bluuebunny/crossref_metadata_2025 huggingface dataset:
Cytologic features of nipple aspirate fluid using an automated non-invasive collection device: a prospective observational study
Authors: Proctor Kerry AS , Rowe Leslie R , Bentz Joel S
Published: August 2005

Background

Detection of cytologic atypia in nipple aspirate fluid (NAF) has been shown to be a predictor of risk for development of breast carcinoma. Manual collection of NAF for cytologic evaluation varies widely in terms of efficacy, ease of use, and patient acceptance. We investigated a new automated device for the non-invasive collection of NAF in the office setting.

Methods

A multi-center prospective observational clinical trial involving asymptomatic women designed to assess fluid production, adequacy, safety and patient acceptance of the HALO NAF Collection System (NeoMatrix, Irvine, CA). Cytologic evaluation of all NAF samples was performed using previously described classification categories.

Results

500 healthy women were successfully enrolled. Thirty-eight percent (190/500) produced fluid and 187 were available for cytologic analysis. Cytologic classification of fluid producers showed 50% (93/187) Category 0 (insufficient cellular material), 38% (71/187) Category I (benign non-hyperplastic ductal epithelial cells), 10% (18/187) Category II (benign hyperplastic ductal epithelial cells), 3% (5/187) Category III (atypical ductal epithelial cells) and none were Category IV (unequivocal malignancy). Overall, 19% of the subjects produced NAF with adequate cellularity and 1% were found to have cytologic atypia.

Conclusion

The HALO system is a simple, safe, rapid, automated method for standardized collection of NAF which is acceptable to patients. Cytologic assessment of HALO-collected NAF showed the ability to detect benign and pre-neoplastic ductal epithelial cells from asymptomatic volunteers.
Macrophages and cytokines in the early defence against herpes simplex virus
Authors: Ellermann-Eriksen Svend
Published: August 2005

Herpes simplex virus (HSV) type 1 and 2 are old viruses, with a history of evolution shared with humans. Thus, it is generally well-adapted viruses, infecting many of us without doing much harm, and with the capacity to hide in our neurons for life. In rare situations, however, the primary infection becomes generalized or involves the brain.

Normally, the primary HSV infection is asymptomatic, and a crucial element in the early restriction of virus replication and thus avoidance of symptoms from the infection is the concerted action of different arms of the innate immune response. An early and light struggle inhibiting some HSV replication will spare the host from the real war against huge amounts of virus later in infection. As far as such a war will jeopardize the life of the host, it will be in both interests, including the virus, to settle the conflict amicably. Some important weapons of the unspecific defence and the early strikes and beginning battle during the first days of a HSV infection are discussed in this review.

Generally, macrophages are orchestrating a multitude of anti-herpetic actions during the first hours of the attack. In a first wave of responses, cytokines, primarily type I interferons (IFN) and tumour necrosis factor are produced and exert a direct antiviral effect and activate the macrophages themselves. In the next wave, interleukin (IL)-12 together with the above and other cytokines induce production of IFN-γ in mainly NK cells. Many positive feed-back mechanisms and synergistic interactions intensify these systems and give rise to heavy antiviral weapons such as reactive oxygen species and nitric oxide. This results in the generation of an alliance against the viral enemy.

However, these heavy weapons have to be controlled to avoid too much harm to the host. By IL-4 and others, these reactions are hampered, but they are still allowed in foci of HSV replication, thus focusing the activity to only relevant sites. So, no hero does it alone. Rather, an alliance of cytokines, macrophages and other cells seems to play a central role. Implications of this for future treatment modalities are shortly considered.
Anti-HIV activity of dibenzylbutyrolactone-type lignans from Phenax species endemic in Costa Rica
Authors: Piccinelli A L , De Simone F , Rastrelli L , Mahmood N , Mora G , Poveda L
Published: August 2005

Previously, we isolated two new dibenzylbutyrolactone-type lignans, named phenaxolactones 1 and 2, from the leaves of Phenax angustifolius Wedd. (Urticaceae). In this investigation three new dibenzylbutyrolactone lignans (phenaxolactones 3–5), together with phenaxolactone 1, and flavones vitexin (6), isovitexin (7), were isolated from Phenax rugosus Wedd. leaves collected in Santa Ana, Costa Rica. The structures were elucidated using 1D and 2D NMR spectroscopy as well as mass spectrometry. Phenaxolactones 1–5 and flavones 6 and 7 were evaluated for their inhibitory activity against HIV-1MN in infected C8166 cells. The most promising compound was phenaxolactone 1 with an EC50 value of 3.0μM, no cytotoxicity at 112μM and a therapeutic index value of 37.3.
Brain permeability of inhaled corticosteroids
Authors: Arya Vikram , Issar Manish , Wang Yaning , Hochhaus Guenther , Talton James D
Published: August 2005

The aim of this study was to evaluate if the permeability of inhaled corticosteroids entering the brain is reduced and if P-glycoprotein (P-gp) transporters are involved. Currently employed inhaled corticosteroids were given intravenously and intratracheally to rats at a dose of 100 μg kg−1. An ex-vivo receptor binding assay was used to monitor over 12 h the glucocorticoid receptor occupancy in the brain and a systemic reference organ (kidney). The involvement of P-gp in the brain permeability of triamcinolone acetonide was assessed in wild-type mice and mdr1a(-/-) knockout mice (mice lacking the gene for expressing P-gp). After both forms of administration, the average brain receptor occupancies were 20–56% of those of the reference organ, with the more lipophilic drugs showing a more pronounced receptor occupation. While the receptor occupancies in the liver of wild-type and mdr1a(-/-) mice were similar after administration of triamcinolone acetonide, brain receptor occupancies in mdr1a(-/-) mice were significantly greater (mdr1a(-/-): 47.6%, 40.2–55.0%, n = 2; wild-type: 11.5±33.0%, n = 3). Penetration into the brain for inhaled corticosteroids (especially those of lower lipophilicity) is reduced. Experiments in mdr1a(-/-) mice confirmed the involvement of P-gp transporters. Further studies are needed to assess whether potential drug interactions at the transporter level are of pharmacological significance.
Effects of 4-piperidinomethyl-2-isopropyl-5-methylphenol on oxidative stress and calcium current
Authors: Huang Mei-Han , Liao Li-Fang , Kuo Shih-Hsien , Chen Chi-Lan , Shen Ai-Yu
Published: August 2005

4-Piperidinomethyl-2-isopropyl-5-methylphenol (THPI) was synthesized by reaction of thymol with piperidine and formaldehyde. The biological effect of THPI on superoxide anion scavenging activity, antiplatelet activity and calcium current inhibition were investigated. THPI (50 μm) was shown to be a scavenger of superoxide radicals in human neutrophils stimulated with N-formyl-Met-Leu-Phe (66% inhibition). Since superoxide anions are essential for platelet aggregation and L-type Ca2+-channel activity, we further found that THPI inhibited platelet aggregation induced by arachidonic acid (IC50 46.80 ± 6.88 μm). The effect of THPI on Ca2+ current in NG108–15 cells was investigated using the whole-cell voltage-clamp technique. THPI inhibited voltage-dependent L-type Ca2+ current (ICa,L). The IC50 value of THPI-induced inhibition of ICa,L was 3.60 ± 0.81 μm. THPI caused no change in the overall shape of the current-voltage relationship of ICa,L. This indicates that THPI is an inhibitor of ICa,L in NG108–15 cells. Therefore, the channel-blocking properties of THPI may contribute to the underlying mechanism by which it affects neuronal or neuroendocrine function. Furthermore, no significant cytotoxic effects of THPI (0.3–50 μm) were observed in NG108–15 cells. The results indicate that THPI is a potential reactive oxygen species scavenger and may prevent platelet aggregation or inhibit L-type Ca2+-channel activity, possibly by scavenging reactive oxygen species.
Evaluation of the cytotoxic effect of the monoterpene indole alkaloid echitamine in-vitro and in tumour-bearing mice
Authors: Jagetia Ganesh Chandra , Baliga Manjeshwar Shrinath , Venkatesh Ponemone , Ulloor Jagadish N , Mantena Sudheer Kumar , Genebriera Joseph , Mathuram V
Published: August 2005

The cytotoxic effect of various concentrations of echitamine chloride was studied in HeLa, HepG2, HL60, KB and MCF-7 cell lines in-vitro and in mice bearing Ehrlich ascites carcinoma (EAC). Exposure of various cells to different concentrations of echitamine chloride resulted in a concentration-dependent cell killing, and KB cells were found to be most sensitive amongst all the cells evaluated. EAC mice treated with 1, 2, 4, 6, 8, 12 or 16 mgkg−1 echitamine chloride showed a dose-dependent elevation in the anti-tumour activity, as evident by increased number of survivors in comparison with the non-drug treated controls. The highest dose of echitamine chloride (16 mg kg−1) caused toxicity in the recipient mice, therefore 12 mg kg−1 was considered the best cytotoxic dose for its anti-tumour effect. Administration of 12 mg kg−1 echitamine chloride resulted in an increase in the median survival time (MST) up to 30.5 days, which was 11.5 days higher than the non-drug treated control (19 days). Administration of 16 mg kg−1 echitamine chloride to EAC mice resulted in a time dependent elevation in lipid peroxidation that reached a peak at 6 h post-treatment, whereas glutathione concentration declined in a time dependent manner and a maximum decline was reported at 3 h post-treatment. Our study demonstrated that echitamine chloride possessed anti-tumour activity in-vitro and in-vivo.
Shaken, not stirred: a serendipitous study of ants and earthquakes
Authors: Lighton John R. B. , Duncan Frances D.
Published: August 2005

There is anecdotal evidence for profound behavioral changes prior to and during earthquakes in many organisms, including arthropods such as ants. Behavioral or physiological analysis has often, in light of these reports,been proposed as a means of earthquake prediction. We report here a serendipitous study of the effect of the powerful Landers earthquake in the Mojave Desert, USA (Richter magnitude 7.4) on ant trail dynamics and aerobic catabolism in the desert harvester ant Messor pergandei. We monitored trail traffic rates to and from the colony, trail speed, worker mass distributions, rates of aerobic catabolism and temperature at ant height before and during the earthquake, and for 3 days after the earthquake. Contrary to anecdotal reports of earthquake effects on ant behavior, the Landers earthquake had no effect on any measured aspect of the physiology or behavior of M. pergandei. We conclude that anecdotal accounts of the effects of earthquakes or their precursors on insect behavior should be interpreted with caution.
Ontogenetic changes in the response properties of individual, primary auditory afferents in the vocal plainfin midshipman fish Porichthys notatus Girard
Authors: Sisneros Joseph A. , Bass Andrew H.
Published: August 2005

The auditory system of adult midshipman fish Porichthys notatusGirard is an important sensory receiver system used during intraspecific social communication to encode conspecific vocalizations, but the response properties and function of this system in the pre-adult stages are unknown. Midshipman fish, like other teleosts, use the saccule as the main acoustic end organ of the inner ear. In this study, we examined the discharge properties and the frequency response dynamics of auditory saccular afferent neurons in pre-adult midshipman (∼4–12 months of age) to determine whether encoding of auditory information, inclusive of conspecific vocalizations,changes across life history stages. Extracellular single unit recordings were made from saccular afferents while sound was presented via an underwater speaker. Comparisons with adult data show that the resting discharge rate and auditory threshold sensitivity increased with age/size,while temporal encoding of frequency did not show any significant shifts. The results indicate that the saccular afferents of juveniles, like those of non-reproductive adults, are best adapted to temporally encode the low frequency components (≤100 Hz) of midshipman vocalizations. This report represents the first in vivo investigation of age-related changes in the encoding properties of individual auditory neurons for any fish species.
The aerodynamic effects of wing–wing interaction in flapping insect wings
Authors: Lehmann Fritz-Olaf , Sane Sanjay P. , Dickinson Michael
Published: August 2005

We employed a dynamically scaled mechanical model of the small fruit fly Drosophila melanogaster (Reynolds number 100–200) to investigate force enhancement due to contralateral wing interactions during stroke reversal (the `clap-and-fling'). The results suggest that lift enhancement during clap-and-fling requires an angular separation between the two wings of no more than 10–12°. Within the limitations of the robotic apparatus, the clap-and-fling augmented total lift production by up to 17%, but depended strongly on stroke kinematics. The time course of the interaction between the wings was quite complex. For example, wing interaction attenuated total force during the initial part of the wing clap, but slightly enhanced force at the end of the clap phase. We measured two temporally transient peaks of both lift and drag enhancement during the fling phase: a prominent peak during the initial phase of the fling motion, which accounts for most of the benefit in lift production, and a smaller peak of force enhancement at the end fling when the wings started to move apart. A detailed digital particle image velocimetry (DPIV) analysis during clap-and-fling showed that the most obvious effect of the bilateral `image' wing on flow occurs during the early phase of the fling, due to a strong fluid influx between the wings as they separate. The DPIV analysis revealed, moreover, that circulation induced by a leading edge vortex (LEV) during the early fling phase was smaller than predicted by inviscid two-dimensional analytical models, whereas circulation of LEV nearly matched the predictions of Weis-Fogh's inviscid model at late fling phase. In addition, the presence of the image wing presumably causes subtle modifications in both the wake capture and viscous forces. Collectively, these effects explain some of the changes in total force and lift production during the fling. Quite surprisingly, the effect of clap-and-fling is not restricted to the dorsal part of the stroke cycle but extends to the beginning of upstroke, suggesting that the presence of the image wing distorts the gross wake structure throughout the stroke cycle.
Phylogenetic approaches in comparative physiology
Authors: Garland Theodore , Bennett Albert F. , Rezende Enrico L.
Published: August 2005

Over the past two decades, comparative biological analyses have undergone profound changes with the incorporation of rigorous evolutionary perspectives and phylogenetic information. This change followed in large part from the realization that traditional methods of statistical analysis tacitly assumed independence of all observations, when in fact biological groups such as species are differentially related to each other according to their evolutionary history. New phylogenetically based analytical methods were then rapidly developed, incorporated into `the comparative method', and applied to many physiological, biochemical, morphological and behavioral investigations. We now review the rationale for including phylogenetic information in comparative studies and briefly discuss three methods for doing this(independent contrasts, generalized least-squares models, and Monte Carlo computer simulations). We discuss when and how to use phylogenetic information in comparative studies and provide several examples in which it has been helpful, or even crucial, to a comparative analysis. We also consider some difficulties with phylogenetically based statistical methods, and of comparative approaches in general, both practical and theoretical. It is our personal opinion that the incorporation of phylogeny information into comparative studies has been highly beneficial, not only because it can improve the reliability of statistical inferences, but also because it continually emphasizes the potential importance of past evolutionary history in determining current form and function.
Structure and function of the esophagus of the American alligator(Alligator mississippiensis)
Authors: Uriona T. J. , Farmer C. G. , Dazely J. , Clayton F. , Moore J.
Published: August 2005

Esophageal structure and function were studied in juvenile American alligators (Alligator mississippiensis). The anatomy of alligators differs from humans in several important aspects: the crocodilian esophagus is more muscular and is composed entirely of smooth muscle. Functionally, the crocodilian esophagus is similar to that of mammals, but alligators have peak esophageal peristaltic pressures that are 2–3-fold greater than pressures in the human esophagus. As is found in humans, the incidence of esophageal reflux increased in postprandial animals compared with the fasting state. We observed a large increase in pressure in the lower esophageal sphincter (LES) during ventilation that ranged from 200% to 3000% of the pressures measured during apnea. These pressure changes appear to be intrinsic to the LES. Alligators lack a mammalian-type diaphragm; thus, there is no crural diaphragmatic contribution to LES pressure. These features recommend the alligator as a useful model for the study of regulation of the LES.
Geometry of elytra opening and closing in some beetles (Coleoptera,Polyphaga)
Authors: Frantsevich Leonid , Dai Zhendong , Wang Wei Ying , Zhang Yafeng
Published: August 2005

Elytra in beetles move actively, driven by their own muscles, only during transient opening and closing. The kinematics of these movements have been inadequately described, sometimes controversially. Our goal was a quantitative 3-D description of diverse active movements of the elytra, in terms of directions of the axes of elytra rotation.

Broad opening and closing was video recorded in beetles, tethered by the mesothorax, and has been analyzed frame by frame. For tracing, small dots or straw arms were glued to the elytra. Opening and closing traces coincided. The trace of the elytron apex was a flat circular arc about the axis of abduction–adduction (AAA). The rising hemiaxis pointed contralaterad. The AAA was tilted forwards in Melolontha hippocastani, Allomyrina dichotoma and Prionus coriarius but backwards in Chalcophora mariana. In Cetonia aurata, the AAA had a low elevation and a strong backward orientation. If another elytra-fixed point was traced in addition to the apex (in M. hippocastani and P. coriarius), then secondary rotation about the sutural edge (supination on opening) occurred. Modeling of abduction–adduction revealed that the elytron rose on opening if the AAA pointed contralaterad. The more the AAA was tilted forward, the more negative was the attack angle of the open elytra. The negative attack angle was partly compensated by positive body pitch and, more effectively, by supination of the costal edge about the sutural edge.

The initial stage of opening included elevation of closed elytra (by 10–12°) and partition to the sides, combined with an inward turn(<2–3°). Axis of rotation at this stage presumably coincided with the AAA. Movement of one elytron with respect to the opposite one at the beginning of opening followed the shallow arc convex down. The geometry of this relative movement describes the initial partition of the elytra and release of the sutural lock.
Influence of host size on the clutch size and developmental success of the gregarious ectoparasitoid Eulophus pennicornis (Nees)(Hymenoptera: Braconidae) attacking larvae of the tomato moth Lacanobia oleracea (L.) (Lepidoptera: Noctuidae)
Authors: Bell H. A. , Marris G. C. , Prickett A. J. , Edwards J. P.
Published: August 2005

The relationship between clutch size, host size and progeny survival in the gregarious ectoparasitoid Eulophus pennicornis was investigated in a number of scenarios. When naive parasitoids were exposed singly to Lacanobia oleracea hosts, clutch size was strongly correlated with the size of the host. However, survival of parasitoid offspring was negatively affected by the size of the host such that, in larger hosts, greater wasp larval and pupal mortality was recorded. As a result, no gain in realised fecundity was achieved through parasitizing L. oleracea larvae of mass >0.4 g over hosts of mass between 0.2–0.3 g. When exposed to populations of mixed stadium hosts (larvae in the fourth, fifth and sixth instars) during the entire lifespan of the wasp, host size and clutch size were correlated in early ovipositions (first three ovipositions). However, as the wasps aged, the relationship was much less apparent. When the parasitoid was restricted to foraging upon populations of sixth instar hosts only, no relationship between host size and clutch size was apparent. Exposure of the parasitoid to mixed and fixed stadium host populations showed that final(sixth) stadium hosts were the most frequently parasitized (ca. 96% of parasitized hosts) and that the average numbers of eggs laid per wasp, and the number of hosts parasitized, was significantly lower when the parasitoid was provided with fourth or fifth instar hosts only. The results indicate that the reproductive success of E. pennicornis does not increase with increasing host size or greater resource availability above a certain threshold, and that the physiological status of the host at the time of parasitism is the governing factor determining oviposition decisions and parasitoid survival. We conclude that E. pennicornis has been selected to preferentially utilize those hosts that maximize progeny survival and to adapt clutch size to the size of such hosts. We hypothesize that the major driver leading to the evolution of this strategy is the ability of the parasitoid to physiologically regulate the host.
Molecule-Based Magnets in Heterospin Systems
Authors: Koga Noboru , Karasawa Satoru
Published: August 2005

Our approaches to the molecule-based magnets by using heterospin systems are reviewed. In our heterospin systems consisting of the organic 2p spins and the metal ion 3d spins, various pyridines carrying the organic spins were used as binding ligands for 3d metal ions. Carbenes generated by photolysis of diazo groups and persistent N-tert-butylaminoxyl radicals were employed as the organic spin sources. First, various model complexes were prepared and their magnetic couplings between the organic spin and the metal ion through the pyridine ligand were revealed. Based on the results of magnetic studies on model complexes, ferri- and ferromagnetic complexes having linear chain structures were designed and successfully prepared. When our heterospin systems were used under solution conditions, new fields were opened. Assemblies formed in frozen solution had magnetic behaviors exhibiting slow magnetic relaxations. Especially, when the anisotropic metal ion, high-spin cobalt(II) ion, was used as the metal ion in our heterospin system, the complex formed in frozen solution functioned as a single-molecule magnet (SMM). Such formation of a monometallic SMM was the first example reported.
Ion-Association Analysis between Inorganic Anions and Symmetrical Tetraalkylammonium Ions in Aqueous-Acetonitrile Media by Capillary Zone Electrophoresis
Authors: Mbuna Julius , Takayanagi Toshio , Oshima Mitsuko , Motomizu Shoji
Published: August 2005

Weak ion-association equilibrium was analyzed in a water-acetonitrile solution at 25 °C by capillary zone electrophoresis using an ordinary silica capillary. The ion associates examined were formed between some inorganic anions and symmetrical tetraalkylammonium ions, where a series of acetonitrile compositions up to 62.2% (m/m) were investigated. Ion-association constants, Kass, were determined by analyzing the changes in the electrophoretic mobility; the Kass values for most of the anions increased up to about 47% (m/m) acetonitrile, beyond which they remained constant, or decreased slightly. The ion-association equilibrium between tetramethylammonium and bromide ions in aqueous-acetonitrile and in aqueous-ethanol media were compared through the Gibbs free energy of transfer, which revealed that the extent of the equilibrium in aqueous-acetonitrile media is dependent mainly on the increasing instability of Br−. On the other hand, those in aqueous-ethanol media depend on the instabilities of both tetramethylammonium and bromide ions.
Selective C–C Bond Activation of 2-Aryl-1-methylenecyclopropanes Promoted by Ir(I) and Rh(I) Hydrido Complexes. Mechanism of Ring-Opening Isomerization of the Strained Molecules
Authors: Nishihara Yasushi , Yoda Chikako , Itazaki Masumi , Osakada Kohtaro
Published: August 2005

[IrH(CO)(PPh3)3] promotes ring opening of 2-phenyl-1-methylenecyclopropane at room temperature to produce the Ir complex with a chelating 2-phenyl-3-butenyl ligand, [Ir{η2-CH2CH(Ph)CH=CH2-κC1}(CO)(PPh3)2] (1). The reaction of excess 2-phenyl-1-methylenecyclopropane with [IrH(CO)(PPh3)3] at 50 °C yields [Ir{η2-(o-C6H4)CH(Me)CH=CH2-κC1}(CO)(PPh3)2] (2), accompanied by the formation of 1-phenyl-1,3-butadiene and 2-phenyl-1,3-butadiene. 2,2-Diphenyl-1-methylenecyclopropane reacts with [IrH(CO)(PPh3)3] to afford [Ir{η2-CH2CPh2CH=CH2-κC1}(CO)(PPh3)2] (3) at 50 °C and [Ir{η2-(o-C6H4)CMe(Ph)CH=CH2-κC1}(CO)(PPh3)2] (4) at 100 °C. Heating a solution of 3 at 100 °C also forms 4 quantitatively. X-ray crystallography of 3 reveals a penta-coordinated structure around the Ir center bonded to a chelating 2,2-diphenyl-3-butenyl ligand. The reactions of 2,2-diphenyl-1-methylenecyclopropane and of 2,2-di(4-fluorophenyl)-1-methylenecyclopropane with [RhH(CO)(PPh3)3] at room temperature yield [Rh{η2-CH2CAr2CH=CH2-κC1}(CO)(PPh3)2] (5a: Ar = Ph, 5b: Ar = C6H4-F-4). The reactions at 50 °C cause ring opening of the substrate and orthometalation of the phenyl group to afford [Rh{η2-(o-C6H4)CMe(Ph)CH=CH2-κC1}(CO)(PPh3)2] (6a) and [Rh{η2-(o-C6H3-F-4)CMe(C6H4-F-4)CH=CH2-κC1}(CO)(PPh3)2] (6b), respectively. Formation of 1,1-diaryl-1,3-butadiene is observed during the reaction. Heating a solution of 5a at 50 °C produces 1,1-diphenyl-1,3-butadiene and an allylrhodium complex, 8, rather than 6a, although the reaction of excess 2,2-diphenyl-1-methylenecyclopropane with 5a at 50 °C affords 6a in 60%. The mechanisms of the above reactions are discussed based on the products and reaction rates. Coordination of P(OMe)3 to the Rh center of 5a causes insertion of the CO ligand into the Rh–C bond to afford [Rh{η2-CO-CH2CPh2CH=CH2-κC1}(P(OMe)3)3] (7).
A New Method for the Synthesis of Carboxylic Esters and Lactones with Di-2-thienyl Carbonate (2-DTC) by the Promotion of DMAP and Iodine
Authors: Oohashi Yoshiaki , Fukumoto Kentarou , Mukaiyama Teruaki
Published: August 2005

The esterification of carboxylic acids with alcohols by using di-2-thienyl carbonate (2-DTC) in the presence of a catalytic amount of 4-(dimethylamino)pyridine (DMAP) proceeded smoothly to afford the corresponding esters in good-to-high yields along with 2(5H)-thiophenone. This esterification was accelerated by the addition of an equimolar amount of iodine to afford the esters in higher yields within a shorter reaction time. Further, cyclization of ω-hydroxycarboxylic acids with an equimolar amount of 2-DTC in the presence of a catalytic amount of DMAP, followed by the addition of 1–4 equimolar amounts of iodine, afforded the corresponding lactones in good-to-high yields under mild conditions. This method was successfully employed in the synthesis of erythro-aleuritic acid lactone.
Substituent-Control of Two Modes of Intramolecular Reactions of Allyloxy-Silyllithiums and Propargyloxy-Silyllithiums
Authors: Kawachi Atsushi , Maeda Hirofumi , Tamao Kohei
Published: August 2005

Intramolecular reactions of the [(allyloxy)silyl]lithiums and the [(propargyloxy)silyl]lithiums have been investigated. The [(allyloxy)silyl]lithiums proceed in two reaction modes depending on the electronic effect of the substituents at the terminus of the olefin. The [(allyloxy)silyl]lithiums bearing hydrogen, n-C6H13, or trimethylsilyl substituent undergo the [2,3]-sila-Wittig rearrangement to afford the lithium allylsilanolates, while those bearing the phenyl, thienyl, or triphenylsilyl substituent experience the 4-exo-trig cyclization and subsequent 1,3-cycloelimination to give the lithium cyclopropylsilanolates. On the other hand, the [(propargyloxy)silyl]lithiums preferentially undergo the 4-exo-dig cyclization over the [2,3]-sila-Wittig rearrangement in all cases.
Total Synthesis of (+)-Tanikolide, Using Regioselective Elimination of a Vicinal Dibromoalkane
Authors: Ohgiya Tadaaki , Nakamura Kensuke , Nishiyama Shigeru
Published: August 2005

Total synthesis of (+)-tanikolide, a bioactive δ-lactone of marine origin, was successfully accomplished by utilizing a bromoalkene derivative conveniently synthesized from the corresponding 1-acyloxy-2,3-dibromoalkane by the regioselective and mild HBr-elimination reaction, along with the Pd-mediated C–C coupling reaction and the Sharpless asymmetric epoxidation as key steps.
Decomposition of Dichlorodifluoromethane with Simultaneous Halogen Fixation by Vanadium Oxide Supported on Magnesium Oxide
Authors: Tamai Tsukasa , Inazu Koji , Aika Ken-ichi
Published: August 2005

Dichlorodifluoromethane (CCl2F2, 1% in He) decomposition with simultaneous halogen fixation by vanadium oxide supported on magnesium oxide was studied at 723 K in a flow apparatus. The pretreatment condition and vanadium loading of supported vanadium oxide samples affected the CCl2F2 decomposition efficiency. Through characterization studies (XRD, IR, Raman, and XPS) and reference experiments, Mg3(VO4)2 was revealed to be the active species to initiate CCl2F2 decomposition, leading to MgF2, MgCl2, and CO2 formation. The model experiments also suggested a detailed mechanism that VOCl3 was formed from Mg3(VO4)2 by a reaction with CCl2F2 or the major intermediate compound CCl4, and that VOCl3 reacted with MgO to regenerate Mg3(VO4)2 and to promote chlorine fixation as MgCl2.
Getting the Properties Right to Secure Property Rights: Dixit's Lawlessness and Economics
Authors: Rauch James E
Published: August 2005

This is a review article of Lawlessness and Economics: Alternative Modes of Governance (Princeton University Press 2004) by Avinash K. Dixit.
Foundations of Human Sociality: A Review Essay
Authors: Samuelson Larry
Published: August 2005

This is a review article of Foundations of Human Sociality: Economic Experiments and Ethnographic Evidence from Fifteen Small-Scale Societies (Oxford University Press 2004) edited by Joseph Henrich, Robert Boyd, Samuel Bowles, Colin Camerer, Ernst Fehr, and Herbert Gintis.
The Electronic Absorption Spectra of Some N-Substituted Pyrroles—Molecular Orbital Calculations
Authors: Abu-Eittah R. , Hilal R. , El-Shall M. S.
Published: August 2005

The electronic absorption spectra of N-phenylpyrrole and some of its parasubstituted derivatives have been investigated in polar and nonpolar solvents. Such an investigation could predict the extent of resonance interaction between the pyrryl and phenyl moieties of the composite molecule. The direction and polarization of the electronic transitions were predicted. Molecular orbital calculations using the SCF-CI procedures were performed on N-phenylpyrrole and some of its p-substituted derivatives. The state functions and energies were computed. The weight of each configuration was evidence for the direction of the electronic transition. The correspondence between the theoretical and experimental results is satisfactory.
A New Possibility for Nondestructive Protein Content Determinations in Viable Seeds
Authors: Rutar V.
Published: August 2005

The use of proton-enhanced magic-angle sample spinning 13C NMR for nondestructive protein content determination is discussed and the first spectra of intact viable seeds are shown. The method has great potential value in plant breeding programs, since selection decisions can be based on the properties of individual seeds.
Frequency Modulation Detection and its Application to Absorption Line Shape Parameters
Authors: de Vreede J. P. M. , Mehrotra S. C. , Tal A. , Dijkerman H. A.
Published: August 2005

The theory for frequency modulation given by Karplus has been extended to include Doppler broadening and arbitrarily large modulation depths. It is shown that the detection limit for second harmonic detection is of the same order as for first harmonic detection: the modulation depth must be approximately the full linewidth of the line profile. Procedures are discussed for extracting from experimental data the linewidth and center frequency of an absorption line with a Voigt profile. At zero detuning information about collisional line broadening can be obtained from the dependence of the second harmonic signal upon the modulation depth. Some experimental examples in the microwave region are presented as a test of the theory. Measurements on the rotational transition J = 2 → 3 (ν2 = 1) of OCS yield collisional self-shift and self-broadening parameters of −0.14 (±0.01) and 5.97 (±0.01) MHz/Torr, respectively; these values are in accordance with literature but are more accurate. For the line center at zero pressure a much more accurate value of 36 571 422.0 ± 0.7 kHz has been found, which is in agreement with recent theoretical calculations.
Vibrational Spectra and Normal Coordinate Calculations of Chlorophosphazene Compounds. I. Hexachlorocyclotriphosphazene
Authors: Painter P. C. , Zarian J. , Coleman M. M.
Published: August 2005

Vibrational spectra and normal coordinate calculations of hexachlorocyclotriphosphazene (HCTP) are presented. Attempts to obtain a common valence force field for HCTP and the two conformers of octachlorocyclotetraphosphazene which were not successful, are discussed. The force field obtained for HCTP is, by necessity, relatively simple. Nevertheless, we have been able to make assignments of the normal modes and resolve some apparent discrepancies in the literature.
Vibrational Spectra and Normal Coordinate Calculations of Chlorophosphazene Compounds. II. Octachlorocyclotetraphosphazene
Authors: Zarian J. , Painter P. C. , Coleman M. M.
Published: August 2005

Vibrational spectra and normal coordinate calculations of octachlorocyclotetraphosphazene (OCTP) are presented. A common valence force field for the two conformers (T and K forms) of OCTP has been developed. A good agreement between the observed and calculated frequencies of OCTP was obtained and the assignments of the normal modes are discussed.
Determination of Monocarbamate to Dicarbamate Ratios in Ethylenediamine Carbamates by NMR Spectroscopy
Authors: Frank Arlen W.
Published: August 2005

The dicarbamate content of the adducts of ethylenediamine with carbon dioxide, carbon disulfide, and carbonyl sulfide can be determined by nuclear magnetic resonance (NMR) spectroscopy. The effect of experimental variables on the dicarbamate content and the stability of the adducts are explored.
Infrared Qualitative Analysis Automated by Use of an Electronic Computer and a Spectral Data File with Band Intensity Information
Authors: Saëki Shinnosuke , Tanabe Kazutoshi , Tamura Tadao , Tasumi Mitsuo , Suzuki Isao
Published: August 2005

An infrared date file with intensity information has been prepared, based on the first 5000 spectra of the data cards of the Infrared Data Committee of Japan (IRDC). A computer program has been developed for the qualitative analysis of binary mixtures using this data file. The program has been applied to 11 binary mixtures; for ten of them it has provided correct answers among the first three compounds outputted by the computer. The computer time necessary for the analysis of a sample mixture was approximately 1 min in TSS mode, excluding the time for the input and output of data. The one unsuccessful case has been proved to be due to the unusual character of the infrared spectrum of one of the components (C2Cl6). Hence this failure does not indicate any serious defect in the program; the developed program has proved to be of practical use.
Tunable Diode Laser Measurements of Water Vapor Line Parameters in the 6-μm Spectral Region
Authors: Mucha J. A.
Published: August 2005

High-resolution infrared diode laser spectroscopy has been used to determine line strengths, foreign-, and self-broadening coefficients for several transitions in the ν2 band of H2O near 6 μm. Sources of systematic experimental error, most notably stray radiation from off-axis modes and thermal etalon effects, were detected and characterized. Their effects on the resulting line parameters were minimized by making appropriate corrections or adjusting experimental conditions such as laser current and temperature. Measured line strengths are found to agree to better than 5% with one published tabulation. Foreign-gas broadening coefficients compare favorably with theoretical values, whereas measured self-broadening coefficients were found to be systematically less.
Infrared Spectra of Aluminum Salt Solutions
Authors: McIntyre J. F. , Foley R. T. , Brown B. F.
Published: August 2005

Aluminum salt solutions activate metallic aluminum surfaces at different rates. The objective of this investigation was to attempt to establish whether or not structural differences at the molecular level could account for the chemical reactivity. The infrared spectra of various concentrations of aluminum chloride, aluminum nitrate, aluminum perchlorate, and aluminum sulfate were measured. The spectra included several general features: (1) a broadening of the OH stretching band of water, (2) a splitting of the OH stretch of water into several absorption bands, (3) the emergence of a new absorption band at 2400 cm−1 (related to dimer formation), (4) splitting of the NO3− absorption band at 1370 cm−1 (5) occasional splitting of the OH bending mode of water, (6) no direct evidence of anion-cation interaction for AlCl3, Al(CIO4)3, and Al2(SO4)3. In general, there was no difference at the molecular level between these aluminum salt solutions that would account for differences in chemical reactivity.
The Determination of Moisture in Some Solid Materials by near Infrared Photoacoustic Spectroscopy
Authors: Jin Q. , Kirkbright G. F. , Spillane D. E. M.
Published: August 2005

An improved technique for the determination of moisture in synthetic single-cell protein, paper, and powdered milk substitute utilizing photoacoustic spectroscopy at 1.93 μm is described. A conventional scanning dispersive system and a simple interference filter assembly have been used.
Applications of Diffuse Reflectance FT-IR to Pigment Photodecomposition in Paint
Authors: Chase D. B. , Amey R. L. , Holtje W. G.
Published: August 2005

Diffuse reflectance FT-IR spectroscopy is used to obtain infrared spectra of paints directly on paper panels. The binder contribution to the spectrum can be effectively eliminated by spectral subtraction and the spectra of photodecomposition products are obtained. Comparison with reference spectra allows the determination of the photodecomposition mechanism.
Analytical Derivatization Reactions Based on Changes in Fluorescence Polarization: A Worthwhile Idea?
Authors: Seitz W. Rudolf
Published: August 2005

When a fluorophor is coupled to an analyte it will necessarily increase in size and, therefore, will depolarize fluorescence less rapidly than fluorophor by itself. Thus, it is possible to distinguish analyte fluorescence from excess reagent fluorescence on the basis of polarization even if the analytical reaction does not otherwise cause a change in fluorescence behavior. This would permit the use of sensitive fluorogenic reagents. However, sensitivity is lost when analyte is distinguished from excess reagent on the basis of polarization because the measured analytical signal is a relatively small difference between large signals. We have calculated detection limits for analyte resolved from excess reagent on the basis of fluorescence polarization relative to the detection limit for fluorophor by itself. Detection limits are calculated as a function of rotational relaxation times for analyte and excess reagent, intrinsic polarization, excess reagent concentrations, and nature of the noise. It is assumed that coupling the fluorophor to analyte does not affect fluorescence efficiency or wavelength distribution. The calculations serve to define the conditions under which it may be practical to resolve analyte from excess reagent on the basis of polarization.
Carbon Measurement in Thin Silicon Wafers (∼400 μm) by Infrared Absorption Spectrometry
Authors: Leroueille J.
Published: August 2005

An original method is developed to determine the carbon content in industrial samples (thin silicon wafers double-side polished) through IR spectrometry. This method permits to remove interference fringes in the infrared spectra by using the properties of Brewster incidence.
Wide Range Two-Crystal Vacuum X-ray Spectrometer for Chemical State Analysis
Authors: Gohshi Y. , Kamada H. , Kohra K. , Utaka T. , Arai T.
Published: August 2005

The design and construction of a new two-crystal x-ray spectrometer are described together with the observed Mg Kα, Al Kα, Si Kα, S Kα, and Cu Kα1 spectra. The spectrometer is designed for x-ray fluorescence analysis and has a wide scanning range (2° to 146° 2θ) under vacuum. Excellent reproducibility of 0.4 s in arc is attainable, which makes possible the observation of chemical shifts in x-ray spectra. Magnesium Kα was found to be influenced by the coordination number, proving that the spectrometer is useful for chemical state analysis.
Natural Abundance N-15 NMR of the Solids from the Reaction of HCN and Ammonia
Authors: Schaefer Jacob , Stejskal E. O. , Jacob Gary S. , McKay R. A.
Published: August 2005

Natural-abundance cross-polarization 15N NMR spectra of the complex solids from the reaction of HCN and ammonia have been obtained at 9.12 MHz with magic-angle sample spinning at 1.5 kHz. The spectra are interpreted in terms of the relative concentrations of nitrile-, aromatic-, amide-, urea-, and ammonia-like nitrogen present. The spectrum of the water-insoluble polymeric fraction of the reaction products shows a diversity of nitrogen functionality as broad as that observed for an isolated bacterial RNA.
Study of Co(or Ni)-Mo Oxide Phase Transformation and Hydrodesulfurization Catalysts by Raman Microprobe Equipped with New Cells
Authors: Payen E. , Dhamelincourt M. C. , Dhamelincourt P. , Grimblot J. , Bonnelle J. P.
Published: August 2005

Heating cells used in optical microscopy are adapted to a laser Raman microprobe to an under air study of the solid phase transformation of cobalt and nickel molybdates in which the molybdenum atoms are in tetrahedral oxygen environment ([a] phase) or in octahedral environment ([b] phase). In each case, the Co or Ni environment is octahedral. In the second part of this paper, a newly designed controlled-atmosphere and temperature cell is described. It permits the study of several problems particularly those related to the reactivity of Co or Ni-Mo-γ-Al2O3 hydrodesulfurization catalysts. Results on (1) sulfidation of the oxide precursor form catalysts by a H2-H2S mixture, (2) interaction with a model sulfided molecule: thiophene, and (3) pyridine chemisorption are reported.
Breaking the One Second Barrier: Fast Kinetics of Protein Adsorption by FT-IR
Authors: Gendreau R. Michael
Published: August 2005

The Battelle Biological Spectroscopy Facility is currently studying the adsorption of blood proteins onto various surfaces using the combination of Fourier transform infrared spectroscopy (FT-IR) and attenuated total reflectance (ATR) optics. We have advanced our capabilities to study this phenomenon to the point where useful infrared spectra are obtained at 0.8-s intervals. This high-time resolution is helping to probe more accurately these important blood-surface interactions.
Design and Construction of a Low-Flow, Low-Power Torch for Inductively Coupled Plasma Spectrometry
Authors: Rezaaiyaan R. , Hieftje G. M. , Anderson H. , Kaiser H. , Meddings B.
Published: August 2005

A detailed study of the importance of various spatial dimensions in an ICP torch is described. Of the various dimensions which were examined, the annular spacing between the coolant (outer) and plasma (flared) tube is the most critical for plasma stabilization at low argon coolant flows and applied radio-frequency powers. Similarly, the inner diameter of the aerosol injection tube was found to be important, with the value of 1.0 mm chosen for a compromise between low-power, low-flow capability and routine analysis of high-solids sample solutions. A constriction at the inlet of the coolant argon was found not to affect plasma stability greatly, but altered significantly the applied powers and coolant flows which were necessary for plasma ignition. With these and other torch dimensions optimized, it was found to be possible to ignite a plasma at a coolant flow of 5 L/min and an applied radio frequency power of 450 W. Continued operation of the plasma during analysis of real samples or during aspiration of a 1% NaCl solution was found to be possible alternatively at 500 W (rf power) and 3.5 L/min coolant argon or 125 W and 5.5 L/min, respectively.
Application of New Least-Squares Methods for the Quantitative Infrared Analysis of Multicomponent Samples
Authors: Haaland David M. , Easterling Robert G.
Published: August 2005

Improvements have been made in previous least-squares regression analyses of infrared spectra for the quantitative estimation of concentrations of multicomponent mixtures. Spectral baselines are fitted by least-squares methods, and overlapping spectral features are accounted for in the fitting procedure. Selection of peaks above a threshold value reduces computation time and data storage requirements. Four weighted least-squares methods incorporating different baseline assumptions were investigated using FT-IR spectra of the three pure xylene isomers and their mixtures. By fitting only regions of the spectra that follow Beer's Law, accurate results can be obtained using three of the fitting methods even when baselines are not corrected to zero. Accurate results can also be obtained using one of the fits even in the presence of Beer's Law deviations. This is a consequence of pooling the weighted results for each spectral peak such that the greatest weighting is automatically given to those peaks that adhere to Beer's Law. It has been shown with the xylene spectra that semiquantitative results can be obtained even when all the major components are not known or when expected components are not present. This improvement over previous methods greatly expands the utility of quantitative least-squares analyses.