based on the concept of entropy, are first presented. These criteria can evaluate the data reduction performance in a sophisticated and comprehensive way. As a result, new data reduction procedures are developed. Using the newly introduced criteria, the proposed data reduction scheme is shown to be efficient and effective. In addition, an outlier-filtering strategy, which is computationally insignificant, is developed. In some instances, this strategy can substantially improve the performance of supervised data analysis. The proposed procedures are compared with related techniques in two types of application: density estimation and classification. Extensive comparative results are included to corroborate the contributions of the proposed algorithms.
Topographic Product Models Applied to Natural Scene Statistics
Authors: Osindero Simon , Welling Max , Hinton Geoffrey E.
Published: December 2005

We present an energy-based model that uses a product of generalized Student-t distributions to capture the statistical structure in data sets. This model is inspired by and particularly applicable to “natural” data sets such as images. We begin by providing the mathematical framework, where we discuss complete and overcomplete models and provide algorithms for training these models from data. Using patches of natural scenes, we demonstrate that our approach represents a viable alternative to independent component analysis as an interpretive model of biological visual systems. Although the two approaches are similar in flavor, there are also important differences, particularly when the representations are overcomplete. By constraining the interactions within our model, we are also able to study the topographic organization of Gabor-like receptive fields that our model learns. Finally, we discuss the relation of our new approach to previous work—in particular, gaussian scale mixture models and variants of independent components analysis.
The Moral Politics of IMF Reforms: Universal Economics, Particular Ethics
Authors: Best Jacqueline
Published: December 2005

The IMF's response to recent financial crises has involved the development of an extensive series of international economic standards that it believes all states should adopt. Fund representatives have justified these reforms by using explicitly moral arguments. In this chapter, I take a closer look at this new turn in order to determine its implications for both financial governance and political ethics. I suggest that although ethical discourse has historically played a crucial role in sustaining financial regimes, the recent turn to moralize finance is novel, for it represents a new kind of economic and ethical liberalism.
The Journey of Excellence: A South Dakota Nursing Program’s Response to Community Needs
Authors: Larson June , Benedict Linda , Brown Robin , Feller Lisa M.
Published: December 2005

This article describes unique partnerships between South Dakota communities and the University of South Dakota that have been established for the purpose of assuring that nursing education opportunities are provided to individuals who are tied to the land. This includes those individuals who cannot uproot their families and move to Vermillion, the home of the University of South Dakota. As a result of these partnerships, there are hundreds of nurses throughout this state practicing nursing rather than dreaming of being a nurse. These registered nurses are providing quality nursing care within the very community that supports the educational efforts, and in turn this approach is addressing the nursing shortage.
Rural South Dakota: The Power of Education and Care Delivery Partnerships
Authors: Feller Lisa M. , Hunsley-McTighe Amy , Ray Annette L. , Schliessmann Lucia A. M.
Published: December 2005

Central South Dakota is a picture of plains, the Missouri River, small towns, ranches, farms, and reservations. This is the setting for the University of South Dakota Department of Nursing, Pierre Campus. The nursing program is a partner with Capital University Center in providing an opportunity that would otherwise be out of reach for students in the central area of the state. Students travel from surrounding towns to attend classes and clinicals, often spending much of the week away from home. Hardiness, pulling from within to overcome any odds and getting by with whatever is available, is seen in the student population. Campus resources are scarce. Partnerships with community groups and leaders enable students to access services readily found on traditional campuses. This important element of community is what makes the nursing program such a unique product that is shared and owned by the people of central South Dakota.
Nursing Education and Nursing Service Partnership: Teaching Leadership Online
Authors: Karpuk Lorall , Manning Kathy , Larson June , Benedict Linda , Yockey Jean
Published: December 2005

In collaboration with practicing nurse leaders, a nursing leadership course was delivered online to a diverse community of learners. The University of South Dakota serves a state population where half of the counties qualify as frontier, and 11 Indian reservations are located within its borders. Today’s professional nurse must have skills to provide leadership and management to deliver effective health care to the community. This article highlights the partnership with rural and urban nurse leaders to jointly teach an online leadership course in an associate of science nursing degree program. This partnership, in concert with an interactive online course, creates a community of learners who benefit from a group of practicing nurse leaders. Identification and steps to recruit nurse leaders are outlined. A description of the course content and overall design is provided. To engage class participants, a variety of interactive teaching strategies are detailed. Testimonials of nurse leaders are presented.
Original surface treatment of copper alloy in ancient Roman Empire: Chemical patination on a Roman strigil
Authors: Mathis F. , Descamps S. , Robcis D. , Aucouturier M.
Published: December 2005

Metal polychromy has been widely used for decorating metallic artworks from ancient antiquity. In Hellenistic and Roman periods, the famous Corinthian bronzes (Corinthium aes) are a typical example of the skill of metallurgical craftsmen striving to obtain various coloured surfaces on copper based alloys; but the existing investigations are devoted mainly to the ‘black bronzes’ obtained by oxidation in a wet medium of copper–gold alloys. The present study is part of a general programme devoted to research into different kinds of special surface oxidation treatments on copper alloys and their environmental behaviour. For archaeological objects, such treatments are difficult to observe, as a consequence of corrosion degradation. The examination and analysis of objects kept in the Department of Greek, Etruscan and Roman Antiquities of the Louvre Museum have evidenced the occurrence on one of them, a strigil dated from the first century AD, of a new type of decoration. The strigil is made of copper–zinc alloy, and its decoration exhibits orange-red coloured motifs visibly obtained by chemical oxidation. The present paper describes analyses performed using different techniques: microscopy, particle induced X-ray emission, X-ray diffraction, Rutherford backscattering spectrometry, micro-Raman spectroscopy, spectrophotocolorimetry and optical profilometry. The steps of the decoration process are detailed: the motifs were coloured together with the neighbouring surface. This neighbouring surface was further cleaned by a mechanical process to make the motif coloration appear. The present paper attempts to describe how the Roman craftsman obtained the decorated appearance.
Sliding behaviour of ion nitrided AISI 420 stainless steel
Authors: Tuckart W. , Insausti J. , Forlerer E. , Iurman L.
Published: December 2005

This paper provides an analysis of the influence of thermal and surface treatments on sliding wear of AISI 420 stainless steel. The specimens were separated into three batches. One was left in the as-received condition for comparison purposes. The other two were subjected to austenitising, oil quenching and tempering at 673 K. One of them was also plasma nitrided under an atmosphere of 25%N2 and 75%H2, at a temperature of 673 K. All the specimens were tested under different normal loads and pure dry sliding conditions. The wear affected surface and subsurface were studied by means of scanning electron microscopy, and phase identification was determined with X-ray diffraction; changes in contact conditions during tests were analysed; initial and final surface roughness were measured. During the tests, surface temperature and friction coefficients were recorded.
AMPH-IMA04: a revised Hypercard program to determine the name of an amphibole from chemical analyses according to the 2004 International Mineralogical Association scheme
Authors: Mogessie A. , Ettinger K. , Leake B. E.
Published: December 2005

In 2004, the International Mineralogical Association (IMA) amended the IMA 97 amphibole classification and nomenclature scheme byadding a fifth group to include the recently discovered B(LiNa) amphiboles ferriwhittakeriite and ferri-ottoliniite, which cannot be fitted into the four major amphibole groups. New root-names such as sodic-pedrizite in the Mg-Fe-Mn-Li group and obertiite and dellaventuraite in the sodic group along with two new prefixes, parvo and magno have also been added. As result it has become necessary to modify the AMPH-IMA97 amphibole-naming program. The new program (AMPH-IMA04) allows single input or automatic input of as many amphibole analyses as are available following a set input format. Any of three different calculation schemes for dealing with an amphibole analysis can be chosen: (1) complete chemical analyses can be calculated to 24(O,OH,F,Cl); (2) analyses with determined FeO and Fe2O3, MnO and Mn2O3 but without H2O can be calculated to 23(O); and (3) electron microprobe analyses with only total Fe determined and without H2O can be calculated to 23(O) with IMA97-recommended normalization for Fe3+ and Fe2+ values. In addition a stoichiometric calculation of Mn2+ and Mn3+ is considered and implemented for the Mn-bearing sodic amphiboles in order to take care of electron microprobe analyses of such amphiboles where the total Mn is given as Mn2+.
Potential risk factors for diabetic neuropathy: a case control study
Authors: Booya Fargol , Bandarian Fatemeh , Larijani Bagher , Pajouhi Mohammad , Nooraei Mahdi , Lotfi Jamshid
Published: December 2005

Background

Diabetes mellitus type II afflicts at least 2 million people in Iran. Neuropathy is one of the most common complications of diabetes and lowers the patient's quality of life. Since neuropathy often leads to ulceration and amputation, we have tried to elucidate the factors that can affect its progression.

Methods

In this case-control study, 110 diabetic patients were selected from the Shariati Hospital diabetes clinic. Michigan Neuropathic Diabetic Scoring (MNDS) was used to differentiate cases from controls. The diagnosis of neuropathy was confirmed by nerve conduction studies (nerve conduction velocity and electromyography). The multiple factors compared between the two groups included consumption of angiotensin converting enzyme inhibitors (ACEI), blood pressure, serum lipid level, sex, smoking, method of diabetes control and its quality.

Results

Statistically significant relationships were found between neuropathy and age, gender, quality of diabetes control and duration of disease (P values in the order: 0.04, 0.04, < 0.001 and 0.005). No correlation was found with any atherosclerosis risk factor (high BP, hyperlipidemia, cigarette smoking).

Conclusion

In this study, hyperglycemia was the only modifiable risk factor for diabetic neuropathy. Glycemic control reduces the incidence of neuropathy, slows its progression and improves the diabetic patient's quality of life. More attention must be paid to elderly male diabetic patients with poor diabetes control with regard to regular foot examinations and more practical education.
Current views concerning the influences of murine hepatic endothelial adhesive and cytotoxic properties on interactions between metastatic tumor cells and the liver
Authors: Wang Hui Helen , Qiu Hongming , Qi Ke , Orr F William
Published: December 2005

Substantial recent experimental evidence has demonstrated the existence of reciprocal interactions between the microvascular bed of a specific organ and intravascular metastatic tumor cells through expression of adhesion molecules and nitric oxide release, resulting in a significant impact upon metastatic outcomes.

This review summarizes the current findings of adhesive and cytotoxic endothelial-tumor cell interactions in the liver, the inducibility, zonal distribution and sinusoidal structural influences on the hepatic endothelial regulatory functions, and the effects of these functions on the formation of liver cancer metastases. New insights into the traditional cancer metastatic cascade are also discussed.
The last three months of life of Italian cancer patients. Methods, sample characteristics and response rate of the Italian Survey of the Dying of Cancer (ISDOC)
Authors: Costantini Massimo , Beccaro Monica , Merlo Franco ,   ISDOC Study Group
Published: December 2005

Study objective: The Italian Survey of the Dying of Cancer (ISDOC) was undertaken to evaluate the experiences of Italian people dying from cancer during their last three months of life in all settings of care. Study design: A two-stage probability sample was used to estimate end-of-life outcomes of about 160 000 Italian cancer deaths. In the first stage, 30 of the 197 Italian Local Health Districts (LHD) were randomly selected after stratification. In the second stage, a fixed proportion of cancer deaths was randomly drawn from each LHD, and 2000 death certificates of patients who died of cancer were identified. The non-professional caregivers were identified and interviewed using a semi-structured questionnaire derived from the Views of Informal Carers - Evaluation of Services (VOICES). Results: Caregivers were successfully identified for 95% of the sample ( n = 1900). The caregiver was the child (42.7%), the spouse (36.5%), another family member (17.3%), or a friend (1.5%). Only 3% of the sample had no non-professional support. An interview was obtained for 1289 (64.5%) of the sample, at a median time of 234 days after death (range: 103-374). Higher response rates were associated with home death (67.7%) and with a higher education (>70%). Conversely, a lower response rate was observed when the caregiver was the spouse (56.2%). Response rates ranged from about 80% for letters sent four to six months after the patients’ death to about 60% for letters sent after eight months or more. A descriptive analysis of refusals, based on the transcripts of the telephone calls, allowed classification of 61% of refusals for at least one of the two dimensions examined: caregiver psychological suffering and quality of care received by the patient. Psychological suffering was present in 99% of refusals examined for this dimension (48%). Conversely, a poor quality of care was reported by 63% of the refusals examined for this dimension (23%). Conclusion: The ISDOC survey provides a representative picture of the needs and problems associated with the last three months of life of Italian cancer patients.
An Efficient Method for the Derivation of Mouse Embryonic Stem Cells
Authors: Bryja Vítězlav , Bonilla Sonia , Čajánek Lukáš , Parish Clare L. , Schwartz Catherine M. , Luo Yongquan , Rao Mahendra S. , Arenas Ernest
Published: December 2005

Mouse embryonic stem cells (mESCs) represent a unique tool for many researchers; however, the process of ESC derivation is often very inefficient and requires high specialization, training, and expertise. To circumvent these limitations, we aimed to develop a simple and efficient protocol based on the use of commercially available products. Here, we present an optimized protocol that we successfully applied to derive ESCs from several knockout mouse strains (Wnt-1, Wnt-5a, Lrp6, and parkin) with 50%–75% efficiency. The methodology is based on the use of mouse embryonic fibroblast feeders, knockout serum replacement (SR), and minimal handling of the blastocyst. In this protocol, all centrifugation steps (as well as the use of trypsin inhibitor) were avoided and replaced by an ESC medium containing fetal calf serum (FCS) after the trypsinizations. We define the potential advantages and disadvantages of using SR and FCS in individual steps of the protocol. We also characterize the ESCs for the expression of ESC markers by immunohistochemistry, Western blot, and a stem cell focused microarray. In summary, we provide a simplified and improved protocol to derive mESCs that can be useful for laboratories aiming to isolate transgenic mESCs for the first time.
The Electrochemical Evaluation of the Metal-Carbon Bond Energies (−ΔGBF) of Alkylated Iron and Cobalt Porphyrins [(por)M-R]
Authors: QIU AIMIN , SAWYER DONALD T.
Published: December 2005

The electron-transfer oxidation-reduction chemistry for the alkyl derivatives of iron and cobalt porphyrins [( por ) M III − R ] has been characterized on the basis of cyclic voltammetric and controlled-potential-electrolysis measurements. The electrogenerated anions of iron and cobalt porphyrins [( por ) M − and ( por −·) M −] are strong nucleophiles that react with alkyl halides ( RX ) via a nucleophilic displacement process to form metal-carbon bonds [( por ) M - R and ( por −·) M - R ]. The difference in the reduction potentials for RX and ( por ) M II provides an approximate measure of the ( por ) M - R bond-formation free energy (−ΔG BF ). The −ΔG BF values for iron porphyrins (14–35 kcal mol−1) and for cobalt porphyrins (20-38 kcal mol−1) depend on the electron density of the porphyrin ring ( OEP > TPP > Cl 8 TPP > F 20TPP) and the structure of the alkyl group (1° > 2° > 3°). Thus, the apparent metal-carbon bond energy (−ΔG BF ) for ( OEP ) Fe III- Bu -n is 28 ± 2 kcal mol−1, and for [( MeO )4 TPP ] Co III- Bu -n is 36 ± 2 kcal mol −1. The ( por −·) M − dianions react with carbon dioxide in an electrocatalysed reduction cycle to give CO and CO 32− via the apparent transient formation of a metal-carbon bond [( por −·) M - C ( O ) O −; −Δ G BF ≥ 12 kcal mol −1 for iron porphyrins].
Comparative 1HNMR and UV-Visible Studies of Polyene Polymer Epoxidations Catalyzed by Iron(III), Manganese(III) and Chromium(III) Porphyrins
Authors: DAVORAS E. M. , DIAPER R. , DERVISSI A. , TORNARITIS M. J. , COUTSOLELOS A. G.
Published: December 2005

The catalytic epoxidation of cis-polybutadiene was studied in two-phase systems, CH 2 CI 2/ H 2 O and PhIO (solid)/ CH 2 Cl 2, using chlorochromium(III), chloromanganese(III) and chloroiron(III) tetraphenylporphyrin complexes as catalysts. Comparison of the catalytic activity of these three catalysts showed that the manganese porphyrin is the most suitable catalyst for this reaction. The results are based on reaction product ratios as determined by 1 H NMR . UV-Visible spectroscopy allowed monitoring of the metalloporphyrin evolution during the catalytic reaction.
Synthesis and Self-aggregation of Zinc 20-Halogenochlorins as a Model for Bacteriochlorophylls c/d
Authors: KUREISHI YASUHIKO , TAMIAKI HITOSHI
Published: December 2005

Zinc 20-halogenochlorins 2(20- F ), 3(20- Cl ) and 4(20- Br ) were synthesized by halogenation of a chlorophyll a derivative at the 20-position as a model for bacteriochlorophyll ( BChl )c, which possesses a methyl group at the 20-position and 20-unsubstituted BChl d. Visible spectra in a polar tetrahydrofuran ( THF ) solution showed that 2-4 were monomeric and the planarity of the chlorin ring, was distorted with increasing bulkiness of the 20-substituent. Visible, circular dichroism and IR spectra revealed that 2-4 self-aggregated to form oligomers similarly with 20-unsubstituted 1 and BChls c/d in the heterogeneous thin film as well as in homogeneous non-polar solvents (1% (v/v) THF-hexane). Therefore, the in vitro self-aggregates of 2-4 are good structural models for in vivo BChls c/d self-aggregates, the main antenna components of photosynthetic green bacteria. Fluorescence spectra showed that monomeric 3 and 4 were less emissive than 1 and 2 due to the heavy atom effect which could not be observed in the oligomeric species, indicating that the in vitro aggregates should be promising as functional (light-harvesting) models.
Charge Transfer of Tetraphenylporphyrin Zinc Complexes Incorporated in a Poly(2-vinylpyridine) Matrix
Authors: ZHANG JIAN , ABE TOSHIYUKI , KANEKO MASAO
Published: December 2005

An indium tin oxide (ITO) electrode was coated by a poly(2-vinylpyridine) (P-2VP) film incorporating tetraphenylporphyrin zinc ( ZnTPP ) as a redox center. A cyclic voltammogram (CV) exhibited a couple of redox waves at 0.7 V (vs Ag / AgCl ). The potential-step chronoamperospectrometry (PSCAS) measurement was carried out on the modified electrode immersed in a 0.1 M LiClO4aqueous solution at pH 3.5 under argon atmosphere. Assuming a random distribution of the redox species in the macromolecular structure, the charge transfer distance between the adjacent ZnTPP complexes was obtained as 1.08 nm. The charge hopping distance between the redox centers (1.01 nm) and the bounded motion distance (0.07 nm after 2h) were obtained according to their different response time in the electrochemical measurement. Considering the contributions from both the charge hopping and bounded motion, the second order rate constant of electron hopping was 4.1 × 104M−1s−1.
Anti-Cyanide Drugs: Kinetics of the Removal of Copper(II) and Nickel(II) from N-Methyl-tetra(4-sulfonatophenyl)porphyrins by Cyanide.LD50s of Common Metalloporphyrins and Metallophthalocyanines
Authors: RAHIMI R. , HAMBRIGHT P.
Published: December 2005

The purpose of this project was to develop prophylactic water-soluble anti-cyanide drugs. The 24 h mean LD50s in mice of 13 common metalloporphyrins and metallophthalocyanines are reported. At doses of 1/4, 1/16 and 1/64 of the LD50administered 15 or 60 min prior to a 2LD50challenge of sodium cyanide, none of these compounds protected mice against cyanide. While Co ( H2O )6Cl2and Ni ( H2O )6Cl2were found to be effective, they are too toxic to be useful. A stable metalloporphyrin that could scavenge cyanide by donating metal ions to produce non-toxic polycyano species in the presence of cyanide would be desirable. We found that nickel(II) and copper(II) are removed from their N-methyl-tetra(4-sulfonato)porphyrins by cyanide and hydrogen cyanide. These reactions are not observed with the parent tetra(4-sulfonatophenyl)porphyrins. Equilibrium constants for cyanide addition to both types of metalloporphyrins and the rate laws for metal removal by cyanide and HCN are reported. The medical implications of these findings are discussed.
Enhanced Ionic Conductivity in Nanostructured, Heavily Doped Ceria Ceramics
Authors: Bellino M. G. , Lamas D. G. , Walsöe de Reca N. E.
Published: December 2005

The electrical properties of nanostructured, heavily yttria‐ or samaria‐doped ceria ceramics are studied as a function of grain size using electrochemical impedance spectroscopy (EIS). A remarkable enhancement in the total ionic conductivity of about one order of magnitude is found in nanostructured samples, compared with the intrinsic bulk conductivity of conventional microcrystalline ceramics. This effect is attributed to the predominance of grain‐boundary conduction in the nanostructured materials, coupled with an increase in the grain‐boundary ionic diffusivity with decreasing grain size.
Using Self‐Assembling Dipole Molecules to Improve Charge Collection in Molecular Solar Cells
Authors: Khodabakhsh S. , Sanderson B. M. , Nelson J. , Jones T. S.
Published: December 2005

Surface modification of indium tin oxide (ITO)‐coated substrates through the use of self‐assembled monolayers (SAMs) of molecules with permanent dipole moments has been used to control the anode work function and device performance in molecular solar cells based on a CuPc:C60 (CuPc: copper phthalocyanine) heterojunction. Use of SAMs increases both the short‐circuit current density (Jsc) and fill factor, increasing the power‐conversion efficiency by up to an order of magnitude. This improvement is attributed primarily to an enhanced interfacial charge transfer rate at the anode, due to both a decrease in the interfacial energy step between the anode work function and the highest occupied molecular orbital (HOMO) level of the organic layer, and a better compatibility of the SAM‐modified electrodes with the initial CuPc layers, which leads to a higher density of active sites for charge transfer. An additional factor may be the influence of increasing electric field at the heterojunction on the exciton‐dissociation efficiency. This is supported by calculations of the electric potential distribution for the structures. Work‐function modification has virtually no effect on the open‐circuit voltage (Voc), in accordance with the idea that Voc is controlled primarily by the energy levels of the donor and acceptor materials.
A Versatile, Molecular Engineering Approach to Simultaneously Enhanced, Multifunctional Carbon‐Nanotube– Polymer Composites
Authors: Chen J. , Ramasubramaniam R. , Xue C. , Liu H.
Published: December 2005

Single‐walled carbon nanotubes (SWNTs) are recognized as the ultimate carbon fibers for high‐performance, multifunctional composites. The remarkable multifunctional properties of pristine SWNTs have proven, however, difficult to harness simultaneously in polymer composites, a problem that arises largely because of the smooth surface of the carbon nanotubes (i.e., sidewalls), which is incompatible with most solvents and polymers, and leads to a poor dispersion of SWNTs in polymer matrices, and weak SWNT–polymer adhesion. Although covalently functionalized carbon nanotubes are excellent reinforcements for mechanically strong composites, they are usually less attractive fillers for multifunctional composites, because the covalent functionalization of nanotube sidewalls can considerably alter, or even destroy, the nanotubes' desirable intrinsic properties. We report for the first time that the molecular engineering of the interface between non‐covalently functionalized SWNTs and the surrounding polymer matrix is crucial for achieving the dramatic and simultaneous enhancement in mechanical and electrical properties of SWNT–polymer composites. We demonstrate that the molecularly designed interface of SWNT–matrix polymer leads to multifunctional SWNT–polymer composite films stronger than pure aluminum, but with only half the density of aluminum, while concurrently providing electroconductivity and room‐temperature solution processability.
Cobalt‐Catalysed Addition of Allylidene Dipivalate to Aldehydes. A Formal Homoaldol Condensation
Authors: Lombardo Marco , Licciulli Sebastiano , Pasi Filippo , Angelici Gaetano , Trombini Claudio
Published: December 2005

A Co(I)‐catalysed condensation of allylidene dipivalate with aldehydes to give (Z)‐4‐hydroxybut‐1‐enyl pivalates in 62 to 87% isolated yields, is reported. Reactions are run in acetonitrile at 0 or 25 °C depending on the nature of the aldehyde, and exploiting the Co(II)/Zn(0) redox couple for the preparation of the catalytic Co(I) species.
Association of dopamine D4 receptor (DRD4) polymorphisms with attention deficit hyperactivity disorder in Indian population
Authors: Bhaduri Nipa , Das Manali , Sinha Swagata , Chattopadhyay Anindita , Gangopadhyay Prasanta Kumar , Chaudhuri Keya , Singh Manoranjan , Mukhopadhyay Kanchan
Published: December 2005

Attention deficit hyperactivity disorder (ADHD) is a childhood onset neurobehavioral disorder. Several studies worldwide have implicated a possible association between ADHD and transmission of different polymorphisms of the dopamine D4 receptor gene (DRD4) in different ethnic groups. However, this is the first report on the transmission of different polymorphisms of DRD4 in Indian subjects. Association of 5′ flanking 120‐bp duplication, exon 1 12‐bp duplication, and exon 3 48‐bp variable numbers of tandem repeats (VNTR) were analyzed in 50 ADHD cases. Haplotype‐based haplotype relative risk (HHRR) analysis and transmission disequilibrium test (TDT) were carried out to ascertain the association of these polymorphisms with the disorder. Linkage disequilibria (LD) between the polymorphisms were calculated using EH+ and 2LD programs. Our preliminary data showed lack of association between ADHD and transmission of the 5′ flanking 120‐bp duplication and exon 1 12‐bp duplication. But, the transmissions of 6 and 7 repeat alleles of exon 3 48‐bp VNTR showed significant association with ADHD. We have also examined the haplotype frequencies and biased transmission of one haplotype was observed in ADHD probands. LD analysis showed very strong disequilibrium between exon 1 12‐bp duplication and exon 3 48‐bp VNTR. Strong LD was also observed between the 5′ flanking 120‐bp duplication and exon 1 12‐bp duplication. The observed association between higher repeat alleles of exon 3 48‐bp VNTR and Indian ADHD children is consistent with some of the earlier reports. © 2005 Wiley‐Liss, Inc.
A resistivity survey of a burial mound in the ‘Valley of the Thracian Kings’
Authors: Tonkov N. , Loke M. H.
Published: December 2005

Geophysical methods, and electrical resistivity in particular, have well‐elaborated techniques and proven efficacy in the prospection of tumuli. This paper presents a good example of the discovery of a rich 5th century BC stone tomb in a large tumulus using geophysical data. The tumulus had been investigated previously both with geophysical surveys and excavation, but without success. In the present survey the common resistivity traversing with Wenner‐Schlumberger arrays was expanded with a two‐dimensional inverse modelling that, on one hand, aided in the more accurate outlining of the buried monument and, on the other, produced for the first time geophysical evidence to support the existing hypothesis that in many cases the tombs were built into previously raised tumulus embankments. Copyright © 2005 John Wiley & Sons, Ltd.
Automatic detection and identification of shocks in Gaussian state‐space models: a Bayesian approach
Authors: Salvador Manuel , Gargallo Pilar
Published: December 2005

An automatic monitoring and intervention algorithm that permits the supervision of very general aspects in an univariate linear Gaussian state–space model is proposed. The algorithm makes use of a model comparison and selection approach within a Bayesian framework. In addition, this algorithm incorporates the possibility of eliminating earlier interventions when subsequent evidence against them comes to light. Finally, the procedure is illustrated with two empirical examples taken from the literature. Copyright © 2005 John Wiley & Sons, Ltd.
Bifurcating saphenous vein aorto‐coronary bypass graft lesions: Treatment of left main equivalent using two filterwire EX™ distal protection devices
Authors: Prosser Verne M. , Bailey Steven R.
Published: December 2005

Distal protection devices for the prevention of embolization during saphenous venous aorto‐coronary bypass graft intervention are currently considered standard of care. Branching or Y‐type saphenous vein grafts present a unique and challenging problem when a distal protection device is anticipated. We present a case in which two Filterwires™ were used simultaneously through two separate guiding catheters in a left main equivalent bifurcating saphenous vein graft (SVG) with significant ostial and proximal atherosclerotic lesions of both limbs, which supplied left anterior descending artery and circumflex artery territories. © 2005 Wiley‐Liss, Inc.
Unexpected Novel Binding Mode of Pyrrolidine‐Based Aspartyl Protease Inhibitors: Design, Synthesis and Crystal Structure in Complex with HIV Protease
Authors: Specker Edgar , Böttcher Jark , Brass Sascha , Heine Andreas , Lilie Hauke , Schoop Andreas , Müller Gerhard , Griebenow Nils , Klebe Gerhard
Published: December 2005

At present nine FDA‐approved HIV protease inhibitors have been launched to market, however rapid drug resistance arising under antiviral therapy calls upon novel concepts. Possible strategies are the development of ligands with less peptide‐like character or the stabilization of a new and unexpected binding‐competent conformation of the protein through a novel ligand‐binding mode. Our rational design of pyrrolidinedimethylene diamines was inspired by the idea to incorporate key structural elements from classical peptidomimetics with a non‐peptidic heterocyclic core comprising an endocyclic amino function to address the catalytic aspartic acid side chains of Asp 25 and 25′. The basic scaffolds were decorated by side chains already optimized for the recognition pockets of HIV protease or cathepsin D. A multistep synthesis has been established to produce the central heterocycle and to give flexible access to side chain decorations. Depending on the substitution pattern of the pyrrolidine moiety, single‐digit micromolar inhibition of HIV‐1 protease and cathepsin D has been achieved. Successful design is suggested in agreement with our modelling concepts. The subsequently determined crystal structure with HIV protease shows that the pyrrolidine moiety binds as expected to the pivotal position between both aspartic acid side chains. However, even though the inhibitors have been equipped symmetrically by polar acceptor groups to address the flap water molecule, it is repelled from the complex, and only one direct hydrogen bond is formed to the flap. A strong distortion of the flap region is detected, leading to a novel hydrogen bond which cross‐links the flap loops. Furthermore, the inhibitor addresses only three of the four available recognition pockets. It achieves only an incomplete desolvation compared with the similarly decorated amprenavir. Taking these considerations into account it is surprising that the produced pyrrolidine derivatives achieve micromolar inhibition and it suggests extraordinary potency of the new compound class. Most likely, the protonated pyrrolidine moiety experiences strong enthalpic interactions with the enzyme through the formation of two salt bridges to the aspartic acid side chains. This might provide challenging opportunities to combat resistance of the rapidly mutating virus.
Four versus six courses of a dose‐escalated cyclophosphamide, doxorubicin, vincristine, and prednisone (CHOP) regimen plus etoposide (megaCHOEP) and autologous stem cell transplantation
Authors: Schmitz Nobert , Kloess Marita , Reiser Marcel , Berdel Wolfgang E. , Metzner Bernd , Dorken Bernd , Kneba Michael , Trumper Lorenz , Loeffler Markus , Pfreundschuh Michael , Glass Bertram ,   for the German High‐Grade Non Hodgkin's Lymphoma Study Group (DSHNHL)
Published: December 2005

BACKGROUND

Patients with aggressive lymphoma and high‐risk features at the time of diagnosis are reported to have a poor prognosis with standard therapy. Attempts to improve the results achieved with the combination of cyclophosphamide, doxorubicin, vincristine, and prednisone (CHOP) using second‐generation or third‐generation chemotherapy have failed. In the current study, the authors increased the doses and dose intensity of drugs used for the conventional first‐line therapy of aggressive lymphoma and designed a Phase II randomized trial that compared four and six courses of dose‐escalated CHOP plus etoposide (megaCHOEP) supported by the transplantation of peripheral blood stem cells.

METHODS

Eighty‐four patients age < 60 years with aggressive lymphoma and elevated lactate dehydrogenase (LDH) levels were randomized to receive either 4 (Arm A) or 6 (Arm B) courses of cyclophosphamide, doxorubicin, vincristine, etoposide, and prednisone (megaCHOEP). The last three treatment courses were supported by autologous peripheral blood stem cell transplantation. Although the total doses of cyclophosphamide and etoposide were comparable, the dose intensity during the first 3 treatment courses was planned to be 2.8‐fold and 2.0‐fold higher, respectively, for patients in Arm A.

RESULTS

Thirty‐seven patients in Arm A (90.2%) but only 18 patients in Arm B (69.2%) were able to complete therapy (P = 0.048). The complete response rate was 65.8% in Arm A and 50.0% in Arm B; the disease recurrence rates were 18.5% versus 61.5% (P = 0.011). Freedom from treatment failure at 2 years was 52.5% (95% confidence interval [95% CI], 36.9–68.2%) in Arm A and 23.1% (95% CI, 6.9–39.3%) in Arm B (P = 0.02). The overall survival rate was 70% (95% CI, 54.9–85.0%) in Arm A and 46.2% (95% CI, 27.0–65.3%) in Arm B (P = 0.037).

CONCLUSIONS

The results of the current study demonstrate that dose intensity, in particular early dose intensity, significantly influences disease control with high‐dose therapy (HDT) and autologous stem cell transplantation. These results also may explain the failure of HDT with low early dose intensity to improve the results obtained with conventional chemotherapy. Cancer 2006. © 2005 American Cancer Society.
Evidence for the involvement of dominant‐negative Notch molecules in the normal course of Drosophila development
Authors: LeComte Matthew , Wesley Umadevi V. , Mok Lee‐Peng , Shepherd Andrew , Wesley Cedric
Published: December 2005

Notch signaling is used to specify cell types during animal development. A high level specifies one cell type, whereas a low level specifies the alternate type. The effector of Notch signaling is the Notch intracellular domain. Upon its release from the plasma membrane in response to Delta binding the Notch extracellular domain, the Notch intracellular domain combines with the transcription factor Suppressor of Hairless and promotes the expression of target genes. Using a panel of antibodies made against different extracellular and intracellular regions of Notch, we show that cell types and tissues with low levels of Notch signaling are enriched for Notch molecules detected only by the extracellular domain antibodies. This enrichment often follows enrichment for Notch molecules detected only by antibodies made against the Suppressor of Hairless binding region. Notch molecules lacking most of the intracellular domain or containing only the Suppressor of Hairless binding region are produced during development. Such molecules are known to suppress Notch signaling, possibly by taking away Delta or Suppressor of Hairless from the full‐length Notch. Thus, it is possible that dominant‐negative Notch molecules are produced in the normal course of tissue differentiation in Drosophila as part of an auto–down‐regulation mechanism. Developmental Dynamics 235:411–426, 2006. © 2005 Wiley‐Liss, Inc.