bluuebunny/crossref_metadata_2025 huggingface dataset:
Synthesis and Conformational Studies of Novel Calixarene‐Analogous Macrocyclic [3.1.1]Metacyclophanes
Authors: Yamato Takehiko , Doamekpor Louis Korbla , Tsuzuki Hirohisa
Published: July 2007

Hydroxy[3.1.1]metacyclophane 4c, which is regarded as an unsymmetric or uncomplete “homocalixarene” bearing a propane bridge, has been synthesized using Nafion‐H catalyzed cyclobenzylation. A novel “pendulum” type motion steered by intramolecular hydrogen bonding has been observed Demethylation of compound 4c with BBr3 in methylene dichloride was carried out at room temperature for 3 h to afford the dihydroxy[3.1.1]metacyclophane 4b in 74% yield along with the triol 4a in 25% yield. Triol 4a was tri‐O‐alkylated with methyl iodide in the presence of NaH to yield partial‐cone conformer 4d in quantitative yield. Similarly, a significant amount of partial‐cone conformer 5 results in the case of O‐alkylation of 4a with N,N‐diethylchloroacetamide. 1H‐NMR titration of partial‐cone amide 5 with NaSCN clearly demonstrates that a 1:1 complex is formed which is stable on the NMR time scale.
New Electron Donor‐Acceptor Compounds, 51. [3](N,N′)‐1,8;4,5‐Naphthalenetetracarboxdiimido‐ [3](2,7)Pyrenophane and Its [4,4]Cyclophane Homologue
Authors: Staab Heinz A. , Zhang De‐Quing , Krieger Claus
Published: July 2007

Electron donor‐acceptor cyclophanes 1 and 2, consisting of pyrene as the donor component and 1,8;4,5‐naphthalenete‐tracarboxdiimide as the acceptor component fixed by methylene chains in parallel face‐to‐face orientations, have been synthesized. The structures, based on an X‐ray analysis of 1 and on spectroscopic properties, are discussed with reference to intramolecular charge‐transfer interactions and are compared to those of the related excimer models [3.3]‐ and [4.4]pyrenophanes 3 and 4.
Complexation Properties of Preorganized Receptor Molecules for Large, Neutral Guests
Authors: Higler Irene , Verboom Willem , van Veggel Frank C. J. M. , de Jong Feike , Reinhoudt David N.
Published: July 2007

Receptor molecules with a preorganized cavity were synthesized by combining two resorcin[4]arene and one calix[4]‐arene building block. Based on predictions from a computational study which matches hosts and guests, several steroids, sugar derivatives, and alkaloids were selected for complexation studies. Experimentally the complexation of such guests by these receptor molecules was proven by 1H‐NMR spectroscopy (association constants of 1.0−6.0 × 102 M−1 in CDCl3). One of these receptors with four hydroxyl groups forms a dimeric capsule (Kdimer = 11 M−1 in CDCl3). Evidence for this dimerization comes from 1H‐NMR, FAB MS spectroscopy, and molecular mechanics and dynamics calculations.
Chemistry of the Ginkgolides, VIII – Synthesis and Crystal Structure of a Dimeric 14,15,16‐Trinorginkgolide Derivative
Authors: Weinges Klaus , Schick Hartmut , Irngartinger Hermann , Oeser Thomas
Published: July 2007

Treatment of the enol acetate 3‐acetoxy‐10‐methoxy‐methoxy‐2,3‐didehydro‐14,15,16‐trinorginkgolide[2] (2) with potassium osmate/N‐methylmorpholine N‐oxide in acetone/acetic acid solution did not yield the expected 2‐hydroxy‐3‐oxo derivative 3, but the dimeric ginkgolide (2S,2′S,3R,3′R)‐bis(10‐methoxymethoxy‐14,15,16‐trinorginkgolido)[2,3‐c;2′,3′‐e]‐1″,4″‐dioxan‐3,3′‐diol (4a). By acid hydrolysis, 4a was converted to the MOM‐deprotected dimeric product 4b. The structure of 4a was elucidated by crystal structure analysis.
Ion Pair Amphiphiles from Sodium Dodecyl Sulfate and Ammonium Amphiphiles Carrying Functionalized Azobenzene Units
Authors: Nieuwkerk Armanda C. , Marcelis Antonius T. M. , Koudijs Arie , Sudhölter Ernst J. R.
Published: July 2007

New ammonium amphiphiles having a N,N‐dimethyl‐N‐hydroxyethylammonium headgroup and various azobenzene mesogenic units connected by a decyl or dodecyl spacer have been synthesized. The azobenzene unit is functionalized at the 4‐position with a cyano, methoxy or fluoro substituent. For the cyano‐substituted amphotropes and the fluoro compound with a dodecyl spacer a smectic phase is formed as was observed by differential scanning calorimetry and polarization microscopy. Complexation with sodium dodecyl sulfate, SDS, in a 1:1 molar ratio induces the formation of a smectic phase for the compounds with a decyl spacer. The compounds with a dodecyl spacer showed rather complex behavior attributed to different crystal morphologies. The ammonium amphotropes form aggregates in water when heated above their Krafft temperature. However, these aggregates are not stable and crystallize upon cooling. The ion pair amphiphiles with SDS as second component form vesicles in water as observed by optical and electron microscopy. The observed blue shift in the UV absorption maximum of the amphotropes upon addition of SDS indicates π–π stacking between mesogenic units resulting from aggregation.
An Enantiodivergent Synthesis of Both Enantiomers of the Macrocyclic Lactone Curvularin
Authors: Bracher Franz , Schulte Brigitte
Published: July 2007

The macrocyclic lactone (S)‐curvularin (10) and its enantiomer ent‐10 were prepared in an enantiodivergent manner from (S)‐methyl 7‐hydroxyoctanoate (4), which was easily obtained on two different ways. Esterification of 4 under either retention or inversion of the chiral centre gave the enantiomeric diesters 7 and ent‐7. Chemoselective cleavage of the methyl ester groups of these diesters followed by intramolecular acylation and O‐debenzylation gave the two enantiomers of curvularin.
Synthesis and Stereochemistry of Some 1,3‐Dioxane Diacetals of o‐Phthaldialdehyde
Authors: Grosu Ion , Mager Sorin , Plé Gerard , Plé Nelly , Toscano Alfredo , Mesaros Eugen , Martinez Roberto
Published: July 2007

The stereochemistry of some diacetals of o‐phthaldialdehyde with 2‐substituted‐1,3‐propanediols was studied using NMR spectroscopy and the solid‐state molecular structure of one compound established by single‐crystal X‐ray diffractometry. The cis and trans isomers of some diacids and diesters, produced as derivatives bearing the desired substituents in the 5 and 5′ positions of the heterocycles, have been separated by preparative TLC and identified by their NMR spectra.
O‐Glycoside Synthesis with Glycosyl Iodides under Neutral Conditions in 1 M LiClO4 in CH2Cl2
Authors: Schmid Uschi , Waldmann Herbert
Published: July 2007

Glycosyl phosphates, imidates, trifluoroacetates, chlorides, and bromides are converted into the respective glycosyl iodides by treatment with LiI or NaI in 1 M solutions of LiClO4 in CH2Cl2. Under these neutral conditions the reactive glycosyl iodides are activated, and react with different glycosyl acceptors to give O‐glycosides in moderate yields, with the α‐anomers predominating. The glycosylation reactions most probably proceed by the initial formation of β‐configured glycosyl iodides from the α‐configured precursors, and subsequent attack of the glycosyl acceptor on the equatorial iodide from the axial direction.
Biscalix[4]arene Ligands for Dinuclear Lanthanide Ion Complexation
Authors: Wolbers Manon P. , van Veggel Frank C. J. M. , Heeringa Remco H. M. , Hofstraat Johannes W. , Geurts A. J. , van Hummel Gerrit J. , Harkema Sybolt , Reinhoudt David N.
Published: July 2007

Three types of lower‐lower rim linked biscalix[4]arenes that contain carboxylic ester (1) and/or amide functions (2 and 3) at their remaining phenolic oxygen atoms were synthesized. The homo‐ and heterodinuclear lanthanide ion complexes based on these ligands were used to study the energy transfer between different lanthanide ions. Photophysical studies comparing the luminescence properties of the homodinuclear Eu3+ complex and the heterodinuclear Eu3+‐Nd3+ complex of 2 indicated that energy transfer is likely to occur from Eu3+ to Nd3+ with an efficiency of > 50%. The luminescence properties turned out to be strongly solvent dependent, which is attributed to structural changes leading to different positions of the lanthanide ions in the cavities provided by the biscalix[4]arene.
Differentiation of spinal cord arteries and veins by time‐resolved MR angiography
Authors: Jaspers Karolien , Nijenhuis Robbert J. , Backes Walter H.
Published: July 2007

Purpose

To dynamically resolve the inlet arteries and outlet veins of the spinal cord, particularly the Adamkiewicz artery (AKA) and great anterior radiculomedullary vein (GARV), using MR angiography (MRA).

Materials and Methods

First, conventional two‐phase angiography (acquisition time = 38–55 seconds) utilizing elliptic centric k‐space ordering was applied to aortic‐aneurysm patients. Changes of vessel intensity were compared between two subsequent dynamic phases. Computer modeling of bolus enhancement and k‐space sampling was performed to demonstrate the relation between vessel enhancement, acquisition time, and vessel diameter. Second, time‐resolved (TR, or “keyhole”) angiography using a reduced number of phase‐encoding steps was explored in healthy volunteers and aortic‐aneurysm patients using acquisition times (range = 6–8.5 seconds) shorter than the spinal cord circulation time.

Results

Using two‐phase angiography the AKA and GARV were covisualized in the early phase, and contrast decreased for the AKA and increased for the GARV in most (70%) but not all cases. Computer modeling showed that the arteriovenous contrast strongly depended on vessel diameter, and complete separation was only obtained with short acquisition times. Using TR MR angiography (TR‐MRA), complete temporal separation of the AKA and GARV was realized in all cases (100%).

Conclusion

The AKA and GARV can be completely separated by TR‐MRA. J. Magn. Reson. Imaging 2007;26:31–40. © 2007 Wiley‐Liss, Inc.
FAIR true‐FISP perfusion imaging of the thyroid gland
Authors: Schraml Christina , Boss Andreas , Martirosian Petros , Schwenzer Nina F. , Claussen Claus D. , Schick Fritz
Published: July 2007

Purpose

To evaluate the feasibility of quantitative perfusion MRI of the thyroid gland using an arterial spin labeling (ASL) method.

Materials and Methods

An ASL technique with flow‐sensitive alternating inversion‐recovery (FAIR) spin preparation and a true fast imaging in the steady state (TrueFISP) signal readout strategy was implemented on a 1.5T whole‐body unit. Anatomical and perfusion imaging of the thyroid gland was performed in eight healthy volunteers and one patient with functioning adenoma. Quantitative perfusion maps were calculated using the extended Bloch equations.

Results

In all subjects the perfusion images showed diagnostic image quality. The mean examination time was 24 minutes for multiplanar perfusion imaging of the entire thyroid gland. Individual perfusion values ranged between 341 ± 91 and 640 ± 90 mL/100 g/minute, with a mean perfusion of 461 ± 90 mL/100 g/minute. The functioning adenoma showed markedly reduced perfusion compared to normal thyroidal parenchyma. No perfusion was noticeable inside four detected thyroid cysts.

Conclusion

Quantitative ASL perfusion imaging of the thyroid gland using a FAIR‐TrueFISP sequence leads to perfusion maps that may provide important information for assessing thyroid gland pathologies and monitoring therapeutic treatment. J. Magn. Reson. Imaging 2007;26:66–71. © 2007 Wiley‐Liss, Inc.
Malignant or borderline mucinous cystic neoplasms have a larger number of loculi than mucinous cystadenoma: A retrospective study with MR
Authors: Okamoto Yoshikazu , Tanaka Yumiko O. , Tsunoda Hajime , Yoshikawa Hiroyuki , Minami Manabu
Published: July 2007

Purpose

To determine whether there is any correlation between the number of loculi and the pathological grade of malignancy in mucinous cystic tumors of the ovary.

Materials and Methods

We retrospectively studied MR images of 67 pathologically proven mucinous cystic tumors of the ovaries. Of these 67 cases, 38 were cystadenomas and 29 were malignant lesions (18 borderline malignancy and 11 adenocarcinomas). We counted the number of loculi and measured the maximum diameter of masses on MRI. We compared the number, the maximum diameter, and the ratio of the number of loculi to the maximum diameter in each adenoma and malignancy using Student's t‐test.

Results

The mean number of loculi was 18.2 in cystadenoma and 80.9 in malignant lesions. The mean maximum diameter of tumors was 13.0 cm in cystadenoma and 18.7 cm in malignant lesions. The mean ratio of the number of loculi to the maximum diameter was 1.3 in adenoma and 5.4 in malignant lesions. The differences between the benign and malignant lesions were statistically significant in number (P = 0.001), maximum diameter (P = 0.011), and ratio (P = 0.002).

Conclusion

Ovarian mucinous neoplasm of borderline malignancy and mucinous adenocarcinomas had a larger number of loculi than adenomas. J. Magn. Reson. Imaging 2007;26:94–99. © 2007 Wiley‐Liss, Inc.
UV Laser Deposition of SiS/Poly(thiacarbosilane) Composites and their Conversion to SiO/Poly(thiacarbosiloxane) Composites
Authors: Tomovska Radmila , Urbanová Markéta , Šubrt Jan , Boháček Jaroslav , Pola Josef
Published: July 2007

ArF laser irradiation of gaseous mixtures of carbon disulfide and silane allows efficient deposition of SiS bond‐containing poly(thiacarbosilanes) incorporating SiS bodies. These SiS/poly(thiacarbosilane) composites are the first example of silicon sulfide/polymer composites. Composite formation is analyzed by GC/MS analysis of volatile products and the structure of the composite as determined by electron microscopy and FT‐IR spectra. The composites undergo reaction with air moisture and methanol vapor, evolve H2S and evolve to nano‐sized poly(thiacarbosiloxane)s and poly(methoxythiacarbosiloxane)s.

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Synthesis and Conformation of Three‐Dimensionally Ordered Macroporous Syndiotactic Polystyrene and Poly(p‐methyl styrene)
Authors: Li Haiqing , Abraham Sinoj , Yan Weidong , Ha Chang‐Sik , Kim Il
Published: July 2007

Three‐dimensionally ordered macroporous (3DOM) syndiotactic polystyrene (sPS) and poly(p‐methyl styrene) (sPPMS) are synthesized using silica colloidal crystal templates with varied diameters in the range of 548–214 nm, and the effect of polymerization space on the conformation of the resulting 3DOM polymers is investigated by spectroscopy and thermal analysis. In‐situ polymerizations of styrene and p‐methyl styrene within the silica templates induce the resulting 3DOM polymers with different conformations and packing of chains, which are different from those of bulk polymers prepared in the absence of templates. Polymerizations in restricted silica templates result in un‐helixication of 3DOM sPS chains and helixication of 3DOM sPPMS chains.

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Meta‐analysis of heart valve abnormalities in Parkinson's disease patients treated with dopamine agonists
Authors: Simonis Gregor , Fuhrmann Joerg T. , Strasser Ruth H.
Published: July 2007

Valvular heart disease in patients being treated with ergot‐derivative dopamine agonists (Ergot‐DA) for Parkinson's disease has been reported to occur as a consequence of serotonine receptor stimulation. Goal of this analysis was to estimate the incidence of those changes from recently published studies and to determine its clinical relevance. Medline searches were performed to identify cross‐sectional, echocardiographic studies comparing patients treated with dopamine agonists or controls, in terms of valvular changes. Observational studies of valve changes in Parkinsonian patients were used to estimate the incidence of severe valvulopathy. The results from 7 cross‐sectional studies including 477 patients treated with Ergot‐DA, 127 patients with non‐Ergot‐DA, and 364 control patients were analyzed. Moderate‐to‐severe valvular changes were detected in 26% of patients treated with Ergot‐DA, 10% of patients treated with non‐Ergot DA, and 10% of control patients. Severe valvulopathy was less than 1% both in cross‐sectional and observational studies. The high rate of moderate valvular changes in patients treated with Ergot‐DA suggests that close surveillance of the patients is required. Severe valvulopathy was less than 1% in the studies analyzed. © 2007 Movement Disorder Society
Physicochemical studies on hydrophobic PEO‐PPO‐PEO triblock copolymer micelles in SDS micellar environment
Authors: James Jilly , Ramalechume Chidambaram , Mandal Asit Baran
Published: July 2007

The shape, size, aggregation, hydration, and correlation times of water insoluble PEO‐PPO‐PEO triblock copolymer micelles with sodium dodecylsulfate (SDS) micelles were investigated using transport studies and dynamic light scattering technique. From the conductance of micellar solutions of the polymer in 25 mM SDS and 5 mM NaCl, the hydration of polymer micelles were determined using the principle of obstruction of electrolyte migration by the polymer. The asymmetry of the micellar particles of polymer and polymer‐SDS mixed micellar systems in 5 mM NaCl and their average axial ratios were calculated using intrinsic viscosity and hydration data obeying Simha–Einstein equation. Hydration number and micellar sizes were variable with temperature. The shape of the polymer micelles has been ellipsoidal rather than spherical. The micellar volume, hydrodynamic radius, radius of gyration, diffusional coefficients as well as translational, rotational and effective correlation times have been calculated from the absolute values of the axes. The partial molal volume of polymer micelles has also been determined and its comparison with the molar volume of pure polymer suggested a volume contraction due to immobilization of the water phase by the hydrophilic head groups of the polymer. The thermodynamic activation parameters for viscous flow favor a more ordered water structure around polymer micelles at higher temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2410–2420, 2007
Risk factors for sleep‐related hypoxia in primary school children
Authors: Urschitz Michael S. , Eitner Steffen , Wolff Judith , Guenther Anke , Urschitz‐Duprat Pilar M. , Schlaud Martin , Poets Christian F.
Published: July 2007

Sleep‐related hypoxia has adverse effects on cognition in children. Knowledge of factors contributing to sleep‐related hypoxia is sparse. We aimed to identify demographic and clinical factors associated with mild (nadir arterial oxygen saturation 91–93%), moderate (nadir arterial oxygen saturation ≤90%), and recurrent (oxygen desaturation index > 3.9) sleep‐related hypoxia in children. Parental questionnaires were distributed and overnight recordings of arterial oxygen saturation performed in a population‐based cross‐section of primary school children (n = 995). Associations were determined using unconditional logistic regression as well as unadjusted and adjusted odds ratios (OR), and their 95% confidence intervals (95% CI) calculated. Male sex, overweight (i.e., body mass index ≥ 75th percentile), household smoking, symptoms of sleep‐disordered breathing, a current respiratory tract infection, and histories of asthma and respiratory allergy were all significantly associated with sleep‐related hypoxia. In multiple regression analysis, (i) overweight (OR, 95% CI: 2.7, 1.7–4.3) and a history of respiratory allergy (1.7, 1.1–2.7) were independent risk factors for mild sleep‐related hypoxia, (ii) overweight (3.2, 1.7–5.8), a history of respiratory allergy (2.4, 1.4–4.4), and household smoking >10 cigarettes/day (1.8, 1.1–2.8) were independent risk factors for moderate sleep‐related hypoxia, and (iii) overweight (2.3, 1.04–5.3), a history of respiratory allergy (2.5, 1.2–5.1), and a current respiratory tract infection (4.4, 2.0–9.8), were independent risk factors for recurrent sleep‐related hypoxia. Our data suggest that overweight, passive smoking, respiratory allergies, and acute lung disease may independently contribute to sleep‐related hypoxia in children. Pediatr Pulmonol. 2007; 42:805–812. © 2007 Wiley‐Liss, Inc.
Effect of electronic compensation on plethysmographic airway resistance measurements
Authors: Broughton Simon , Rafferty Gerrard F. , Milner Anthony D. , Greenough Anne
Published: July 2007

Objectives

To compare the performance of a plethysmograph which incorporated electronic compensation (Jaeger) to one which incorporated a heated humidified breathing system (Hammersmith plethysmograph).

Working hypothesis

The performance of a plethysmograph which incorporated electronic compensation would be impaired compared to that which incorporated a heated humidified system.

Study design

In vitro and in vivo comparison.

Patient selection

Eleven children, median postnatal age 13 (range 5–15) months.

Methods

In vitro, the plethysmographs were assessed using known resistances (1.94, 4.85, and 6.80 kPa, equivalent to 20, 50, and 70 cm H2O/L/sec, respectively). In vivo, comparison was made of the results of children studied in both plethysmographs.

Results

In vitro, the resistance results of the two plethysmographs were similar to each other and to the known resistances. In vivo, the median “effective” airways resistance result of the Jaeger (4.15 kPa/L/sec) was significantly higher than the inspiratory resistance of the Hammersmith plethysmograph (3.0 kPa/L/sec), but the median inspiratory resistances of the Jaeger were significantly lower than those of the Hammersmith plethysmograph (2.8 kPa/L/sec vs. 3.0 kPa/L/sec). The mean within patient coefficient of variability for inspiratory resistance of the Jaeger plethysmograph (16.7%) was significantly higher than that of the Hammersmith plethysmograph (11.6%) (P = 0.014).

Conclusion

These results suggest plethysmographs which incorporate electronic compensation may be inappropriate for use in infants and very young children. Pediatr Pulmonol. 2007; 42:764–772. © 2007 Wiley‐Liss, Inc.
Analysis of oil and meal fromLesquerella fendleri seed
Authors: Carlson K. D. , Chaudhry A. , Bagby M. O.
Published: July 2007

Attention is being focused onLesquerella species as a source of hydroxy acids to replace imported castor oil. Genetic and agronomic improvement and utilization of the seed oil and meal are being studies. We have conducted laboratory experiments to extract oil fromL. fendleri seed in preparation for extracting large quantities of seed.L. fendleri is a member of the Cruciferae family, and when seeds are crushed glucosinolates release isothiocyanates by the action of a thioglucosidase enzyme system. Therefore, our experiments included moist heat treatment of whole seeds to inactivate this enzyme. The seed was then flaked in a Wolf mill, and the flakes were exhaustively extracted with hexane. The oil was degummed and bleached, and then analyzed for hydroxyl (103), saponification (174), and iodine values (107), and for unsaponifiables (1.5%), FFA (1.13%) and P (10 ppm) contents. Hydroxy fatty acids, 55% lesquerolic (14‐hydroxy‐cis‐11‐eicosenoic) and 3% auricolic (14‐hydroxy‐cis‐11,cis‐17‐eicosadienoic), and total fatty acid distribution were determined by gas chromatography of the methyl esters. The defatted meal was analyzed for residual oil (1%), protein (29.8%), non‐protein nitrogen (0.7%), ash (6.45%). crude fiber (12.9%), and for distribution of amino acids. DefattedL. fendleri meal has an excellent distribution of amino acids, including favorable levels of lysine, methionine and threonine compared with soybean meal.
Infrared studies on the isomers of kamlolenic acid
Authors: Gupta Sharda Das , Aggarwal J. S.
Published: July 2007

Thecis‐trans and positional configuration of α‐and β‐kamlolenic acids have been investigated. Infrared data of the two isomers, their acetyl derivatives and maleic anhydride adducts, and the permanganate oxidation products of the addition compounds, together with the selective epoxidation of the exocyclic double bond of the maleinated derivatives, have been used to confirm the structure of the three conjugated double bonds in α‐kamlolenic acid ascis‐9‐trans 11‐trans 13. and β‐kamlolenic acid astrans 9‐trans 11‐trans 13.
Free glycerol in soap
Authors: Pohle W. D. , Rockwood B. N. , Mehlenbacher V. C.
Published: July 2007

The determination of free glycerol in soap has been improved and shortened.

When it is known that there are no substances which interfere with periodic acid reaction, the directiodimetric method is applicable. However, if the glycerol content is below 1%, the accuracy and precision are only fair.

The extraction‐iodimetric method is applicable when the sample contains no periodic acid reducing substance other than glycerol or when such substances are soluble in chloroform.

The extraction‐acidimetric method is preferable when the sample contains periodic acid reducing substances other than glycerol and which are soluble in the aqueous acid solution along with the glycerol.
Acetonitrile as eluent in silver resin column chromatography
Authors: DeJarlais W. J. , Adlof R. O. , Emken E. A.
Published: July 2007

Acetonitrile (ACN) is shown to be an effective eluent in combination with methanol (MeOH) or acetone for the rapid separation of polyunsaturated fatty acid methyl esters on a fully silver‐loaded ion‐exchange (XN1010) column. ACN‐containing eluents thus provide on one fully siliver‐loaded resin column an attractive alternative separation system to a series of partially silvered resin columns (“PARC” columns), which previously have been used for such separations. Solvent programming from 0 to 15% ACN in MeOH allows the separation of methyl oleate, linoleate, linolenate and arachidonate within 3 hr. Preparative (up to 800 mg) isocratic separations of a number of polyunsaturated fatty acid esters from natural sources (methyl linoleate from safflower esters, for example) were readily achieved.
Interpreting the appearance of dispersed systems: II. A guide for surfactant systems
Authors: Franses E. I. , Scriven L. E. , Miller W. G. , Davis H. T.
Published: July 2007

We first analyze how color and transparency are perceived. Drawing on principles of light scattering investigated in Part I, we suggest simple rules and procedures in a diagnostic form for visually observing fluid surfactant systems to estimate sizes of dispersed particles. Rules and procedures are organized into a guide, the use of which we illustrate by observing certain important surfactant systems. We conclude that it is possible to estimate particle sizes in the Rayleigh, Rayleigh‐Debye‐Gans, and Mie scattering regimes from such observations alone.
Quantitative Determination of phosphatidylcholine by an HPLC‐RI system
Authors: Yamagishi Toshihiko , Akiyama Hiroshi , Kimura Shinichi , Toyoda Masashi
Published: July 2007

The following describes the quantitative determining method for phosphatidylcholine (PC) using the HPLC‐RI system which we have developed. It uses Lichromsorb, Si 60 (10 μm), 4.6 mm × 250 mm as the column and a mobile phase consisting of n‐hexane/isopropanol/water =1:4:1. In this report, we compared data from selected high‐purity (60–100 wt%) samples using the HPLC‐RI, HPLC‐UV and conventional TLC‐P methods.

Under the conditions we described, the HPLC‐UV method was somewhat affected by fatty acid compositions. As a result, there were some inconsistencies in the measured values. However, the HPLC‐RI method we propose was applicable to PC from both egg yolk and soybeans. In addition, the HPLC‐RI method produced data which correlated well with data from the TLC‐P method, and this data was highly accurate and exhibited satisfac‐tory reproductibility.
Biorefining of high acid rice bran oil
Authors: Bhattacharyya S. , Bhattacharyya D. K.
Published: July 2007

Rice bran oil with a high free fatty acid content (FFA) after degumming and dewaxing can be converted into edible quality oil of satisfactory refining characteristics by first adopting the biorefining process to reduce the major portion of the FFA by converting them into neutral glycerides with the aid of 1,3‐specific lipase under optimum conditions and later deacidifying the residual FFA of the biorefined oil by alkali neutralization.
Selection of surfactant pairs for optimization of interfacial properties
Authors: Rosen Milton J.
Published: July 2007

Guidelines are provided for the selection of surfactant pairs when synergism in various interfacial properties in aqueous media is desired. To maximize the reduction of the critical micelle concentration, the two surfactants should show strong attractive interaction in the mixed micelle; in order to maximize efficiency in surface tension reduction, strong interaction in the mixed monolayer at the aqueous solution/air interface (large negativeβ values is needed). The more surface‐active material should predominate in the mixture. When interaction is not strong, the two surface‐active materials used should have approximately equal surface activities and should be used at equimolar concentration in the aqueous phase. To minimize the surface tension (γ) of the solution, the surfactant‐surfactant attractive interaction in the mixed monolayer at the aqueous solution/air interface must exceed that in the mixed micelle. Optimization can be achieved by using two surfactants with approximately equal γ values at their respective critical micelle concentrations (CMC’s). When these γ values are not equal, the surfactant with the higher γ value at its CMC should have the smaller area/molecule at the surface. The greater the difference between attractive interaction at the interface and in the micelle, the lower the value of the surface tension.
Petroleum‐free extraction of oil from soybeans with supercritical CO2
Authors: Friedrich J. P. , List G. R. , Heakin A. J.
Published: July 2007

Full‐fat soyflakes are readily extracted with supercritical carbon dioxide (SC‐CO2) at pressures of 3,000~10,000 psig and 50 C. Under these conditions, SC‐CO2 has the density of a liquid and the diffusivity of a gas. Therefore, equilibrium solubility is readily achieved in a short‐path batch extractor which permits high gas flow rates. Soybean oil extracted with SC‐CO2 is lighter in color and contains less iron and about one‐tenth the phosphorus of hexane‐extracted crude oil from the same beans. The lower phosphorus content is reflected in a chromatographic refining loss of 0.6% compared to 1.9% for hexane crude. Refined oils from hexane and SC‐CO2 extraction had equivalent odor and flavor scores initially and after 4 days' storage at 60 C. Carbon dioxide, an ideal solvent for extraction of food products, is low‐cost and readily available from fermentation processes and could free over 20 million gallons of costly hexane per year for essential energy uses.
Production of branched‐chain fatty acids from sterculia oil
Authors: Kai Y. , Pryde E. H.
Published: July 2007

Methyl sterculate was rearranged by use of 0.5% of rhodium catalyst to isomeric conjugated diene fatty acid methyl esters containing both methylene‐and methyl‐branched isomers. The rearanged products were hydrogenated directly to saturated, methyl‐substituted, branched‐chain fatty acid methyl esters with the methyl substituent at one of the positions formerly occupied by the cyclopropenoid ring. The crude branched‐chain fatty acids from these esters were purified by recrystallization from a mixed solvent of ethanol and water (80:20, v/v) and flash distillation; the product contained about 90% of branched‐chain fatty acids (C19:80%, C18:10%). Esters of the branched‐chain fatty acid were prepared with 2‐ethylhexyl alcohol or trimethylolpropane, and the characteristic properties of these esters were investigated. The branched‐chain fatty esters appear to have potential utility in lubricants; other uses may be possible.
Effects of soaking soybeans in dilute acids on biologically active components
Authors: Che Man Y. B. , Wei L. S. , Nelson A. I. , Yamashita N.
Published: July 2007

Soaking soybeans in dilute acids affected activities of lipoxygenase, trypsin inhibitor and urease. Effects of soaking time, acid concentration and soaking temperature were investigated. Lipoxygenase activity was completely eliminated by soaking in 0.3 M HC1 at either 23°C or 40°C for 8 hr. Less than 50% trypsin inhibitor remained and urease was inactivated to an acceptable level (0.04 ΔpH).
Pre‐Ripening damage to cottonseed byaspergillus flavus is not influenced by seed coat permeability
Authors: Halloin J. M. , Lee L. S. , Cotty P. J.
Published: July 2007

Infection of cottonseed (Gossypium hirsutum L.) byAspergillus flavus and associated production of aflatoxins are problems in the arid portions of the United States cotton belt. The hard seed (impermeable to water) characteristic confers resistance to these problems in ripened cottonseed. Experiments were done to determine if low seed coat permeability to water or impermeability protect developing seeds from deterioration and aflatoxin formation. No differences were observed in the degree of seed deterioration in the various cotton lines that could be attributed to seed coat permeability. It is likely that, because the impermeable or low permeability phenotypes are expressed only upon seed ripening, these characteristics afford no protection to cottonseed against attack byA. flavus during seed development.
New detergent mechanism with use of novel alkaline cellulose
Authors: Murata Moriyasu , Hoshino Eiichi , Yokosuka Michio , Suzuki Akira
Published: July 2007

Microscopic studies of naturally soiled cotton undershirts showed that there was sebum in the microscopic spaces in the interior of the cotton fibers. Ordinary detergents did not remove this soil satisfactorily, although they readily removed sebum on the exterior of the fibers. Alkaline cellulase, which was compatible with the alkaline ingredients of detergents and which interacted selectively with celluloses in interfiber space in the interior of fiber, effectively removed sebum soil in the interfiber spaces in the presence of usual detergent ingredients. The removal of soil by the hydrolysis of the amorphous regions of fibers with cellulase is a new detergent mechanism.
Edible quality rice bran oil from high ffa rice bran oil by miscella refining
Authors: Bhattacharyya A. C. , Majumdar S. , Bhattacharyya D. K.
Published: July 2007

Rice bran oils high in free fatty acids (FFA) can be converted to cooking oil having low unsaponifiable matter and light color by a combination of miscella dewaxing and miscella refining.
Gas liquid chromatography of the hydroxy‐, acetoxy‐and oxo‐stearic acid methyl esters
Authors: Tulloch A. P.
Published: July 2007

Carbon numbers have been determined for all the 17 isomeric methyl hydroxy‐ and acetoxystearates and for 15 of the 16 isomeric methyl oxostearates using silicone SE‐30, silicone QF‐1, and ethylene glycol succinate (EGS) as liquid phases. The carbon numbers of the isomers increase with increasing distance of the point of substitution from the carboxyl end of the fatty acid chain (the increases for the 4‐ and 5‐hydroxy esters are unexpectedly large). The change in carbon number from one isomer to the next is greatest when the substituents are attached near either end of the chain. The best separation of isomers with the substituent near the carboxyl end is obtained for oxo esters using the QF‐1 column, and that of isomers substituted near the methyl end is obtained for acetoxy esters using the EGS column. Isomers with substituents at carbons 9<13 are not distinguishable on any of the columns used, but the other isomers are partly or completely separated. The quantitative aspects of the separations have not been investigated.
Analytical fractionation of complex lipid mixtures: DEAE cellulose column chromatography combined with quantitative thin layer chromatography
Authors: Rouser George , Galli Claudio , Lieber Ellen , Blank M. L. , Privett O. S.
Published: July 2007

A quantitative chromatographic procedure for the fractionation of complex lipid mixtures is described. The method utilizes diethylaminoethyl (DEAE) cellulose column chromatography followed by thin layer chromatography (TLC). Spots produced in TLC are charred with sulfuric acid‐potassium dichromate and heat and are then measured by quantitative densitometry. Results obtained with beef brain and beef heart mitochondrial lipids are presented, and the close correspondence between column isolation procedures and the new procedure is demonstrated. Methods utilizing only column chromatography, column chromatography and TLC, and one‐ and two‐dimensional TLC without column chromatography are compared.
Energy conservation in the solvent extraction area1
Authors: Kingsbaker C. Louis
Published: July 2007

Both old and new ways to conserve energy are discussed. The old ideas are basic fundamentals and will save 14% ‐ the 1980 goal. Some present methods can be incorporated for additional savings. Thought must be given now to long range plans for energy savings in the future. Today, energy savings can and must be made by running the plandt as it now exists to its maximum efficiency. Suggestions in this paper should be reviewed and applied to your plant. Last of all, think energy conservation twenty‐four hous a day you wil then meet the Federal Energy Administration target of saving 14% energy in 1978 and not in 1980.
Interaction of fat‐ containing food with plastics packaging
Authors: vom Bruck C. G. , Figge K. , Rudolph F.
Published: July 2007

Packagings for fatty food should protect against light, oxygen, microorganisms, and loss of water vapor and flavor substances. Low off‐taste and adequate mechanical stability is required. Pigmented plastics fulfill most of these requirements. Two main effects caused by the interaction of fatty food components with plastic packaging materials are described: stress cracking and migration. A method for characterizing fatty foodstuffs was developed to distinguish between foodstuffs containing free fat available on the surface and those actually having an aqueous surface. The basic types of migration behavior are shown by typical migration curves of an antioxidant from rigid PVC and from HD‐PE into test fat. In model experiments, the swelling of the HD‐PE as well as the migration of the antioxidant was determined quantitatively as a function of time by means of radiotracer techniques. Based on these results and Fick’s diffusion equations, a theory was developed with which it is possible to describe the migration behavior of antioxidants from polyolefins and PVC quite precisely. It was also possible to solve some problems with HI‐PS. This mathematical model permits calculation of the migration at constant temperature as a function of time and concentration of the antioxidant in the polymer. As there is a definite mathematical relationship between the concentration of an additive in the polymer and the migration into test food or actual food, it is recommended that regulations for plastic food packaging are based on compositional limits, rather than migration limits, because of definite advantages in compliance and control.
Modeling of reaction rate constants and selectivities in soybean oil hydrogenation
Authors: Chen A. H. , Mclntire D. D. , Allen R. R.
Published: July 2007

A simple approach to model the rate constants and selectivities for soybean oil hydrogenation with nickel catalyst is presented. The rate constant models were constructed on the basis of Arrhenius Law and Power series. The parameters were temperature, hydrogen pressure, concentration of catalyst and agitation expressed in terms of power per unit volume of oil. The models agree with the general knowledge in hydrogenation and the data were fitted fairly well by the models.
Gas chromatographie separation of cis and trans isomers of long chain amines
Authors: Metcalfe L. D. , Wang C. N.
Published: July 2007

There are important differences in the physical properties of the cis and trans isomers of unsaturated long chain amines. Because of these differences, it is desirable to know the ratio of the cis and trans isomers. This separation can be accomplished by capillary column gas chromatography of the amine derivatives; however, the use of capillary columns is too slow for routine analysis. It was found that the cis and trans isomers of unsaturated amines can be rapidly separated on packed columns containing cyanopropyl‐phenylsilicone liquid phases (Apolar 10C). The primary amines are converted to the trifluoroacetamides and separated on 6‐ to 10‐ft columns containing 10% Apolar 10C at 180 C. The technique has been applied to unsaturated long chain primary amines and diamines. Useful information on the isomerization of these compounds during their synthesis can be obtained.
Participation of sesamol in stability of sesame oil
Authors: Kikugawa K. , Arai M. , Kurechi T.
Published: July 2007

Sesame oil is known to be the most resistant to oxidative rancidity. Constituents of sesame oil such as sesamolin, sesamol and sesamol dimer (a possible intermediate of oxidative degradation of sesamol) were determined by high performance liquid chromatography using a reverse‐phase column. Sesamol was specifically determined in an alternative way by use of hydrogen peroxide/horseradish peroxidase. Sesamolin was relatively stable but sesamol and sesamol dimer were unstable when irradiated in benzene, and the final degradation products were identical. Whereas sesamolin was inactive, sesamol and sesamol dimer showed significant antioxidant activity in several kinds of fat and oils. Stability of Japan Pharmacopoeia sesame oil free from sesamol was relatively low; antioxidant activity of sesamol incorporated in the oil was unexpectedly low and was rapidly lost in the oil activated by oxygen. Edible sesame oil with intrinsic sesamol was highly stable. Activation of the edible oil gradually increased the sesamol content with concomitant decrease of sesamolin. High stability of edible sesame oil could not be ascribed to sesamol, but it could be explained by another powerful antioxidant(s) which might stabilize both the oil and unstable sesamol.
Studies on nitrosochlorination of olefinic fatty acids: I
Authors: Hasan S. Q. , Ahmad I. , Ahmad Fashih , Osman S. M.
Published: July 2007

Nitrosochlorination of methyl oleate yielded methyl 9(10)‐chloro‐10(9)‐nitrosooctadecanoate, methyl 9(10)‐chloro‐10(9)‐oximinooctadecanoate and an abnormal product 9(10)‐chloro‐10(9)‐nitriminooctadecanoate. A similar reaction with 10‐undecenoate yielded a dimer of methyl 10‐chloro‐11‐nitrosoundecanoate, methyl 10‐chloro‐11‐oximinoundecanoate and methyl‐10‐chloro‐11‐nitriminoundecanoate. On the other hand, methyltrans‐2‐doxosenoate reacted reluctantly up to 10%, yielding methyl 2‐oximino‐3‐chlorodocosanoate. All these products have been characterized with the help of compositional and spectral data.
The determination of hydrotropes in detergent products by reverse‐phase and ion‐pair high performance liquid chromatography
Authors: McPherson B. P. , Omelczenko N.
Published: July 2007

The three aromatic sulfonates most commonly used as hydrotropes in detergent products can be qualitatively and quantitatively determined by high performance liquid chromatography (HPLC). Reverse‐phase and paired‐ion methods are described for separating sodium toluene, xylene and cumene sulfonates using conventional C18, C8, hexyl, and cyano columns as well as radially compressed HPLC cartridges. Ultraviolet (UV) detection at 254 nm gives more than adequate sensitivity for hydrotropes formulated between 0.5 and 15%. Sample preparation is simple and all components can be eluted within 15 min. The quantitation has been proven precise and accurate during routine analyses of either powdered or liquid detergent products.
Complex formation between oxidized lipids and egg albumin
Authors: Narayan K. A. , Sugai Masuo , Kummerow F. A.
Published: July 2007

The nature of the reactions leading to the formation of complexes between oxidized lipids and proteins is little understood. Complexes were formed between thermally oxidized and thermally polymerized corn oils and egg albumin. The results indicated that the thermally oxidized oil was much more reactive than the thermally polymerized oil. The nature and extent of oxidative groups in the lipid were varied and reacted withegg albumin. The keto and epoxy groups seemed to have a pronounced influence on complex formation while the hydroxy and hydroperoxide groups were observed to be less reactive. Acetylation of egg albumin did not significantly decrease its complexing ability with thermally oxidized corn oil. Further confirmation that the reactive groups in the protein were not covalently tied up to the lipid was obtained by estimating these groups in the original protein and in the complexed protein. IR analyses of oxidized lipid‐alumina, oxidized lipid‐egg albumin and fatty acid‐urea complexes indicated that the characteristic absorption was due to bonded O‐H stretching vibration in the first two complexes and the bonded N‐H stretching vibration in the two latter complexes.
Experiments on film elasticity and surface relaxation
Authors: Razouk Rashad I. , Mysels Karol J.
Published: July 2007

The effect of extensive purification by foaming (and foam removal) upon the surface tension, the Marangoni effect, and upon the film elasticity of solutions of sodium dodecyl sulfate and sulfonate has been studied. Evidence is presented that com‐plete purification was not obtained and that the persistence of a Marangoni effect with a long relaxation time is a sensitive test for surface impurities.
Comparison of total fat, fatty acids, cholesterol, and other sterols in mayonnaise and imitation mayonnaise
Authors: Newkirk David R. , Sheppard Alan J. , Hubbard Willard D.
Published: July 2007

Nine brands of mayonnaise and five brands of imitation mayonnaise were purchased from supermarkets in the Washington, DC, area. The samples were analyzed for total fat, fatty acids, sterols, and moisture. Little variation in total fat and saturated fatty acid values was observed among the brands of mayonnaise. The polyunsaturated fatty acid content of mayonnaise ranged from 28.0 to 47.9 g/100 g product. The cholesterol levels were divided between two ranges, 50‐55 and 75‐79 mg/100 g product. In contrast, there was wide variation in the lipid composition of the different brands of imitation mayonnaise. The total fat values for these products varied from 14.3 to 50.4 g/100 g product. The cholesterol content varied between 0 and 72 mg/100 g product; the latter figure equals the cholesterol content of many of the mayonnaise samples.
Polyglycerol Esters
Authors: McIntyre R. T.
Published: July 2007

When glycerol is heated with an alkaline catalyst to over 230 C, water is evolved and polymerization occurs to form a whole family of polyglycerols ranging from diglycerol with 3 hydroxy groups, to triacontaglycerol with 32 hydroxy groups. The carboxylic acid esters of polyglycerols prepared by direct esterification or by interchange, may be solid or liquid; saturated or unsaturated; aliphatic or aromatic; mono, di‐ or polycarboxylic acid esters; mono‐, di‐, or polyesters of the polyglycerol; single or mixed acid esters; high or low molecular weight; water or oil soluble; and with an HLB from about 4 to about 13. Polyglycerol esters find utility in a wide variety of food products including beverages, desserts, topping and baked goods. They are thermally stable and find application in several industrial systems.
Study of the accelerated oxidation of low and high erucic rapeseed oil
Authors: Erkilla I. , Fung T. , Kandiah M. , Wilkins J. , Moran J. J. , Blake J. A.
Published: July 2007

The oxidation of a low erucic rapeseed oil was compared to the oxidation of a high erucic rapeseed oil in the temperature range 100 to 140 C. The two oils were found to be very similar in the rate of peroxidation, viscosity increase, change of refractive index, oxidation of the individual fatty acids, and hydroperoxide decay. Rate constants and activation energies for the change of these quantities were determined. The rate of hydroperoxide decomposition was found to be of first order for both oils, but there was evidence that a second order mechanism becomes important at temperatures less than 100 C. Butylated hydroxy anisole (BHA) caused decomposition of hydroperoxide and reacted with fatty acid and possibly with natural antioxidants in the oil. It did not react with oxygen. BHA decomposed thermally between 110 and 140 C. BHA is not an effective antioxidant at these temperatures in an oil which contains esters of highly reactive fatty acids.