text:
Mtoni Marine
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- Continental Breakfast
- Suites
- Free High-Speed Internet
- Swimming pool
- Restaurant
- Beach
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Beach boys are not what you think
... Pretty cool to be there for that....although, not surprisingly, the fireworks didn't really compare to the craziness that is American 4th of July fireworks. The bar was filled with locals and what I learned were 'beach boys'. These are men that like to 'visit' with tourist women and show them a 'good' time. No longer was I a dumb white unicorn, but now, I became a doe during hunting season. Thankfully, I could seek ...
Stonetown, Zanzibar
... br>
We actually departed early from the hotel, went to the airport where we left early and even arrived in Dar es Salaam before we were supposed to be leaving! Then everything ground to a halt as we couldn't check our bags in and there were no coffee shops available until we did! Wendy, Rick and Rod had ...
We arrive on Zanzibar!
... climbed to the top of a very tall coconut tree whilst singing. This guy was mad! We were then gifted with a flax crown, ring and handbag while the boys only got a flax hat (like King Julian's off Madagascar!). We enjoyed these gifts while drinking coconut. When the tour had finished we had the opportunity to buy different spices and try some of the local fruit. Excellent tour! At around 5 our group: Me, Matt, Rach, Leigh, Nat and Annie ventured out ...
... weirdly tart. It was delicious!
After the spice tour our guide drove us to the northern beach where we had a late lunch and then relaxed on one of the prettiest beaches I've ever seen. Campbell and I even got in on a little beach volleyball! The water in Zanzibar was gorgeous, and there were actually quite a few people (honeymooners, I think) on the beach.
Then, our guide drove us back to our hotel/hostel where we showered and then went out to dinner ...
You never know when the next yacht party is coming
... boat and for the first (and likely last) time in my life, I feel like I'm a Bond villain. I'm already well and truly off the boat before I realise that I only learned to swim last year and my sum total snorkelling experience is about 5 minutes. I quickly get the hang of it and it is well worth my two minutes of flailing. With my head fully submerged, all that surrounds me are sparkling plankton, which seem to fizz as they pass by my ears. Underneath is the reef, filled with turtles ...


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You can now filter search results with text. Example: "person: john" will search only person pages for "john".
You've seen him on 'Star Wars: Rebels.' Now you can see how he survive the aftermath of the Clone Wars.
Black Bolt is back and is on a mission. Almost seems like that mission is to simply kick butt.
As Ultron attacks at a grand scale, we get a look at what he's really all about.
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Ghost Rider appears in 961 issues.
The realm of Mephisto is (one of) Marvel's appropriations of the concept of Hell.
The Night Club was a hiding place and base of operations for the Blood who fought against Zarathos. It would later be used by the Midnight Sons during their fight against Lilith and later Zarathos.
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subset: commoncrawl


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Surnames Zelaschonski to Zelba Free Family Genealogy
Discover your family genealogy by browsing surnames below. All genealogy records available at AncientFaces are free of charge and are categorized by surname. Discover your family genealogy for free then upload photos under your surname.
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Cocaine seizure
(Over $1 million of cocaine seized)…It happened at the Highway 86 checkpoint.
(Over $1 million of cocaine seized)…It happened at the Highway 86 checkpoint.
(It is the fun time of year)…Family activities are held this time of year.
(CBP releases report card for the last fiscal year)…The report is for Customs and Border Protection activity along the US/Mexico Border.
(Several injured in collision)…None of the injuries were serious.
(December unemployment down)…The numbers were released Friday.
(The 24th Annual Rib Cook-off a big success)….It is expected between 12,000 and 15,000 attended the event Saturday.
(Woman found with narcotics inside her)…28 year old Adriana Chaidez Garcia a Thermal resident was arrested late last week.
(56 year old Calexico woman suffers fatal injuries)….Angelina Cano was driving on Highway 111 over the weekend.
Page 35 of 388


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OP Senior Member
Thanks Meter: 67
424 posts
Join Date:Joined: Jul 2012
Best CDMA 2.3.3 ROM you'll find!
Razr M theme (Thanks to @ATTACK)
Replaced Launcher2 with Holo launcher
Beats Audio
Themed Holo Locker @ATTACK)
Has 250 mb of ram
Droid Razr boot animation
Razr M Chrome Rings Clock
JB and ICS Search Bar
ICS Gallery and Camera
ICS Calculator
ICS Keyboard
Bravia Engine
GUI Rendering
Playstion Mobile
New Xperia Play Game launcher and Get Games.
Highly customizable music player from Cyanogenmod called Apollo
Make a nandroid before install in case you want to go back
Wipe Cache
Wipe Dalvik
Restore through CWM
Flash your preferred CDMA kernel
[OPT.]Backup your apps via Titanium Backup. Then reboot into Recovery.
Download the Gin2Blur nandroid backup from the downloads section below
Place it in /sdcard/Clockwordmod/backup
Boot into Clockwordmod Recovery
Hit Restore, then highlight the nandroid backup you downloaded from before.
Reboot device
[OPT.]Reinstall apps via Titanium Backup
Soon to come
Google Play error fixed and implemented.
Any requests??
Next Update
Add modified Moblynx Apps, thanks to ATTACK
Add TT Lancher (here)
Add Adreno Booster (found here)
Fix Google Play Error
Updated Google Play
Transparent Status Bar (tell me what you think!)(Maybe)
Project Lard (will give credit when back on computer)
Add Kii Keyboard for 4.2.2 swipe keyboard
Moto X BootAnim
Will be uploaded before the end of summer (hopefully) Right now I'm in Taiwan seeing my family. Will try as soon as I get back!
The update will take a lot longer. I am encountering a lot of errors right now.
Known Bugs:
Google Talk Authentication Error, to fix it, clear data on Google Play/Market, Google Services Framework, Google Play Services (if applicable) (http://forum.xda-developers.com/show...00&postcount=3)
v1.5.1: HERE (Dev-Host) or HERE (MediaFire)
Razr M wallpapers (including 2 Droid DNA wallpaper ): HERE
Banner to show your support
URL-http://imageshack.us/a/img196/9629/1352941434480.jpg (this one has one of the Droid DNA Wallpaper )
FUTURE IDEAS (Please don't steal)
Gin2JB CDMA Version
Last edited by HwaA18; 23rd August 2013 at 08:26 AM.


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VOICES is an auditioned chorus with more than fifty members from central NJ and eastern Pennsylvania. Each year, the Chorale presents a varied repertoire of choral music at a high artistic level. The VOICES Young Composer program encourages young children to write and perform their own music.
Donate to VOICES
Irish Harp and Song
featuring the Jameson Sisters
with Mary Malone, fiddle
Saturday, March 14, 8 PM
Nassau Presbyterian Church, Princeton, NJ
Sunday, March 15, 3 PM
St. John's Methodist Church, Ivyland, PA
Classic Irish music, reels, ballads, and jigs. Harpist Ellen Tepper will play both the ancient Irish wire-strung harp and the Celtic harp, accompanying singer and mandolinist, Terry Kane.
2015 Young Composers Project
Submissions due: March 1, 2015
Concert: April 21, 2015
VOICES Singers:
Please review our Gaelic
pronunciation guide at home.
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I'm [Sob] So Proud
[Dabs eyes, sniffles]
As you may remember, dear daughter spent the summer working in the kitchen at a camp up near Yosemite National Park. Working eight hours a day, six days a week, often in 100 F temperatures, sleeping in bare plywood huts, 20 miles from the nearest town. For a 16 year-old, it was the best summer ever. She made lots of new friends. Went to her first rowdy party. Tasted her first beer. Got an award as the best kitchen staffer. Was asked to apply for a supervisor's position next summer. And learned, to some degree, her way around a commercial kitchen. Her previous cooking skill was the painstaking frying of perfect cubes of tofu for our family's Chinese meals. This summer she was grilling burgers for 200. Oh, and all the work made her lose ten pounds.
Now she is home, and, besides the tan and the uncontrollable desire to bleach all the kitchen counters, there is another change in DD.
She has made herself dinner and photographed it.
I'm so proud. [weeps a little]
Herewith, a WFD image by DD, she calls it . . . "Ratatouille".
You ALL should be very proud - both parents and young lady! I don't know too many sweet sixteen young people that would work that hard in those conditions and succeed as she has done. A big "atta girl" to your DD!
Sounds like a great summer! The ratatouille looks great; I'm impressed with her choice of meals to prepare. I'm sure that's not first on many teenagers' lists.
How quickly they grow up, huh? I just put my daughter on the bus for her first day of Kindergarten [sobbing with you] and I'm sure it'll seem like no time at all that she's off doing her own thing for the summer break.
I hope she keeps cooking and snapping pictures, and that you keep posting them. If she really gets into cooking it'll be fun to watch the progression.
Wow! What an amazing young lady in this age of girls mainly interested in how many parties they can attend, how much makeup they can wear, what daring fashion statements they can attempt and experimenting with as many various nail polishes as possible. You've got very good reason to be proud of her and she needs to be very proud of her accomplishments. Your young lady should go far in this world!
Obviously she has learned from you, and SWMBO
probably helped also. But you, my man, are the
true 'Chef'.
I have always been of the mindset that EVERYONE
should know how to prepare food for themselves,
so as not to starve. And you have taken it several
steps beyond that.
The congratulations go to you, Johnliu.
And maybe Dcarch should take some of the accolades,
because of the rectangular plate that she used,
(shhhhh, don't tell Ritaweeda).
Her Ratatouille looks delicious and nicely plated and photographed. I was the most impressed that after her poor blistered feet she got back in the game as soon as she could and now she can add expanded cooking to her accomplishments. I hope we see and hear more about her adventures.
Yes, definitely growing up.
Kudos to all of you.
Oh that is just an amazing story...You have every reason to be proud. Your daughter is following in her Daddys footsteps. That can only mean this cooking forum will benefit by having 2 very accomplished contributors , from the same family to this forum. Congratulations.
Oh that is just an amazing story...You have every reason to be proud. Your daughter is following in her Daddys footsteps. That can only mean this cooking forum will benefit by having 2 very accomplished contributors , from the same family to this forum. Congratulations.


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Get the latest news, traffic and weather with the Bay News 9+ app.
Watch Weather on the Nines for the latest forecast, travel weather and more.
Anton Stragaj, 34, of Palm Harbor has been charged with first-degree murder in the death of Dr. Steven Schwartz, 74. FULL STORY
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Bay News 9's Gas Tracker can help you save a few pennies with our County by County daily check for cheaper gas.
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See the latest news from Tallahassee and details on the bills and laws that will affect you.
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Abstract available in
Claims available in
Description (OCR text may contain errors)
7 us. c1. 252- 102 3,650,963 WASHING, BLEACHING AND CLEANSING AGENTS CONTAINING POLY-(N-ACETIC ACID)-ETHYLENEIMINES Achim Werdehausen, Monheim, and Manfred Dohr, Dusseldorf-Holthausen, Germany, assignors to Henkel & Cie GmbH, Dusseldorf, Germany No Drawing. Filed Dec. 1, 1969, Ser. No. 881,301 Claims priority, application Germany, Dec. 21, 1968, P 18 16 280.6 Int. Cl. Clld 7/54 4 Claims ABSTRACT OF THE DISCLOSURE A washing, bleaching and cleansing agent having a content of from 50% to 99.9%, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of a polyethyleneimine selected from the group consisting of (1) linear poly-(N-acetic acid)-polyethyleneimines of the formula wherein n is an integer from 3 to 50 and (2) their alkali metal, ammonium and organic ammonium salts.
THE PRIOR ART It has been common in the prior art to add to washing and cleansing agents, particularly those which contain bleaching compounds having active oxygen, complexing aminopolycarboxylic acids or their alkali salts, such as nitrioltriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), or diethylenetriamine pentaacetic acid (DTPA), in order to increase the stability of the bleaching agent, or to protect the optical brighteners contained in the detergents against an attack by the oxidizing agents. These compounds have, however, certain disadvantages. NTA can protect the optical brighteners only insufliciently from an oxidizing attack, while EDTA and DTPA are not completely stable against oxidizing agents and are oxidized to inactive compounds. The compounds named indeed increase the cleaning properties of washing agents. They are, however, in this respect inferior to the known inorganic builders, particularly to the polymeric phosphates.
In the German Auslegeschrift 1,060,849, as well as the essentially identical British Pat. 866,492, there is suggested as stabilizing agents for perborates or for washing and bleaching agents containing perborates, in additional to DTPA, where n is 1, complexing polyaminopolycarboxylic acids of the formula as are obtained by the reaction of ethylene chloride with ammonia and a subsequent carboxymethylation of the reseulting polyamines. In German Auslegeschrift 1,060,849, 11 is indicated as being 1 to 10.
In the corresponding British patent, however, it is shown that the stability of the described compounds against oxidizing agents is the best with the diethylenetriamine pentaacetic acid (DTPA) and triethylenetetramine hexaacetic acid (TTHA) and decreases again with increasing molecular weight. Polymers in which the number n is greater than 3 differ unessentially from EDTA in their stability against oxygen. A similar behavior is shown by these compounds in washing and ice cleansing agents in regard to their property of increasing the cleaning properties. The increase in cleaning property, also often called the builder eifect, attains its highest value with EDTA and DTPA and thereafter decreases with increasing molecular weight. It had to be assumed, therefore, that polyamino carboxylic acids prepared in another way but whose structure differed little from the deescribed compounds, would behave quite similarly and that the stability against oxidizing agents and the builder effect would also decrease with increasing molecular weight. One skilled in the art would assume that DTPA and TTHA represent anoptimum within the known aminopolycarboxylic acids in regard to their properties.
OBJECTS OF THE INVENTION An object of the present invention is the obtaining of washing, bleaching and cleansing agents which have incorporated therein complexing aminopolycarboxylic acids or their salts which increase the stability and cleaning properties of the washing agents and stabilize the optiical brighteners present.
Another object of the invention is the obtaining of a washing, bleaching and cleansing agent having a content of from 50% to 99.9%, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of a polyethyleneimine selected from the group consisting of 1) linear poly-(N-acetic acid)-polyethyleneimines of the formula wherein n is an integer from 3 to S0 and (2) their alkali metal, ammonium and organic ammonium salts.
These and other objects of the invention will become more apparent as the description thereof proceeds.
DESCRIPTION OF THE INVENTION It has now been discovered that complexing aminopolycarboxylic acids or their salts of linear poly-(N- acetic acid)-ethyleneimines of the formula wherein n is a number between 3 and 50, are complexing compounds for washing, bleaching and cleansing agents which, incorporated in said agents, are distinguished by a good stability against oxidizing substances, by an improved cleaning property, and by an effective stabilizing of the optical brighteners.
The invention, therefore, comprises a washing, bleaching and cleansing agent having a content of from 50% to 99.9%, by weight, of customary components of wasl1- ing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of a polyethyleneimine selected from the group consisting of (1) linear poly-(N-acetic acid)-polyethyleneimines of the formula wherein n is an integer from 3 to 50 and (2) their alkali metal, ammonium and organic ammonium salts.
Although the polymeric (N-acetic acid)-ethyleneimines, to be used according to the invention, differ from the known polyamino carboxylic acids only in that both terminal nitrogen atoms each time a single acetic acid group is replaced by hydrogen, they are considerably superior to the known agents in their stability against oxidizing agents, their cleaning properties and their complexing properties. This is the more surprising as it is known that in comparative cases, such as that of iminodiacetic acid and nitrilo triacetic acid, the replacement in NTA of an acetic acid group by hydrogen is connected with a very considerable decrease of the cleaning properties and of the complexing properties.
The linear poly-(N-acetic acid)-ethyleneimines or their salts utilized in the invention can be obtained by polymerization of an ester, amide or nitrile of (N-acetic acid)- aziridine and subsequent saponification to the carboxylic acid salts. Suitable starting materials are especially the lower alkyl esters, such as the methyl, ethyl, propyl, isopropyl and butyl esters of the (N-acetic acid)-aziridine. The polymerization takes place in the presence of Lewis type acids, for example, neutral sulfuric acid esters, preferably di-lower alkyl sulfates, such as dimethyl sulfate, diethyl sulfate, dipropyl sulfate, and dibutyl sulfate, or sulfonic acid esters, preferably lower alkyl alkylsulfonates and arylsulfonates, such as the methyl, ethyl, propyl and butyl esters of methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acidfThe polymerization can also be conducted in the presence of solvents, especially of the lower halogenated hydrocarbons. The polymerization time is usually 2 to 60 hours. The reaction temperature is appropriately held between 30 and 90 C. by cooling. The polymers obtained are saponified in a known manner, for example, by heating with an alkali metal hydroxide solution such as aqueous sodium or potassium hydroxide. The alkali metal salts formed can be converted into the free acids by treating with ion-exchange resins and by subsequent neutralization with ammonia or organic ammonium bases, such as mono, di or triethanolamine, morpholine, or N-methylmorpholine. The free acids can be converted to the corresponding organic ammonium salts.
The average molecular weights of the polymeric (N- acetic acid)-ethyleneimines obtained in this way are between 500 and 2,000. By separating out the low molecular component often present in the mixture, for example, by gel-chromatography on polymerized dext'ranes ('Sephadex), polymers with an average molecular weight of 1,500 to 5,000 are obtained. Since the low molecular components do not disturb, they can remain in the product. Preferably such polymeric -(N-acetic acid)-ethyleneimines are used which have an average molecular weight of 600 to 2,000.
The polymeric (N-acetic acid)-ethyleneimines can be added to the washing, bleaching, and cleansing agents in forms of salts or the free acid, if, in the latter case, the substrate contains sufficient amounts of alkaline reacting compounds so that on dissolving the agents in water a neutralization of the free acid groups takes place. The agents according to the invention contain at least one other cleaning or bleaching component, such as nonionic, anionic and amphoteric surface-active materials, inorganic or organic builders, oxygen-containing bleaching agents, as well as other conventional washing and cleansing ingredients.
Among the surface-active materials present as a component in the washing, bleaching and cleansing agents of the invention are, in the case where little foaming is essential, nonionic compounds, such as the polyalkyleneglycolether derivatives of alcohols, fatty acids and alkylphenols which contain 3 to 30 alkyleneglycolether groups and 8 to 20 carbon atoms in the hydrocarbon radical. Particularly suitable are polyalkyleneglycolether derivatives in which the number of oxyethylene groups is from to 15 and whose hydrocarbon radicals are derived from straight-chain primary alcohols with 12 to 18 carbon atoms, or from alkylphenols with a straight-chain alkyl chain of 6 to 14 carbon atoms. By the addition of 3 to 15 mols of propylene oxide to the last-named polyethyleneglycolethers, or by converting them into acetals, detergents are obtained which are distinguished by a specially w foaming power.
Other suitable nonionic basic washing components are the water soluble polyethylene oxide addducts, adducted to polypropyleneglycol, ethylenediamine-polypropyleneglycol and alkylpolypropyleneglycol with 1 to 10 carbon atoms in the alkyl chain. Preferably, these adducts contain from 20 to 250 oxyethylene groups and 10 to oxypropylene groups in the molecule. The named compounds contain usually 1 to 5 oxyethylene units per oxypropylene unit. Also nonionic compounds of the type of aminooxides and sulfoxides which, if necessary, can also be ethoxylated, are usable.
The washing and cleansing agents can also contain anionic basic washing components of the sulfonate or sulfate type. Primarily alkylbenzene sulfonates, such as dodecylbenzene sulfonate are suitable. However, olefin sulfonates, such as are obtained by sulfonation of pri mary and secondary aliphatic monoolefins with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis, as well as alkylsulfonates obtainable from n-al-kanes by sulfochlorination or sulfoxidation and subsequent hydrolysis, or neutralization, or by addition of bisulfite to olefins are also suitable. Also asulfo fatty acid esters, primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated higher alcohols are suitable. Other compounds of this class which can be occasionally present in the detergents are the higher molecular weight sulfated partial ethers and partial esters of polyhydric alcohols, such as, the alkali metal salts of the monoalkyl ethers, or mono-fatty acid esters of the glycerine monosulfuric acid esters, or, of 1,2 dihydroxypropanesulfonic acid. Also sulfates of ethoxylated or propoxylated fatty acid amides and alkyl phenols as well as fatty acid taurides and fatty acid isethionates are suitable.
Other appropriate anionic basic washing components are alkali metal soaps of natural or synthetic fatty acids, such as, sodium soaps of coconut, palm kernel, or tallow fatty acids. As amphoteric basic washing components, alkylbetaines and, particularly, alkylsulfobetaines are suitable, for example, 3-(N,N-dimethyl-N-alkylammonium)- propane-l-sulfonate and 3-(N,N-dimethyl-N-alkyl-ammonium)-2-hydroxypropane-l-sulfonate, preferably where alkyl is a lower alkyl such as methyl or ethyl.
The anionic basic washing components can be present in the form of the alkali metal salts such as the sodium and potassium salts as well as the ammonium salts, or as salts of organic bases, such as mono, di, and triethanolamine. Where the named surface-active nonionic, anionic and amphoteric compounds have a long-chain aliphatic hydrocarbon radical, the latter should preferably be straight-chained and should have from 8 to 22 carbon atoms. In the compounds with araliphatic hydrocarbon radicals the preferred straight alkyl chains contain an average of from 6 to 16 carbon atoms.
Appropriate mixture ingredients in addition to the above are also inorganic builders, particularly condensed phosphates, such as, pyrophosphates, triphosphates, tetraphosphates, trimetaphosphates, tetrametaphosphates as well as more highly condensed phosphates in the form of the neutral or acidic alkali metal salts such as the sodium and potassium salts as well as the ammonium salt. Preferably alkali metal triphosphates and their mixture with pyrophosphates are used. The condensed phosphates can also be partly or completely substituted by organic complexing agents containing phosphorus or nitrogen atoms. Such compounds are the alkali metal or ammonium salts of aminopolyphosphonic acids, particularly aminotri- (methylenephosphonic acid)ethylenediamino-tetra- (methylenephosphonic acid), 1-hydroxyethane-1,1 diphosphonic acid, methylene diphosphonic acid, ethylene diphosphonic acid as well as the higher homologs of the named polyphosphonic acids, as well as the alkali metal or ammonium salts of low-molecular-weight aminopolycarboxylic acids, such as, NTA and EDTA. As other builders, alkali metal silicates are suitable, particularly sodium silicate in which the ratio Na O:SiO is 123.5 to 1:1.
As further mixture ingredients are neutral salts, such as, sodium sulfate and sodium chloride, as well as compounds for adjustment of the pH, such as bicarbonates, carbonates, borates and hydroxides of sodium and potassium and acids, such as, lactic and citric acid. The amount of the alkaline reacting substances should be calculated so that the pH of a serviceable washing liquor for coarse laundry is 9 to 12 and for fine laundry 6 to 9.
By appropriate combination of various surface-active basic washing components or builders with each other, in many cases increased effectiveness, such as a higher cleaning property or lower foaming power can be attained. Such improvements are possible, for example, by combination together of anionic with nonionic and/or amphoteric compounds, by combination of various nonionic compounds with each other or also by mixtures of basic washing components of the same type which dilfer in regard to the number of carbon atoms or the number and position of double bonds or branched chains in the hydrocarbon. Synergistically effective mixtures of inorganic and organic builders can also be used or combined with the precedingly named mixtures.
Depending upon their respective use, the washing agents of the invention can contain oxygen-releasing bleaching compounds, such as, hydrogen peroxide, alkali metal perborates, alkali metal percarbonates, alkali metal perphosphates, urea hydrogen peroxide and alkali metal persulfates or active-chlorine compounds, such as, alkali metal hypochlorites, chlorinated trisodium phosphate and chlorinated cyanuric acid, or its alkali metal salts. The peroxide compounds can be present in a mixture with bleaching activators and stabilizers, such as, magnesium silicate.
Optical brighteners suitable for cellulosic fibers used in the washing agents of the invention are those of the diaminostilbene disulfonic acid type of the formula:
in which X and Y have the following meanings: NH NHCH NHCH -CH OH,
N(CH --CH OH) morpholino, dimethylmorpholino, NH-C H NH--C H SO H, OCH Cl where X and Y can be the same or not. Particularly suitable are those compounds in which X is an anilino and Y a diethylamino, or a morpholino group.
As optical brighteners for polyamide fibers suitable for use in the washing agents of the invention are those of the diarylpyrazoline type of the following formula:
In this formula Ar and Ar are aryl radicals, such as, phenyl, diphenyl, or naphthyl which can have further substituents, such as, hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid, and sulfonamide groups, or halogen atoms. Preferred is a 1,3 diarylpyrazoline derivative in which the radical Ar is a p-sulfonamidophenyl group and the radical Ar is a p-chlorophenyl group. In addition to the brighteners, whiteners suitable for the brightening of other fiber types can be present, for example, compounds of the type of naphthotriazolestilbene sulfonates, ethylene-bis-benzimidazoles, ethylene-bisbenzoxazoles, thiophene-bis-benzoxazoles, dialkylaminocoumarins, and the cyanoanthracenes. These brighteners or their mixtures can be present in the washing agents in amounts of from 0.01% to 1.5% by weight, preferably from 0.1% to 1% by weight.
Further suitable mixture ingredients for the washing agents of the invention are greying-inhibiting compounds, such as, sodium celluloseglycolate, as well as the water soluble sodium salts of synthetic polymers which contain free carboxylic groups. These latter include the polyesters or the polyamides of tri and tetracarboxylic acids and dihydric alcohols or diamines, and also polymeric acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and aconitic acid as well as the mixed polymerizates of the named unsaturated carboxylic acids, or their mixed polymerizates with olefins and vinylethers.
Washing agents intended for the use in drum-washing machines contain appropriately known foam-suppressing substances such as saturated fatty acids with to 24 carbon atoms, or their alkali metal soaps, or triazine derivatives which can be obtained by reacting one mol cyanuric chloride with 2 to 3 mols of aliphatic, straightchained, branched-chained or cyclic primary monoamines or by propoxylating, or, butoxylating melamine.
For a further improvement of the dirt-loosening properties of the washing agents according to the invention they can also contain enzymes from the class of proteases, lipases, or amylases. These enzymes can be of animal or plant origin, for example, those obtained from digestive ferments or yeasts, such as pepsin, pancreatin, trypsin, papain, catalase and diastease. Preferably used are enzymatic active substances obtained from bacterial strains or molds, such as, Bacillus subrilis and Streptomyces griseus which are relatively stable against alkalis. peroxide compounds and anionic detergents and essentially not inactivated even at temperatures between 45 C. and 70 C.
The washing and cleansing agents can be present in liquid, pasty or solid form, as powder, granules or lumps. Liquid preparations may contain water-miscible solvents, particularly lower alkanols such as ethanol and isopropanol, as well as dissolving asids, such as, the alkali metal salts of benzene, toluene, xylene, or ethylbenzene sulfonic acids. For increasing of the foaming power and for the improvement of the skin compatibility alkylolamides, such as, fatty acid mono, or diethanolamides may, if necessary, be added. The mixture can also contain dyes or odorizing substances, bactericidally-active materials, activators as well as fillers, for example, urea.
The preparation of the agents according to the invention can be done in customary manner by mixing, granulating or spray-drying. Insofar as enzymes are used, it is recommended to mix them with the nonionic basic washing components and, if necessary, odorizing substances, or to disperse them in the melt of a salt containing water of crystallization, such as Glaubers salt, and to combine these premixtures with the other powdery ingredients. By this procedure, the enzymes are cemented with the other powder particles so that the mixtures do not tend to dust or separate.
The content of the washing, bleaching and cleansing agents of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts amounts from about 0.1% to 50% preferably 0.2% to 25% by weight, depending upon their use. The difference to 100% is taken up by the previously named detergent and bleaching active substances as well as, if necessary, the additional builders to improve the cleaning power. The qualitative and quantitative composition of these additional ingredients depend widely upon the special use of these agents. It corresponds in the case of the technically particular important washing and cleansing agents to the following recipe: (Data in percent by weight) 1% to of at least one compound from the class of the anionic, nonionic, and amphoteric detergents.
0 to 80%, preferably 10% to 80% of at least one non-surface-active cleaning intensifying or complexing builder.
0 to preferably 10% to 50% of a per-compound, especially sodium perborate, with or without water or crystallization, as well as their mixtures with stabilizers and activators.
to 60%, preferably 0.1% to 20% of other auxiliary and supplementary substances.
The detergent substances can consist of up to 100%, preferably from to 70%, of compounds of the sulfonate and/ or sulfate type, up to 100%, preferably from 5% to 40% of the nonionic polyglycolether type, and up to 100%, preferably from to 50% of soaps. The builders can consist of up to 100%, preferably from 25% to 95%, of alkali metal triphosphates and their mixtures with alkali metal pyrophosphates, up to 100%, preferably from 5% to 50%, of an alkali salt of a complexing agent from the class of polyphosphonic acids, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and up to 100%, preferably from 5% to 75% of at least one compound of the class of alkali metal silicates, alkali metal carbonates and alkali metal borates.
To the additional auxiliary and supplementary substances belong, in addition to the optical brighteners, es pecially the foam inhibitors which can be present in the agents according to the invention in an amount of up to 5%, preferably from 0.2% to 3%; also the enzymes which can be present in an amount up to 5 preferably from 0.2% to 3%; and the greying-inhibitors which can be present in an amount up to 5%, preferably from 0.2% to 3%.
The following examples are illustrative of the practice of the invention without being limitative. In the following, some recipes *are given which have proven particularly good in practice.
EXAMPLES (A) Powdery, low-foaming Washing agent 3% to of a sulfonate basic washing component from the class of alkylbenzene sulfonates, olefin sulfonates and n-alkane sulfonates (sodium salts) 0.5% to 5% of an alkylpolyglycolether (alkyl C to C or alkylphenolpolyglycolether (alkyl C to C with 5 to 10 oxyethylene groups 0 to 5% of a C to C soap (sodium salt) 0.2% to 5% of foam inhibitors from the class of trialkylmelamines and saturated fatty acids with 20 to 24 carbon atoms, or their alkali metal soaps.
10% to 50% of a condensed alkali metal phosphate from the class of the pyrophosphates or the tripolyphosphates.
0.1% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salt 1% to 5% of sodium silicate 10% to of sodium perborate tetrahydrate 0 to 5% of enzymes 0.05% to 1% of at least one optical brightener from the class of diaminostilbenedisulfonic acid or diarylpyrazoline derivatives 0.1% to 30% of an inorganic alkali metal salt from the class of the carbonates, bicarbonates, borates, sulfates and chlorides 0 to 4% of magnesium silicate 0.5 to 3% of sodium celluloseglycolate (B) Powdery foaming fine washing agent 1% to 30% of a sulfonate basic washing component (sodium salt) 0.5 to 10% of alkylpolyglycolether sulfate (alkyl C to C 1 to 5 oxyethylene groups) 0 to 20% of an alkylpolyglycolether (alkyl C to C or alkylphenolpolyglycolether (alkyl C to C with 5 to 12 oxyethylene groups 0.2% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salt 0 to 5% of a higher fatty acid ethanolamide or diethanolamide 8 0 to 20% of sodium tripolyphosphate 0 to 1% of a brightener from the class of the diarylpyrazoline derivatives and its mixtures with polyester brighteners 3% to 70% of sodium sulfate (C) Liquid washing agent 0.5% to 10% of a sulfonate basic washing component (potassium salt) 0 to 10% of alkylpolyglycolether sulfate (alkyl C to C 1 to 5 oxyethylene groups) 0.2% to 25 of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 0.1% to 5% of fatty amide-glycolether condensate (alkyl C to C 1 to 10 oxyethylene groups) 1% to 10% of solution aids from the class of the alkali metal salts of benzene, toluene, or xylene sulfonic acids 0 to 30% of neutral or acid potassium pyrophosphate 0 to 10% of organic solvent media from the class of the C to C alcohols and ether alcohols 0 to 1% of optical brighteners from the class of the diaminostilbene disulfonic acids and diarylpyrazoline derivatives Residue: Water, perfumes, dyes, preservatives (D) Steeping and pre-washing agent 0.5% to 5% of sulfonate basic washing component (sodium salt) 0 to 3% of compounds from the clas of alkylpolyglycolethers (alkyl C to C and alkylphenolpolyglycolethers (alkyl C to C with 5 to 12 oxyethylene groups 0.1% to 10% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 10% to 50% of sodium carbonate 1% to 5% of water glass 0 to 5% of magnesium silicate 0 to 5% of enzymes (E) Dishwashing-machine washing agents 0.1% to 3% of compounds from the class of the alkylpolyglycolether (alkyl C to C alkylphenolpolyglycolether (alkyl C to C with 5 to 30 oxyethylene groups and 5 to 30 oxypropylene groups, and ethoxylated polypropyleneglycols 0.2% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 45% to of pentasodium triphosphate 1% to 40% of sodium silicate (Na O:SiO =1:1 to 1:3)
0 to 5% of potassium dichloroisocyanurate 0 to 2% of foaming inhibitors (G) Bleaching agents 0.2% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 10% to 95% of percompounds 0 to 50% of alkaline reacting compounds from the class of alkali metal hydroxides, carbonate, silicates and phosphates 0 to 5 0% of bleaching activators 0 to 5% of anionic and/ or nonionic detergents 0 to 10% of other ingredients, such as, corrosion inhibitors, optical brighteners, neutral salts, magnesium silicate.
9 (H) Alkaline cleansers 0.1% to 25% of poly-(N-acetic acid)-ethyleneimine or its alkali metal salts 0.5% to 50% of sodium silicate (Na O:SiO =1.1 to
10 2% Magnesium silicate 1% Sodium celluloseglycolate 25% Sodium perborate-tetrahydrate 8% Water 13) 5 0.8% Brightener of the pyraz oline type 05 to 80% of Sodium hydroxide 0.2% Brlghtener of the diaminostllbene type. to 40% of trisodium phosphate The brighteners had the following structures: 0 to 40% of condensed alkali metal phosphates 0 to 40% of sodium carbonate 2 0 to 10% of hydroxyethanc diphosphonate (sodium salts) 10 ii (311: 0 to 5% of anionic and/or nonionic detergents (I) Scouring agent 1% to of anionic and/or nonionic basic washing components 0.1% to 5% of alkali metal salts of poly-(N-acetic acid) ethyleneimine l 80% to 95% of abrasive agents SO2NH2 0 to 10% of cleansing salts of the class of alkali metal Pyrazohnetype polyphosphate's, alkali metal silicates, alkali metal borates, and alkali metal carbonates 0 to 10% of alkali metal dichloroisocyanurate. =K EXAMPLE 1 E The cleaning action of washing agents that contained S I I( 2H10H)z 2 an anionic basic washing component, Na-n-dodecylben- Diaminostilbene type zene sulfonate) and different builder components were To this agent were added each time 2%, by weight of conpared- With Washing agents grey co tton S P the linear Na poly-(N-acetic acid)-ethyleneimine. The which had been so1led with a synthetic so1l containing linear polymeric carboxylic acids were prepared by 1 sootglron oXldF and 3km fat was W e a laboratory erization of (N-acetic acid)-aziridine in the presence of washing machine where the Washing 11qu0r Was heated dipropyl sulfate and had, in Example 2, an average molecfrom 20 to 90 wlthm 15 mmlltes and kept at 900 ular weight of 870; in Example 3, 1230, and in Example 4, for another 15 minutes. The washing agent concentra- 1720 As comparison, the washing agent was utilized to tion was 3 grn./l. The water hardness was 16 dH. The which instead of the linear polymers according to the inweight ratio of textile to liquor Was 1:12. Subsequently, vehtioh, f Na nitrolotriacetate (NTA), or 2% f the textiles were rinsed with Water four times, centrif uged Na ethylenediaminetetraacetate (ED-TA) were added. and dried. The percent whiteness was determined with a w these washing agents, textiles of polyamide fibers photometer (soiled cloth 0%, onginal cloth 100%) a (Perlon) were washed in a laboratory washing machine 18 shown In Table L a Well as the composltlcn of the where the washing liquor was heated from 20 C. to 60 agents- C. within 15 minutes and was kept at this temperature for t f Salt of the P y f acld)ethyl an additional 15 minutes. The washing agent concentraenelmlne Utlllled, Was P p y heatlng 130 05 tion was 5 gm./l. and the weight ratio of textiles to liquor N-(methylcafbethoXy)-aZiridi1'1B and of p py was 1:30. The water used had a hardness of 16 dH as sulfate in 1500 ml. of 1,2dichloroethane for 3 hours in Well as a copper ion content f 05 mols per m The the absence of air. Thereafter, the solvent was separated degrees of whiteness of h f mi i d d h aI 1d the Polymerizate W Saponified y heating to dried wash was determined by a photometer. The results Wlth 3 N NaOH for 3 hours- The Polymer had an average are summarized in Table II. These results demonstrate the molecular weight of 1230. The results of Table I show superiority of the compounds used according to the inthat the linear poly-(N-acetic acid)-ethyleneimine of the ti invention is superior in its cleaning properties to other TABLE H known builders, among them pentasodium triphosphate which is known for its effectiveness. g ffi Addition (2% by Weight to the TABLE I Example washing agent) 1 wash 5washings 2 Poly-(N-aceticacid)-ethyleneimine 105 114 3 "do! 106 114 Amounts in gm./liter 4 "(10. 106 115 NTA 100 104 E EDTA 103 110 Composition: ample Comparisons 1 Average molecular weight 870. Na-N-dodeeylbenzene sulfonate 1 1 1 1 2 Average molecular weight 1,230. N a poly-(ljl-acetio1 acigr-eglgiylltlahfiso) 2 3 Average molecular weight 1,720. gfiaalfifi figfifi hm.E. EXAMPLES 5 AND 6 N a tfiiiiiiiaii'aetaseta An aqueous solution containing 0.62 gm./l. sodium per- Pemnt bnghtemng borate was prepared from a bleaching agent composition 65 consisting of 154 gm. of sodium perborate and of 124 gm. EXAMPLES 2 TO 4 of a sodium salt of a linear poly-(N-acetic acid)-ethylene- A washing agent of the following composition was mum of: used (data in weight percent): in Example 5, an average molecular weight of 810, 8% Na n dodecylbenzene sulfonate in Example 6, an average molecular weight of 1500. 5% Sodium soap of C to C fatty acids The sodium salt of linear poly-(N-acetic acid)-ethyl- 3% Oleyl alcohol polyethyleneglycol ether (10 oxyethyleneimine was prepared by polymerization of (N-methylene units) carbomethoxy)-aziridine in the presence of diethylsulfate, 40% Pentasodium triphosphate saponification of the polymerizate with sodium hydroxide, 5% Sodium silicate (Na O.3.3 SiO and adjustment to a pH of 10 with dilute sodium hydroxide. The decrease of the active-oxygen content of this solution at 90 C. was determined every 30 minutes by iodometric titration. For comparison the determination was repeated with equal amounts of known perborate stabilizers. The results are summarized in Table III. These results demonstrate the superiority of the agents according to the invention.
We claim:
1. A washing, bleaching and cleansing agent having a content of from 50% to 99.9%, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1% to 50%, by weight, of a polyethyleneimine selected from the group consisting of (1) linear poly- (N-acetic acid)-polyethyleneimines of the formula TABLE III Percent active oxygen after- 30 60 90 120 150 Example Stabilizer min. min. min. min. min.
Poly-(N-acetic acid)ethylenelmine: 5 Average molecular weight 8l0 80 W 71 W 65 59 52 6 Average molecular weight 1,500.. 83 73 69 64 58 52 26 3 40 5 2 Oarboxymethylated polyamine ace cording to German Pat. 1,060,849 of an average molecular Weight of 900. 48 22 9 5 Without addition 35 is s 4 In the following Table IV are summarized some recipes N CH2 CH2 of washing, bleaching and cleansing agents accordmg to 1 000E] the invention for the following fields of application: 2- l 7 F h a 11.! ant wherein n is an integer from 3 to 50 and (2) their alkali i g? teavy w S 1 g ag metal, ammonium and organic ammonium salts with E f 5 agen t bases selected from the group consisting of mono-, di- 3 i agent and triethanolamine, morpholine and N-methyl morpho- E 00 mgtagen line, said customary components of washing, bleaching 12 i gi agen t and cleansing agents consisting essentially of from 1% gi t to 40% by weight of at least one compound selected Examp 1 g f from the group consisting of anionic, non-ionic and am- 15 S or eztwy Sol mg photeric surface-active basic washing components, from xamp e couring agen. 0% to 80% by weight of at least one builder selected The ingredients (a) to (d) and (f) to (i) were present from the group consisting of condensed inorganic phosas the sodium salts, the pyrophosphate [ingredient (k)] phate builders, alkali metal silicates, carbonates, bicarwas, in Example 9, the potassium salt, and in all other bonates, borates, sulfates and chlorides, alkali metal and examples, the sodium salt. As enzyme [ingredient (q)] ammonium salts of aminopolyphosphonic acids and lowa preparation (Maxatase) made from Bacillus subtilis, with an activity of 100,000 LVA/gm. was utilized. The foam suppressor [ingredient (v)] is a reaction product of 1 mol of cyanuric chloride with 2.7 mols of a primary n-alkylamine with a C to C chain length.
TABLE IV molecular-weight aminopolycarboxylic acids, from 0% to by weight of a bleaching compound selected from the group consisting of hydrogen peroxide, urea hydrogen peroxide, alkali metal perborates, percarbonates, perphosphates, persulfates, hypochlorites, chlorinated trisodium Example (Data in weight percent) Ingredient 7 8 (a) n-Dodecylbenzene sulionate 012 to C olefin sulfouate (c) 014 to C17 alkane sulfonate (d) Coconut alcohol glycol ether sulfate (2 E0) (e) Oleyl alcohol polyglycol ether (10 E0) (f) 012 to Cnsoap (g) 02a to C22 soap-. (h) Poly-(N-aeetic acid) ethylene (i) Tripolyphosphate (k) Pyrophosphate (1) Sodium carbonate (n) Sodium sulfate t. (0) Sodium perborate (D) Magnesium silicate Na toluenesulfonate (t) Coconut fatty acid diethanolamide (u) Optical brightener (v) Foam suppressor (w) Water (x) Dichloroisocyanurate (y) Coloring and odorizing agent (2) Quartz powdsr N OTE.EO =oxyethylene units.
The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art may be employed without departing from the spirit of the invention or the scope of the appended claims.
phosphate and chlorinated cyanuric acid and its alkali metal salts, and mixtures thereof with magnesium silicates, and from 0% to of other auxilliary and supplementary components of washing agents selected from the group consisting of optical brighteners, greying-inhibi- 13 14 tors, foam-suppressors, enzymes, water-miscible solvents, 4. The washing, bleaching and cleansing agent of claim water and dissolving aids, said ingredients totalling 100% 3 wherein said average molecular Weight is from 600 by Weight of said customary components. to
References Cited 2. The Washing, bleaching and cleanslng agent of claim 5 1 wherein said polyethyleneimine is present in an amount FOREIGN PATENTS of fro 05% to 25% by weight 231,499 10/1960 Australia 252-102 3. The washing, bleaching and cleansing agent of claim 1 wherein said linear poly-(N-acetic acid)-polyethyleneimine has an average molecular weight of from 500 to 10 5,000. 252-486; 260-2 EN, 534 E MAYER WEINBLA'IT, Primary Examiner
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The ever-eclectic DJ Moneyshot has won a mad decent following for his killer mixtapes, bubbling live sets, and party-smacking tunes. He's an all round good egg, and jaw-droppingly nimble 'pon the decks. His style is mad tight, and best described as "dancefloor beats, booties and bass with hip-hop skills". A fellow Solid Steel compatriot and XFM disc-jockey, Moneyshot has smashed parties across the globe.
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Quote 10-15-10
don_socalOctober 15, 2010
Every man ought to be inquisitive through every hour of his great adventure down to the day when he shall no longer cast a shadow in the sun. For if he dies without a question in his heart, what excuse is there for his continuance?
Frank Moore Colby
The friends whom I have are invaluable, and although not numerous they are sufficient for my enjoyment; and the texture of my own mind renders me very indifferent to the rest of the world.
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Tom Zart
World War III, Boston & Formidable Foe = 2013 Poem by Tom Zart
Our sons and daughters serve in harm's way
To defend our way of life.
Some are students, some grandparents
Many a husband or wife.
They face great odds without complaint
Gambling life and limb for little pay.
So far away from all they love
Fight our soldiers for whom we pray.
The plotters and planners of America's doom
Pledge to murder and maim all they can.
From early childhood they are taught
To kill is to become a man.
They exploit their young as weapons of choice
Teaching in heaven, virgins will await.
Destroying lives along with their own
To learn of their falsehoods too late.
The fearful cry we must submit
And find a way to soothe them.
Where defenders worry if we stand down
The future for America is grim.
Now's not the time to fight one another
Or kiss our enemy's cheek.
All through history it remains the same
The strong enslave the weak.
May God continue to bless America
Refusing evil, the upper hand.
It's up to us to stay resolute
Defending the liberty of Man.
America is the birthday cake of Earth
As the ants march from every direction.
Thank God for all who have sworn to defend her
Serving with love, honor, pride, and affection.
Since the first day George Washington marched off to war
There have been those who have wished our demise.
Their hatred, fueled by jealousy and greed
Was defeated by our brave and the wise.
Once again, we must face a formidable foe
Who have pledged by their God to destroy us all
Misusing their faith as an excuse to kill
As for a worldwide jihad, their leaders call.
Some say we should try to appease them
For if we resist, they'll hate us even more.
But the David's among us shall cast our stones
Defeating them, as it was done before.
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Supervisory Human Resources Specialist
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Deus Ex: The Fall is now available for Macs
Last month Deus Ex: The Fall made the jump over to the PC on Steam, and now it's available for the Mac. As always, if you already bought the game at release, you can just load it up on a Mac with the same account and you're good to go.
It was neat on a portable device, but it seems as if the game hasn't translated well to the PC, so buyer beware. It would be perfect for a high percentage drop Steam sale, though, if you're a hardcore franchise fan.
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8:30 PM on 07.11.2013
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Deus Ex: The Fall gets a July 11 release date
10:30 AM on 07.08.2013
Deus Ex: The Fall is a full-fledged experience
10:00 AM on 06.07.2013
Deus Ex: The Fall Updates, Screenshots, & Videos
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How to locate the final hidden boss in Bloodborne, and achieve the true ending
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Listen Live
in Music
The guitarist is contemplating developing a musical based on songs of the Eagles.
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Industry insiders claimed the trio's most recent reunion fell apart amid backstage squabbles, but the guitarist says it's just not true.
The pop singer breaks his silence following his surprise departure from the boy band.
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text:
A method for segmenting an image is disclosed wherein a fractal map of the image is generated by estimating the fractal dimension of each pixel in the image. The image is segmented by thresholding the fractal map of the image.
1. A programmed system for automatically identifying an illuminated target image comprising:
an image capture sensor for capturing the target image, the image comprising at least one pixel, the pixel characterized by a location of the pixel within the image and a pixel value;
means for generating a fractal map of a plurality of boundary images of the image;
means for segmenting and storing the target image based on the fractal map of at least two boundary images at different focal distances;
means for detection of the target image at a pixel threshold of dp applied to the fractal map; and
means for offsetting at a predetermined value range based on fractal image illumination or contrast pixel value, dp.
2. The system of
means for estimating the fractal dimension of the at least one pixel of the image and assigning the estimated fractal dimension to a pixel value of a pixel in the fractal map corresponding to the location of the at least one pixel of the image.
3. The system of
means for applying a first structuring element to the at least one pixel of the image, the first structuring element characterized by a first scale length L1; and
means for applying a second structuring element to the at least one pixel of the image, the second structuring element characterized by a second scale length L2, wherein the second scale length L2 is greater than the first scale length L1.
4. An automated method of identifying an illuminated microscopic target image, comprising:
forming a plurality of boundary images from the target image segmenting the target image by generating a fractal map of each of at least two of the boundary images;
applying an illumination detection threshold to the fractal map wherein the threshold represents a fractal dimension of a pixel value, dp; and
electronically capturing and storing each fractal map of the at least two boundary images at different focal distances.
5. A computer program product for use with an automated microscopy system, the computer program product comprising a computer usable medium having computer readable program code means embodied in the computer usable medium for causing the automated microscopy system to automatically perform the steps of
6. The method of
applying a structuring element L�L on the pixel value, dp wherein a scale L2 is greater than a scale L1 such that a ratio R=L2/L1>1.
7. The method of
8. The method of
9. The method of
10. The method of
11. The method of
12. The method of
13. The method of
14. The method of
15. The method of
16. The method of
17. The method of
18. The method of
where dp is the fractal dimension of the at least one pixel of the image, N2 is the sum of the pixel values in an L2�L2 structuring element, N1 is the sum of the pixel values in an L1�L1 structuring element, and L2 and L1 are the sizes (in pixels) of the respective structuring elements.
19. The method of
calculating a fractal dimension for the at least one pixel; and
segmenting the image based on the fractal dimension of the at least one pixel.
The present invention relates to digital image processing. More specifically, the invention relates to methods for segmenting an image based on a threshold representing the fractal dimension of the pixel.
A human can view an image and effortlessly distinguish a face from the background even when the image is of poor quality. Providing this same capability to a computer requires more effort. Distinguishing objects in an image is called pattern recognition and comprises three major steps: isolation; extraction; and classification. The first step, isolation, segments each object in the image. Extraction measures a set of features, such as size or color that characterizes each object. Lastly, classification assigns each object to a class based on the set of measured features of the object. Castleman, Digital Image Processing, pp. 447-546, Prentice-Hall, (1996) describes each of the steps and is herein incorporated by reference.
Thresholding is one method of segmenting an image and has the advantage of being computationally simple. The pixel value of each pixel in the image is compared against a threshold value and assigned a new pixel value depending on whether the original pixel value is greater than or less than the threshold value. Thresholding works well when the object, or target, of interest has a substantially uniform gray level that is significantly different from the gray level of the background.
A common problem in automated image processing systems is that the threshold value required to properly segment the image depends on the quality of the images being processed. Adaptive threshold systems adjust the threshold value according to the image characteristics, but require more computational resources that may make the application cost prohibitive. Alternatively, if the samples are fairly uniform, such as PC boards, and the lighting conditions during image capture are tightly controlled, the threshold value may be set once at the beginning of the automated inspection process.
The automated system 100 includes a controller that enables the stage 110 supporting the slide 107 to move a portion of the sample 105 into the focal plane of the objective lens and to translate the stage within the focal plane of the objective lens to allow different portions of the sample to be viewed and captured. The camera 128 captures an image of the sample and sends the image signal to an image processor for further processing and/or storage. In the example, shown in
The controller may also control a sample handling subsystem 160 that automatically transfers a slide 109 between the stage 110 and a storage unit 162. The prepared sample slides are loaded into the storage unit 162 and the storage unit 162 is loaded on the sample handling subsystem 160. The loading of the slides into the storage unit or the loading of the storage unit into the handling subsystem may be done manually by an operator or may be automated. After the handling subsystem is loaded, the operator may enter information describing or identifying the samples into the processor. The operator may also enter or select parameters that govern how the scanning microscopy system will operate during the automated run. For example, the operator may choose to process all of the loaded sample slides in one continuous run or choose to terminate the run after a selected number of slides have been processed. As a further example, the operator may view one or more images captured from the samples and set threshold values such as the ones described below. After the run parameters are entered, the operator starts the run and the processor takes control of the system until the run is completed or terminated by the controller.
The image captured by the camera 128 may be preprocessed before being stored or sent to the image processor. The hardware and basic software components for the capture, storage, retrieval, display, and manipulation of the image are known to one of skill in the art and are not further discussed. The image processor may correct for camera artifacts, enhance particular objects of the image to simplify the object recognition process, or adjust or compensate for the lighting conditions used to capture the image.
In many situations, however, the properties of the sample itself produce images where the pixel values (gray levels) of the background do not differ significantly from the pixel values of the target. For example, epifluorescence microscopy of biological samples usually produces low light signal images because of the low signal strength of the fluorophore used to tag the biological samples. Under low light conditions, the average pixel value of the image is close to zero. A similar situation occurs under low contrast conditions where the difference between the average pixel value of the target and the average pixel value of the background is close to zero. In both conditions, closeness is relative to the maximum pixel value. For example, if the pixel depth is eight bits, the maximum pixel value is 255 and a pixel difference of 16 may be considered close. Similarly, if the pixel depth is 16 bits, the maximum pixel value is 65,535 and a pixel difference of 512 may be considered close. If the threshold is set to the average pixel value when the average value is close to zero, the segmentation will be susceptible to false positives due to background noise.
Therefore, there remains a need for a method of image segmentation that may be used in automated image processing systems that is capable of handling low light/low contrast images.
One embodiment of the present invention is directed to a method of segmenting an image comprising generating a fractal map of the image; and segmenting the image based on the fractal map. In some embodiments, the method of segmenting the image further includes applying a threshold to the fractal map, the threshold representing a fractal dimension. In some embodiments, generating the fractal map further includes: forming a plurality of boundary images from the image, each of the plurality of boundary images characterized by a scale; estimating the fractal dimension of at least one pixel of the image from the plurality of boundary images; and setting a pixel in the fractal map corresponding to the location of the at least one pixel of the image a value equal to the estimated fractal dimension of the at least one pixel. In some embodiments, forming the boundary image further includes: eroding the image by an L�L structuring element to form an eroded image; dilating the image by an L�L structuring element to form a dilated image; and forming the boundary image by subtracting the eroded image from the dilated image, the scale of the boundary image defined by L.
Another embodiment of the present invention is directed to a system for automatically segmenting an image comprising: an image capture sensor for capturing the image, the image comprising at least one pixel, the pixel characterized by a location of the pixel within the image and a pixel value; means for generating a fractal map of the image; and means for segmenting the image based on the fractal map. In some embodiments, the means for generating the fractal map further comprises means for estimating the fractal dimension of the at least one pixel of the image and assigning the estimated fractal dimension to a pixel value of a pixel in the fractal map corresponding to the location of the at least one pixel of the image. In some embodiments, the means for estimating the fractal dimension further includes: means for applying a first structuring element to the at least one pixel of the image, the first structuring element characterized by a first scale length; and means for applying a second structuring element to the at least one pixel of the image, the second structuring element characterized by a second scale length, wherein the second scale length is greater than the first scale length.
The invention will be described by reference to the preferred and alternative embodiments thereof in conjunction with the drawings in which:
Low light/low contrast images may be adjusted by mapping the pixel values to a transformed set of pixel values. For the purposes of illustration, suppose an image having a depth of eight bits has pixel values between 0 and 31. The image is a low light image because the greatest pixel value of the image, 31, is much less than the maximum possible pixel value of 255. Histogram equalization maps the pixel values of the original image to pixel values that span the entire pixel depth. In this example, pixels having a pixel value of 31 are given an equalized pixel value of 255, pixels having a pixel value of 16 are given an equalized pixel value of 128, etc. Histogram equalization is a linear mapping, but contrast may be further enhanced by a non-linear transformation such as a power law. One such non-linear transformation is the gamma correction that calculates the corrected pixel value based on the original pixel value raised to a constant, γ.
Both histogram equalization and gamma correction are point transformations in that the transformed pixel value does not depend on the pixel values of the neighboring pixels. Filtering operations such as, for example, smoothing calculate the new pixel value based on the pixel values in the neighborhood of the structuring element. The filtering operation is completed in one sweep through all the pixels in the image using the same sized structuring element or filter kernel. The size of the structuring element determines the extent of sampling of the neighboring pixels. These operations are described in Castleman and do not require further discussion.
In one embodiment of the present invention, a fractal map is generated for each image that allows thresholding for low light/low contrast images without the need for histogram equalization or gamma corrections. Unlike histogram equalization or gamma corrections, the fractal transformation is not a point operation and uses the pixel values of neighboring pixels to calculate the transformed pixel value. Unlike filtering operations, the fractal transformation samples at least two neighborhoods, where each neighborhood is characterized by a different size, or scale.
The fractal map is generated by assigning to each pixel in the image a pixel value that represents the fractal dimension of the pixel. A description of fractals is given in Mandelbrot, The Fractal Geometry of Nature, W. H. Freeman, San Francisco (1982) and is herein incorporated by reference. Mandelbrot uses the fractal dimension to describe self-similar objects such as the Koch curve or fracture surfaces in materials.
The fractal dimension is the exponent in a power law function relating a measurable quantity to a length raised to the exponent, i.e.,
Mandelbrot describes one method of determining the fractal dimension of an object by counting the number of covering spheres required to cover the object as a function of the covering sphere size. The fractal dimension of the object is the slope of the number of covering spheres versus covering sphere size when plotted on log axes. If only two sphere sizes are used, the fractal dimension may be estimated by the equation:
The fractal dimension, as described by Mandelbrot, is a single number that characterizes the whole object and is therefore global in the sense that it represents the whole object. In a similar fashion, the fractal dimension has been used to characterize fracture surfaces as described in Russ, Handbook of Image Processing 4th ed., pp. 261-263, 694-696, CRC Press, 2002, herein incorporated by reference. In both cases, the fractal dimension is associated with the whole object and is determined once for the object. The fractal dimension may be interpreted as representing a measure of the shape and degree of self-similarity of the object. Assuming this interpretation is correct, then each portion of the object should also have the same fractal dimension as long as the size of the portion lies within the self-similar range of the object. Therefore, a single determination of the fractal dimension of the object should be sufficient to characterize the object.
The inventor, however, has discovered that when each pixel of an image is assigned a fractal dimension using an equation of the same form as equation (2), but where N1 and N2 are the sums of pixel values instead of the number of pixels, the resulting gray scale fractal map of the image may be segmented simply and accurately even for low light/low contrast images. As used hereinafter, the term fractal dimension refers to the quantity, d, estimated using the equation (2) where N1 and N2 are the sums of pixel values instead of the number of pixels
The structuring element may be represented by an L�L matrix comprised of ones and zeros. The structuring element is characterized by an origin pixel and a neighborhood. The neighborhood comprises all the matrix elements that are set to one and is contained within the L�L matrix. An image is generated by calculating a pixel value for the pixel at the origin of the structuring element based on the pixel values of the pixels in the neighborhood of the structuring element. In the case of erosion, the pixel value of the origin pixel is set to the minimum of the pixel values in the neighborhood. Dilation, in contrast, sets the pixel value to the maximum of the pixel values in the neighborhood. In one embodiment, the neighborhood is coextensive with the structuring element where the L�L matrix comprised of all ones, as shown in
Referring to
The fractal dimension, dp, for each pixel in I0 is estimated from the boundary images IB1 and IB2 in step 220. The fractal dimension for each pixel may be estimated by the equation (3):
The image generated by the of dp-values is called the fractal map or fractal image. Unlike I0 where the pixel values represent a light intensity for the pixel location in the image, the pixel values in the fractal map represent the fractal dimension for that pixel location in the image.
The form of equation (3) clearly shows that the fractal dimension is estimated by taking ratios of pixel values and therefore should provide a more robust method than histogram equalization or gamma correction for distinguishing objects in low light or low contrast conditions. Furthermore, it is believed that the use of sums in N1 and N2 reduces the statistical variations that may be expected in low light conditions.
The image, I0, is segmented in step 230. In a preferred embodiment, the segmentation of I0 is accomplished by thresholding the fractal map of I0 and using the one-to-one correspondence of a fractal map pixel to the image pixel to segment the image. The threshold value may be set once by an operator prior to an automated run of a batch of samples, or may be dynamically adjusted during the automated run via the techniques described in, for example, Russ. The threshold value may be determined using a calibrated sample or, more preferably, by using a few samples from the batch.
Images 510 and 530 have been histogram equalized and gamma corrected in an attempt to visually enhance the quality of the images and allow the viewer to see the relevant objects of the images 510 and 530. In spite of these enhancements, the images still do not clearly display the objects of interest. The maximum pixel value for each image 510 and 530 are indicated in FIG. 5. The X-probe image 510 has a maximum pixel value of 74. The X-probe image 510 also shows a second object, an artifact, having a pixel value of about 36. The maximum pixel value of the Y-probe image 530 is 42. Both images 510 and 530 are low light images because the maximum pixel value of each image is much less than the gray scale range for the images, which, in this case, is 28 or 255.
The difficulty in segmenting both images 510 and 530 using a single gray scale threshold value is clear. If the gray scale threshold value is set to, for example, 60 in order to separate the X-probe signal from the artifact signal in the X-probe image, the Y-probe signal will not be detected because its pixel value is less than the gray scale threshold value of 60. If, on the other hand, the gray scale threshold value is set to a value around 30 in order to pick out the Y-probe signal, both the X-probe signal and the artifact will be segmented in the X-probe image. In order to select the Y-probe signal and reject the artifact, the threshold must be set to a very narrow range between 36 and 42. Setting the threshold to such a narrow range makes the segmentation process susceptible to many errors if the image quality is changed slightly. Unless the gray scale threshold is adjusted for each image, segmentation errors such as the ones described above are likely to occur. Adjusting the threshold value for each image, either manually or automatically, will, however, reduce the throughput rate of the sampling system.
The X-probe fractal map 515 and the Y-probe fractal map 535 shown in
In another embodiment of the present invention, an automated method for identifying male fetal cells in maternal blood is now described. A sample of maternal blood is prepared by staining the nuclear material with a dye such as DAPI following procedures known to one of skill in the art. The sample is also tagged with FISH probes targeted to the X and Y-chromosomes. High magnification (about 100�) images of a portion of the prepared sample are captured by a monochrome camera after passing through a filter that passes one of the probe signals through to the camera. The images captured through the X-probe filter are hereinafter referred to as the X-images. Similarly, the images captured through the Y-probe filter are hereinafter referred to as the Y-images. For each portion of the sample, n images, each taken at a different focal distance, are captured and stored. The number, n, is selected to ensure that the probe lies in the focal plane of one of the n images and depends on the depth of field of the objective used to capture the image and the expected thickness of the sample. As an illustrative example, if the objective has a depth of field of about 0.8 μm and the estimated sample thickness is about 7 μm, a set, or stack of n=9 images should be sufficient to ensure that the probe lies in the plane of at least one of the images in the stack.
A binary mask isolating the nucleus from the rest of the image is created in step 610. The mask is created by thresholding the DAPI signal followed by a closing operation. The threshold value is preferably set to between 1.2-2.0 times the background and most preferably set to between 1.4-1.6 times the background.
A composite image, referred to as the Max image, is generated in step 620. The pixel value for each pixel in the Max image is the maximum of the corresponding pixel values among the n images in the image stack, i.e.,
The objects external to the nucleus are eliminated in step 630 by performing an AND operation with the binary mask created in step 610 and the Max image generated in step 620.
A fractal map of the image created in step 630 is generated in step 640 following the procedure described above. In an alternative embodiment, the fractal map is generated directly from the Max image. The fractal dimension for a pixel is estimated by centering a L1�L1 structuring element on the pixel and summing the pixel values of the pixels within the structuring element to form a first sum, N1. A second structuring element of size L2�L2, where L2>L1, is centered on the pixel and a second sum, N2, of the pixel values of the pixels within the second structuring element is calculated. The fractal dimension of the pixel is estimated using the equation
In one embodiment, L1 may be chosen from the group consisting of 1, 2, 3, 4, 5, and greater than 5. In a preferred embodiment, L1 is set to L1=3. L2 is selected such that L2 is greater than L1 or, stated differently, the ratio, R=L2/L1>1. In one embodiment, R is in the range selected from a group consisting of 1-16, 16-64, 64-128, and greater than 128. In a preferred embodiment R=10.
The fractal map is segmented in step 650 by thresholding. In one embodiment, a single threshold value may be used to segment the fractal map. In a preferred embodiment, two segmented images are generated from the fractal map using a first threshold value to generate a first segmented fractal image and a second threshold value to generate a second segmented fractal image. The threshold values are preferably set by an operator before the automated analysis of the sample run. The threshold value may be optionally adjusted automatically during the automated run to compensate for sample-to-sample variations.
Objects in the segmented fractal images are shrunk to points in step 660. The shrinking operation is repeated applied to the segmented fractal image until the target objects are single pixels, referred to hereinafter as dots. Alternatively, the shrinking operation may be repeated S times where S is a predetermined number that depends on the object size and desired throughput rate.
The dots remaining after the shrinkage operation 660 should correspond to the probe signals in the Max image. As a check, the dots in the segmented fractal image are compared to the corresponding location in the Max image in step 670. If the dots represent true probe signals, the pixel value of the corresponding pixel in the Max image should be one of the largest pixel values in the Max image.
The background adjusted Max image, Mb, is generated in 720 by setting pixels in the Max image having a pixel value that is less than twice the background estimated in step 710 to zero as shown in equation 6:
A threshold for Mb is set in step 730. In a preferred embodiment, a histogram is generated for Mb. Starting at the bin containing the darkest or lowest pixel value, one or more bins are examined for a non-zero value. A bin containing a zero value indicates that no pixels in Mb have a pixel value represented by the bin. Conversely, a bin containing a non-zero value indicates that there is at least one pixel in Mb having a pixel value represented by that bin. The bins are sequentially searched until the first non-zero value is found. The pixel value represented by the bin with the first non-zero value is added to an offset and the sum is set as the threshold, T.
The offset may be determined and set by an operator before a run. The offset will depend on the quality of the images in the run but may be easily determined empirically by one of skill in the art. As an illustrative example, gray scale images 510, 530 of
In step 740, the objects (dots) identified in the fractal map are checked to confirm the existence of corresponding objects in Mb. The pixel value of Max pixel corresponding to the location, (xf,yf), where an object was detected in the fractal map is compared to the threshold, T, i.e.,
If the Max pixel is not greater than the threshold, the object is considered to be a false signal and is not counted. If, on the other hand, the Max pixel is greater than T, the object is recognized as a true signal and is counted in step 745 by incrementing a count value.
In step 750 , a check is made to verify that all detected objects in the fractal map have been compared to its corresponding Max image pixel value. If all objects have been compared, the process exits in step 760. If there are remaining objects, the process returns to step 740 using the location of the remaining object.
Count step 745 may store the count value for latter processing. In an alternative embodiment, the count value may be compared to an expected value and an error flag set if the count value exceeds the expected value. As an illustrative example, if only one probe signal is expected per nucleus, the expected value may be set to 1. As another illustrative example, if the probe signal represents the Y chromosome, the number of expected signals is either 0 (for female) or 1 (for male). The expected value may be set to 1 because a count of 2 would represent a genetic abnormality or a false positive. In either situation, the image could be flagged for further analysis by an operator.
Having described at least illustrative embodiments of the invention, various modifications and improvements will readily occur to those skilled in the art and are intended to be within the scope of the invention. Accordingly, the foregoing description is by way of example only and is not intended as limiting. The invention is limited only as defined in the following claims and the equivalents thereto.
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Midnight Dragonfly Soup Bowl
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text: It was hard to choose our meals since many things on the menu sounded good. My son had the fideo seco, my bf the pozole blanco and I had a spinach salad with pear and goat cheese. Everything was delicious! The pozole had a lot of meat and the pear in my salad had been marinated in jamaica. The... read more