Know the enemy: More data on polysorbate 80.

[Prepuce]

It's likely that polysorbate 80 is not the only demon fouling our beakers, but from SWIMs point of view it remains a mostly undefeated enemy. What is written below is presented solely for the hell of it. Neither I nor SWIP wrote any of it. It is a compilation from a variety of sources which are cited whenever they are known.

Some of the data may not be directly relevant, but for the sake of completeness and because SWIPs judgement might not be flawless) the task of determining what should and should not be included is left to the reader.

It is believed that some will find the section on detergent removal to be particularly interesting. There is also a little bonus section at the end dealing with PEG.


PP

P.S. Appologies in advance for the formatting of the tables.
SWIP worked on them several hours to translate them from a
variety of document types to plain text, only to find out
that the Hive reformats it all after it's posted in. Anyone
who is interested can fairly easily see how it ought to be anyway.
SWIP just doen't have it in him to do it all again, but has the
formatted source which could be uploaded. . .
somewhere?

============================
Polysorbate 80: miscellaneous data.

Multiple entries are separated by a slash (/)

8(e) Number: 8(e)-03636A
CBI? Submission contains confidential business information
CAP? Submitted as part of Compliance Audit Program
Submitter: DOW CHEMICAL U.S.A.

Name(s): MIXTURE:  STYRENE,HALOGENATED / DOWANOL DPM / DIPROPYLENE GLYCOL MONOMETHYL ETHER / TWEEN 80
CAS #: CONFIDENTIAL / 034590-94-8 / 034590-94-8 / 009005-65-6
Smoke point 174 C.

Tween(R) 80  [9005-65-6]
Synonyms: armotan pmo-20; capmul poe-o; Sorethytan (20) mono-oleate; Sorlate; Tween 80; Tween(R) 80; (x)-sorbitan mono-9-octadecenoate poly(oxy-1,2-ethanediyl) derivs; drewmulse poe-smo; emsorb 6900; glycosperse 0-20; glycosperse 0-20 veg; glycosperse 0-20x; liposorb 0-20; Olothorb; PEG-6 Sorbitan Oleate; POE (20) sorbitan monooleate; POE (5) sorbitan monooleate; POE(6) Sorbitan Monooleate; Polyethylene oxide sorbitan mono-oleate; Polyoxyethylene (20) sorbitan monooleate; polyoxyethylene (5) sorbitan monooleate; POLYOXYETHYLENESORBITAN MONOOLEATE (TWEEN 80); Polyoxyethylene Sorbitan Monooleate; polysorbate 80; polysorbate 80 b.p.c.; protasorb o-20; sorbimacrogol oleate 300; Sorbitan, mono-9-octadecanoate, poly(oxy-1,2-ethanediyl) derivs., (Z)-; Sorbitan, mono-9-octadecenoate, poly(oxy-1,2-ethanediyl) derivs., (Z)-; Sorbitan mono-oleate polyoxyethylene; sorbitan, monooleate polyoxyethylene deriv.;
Physical Properties
Yellow liquid. Hydrophilic emulsifier; solubilizer; dispersant; water soluble.
water sol.: 5-10 g/100 mL at 23 C

Uses
Emulsifier for soluble oil; water dispersible; oil soluble
Standard Report                                                    
8(e) NUMBER: 8(e)-03636A

===============================================================


source:

http://www.roche-applied-science.com/indbio/dia/pdf/Biocides_Buffers_and_Detergent/S167.pdf

Tween 80

Specification
Catalog No. 1 1 334 018
Poly(oxyethylene)(20)-sorbitane monooleate
Formula C64H124O27 (w + x + y + z = 20)
Molecular weight 1310
Appearance clear yellow solution in water, 10 % (w/v)
Peroxides (as H2O2)   2 ppm
Conductivity approx. 50 mS
Aldehyde  0.02 mg/ml
Stability at 4 ° C 24 months; under N2 and protected from light
Properties
Detergent type non-ionic polyethylene type
(page also shows molecular structure.)

 ===========================================

source:

http://www.surfactant.co.kr/surfactants/sorbitan.html

The Properties of Nonionic Surfactants

   GENERAL PROPERTY

Composition       Appearance      HLB      OHV      SV      AV      Color      Moisture
            (at 30¡É)                        (max.)   Gardner,    (%, max.)
                                              max.)

Sorbitan Monolaurate   Oily liquid      8.6      330~358   158~170   8.0      5      1.5
Sorbitan Monopalmitate   Solid         6.7      275~305   140~150   7.5      5      1.5
Sorbitan Monostearate   Solid         4.7      230~260   145~157   10.0      5      1.5
Sorbitan Tristearate   Solid         2.1      66~80      176~188   14.0      5      1.5
Sorbitan Monooleate   Oily liquid      4.3      198~224   143~151   10.0      8      1.0
Sorbitan Sesquioleate   Oily liquid      3.7      188~210   149~160   12.0      8      1.0
Sorbitan Trioleate   Oily liquid      1.8      56~68      172~186   14.0      9      1.0

   SOLUBILITY
Composition   Solubility (10% sol., 25¡É)
   Water   Ethanol   n-Hexane   Xylene
Sorbitan Monolaurate   H   S   H   S
Sorbitan Monopalmitate   H   D   H   S
Sorbitan Monostearate   H   D   H   S
Sorbitan Tristearate   I   H   D   S
Sorbitan Monooleate   I   S   S   S
Sorbitan Sesquioleate   H   S   S   S
Sorbitan Trioleate   I   D   S   S
        S : Clearly soluble,   H : Hazy,   I : Insoluble,   D : Slightly soluble, 

   APPLICATION
 
Fibre lubricant and softener.
Antistatic agent for plastics and other high molecular products.
Cutting lubricant emulsifier.
Dispersant for ink, pigment.
Defoamer.
Emulsibility adjustor.
Additive for cutting lubricants.
Antistatic agent for Synthetic textiles and resin.
Dyestuff solubilizer.
Emulsifier and dispersant for emulsion paints.
Antigogging agents for plastic films.

   GENERAL PROPERTY
Composition          Appearance      HLB      OHV      SV      AV      Color      Moisture
               (at 30¡É)                        (max.)   Gardner,    (%, max.)
                                                 max.)
POE(20) Sorbitan Monolaurate   Oily liquid      16.7      96~108   40~50      2.2      5         2.5
POE(20) Sorbitan Monopalmitate   Paste      15.6      89~105   43~49      2.0      4         2.5
POE(20) Sorbitan Monostearate   Paste         14.9      81~96      45~55      2.2      4         3.0
POE(20) Sorbitan Tristearate   Paste         10.5      44~60      88~98      2.0      4         3.0
POE(6) Sorbitan Monooleate   Oily liquid      10.0      134~150   96~104   2.0      6         3.0
POE(20) Sorbitan Monooleate   Oily liquid      15.0      65~80      45~55      2.2      6         3.0
POE(20) Sorbitan Trioleate   Oily liquid      11.0      39~52      83~93      2.0      6         4.8

   SOLUBILITY
      Composition   Solubility (10% sol., 25¡É)
               Water   Ethanol   n-Hexane   Xylene
POE(20) Sorbitan Monolaurate   S   S   I   D
POE(20) Sorbitan MonopalmitateS   S   I   D
POE(20) Sorbitan Monostearate   S   S   I   D
POE(20) Sorbitan Tristearate   G   S   S   D
POE(6) Sorbitan Monooleate   G   S   S   D
POE(20) Sorbitan Monooleate   S   S   I   D
POE(20) Sorbitan Trioleate   G   S   S   H
          S : Clearly soluble,   H : Hazy,   I : Insoluble,   D : Slightly soluble,  G : Gel

   APPLICATION
 
    Fibre lubricant and softener.
Antistatic agent for plastics and other high molecular products.
Cutting lubricant emulsifier.
Dispersant for ink, pigment.
Defoamer.
Emulsibility adjustor.
Additive for cutting lubricants.
Antistatic agent for Synthetic textiles and resin.
Dyestuff solubilizer.
Emulsifier and dispersant for emulsion paints.
Solubilizer for colorants.
                                                                                
Discussion

   Nonionic surfactants become water soluble by the hydration of ether oxygens of the
polyoxyethylene group. The longer chain of ethylene oxides containing ether oxygens is,
the more hydration, and consequently, the more solubility. An increase in temperature
causes the cleavage of the hydrogen bond between the ether oxygen of the ethylene oxide
group and the hydrated hydrogen to the ether oxygen.

   The depletion of water from nonionics results in the decreases of the water solubility
of nonionics. The water depleted nonionic surfactant solution, therefore, becomes turbid
and seperates into two phases including a insoluble hydrophobic precipitate. This sudden
onsetting of turbidity of a nonionic surfactant solution when the temperature is raised is
called the "cloud point". In general, nonionics having a longer polyoxyethylene chain
consequently have a higer cloud point, meaning a greater capacity to hydrate.

The Concept of HLB
  The term "HLB" was first employed by the lab staff of the Atlas Powder Co. in America.
This means the balance between the oil soluble and water soluble moieties in a surface
active molecule, and is expressed as the "Hydrophile-Liphophile Balance".  A more oil-
soluble emulsifier shows a lower HLB and a more water-soluble emulsifier shows the reverse.
HLB is a very useful method in selecting an emulsifier, but it still has several limitations
to application for every surfactant.   The HLB concept is not enough to describe all the
characteristics of emulsion.

Calculation of the HLB number from a mixture of surfactants

   The HLB number of a mixture composed of x% of surfactants of HLB A and y% of surfactants
of HLB B is obtained by the following formula.
                                              
      HLB ( A + B ) = ( Ax + By ) / ( x + y )

For instance, if 60 wt.% of POE(3) Octyl Phenol of HLB number 8 is mixed with 40 wt.% of
POE(5) Nonyl Phenol of HLB number 10, then the HLB number of this mixture becomes 8.8.
Reversely, to make the mixture of HLB number 11 which is composed of POE(15) Nonyl Phenol
of HLB number 15 and POE(2) Nonyl Phenol of HLB number 5.5, then one should mix 42 wt.% of
POE(2) Nonyl Phenol wuth 58 wt.% of POE(15) Nonyl Phenol.



 
source:

http://www.uniqema.com/products/pdf/Tween.pdf

Tween Solubilities
   Water 1%   water 10%   propylene    propylene    IPA 1%   IPA 10%   xylene 1%   xylene 10%   cottonseed    cottonseed    mineral    mineral
               glycol 1%   glycol 10%                           oil 1%   oil 10%   oil 1%   oil 10%               
80      S   S      D      D      S      S      S      I      S      I      I         I
80K      S   S      D      D      S      S      S      I      S      I      I         I
(Tween 80K is Kosher grade)


S = Soluble, clear
H = Soluble with haze, hazy, turbid
D = Insoluble, self-dispersing or self-emulsifying;
on standing, separates into distinct phases
I = Insoluble, gross separation into distinct phases
G = Insoluble, forms gel

Formulation Example
------------------------------------Formulation example
Paraffin wax example
Part A Paraffin wax 50
Span™ 60/Tween 60 (1/1) 5
Part B Water 45
Preparation: Combine Part A and
mix with water to form emulsion

===================================================

Source:

http://www.ufrgs.br/ppgbcm/artigo/bmestre.pdf

Tween 80 is an ester of palmitic acid which has 18 carbons. LB agar containing
1% of Tween 80 (Sigma Chemical Co., St. Louis, Mo) and 1 mM CaCl2 was used for
the selection of lipase clones. Tween 80 can be cleaved by lipases to produce a
fatty acid and an alcohol. The presence of Ca2þ causes the formation of an insoluble
fatty acid salt which is seen as a white precipitate around lipase positive colonies.

[Prepuce]

================================================

Source:

http://www.piercenet.com/Objects/View.cfm?type=Page&ID=D7FFC384-8E49-4DB4-BC2B-44375CA65558

Detergent Removal from Protein Samples    
 
  
Proteins that are bound strongly to the hydrophobic portion of cell membranes require
detergents to facilitate dissociation. Because detergents can interfere with many
downstream applications, detergent removal is necessary for such applications. Several
different detergent removal methods are available: gel filtration, dialysis, Extracti-Gel
D Detergent Removing Gel, SDS-Out SDS Precipitation Reagent and ion-exchange chromatography.

Gel filtration (e.g., Pierce D-Salt Desalting Columns) removes detergents by size exclusion.
Detergent monomers remain in the internal pores of the gel, and the protein is free to
pass through the void volume. Pierce offers desalting columns with Excellulose, dextran
and polyacrylamide matrices.

Dialysis also removes detergents by size exclusion, but the dialysis process takes more
time than gel filtration. Pierce Slide-A-Lyzer Dialysis Cassettes (U.S. Patent # 5,503,741),
which can reduce dialysis time and provide excellent sample recovery, are available for
several sample volumes and with 10 kD, 7 kD and 3.5 kD molecular weight cutoff membranes.
Pierce offers Slide-A-Lyzer MINI Dialysis Units (U.S. Patent # 6,039,871) for dialyzing
very small (10-100 µl) sample volumes.

Alternatively, the Pierce Extracti-Gel D Detergent Removing Gel and the SDS-Out SDS
Precipitation Reagent and Kit are quick, convenient methods for removing detergents
that cannot be removed by either dialysis or gel filtration.

Ion-exchange chromatography will remove nonionic and zwitterionic detergents. In this
method, the protein is adsorbed on the resin and the micelles pass through. Changing
either the ionic strength or the pH can then elute the protein.

Because the physical properties of detergents can affect how easily they can be removed
from a sample, their properties will have an impact on which removal method is chosen.
The critical micelle concentration (CMC) of a detergent is the concentration at which
micelles form. CMC is also an indicator of the strength at which detergent binds to
protein; i.e., low values indicate strong binding and high values indicate weak binding.
It is a numerical value of hydrophilicity. When choosing between dialysis or gel filtration
for detergent removal, the detergent concentration needs to be below the CMC because
only detergent monomers can be removed by these methods. However, detergents with
micelles of low molecular weights (e.g., CHAPS and Octyl-ß-Glucoside) can be removed
by dialysis or gel filtration even when the CMC has been exceeded.

The table below indicates the detergent concentrations that can be removed by dialysis
or desalting. When detergent removal is desired, it is better to choose a detergent with
a high CMC and a low molecular weight (e.g., Octyl-ß-Glucoside). Conversely, detergents
with a low CMC and a high molecular weight (e.g., Triton X-100) are very difficult to
remove from solution.


Nonionic Detergents   Molecular     MW of    CMC    CMC       Pierce Product #
Triton X-100      Weight(MW)   CMC      (mM)   (% w/v)
            628      90 kD      0.24   0.0151   28314
Triton X-114
            537             0.21   0.0113   28332
NP-40
            602      90 kD      0.29   0.0175   28324
Brij-35
            1225      49 kD      0.09   0.0101   28316
Brij-58
            1120      82 kD      0.077   0.0086   28336
Tween -20*
            1228             0.06   0.0074   28320
Tween -80
            1310      76 kD      0.012   0.0016   28328
Octyl-ß-Thio-glucopyranoside
            308             9   0.2772   28351                     
Anionic Detergent                   
SDS
            288      18 kD      6-8   0.1728-    28312
                           0.2304                     
Zwitterionic Detergents                   
CHAPS
            615      6 kD      8-10   0.4920-    28300
                           0.6150
CHAPSO
            631      10 kD      8   0.5048   28304

*The aggregation number in micelles has not been determined for Triton X-114,
Tween-20 and Octyl-ß-Thio-glucopyranoside.

Triton X-100, Triton X-114 and NP-40 detergents are used to solubilize membrane
proteins under non-denaturing conditions. Because these detergents have low CMCs,
they are difficult to remove by dialysis or gel filtration. Extracti-Gel D Detergent
Removing Gel works well to remove these detergents from solution.

Brij Detergents have varying lengths of a polyoxyethylene chain attached to a
hydrophobic chain. Brij-58 is a cetyl ether (C16), and Brij-35 is a lauryl ether
(C12). Brij-35 is commonly used in high-performance liquid chromatography (HPLC)
applications and to prevent nonspecific binding to gel filtration and affinity
chromatography supports. Brij-58 has been used in the incubation buffers for nick
translation of ribonucleotides or deoxyribonucleoside triphosphates. Brij Detergents
are difficult to remove from solution by dialysis, but they may be removed by Extracti-Gel
D Detergent Removing Gel.

Octyl ß-Glucoside and Octyl ß-Thioglucopyranoside are nondenaturing, nonionic detergents.
These detergents have been useful for solubilizing membrane proteins. Because the
detergents' micelles have small molecular weights, they are dialyzed easily from
solution even at high concentrations. Dialysis of a 43 mM Octyl ß-Thioglucopyranoside
solution for 6 hours using 200 volumes of buffer can remove 95% of the detergent.
Extracti-Gel D Detergent Removing Gel will also remove these detergents from solution.


Tween-20 and Tween-80 are nondenaturing, nonionic detergents that are polyoxyethylene
sorbitan esters of fatty acids. They are used most commonly as blocking agents in
biochemical applications and to reduce nonspecific binding to hydrophobic materials.
These detergents are difficult to remove from solution by dialysis, but Tween-20 can be
removed by Extracti-Gel D Detergent Removing Gel. Alternatively, detergent may be removed
by ion-exchange chromatography.
(back to top)

Sodium dodecyl sulfate (SDS) and SDS-Lauryl have a polar anionic sulfate group at one end
of their structures and a straight chain nonpolar region at the other end. The dual polarity
of SDS allows it to solubilize proteins by imitating their structure. The CMC of SDS is
dependent on salt concentration. The CMC for SDS is 8.0 mM in water, 3.5 mM for 10 mM NaCl,
and 1.4 mM for 100 mM NaCl in water. Although SDS has a high CMC and a low CMC molecular
weight, it tends to bind tightly to cationic molecules because of its anionic nature. SDS
that is bound to molecules cannot be removed by dialysis.
 

Pierce Extracti-Gel D Detergent Removing Gel has been used successfully to remove nonprotein-
bound SDS from solutions. One milliliter of gel can remove up to 80 mg of SDS in a 100 mM
phosphate buffer, pH 7.0. For small samples, the SDS-Out SDS Precipitation Reagent is a
convenient method of SDS removal. However, these methods will not remove SDS that is bound
to protein.


CHAPS and CHAPSO have been used to solubilize intrinsic membrane proteins and receptors and
to maintain the functional capability of the protein. These detergents are removed easily by
dialysis, gel filtration, Extracti-Gel D Detergent Removing Gel or ion-exchange chromatography.




==========================================================

[Prepuce]

PEG

   GENERAL PROPERTY
 
Composition   Av. Molecular weight   Appearance   OHV      Melting point (¡É)
PEG 200   190 ~ 210         Oily liquid   534 ~ 590   
PEG 300   285 ~ 315         Oily liquid   356 ~ 392   
PEG 400   380 ~ 420         Oily liquid   268 ~ 294   
PEG 600   570 ~ 630         Oily liquid   178 ~ 196      17 ~ 22
PEG 1000   950 ~ 1050         Solid      108 ~ 117      35 ~ 40
PEG 4000   3800 ~ 4400         Solid      22.5 ~ 29.5      53 ~ 58
PEG 6000   5600 ~ 6400         Solid      17.5 ~ 20      55 ~ 60
PEG 8000   7500 ~ 8500         Solid      13 ~ 15      58 ~ 65


   CHARACTERISTIC

Highly compatible to various kinds of organic compounds.
PEG is compatible with most organic solvents, and has excellent water-solubility.

High boiling point.
Effective as a non-volatile solvent because of its high boiling point.

Easy control of the degree of condensation.
As the degree of condensation is properly governed, PEG has a broad spectrum of products
ranging from rigid solids to oily liquids.

Controllable hygroscopic property.
Every PEG type surfactant has excellent hygroscopic property, and this is controllable by
adjusting the degree of condensation. As the degree of condensation increases, the
hygroscopic property is degreased.

Less toxicity
PEG is characterized by less toxicity and less skin irritation. There is no damage
in case of contact with skin or lips.


   APPLICATION
 Rubber industries
 As PEG has good water-solubility even in its solid state, it is used as a releasing agent
for foam rubber, latex rubber, etc. PEG is also used as an airpack releasing agent, inner
releasing agent, and lubricant in the tire industry.
 
Textile industries
Because PEG has a broad range of applications, it is used as a softener, antistatic agent,
scouring agent, sizing agent, dyeing auxiliary, etc. in the textile industry.

 Paper industries
 PEG has a softening effect on paper.

 Metal industries
 PEG improves grinding effects by being added to the grinding powder and it is used as a raw
 material for anticorrosion and the cleaning of metals.

 Wood industries
 By dipping wood in a PEG solution in advance, contraction and cracking of wood can be avoided.

 Phamaceutical industries
 PEG is used as a base materials of oinments.

 Cosmetic industries
 PEG can be used in shampoos, hand creams, lotions, etc.

 Resin and Paint industries
 PEG is used as the raw material of paints and resins.

[wareami]

Antistatic agent for plastics and other high molecular products.

Hahaha! They put that in there to keep squiddy from sucking the Gaak UP with his statically charged balloon
Which BTW was simply genius.

It's getting to the point...ware...
"incorporating oils into extraction may be an attractive proposal at some point."
How many thought I was going to say "I'm No Fun An-E-More"?

Thanx Prepuce for the outline and info.
Great Info in that data!

[Coitus]

I think the polysorbate 80 is there strickly as a presertive. They put the shit on just about everything you eat.

[UncleFester]

Just another polymer with easily cleaved ester links, and the monomers are easily separated from sudo chemically. The jig is up for the gakkers.

[Prepuce]

"Hahaha! They put that in there to keep squiddy from sucking the Gaak UP with his statically charged balloon
Which BTW was simply genius."

SWIP must have missed that one. Not that he's particularly interested in what anyone wants to suck up their baloon, but as enquiring minds don't have much choice in their need to know, he's going to have to look it up.

Glad you found the information interesting. SWIP certainly did as well. The more he thinks about it the more it starts to add up. The JD, for example. Obviously SWIW didn't need to be told that heavy metals do as they do! But now the whole dueling-PH thing starts to make sense, and it looks like killing the PEGs of whatever flavor needs to be the first step, whatever your process, if yeilds are to get better.

SWIPs current crackpot theory is that polysorbate has been the big problem for some time. As you and Geez observed early on, it doesn't take much of it to foul things up. Although it didn't turn out to be very practical, (although the jury's still out on that) SWIPs adventures in sublimation showed him that in spite of his best efforts he wasn't getting things as clean as he thought. Just a drop or two of this nasty oil is too much in his favorite rxn dream.

PP

[Osmium]

> Just another polymer with easily cleaved ester links

No, it's ether links, and they are very hard to cleave.

[UncleFester]

My Merck tells me that the polymer is made up of "an oleate ester of sorbitol and its anhydrides copolymerized with approx 20 moles of ethylene oxide for each mole of sorbitol"
This was listing 7559 in that ed...show me your ref...this is easily broken down just as Granny can make Lye soap...Fester

[amalgum]

Ethylene oxide is an ether, is it not?  Maybe HBr cleavage or something more radical like pyridine and microwaves, or H2SO4 in acetonitrile, and heat?

[wareami]

Prepuce: I was referring to this thread

Post 385115 (missing)

(SQUIDIPPY: "Squiddly's "Poly Magnet" ??", Stimulants)
I shared in Squiddy's excitement at the proposal until it was discovered that the inclusion of some shifty polymers made the proposal obsolete.

Merck 13th listing for Polysorbates
Monograph Number:  7664
Title:  Polysorbates
Additional Names:  Polyoxyethylene sorbitan esters;  POE sorbitan esters
Literature References:  Nonionic surfactants derived from sorbitan esters, q.v.  Comprehensive description:  P. Becher, "Polyol Surfactants" in Nonionic Surfactants, M. J. Schick, Ed. (Dekker, New York, 1967) pp 247-299.  Description of prepn and uses:  L. R. Chislett, J. Walford, Int Flavours Food Addit. 7, 61 (1976).  Pharmacology of polysorbate 80:  R. K. Varma et al., Arzneimittel-Forsch. 35, 804 (1985).  Determn in foods:  H. Kato et al., J. Assoc. Off. Anal. Chem. 72, 27 (1989).

Derivative Type:  Polysorbate 80
CAS Registry Number:  9005-65-6
Additional Names:  Polyoxyethylene (20) sorbitan monooleate;  POE (20) sorbitan monooleate
Trademarks:  Emsorb 6900 (Emery);  Liposorb O-20 (Lipo Chem.);  Monitan (Ives);  Sorlate (Abbott);  T-Maz 80 (Mazur);  Tween 80 (ICI)
Properties:  Lemon- to amber-colored, oily liquid.  d 1.06-1.09.  Viscosity (25°):  300-500 centistokes.  Very sol in water; sol in alcohol, cottonseed oil, corn oil, ethyl acetate, methanol, toluene.  Insol in mineral oil.  pH of 5% aq soln between 6 and 8.  LD50 in mice, rats (ml/kg):  7.5, 6.3 i.p. (Varma).
Density:  d 1.06-1.09
Toxicity data:  LD50 in mice, rats (ml/kg):  7.5, 6.3 i.p. (Varma)

Use:  As emulsifiers and dispersing agents in medicinal products; as defoamers and emulsifiers in foods.  Pharmaceutic aid (surfactant).

[WizardX]

http://www.heterene.com/products/index.html#polyoxyethyleneesters

http://www.camfordinfo.com/Prod.htm

http://www.wholefoods.com/healthinfo/polysorbate80.html

Polysorbate 80 & Polyoxyetheylene Sorbitan Fatty Esters
Polyethylene sorbitan monooleate (Polysorbate 80) functions as an emulsifier, holding water and oils in suspension, in various foods and supplements. Polyethylene sorbitan monooleate is derived from the fatty acids from vegetable oil that has undergone "esterification," a chemical process that changes the oil molecule, which keeps other ingredients from separating.
Polyethylene sorbitan monooleate (Polysorbate 80) belongs to a general class of emulsifiers called Polyoxyetheylene Sorbitan Fatty Esters or Polysorbates. Other common polysorbates include polysorbate 20 (polyoxyethylene [20] sorbitan monolaurate) and polysorbate 65 (polyoxyethylene [20] sorbitan tristearate).

Polysorbates are made by reacting ethylene oxide (a gas) with sorbitan esters (derivatives of sorbitol, another sugar alcohol similar in function to mannitol). Polysorbates are generally used in combination other emulsifiers such as mono- and diglycerides or sorbitan monostearates for various purposes such as to disperse flavors and colors, to make essential oils and vitamins soluble and to improve volume and texture in baked goods. Typical Usage level ranges from 0.05 to 0.10 percent.

[UncleFester]

To smack the polymer it only needs to be cleaved at the sorbitol link...then it is useless and easily dealt with by solubility...ester polymer...and the ethylene section falls by the wayside during cleanup...my kids have a foam bonk stick to whack stupid people, or mostly each other. This site needs a bonk stick.

[Prepuce]

One of the above references did say, "Tween 80 can be cleaved by lipases to produce a fatty acid and an alcohol.", but it didn't say how to go about it. (Anyone have any lipases on them?) SWIP did a rather exhaustive search but was not able to gather that information.

Another reference says that it can easily be broken down by oxidation, and cites H202 as a means. SWIP isn't sure what that would do to pfed, but he's not planning to try it :-)

Finally, there was another and SWIP doesn't recall where he saw it, that said something to the effect that tween 80 doesn't tolerate strong bases very well. The first thing he tried after reading that was to nail some polysorb with some strong NaOH, but with no evident effect.

The only thing that he has found that seems to really break it down is japan dryer, and he still doesn't really understand the mechanism. It doesn't seem to do much of anything by itself, but mix it with some xylene and the detergent breaks down immediately. (Would be nice if there was an alternative to using a heavy metal, though.)

If you don't get the polysorb right away, it plays games with the PH of the solution containing it, and is the reason you can gas till the cows come home and not be able to pull all the pfed out. As a detergent, the polysorb decides your precious pfed it dirt, and locks hold of it. Where the pfed goes, it goes, and vice versa, and what little of the hcl you do pull will bring it's guest along uninvited. But if you do the JD thing first off and follow that up with several acetone rinses, you get most of it (all of it?) out, and the PH blues are history.

On the other hand, what would we do without PEGs as lubricants for our abrasives?

Ah, these damn detergents. Can't live with 'em, can't live without 'em!

PP

[elfspice]

strong base hydrolysis will kick out all those oleic acids attached to the sorbitol. The sorbitol is the molecule vulerable to ether bonding, the fatty acids are unsaturated but only contain one functional group which attaches to the alcohol in esterefication.

I think the result of doing this would be the sorbitol/ether linked chains, and a bunch of free fatty acids. It would be helpful to some extent, the ffa's would float to the top and the polyalcohol-ether chains would probably be simple enough to eliminate, not least of all because of its high molecular weight. I would think pfed.hcl whatever would become relatively insoluble in the result... and washing with nonpolars would make this easier... just acidify again after hydrolysing it. and defatting should remove most of the nastiness.

hydrolysing esters can take a bit of time... half an hour to an hour in a small flask, cooking up soap in a large pot and all that, it can be up to 3 hours before the reaction is complete.

[Osmium]

Here's the chemical formula of Tween80:


With NaOH you will be able to remove the oleic acid on the bottom (that C18 carbon chain with the double bond). The rest of the molecule will be unaffected by NaOH. So there.

The solution: CHRO-MA-TO-GRA-PHY. I told you so, but nobody wants to listen.

[UncleFester]

You are invited to check out the experimental section of the Deconstructionist Thought thread. It has been years since sudo crystals came out so nicely directly from HCl gassing.

[elfspice]

I say this because nobody seemed to read the info on the msds at the top which said it's insoluble in water, and sparingly soluble in pet ether, ethanol etc.

how is it gonna be a problem anyway? I would think it would filter out, if not in a simple filter, then in a column of celite or sand or someting.

[Scottydog]

If you don't get the polysorb right away, it plays games with the PH of the solution containing it, and is the reason you can gas till the cows come home and not be able to pull all the pfed out.

So instead of Swim paying attention to some unlisted methacrylate supergakk, he should have been focusing on what IS actually listed on the box?  

In reference to:

Post 491712

(Scottydog: "Problem gassing generic 120's", Stimulants)

Theoretically, after using a tetra trap extraction to pull pseudo into Xylene, drying the NP solvent and then gassing. Polysorbate 80 hitches a ride and bonds with the pseudo, causing the PH problem.

Elfspice says it is insoluble in water. Does that mean that "in the end" a simple dissolve and filter of the crude pseudo is all that is required or does Swim's added titration step (using fresh xylene and water) take care of it in the process? The tween stays behind in the xylene?

With perrigogo generic 120's, the PEGs and dry matrix inactives are dealt with first, once the crude pseudo is isolated from these, then water can bee used to later deal with the polysorbate 80?

Or once bonded with the pseudo, it isn't that simple?

If the pseudo can bee cleaner, Swim is always open to improvements.

[Prepuce]

SWIP hopes that everything he says on this topic is understood to include the phrase, "as far as he knows." He is not a chemist!

What SWIM thinks is happening is that the polysorb--advertised to hold the PH in the basic range--does just that, very well thank you. If it isn't removed right away, every chance it gets it will be turning your pfed into freebase. From there it leeches into any nonpolor you douse it with, and you either throw it away or litter your bench with 100 beakers because they may contain something you want.

If you don't remove it, polysorb follows the pfed into the reaction. And if it can withstand being gassed and still keep pfed based, and it evidently can, imagine what it does with HI. That is how SWIP believes it fucks the reaction. It neutralizes HI.

Therefore SWIP says you've got to remove it first thing. From there just follow whatever routine you like. Certainly there are other gaks that will still be waiting for you.

"Elfspice says it is insoluble in water. "

SWIP didn't see that, but it's not correct. Poloysorb 80 is soluble in H2O. It is supposedly not soluble in xylene, but SWIP has  seen little evidence that it can be pulled with xylene. In fact he's pretty sure that it absolutely cannot be pulled in that way.

Even if it could be pulled as SWIS suggests, if you left it mixed in until the end you're going to be dealing with the PH shuffle the whole time.

SWIM did notice the other day that povidone is reportedly insoluble in H2O.

PP

[Prepuce]

Elf: Sorry to have brought on that exasperated sigh, but thanks for spelling it out. SWIP will report back on his findings.

He should have been familiar with the terminology, but with no tests in this class it's easy to allow memory of such data to slide away.

Os: SWIP has been harping on chromatography, he thinks, longer than you have. He has even made a few sad, abortive attempts. The more he learns the more complicated it all sounds, however. Suppose, for example, we found just the right mix of materials to seperate out polysorb. Everyone would start using it until they stick something new in the mix. Then it would all start again.

That's what we do now, but column chromatography looks like a fairly painstaking, complicated process. If it could really be done effectively with something like diatomaceous earth as a substrate, a florescent tube, and an eluent that wasn't any more exotic than what's found at the hardware store it would be great. Any suggestions along those lines will be gratefully accepted.

None of the research he did on polysorb 80 spoke at any length on CC, but SWIPs impression is that it is one of the more difficult substances to deal with. He might be wrong, but for now it didn't look like it was going to be an expedient means.

PP

[auntyjack]

what items do you need for column chromatography....i've got a column!!.....no, a real one....

[Rhodium]

See the chromatography section at my page.

[ADDkid]

The polysorbate is a long fucking carboxylic acid right?  Then if you put the P-fed powder in a sep. funnel (Don't extract with any solvent at all), and put either ether chloroform, toluene, or one time with each, and and add enough water to disolve the p-fed, then make the shit very strongly acid, like pH of 1 and below. Then all the acid(carboxylic acid) should go to the organic layer, well maybe not with chloroform, not sure. Isn't Carboxylic acids neutral in strong acid solutions, and since it contains amines, it is not in strong acid solutions to begin with. I also read that gak is put in the pills in both salt form and organic form to make it more difficult.

[Rhodium]

The polysorbate is a long fucking carboxylic acid right?

No, it is an ester of a C18 fatty acid (oleic acid) and a behemoth-sized alcohol. See

Post 501313

(Osmium: "Here's the chemical formula of Tween80: ...", Stimulants)

(the oleic acid is by mistake drawn as oleyl alcohol instead in that picture though. Imagine a carbonyl next to the oxygen bridge for completeness)

[Osmium]

Let me repeat it, removing that C18 chain by NaOH hydrolysis will not significantly alter the surfactant/gaak properties of the residual big ass molecule. You will still be fucked with that shit being present in your precursor extraction.

[ADDkid]

Even if it is an ester, any ester in water and proton source can be turned into a carboxylic acid right, does this including fatty acids?

[Rhodium]

Yes, but as Osmium says, it's still the alcohol which is the problem.

[ADDkid]

Rhodium have your looked at my Adderall extraction post? I understand the problem now, however I have notice a big drop in gak when I just extracted with water and added a mineral acid, to acheive a pH of 1 or below, then I put my N.P. Sovlent in the sep. funnel, to remove any gak.  I then took that layer and I let it dry on a pyrex dish to see what gak was present.  NO doubt, the acid addition in the first part, push a shit load of gak to the N.P. layer. I belive this to be mostly carboxylic acids. Since I mention the adderall extraction,

P.S. I might have been wrong to assume that the shit left in the foil (adderall) was salt. Is the HCL a less smokeable form then sulfate, because of dipole forces.  I am not quite sure why they use sulfate, is it better for aborbtion?

[embezzler]

since the links are ether then the gaak can be broken own by HI and heat correct? the gaak would seem to work also by depleting the HI for the desired reduction.

i just came across this in a txt book while revising.
as an example:

CH3CH2OCH(CH3)2 + HI ->(heat) ->CH3CH2I + HOCH(CH3)2

perhaps this is not the case for our gaak maybe a better bee can shed some light on this how likely is this mode of action? anyone got more info on the reaction mechanism or conditions (how much heat)?

[Rhodium]

since the links are ether then the gaak can be broken own by HI and heat correct? the gaak would seem to work also by depleting the HI for the desired reduction.

Yes, that is a real possibility. And as the product of that ether cleavage is ethylene glycol, it can in turn deplete even further equivalents of HI, see

Post 499279 (missing)

(Rhodium: "Pop Quiz: Why is ethylene glycol a bad idea?", Stimulants)

[embezzler]

deconstructing this isnt going to be enough is it? chromatography or distillation seem the only options now.

breaking this own could leave us with a bigger problem then we would have with it intact, the high relative mol weight difference(between this and ephedrine) would lead one to assume chromatography would be made easier than with dozens of unknown byproducts.

[elfspice]

I'm inclined to think that one should exploit the fact they're putting such goddamn large molecules to fuck with extraction, and use heat to superheat the ephedrine so that it can be crystallise on a cooling surface. Under vacuum would probably be a good idea, to reduce pyrolysis.

Some kind of pre-extraction would help of course.

I wonder how they could defeat that... they would have to make a binding compound which is hard to chemically and thermally separate. If they make something which defeats molecular distillation i think they probably deserve a nobel prize for achieving it despite the vast amount of problems working against such a compound being found. Ephedrine is a tough molecule, so the binding system would have to be at least as tough.


oh, another vague possiblity - what about using osmosis somehow. I know that this has been explored in the tyvek tea bag method to some extent. And there's always the idea of adsorbing the stuff onto an ion exchange matrix and fractionating the adsorbed materials via progressive elution with increasingly stronger alkaline solution.

[UncleFester]

You overestimate the opposition. After hydrolysis, the goods is separable easily from the gak. Don't build an imaginary mountain for yourself. They are working from off the shelf pre- approved additives.

[elfspice]

well, i think it was me that said hydrolysing the ester will change solubilities, and fester's experiment proves it.

as for overestimating them, there might still be approved food grade additives out there, or a novel combination which creates a little cage to hold the molecules in, and that's all i was meaning by what i said. Those kinds of defenses probably can be violated through using methods involving adsorbing the gak laden nectar (that's the right name for the precursor for honey isn't it?)... so they don't really present any ultimate threat...

as fester points out, they are hamstrung by the FDA approving the compounds that might do it but just happen to be highly toxic, and added to that, when it comes down to it, they cannot do anything that would interfere with absorption through the stomach. Thus methods connected with the kinds of processes that happen in the stomach and small intestines (which does a nice acid/base/enzyme combo attack which renders all gaks null and void) - these must always work, and therefore, there is no way to stop it happening short of taking them off the market.

thinking of the chemistry of absorbing them, isn't the main method that things get through the stomach walls into the bloodstream some kind or kinds of osmosis through special membranes? What about some kind of polymer fabric which has electrical properties which permit polar substances to cross but don't let less polar substances...

hell, has anyone thought of using a phase separating filter (silicone impregnated) which only lets polar compounds through? There's probably a readily available compound which can be soaked into paper that will do the job better than any tyvek tea bag.

[Prepuce]

"I'm inclined to think that one should exploit the fact they're putting such goddamn large molecules to fuck with extraction, and use heat to superheat the ephedrine so that it can be crystallise on a cooling surface."

Elf: SWIP has had success in just extracting with methanol, basing the mixture with a little washing soda (or even in just using the base already resident in 120's), then then carefully heating the bubblegum-like mass in a flask. Into the flask was inserted a test-tube, wrapped the top 1/2 inch or so with a strip of rubber from an inner tube, until it made a nice sealed fit with the neck of the flask. The rubber was then completely covered with teflon tape. After filling the tube with crushed ice, the flask was carefully heated just to the point that a vapor began rising from the mass at the bottom. This was continued, along with replacement of the melted ice and removal with an eye dropper of the water, until no more vapor was produced. It went a little faster when a fan was placed to blow on the outside of the flask, keeping it a bit cooler.

The flask was allowed to cool for several minutes, and then the crystals clinging to the sides of the flask and to the test tube were gently shaken, then scraped, into a beaker.

It's a time conuming and messy process, but yeilds are very clean. The key to the process is to not let the flask get too hot, or the nasty gaak will vaporize along with the pfed fb.

PP

[Prepuce]

"hell, has anyone thought of using a phase separating filter (silicone impregnated) which only lets polar compounds through?"

As SWIP understands it, polysorb has one "end" that's positive and the other "negative" (that's a very crude explanation, but the best SWIP can do without looking it up. It's all in this thread anyway.) Another way he has seen it described is to say that one end of the molecule is attracted to polar solvents and the other to nonpolar. So the net effect is that it grabs hold of the pfed, keeps it mostly basic enough to stay in the fb form, and tends to hold it in suspension in whatever liquid it's combined with. Put it together with two liquids, like H3O and xylene, and you get a nice emulsion that's nearly impossible to deal with.

PP

[elfspice]

i always wondered whether sublimation recrystallisation would work on these things...

here's some info on the use of this shit to encapsulate proteins in emulsions:

http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?cmd=Retrieve&db=PubMed&list_uids=10100311&dopt=Abstract

it's good at it.

I would wonder whether it would in fact be possible to defeat sublimation recrystallisation... how many substances that are fda approved (btw, i am appalled to read in chemfinder's entry that polysorbate is a 'toxic food preservative') have the same BP as ephedrine that would also be hard to separate via other methods afterwards... sounds like a good research project for someone who's got some time on their hands

i wonder what is next in the gak war. I know they put phentermine adsorbed onto ion exchange resin beads to make them hard to get off, but i imagine that would just take a long heating to extract.