bluuebunny/crossref_metadata_2025 huggingface dataset:
The Vibrational Fine Structure of the 1T1g←1A1g Absorption Band of [Co(NH3′)6]3+
Authors: Komi Yoshinori , Urushiyama Akio
Published: July 2006

The crystal absorption spectra of [Co(NH3)6][Ir(CN)6] and [Co(ND3)6][Ir(CN)6] were studied at 4.2 K. The vibrational fine structure observed on the 1T1g←1A1g absorption band of the hexaamminecobalt(III) complexes was interpreted in terms of a vibronic intensity scheme in comparison with the vibrational frequencies of the complexes. The deuteration shifts helped to confirm the assignments of the structure. It was found that, as well as the skeletal vibrations of the CoN6 group, the NH3 (and ND3) rocking and the H–N–H symmetric deformation modes are effective in the vibronic intensity mechanism of the bands.
The X-Ray Study of Several Reaction Products of Substituted Benzodicyclobutene. I. 2,7-Di-t-butyl,11,11,12,12-tetracyano-4,5,9,10-tetraphenyltetracyclo[4.4.2.01,8.03,6]dodeca-2,4,7,9-tetraene
Authors: Tsukada Harumichi , Shimanouchi Hirotaka , Sasada Yoshio
Published: July 2006

As a part of the studies of the reaction mechanism of a substituted benzodicyclobutene (1), the X-ray analysis of the title compound was carried out. The crystals are monoclinic; space group P21/a, a=23.159(3), b=20.369(3), c=8.589(1) Å, β=104.27(1)°. The structure was solved by the direct method and was refined by the block-diagonal least-squares method to the final R factor of 0.070 for 5553 observed reflections. In the molecular structure, there is a bridge-bond formed by the “cross” addition of tetracyanoethylene (TCNE) to the C(1) and C(6) sites of 1. The intermolecular interaction was calculated so as to make clear what kind of addition reaction is preferable for the molecule 1. The result is consistent with the observation that, in addition to the linear adduct, a cross adduct is also obtained as a by-product.
The Conformations and the Ring Inversions of Some 8- and 10-Methyl-substituted 8,9,10,11-Tetrahydro-7H-cycloocta[de]naphthalenes and Their 9-Oxo Derivatives
Authors: Kamada Toshihiro , Yamamoto Osamu
Published: July 2006

The IR and NMR studies on the conformations of several 8- and 10-methyl-substituted 8,9,10,11-tetrahydro-7H-cycloocta[de]naphthalenes (cis-8,10-dimethyl (3a), trans-8,10-dimethyl (4a), 8,8-dimethyl (5a), 8,8,10-trimethyl (6a), and 8,8,10,10-tetramethyl (7a)) and their 9-oxo derivatives (3b–7b) have been described. It was found that compounds 3–7 exist exclusively in a boat conformation in the ground state, the peri ring of which is somewhat distorted (puckered) as a result of the steric repulsion between the interior benzyl protons; the molecules of 3a and 3b are rather strongly puckered, while those of 7a and 7b exist in a less puckered form than the conformations of the other methylated compounds. In the latter case, a novel type of the reflex effect was found arising from the 1,3-synaxial CH3–CH3 steric interaction and the interior benzyl H–H interaction. Moreover, it was revealed that free energy barriers (ΔG\ewq) to boat inversion for compounds 5a, 5b, 7a, and 7b are markedly increased (ΔΔG\ewq=4.8–5.9 kcal/mol) as compared with the unmethylated compounds. These results were discussed in terms of the boat-to-boat interconversion process in which the pseudorotations of the peri bonds are involved. Some discussion was also made on the spectral and conformational features of the eight-membered pericyclized naphthalene ring system.
Ion-Molecule Reactions of ArN2+ with Butane and Isobutane at Thermal Energy
Authors: Tsuji Masaharu , Matsumura Ken-ichi , Kouno Hiroyuki , Funatsu Tsuyoshi , Nishimura Yukio
Published: July 2006

Product ion distributions and rate constants have been determined for thermal energy reactions of ArN2+ with n-C4H10 and i-C4H10 by using an ion-beam apparatus. C4H9+, C3Hn+ (n = 5—7), and C2Hn+ (n = 4,5) are produced from n-C4H10 with branching ratios of 6, 57, and 37%, while C4H9+ and C3Hn+ (n = 5—7) are formed from i-C4H10 with branching ratios of 13 and 87%, respectively. A comparison of the product ion distribution in the ArN2+/n-C4H10 reaction with that predicted from the fragmentation pattern of n-C4H10+ suggests that most of all fragment ions are formed through (pre)dissociation of precursor n-C4H10+ states at ca. 13.2 eV. Since this energy is close to the effective recombination energy of ArN2+ (ca. 13.5 eV), it is concluded that the ArN2+/n-C4H10 dissociative charge-transfer reaction proceeds through near-resonant n-C4H10+ states. The total rate constants are (6.9 ± 2.3) × 10−10 cm3 s−1 for n-C4H10 and (9.0 ± 2.6) × 10−10 cm3 s−1 for i-C4H10, which amount to 58 and 75% of the collision rate constants estimated from Langevin theory, respectively.
Nuclear Magnetic Resonance Studies on the Structure of Ruthenium(II) Complexes of Di-2-pyridylamine in DMSO Solution
Authors: Nagao Noriharu , Mukaida Masao , Tachiyashiki Satoshi , Mizumachi Kunihiko
Published: July 2006

The complete assignments of the 1H and 13C NMR spectra of [Ru(bpy)n(Hdpa)3−n]2+ (n = 0—2) have been carried out on the basis of proton–proton coupling constants, H–H COSY, C–H COSY, and the aromatic ring-current effects of the ligand. The observed aromatic ring-current shifts of the assigned 1H NMR signals were compared with the calculated ones by using a current-loop model. The flapping of the Hdpa ligands showed that the structures of [Ru(bpy)2(Hdpa)]2+, [Ru(bpy)(Hdpa)2]2+, and [Ru(Hdpa)3]2+ in solution have apparent C2, C2, and D3 symmetries, respectively.
Energy and Electron Transfer in Synthetic Oligoproline-BridgedPorphyrin Donor–Acceptor Molecules
Authors: Tamiaki Hitoshi , Nomura Kimiatsu , Maruyama Kazuhiro
Published: July 2006

Oligo-l-proline-bridged bis(porphyrin) compounds were synthesized. The protected oligoprolines in ethanol might take a fairly stable helical conformation at an oligomerization number ≥4. An intramolecular singlet energy transfer occurred in ethanol from a photoexcited zinc porphyrin moiety in the N-terminal to a metal-free porphyrin moiety in the C-terminal at the same efficiency as from the zinc porphyrin moiety in the C-terminal to the metal-free porphyrin moiety in the N-terminal. A photoinduced electron transfer also occurred in ethanol from the zinc(II) porphyrin to the iron(III) porphyrin in the molecule, which was independent of the direction of the spacer as well as the energy transfer. A weak change in the intramolecular electron-transfer efficiency with the distance between the zinc and iron porphyrins suggested that electrons should move through the amide bonds in the oligoproline linkage.
The Missouri Lottery Optimizes Its Scheduling and Routing to Improve Efficiency and Balance
Authors: Jang Wooseung , Lim Huay H. , Crowe Thomas J. , Raskin Gail , Perkins Thomas E.
Published: July 2006

The Missouri lottery, a profit-driven nonprofit organization, generates annual revenues of over $800 million by selling lottery tickets; 27.5 percent of the revenue goes to Missouri’s public education programs. The lottery sales representatives (LSRs) play a central role in increasing sales by providing excellent customer service to ticket retailers throughout the state. Hence, LSRs must have equitable, balanced work schedules and efficient routes and navigation sequences. Our objective was to provide scheduling and routing policies that minimize LSRs’ total travel distance while balancing their workloads and meeting visitation constraints. We modeled the problem as a periodic traveling-salesman problem and developed improvement algorithms specifically to solve this problem. The newly implemented schedules and routes decrease the LSRs’ travel distance by 15 percent, improve visitation feasibility by 46 percent, increase the balance of routes by 63 percent, decrease overtime days by 32 percent, and indirectly increase the sales of lottery tickets by improving customer service.
Book Reviews
Authors: Lev Benjamin
Published: July 2006

The range of books reviewed is wide, covering theory and applications in operations research, statistics, management science, econometrics, mathematics, computers, and information systems (no software is reviewed). In addition, we include books in other fields that emphasize technical applications. Publishers who wish to have their books reviewed should send them to Professor Benjamin Lev. We list the books received; not all books received can be reviewed because space is limited. Those who would like to review books are urged to send me their names, addresses, and specific areas of expertise. We commission all reviews and do not accept unsolicited book reviews. Readers are encouraged to suggest books that might be reviewed or to ask publishers to send me copies of such books.

The authors or editors of the books reviewed in this issue are Massoud Bazargan, Kenneth N. McKay, Vincent C. S. Wiers, John A. Muckstadt, Joel A. Nachlas, Zhaohao Sun, and Gavin R. Finnie.
Robust Airline Crew Pairing: Move-up Crews
Authors: Shebalov Sergey , Klabjan Diego
Published: July 2006

Due to irregular operations, the crew cost at the end of a month is typically substantially higher than the crew cost projected in planning. We assume that the fleeting and the aircraft routing decisions have already been made. We present a model and a solution methodology that produces robust crew schedules in planning. Besides the objective of minimizing the crew cost, we introduce the objective of maximizing the number of move-up crews, i.e., the crews that can potentially be swapped in operations. To solve the resulting large-scale integer program, we use a combination of delayed column generation and Lagrangian relaxation. The restricted master problem is solved by means of Lagrangian relaxation and the “duals” of the restricted master problem, which are used in delayed column generation, and correspond to the Lagrangian multipliers. We report computational experiments that demonstrate the benefits of using the robust crew schedule instead of the traditional one. We evaluate various crew schedules by generating random disruptions and then running a crew recovery module. We compare solutions with respect to the direct crew cost and indirect costs such as uncovered legs, reserved crews, and deadheading. The main conclusion is that robustness leads to reduced operational crew cost; however, in planning the trade-off between the inflated direct crew cost and robustness needs to be exploited judicially.
Primal Method for Determining the Most Likely Route Flows in Large Road Networks
Authors: Bar-Gera Hillel
Published: July 2006

This paper presents a method to identify the set of routes and their flows in a user-equilibrium traffic assignment solution. We present a general consistency condition that is satisfied by any set of minimum-cost routes, and show how it can be used in choosing a set of routes that is likely to be similar to the set of user-equilibrium routes. The proposed consistency condition is also essential for finding the entropy-maximizing route flows solution, which may be regarded as the most likely one. An efficient method for finding the entropy-maximizing solution is presented. Numerical results on several networks, including one of large scale, demonstrate the effectiveness of the proposed method. In most cases the method achieves a duality gap of practically zero in a short computation time.
Social support and quality of life of patients prior to stem cell or bone marrow transplantation
Authors: Frick Eckhard , Ramm Gesa , Bumeder Irmgard , Schulz‐Kindermann Frank , Tyroller Michael , Fischer Norbert , Hasenbring Monika
Published: July 2006

Objectives. To determine the positive and detrimental aspects of social support prior to allogeneic or autologous bone marrow transplantation/stem cell transplantation.

Design. Cross‐sectional.

Methods. Patients completed the German version of the Illness‐specific Social Support Scale (ISSS) and the Quality of Life (QoL) Questionnaire Core 30 (EORTC QLQ‐C30).

Results. Participants were 282 patients (62% autologous SCT, 39% women, 97% haematological malignancies, 72% with partner). We found satisfactory reliability values for both ISSS scales: positive support (Cronbach's α = .91) and problematic support (= .73). Patients living with a partner displayed higher scores in positive interaction than patients living alone (p <.001). Analysis showed a significant main effect of partnership, p <.001; F (1) = 8.345, and better scores for women, p <1; F (1) = 2.758. Furthermore, we determined a negative correlation between problematic interaction and emotional/social function (p <.001) and a positive correlation with insomnia, but no correlation between positive interaction, QLQ‐C30, and Karnofsky's index.

Conclusions. We could distinguish between helpful and harmful support, and determine clinically important associations of problematic support. Partnership seems to be a major source of positive interaction.

Abbreviations. HCT, Haematopoietic cell transplantation; HRQoL, Health related quality of life; ISSS, Illness‐specific Social Support Scale; QLQ‐C30, QoL Questionnaire Core 30 (EORTC).
Age differences in control beliefs regarding health: Control, strategy and capacity
Authors: Bernardes Sónia F. , Luisa Lima Maria
Published: July 2006

Objectives.A new model of perceived control has been proposed (Skinner, 1995) in which 3 types of control‐related beliefs were distinguished: control, strategy and capacity. This model has not yet been applied to health issues. Hence, the main purpose of this study was to apply it to the health domain, exploring age differences in the way children and teenagers conceptualize control‐related beliefs.

Design and setting.A prospective age cohort study was carried out with older children and teenagers attending public schools in Lisbon's metropolitan area.

Method.A newly developed instrument (HPCQ) was administered to 188 healthy participants (91 6th graders and 97 11th graders).

Results.Analyses of variance showed no age differences in individuals' strategy beliefs. Generally, children showed stronger capacity beliefs and a higher perceived control over their own health than teenagers. Hierarchical regression analyses showed that the belief in being a lucky person was a central predictor of control in later childhood. In adolescence, chance‐related factors lost their predictive power, and effort and attributes‐related beliefs remained controls' primary predictors.

Conclusions.These results emphasize the heuristic value of this recent conceptualization of control‐related beliefs. Moreover, they contribute to the development of more effective and reliable health‐related school‐based prevention/intervention programmes aiming at these particular age cohorts.
Quantification of IgG Antibodies to Aspergillus fumigatus and Pigeon Antigens by ImmunoCAP Technology: An Alternative to the Precipitation Technique?
Authors: Van Hoeyveld Erna , Dupont Lieven , Bossuyt Xavier
Published: July 2006

Background: We evaluated the ImmunoCAP technique for measurement of IgG specific to Aspergillus fumigatus and pigeon antigens.

Methods: We used ImmunoCAP and precipitation technique to measure concentrations of IgG to A. fumigatus or pigeon antigens in sera from 265 patients and 42 controls. We also evaluated linearity, interference, imprecision, concordance, and diagnostic accuracy of the measuring techniques.

Results: The precipitation and ImmunoCAP technique showed moderate concordance (κ, 0.46 for both A. fumigatus and pigeon antibodies). Specific IgG results for A. fumigatus and pigeon were linear (r = 0.98 and 0.97, respectively), with interrun reproducibility rates of 23% and 14% and maximal interference of 36.5% and 8% by lipid and 24% and 21% by hemolysis, respectively. A. fumigatus antibody concentrations were higher in patients with aspergillosis and allergic bronchopulmonary aspergillosis (ABPA) (median, 103 and 70.1 mgA/L, respectively) than in patients with other pulmonary diseases (median, 18.15–33.40 mgA/L). Antibodies to pigeon antigens were high in patients with hypersensitivity pneumonitis (median, 1024 mgA/L) but also in patients with other pulmonary diseases (median, 445 mgA/L). Antibody titers were substantially higher in patients with other pulmonary diseases and contact with pigeons (median, 1060 mgA/L) than in patients without antigen contact (median, 27.35 mgA/L) (P <0.004).

Conclusions: Agreement between the precipitation and ImmunoCAP technique was 86% for A. fumigatus and 70% for pigeon antigens. Highest concentrations of specific IgG to A. fumigatus were found in patients with aspergillosis and ABPA. Our results suggest that antigen contact was the most important variable affecting the presence of antibodies to pigeon antigen.
Automated Chemiluminescence-Immunoassay for Aldosterone during Dynamic Testing: Comparison to Radioimmunoassays with and without Extraction Steps
Authors: Schirpenbach Caroline , Seiler Lysann , Maser-Gluth Christiane , Beuschlein Felix , Reincke Martin , Bidlingmaier Martin
Published: July 2006

Background: Measurements of aldosterone have become more common since the recognition that primary aldosteronism is a more frequent cause of hypertension than previously believed. Our aim was to compare concentrations reported by 4 assays for samples obtained after saline infusion during dynamic testing.

Methods: We tested 104 participants (27 with primary aldosteronism, 30 with essential hypertension, and 47 healthy controls) with the intravenous saline infusion test (2.0 L isotonic saline over 4 h), with repetitive sampling. In all blood samples, aldosterone concentration was measured by an in-house RIA after extraction and chromatography, by 2 commercially available RIAs without extraction (Aldosterone Maia, Adaltis; Active Aldosterone, Diagnostics Systems Laboratories) and by an automated CLIA (Advantage, Nichols Institute Diagnostics).

Results: Correlation coefficients for results of pairs of assays ranged from 0.74 to 0.98. Agreement between commercial assays and in-house RIA was best at the low to intermediate concentrations after saline infusion. Mean (SD) Adaltis and DSL RIA results were 2- to 3-times higher [healthy participants: 78 (25) ng/L and 56 (18) ng/L, respectively] than those obtained by Nichols CLIA [17 (8) ng/L] and in-house RIA [23 (18) ng/L]. Aldosterone concentrations measured by the Nichols CLIA were below the limit of detection (limit of the blank) in 27 of 47 healthy participants.

Conclusions: Aldosterone concentrations reported by the Adaltis and DSL nonextraction RIAs were consistently higher than those produced by the Nichols CLIA and the in-house RIA. The convenient Nichols CLIA showed better agreement with the in-house RIA, but the concentrations in healthy participants were frequently undetectable by this method. Uncritical application of cutoff values from the literature must be avoided.
Human cathepsin L rescues the neurodegeneration and lethality in cathepsin B/L double-deficient mice
Authors: Sevenich Lisa , Pennacchio Len A. , Peters Christoph , Reinheckel Thomas
Published: July 2006

Cathepsin B (CTSB) and cathepsin L (CTSL) are two widely expressed cysteine proteases thought to predominantly reside within lysosomes. Functional analysis of CTSL in humans is complicated by the existence of two CTSL-like homologs (CTSL and CTSL2), in contrast to mice, which possess only one CTSL enzyme. Thus, transgenic expression of human CTSL in CTSL-deficient mice provides an opportunity to study the in vivo functions of this human protease without interference by its highly related homolog. While mice with single-gene deficiencies for murine CTSB or CTSL survive without apparent neuromuscular impairment, murine CTSB/CTSL double-deficient mice display degeneration of cerebellar Purkinje cells and neurons of the cerebral cortex, resulting in severe hypotrophy, motility defects, and lethality during their third to fourth week of life. Here we show that expression of human CTSL through a genomic transgene results in widespread expression of human CTSL in the mouse that is capable of rescuing the lethality found in CTSB/CTSL double-deficient animals. Human CTSL is expressed in the brain of these compound mutants, predominantly in neurons of the cerebral cortex and in Purkinje cells of the cerebellum, where it appears to prevent neuronal cell death.
Optical Properties
Authors: Galiatsatos Vassilios
Published: July 2006

This article contains a general overview of optical properties of polymers. The article starts with fundamental considerations of basic optical properties of molecules. It then moves on to cover single polymer chains, semicrystalline polymers, glassy polymers, and elastomers. The article closes with a reference to nonlinear optical properties.
Colorectal Cancer
Authors: Compton Carolyn C.
Published: July 2006

Colorectal cancer is the second leading cause of site‐specific cancer mortality in Western nations. Over 130,000 new cases and 56,500 deaths were expected in the United States in 1998. Approximately 70–80% of patients will present with apparently localized disease that is surgically resectable. A proportion of these patients harbor occult micrometastases and will relapse after initial therapy. Randomized, Phase III clinical trials evaluating adjuvant chemotherapy (combined with radiotherapy in rectal cancer) for patients with local/regional lymph‐node involvement have clearly shown some of these patients can be cured with adjuvant therapy.

A recent pooled analysis as well as the individual prospective randomized clinical trials of adjuvant chemotherapy in patients with Stage II disease (no involvement of local/regional lymph nodes) have not clearly shown a survival benefit in these patients. Yet a significant minority of these patients will relapse and eventually die of their disease. A review by the National Surgical Adjuvant Breast and Bowel Project (NSABP) of four consecutive adjuvant chemotherapy trials in Stages II and III colorectal cancer argues that adjuvant chemotherapy does improve survival for Stage II patients. The use of molecular markers that have prognostic significance in addition to pathologic and clinical factors has the potential to identify high‐risk patients who may benefit from therapy. This may allow treatment of those at highest risk while sparing those with minimal risk the toxicity and expense of adjuvant chemotherapy.

Prognostic factors can also serve a useful role in advanced disease. Some factors may be predictive of response to therapy, thereby aiding in the choice of palliative treatment. In a small subset of patients with metastatic colorectal cancer, patient‐and tumor‐related factors impact on the potential for curative resection of metastatic disease.
Hepatocellular Carcinoma
Authors: Palmer Daniel H. , Johnson Philip J.
Published: July 2006

Hepatocellular carcinoma (HCC) is a common tumor that is responsible for over 5% of all cancer deaths worldwide. It is highly malignant and therapy has, to date, had little impact on overall survival. Although the natural history of the disease and the essential prognostic variables are now clearly defined, we must recognize that the overall prognosis is universally poor, with most patients dying within one year of diagnosis. Part of the reason for this dismal state of affairs is that, as well as having HCC, at least 75% of patients will have an associated chronic liver disease, usually at the stage of cirrhosis. The tumor and the chronic liver disease have independent natural histories and both contribute significantly to the patient's prognosis. In a disease such as HCC, where a significant proportion of patients will die within a few weeks of diagnosis, accurate prognostication is important. Information on the expected course of the disease is essential to provide a time frame in which these unfortunate patients can sort out their affairs.

In reviewing prognostic factors it is important to bear in mind that the tumor is relatively rare in the West where the incidence is only in the order of 1–2/100,000 compared to over 50/100,000 in many areas of Africa and the Far East. There is therefore a tendency for patients in the West to be referred to a few specialist centers, and this process can be the source of considerable bias in reported series. For example, the figure for the rate that HCC can be resected with curative intent, an essential determinant of prognosis, has been reported to be up to 40% in series from Western surgical units. This may reflect, however, the fact that only those patients who the referring physician perceives to be good candidates for resection are referred and operated upon. The “true” rate is nearer to 10%. Another consequence of the wide geographic variation is that surgeons in high‐incidence areas may have significantly more experience of operating on HCC in cirrhotic livers and may expect better results.
Hodgkin Lymphoma
Authors: Specht Lena
Published: July 2006

The Ann Arbor staging classification remains the basis for the evaluation of patients with Hodgkin's disease. The Ann Arbor classification has been adopted by the American Joint Committe on Cancer (AJCC) and International Union Against Cancer (UICC) as the recommended staging classification for Hodgkin's disease. It is evident, though, that this staging cannot be relied on as the only prognostic tool in Hodgkin's disease. A modification of the Ann Arbor system was proposed at the Cotswold meeting to incorporate a designation for number of sites and bulk. These recommendations have not been universally adopted, however, and a multitude of other factors and combinations of factors are currently being employed worldwide. The anatomic extent of disease is the most important prognostic factor in Hodgkin's disease and forms the baseline for decision making regarding treatment. Because of this, the prognostic factors will be considered in the context of stage.
Retinoblastoma
Authors: Khetan Vikas , Chan Helen S. L. , Wang Lisa , Gallie Brenda L.
Published: July 2006

Retinoblastoma is the commonest malignant eye tumor of childhood affecting 15 per 100,000 live births. Children predisposed to hereditary retinoblastoma as a result of carrying a mutant
RB1
allele usually develop bilateral disease, but may be having only unilateral disease. However, only 10% of children have familial retinoblastoma, and most germline
RB1
alleles are novel. Discussion here will center on prognostic risk factors for retinoblastoma at three levels: risk of developing retinoblastoma; risk of losing the eye with intraocular disease despite current therapies; and risk of death due to metastatic disease in spite of the best therapies. No multicenter clinical trials have been conducted to evaluate systematic therapy for intraocular or extraocular retinoblastoma. Such trials will require global collaboration. Since 1990, chemotherapy with focal (laser and cryo) therapy has replaced external beam radiation (EBRT) as primary therapy, to avoid the severe long‐term side effect of EBRT. However, EBRT remains a valuable tool to salvage eyes that fail chemotherapy/focal therapy. With full molecular analysis 93% of
RB1
mutant alleles can be identified, supporting accurate identification of infants at risk, facilitating early diagnosis and intervention and vastly improving visual outcome and saving eyes in the long run. The 2002 TNM classification for metastatic retinoblastoma does not reflect differences in outcome for disease affecting the CNS versus bone marrow. Whereas, the newly proposed International Retinoblastoma Classification (IRC) addresses these issues. Current treatment of metastatic retinoblastoma offers hope. “Cure” with long‐term follow‐up is possible with chemotherapy, orbital and focal radiation, intrathecal chemotherapy, and bone marrow/stem cell transplant.
Propagation of uncertainty in chemically activated systems
Authors: Androulakis Ioannis P. , Grenda Jeffrey M. , Barckholtz Timothy A. , Bozzelli Joseph W.
Published: July 2006

Chemically activated systems play an important role in combustion and atmospheric chemistry. The overall reaction paths exhibit complex pressure and temperature dependencies because each intermediate involves a coupled system of competing multistep isomerization, dissociation, and stabilization paths. A number of estimation techniques exist for deriving the required thermochemical and elementary kinetic input parameters for rate coefficient estimation. The availability of high‐level ab initio methods promises to reduce the inaccuracies associated with older empirical methods. The objective of this study is to evaluate the importance of the various thermochemical parameters entering the rate coefficient calculation. We describe and illustrate a computational framework to quantify the functional relationship between the thermochemical properties and the macroscopic observables through appropriate response surface methods. The approach is demonstrated by analyzing the impact of thermochemical properties in estimating autoignition delays in propane oxidation. © 2006 American Institute of Chemical Engineers AIChE J, 2006
CF3‐substituierte aromatische und heterocyclische Bausteine
Authors: Schlosser Manfred
Published: July 2006

Fluor bleibt ein Geheimtipp in den Lebenswissenschaften, da sich mit diesem Element biologische Eigenschaften abstimmen lassen. Die Synthese fluorhaltiger Zielverbindungen ist jedoch nicht immer einfach: Praktisch jedes Fluor‐Atom, das an ein organisches Gerüst angeheftet wird, muss letztlich einer anorganischen Quelle entnommen werden. Ausschlaggebend für die Syntheseplanung ist die Entscheidung, auf welcher Stufe und wie das Halogen eingeführt werden soll. Gängige technische Verfahren, insbesondere die Verdrängung von Chlor mit wasserfreiem Fluorwasserstoff oder mit Kaliumfluorid, lassen sich schwerlich zweckmäßig im Labormaßstab ausführen. Allgemeingültige Methoden für Industrie wie Hochschulbereich finden deshalb großen Anklang. Für die Synthese CF3‐substituierter Arene oder Heterocyclen gibt es zwei hervorragende Möglichkeiten: Die CF3‐Gruppe kann paketweise durch Kupplung eines geeigneten Substrats mit in situ erzeugtem (Trifluormethyl)kupfer übertragen werden, oder man kann von einem CF3‐haltigen Aren oder Heterocyclus als Grundgerüst ausgehen und dieses mit den noch fehlenden Teilen vervollständigen.
CF3‐Bearing Aromatic and Heterocyclic Building Blocks
Authors: Schlosser Manfred
Published: July 2006

Fluorine remains an insiders' tip in the life sciences as it enables the fine‐tuning of biological properties. However, the synthesis of fluorine‐substituted target compounds is not always trivial. Virtually any fluorine atom attached to an organic backbone has ultimately to be imported from inorganic sources. Crucial for the entire synthetic planning in medicinal and agricultural research is the decision on at what stage and how the halogen will be introduced. Standard technical processes, in particular the displacement of chlorine using anhydrous hydrogen fluoride or potassium fluoride, can hardly be implemented rationally on the laboratory scale. Universal methods that are applicable by both industrial and academic researchers thus have great appeal. If a trifluoromethyl‐substituted arene or heterocycle is the target compound, two splendid options exist. The CF3 group can be delivered packagewise by coupling an appropriate substrate with in situ generated (trifluoromethyl)copper. Alternatively, one may start from a CF3‐substituted arene or heterocycle as a core and complete it with the missing parts of the ultimate structure.
Using Bioconjugated Nanoparticles To Monitor E. coli in a Flow Channel
Authors: Mechery Shelly John , Zhao Xiaojun Julia , Wang Lin , Hilliard Lisa R. , Munteanu Alina , Tan Weihong
Published: July 2006

A simple and portable flow channel optical detection system combined with bioconjugated luminescent nanoparticles allows the rapid detection of single bacterial cells without sample enrichment. The optical system is designed to have single‐molecule‐detection capability in a microcapillary flow channel by decreasing the laser excitation probe volume to a few picoliters, which consequently results in a low background. Specific monoclonal antibodies were immobilized on nanoparticles to form nanoparticle–antibody conjugates. The bioconjugated nanoparticles bind to the target bacteria when they recognize the antigen on the bacterium surface, thus providing a bright luminescent signal for the detection of individual bacteria cells. The high sensitivity provided by the luminescent and photostable silica nanoparticles eliminates the need for further enrichment of bacteria samples and signal amplification. This flow channel detection system is convenient and allows the detection of single bacterial cells within a few minutes.
Mining plant diversity: Gerbera as a model system for plant developmental and biosynthetic research
Authors: Teeri Teemu H. , Elomaa Paula , Kotilainen Mika , Albert Victor A.
Published: July 2006

Gerbera hybrida is a member of the large sunflower family (Asteraceae). Typical of Asteraceae, Gerbera bears different types of flowers in its inflorescence. The showy marginal flowers comprise elongate, ligulate corollas that are female, whereas the central and inconspicuous disc flowers are complete, with both male and female organs. As such, Gerbera offers great potential for comparative developmental research within a single genotype. Moreover, different Gerbera varieties show an impressive spectrum of color patterns, directly displaying responses to developmental cues at all important morphological levels (flower type, flower organ and within organs). Further, Gerbera harbors an arsenal of Asteraceae‐type secondary metabolites, not present in other model plants. With powerful reverse genetics methods, a large collection of EST sequences and a new cDNA microarray, Gerbera has become a model plant of the sunflower family. BioEssays 28: 756–767, 2006. © 2006 Wiley Periodicals, Inc.
New instruments – old practices? The implications of environmental management systems and extended producer responsibility for design for the environment
Authors: Kautto Petrus
Published: July 2006

As the focus of environmental policy and management is shifting from cleaner production at the process level towards greener products, there is a need for new kinds of policy instruments and initiatives. Environmental management systems (EMSs) and extended producer responsibility (EPR) systems are efforts to overcome the limitations of the traditional regulatory approach. In this paper, I illustrate how EMSs and EPR systems have influenced the emergence of greener products in three case companies. These case studies are complemented by results from a survey on design for the environment in the electrical and electronics industry. Both the case studies and the survey indicate that the linkage between EMSs and product development is weak or completely missing. Therefore, the mere existence of an EMS can hardly be used as a convincing indicator of the implementation of an environmentally friendly design process. The results regarding the EPR systems are more positive. Copyright © 2006 John Wiley & Sons, Ltd and ERP Environment.
Sustainable supply chain management in tourism
Authors: Font Xavier , Tapper Richard , Schwartz Karen , Kornilaki Marianna
Published: July 2006

Sustainable supply chain management (SSCM) encapsulates the trend to use purchasing policies and practices to facilitate sustainable development at the tourist destination. Most research has focused on environmental aspects of manufacturing, while other aspects of sustainability or the challenges for the service sector are largely ignored. Yet SSCM is particularly important for tour operators, as the product depends on the activities of suppliers, such as accommodation, transport and activities. Therefore, tour operators' contribution to sustainable tourism will be more effective through the definition and implementation of policies that acknowledge responsibility for the impacts of suppliers. Exploratory research of SSCM practices amongst tour operators generated a wide range of examples of good practice across the whole supply chain, and recommendations are made for more widespread engagement. Copyright © 2006 John Wiley & Sons, Ltd and ERP Environment.
Asymmetric Total Syntheses of Marine Cyclic Depsipeptide Halipeptins A–D
Authors: Yu Shouyun , Pan Xianhua , Ma Dawei
Published: July 2006

Halipeptins A–D (1 a–d) are a family of natural cyclic depsipeptides isolated from marine sponges. Total syntheses of these four compounds are detailed in this report. The key elements in this synthesis include the elaboration of the polysubstituted decanoic acid parts by two asymmetric aldol reactions, assembly of the N‐methyl‐δ‐hydroxyisoleucine residue by using either aza‐Claisen rearrangement or methylation of aspartates as the key steps, and macrocyclization at the polysubstituted decanoic acid alanine site.
Unexpected Reactions of [60]Fullerene Involving Tertiary Amines and Insight into the Reaction Mechanisms
Authors: Wang Guan‐Wu , Chen Xiao‐Ping , Cheng Xin
Published: July 2006

Thermal reactions of [60]fullerene with amino acid ester hydrochlorides and triethylamine in o‐dichlorobenzene at reflux afforded pyrrolidinofullerene derivatives containing the CH3CH moiety and originating from triethylamine through an unusual CN bond cleavage. Detailed investigation of these thermal reactions resulted in the discovery of unprecedented reactions between C60 and tertiary amines and of reactions of C60 with tertiary amines and aldehydes, giving cyclopentafullerene derivatives with high stereoselectivity. Plausible reaction mechanisms for the product formation involving the uncommon CN bond cleavage of tertiary amines were proposed on the basis of extensive experimental results.
Neutrophil recruitment in immunized mice depends on MIP‐2 inducing the sequential release of MIP‐1α, TNF‐α and LTB4
Authors: Ramos Cleber D. L. , Fernandes Karla S. S. , Canetti Claudio , Teixeira Mauro M. , Silva João S. , Cunha Fernando Q.
Published: July 2006

Neutrophils are thought to play an important role in the tissue damage observed in various autoimmune diseases. Chemokines, cytokines and leukotrienes have recognized roles in the orchestration of neutrophil migration. We have recently shown that antigen‐induced neutrophil migration into the peritoneum of immunized mice is mediated by macrophage‐inflammatory protein (MIP)‐1α which interacts with CCR1 and induces the sequential release of TNF‐α and leukotriene B4 (LTB4). The present study investigates the role of MIP‐2 and CXCR2 in the cascade of events leading to mediator generation and neutrophil influx. Antigen challenge of immunized mice induced the expression of CXCR2 and the production of KC and MIP‐2 proteins. Antigen‐induced neutrophil migration was inhibited by a CXCR2 receptor antagonist (repertaxin) or an anti‐MIP‐2 antibody, but not by an anti‐KC antibody. Administration of MIP‐2 promoted a dose‐dependent neutrophil migration in naive mice which was inhibited by repertaxin, anti‐TNF‐α, anti‐MIP‐1α antibodies or by MK886 (leukotriene synthesis inhibitor). MIP‐2 administration induced the release of MIP‐1α, TNF‐α and LTB4, and the release of the latter two was inhibited by anti‐MIP‐1α antibody treatment. Our studies highlight the intricate balance between mediator production and action during an immune‐mediated inflammatory response and suggest a mediator cascade leading to neutrophil influx following antigen challenge of immunized mice: MIP‐2 → MIP‐1α → TNF‐α → LTB4.
Distinct patterns of gene expression in the left and right hippocampal formation of developing rats
Authors: Moskal Joseph R. , Kroes Roger A. , Otto Nigel J. , Rahimi Omid , Claiborne Brenda J.
Published: July 2006

A central problem in neurobiology is the elucidation of the mechanisms that underlie left–right asymmetries in brain structure and function. Using a transcriptome screening approach, we found asymmetric gene expression patterns in the right when compared with the left hippocampal formation at postnatal days (P) 6, 9, and 60 in the rat. Of those genes that were differentially expressed, most were predominantly expressed in the right hippocampus at P6, whereas most were predominantly expressed in the left at P9 and P60. Real‐time PCR analysis of genes associated with synaptic vesicle trafficking confirmed this pattern. At P6, 9 of 13 such genes were more robustly expressed in the right hippocampus, while only 1 gene was predominantly expressed in the left. Conversely, at P9, 5 of the 13 genes were more highly expressed in the left hippocampus and only 1 gene was predominantly expressed in the right. This pattern persisted at P60: eight genes were more robustly expressed in the left hippocampus, and the remaining five showed no hemispheric preference. These data demonstrate a pattern of early lateralized gene expression that is likely to underlie the establishment of functional asymmetry in the adult hippocampus. © 2006 Wiley‐Liss, Inc.
Epigenetic silencing of multiple genes in primary CNS lymphoma
Authors: Chu Linda C. , Eberhart Charles G. , Grossman Stuart A. , Herman James G.
Published: July 2006

Epigenetic silencing of functionally important genes is important in the development of malignancies and is a source of potential markers for molecular detection. Primary central nervous system lymphoma (PCNSL) is an increasingly common tumor that has not been extensively examined for changes in promoter region methylation. We examined 14 tumor suppressor genes in 25 cases of PCNSL using methylation‐specific PCR. Methylation was observed in DAPK (84%), TSP1 (68%), CRBP1 (67%), p16INK4a (64%), p14ARF (59%), MGMT (52%), RARβ2 (50%), TIMP3 (44%), TIMP2 (42%), p15INK4b (40%), p73 (28%), hMLH1 (12%), RB1 (8%) and GSTP1 (8%). Promoter methylation of p14ARF, p16INK4a and MGMT was correlated with loss of expression by immunohistochemical staining. The methylation of many of these genes in PCNSL is similar to that reported in other high‐grade B‐cell lymphomas. All 25 cases of PCNSL had methylation of at least 2 genes. Methylation of DAPK, p16INK4a or MGMT was found in 96% of the tumors, suggesting simple marker strategies to detect circulating methylated DNA in serum that might facilitate early tumor detection. Our study provides insight into the epigenetic alterations in PCNSL and provides potential biomarkers of disease. © 2006 Wiley‐Liss, Inc.
Circadian rhythms of heart rate and locomotion after treatment with low‐dose acetylcholinesterase inhibitors
Authors: Scremin Oscar U. , Shih Tsung‐Ming , Huynh Ly , Roch Margareth , Sun Wei , Chialvo Dante R. , Jenden Donald J.
Published: July 2006

This study tested the hypothesis that repeated exposure to low levels of sarin, pyridostigmine bromide (PB) or their combination, at doses equivalent to those possibly experienced by veterans of the 1991 Persian Gulf War, could lead to persistent or delayed autonomic effects and thus help to explain the cause of clinical findings in this population. Male Sprague‐Dawley rats were treated for 3 weeks with: saline injection (0.5 ml kg−1, s.c., 3 times weekly) with tap drinking water (control); saline injection with PB (80 mg l−1 in drinking water); sarin injection (62.5 µg kg−1, s.c., 0.5 × LD50, 3 times weekly) with tap drinking water (sarin); or sarin injection with PB in drinking water (sarin + PB). At 2, 4 or 16 weeks post‐treatment, heart rate (HR) and locomotor activity (LA) were studied by radiotelemetry. Two weeks posttreatment, HR in drug‐treated animals was significantly lower than in controls. A decrease in low‐frequency HR power spectrum (PS) was found at 00:00 h and 08:00 h with sarin + PB and at 00:00 h with sarin, while total power was enhanced with sarin + PB at 22:00 h. Minimal effects of drug treatments on HR and HR PS were detected at 4 and 16 weeks post‐treatment. No significant differences in LA between control and other groups were found. Since no consistent long‐term effects were found in any of the variables studied, these experiments do not support the hypothesis that repeated administration of low doses of PB and the nerve agent sarin can induce persistent or delayed alterations in autonomic function. Copyright © 2006 John Wiley & Sons, Ltd.
γ‐Radiation‐induced changes in structure and properties of tetracalcium phosphate and its derived calcium phosphate cement
Authors: Tsai Chih‐Hung , Lin Jiin‐Huey Chern , Ju Chien‐Ping
Published: July 2006

The purpose of the present study was to investigate the γ‐radiation effect on the structure and properties of the single‐phase tetracalcium phosphate (TTCP) powder and its derived calcium phosphate cement (CPC). Experimental results show that low‐dosed (0–30 kGy) CPC has a setting time of 10–12 min, while high‐dosed (40–120 kGy) CPC has a setting time of 8–10 min. The low dose γ‐radiation does not significantly change porosity volume fraction or compressive strength of the CPC. The pH values of all CPC samples fell in a relatively narrow band, with a band width of 8.5–9.1 (in terms of pH value). With a dose of 10 or 20 kGy γ‐radiation, the TTCP–apatite conversion ratio does not change much. With 30 kGy the conversion ratio significantly increases and reaches a maximum value. With further increases in dose, the conversion ratio quickly declines. With increasing γ‐ray dose, the CPC morphology becomes more porous/loose and apatite particles become larger in size. When exposed to a high dose (120 kGy) of γ‐radiation, TTCP structure is radiation‐damaged, and γ‐ray‐induced formation of apatite is confirmed by transmission electron microscopic/selected‐area diffraction/lattice imaging analyses. © 2006 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2007
Characterization of photopolymerization of dentin adhesives as a function of light source and irradiance
Authors: Ye Qiang , Wang Yong , Williams Karen , Spencer Paulette
Published: July 2006

Manufacturers have attempted to address the limitations associated with dentin bonding by eliminating as many steps as possible in the bonding protocol. Theoretically, this approach increases the efficiency of the procedure and reduces technique sensitivity. These trends are reflected in the introduction of all‐in one, single‐step adhesive systems; the increased concentration of acidic resin monomers in these systems allows for simultaneous etching and priming of the prepared dentin surface. Ideally, the degree of monomer conversion would be high enough that the acidic reaction would be self‐limiting. The purpose of this study was to investigate the effect of light irradiance and source on the photopolymerization of three commercial dental adhesives by monitoring the double bond conversion as a function of time during and after irradiation. The photopolymerization curing efficiency of the commercial adhesives investigated in this study varied as a function of light source and distance. The use of LED performed better than the halogen light in terms of polymerization rate and degree of conversion for the commercial single‐step, sixth generation adhesive, Adper Prompt. In contrast, polymerization of commercial single‐bottle, fifth generation adhesive, Single Bond and One‐Up Bond F, was mainly a function of exposure time, irrespective of the two light units or intensities. © 2006 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2007