bluuebunny/crossref_metadata_2025 huggingface dataset:
Cranial Visceral Afferent Pathways through the Nucleus of the Solitary Tract to Caudal Ventrolateral Medulla or Paraventricular Hypothalamus: Target-Specific Synaptic Reliability and Convergence Patterns
Authors: Bailey Timothy W. , Hermes Sam M. , Andresen Michael C. , Aicher Sue A.
Published: November 2006

Cranial visceral afferents activate central pathways that mediate systemic homeostatic processes. Afferent information arrives in the brainstem nucleus of the solitary tract (NTS) and is relayed to other CNS sites for integration into autonomic responses and complex behaviors. Little is known about the organization or nature of processing within NTS. We injected fluorescent retrograde tracers into two nuclei to identify neurons that project to sites involved in autonomic regulation: the caudal ventrolateral medulla (CVLM) or paraventricular nucleus of the hypothalamus (PVN). We found distinct differences in synaptic connections and performance in the afferent path through NTS to these neurons. Anatomical studies using confocal and electron microscopy found prominent, primary afferent synapses directly on somata and dendrites of CVLM-projecting NTS neurons identifying them as second-order neurons. In brainstem slices, afferent activation evoked large, constant latency EPSCs in CVLM-projecting NTS neurons that were consistent with the precise timing and rare failures of monosynaptic contacts on second-order neurons. In contrast, most PVN-projecting NTS neurons lacked direct afferent input and responded to afferent stimuli with highly variable, intermittently failing synaptic responses, indicating polysynaptic pathways to higher-order neurons. The afferent-evoked EPSCs in most PVN-projecting NTS neurons were smaller and unreliable but also often included multiple, convergent polysynaptic responses not observed in CVLM-projecting neurons. A few PVN-projecting NTS neurons had monosynaptic EPSC characteristics. Together, we found that cranial visceral afferent pathways are structured distinctly within NTS depending on the projection target. Such, intra-NTS pathway architecture will substantially impact performance of autonomic or neuroendocrine reflex arcs.
Messanordnung zur kapazitiven Luft- und Gasfeuchtemessung (Test Set-up for the Capacitive Humidity Measurement)
Authors: Mikuta Reinhard , Wennmacher Christian , Burte Edmund P.
Published: November 2006

In diesem Beitrag wird eine einfache und kostengünstige Schaltung zur Messung der relativen Luft- bzw. Gasfeuchte mittels kapazitiver Feuchtesensoren beschrieben. Die Messung der relativen Feuchte wird auf eine Quotientenbildung zurückgeführt, wobei einer der beiden Feuchtesensoren als Referenzelement ausgeführt ist. Der Quotient führt zu einem digitalen Informationsparameter, einer Zählmenge.
Das Problem der linearen Ausgleichung im R2 (The Problem of the Linear Fit in R2)
Authors: Kolaczia Wilhelm
Published: November 2006

Vor einiger Zeit wurde in dieser Zeitschrift ein Beitrag mit dem Titel “Ausgleichsgeraden in der Ebene” [1] abgedruckt, in dem das Problem der linearen Ausgleichung im R2 kurz angesprochen und in der Folge die lineare Ausgleichung mittels der Methode des Total least-square fit, bei der die Ausgleichung nach der Minimierung der Normalabstände erfolgt, anderen Methoden der linearen Ausgleichung gegenübergestellt wird. Im vorliegenden Beitrag sollen als Ergänzung einige grundsätzliche Gedanken zu diesem Problem vorgetragen werden.
Appraising Adjuvant Aromatase Inhibitor Therapy
Authors: Perez Edith A.
Published: November 2006

Learning Objectives

After completing this course, the reader will be able to: Discuss the efficacy and safety of third-generation aromatase inhibitors as therapeutic options for patients with hormone-responsive breast cancer.Describe the impact of aromatase inhibitors on comorbidities that are common in this patient population.Identify the cost-effectiveness and quality-of-life effects of aromatase inhibitors.

Access and take the CME test online and receive 1 AMA PRA Category 1 Credit™ at CME.TheOncologist.com

Tamoxifen, once the gold standard adjuvant endocrine therapy for early breast cancer, is being challenged by third-generation aromatase inhibitors (AIs) that have demonstrated improved disease-free survival in a variety of adjuvant settings for early breast cancer. Tamoxifen and AIs have different safety profiles, which should allow physicians to begin to individualize treatment based on a patient's comorbidities and risk factors. Because of its properties as a partial estrogen agonist, tamoxifen has a positive effect on serum lipids and may confer a cardioprotective benefit, as well as a beneficial effect on bone health. However, tamoxifen increases the risk for endometrial cancer and cerebrovascular/thromboembolic events. In comparison, the major side effect of AIs is increased bone loss, which may heighten the risk for osteoporotic fractures and bone pain. Because of their superior efficacy and manageable side effects, AIs are a cost-effective alternative to tamoxifen, and clinical guidelines now embrace AIs as appropriate adjuvant therapy for hormone-sensitive early breast cancer. The anticipated results of ongoing trials will provide further insights into the long-term safety and application of AI therapy in the adjuvant setting.
Chemotherapy Given Near the End of Life by Community Oncologists for Advanced Non-Small Cell Lung Cancer
Authors: Murillo Jose R. , Koeller Jim
Published: November 2006

Purpose. To characterize the chemotherapy given near the end of life to advanced non-small cell lung cancer (NSCLC) patients treated in the community oncology setting using a medical records database.

Methods. We conducted a retrospective chart review of expired advanced (stage IIIb/IV) NSCLC patients treated with chemotherapy. Patients who initiated chemotherapy in 2000–2003 were eligible. Patient demographics, all chemotherapy including dose and schedule, and disease-related events were collected.

Results. We report data from 10 community practices including 417 patients treated for advanced NSCLC in 2000–2003. The mean age was 67 years (median, 62 years) and 54% were male. Forty percent of patients were >69 years of age and 35% had an Eastern Cooperative Oncology Group performance status score of ≥2. First-line chemotherapy included combination therapy in 84% of patients. Second-line therapy was given to 56% of patients. Twenty-six percent of patients received third-line therapy, while 10% received fourth-line therapy and 5% received fifth-line therapy or greater. Patients received a mean of 6.1 cycles of chemotherapy. For patients receiving chemotherapy at the time of death, the mean line of therapy being given was second line. Chemotherapy was given within 1 month and 2 weeks of death to 43% and 20% of patients, respectively.

Conclusion. The availability of new chemotherapeutic agents has caused a subsequent increase in the length of time patients are receiving chemotherapy with advanced NSCLC. This would suggest an increased use of chemotherapy near the end of life, which was identified in this study.
Oil splitting in industrial cleaning systems as studied by conductivity and interfacial tension
Authors: Adamy S. T. , Cala F. R.
Published: November 2006

Characteristics of emulsion formation and splitting into aqueous and oily phases in simple and formulated surfactant systems were studied via conductivity. In systems composed of mixed nonionic ethoxylated alcohol surfactants, K2CO3, and emulsified n‐hexadecane, conductivity decreased linearly with increasing oil volume fraction at HLB (hydrophile‐lipophile balance) values of 12.9 and 13.9. The slope of the plot was ca. −3/2, in agreement with the Maxwell expression. At values less than or equal to an HLB of 11.3, conductivity first increased with a small addition of oil and then decreased nearly linearly with subsequent amounts. This was probably due to low HLB surfactants partitioning into the oily phase. When the type of oil was varied, the reduced conductivity also decreased linearly with volume fraction of emulsified oil. The slope was ca. −3/2 for oil weights ranging from very light (n‐hexadecane) to very heavy (80W–90 gear oil), also in agreement with the Maxwell expression. Oil separation rates were measured by monitoring the change in conductivity in the lower region of the emulsion (where the aqueous layer formed) during splitting of the oily phase. Heavier oils were found to separate faster than light oils. Oils containing lubricity agents split at the slowest rate. Systems with lower HLB surfactants also displayed slower splitting rates. Splitting rates for a variety of systems, from simple oil and saline systems to more complex formulated systems, over temperatures from 23 to 75°C, were related to oil‐aqueous interfacial tension values through a power law expression composed of the maximum splitting rate and the interfacial tension between saline and oil at 23°C.
Synthesis and surface properties of new dicephalic saccharide‐derived surfactants
Authors: Wilk Kazimiera A. , Syper Ludwik , Burczyk Bogdan , Sokoŀowski Adam , Domagalska Beata W.
Published: November 2006

A new group of nonionic dicephalic saccharide amides, N‐dodecyl‐N,N‐bis[(3‐d‐gluconylamido)propyl]‐amine, N‐dodecyl‐N,N‐bis[(3‐d‐glucoheptonylamido)propyl]‐amine, and N‐alkyl‐N,N‐bis[(3‐lactobionylamido)propyl]amines (alkyl: n‐C12H25′n‐C16H33′, n‐C18H37) were synthesized and characterized. Their structure and purity were confirmed by means of 1H and 13C nuclear magnetic resonance analysis and electrospray ionization mass spectrometry. Carbon spectra were verified using a DEPT experiment. The surface and interfacial properties such as critical micelle concentration (CMC), standard free energy of micellization, ΔGCMC, surface excess concentration, ΓCMC, and surface area demand per molecule, ACMC, were determined. The tertiary nitrogen atom seems to have a surprising effect on surfactnat packing at the interface.
Separation and extraction of Φ‐methyl ester sulfoxylates: New features
Authors: Cohen L. , Soto F. , Luna M. S.
Published: November 2006

This paper deals with the separation and purification of Φ‐methyl ester sulfoxylates obtained through the sulfoxidation process. Two new steps are implemented during separation of the final product from the nonreacted reagent: (i) hot water is used instead of water/ethanol mixture, and (ii) n‐butanol is used as the extractive phase after neutralization instead of ethanol, leading to a product with more than 75% active ingredient. A significant improvement in the separation and purification steps has been obtained. The new procedure allows a complete material balance of the main products formed during sulfoxidation of fatty acid methyl esters and thus can lead to study of the reaction conditions, which can improve both conversion and selectivity.
Sulfoxylated methyl esters as potential components of liquid formulations
Authors: Cohen L. , Soto F. , Luna M. S.
Published: November 2006

Sulfoxylated methyl esters (Φ‐MES) are obtained via sulfoxidation of fatty acid methyl esters with SO2, O2, and ultraviolet light of appropriate wavelength. These products may be used as co‐surfactants with linear alkylbenzene sulfonate and alkyl ether sulfate, either in heavy‐duty or in hand dishwashing liquids. Standard hand dishwashing formulations based on Φ‐MESC16 are presented and discussed with regard to solubility, viscosity, performance, and skin compatibility. The experimental results obtained indicate that the above‐mentioned products can be regarded as potential components for liquid formulations.
Novel new ester quaternaries for improved performance benefits as rinse cycle fabric softeners
Authors: Friedli Floyd E. , Keys Robert , Joe Toney C. , Portwood Owen , Whittlinger Dave , Doerr Markus
Published: November 2006

A number of new diesterquats and anidoester quats were synthesized and tested for biodegradation and softening. Methyldiethanolamine, 3‐methoxylpropylamine, diethanolaminopropylamine, aminoethylethanolamine, dimethylethanolamine, and diethanolamine were reacted, either “as is” or after alkoxylation, with tallow fatty acid and further converted into dialkyl quats. The diesterquat from diethanolisopropanolamine was by far the best of the ester quats synthesized in overall biodegradation, softening, and cost/ease of manufacture. It appears that two ester groups are needed for ready biodegradation as opposed to an amide‐ester combination. Increasing unsaturation of the alkyl chains within a molecule increases its rate of biodegradation slightly.
Characterization of the micellar structure of a barium nonylphenolate/Barium carbonate complex by nuclear magnetic resonance spectroscopy
Authors: Su Biing‐Ming
Published: November 2006

The micellar structure of a barium nonylphenolate/barium carbonate complex was characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. Several NMR techniques, including measurement of spin‐lattice relaxation time, chemical shift variation, and line width of the 1H NMR signal and solid‐state 13C NMR data, were used in this study. NMR results indicate that the prepared barium nonylphenolate and barium carbonate complex formed a micelle structure with the oxygen atom of the nonylphenolate ring oriented toward the solid‐state center core of barium carbonate while the highly branched aliphatic chain pointed outward to the hydrocarbon solvent.
Lipid distribution on cotton textiles in relation to washing with cellulase
Authors: Obendorf S. Kay , Varanasi Arindam , Mejldal Rie , Nielsen Vibeke Skovgaard
Published: November 2006

Enzymes are used widely as effective additives to laundry detergents for improved detergency on soiled fabric. They have potential for cleaning of “dingy” soils in addition to the stain removal benefits. Cellulases contribute to the overall whiteness of cotton‐containing textiles when worn and washed several times, meaning that their cleaning is not associated solely with the regions characterized by high amounts of fatty material, e.g., collars/cuffs. The focus of this research was to study further the performance of cellulases for whiteness maintenance of cotton textiles. Cotton garments soiled by multiple wearings and washed using a cellulase treatment were evaluated using scanning electron microscopy and X‐ray microanalysis. Washing with cellulase significantly reduced residual soil concentrations at all morphological locations on the cotton fibers for each set of matched garments. The relative concentrations of residual soil on the fabrics agreed well with the color differences measured at 440 nm. Cellulase affected removal of oily soil from within the cotton fiber secondary wall, resulting in residual oil concentrations similar to those at morphological locations that were more accessible for detergency such as the fiber surface and crenulations. Since cellulase hydrolyzes cellulose, it was expected that the effect would be within the structure of the fiber, i.e., secondary wall. The cellulase effect on redeposition garments was similar to garments worn and washed. As with lipase, the enhanced removal of soil from the interior bulk structure of the cotton fiber with use of cellulase is unique, since most other detergent components have higher functionality at fabric, yarn, and fiber surfaces. We think that cellulase is functioning by hydrolyzing cellulose from the internal surfaces of fibrils within the secondary wall, opening up the pore structure for enhanced detergency and forming a new surface with each washing.
Terpyridine‐manganese complexes: A new class of bleach catalysts for detergent applications
Authors: Wieprecht Torsten , Heinz Uwe , Xia Juntao , Schlingloff Gunther , Dannacher Josef
Published: November 2006

Oxidation catalysis is one approach used to improve the performance of hydrogen peroxide in laundry bleach applications. We introduce herein a new class of bleach catalysts based on the ligand 2,2′∶6′,2″ terpyridine. A set of manganese complexes of substituted terpyridines was investigated with respect to their physicochemical properties and bleach performance. Introduction of electron‐donating hydroxy and amine substituents in the 4‐position of the individual pyridine rings improves the bleach performance in model experiments with morin (2′,3,4′,5,7‐pentahydroxyflavone) in solution as well as on tea‐stained cotton fabrics. All the catalysts show excellent bleach performance at 40 and 25°C under European washing conditions. Performance is superior to that of the activator tetraacetyl ethylenediamine (TAED) but depends critically on the substitution pattern. Dye damage caused by the catalysts is similar to that of TAED, proving that catalytic bleach systems with high performance and low damage are indeed feasible. Model experiments revealed that the complexes are highly stable under aqueous alkaline conditions in the presence of hydrogen peroxide. The optimal pH for catalytic activity is about 10. For a catalyst to have a high bleach performance, it must possess a sufficiently low activity to catalyze disproportionation of hydrogen peroxide, which is a major side reaction of catalytic bleach with manganese complexes. All the catalysts showed a similar affinity for the cotton fabric, suggesting that differences in bleach activity of complexes are not caused by differences in the fabric affinity.
Synthesis and surface‐active properties of trimeric‐type anionic surfactants derived from tris(2‐aminoethyl)amine
Authors: Yoshimura Tomokazu , Kimura Nobuhiro , Onitsuka Emika , Shosenji Hideto , Esumi Kunio
Published: November 2006

Trimeric‐type anionic surfactants (3CntaAm, where n is a hydrocarbon chain length of 8, 10, or 12) with three hydrocarbon chains and three carboxylate headgroups were synthesized from tris(2‐aminoethyl)amine, and their properties were investigated by surface tension, electrical conductivity, dynamic and static light‐scattering, fluorescence of pyrene, and emulsification power techniques. The critical micelle concentrations (CMC) of 3CntaAm were 0.00092–0.00834 mmol dm−3, and the surface tensions at the CMC were 33.3–39.9 mN m−1. The areas per molecule occupied by 3C10taAm and 3C12taAm were extremely small, showing they were highly compact at the air/water interface. In addition, adsorption or micellization behavior of 3CntaAm was estimated by parameters such as pC20 (the efficiency of surface adsorption), CMC/C20 (the ease of adsorption relative to the ease of micellization), and ΔGMo (Gibbs energy of micellization). Dynamic and static light‐scattering mesurements of 3CntaAm showed a hydrodynamic radius of 45–61 nm above the CMC and aggregation numbers of 10–82 at the CMC, respectively. The fluorescence intensity ratio of the first to the third band in the emission spectra of pyrene started to lower from far above the CMC for 3C8taAm and 3C10taAm, and below the CMC for 3C12taAm. This suggests that loose micelles or premicellar aggregates are formed in solutions. Mixtures of aqueous solutions of 3CntaAm and toluene formed oil‐in‐water‐type emulsions, and the stabilizing abilities were in the order of 3C8taAm>3C10taAm>3C12taAm. The degree of emulsification of 3C8taAm remained at 69% after 24 h of standing. Thus, 3CntaAm exhibited unique properties superior to monomeric or dimeric surfactants that were significantly influenced by their hydrocarbon chain lengths.
Adsorption of some anionic surfactants on barite and at solution/Air interfaces
Authors: Omar A. M. A. , Azzam E. M. S.
Published: November 2006

The adsorption behavior of synthesized anionic surfactants with the chemical structure RO‐Ph‐N=N‐Ph‐SO3Na, where R is an octyl, dodecyl, or cetyl group, was analyzed by using a modified version of the Frumkin adsorption isotherm. The values of thermodynamic parameters (including free energy of micellization, ΔGmic, and of adsorption, ΔGads) at the solution/air interface and the solid/liquid interface were calculated, and the relation between the adsorption of the surfactants at these interfaces was investigated. Studies of the surface properties of these synthetic surfactants showed that the length of the hydrocarbon chain of these surfactants plays a major role in determining their surface and thermodynamic properties and that there is a good relationship between the effectiveness of adsorption of the surfactant and its efficiency as a collector.
Use of a liquid chromatograph‐ion trap mass spectrometer for end‐group characterization of various polyethoxylate materials
Authors: Combs Michael T. , Johnson David D. , Szekely‐Klepser Gabriella
Published: November 2006

The separation and detection properties of various ethoxylated polymers were investigated with atmospheric pressure ionization liquid chromatography/mass spectrometry (LC/MS). Interesting chromatographic elution behavior based on functionality was noted. LC/MS using in‐source CID (collision‐induced dissociation) and tandem mass spectrometry (MS/MS) detection was compared for end‐group identification. Excellent end‐group identification was achieved when the end‐group molecular weight (MW) was greater than 100 Da and the average MW of the polymer was less than 400 Da by both MS/MS and in‐source CID. In cases where the end‐group MW was less than 100 Da, because of the low mass cut‐off in a quadrapole ion trap analyzer, in‐source CID produced the only characteristic end‐group ions. The use of a dual scan function allowed investigation of the oligomeric distribution followed by a narrow low‐mass scan using in‐source CID to generate end‐group information. This approach is applicable on instruments without MS/MS capability.
Synthesis of a novel dialkylaryl disulfonate gemini surfactant
Authors: Zaijun Li , Rui Yuan , Zhongyun Liu , Fushan Yin
Published: November 2006

A single‐step route was developed for synthesizing a dialkylaryl disulfonate gemini surfactant using α‐olefin sulfonic acid. The new process is very simple and effective, requiring neither the conventional alkylation unit nor strong acid catalysts. The resulting dialkylaryl disulfonica acids differ from existing products by having the sulfonyl group attached to the alkyl chain rather than the aromatic ring. To optimize the reaction conditions, a reliable double‐wavelength spectrophotometric method was studied to analyze the conversion of an aromatic (benzene or methylnaphthalene) based on the difference in ultraviolet absorption spectra between the aromatic and the corresponding dialkylaryl disulfonate. The experiments suggested that the reaction time and temperature affected the conversion and optimal condition; a reaction time of 5 h (or 4 h) and a reaction temperature of 150°C were obtained and applied to the products ditetradecylmethylnaphthalene disulfonate (DTMNDS) and ditetradecylbenzene disulfonate (DTBDS). In addition, the surface‐active properties of DTMNDS and DTBDS were investigated in detail. Their critical micelle concentrations were 2×10−5 and 1.7×10−4 mol·L−1, respectively. The data showed that the two new dialkylaryl disulfonate gemini surfactants had higher surface activities than the conventional dodecylbenzene sulfonate, suggesting they will have broad utility in industrial and household applications in the future.
Design and manufacturing of solid detergent products
Authors: Borchers Georg
Published: November 2006

As a result of increasing demands on the product profile of solid detergent products, the requirements on the ingredients and the manufacturing process for these components are growing as well. A suitable way to achieve the objectives embraces the transformation to a granulated product with tailor‐made properties. During development, a main focus has to be put on an optimum granule formulation to fulfill the manifold product and performance criteria. Due to the complexity of the product mixtures, the selection of suitable formulation components most often has to be done experimentally. Unfavorable physical and chemical product properties require additional efforts and multiply the complexity. Finally, the selection of a suitable granulation process which is capable of processing the materials has to be considered from the outset to deliver the desired product quality.
Synthesis and some studies on fluorinated cationic surfactants: surface and biocidal activities
Authors: Mohamed M. Z. , Ghazy E. A. , Badawi A. M. , Kandil N. G.
Published: November 2006

Three fluorinated cationic surfactants were prepared by condensing N‐(2‐bromoethyl)perfluoroalkylamides with stoichiometric amounts of pyridine, triethanolamine, and triethylamine to produce three quaternary ammonium salts. The surface and biocidal properties of these surfactants were investigated to find the relation between the structure of the hydrophilic portion of the compounds and their efficiency as biocides. The properties studied included critical micelle concentration (CMC), effectiveness (IICMC), surface excess concentration (Tmax), and area occupied by a molecule (Amin). Free energies of micellization (ΔGmico) and adsorption (ΔGadso) of the surfactants in aqueous solution were calculated. The minimal inhibitory concentrations of the prepared compounds were tested against five strains as representative group of microorganisms.
Catalytic destruction of paraoxon by metallomicelle layers of Co(II) and Cr(III)
Authors: Hafiz A. A. , El Awadi M. Y. , Badawi A. M. , Mokhar S. M.
Published: November 2006

Two micellized ion complexes, Co(II) and Cr(III), were synthesized and found to possess good catalytic activity in cleaving the paraoxon/cobalt (chromate) complex phosphate ester. The complexes orm metallomicelles, which bind the substrate by coordinating with the phosphorus in the paraoxon (which is chemically similar to the nerve agents sarin and soman). Possible reasons for the acceleration include enhanced electrophilicity of the micellized metals, enhanced surface activity, and the recognized ability of cationic micelles to accelerate the cleavage of phosphate ester. The results of kinetic data (half‐lives) for paraoxon degradation were 16.5 and 28.9 min in the presence of Co(II) and Cr(III) metallomicelle layers, respectively. The higher the value of the stability constant, the more stable the Co(II) and Cr(III) complexes.
Tuning the polydispersity of alcohol ethoxylates for enhanced oily soil removal
Authors: Goe Satish K.
Published: November 2006

Commercially available alkyl alcohol ethoxylates have a broad distribution of ethylene oxide (EO) units and also a somewhat narrower distribution of alkyl chain length. Generally, the purer the surfactant sample (narrower distribution), the better is its detergency performance, and detergency peaks at the phase inversion temperature (PIT) for a given oil. However, in real detergency processes this may not hold true since soils are typically mixtures of several oily components, and temperature variations are significant. Therefore, if a polydispersity index (PDI) of ethoxylates is defined as the ratio of weight average EO moles to number average EO moles in the sample, then it is conceivable that an optimal PDI might be obtained. We compared the detergency of hexadecane for pentaethylene glycol monododecyl alcohol (C12EO5) samples in a broad PDI range, using an oil‐soluble dye. While detergency at 55°C (PIT of hexadecane with C12EO5) decreases monotonically with increasing creasing PDI, average detergency over a 20°C temperature range around the PIT tends to show a maximum at PDI of ca. 1.1 (narrow‐range ethoxylate). Similarly, for a mixture of undecane/hexadecane/tetracosane (30∶50∶20 w/w/w) for which the average PIT is approximately the same as that of hexadecane detergency at 55°C shows a maximum as a function of PDI at a value of ∼1.37 (broad‐range ethoxylate). All detergency results are in general agreement with the reverse trends in oil/water interfacial tension and suggest that, having decided the optimal EO moles for a given application based on PIT, one can further improve the performance of alcohol ethoxylates in real detergency processes by tuning their polydispersity.
Effectiveness of a new water‐based oil spill dispersant comprised of an alkyl polyglycoside
Authors: Kim Jong‐Yun , Song Myung‐Geun , Kim Tae‐Seong , Kim Jong‐Duk
Published: November 2006

Alkyl polyglycoside (AP) used in a water‐based oil dispersant system showed maximal performance at typical concentrations. Premixtures of AP aqueous solutions and fuel oil contributed to higher performance, and therefore its physicochemical characteristics, such as rheology and conductivity, were studied and compared with effectiveness. When an AP containing an electrolyte (NaCl) is used, effectiveness and stability improve further.
Fatty acid composition of pinaceae as taxonomic markers
Authors: Wolff Robert L. , Lavialle Olivier , Pédrono Frédérique , Pasquier Elodie , Deluc Laurent G. , Marpeau Anne M. , Aitzetmüller Kurt
Published: November 2006

Following our previous review on Pinus spp. seed fatty acid (FA) compositions, we recapitulate here the seed FA compositions of Larix (larch), Picea (spruce), and Pseudotsuga (Douglas fir) spp. Numerous seed FA compositions not described earlier are included. Approximately 40% of all Picea taxa and one‐third of Larix taxa have been analyzed so far for their seed FA compositions. Qualitatively, the seed FA compositions in the three genera studied here are the same as in Pinus spp., including in particular the same Δ5‐olefinic acids. However, they display a considerably lower variability in Larix and Picea spp. than in Pinus spp. An assessment of geographical variations in the seed FA composition of P. abies was made, and intraspecific dissimilarities in this species were found to be of considerably smaller amplitude than interspecific dissimilarities among other Picea species. This observation supports the use of seed FA compositions as chemotaxonomic markers, as they practically do not depend on edaphic or climatic conditions. This also shows that Picea spp. are coherently united as a group by their seed FA compositions. This also holds for Larix spp. Despite a close resemblance between Picea and Larix spp. seed FA compositions, principal component analysis indicates that the minor differences in seed FA compositions between the two genera are sufficient to allow a clear‐cut individualization of the two genera. In both cases, the main FA is linoleic acid (slightly less than one‐half of total FA), followed by pinolenic (5,9,12‐18:3) and oleic acids. A maximum of 34% of total Δ5‐olefinic acids is reached in L. sibirica seeds, which appears to be the highest value found in Pinaceae seed FA. This apparent limit is discussed in terms of regio‐ and stereospecific distribution of Δ5‐olefinic acids in seed triacylglycerols. Regarding the single species of Pseudotsuga analyzed so far (P. menziesii), its seed FA composition is quite distinct from that of the other two genera, and in particular, it contains 1.2% of 14‐methylhexadecanoic (anteiso‐17:0) acid. In the three genera studied here, as well as in most Pinus spp., the C18Δ5‐olefinic acids (5,9‐18:2 and 5,9,12‐18:3 acids) are present in considerably higher amounts than the C20Δ5‐olefinic acids (5,11‐20:2 and 5,11,14‐20:3 acids).
Cytotoxic effect of conjugated trienoic fatty acids on mouse tumor and human monocytic leukemia cells
Authors: Suzuki Rikako , Noguchi Ryoko , Ota Tomoki , Abe Masayuki , Miyashita Kazuo , Kawada Teruo
Published: November 2006

The cytotoxicity of fatty acids from seed oils containing conjugated linolenic acids (CLN) was studied. Fatty acids from pomegranate, tung, and catalpa were cytotoxic to human monocytic leukemia cells at concentrations exceeding 5 μM for pomegranate and tung and 10 μM for catalpa, but fatty acids from pot marigold oil had no effect at concentrations ranging up to 163 μM. The main conjugated fatty acids of pomegranate, tung, catalpa, and pot marigold were cis(c)9, trans(t)11, c13‐CLN (71.7%), c9,t11,t13‐CLN (70.1%), t9,t11,c13‐CLN (31.3%), and t8,t10,c12‐CLN (33.4%), respectively. Therefore, the cytotoxicities of fatty acids from pomegranate, tung, and catalpa were supposed to be due to 9,11,13‐CLN isomers. To elucidate the cytotoxicity of these CLN, we separated each CLN isomer from the fatty acid mixtures by high‐performance liquid chromatography and analyzed its cytotoxicity. The cytotoxicities of c9,t11,c13‐CLN, c9,t11,t13‐CLN, and t9,t11,c13‐CLN were much stronger than that of t8,t10,c12‐CLN. Therefore, the higher cytotoxicity of fatty acids from pomegranate, tung, and catalpa than those from pot marigold would be derived from the different activities of 9,11,13‐CLN and 8,10,12‐CLN. Since there was little difference in the cytotoxicities of c9,t11,c13‐CLN, c9,t11,t13‐CLN, and t9,t11,c13‐CLN, it is suggested that the cis/trans configuration of 9,11,13‐CLN isomers had little effect on their cytotoxic effects. The mechanism of the cytotoxicity of the four fatty acids above may involve lipid peroxidation, because the order of toxicity of the fatty acids was consistent with their susceptibility to peroxidation in aqueous phase. This was supported by the decrease in the cytotoxicity of the fatty acids by addition of butylated hydroxytoluene.
Cloning and expression of group IB phospholipase A2 isoforms in the red sea bream, Pagrus major
Authors: Iijima N. , Fujikawa Y. , Tateishi Y. , Takashima Y. , Uchiyama S. , Esaka M.
Published: November 2006

Two cDNA encoding red sea bream DE‐1 and DE‐2 phospholipases A2 (PLA2) were cloned from the hepatopancreas of red sea bream, Pagrus (Chrysophrys) major. The cDNA of DE‐1 PLA2 encoded a mature protein of 125 amino acid residues with an apparent signal peptide of 20 residues and propeptide of 5 residues, and that of DE‐2 PLA2, a mature protein of 126 amino acid residues with an apparent signal peptide of 17 residues and propeptide of 6 residues. Comparison of the predicted amino acid sequences for mature DE‐1 and DE‐2 PLA2 showed that both proteins contain 14 cysteines including Cys 11 and 77 and a pancreatic loop, which are commonly conserved in group IB PLA2; however, the identity in amino acid sequence between DE‐1 and DE‐2 PLA2 was low (47%). A previous report concerning the cDNA cloning of red sea bream gill G‐3 PLA2 and the present results represent the first cloning and sequencing of three distinct isoforms of group IB PLA2 in a single fish species, red sea bream. Reverse transcription‐polymerase chain reaction analysis showed that DE‐1 PLA2 mRNA was expressed in the hepatopancreas, pyloric ceca, intestine, spleen, gonad, stomach, and kidney, whereas gill G‐3 PLA2 mRNA was expressed only in the gills and gonad. The expression of DE‐2 PLA2 mRNA was detected in all of the tissues analyzed. These results indicate that three distinct isoforms of group IB PLA2, DE‐1 and DE‐2 PLA2 in hepatopanceas and gill G‐3 PLA2, are expressed in a tissue‐specific manner in red sea bream.
Fullerenoid lipids: First synthesis of structured triacylglycerols containing an aza‐[60]fullerence unit
Authors: Lie Ken Jie Marcel S. F. , Cheung Sunny W. H. , Ho Janette C. M.
Published: November 2006

Some 1,2‐ and 1,3‐diacyl glycerols (with acyl groups as stearyl, oleyl, linoleyl, or stearolyl) were synthesized by conventional methods. The diacyl glycerols were esterified with 6‐bromo‐hexanoic acid to give the corresponding bromotriacylglycerols (of the type AAB and ABA containing a bromo group at the distal part of the hexanoate chain). The bromo function was transformed to an azide group by reaction of the bromotriacylglycerols with sodium azide. The resulting azido‐triacylglycerols were then reacted with [60]fullerence to give the requisite aza‐fullerenoid triacylglycerol of the type ABA or AAB (45–62% yield based on the amount of [60]fullerence reacted). The nitrogen atom attached to the carbon cage formed a “[5,6]‐open” type aza substructure, which was confirmed by the appearance of 31–32 signals in the region of δC 133–148 (carbon shifts of sp2 carbons of the cage) in the 13C nuclear magnetic resonance spectra. The spectroscopic and mass spectrometric properties of these novel fullerenoid triacylglycerols are reported.
Trans‐7,cis‐9 CLA is synthesized endogenously by Δ9‐desaturase in dairy cowsin dairy cows
Authors: Corl Benjamin A. , Baumgard Lance H. , Griinari J. Mikko , Delmonte Pierluigi , Morehouse Kim M. , Yurawecz Martin P. , Bauman Dale E.
Published: November 2006

Cis‐9,trans‐11 and trans‐7,cis‐9 CLA are the most prevalent CLA isomers in milkfat. The majority of cis‐9,trans‐11 CLA is synthesized endogenously by Δ9‐desaturase. We tested the hypothesis that trans‐7,cis‐9 CLA originates from endogenous synthesis by inhibiting Δ9‐desaturase with a source of cyclopropene FA (sterculic oil: SO) or with a trans‐10,cis‐12 CLA supplement. Experiment 1 (four cows; Latin square) involved four treatments: control, SO, partially hydrogenated vegetable oil (PHVO), and PHVO+SO. Milk, plasma, and rumen fluid were collected. Experiment 2 treatments (four cows) were 0 or 14.0 g/d of 10,12 CLA supplement; milk and plasma were collected. Samples were analyzed by GC and Ag+‐HPLC to determine FA. In Experiment 1, SO decreased milkfat content of trans‐7,cis‐9 CLA by 68 to 71% and cis‐9,trans‐11 CLA by 61 to 65%. In Experiment 2, the 10,12 CLA supplement decreased milkfat content of trans‐7,cis‐9 CLA and cis‐9,trans‐11 by 44 and 25%, respectively. Correcting for the extent of treatment‐induced inhibition of Δ9‐desaturase based on changes in myristic and myristoleic acids, endogenous synthesis of trans‐7,cis‐9 CLA represented 85 and 102% in Experiments 1 and 2, respectively. Similar corrected values were 77 and 58% for endogenous synthesis of cis‐9,trans‐11 CLA. Thus, milkfat cis‐9,trans‐11 CLA was primarily from endogenous synthesis with a minor portion from rumen escape. In contrast, trans‐7,cis‐9 CLA was not present in rumen fluid in significant amounts. Results indicate this isomer in milkfat is derived almost exclusively from endogenous synthesis via Δ9‐desaturase.
High intake, but not low intake, of CLA impairs weight gain in growing mice
Authors: Hayman Ann , MacGibbon Alastair , Pack Rodger J. , Rutherfurd Kay , Green J. Hilary
Published: November 2006

CLA has a range of biological properties, including effects on lipid metabolism and body composition in experimental animals. The prevalent isomer of CLA found in the human diet is 9c, 11t‐CLA, and it is predominantly found in products containing fat from ruminant animals. This study investigated the effect of dietary CLA on energy balance in mice. Synthetic CLA reduced body fat in growing male BAI B/c mice in a dose‐dependent manner over the range 0.25–1.0% w/w CLA in the diet. Weight gain was also reduced at the highest levels of dietary CLA, being only 5.88±2.68 g/4 mice (mean±1 SD) after 4 wk of 2.0% CLA in the diet, compared with weight groups. There was no significant effect on weight gain if diets contained 0.5% synthetic CLA or less. These results suggest that high levels of a synthetic mixture of CLA isomers modify energy metabolism and body composition and that high levels of synthetic CLA impair weight gain and reduce body fat pad mass in growing mice.
Positional and geometric isomer separation of FAME by comprehensive 2‐D GC
Authors: Western Robert J. , Lau Sally S. G. , Marriott Philip J. , Nichols Peter D.
Published: November 2006

The technique of comprehensive GC (GC×GC) was applied to the analysis of a standard mixture of FAME. The methodology involved the use of two directly coupled capillary GC columns providing different retention mechanisms, with a pulsing modulator located near their union. The first column was chosen to elute analytes based on b.p. variations, and the second column was based on polarity. Thus, the separation in the two dimensions was orthogonal, since solutes delivered simultaneously to the second column had similar b.p., and the second column separated these primarily on their differentiating mechanisms of polarity. Greater sensitivity of detection and narrower peak widths were obtained; here, peak response increases of about 20‐fold were obtained, with pulsed peak widths of about 150 ms. Peaks were displayed in a 2‐D contour plot to allow the complexity of the compounds to be seen and their b.p. and polarity properties to be readily recognized. Chromatographic separation of geometric and positional isomers of FAMF in the 2‐D space is possible. Since retention can be related to the degree and manner of unsaturation and isomerization, and as peak positions are highly reproducible in the 2‐D retention map, this is a useful aid for component identification in the absence of appropriate standards. In this work, two column combinations were used to examine the effects of polarity changes on component separation. Improved quantitation based on FID area measurement was demonstrated. A sample of marine oil gave 49 resolved, identified peaks, with at least an additional 20 peaks resolved but not identified.
The types of circulating fatty acids influence vascular reactivity
Authors: Lind Lars , Södergren Eva , Gustafsson Inga‐Britt , Millgård Jonas , Sarabi Mahziar , Vessby Bengt
Published: November 2006

The objective of this study was to investigate the relationship between the composition of FA in serum lipids, a marker of dietary fat intake, and vascular reactivity using a combination of cross‐sectional and intervention approaches. Fifty‐six middle‐aged subjects were evaluated in a cross‐sectional protocol regarding the relationship between the proportion of FA in serum cholesterol esters and vascular reactivity using measurements of forearm blood flow (FBF) with venous occlusion plethysmography during hyperemia. Another 19 middle‐aged subjects were given a rapeseed oil‐based diet rich in mono‐and polyunsaturated FA or a control diet rich in saturated FA during two consecutive 4‐wk periods separated by a 4‐wk washout period. In the cross‐sectional protocol, the FA 18:0 and 20:3 were positively related to resting FBF, whereas an inverse relationship was seen for the FA 20:5 and 22:6 (P<0.05−0.01). Opposite relationships were seen between these four FA and the relative increase in maximal FBF during hyperemia (P<0.05−0.01). In the intervention protocol, the saturated diet increased resting FBF, as well as the relative increase in maximal FBF during reactive hyperemia, compared to the diet rich in unsaturated FA (P<0.05). Both the cross‐sectional and intervention data support the view that the composition of serum FA, which at least partly reflects the quality of dietary fat, plays a role in determinations of vascular reactivity.
New chemical syntheses of cholest‐4,6‐dien‐3‐one
Authors: Parish Edward J. , Sun Hang , Lu Ding , Kizito Stephen A. , Qiu Zhihai
Published: November 2006

Steroidal dienones represent a significant class of compounds that are useful intermediates in the further functionalization of the steroid nucleus. Their chemical synthesis can be problematic owing to the lack of a simplified method of preparation and the occurrence of impurities that can be difficult to remove. We have endeavored to develop new methods of chemical synthesis of cholest‐4,6‐dien‐3‐one that would yield a product of high purity.
Pharmacological modulation of fatty acid desaturation and of cholesterol biosynthesis in THP‐1 cells
Authors: Risé P. , Ghezzi S. , Levati M. G. , Mirtini R. , Colombo C. , Galli C.
Published: November 2006

In THP‐1 cells, simvastatin decreases, in a concentration‐dependent manner, cholesterol synthesis and increases linoleic acid (LA) conversion to its long‐chain derivatives, in particular to arachidonic acid, activating Δ6 and Δ5 fatty acid (FA) desaturases. The intermediates in cholesterol synthesis, mevalonate and geranylgeraniol, partially reverse the effects of simvastatin on the LA conversion. The aims of this work were to evaluate: (i) the correlation between cholesterol synthesis and desaturase activity and (ii) the possible involvement of protein isoprenylation in desaturase activity, assessed through pharmacological treatments. THP‐1 cells were incubated with [1‐14C]LA or with [1‐14C]di‐homo‐γ‐linolenic acid (DHGLA) and treated with simvastatin or with curcumin and nicardipine, inhibitors of desaturases. Curcumin was more active than nicardipine in inhibiting LA and DHGLA conversion: 20 μM curcumin, alone or with simvastatin, totally inhibited Δ6 and Δ5 desaturation steps; 10 μM nicardipine only partially inhibited the enzymes, being more active on Δ5 desaturase. Simvastatin treatment decreased the incorporation of acetate in cholesterol (−93.8%) and cholesterol esters (−70.2%), as expected. Curcumin and nicardipine also decreased cholesterol synthesis and potentiated simvastatin. Finally, the isoprenylation inhibitors (perillic acid and GGTI‐286) neither affected the conversion of LA nor inhibited the Δ5 desaturase activity. In conclusion, our results indicate that there is no direct relationship between cholesterol synthesis and desaturase activity. In fact, simvastatin decreased cholesterol synthesis and enhanced LA conversion (mainly Δ5 desaturation), whereas curcumin and nicardipin decreased Δ5 desaturation, with a limited effect on cholesterol synthesis.
Synthesis and characterization of deoxycholyl 2‐deoxyglucuronide: A water‐soluble affinity labeling reagent
Authors: Mano Nariyasu , Nishijima Akira , Saito Shuntaro , Ikegawa Shigeo , Goto Junichi
Published: November 2006

Acyl glucuronides, which are biosynthesized by the action of glucuronosyltransferases to material for detoxification, are water‐soluble and chemically active; they produce irreversible protein adducts via both the transacylation mechanism and the imine mechanism. The acyl group at the C‐1 position migrates from the anomeric carbon to the C‐2 position of the glucuronic acid moiety, producing the aldehyde group at the C‐1 position, where the protein easily condenses through a Schiff's base, in the open‐chain aldose form. The elimination of the hydroxyl group at the C‐2 position therefore may prevent a protein‐bound adduct via the imine mechanism. In this paper, we describe the synthesis and characterization of an acyl 2‐deoxyglucuronide of deoxycholic acid as a model compound to investigate its possible utility as a water‐soluble affinity labeling reagent for lipophilic carboxylic acids. The solubility of deoxycholyl 2‐deoxyglucuronide in an aqueous solution was sufficient under physiological conditions, and the desired material reacted with model peptides to produce covalently bound adducts only via the transacylation mechanism.
Fourier transform infrared spectroscopy evaluation of low density lipoprotein oxidation in the presence of quercetin, catechin, and α‐tocopherol
Authors: Lam Henry S. , Proctor Andrew , Nyalala John , Morris Manford D. , Smith W. Grady
Published: November 2006

We investigated the changes in human LDL primary and secondary lipid oxidation products and modification of the apolipoprotein B‐100 (apoB‐100) secondary structures during Cu2+‐mediated oxidation by FTIR spectroscopy in the presence of catechin, quercetin, and α‐tocopherol at physiological concentrations. Catechin‐ and quercetin‐containing samples had slower rates and longer lag phases for conjugated diene hydroperoxide (CD) formation than α‐tocopherol‐containing samples; however, all antioxidant‐treated LDL samples generated similar CD levels (P<0.05). A lower maximum (98.4 nmol/mg LDL protein) of carbonyl compounds was produced in the quercetin‐ and catechin‐treated samples than in α‐tocopherol samples. Modification of the apoB‐100 secondary structures corresponded closely to the formation of carbonyls and was hampered by the presence of antioxidants. Physiological concentrations of catechin and quercetin offered similar levels of protection against modification by carbonyls of the apoB‐100 at advanced stages (carbonyls ∼96.0 nmol/mg LDL protein) but not at the intermediate stages (carbonyls ∼58.0 nmol/mg LDL protein) of LDL oxidation probably owing to differences in the protein‐binding mechanisms of catechin and quercetin. Relationships between peroxide formation, carbonyl products, and LDL protein denaturation were shown by the FTIR approach. The FTIR technique provided a simple new tool for a comprehensive evaluation of antioxidant performance in protecting LDL during in vitro oxidation.