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VIEWS: 27 PAGES: 9 CATEGORY: Chemical Compositions POSTED ON: 10/18/2010
The present invention relates generally to the field of flavorings and fragrances. More particularly, the present invention relates to citral derivatives that provide beverages and other food products, as well as perfumes and other fragrantarticles with a lemony scent, while at the same time overcoming the stability limitations of the native citral compound.BACKGROUND OF THE INVENTIONCitral (3,7 dimethyl 2,6 octadienal) is a major component of lemon smell, and has the sweet-acidulated character of natural lemon. For largely historical reasons, lemon smell has become associated with freshness and cleanliness, both in drinksand in household products, and in fragrances and flavorings, generally. Lemon drinks, whether natural or synthetic, are naturally acid, which causes rapid degradation of citral to unpleasant-smelling products like cresol. This means that the shelf lifeof lemonade is correspondingly short, creating an expensive logistical problem. In household products, the problem is of a different nature. In order to associate bacteriological cleanliness with the smell of lemon these products frequently uselemon-scented bleach (hypochlorite). Citral is unstable in bleach, and cannot therefore be used. Instead, its nitrile analogue, geranyl nitrile, with its less satisfactory oily-metallic lemon note has to be used.The chemical instability of citral is largely due to the two double bonds and an aldehyde group, all of which are potentially susceptible to reaction, particularly when used in harsh environments, such as lemon-scented bleach. It would bedesirable to develop citral derivatives with improved useful lifetimes, and, preferably, improved odor intensity, while maintaining the lemon note of citral. The present invention provides such citral derivatives.SUMMARY OF THE INVENTIONImproved fragrances and flavorings that have a longer useful shelf life than citral are disclosed. In particular, citral derivatives that maintain the fragrance characteristics
United States Patent: 7704941 ( 1 of 1 ) United States Patent 7,704,941 Turin April 27, 2010 Citral derivatives Abstract Improved citral derivatives, and fragrances and flavorings including the derivatives, that have a longer useful shelf life than citral and/or fragrances and flavorings including citral, are disclosed. In particular, the derivatives maintain the fragrance characteristics of citral, while lowering the allergic properties, and lemony flavors and fragrances with a longer shelf-life than citral, are disclosed. Also disclosed are methods of making the derivatives, and articles of manufacture including the derivatives. In one embodiment, the derivatives are prepared by replacing one or more double bonds in citral with a cyclopropyl group, which can be unsubstituted, or substituted with one or two lower alkyl, preferably methyl groups. The alkyl groups can optionally be substituted, for example, with electron donating groups, electron with drawing groups, groups which increase the hydrophilicity or hydrophobocity, and the like. In another embodiment, the derivatives are prepared by replacing the aldehyde group in citral with a nitrile, methyl ether or acetal group. The acetal groups can provide the compounds with a long lasting flavor or fragrance, where the acetals slowly hydrolyze to provide the aldehyde group in citral. In some embodiments, both the aldehyde and at least one of the double bond functional groups are both derivatized as described herein. Examples of suitable articles of manufacture include candles, air fresheners, perfumes, disinfectant compositions, hypochlorite (bleach) compositions, beverages such as beer and soda, denture cleanser tablets and flavored orally-delivered products such as lozenges, candies, and the like. Inventors: Turin; Luca (London, GB) Assignee: Flexitral, Inc. (Chantilly, VA) Appl. No.: 11/861,610 Filed: September 26, 2007 Related U.S. Patent Documents Application NumberFiling DatePatent NumberIssue Date 10869626Jun., 20047309795 PCT/US02/26446Aug., 2002 60377914May., 2002 60389298Jun., 2002 60355052Feb., 2002 60342150Dec., 2001 60348580Jan., 2002 Current U.S. Class: 512/6 ; 558/434 Current International Class: A61K 8/40 (20060101); C07C 255/46 (20060101) Field of Search: 558/434 512/6 References Cited [Referenced By] U.S. Patent Documents 3770836 November 1973 Comes 3950429 April 1976 Lamparsky et al. 4097531 June 1978 Bledsoe, Jr. et al. 4151103 April 1979 Evers et al. 4435428 March 1984 Boden et al. 4521331 June 1985 Martel et al. 4536583 August 1985 Mookherjee et al. 4658067 April 1987 Pittet et al. 6051548 April 2000 Boden et al. 2008/0103085 May 2008 Schroder Foreign Patent Documents 2617816 Nov., 1977 DE 0 219 146 Apr., 1987 EP 0 418 680 Mar., 1991 EP 0 801 049 Oct., 1997 EP 1 393 451 Feb., 1965 FR 2 543 134 Feb., 1994 FR 1061732 Mar., 1967 GB 1 082 364 Sep., 1967 GB 01/06853 Feb., 2001 WO Other References Database Xfire, Beilstein Registry No. 6383807. cited by other . 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Database Crossfire Beilstein Beilstein Institut zur Forderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002233853. cited by other . Gagniant P et al: "Recherche dans la serie thiophenique. -1.- Etude de quelques acides omeg.2-thienylaliphatiques de formule generale: C4H3S.(CH2)n.COOH" Bulletin De La Societe Chimique De France, 1948, pp. 1083-1087, XP002233849. cited by other . Tamaru Y et al: "The palladium catalyzed thienylation of allylic alcohols with 2- and 3- bromothiophenes and their derivatives" Tetrahedron, vol. 35, No. 3,1979, pp. 329-340, XP002233850. cited by other . Arena G et al.: "Thermodynamics of protonation of some five-membered herteroaryl-carboxylates,--Alkannoates and -Trans-Propenoates", Journal of the Chemical Society, Perkin Transations 2, No. 10, Oct. 1993 pp. 1941-1945-XP002233851. cited by other . Garrigues B et al: "Synthese de 2-tert-butylthiophenes substitutes en position 5" Bulletin De La Societe Chimique De France, vol. 130, No. 1,1993, pp. 58-63, XP002233852. cited by other . Rabinowitz M H et al: "Design of selective and soluble inhibitors of tumor necrosis factor -alpha converting enzyme (TACE)" Journal of Medicinal Chemistry, vol. 44, No. 24, Nov. 22, 2001, pp. 4252-4267, XP002266978. cited by other . Tashtoush H I et al: "Free radical coupling of alkyl and aryl halides with electron-deficient alkenes medated by chromium(II) complexes" Chemische Berichte, vol. 126, No. 7, Jul. 2, 1993, pp. 1759-1761. cited by other. Primary Examiner: Dentz; Bernard Attorney, Agent or Firm: Dickinson Wright PLLC Parent Case Text CROSS-REFERENCE TO RELATED APPLICATIONS This application is a divisional of application Ser. No. 10/829,626, filed Jun. 16, 2004, which is a continuation of PCT/US02/26446, filed Aug. 20, 2002, which claims priority to U.S. Provisional applications: 60/377,914, filed May 3, 2002; 60/389,298, filed Jun. 17, 2002; 60/355,052, filed Feb. 7, 2002; 60/342,150, filed Dec. 19, 2001; 60/348,580, filed Jan. 15, 2002; PCT/US02/22120, filed Jul. 12, 2002 and PCT/US02/22441, filed Jul. 12, 2002, the contents of each which are hereby incorporated by reference. Claims I claim: 1. A composition comprising at least one compound of the following formulas: ##STR00004## wherein R.sub.1 is H, R.sub.2 is methyl, R.sub.3 and R.sub.4 are H, R.sub.5 and R.sub.6 both methyl, Z is C(R).sub.2, or saturation at the two carbons to which it is bound, provided that at least one Z is C(R).sub.2, R is, independently, H, or C.sub.1-5 alkyl, wherein X is CN, and wherein the double bond attached to X can be in the E or Z configuration. 2. The composition of claim 1, wherein at least one R in at least one C(R).sub.2 group is methyl. 3. The composition of claim 1, wherein at least one R in at least one C(R).sub.2 group is H. 4. The composition of claim 1, wherein both R moieties in at least one C(R).sub.2 group are H. 5. The composition of claim 1, wherein both R moieties in at least one C(R).sub.2 group are methyl. 6. A compound having one of the following formulas: ##STR00005## wherein R.sub.1 is H, R.sub.2 is methyl, R.sub.3 and R.sub.4 are H, R.sub.5 and R.sub.6 are both methyl, Z is C(R).sub.2, or saturation at the two carbons to which it is bound, provided that at least one Z is C(R).sub.2, R is, independently, H, or C.sub.1-5 alkyl, X is --CN, and wherein the double bond attached to X can be in the E or Z configuration. 7. The compound of claim 6, wherein at least one R in at least one C(R).sub.2 group is H. 8. The compound of claim 6, wherein both R moieties in at least one C(R).sub.2 group are H. 9. The compound of claim 6, wherein at least one R in at least one C(R).sub.2 group is methyl. 10. The compound of claim 6, wherein both R moieties in at least one C(R).sub.2 group are methyl. 11. A perfuming composition comprising at least one compound of claim 6, wherein the at least one compound in admixture with other perfuming ingredients, solvents, or adjuvants. 12. The perfuming composition of claim 11, in the form of a perfume or cologne, a soap, a bath or shower gel, a shampoo or other hair care product, a cosmetic preparation, a body deodorant or antiperspirant, an air freshener, a fabric detergent or softener or an all-purpose household cleaner. 13. A bleach composition comprising at least one compound of claim 6. 14. A beverage comprising at least one compound of claim 6. 15. The beverage of claim 14, wherein the beverage is selected from the group consisting of beer, malt liquor, lemonade and cola. 16. A flavored orally-delivered product comprising at least one compound of claim 6. 17. A method to improve, enhance or modify the odor of a perfuming composition or a perfumed article comprising adding to said composition or said article an effective amount of at least one compound of claim 6. 18. The method of claim 17, wherein the at least one compound is present in admixture with other perfuming ingredients, solvents, or adjuvants. Description FIELD OF THE INVENTION The present invention relates generally to the field of flavorings and fragrances. More particularly, the present invention relates to citral derivatives that provide beverages and other food products, as well as perfumes and other fragrant articles with a lemony scent, while at the same time overcoming the stability limitations of the native citral compound. BACKGROUND OF THE INVENTION Citral (3,7 dimethyl 2,6 octadienal) is a major component of lemon smell, and has the sweet-acidulated character of natural lemon. For largely historical reasons, lemon smell has become associated with freshness and cleanliness, both in drinks and in household products, and in fragrances and flavorings, generally. Lemon drinks, whether natural or synthetic, are naturally acid, which causes rapid degradation of citral to unpleasant-smelling products like cresol. This means that the shelf life of lemonade is correspondingly short, creating an expensive logistical problem. In household products, the problem is of a different nature. In order to associate bacteriological cleanliness with the smell of lemon these products frequently use lemon-scented bleach (hypochlorite). Citral is unstable in bleach, and cannot therefore be used. Instead, its nitrile analogue, geranyl nitrile, with its less satisfactory oily-metallic lemon note has to be used. The chemical instability of citral is largely due to the two double bonds and an aldehyde group, all of which are potentially susceptible to reaction, particularly when used in harsh environments, such as lemon-scented bleach. It would be desirable to develop citral derivatives with improved useful lifetimes, and, preferably, improved odor intensity, while maintaining the lemon note of citral. The present invention provides such citral derivatives. SUMMARY OF THE INVENTION Improved fragrances and flavorings that have a longer useful shelf life than citral are disclosed. In particular, citral derivatives that maintain the fragrance characteristics and lemony flavor of citral, while lowering the allergic properties, providing a longer shelf-life than citral, and/or increasing the odor intensity relative to citral are disclosed. Also disclosed are methods of making the derivatives, and articles of manufacture including the derivatives. In one embodiment, the citral derivatives are prepared by replacing one or more double bonds in the parent molecule with a cyclopropyl group, which can be unsubstituted, or substituted with one or two lower alkyl, preferably methyl groups. The alkyl groups can optionally be substituted, for example, with electron donating groups, electron withdrawing groups, groups which increase the hydrophilicity or hydrophobicity, and the like. In another embodiment, the derivatives are prepared by replacing one or more aldehyde groups in citral with a nitrile, methyl ether or acetal group. The acetal groups can provide the compounds with a long lasting flavor or fragrance, where the acetals slowly hydrolyze to provide the parent aldehyde compounds. In some embodiments, suitable derivatives are prepared such that the aldehyde and at least one double bond functional group is derivatized as described herein. Examples of suitable articles of manufacture include candles, air fresheners, perfumes, disinfectant compositions, hypochlorite (bleach) compositions, beverages such as beer and soda, denture cleanser tablets as described, for example, in U.S. Pat. No. 5,571,519, the contents of which are hereby incorporated by reference in their entirety, and flavored orally-delivered products such as lozenges, candies, and the like. DETAILED DESCRIPTION OF THE INVENTION Improved citral derivatives, which can be used, for example, as fragrances and flavorings that have a longer useful shelf life than citral, are disclosed. The citral derivatives have a similar odor to citral and also have improved physical and/or chemical properties relative to citral. These improved properties include increased stability to high pH, low pH, improved half-life, lower likelihood of causing allergic reactions, and/or increased odor intensity. The compounds of Formulas 2-4 described herein have one or more double bonds of citral or the citral derivatives in Formula 1 replaced with a suitable three membered ring. The compounds, and mixtures thereof, are stable in various media in which citral itself is relatively unstable and also have unstable, and also have odor characteristics which are very similar to that of citral. The odor of the compounds of formulas 2-4, or mixtures thereof, possess the same fresh-citrus connotation as citral. I. Improved Citrals ##STR00001## Formula 1 represents citral and citral derivatives that can be modified using the chemistry described herein to replace one or both of the double bonds with appropriate ring structures, thus improving the various physical and/or chemical properties of the molecule. In Formula 1, citral is depicted where X is --C(.dbd.O)H, R.sub.1-4 are H, and R.sub.5 and R.sub.6 are methyl. However, R.sub.1-6 can be, independently, H, C.sub.1-5 alkyl, substituted C.sub.1-5 alkyl, halo, hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid, urea, and thiourea, where the substituents on the alkyl groups are selected from halo, hydroxy, thiol, thioether, amine, carboxylic acid, ester, nitro, cyano, isocyano, sulfonic acid, urea, thiourea, and the like. X can be --C(.dbd.O)H, --OCH.sub.3, --C(OR).sub.2H, --CN, --C(.dbd.O)CH.sub.3, --NC, --C.ident.C-- (alkyne), oxime, C(.dbd.O)OR.sup.7 (where R.sup.7 is a C.sub.1-5 alkyl), or an oxalate ester, where R is H, C.sub.1-5 alkyl or C.sub.1-5 substituted alkyl. The attachment to X shows that the double bond including X can be in the E or Z configuration. In one embodiment, the double bond adjacent to the aldehyde group in citral is saturated (i.e., citronellal), and the derivatives are the same but for the saturated double bond at this position. Formulas 2-4 below represent citral derivatives as described herein, where one or both of the double bonds are replaced with a suitable three membered ring. ##STR00002## wherein: Z is O, S, or C(R).sub.2, R is H, C.sub.1-5 alkyl, such as methyl, or C.sub.1-5 substituted alkyl, and X is --C(.dbd.O)H, --OCH.sub.3, --C(OR).sub.2H, --CN, --C(.dbd.O)CH.sub.3, --NC, --C.ident.C-- (alkyne), oxime, C(.dbd.O)OR.sup.7 (where R.sup.7 is a C.sub.1-5 alkyl), or an oxalate ester, where R.sub.1-6 are as described above with respect to Formula 1, and in Formula 3, the attachment of the double bond to X indicates that the double bond can exist in the E or Z configuration. The single bond attachments to X, R.sup.1, R.sup.2, R.sup.5 and R.sup.6 are not intended to reflect any specific stereochemistry. In one embodiment of Formulas 2-4, R.sub.1-4 represent hydrogen, R.sub.5-6 represent methyl, and Z represents C(R).sub.2. In this embodiment, it is preferred that one or more R groups are methyl, with the other R groups representing hydrogen. In Formulas 2-4, where the molecule includes two Z groups, one Z can represent saturation at both carbons to which it is bound (i.e., no double bond or cyclopropane, oxirane or thiirane ring), so long as one Z is O, S or C(R).sub.2. Citral can be cyclopropanated in one or both of the positions, corresponding to the two double bonds of the molecule. Cyclopropanation of the double bond alpha to the carbonyl provides four possible diastereomers, (R,R), (R,S), (S,R) and (S,S). Cyclopropanation of the double bond of the isoprene unit provides two stereoisomers for each of the E and Z isomers of the double bond alpha to the carbonyl, for a total of four isomers. Dicyclopropanation provides eight steriosomeric forms, including all four diastereomers from the cyclopropanation of the double bond alpha to the carbonyl coupled with the R stereoisomer from the cyclopropanation of the double bond in the isoprene unit, and all four diastereomers coupled with the S stereoisomer. The double bond in the isoprene unit of citronnelal can also be cyclopropanated to yield two stereoisomers. The cyclopropanation reaction can be performed to exhaustion, providing the dicyclopropanated product, or can be performed stepwise, yielding a mixture of mono and di-cyclopropanated products. The mono- and di-cyclopropanated products can be separated on the basis of different physical and chemical properties. Diastereomeric forms can be separated on the basis of different properties as well, such as different boiling points and/or crystallization conditions, as is known in the art. Stereoisomers can be isolated using known techniques, such as column chromatography using a chiral solid phase, enzymatic degradation, and reversible formation of diastereomers and separation of the diastercomeric forms, as is known in the art. The presence of the aldehyde functionality permits the rapid and reversible formation of diastereomers by reaction with chiral alcohols to form hemiacetals or acetals, which can be hydrolyzed to reform the aldehyde functionality. Suitable chiral alcohols are well known to those of skill in the art. Accordingly, should it be desired to isolate particular stereoisomers or diastereomers, it would be routine in the art to do so. While the disclosure is not limited to the following drawing, all sixteen stereoisomeric forms of mono- and di-cyclopropropanated citral derivatives, and both stereoisomeric forms of cyclopropanated citronnelal are shown below. The replacement of double bonds with cyclopropane rings in other compounds will likewise often result in the formation of stereoisomers and/or diastereomers, and individual stereoisomers and/or diastereomers can similarly be isolated using conventional separation techniques. Such stereoisomers and/or diastereomers are intended to be within the scope of the invention described herein. ##STR00003## The cyclopropane rings can include a CH.sub.2 moiety, or can be substituted with one or two C.sub.1-5 alkyl (i.e., methyl) groups. The methyl or dimethyl analogues have a tunneling vibrational spectrum that more closely matches citral than the unsubstituted cyclopropane derivatives, and has a sweeter smell than the unsubstituted cyclopropyl derivatives. The citral derivatives described herein include derivatives in which one or both of the double bonds is replaced with a (unsubstituted, monoalkyl or dialkyl, where alkyl can be substituted or unsubstituted, and is preferably methyl)cyclopropyl group. The compounds can include, in combination with or in place of a cyclopropyl group, the replacement of the aldehyde with a methyl ether, a nitrile or an acetal group. II. Methods for Preparing the Citral Derivatives The citral derivatives of Formulas 2-4 can be prepared using any of the citral derivatives described above in Formula 1, to the extent that the synthetic route is not incompatible with any of the substituents that may be present. In one embodiment, citral (or citronellal) is used as a starting material to prepare various citral (or citronellal) derivatives described in Formulas 2-4 where R.sub.1-4 are hydrogen and R.sub.5-6 are methyl. The synthesis of methyl, dimethyl or unsubstituted cyclopropane derivatives is well known to those of skill in the art, and involves, for example, bromoform reaction to form the dibromocyclopropane derivative, followed by stoichiometric reaction with methyl lithium. The aldehyde group is typically protected as an acetal during the reaction, and deprotected as desired after the reactions take place. In one embodiment, however, the acetals (for example, dimethyl, diethyl, or ethylene glycol) are not deprotected to the aldehyde, such that the flavoring or fragrance includes a portion or entirely the acetals. The acetals can then slowly hydrolyze over time, releasing the lemon scent/flavoring. Alternatively, citral derivatives, including one or two cyclopropane rings, can also include a nitrile or methyl ether group as a replacement for the aldehyde group. These simple procedures yield derivatives of citral with odor profiles close to citral itself, with greater potency and with far greater acid and bleach stability since the unstable feature, namely the double bond, has been removed. The same applies to epoxide (OX) and thiirane (TH) rings, shown in the formulas above where Z is O or S. Not counting mixed C.dbd.C double bond replacements and stereoisomers, this generates 9 possible molecules from citral alone, all readily accessible in one or two step syntheses from citral itself by processes well known in the art, such as: Cyclopropanyl replacement: Simmons-Smith cyclopropanation of the aldehyde or corresponding alcohol, followed by periodinane oxidation for the latter to give the aldehyde.sup.1 .sup.1 Vogel's textbook of practical organic chemistry 5th edition (1989) pp 1106-1108 Oxiranyl replacement: m-chloroperbenzoic acid epoxidation.sup.2 .sup.2 Ibid, pp 1127-1129 Thiiranyl replacement: bromination of double bond on Amberlite, followed by S'-substitution in sodium sulfides.sup.3 .sup.3 Choi, J. et al. (1995) Bull. Korean. Chem. Soc., 16, 189-190 Convenient Synthesis of Symmetrical Sulfides from Alkyl Halides and Epoxides Aldehyde Replacement with Nitrile The replacement of aldehyde with nitrile is well known in the art, and described, for example, in U.S. Pat. No. 5,892,092. The '092 patent teaches a process for forming nitrites from aldehydes. Citral derivatives can further be prepared in which one or more a double bonds are converted to (unsubstituted, methyl or dimethyl)cyclopropyl derivatives that also include a nitrile group in place of the aldehyde using the chemistry described above. III. Articles of Manufacture Including the Citral Derivatives The citral derivatives can be included in virtually any article of manufacture that can include citral, or for that matter, other lemon fragrances, whether natural or artificial. Examples include bleach, detergents, flavorings and fragrances, beverages, including alcoholic beverages, and the like. The citral derivatives can be used in applications like soaps, shampoos, body deodorants and antiperspirants, solid or liquid detergents for treating textiles, fabric softeners, detergent compositions and/or all-purpose cleaners for cleaning dishes or various surfaces, for both household and industrial use. Of course, the use of the compounds is not limited to the above-mentioned products, as they be used in other current uses in perfumery, namely the perfuming of soaps and shower gels, hygiene or hair-care products, as well as of body deodorants, air fresheners and cosmetic preparations, and even in fine perfumery, namely in perfumes and colognes. These uses are described in more detail below. Perfume Compositions The compounds can be used as perfuming ingredients, as single compounds or as mixture thereof, preferably at a range of at least about 30% by weight of the perfume composition, more preferably at a range of at least about 60% by weight of the composition. The compounds can even be used in their pure state or as mixtures, without added components. The olfactive characteristics of the individual compounds are also present in mixtures thereof, and mixtures of these compounds can be used as perfuming ingredients. This may be particularly advantageous where separation and/or purification steps can be avoided by using compound mixtures. In all cited applications, the citral derivatives can be used alone or in admixture with other perfuming ingredients, solvents or adjuvants of current use in the art. The nature and the variety of these co-ingredients do not require a more detailed description here, which, moreover, would not be exhaustive, and the person skilled in the art will be able to choose the latter through its general knowledge and as a function of the nature of the product to be perfumed and of the desired olfactive effect. These perfuming ingredients typically belong to chemical classes as varied as alcohols, aldehydes, ketones, esters, ethers, acetates, nitrites, terpene hydrocarbons, sulfur- and nitrogen-containing heterocyclic compounds, as well as essential oils of natural or synthetic origin. A large number of these ingredients described in reference textbooks such as the book of S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, N.J., USA, the contents of which are hereby incorporated by reference in its entirety, or its more recent versions, or in other works of similar nature. The proportions in which the citral derivatives can be incorporated in the various products vary within a large range of values. These values depend on the nature of the article or product that one desires to perfume and the odor effect searched for, as well as on the nature of the co-ingredients in a given composition when the compounds are used in admixture with perfuming co-ingredients, solvents or adjuvants of current use in the art. As an example, the citral derivatives are typically present at concentrations between about 0.1 and about 10%, or even more, by weight of these compounds relative to the weight of the perfuming composition in which they are incorporated. Far lower concentrations than those mentioned above can be used when the compounds are directly applied for perfuming the various consumer products cited beforehand. The compounds are relatively stable in typically aggressive media for perfumes. Accordingly, they can be used in detergents containing bleaching agents and activators such as, for example, tetraacetylethylenediamine (TAED), hypohalites, in particular hypochlorite, peroxygenated bleaching agents such as, for example, perborates, etc. The compounds can also be used in body deodorants and antiperspirants, for example, those containing aluminum salts. These embodiments are described in more detail below. Conventional Detergent Ingredients In addition to the derivatives described herein, the compositions herein include a detersive surfactant and optionally, one or more additional detergent ingredients, including materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.). The following are illustrative examples of detersive surfactants and other detergent ingredients. Detersive Surfactants Non-limiting examples of synthetic detersive surfactants useful herein typically at levels from about 0.5% to about 90%, by weight, include the conventional C.sub.11-18 alkyl benzene sulfonates ("LAS") and primary, branch-chain and random C.sub.10-20 alkyl sulfates ("AS"), the C.sub.10-18 secondary (2,3) alkyl sulfates of the formula CH.sub.3(CH.sub.2).sub.x(CH(CH.sub.3)OSO.sub.3.sup.-M.sup.+) and CH.sub.3(CH.sub.2).sub.y(CH(CH.sub.2CH.sub.3)OSO.sub.3.sup.-M.sup.+) wherein x and y are integers and wherein each of x and (y+1) is least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C.sub.10-18 alkyl alkoxy sulfates ("AEx S"; especially EO 1-7 ethoxy sulfates), C.sub.10-18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C.sub.10-18 glycerol ethers, the C.sub.10-18 alkyl polyglycosides and their corresponding sulfated polyglycosides, and C.sub.12-18 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic and amphoteric surfactants such as the C.sub.12-18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C.sub.6-12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxylates), C.sub.12-18 betaines and sulfobetaines ("sultaines"), C.sub.10-18 amine oxides, and the like, can also be included in the overall compositions. The C.sub.10-18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C.sub.12-18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C.sub.10-18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C.sub.12-18 glucamides can be used for low sudsing. C.sub.10-20 conventional soaps may also be used, however synthetic detergents are preferred. If high sudsing is desired, the branched-chain C.sub.10-16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. See also U.S. Pat. No. 3,664,961 to Norris. Preferred compositions incorporating only synthetic detergents have a detergent level of from about 0.5% to 50%. Compositions containing soap preferably comprise from about 10% to about 90% soap. Although the detergent compositions herein can only detersive surfactants and the citral derivative(s), the compositions preferably contain other ingredients commonly used in detergent products. Builders Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils. The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded. Inorganic or detergent builders include, but are not limited to phosphate builders such as, the alkali metal, ammonium and allanolammonium salts of polyphosphates (exemplified by the tripolyphosphate, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, and phytic acid, and non-phosphorous builders such as silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates. Non-phosphate builders are required in some locales. Organic builders suitable for use herein include polycarboxylate builders such as disclosed in U.S. Pat. No. 3,308,067 to Diehl; U.S. Pat. No. 4,144,226 to Crutchfield and U.S. Pat. No. 4,246,495 to Crutchfield. Soil Release Agents Soil Release agents are desirably used in laundry detergents of the instant invention. Suitable soil release agents include those of U.S. Pat. No. 4,968,451 to Scheibel and Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4,711,730 to Gosselink et al, for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly- and fully-anionic-end-apped oligomeric esters of U.S. Pat. No. 4,721,580 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. Pat. No. 4,702,857 to Gosselink, for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. Pat. No. 4,877,896 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400. Another preferred soil release agent is a sulfonated end-capped type described in U.S. Pat. No. 5,415,807. Other Optional Ingredients The compositions herein can contain other ingredients such as enzymes, bleaches, fabric softening agents, dye transfer inhibitors, suds suppressors, and chelating agents, all well known within the art. For purposes of defining detergent compositions of the present invention, the pH of the detergent composition is that which is measured at 1% concentration of the detergent composition in distilled-water at 20.degree. C. The detergent compositions herein have a pH of from about 7.1 to about 13, more typically from about 7.5 to about 9.5 for liquid detergents and from about 8 to about 12 for granular detergents. Formulation with Detergents with or without Conventional Perfumery Materials While the derivatives described herein can be used alone and simply mixed with essential detergent ingredient, most notably surfactant, they can also be desirably combined into three-part formulations which combine (a) a non-fragranced detergent base comprising one or more synthetic detergents and (b) one or more of the derivatives described herein. In one embodiment, both aldehydes and acetals are present, such that the aldehydes provide desirable in-package and in-use (wash-time) fragrance, while the acetals provide a long-term fragrance to the laundered textile fabrics. In formulating the present detergents, the fully-formulated fragrance can be prepared using numerous known odorant ingredients of natural or synthetic origin. The range of the natural raw substances can embrace not only readily-volatile, but also moderately-volatile and slightly-volatile components and that of the synthetics can include representatives from practically all classes of fragrant substances, as will be evident from the following illustrative compilation: natural products, such as tree moss absolute, basil oil, citrus fruit oils (such as bergamot oil, mandarin oil, etc.), mastix absolute, myrtle oil, palmarosa oil, patchouli oil, petitgrain oil Paraguay, wormwood oil, alcohols, such as farnesol, geraniol, linalool, nerol, phenylethyl alcohol, rhodinol, cinnamic alcohol, aldehydes, such as citral, Helional.TM., alpha-hexyl-cinnamaldehyde, hydroxycitronellal, Lilial.TM. (p-t-butyl-alpha-methyldihydrocinnamaldehyde), methylaonylacetaldehyde, ketones, such as allylionone, alpha-ionone, beta-ionone, isoraldein (isomethyl-alpha-ionone), methylionone, esters, such as allyl phenoxyacetate, benzyl salicylate, cinnamyl propionate, citronellyl acetate, citronellyl ethoxolate, decyl acetate, dimethylbenzylcarbinyl acetate, dimethylbenzylcarbinyl butyrate, ethyl acetoacetate, ethyl acetylacetate, hexenyl isobutyrate, linalyl acetate, methyl dihydrojasmonate, styrallyl acetate, vetiveryl acetate, etc., lactones, such as gamma-undecalactone, various components often used in perfumery, such as musk ketone, indole, p-menthane-8-thiol-3-one, and methyl-eugenol. Likewise, any conventional fragrant acetal or ketal known in the art can be added to the present composition as an optional component of the conventionally formulated perfume (c). Such conventional fragrant acetals and ketals include the well-known methyl and ethyl acetals and ketals, as well as acetals or ketals based on benzaldehyde, those comprising phenylethyl moieties, or more recently developed specialties such as those described in a United States patent entitled "Acetals and Ketals of Oxo-Tetralins and Oxo-Indanes, see U.S. Pat. No. 5,084,440. Of course, other recent synthetic specialties can be included in the perfume compositions for fully-formulated detergents. These include the enol ethers of alkyl-substituted oxo-tetralins and oxo-indanes as described in U.S. Pat. No. 5,332,725; or Schiff Bases as described in U.S. Pat. No. 5,264,615. It is preferred that the pro-fragrant material be added separately from the conventional fragrances to the detergent compositions of the invention. Formulation with Other Special-Purpose Fragrance Delivering Compounds Detergents including the derivatives described herein may further, optionally, if desired, contain other known compounds having the capability to enhance substantivity of a fragrance. Such compounds include, but are not limited to, the aluminium alkoxides such as isobutylaluminium diferanylate as disclosed in U.S. Pat. No. 4,055,634; or the known titanate and zirconate esters or oligoesters of fragrant materials such as those disclosed in U.S. Pat. No. 3,947,574, and U.S. Pat. No. 3,779,932, the contents of each of which are hereby incorporated by reference in their entirety. When using such organoaluminum, organotitanium or organozinc derivatives, they may be incorporated into the present formulations at their art-known levels. Beverage Compositions The citral derivatives described herein can be incorporated into beverages and impart various flavorings to the beverages. The beverage composition can be a cola beverage composition, and can also be coffee, tea, dairy beverage, fruit juice drink, orange drink, lemon-lime drink, beer, malt beverages, or other flavored beverage. The beverages can be in liquid or powdered form. The beverage compositions can also include one or more flavoring agents; artificial colorants; vitamin additives; preservatives; caffeine additives; water; acidulants; thickeners; buffering agents; emulsifiers; and or fruit juice concentrates. Artificial colorants which may be used include caramel color, yellow 6 and yellow 5. Useful vitamin additives include vitamin B2, vitamin B6, vitamin B12, vitamin C (ascorbic acid), niacin, pantothenic acid, biotin and folic acid. Suitable preservatives include sodium or potassium benzoate. Salts which may be used include sodium, potassium and magnesium chloride. Exemplary emulsifiers are gum arabic and purity gum, and a useful thickener is pectin. Suitable acidulants include citric, phosphoric and malic acid, and potential buffering agents include sodium and potassium citrate. In one embodiment, the beverage is a carbonated cola beverage. The pH is generally about 2.8 and the following ingredients can be used to make the syrup for these compositions: Flavor Concentrate, including one or more of the derivatives described herein (22.22 ml), 80% Phosphoric Acid (5.55 g), Citric Acid (0.267 g), Caffeine (1.24 g), artificial sweetener, sugar or corn syrup (to taste, depending on the actual sweetener) and Potassium Citrate (4.07 g). The beverage composition can be prepared, for example, by mixing the foregoing syrup with carbonated water in a proportion of 50 ml syrup to 250 ml of carbonated water. In another embodiment, the beverage is a beer or malt beverage. Preferred flavorings for beer and malt beverages include lemon, lime and lemon-lime. Advantageously, the flavorings include citral derivatives in which one of both of the double bonds are replaced with a cyclopropane group, where the cyclopropane groups can, independently, be unsubstituted, or include one or two alkyl or substituted alkyl groups, preferably methyl groups. The amount of flavoring can be adjusted according to taste. Orally-Delivered Products Flavored food and pharmaceutical compositions including one or more of the derivatives described herein can also be prepared. The derivatives can be incorporated into conventional foodstuffs using techniques well known to those of skill in the art. Alternatively, the derivatives can be incorporated within polymeric particles, which can, in turn, be dispersed within and/or over a surface of an orally-deliverable matrix material, which is usually a solid or semi-solid substrate. When used in chewable compositions, the derivatives can be released into the orally-deliverable polymeric matrix material as the composition is chewed and held in the mouth, thus prolonging the flavor of the composition. In the case of dried powders and mixes, the flavor can be made available as the product is consumed or be released into the matrix material as the composition is further processed. When two flavors are combined with the polymeric particles, the relative amounts of the additives can be selected to provide simultaneous release and exhaustion of the compounds. In one embodiment, the flavored composition includes an orally-deliverable matrix material; a plurality of water insoluble polymeric particles dispersed in the orally-deliverable matrix material, where the polymeric particles individually define networks of internal pores and are non-degradable in the digestive tract; and one or more derivatives as described herein entrapped within the internal pore networks. The derivatives are released as the matrix is chewed, dissolved in the mouth, or undergoes further processing selected from the group consisting of liquid addition, dry blending, stirring, mixing, heating, baking, and cooking. The orally-deliverable matrix material can be selected from the group consisting of gums, latex materials, crystallized sugars, amorphous sugars, fondants, nougats, jams, jellies, pastes, powders, dry blends, dehydrated food mixes, baked goods, batters, doughs, tablets, and lozenges. Chewing Gum A flavorless gum base can be combined with a citral or other suitable derivative as described herein to a desired flavor concentration. Typically, a blade mixer is heated to about 110 F, the gum base is preheated so that it is softened, and the gum base is then added to the mixer and allowed to mix for approximately 30 seconds. The flavored derivative is then added to the mixer and mixed for a suitable amount of time. The gum can be then removed from the mixer and rolled to stick thickness on waxed paper while warm. Time Release Formulations In one embodiment, the derivatives described herein are incorporated into a system which can release a fragrance in a controlled manner. These include substrates such as air fresheners, laundry detergents, fabric softeners, deodorants, lotions, and other household items. The fragrances are generally one or more derivatives of essential oils as described herein, each present in different quantities. U.S. Pat. No. 4,587,129, the contents of which are hereby incorporated by reference in their entirety, describes a method for preparing gel articles which contain up to 90% by weight of fragrance or perfume oils. The gels are prepared from a polymer having a hydroxy (lower alkoxy) 2-alkeneoate, a hydroxy (lower alkoxy) lower alkyl 2-alkeneoate, or a hydroxy poly (lower alkoxy) lower alkyl 2-alkeneoate and a polyethylenically unsaturated crosslinking agent. These materials have continuous slow release properties, i.e., they release the fragrance component continuously over a long period of time. Advantageously, all or a portion of those derivatives that include an aldehyde group can be modified to include an acetal group, which can cause the formulations to release fragrance over a period of time as the acetal hydrolyzes to form the aldehyde compound. The invention will now be illustrated with reference to the following non-limiting example. EXAMPLE 1 Preparation and Flavor Characteristics of a Cyclopropanated Citral Derivative Cyclopropanation of Citral to Produce Citral-6,7-cyclopropane. The following experimental was based on a well-known method for cyclopropanating olefins, and was conducted numerous times with various stoichiometric equivalents of the cyclopropanation reagents. Optimum results for synthesizing the above-identified mono-cyclopropanated citral derivative were obtained using the amounts shown below. Attempts to increase relative amounts of reagents resulted in the formation of a significant amount of side products. However, this reaction has not been optimized. The use of less than a stoichiometric amount of the diethylzinc and diiodomethane reactants might be advisable if the separation of citral and citral-6,7-cyclopropane were optimized. However, since the separation was not optimized, the cyclopropanation reaction was allowed to proceed to completion. The reactions were conducted behind a blast shield due to the reported possible explosive nature of these reactions. It is believed that cyclopropanations using these reaction conditions may be problematic if the diiodomethane is added too quickly to the reaction mixture Citral-6,7-cyclopropane To an oven dried 500 mL round bottomed flask was added 1,2-dichloroethane (85 mL) under a nitrogen atmosphere. Diethylzine (30 mL, 1M in hexanes) was added, and then diiodomethane (15 g) was introduced dropwise over 1 hour. Following stirring for 30 mins (a white precipitate formed) citral (1.1 g) was added and the reaction was stirred overnight at room temperature. The reaction mixture was poured into a potassium carbonate solution (100 mL, 20%) and then filtered through a pad of Celite.RTM. in a sintered funnel. The organic layer was separated and dried over sodium sulfate. Filtration of the drying agent, concentration and flash column chromatography with dichloromethane as eluant gave the title compound. The compound was tasted by two experienced flavorists, who both declared it lemony. Having hereby disclosed the subject matter of the present invention, it should be apparent that many modifications, substitutions, and variations of the present invention are possible in light thereof. It is to be understood that the present invention can be practiced other than as specifically described. Such modifications, substitutions and variations are intended to be within the scope of the present application. * * * * *
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Our Cinnamon Babka will get noticed on your desert table. Good for a kids snack afterschool, and fine enough for corporate or family gatherings of any size. As rich as our Chocolate Babka with the light, spicy touch of fresh cinnamon.
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Dr. Daniel J. Geenen, MD
- 2424 S 90th St Ste 410
Milwaukee, WI 53227
- 3 Locations
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Dr. Daniel J. Geenen graduated from the Medical College of Wisconsin School of Medicine in 1989. He works in Milwaukee, WI and 2 other locations and specializes in Gastroenterology. Dr. Geenen is affiliated with Aurora Medical Center, Aurora Medical Center Kenosha, Aurora Saint Lukes South Shore, Aurora St Lukes Medical Center and Wheaton Franciscan St Francis Hospital. He speaks English, German and Spanish.View More
Gender: Male
Languages Spoken: English, German, Spanish
Medical School: Medical College of Wisconsin School of Medicine; Graduated 1989
*This physician has multiple office locations. See Office Information for details.


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Collin County
TxDOT May Change Plans To Place Toll Lanes On Central Expressway
In Collin County, there's the Dallas North Tollway, the Sam Rayburn Tollway, and the President George Bush Turnpike. All are toll roads.
Teen Accused Of Killing Parents To Remain At Juvenile Center
A teenager accused of murdering his parents will remain in the Collin County Juvenile Detention Center, at least for the next 10 business days. The decision was made after a brief hearing on Tuesday.
Wylie Firefighters Battle Flames At Church
Emergency crews responded to a two-alarm fire at a church near Wylie on Tuesday morning. One firefighter was injured during the incident after falling from a ladder.
Standing Room Only At Collin County Meeting About Immigrant Children
With the threat of a so-called "immigrant tsunami," Collin County Commissioner Mark Reid invited the public to attend commissioner's court on Monday –- and they did.
Dallas Rally Aims To Ease Immigration Fears
Supporters of the plan to house undocumented kids in North Texas will gather in Dallas on Monday. Community and religious leaders want to ease fears about the plan.
Collin County Commissioner Warns of "Illegal Immigrant Tsunami"
Collin County Commissioner Mark Reid is warning of an "illegal immigrant tsunami" if "illegal immigrant children" are housed there.
Suspected Illegal Immigrant Arrested For Taking Lewd Pictures Of Women
A suspected illegal immigrant has been thrown in the Collin County jail, accused of using his cell phone camera in a most improper way.
Development Plans For Last Coveted Piece Of Collin County Property
A particular piece of land is considered one of the last coveted undeveloped properties in Collin County — now a Dallas lawyer is about to change that. The attorney gave CBS 11 News an exclusive look at the big plans for Highway 380 and the Dallas North Tollway.
Record Low Water Levels At Lake Lavon
The water source for Collin County is 5 feet away from the threshold where the North Texas Municipal Water District will initiate Stage 4 water restrictions.
New Frisco Restrictions Limit Watering To 2x's A Month
Twice a month — starting today that's how many times Frisco residents can water their lawns. The new restrictions are part of the city's newly adopted water rules.
Daycare Owner Accused Of Indecency With Child
Neighbors and parents in McKinney are in shock after a home daycare owner has been arrested for allegedly abusing one of the kids that she was supposed to protect.
Police Release Car Of Frisco Mom Accused Of Murder
Frisco police have apparently relented and are giving a woman accused of the first-degree murder of her 10-year-old son her car back. Attorney David Finn says the family of Pallavi Dhawan is at the Frisco Police Department.


text: http://serverfault.com – Mysql server is installed on my quest OS Centos6 (192.168.1.50) and using port 3306. I'm trying to connect from my Windows OS (192.168.1.2). I'm getting error #1045 Access denied for user 'root'@'192.168.1.2' (using password: YES) So, as far as I understand this error is telling me that I have no rights to access mysql using user root from 192.168.1.2 host. Ok, I've tried to add nessesary privileges: [root@localhost etc]# mysql -u root -p Enter password: mysql> use mysql; Reading table information for completion of table and column names You can turn off this feature to get a quicker st (HowTos)


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Subaru Legacy in Moorhead, MN
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Hot stocks: 5 sizzling performers in May
CNN — NEW YORK (CNNMoney) -- U.S. stocks bounced back in May, led by many of the technology and momentum names at the heart of the spring slump.
While there were many winners this month (sorry Whole Foods -- you definitely didn't make the cut), check out the rankings of the five hottest companies in the S&P 500 in May.
1. Netflix: Binge watching is the new black
Netflix was hammered by the risk aversion on Wall Street in recent months. The streaming movie rental service saw its shares slump 26% in March and April.
But investors quickly realized that lovers of "Breaking Bad" and "House of Cards" aren't abandoning Netflix any time soon. Shares spiked 30% in May, making it easily the best performer in both the S&P 500 and Nasdaq 100.
Netflix also announced a price increase for new members and plans to expand services to six more European countries: France, Germany, Austria, Switzerland, Belgium and Luxembourg.
2. Electronic Arts: The World Cup effect?
The second hottest S&P 500 stock this month can trace its sparkling performance to a single day: May 6.
That was the day Electronic Arts blew Wall Street's socks off with earnings that crushed expectations. Buoyed by sales of games for PlayStation 4 and Xbox One, the video game maker also sounded a very positive tone for the rest of the year and unleashed a $750 million stock buyback.
The company, known as EA, also highlighted how strong its sports titles are, especially the blockbuster FIFA game ahead of this summer's World Cup. EA is one of the few non-apparel companies to serve as a major sponsor of top soccer stars.
Other video game makers have also enjoyed success this year, including France's Ubisoft, Activision Blizzard and Take-Two Interactive.
After EA's 23% surge in May, the company has spiked 52% so far this year, good for No. 3 in the S&P 500 in 2014.
3. Green Mountain juiced by Coke (again)
It's been a wild ride this year for investors of the company formerly known as Green Mountain Coffee Roasters.
Keurig Green Mountain spiked 36% in February after Coca-Cola acquired a 10% stake in the company for $1.25 billion. But the coffee maker slumped 11% in April and continued to face skepticism from short sellers like hedge fund giant David Einhorn.
Coke came to the rescue once again, announcing plans on May 13 to boost its stake to 16%, adding more than $1 billion more. Green Mountain also impressed Wall Street wtih a 22% jump in profits.
The final result for Green Mountain is a heavily caffeinated 21% return for the month.
4. TripAdvisor charts an upward course
The online travel site finished April a hefty 26% below its all-time high, which was just the month before. But TripAdviso didn't stay home and pout.
The company unveiled a flurry of acquisitions during the month, including European restaurant service Lafourchette, travel guide site Tripbod and Vacation Home Rentals.
TripAdvisor also pleased investors by posting bullish results on May 6 that revealed a 22% jump in revenue and a 44% boost to traffic.
The stock is up 20% in May.
5. SanDisk by a nose
SanDisk, which makes flash memory, benefited from an overall rebound in tech stocks this month.
The company ended May with a 13.7% rally, narrowly besting Tiffany for the No. 5 spot amongst S&P 500 stocks.
SanDisk pleased investors by hiking its quarterly dividend by 33% on May 7 after posting a 62% jump in earnings in April.
Honorable mention: Tiffany soared 13.6% during May and was easily the month's best performing retailer in the S&P 500. The company has sparkle, but not quite enough for the top 5.
Correction: An earlier version of this article incorrectly reported that investor Carl Icahn increased his stake in Netflix during the month.
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Dr. Jarrod A. Little, MD
Plastic Surgery
- 401 E Chestnut St Unit 710
Louisville, KY 40202
- 2 Locations
- (502) 583-8303
Dr. Jarrod A. Little graduated from the University of Texas Medical School at Houston in 2002. He works in Louisville, KY and 1 other location and specializes in Plastic Surgery. Dr. Little is affiliated with Jewish Hospital, Kosair Childrens Hospital, Norton Hospital, Norton Suburban Hospital and University Of Louisville Hospital. He speaks English and Spanish.
Gender: Male
Languages Spoken: English, Spanish
Plastic Surgery
Medical School: University of Texas Medical School at Houston; Graduated 2002
*This physician has multiple office locations. See Office Information for details.


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I've been using the Sea Hag recipe (I think I'm partial to it because they're a local brewery for me and all-around good guys). My major hit on the recipe is the high level of salt. I may back up to two teaspoons of regular salt next time.
That said, I love how they come out and did my third batch last night. Made 4 pint jars=worth, and had space in the 4th, so I threw in some sliced radishes. As of this morning, the red skin has turned white and the brine is now red.
I made a batch today following the Sea Hag recipe for the brine, but using Alaskan IPA because it was what I had. The rest I just kind of winged it, a couple cloves of garlic in each jar and a couple tablespoons each of dill seed and pickling spice. I had some brine left over after doing two jars of cucumbers (I packed one with the skins out and one with skins in) so I got some baby carrots from the fridge and tried them. I'm hoping those turn out ok because I didn't use any spices in that jar, I'm sure they'll be fine just not as flavorful. I really liked that brine too, I think I can see myself brining a piece of meat in it some day.
So 24 hours later I snuck a taste of cucs and they weren't bad, but I wasn't 100% pleased either. They were good but I like more of a sour and zingier pickle. Next batch I might use white vinegar instead of cider vinegar just to get more neutral of a flavor, then step up the garlic and add some red pepper flakes. The carrots I sampled I actually liked better but they were still missing something. I'll see how they are in a week or two.
Lets leave our s**t where it is and go live in the woods.
These things age well. Snacking on some I made back in April and they're great.
Unprocessed, just kept in the fridge the whole time.
It was kind of funny today. I tried another carrot pickle and my 2 year old son asked for one so I gave it to him. He kind of made a funny face but he finished the whole thing. I asked if he wanted another one and he shook his head no and walked away. I'm guessing he wasn't impressed.....
I made bread and butter pickles tonight while drinking IPA. Will that count?
I've got a lot of cukes and will try this over the weekend.
Holy smoke these things are great. Everyone really enjoys them and they are with out a doubt the best pickles I have ever had. I followed the first recipe, but left out the cloves, as I do not care for cloves..... When I polish off the pickles in one of the jars I am gonna throw a couple hard boiled eggs in there and wait a few days and see how they taste... Should be glorious .......
I make a lot of various refrigerator pickles with a ratio formula derived somewhere from Michael Ruhlman & Michael Simon:
1.5 cups vinegar
1.5 cups water
2 tsp kosher salt
2 Tbl sugar (or to taste. I add a lot more.)
1 Tbl more or less (more is better) of your favorite pickling spices
Bring all ingredients to boil. Pour over vegetables packed in jars. Cool. Refrigerate.
Adjusting the amounts depending on how much liquid you need to cover your vegetables is simply a matter of scaling ratios up or down.
Now, if one were to sub beer for the water, and add hop cones off boil, as well as some cones to the jars, would this work to make hoppy pickles?
Will try tomorrow and post results.


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Oak Hill Court
Cassville, Missouri
Visit Campground Website
Sites: 18
Recent Rate: $16 3/2007
Latitude: 36.6057153759685
Longitude: -93.8375342484131
These reviews are the opinion of an RVParkReviews' member and not the views of RVParkReviews.com
Date of Stay: March, 2007 - $16.00
I'll keep it simple, this place is nice. 10 gravel pull through WSE sites plus 8 electric only back ins along a circular gravel road. Owner left enough of the mature trees to create abundant shade without interfering with rigs. Brand new shower/laundry house. Has a playground and game room for kids. Diligent and friendly staff. Five minutes to Roaring river, 30 to Eureka Springs. Also features some nice cabins reasonably priced. On top of hill so I got pretty good TV reception. Stayed here four nights and planning a return in fall. I could go on but see for yourself. We camped at Oak Hill Court in a Travel Trailer.Undo
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I guys I'm the proud owner of an AC43 p38 no import stamps and a matching hard shell holster also all numbers match all nazi stamped and has 1 genuine mag aswell. Guns is in good shape the grips have a bad scratch Mark and that's it
My question is how much do u guys think it's worth?
I saw one on an auction website that was an ac42 that was asking 1400. I know different years are more desirable because of production numbers etc, reason I'm asking is that I brought it up to my local store and he said the lot was worth 700. Don't really trust him
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Good quality, close-up photos would help for a decent evaluation.
there is a couple of pics sorry no holster pic and wont be able to get one soon as im abroad at the min the hollster is in good shape
Too many factors to give you an accurate dollar value. Without seeing it it would be pure speculation. It comes down to it is worth what someone will pay.
Freedom is not free. The best of us always leave too soon.
Yea I see your point. Il be home in about a month so il take a bunch of more comprehensive photos with it stripped etc
I was at a gun show in Cuyahoga County, Ohio today. There were a number of P-38s there, mostly WWII vintage, but some post war also. The WWII ones varied from about $600 to well over $1000. Of course, there are the variables with any old military weapon.
Yea why diddnt I think of that. Bought a gun there before good store


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Wal-Mart will scale back free home shipping in Canada
The world's largest retailer will end free shipping for online orders under $50 Canadian starting April 2.
Wal-Mart will scale back free home shipping in Canada
The world's largest retailer will end free shipping for online orders under $50 Canadian starting April 2.
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The daily deal operator rolls out an automated way for e-retailers and other businesses to craft discount promotions. Groupon aims to expand the number of deals on its site.
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When Jonathan Bernier was announced as the Leafs' starting goaltender for Tuesday night's matchup against the New York Islanders, there were quite a few from Leafs Nation who found fault with the decision, given the up until now somewhat split between Bernier and Reimer in net, as well as the fact that Bernier was most recently pulled in a 7-1 shelling at the hands of the New York Rangers. Here is just a sample of the many who felt Reimer was being unfairly treated.
EXCUSE ME COACH CARLYLE, DO YOU REALIZE THAT REIMER DESERVES THE START AND NOT BERNIER? #TMLtalk #NOOFFENSEBERNIER
— Nazia M (@NaziaM_) January 7, 2014
so the leafs are giving up on reimer I see.. #Gutless #NotCool
— Frank De Leonardis (@cheechello) January 7, 2014
Giving Bernier the start seriously !!! give Reimer the chance, the fans love him and guided the Leafs to the playoffs #TMLtalk @MapleLeafs
— Irtaaza Jafri (@The_Irt) January 7, 2014
im a bit late but i feel bad for reimer not getting the start tmrw. He deserves it for what he did for us in last yrs playoffs #FreeReimer
— Stuff TML fans say (@TMLfanssay) December 31, 2013
Many Leaf fans felt there was never a need to trade for a goaltender in the first place, and the Bernier deal was a case of Nonis strengthening an area that was already a strength, while ignoring more pressing issues. Reimer had provided the first above average goaltending the club had seen since a pre 2004-2005 lockout Eddie Belfour, and took a consistently out-possessed team to the playoffs for the first time in nine years.
There is, of course, the other side of Leafs Nation which believes Bernier is a significant upgrade in goal over Optimus Reim, who has a weak glove hand, and whose rebound control was the primary reason for the epic game 7 collapse against the mighty Boston Bruins. For them, Bernier becoming the clear-cut starter couldn't have happened soon enough. In their eyes, he has the better reflexes, glove, and puck handling abilities.
Bernier is without a doubt our number one goalie. #TMLtalk #SEAofBLUE
— Patrick Meredith (@TheInsignia46) January 8, 2014
Nice to know Leafs prepared to live and die with Bernier in goal. #Islanders #Leafs #TMLtalk
— Jonny Adornetto (@jonnyrants) January 8, 2014
@tweeterbugs77 @ComEnjoylife @PhaneufLupul319 BERNIER is our No. 1 starter right now, accept it already #TMLTalk
— Corey Kendall (@ckendall77) January 8, 2014
I'm not here to argue if one side is right or wrong – evaluating goalies is tricky. That's why Mike Smith went from top prospect and key piece in a Brad Richards trade, to being basically let go, to being a Vezina candidate and a goaltender for Team Canada. Both goalies are good, and both are young, with Bernier having turned 25 this past August, and Reimer only five months his senior.
It's easy to see why Bernier is so favoured. He was a first round draft pick, and won the QMJHL's version of the Conn Smythe, as well as the Aldege "Baz" Bastien Memorial Award as the AHL's best goalkeeper in the 2009-2010 season. Reimer was a fourth round pick, who has started 60 games in a season only once, with the Red Deer Rebels of the WHL in 2006-2007. However, despite a narrative that describes Bernier as the far superior goalie, I'm not sure I necessarily agree. At one point, Reimer's play had led to him being considered one of Canada's best goalies by a certain analyst. And for all the talk about Bernier's deftness with the puck, he has shown a tendency to be overconfident in his own abilities, leading to some pretty bad goals. Reimer, knowing he's no Brodeur with the puck, most likely plays those chances with much more caution.
The fact is the Leafs have themselves two capable netminders that are both signed to reasonable contracts, for now. Reimer becomes a restricted free agent this off-season and whether or not you believe Reimer deserves better, by keeping his playing time limited, the Leafs are probably keeping his next contract worth less, assuming he's a) wiling to sign b) not traded in the meantime.
Even if he's not too keen on re-signing, as a RFA, Reimer won't really have much of a choice. That is, unless a team is willing to sign him to an offer sheet, giving up draft picks in the process. The second condition is tricky, and given Toronto's lack of quality in areas other than goaltending, trading Reimer for talent seems to be a decent option. At this point, many of those on Team Reimer would welcome their darling getting the chance he deserves, even if it's with another club.
If you ask me however, Reimer should be kept. You can sign him to a reasonable deal in the off-season, and then see what happens in the last year of Bernier's deal before he becomes an RFA himself. As of now, both goalies are signed to a combined $4.7 million per year, which is a pretty good amount to pay for above average goaltending. I don't see why Reimer's next contract should be that much higher than the paltry $1.9 million he is currently earning, as long as he gets backup playing time.
Of course, given Bernier's less than stellar performance against the Islanders on Tuesday, logic points to Reimer getting the start on Thursday against the Hurricanes, and with it, another chance to seize the net for good. Given that they play again the next night, he'd probably have to put on quite a performance in order to get two games in a row. Either way, for all the hand wringing over Nonis' cap management last summer, he appears to be in good shape for at least this one position.
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Not to be a dick, but I'm not buying what the author here is selling.
First off, "people on Twitter feel this" is the bulk of the intro, in an attempt to show a status quo in the fanbase. I can find multiple people saying that Randy Carlyle looks like a potato through a Twitter search. Does that mean Leafs Nation believes Randy Carlyle to be a potato? You can find enough random people to give a positive or negative opinion on anything hockey related.
Secondarily, and this is minor, but when giving an analysis, one shouldn't be referring to guys with nicknames. Mind you, the idea of this being taken seriously was already removed by the first point.
Moving forward. High glove and rebound control are knocks that have been given to Reimer with no quantifiable evidence.
Reimer does face more attempts per game, leaving some validity to the rebound control argument; but that may be because he's been started against teams higher in the standings on average. The Leafs also attempt fewer shots with him on the ice. In any event, their even strength save percentages are an equal 0.932, so the stylistic difference may not matter.
As for high glove, I wish there was a site with heat maps for every goaltender in the league. You'll find that almost every goalie gets burned high glove, because, well, high glove is the most targeted and lethal place to aim. This is similar to Dion Phaneuf's "missed shots" stigma; you're looking for a mistake that is frequent to anybody in his position, but you're only looking for it on one player.
Blaming Game 7 v. Boston on these traits is a gross over simplification as well. Boston dominated possession throughout that entire third period; blaming Reimer for the Leafs getting out-attempted 25-8 after the 4-1 goal is ridiculous.
Furthermore, throwing Reimer under the bus for only starting 60 games in a season once was a good catch! Actually, no it wasn't, because Bernier has never started 60 games in a season. That's an incredibly deceptive point. As well as using "a certain analyst" to give a guy with a limited reputation more clout; thought that's language twisting more than anything.
I'm also not a fan of using their draft positions from over half a decade ago to judge their current potential. If anything, Reimer has proven to be a consistently growing late bloomer, while Bernier's development sputtered a little bit before catching the rail in his second full AHL season. Either way, it's unimportant.
Pointing out Bernier's ability to let in "bad goals" is kind of irrelevant as well. The quality of what he allows really shouldn't matter, the ends will always justify the means. If I had the choice between a 0.930 goalie who allowed all his goals from 200 feet away and a 0.925 goalie who only allowed breakaways, I'd take the former in a heart beat. Sure, weak goals came back to haunt him last night, but that's the first time in a while that you could say sketchy goaltending lost the Leafs a game.
Lastly, we come to the conclusion, which appears to be "the Leafs may have to let Reimer sign an offer sheet, so maybe should trade him, but they should actually keep him, oh and he'll probably play Thursday".
Yes, through all of this, the author doesn't draw an actual conclusion, basically landing at "shit is all weird and we'll see what happens". Which is fine; that's actually how I feel about them too. Both are producing stellar results, and while I'd like to see Reimer get more starts in (to maintain value and confidence, while keeping him content with the team), I'm not prepared to call one or the other a better long term option.
He doesn't have to either. But his arguments, which are thrown away in the end anyway, are flawed.


text: Home > Medical > Sleep Disorders > News Updated 13 February 2013 Poor sleep can affect your relationship Spouses and other romantic partners often complain about feeling unappreciated, and a new study suggests poor sleep may play a hidden role. 0 Spouses and other romantic partners often complain about feeling unappreciated, and a new study from the University of California, Berkeley, suggests poor sleep may play a hidden role. A UC Berkeley study looking into how sleep habits impact gratitude found that sleep deprivation can leave couples "too tired to say thanks" and can make one or the other partner feel taken for granted. "Poor sleep may make us more selfish as we prioritise our own needs over our partner's," said Amie Gordon, a UC Berkeley psychologist and lead investigator of the study, which she conducted with UC Berkeley psychologist Serena Chen. Gordon will present her findings at the annual meeting of the Society for Personality and Social Psychologists in New Orleans. The results shed new light on the emotional interdependence of sleep partners, offering compelling evidence that a bad night's sleep leaves people less attuned to their partner's moods and sensitivities. For many couples, nighttime can turn into a battleground due to loud snoring, sheet-tugging or one partner tapping on a laptop while the other tosses and turns. "You may have slept like a baby, but if your partner didn't, you'll probably both end up grouchy," Gordon said. The experiment A sixth year PhD student who focuses on the psychology of close relationships, Gordon noted that many people claim to be too busy to sleep, even priding themselves on how few hours of slumber they can get by on. The observation inspired her, in part, to study how a lack of zzzs might be affecting love lives. More than 60 couples, with ages ranging from 18 to 56, participated in each of Gordon's studies. In one experiment, participants kept a diary of their sleep patterns and how a good or bad night's rest affected their appreciation of their significant other. In another experiment, they were videotaped engaged in problem-solving tasks. Those who had slept badly the night before showed less appreciation for their partner. Overall, the results showed poor sleepers had a harder time counting their blessings and valuing their partners. How to remedy that? "Make sure to say to say 'thanks' when your partner does something nice," suggested Gordon. "Let them know you appreciate them." (EurekAlert, January 2013) Read More: Poor sleep as teen bad for the heart longterm Poor sleep makes the brain age faster From our sponsor Sleep disorders increase during pregnancy How post traumatic stress disorder affects sleep Read Health24's Comments Policy Comment on this story 0 comments Add your comment Thank you, your comment has been submitted. Logout Comment 0 characters remaining Share on Facebook Logout Comment 0 characters remaining Share on Facebook Loading comments... Ask the Expert Sleep disorders expert Dr Alison Bentley is a general practitioner who has consulted in sleep medicine and sleep disorders, in both adults and children of all ages, for almost 30 years. She also researches and publishes on a number of sleep-related topics both in formal research journals and lay publications including as editor of Sleep Matters, an educational newsletter on sleep disorders for doctors. Ask a question Questions posted to Sleep disorders expert questions answered by the expert Q: Restless leg (RSL) -how long should it take to get better? posted on 25-03-2015 Q: Zopimed addiction- how to stop? posted on 24-03-2015 Q: can child breath holding spells cause adult sleep apnoea posted on 22-03-2015 Q: girlfriend never sleeps but she's always tired, i have tried most if not all sleeping pills, nothing works! posted on 22-03-2015 Q: Bad insomnia posted on 09-03-2015 Q: Restless posted on 04-03-2015 Q: Seriously worried about daily blackouts and insomnia posted on 25-02-2015 Q: Does Serdep make you feel drowsy posted on 24-02-2015 Q: Stops breathing while falling asleep. posted on 22-02-2015 Q: Always tired yet cant sleep posted on 17-02-2015 1 comment Q: Restless Legs posted on 12-02-2015 Q: High dosage and still not sleeping posted on 10-02-2015 Q: Sleep disorders posted on 10-02-2015 Q: haven't been sleeping properly posted on 10-02-2015 Q: z dorm posted on 08-02-2015 load more × Still have a question? Get free advice from our panel of experts Your question More detail Your name (optional) The information provided does not constitute a diagnosis of your condition. You should consult a medical practitioner or other appropriate health care professional for a physical exmanication, diagnosis and formal advice. Health24 and the expert accept no responsibility or liability for any damage or personal harm you may suffer resulting from making use of this content. I agree * You must accept our condition To prevent spam please solve this simple math problem: Forum Rules


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Edwards and Stewart leave Richmond unhappy
RICHMOND, Va. Not even a meeting with NASCAR officials helped Carl Edwards understand why he was given a penalty at Richmond International Raceway.
"We had to just agree to disagree and that's the way it is," Edwards said.
In contrast, Tony Stewart knew exactly why he lost Saturday night's race.
"We did everything we could to throw it away, it got taken away," the defending Sprint Cup champion said. "I'm pretty ticked off about it."
Both drivers were less than pleased when they left Richmond, where late drama spiced up what had been yet another bland NASCAR race. There were just three cautions - one was a NASCAR-planned competition - through the first 310 laps and none had much impact on the race.
That changed when Jeff Burton smacked the wall, leaving behind debris that brought out the yellow with 89 laps remaining. It was Stewart and Edwards on the front row for the restart, and both believed they were the leader.
Edwards sailed away at the green flag, and was immediately penalized for jumping the restart and passing the leader before it was permitted.
What followed was a heated confrontation between crew chief Bob Osborne and the NASCAR official assigned to his pit stall, and a lengthy discussion on the team radio between Edwards and Osborne as they tried to figure out exactly what happened.
Edwards had been told by his spotter he was the leader, and the spotter said that information came from NASCAR. And the leaderboard backed it up, as Edwards was shown in first place. So when he was lined up on the outside of the track, Edwards said he figured NASCAR had made a mistake, and he made a split-second decision to try to get the best restart he could.
This part is not in dispute: Replays clearly showed Edwards rocketed past Stewart and had cleared him before reaching the official restart zone.
And that's against the rules, no matter who was leading the race.
"At the end of the day, it comes down to jumping the restart and that's pretty straightforward," Osborne said. "Our issue was the confusion about who was the leader and who wasn't the leader."
But why was Edwards being shown as the leader? NASCAR vice president of competition Robin Pemberton said Edwards had tripped the timing and scoring when he crossed the line ahead of Stewart under caution while cleaning his tires.
"What you've got to understand is the electronics," Pemberton said. "When the transponder crosses the start/finish line - when Carl was scrubbing his tires, he beat (Stewart) to the line - so that instantaneously puts him up top.
"It happens all the time, but these circumstances don't stack on top of it. That put him up on top of the board just because he was coming to the line with one to go."
The penalty dropped Edwards to 15th. He briefly fell a lap down, and wound up finishing 10th. It was a disappointment considering Edwards led a race-high 206 laps and is still seeking his first win of the season. And it didn't seem to matter what NASCAR's explanation was, Edwards believed he had a win taken away from him.


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Local photographers Gigi Muir and Kay Wuske embarked on their own Canalway trek in 2010, spending 300+ days taking more than 80,000 photos along the 81+ mile Towpath Trail. We asked for their suggestions on photo ops to watch for in the coming months - enjoy!
Summer Along the Towpath Trail — A quick guide to highlights and natural photo ops you might want to get out and photograph along the Towpath Trail.
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A Towpath was a Towing Path Bicyclists and walkers on the Ohio & Erie Canal Towpath Trail today follow the same path that in the 1800s was used by mules and mule-drivers to pull canal boats—with some exceptions. Canal Fever , KSU Press, 2009 More »