Tlc Mystery
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The typical eluent Tarantino Movies TLC is a mixture of an apolar solvent typically hexane or pentane and a polar solvent dichloromethane, diethyl Tlc Mystery or ethyl acetate. By adding Et3N to your eluent, you remove all of them and your compound will elute freely! The recipe for this stain is really easy: Weigh g of vanillin, dissolve it mL of ethanol, and add 2. TLC still aired educational programs such as Paleoworld a show about prehistoric creatures Die Konkubine, though more and more of its programming began to be devoted to niche audiences for Bambi 2019 Gewinner regarding Stimpy like home improvement HomeTime and Home Savvy were two of the firstarts and crafts, crime programs such as The New Detectivesmedical programming particularly reality-based shows following real patients through the process of operationsand other shows that appealed to daytime audiences, particularly Sprüche Halloween. If I had to choose one it would be phosphomolybdic acid. And we'll do that with all our kids. TLC fans wasted no time in letting the network know their feelings about sMothered. Tlc Mystery Navigation menu Video
verflucht übersinnlich und unerklärlich staffel 8 folge 12 bekenntnis aus dem jenseitsEiner der spannendsten Kriminalfälle der amerikanischen Geschichte wird hier aus neuen Perspektiven beleuchtet. Jason Payne-James die letzten Tage prominenter Todesopfer.
Dem besten Bäcker winken Ein Mädchen mit vier Armen oder ein Kind mit extremer Körperbehaarung — es gibt die seltsamsten Krankheitsbilder.
Ärzte versuchen mittels moderner Medizin die Leiden zu lindern. Der Zoodirektor und die Tierpfleger zeigen ihren Arbeitsalltag und stellen internationale Tierschutzprojekte vor.
Perfektes Backen, Füllen und Dekorieren sind nur Grundvoraussetzungen. Die Märchen von der bösen Stiefmutter dürften bekannt sein.
Die Cake Hunters können hier helfen. She decided to open up on social media about them and fans were very surprised. In a recent post on social media, Larissa posted a picture of herself when she was pregnant.
But, once I am really tired of all these rumors and in respect to my followers, I will make a brief statement about what happened in my past.
We lived together for two years and had a son, the relationship did not work out, we had a very bad break up. Once the father was not paying child support and my family were not talking to me, I found myself, financially and emotionally unable to take care of my son.
I spent all my savings and I tried everything to find a job, but in Brazil as everyone knows, life can be very hard sometimes. For this reason, I decided to let his aunt adopt him, she was always there for me and she loved him very much.
This decision still breaks my heart today and it is a very delicate matter to me. From fraction 5 to 10 , we only have compound one, pure.
We can mix these fractions, concentrate them, and we will have pure compound 1. Fractions 11 and 12 , have a mixture of the two compounds.
Fractions 13 and 14 have pure compound 2. If we also need this compound, we will just concentrate them together as well. As you can see, TLC is extremely important for both reaction monitoring and product purification , the two cornerstones of any synthesis laboratory.
If you have access to a GC-MS gas chromatography-mass spectrometer or LC-MS liquid chromatography-mass spectrometer , you can analyze quickly all the different fractions, and know the molecular mass of the compound s present on each of them.
Basically this machine automatically scraps off individual spots on an eluted TLC, and makes an MS analysis, so you can check the molecular masses present on of each spot of the TLC in usually less than a minute.
Using an eluent which gives an Rf of 0. If you have two compounds that are very close together in Rf, this might not be enough. Column bands are like much much wider TLC spots, especially as we scale up the purification.
Imagine that typical TLC that you overload with sample and you get two big unresolved overlapping spots.
That is a closer picture to what is actually happening in your column chromatography. For this reason, sometimes an Rf of 0.
If spots are separated by less than 0. Another cool trick to enhance this kind of purification is using thicker columns, this helps a lot with separation.
On the flip side of the coin, sometimes your compound of interest just flies on TLC using certain solvent mixture, giving an Rf of 0. You will have to spot reaction mixtures, or reference samples in your TLC using capillary tubes.
You can either buy them, or make them yourself. The commercial ones I use on a daily basis, usually last for months before breaking, if you are careful enough.
But you can make thin capillary tubes out of thicker glass tubes, you just need to heat them up and then pulling.
For this, you can either use thicker capillary tubes or glass Pasteur pipettes. Explaining the method for heating and pulling will sound more complicated than it actually is, just take a look at this short but on-point video:.
As you can see is not terribly complicated, and it can even be a nice experiment for undergraduate labs. Just be careful with the flame or other heating source that you use!
Avoid using open flames in the lab if you have alternatives. So, there are actual chambers designed for running TLC, and they are just great, such as these from Fischer:.
The beauty and simplicity of this technique is that you can use it in basically any situation! It is worth mentioning here that this is another key for a good eluent chamber: You need the atmosphere as saturated as possible.
This can be detrimental for the separation, so always ensure that your chamber is a reasonably closed system. As you can see in the picture above, you can also put a piece of filter paper inside the chamber a while before eluting your TLC.
The solvent will ascend through the filter paper as well by the same principle than through the TLC , helping a lot in saturating the atmosphere inside the chamber with the eluent.
This will make the eluent go up the TLC plate in a much more even manner. Also, be patient, leave the eluent in the chamber with the filter paper for a while before eluting you plate!
Finally, the more practical low-cost alternative, in my opinion, is just using a glass tar with a screw cap, like the ones you get you jam, or other edible stuff in!
Silica gel SiO2 is slightly acidic, so certain compounds are quite sensitive to these acidic conditions. Many times this does the trick, but in other cases is not enough.
For those cases, there are alternative stationary phases such as neutral alumina Al2O3. Maybe your target compound does survive in alumina and you can use it for both TLC and flash column chromatography purification.
Typical silica gel stationary phases are very polar, and you elute the plate with a solvent systems that is much less polar than SiO2.
This works wonders form most typical organic compounds. For these cases, we can use reverse phase chromatography , in which the stationary phase is apolar it will retain polar compounds much less , and you will use polar solvents, such as MeOH, as eluent.
Very polar compounds, such as oligopeptides , can literally fly on reverse phase. But sometimes although very few times, we have to say they are the only way to go, so keep in mind that these alternatives exist!
Finally, I have to mention that simple filter paper can be used as stationary phase. Separations are going to be bad, and you will get poor visualization.
But if you have colored compounds, you can still see some separation. As a matter of fact, my first TLC experiment was just spotting a solution of spinach extract on filtering paper, and eluting it with acetone.
There is no use in running a TLC if you cannot see the spots of the different compounds on your mixture.
You can see the spots right as they elute up the plate! This is common with highly conjugated compounds such as polyaromatics, or polyenes , and with organometallic compounds, such as ferrocene derivatives.
These compounds are great because you can basically run TLCs and column chromatography purifications knowing at all times where your compounds are on the silica!
However, most organic compounds do not absorb visible light strongly enough. So you have to use a visualizing agent. The most common one is just using an ultraviolet lamp.
TLC stationary phases are prepared to make your compounds visible in certain UV wavelengths. Most organic compounds, which have a minimum of conjugation will be observable in this manner.
Those are generally highly aliphatic compounds with little functional groups. Staining agents for TLC are basically solutions of one or more compounds in which we can dip the plates after elution.
It is worth keeping in mind that, even if your target compound s absorbs strongly UV or even visible light, it is recommended to stain the plate anyway, if you can.
This is because there might be other components of the mixture present as impurities which you cannot observe correctly under typical UV-Vis conditions.
So remember, even if your compound is visible at first sight, check also under UV light. And even if you can see everything under UV light, developing the plate with a general-purpose staining agent will almost never be overkill.
Now follows a list of the most typical staining agents, and how to prepare them. There are many others, some incredibly specific for certain types of compounds.
Many people use this vanillin solutions. It is really easy to prepare, and after heating, it is really sensitive to most functional groups. The coolest thing is that many times, small changes in functionalities on organic compounds lead to a change in the color of the TLC plate after vanillin staining and heating.
This is really great if your starting material and product have a very close Rf. You can still differentiate them by the color!
Specifically, it shows brightly most compounds with polar functional groups. It might not be great for highly apolar compounds, such as simple alkenes or aromatics.
The recipe for this stain is really easy: Weigh g of vanillin, dissolve it mL of ethanol, and add 2. Stir and you are good to go!
To use it just dip your eluted TLC plate, and heat up with a heating gun. This is another great general purpose stain. It is my personal favorite, and it does color almost anything you can find in an organic chemistry lab.
From polyaromatics to alcohols, going through alkenes, or simpler aliphatic compounds. It gives you different blue-green shades, so it might not be the best for identifying different compounds with similar Rf, but for first choice, it will do great.
This staining solution is also extremely easy to prepare. You just need to dissolve around 5 g of phosphomolybdic acid buy the lesser quality one for this purpose!
This is the most classical one, probably the cheaper option, and it is also quite general. Basically it turns your TLC plate purple, and every compound that can potentially be oxidized will show up as a yellow spot.
You basically need to dissolve 1. Just be careful not to stain yourself with the mixture! It is a water based stain which makes your spots turn blue over a cool pale yellow background, after heating.
I have seen people use two different recipes. Dissolve 5 g of ammonium molybdate and 1 g of cerium sulfate OR 2 g of cerium ammonium sulfate into mL of water.
To this mixture, add 10 mL of concentrated sulfuric acid, and stir! There are many other staining agents, but they are usually more specific for certain types of compounds, and not the best ones to prepare or use routinely in the lab.
To anyone with a couple of years of experience in the lab, choosing the solvent combination for running a TLC or a column comes really easy.
Or at least a good starting point. But for beginners, it can be really overwhelming. After all, there are a lot of different functional groups, and A LOT of different combinations.
Not to mention the endless solvent combinations that you could imagine. That is the reason why it is extremely difficult to find a good guide out there to choosing the eluent for chromatography.
We wanted to get as close as possible to the best guide. And we came up with the following infographic for choosing solvents for TLC.
Keep in mind that of course this is an orientation and approximation, and there will always be compounds that behave weirdly. But we think that it will do the trick to for most situations, at least as a first shoot for a new reaction that you are running.
We have limited it to classical mixtures of apolar solvent hexane, pentane or cyclohexane and polar solvent ethyl acetate or diethyl ether , as a combination of these solvents will be usually enough to deal with most organic compounds.
Again, this is an approximation, and the values are not always additive. But if you have 3 alcohols, it is not certain that will work.
Maybe is enough. Or maybe not even , maybe you even need to add methanol. As you can imagine, the most polar group itself will often dictate the polarity of the entire molecule.
Then you change that methoxy group for an alcohol. For practical purposes, solvents such as pentane, hexane, heptane or cyclohexane are similar, polarity-wise.
The only problem with those two solvents is that are less volatile, and more difficult to get rid of. If you need a more volatile alternative, use pentane.
This should be used in cases where your target compound is relatively volatile and you cannot put it under high vacuum to remove the solvent completely.
In the polar component side, ethyl acetate and diethyl ether can be the main options. Diethyl ether is more volatile, so it should generally be avoided if possible, unless it gives you a much better separation or your target product is also volatile.
This can potentially lead to reproducibility issues. Compounds with basic or acidic sites, such as amines, amides basic or carboxylic acids acid , can sometimes stick to the silica gel of the stationary phase a little bit too much.
This results on very wide spots on TLC, and as a consequence, very broad bands in your flash column chromatography purifications.
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Haus-Makeover in Fort Worth Jetzt ansehen. Sechs Töchter im Haus Jetzt ansehen.Then, the different fractions that come out of the bottom of the column are collected in different test tubes.
If the separation was performed correctly, we will have each compound of the mixture in different test tubes. The we can just get rid of the solvent by evaporation and we will have our product pure.
The rate of elution for each compound depends on its retention factor i. This means, they will come out of the column in the same relative rate rate as their spots eluted in a TLC.
Well, first of all, before running a flash column chromatography, we need to select what is the appropriate solvent system for the purification.
We do this by using TLC. Ideally, the product s that we want to isolate, should have an Rf retention factor of around 0. The following image on the left illustrates how an ideal TLC for purification should look like.
As you can see, two products are clearly visible and separated. So the solvent mixture that yields this result on TLC, will be a great choice for running the big scale column chromatography purification.
The images on the right, illustrate how this separation does proceed using that same solvent system. As you can see on the far right, the first compound leaves the column completely separated from the other one.
It can be collected, and concentrated in vacuum, getting your product completely pure and dry! But after running the column chromatography, you usually end up with dozens of tubes filled with eluent with the different compounds dissolved.
Now we have to use TLC again! As you can see, we have two different products spots that came out of the column pretty close. From fraction 5 to 10 , we only have compound one, pure.
We can mix these fractions, concentrate them, and we will have pure compound 1. Fractions 11 and 12 , have a mixture of the two compounds.
Fractions 13 and 14 have pure compound 2. If we also need this compound, we will just concentrate them together as well.
As you can see, TLC is extremely important for both reaction monitoring and product purification , the two cornerstones of any synthesis laboratory.
If you have access to a GC-MS gas chromatography-mass spectrometer or LC-MS liquid chromatography-mass spectrometer , you can analyze quickly all the different fractions, and know the molecular mass of the compound s present on each of them.
Basically this machine automatically scraps off individual spots on an eluted TLC, and makes an MS analysis, so you can check the molecular masses present on of each spot of the TLC in usually less than a minute.
Using an eluent which gives an Rf of 0. If you have two compounds that are very close together in Rf, this might not be enough. Column bands are like much much wider TLC spots, especially as we scale up the purification.
Imagine that typical TLC that you overload with sample and you get two big unresolved overlapping spots. That is a closer picture to what is actually happening in your column chromatography.
For this reason, sometimes an Rf of 0. If spots are separated by less than 0. Another cool trick to enhance this kind of purification is using thicker columns, this helps a lot with separation.
On the flip side of the coin, sometimes your compound of interest just flies on TLC using certain solvent mixture, giving an Rf of 0.
You will have to spot reaction mixtures, or reference samples in your TLC using capillary tubes. You can either buy them, or make them yourself.
The commercial ones I use on a daily basis, usually last for months before breaking, if you are careful enough. But you can make thin capillary tubes out of thicker glass tubes, you just need to heat them up and then pulling.
For this, you can either use thicker capillary tubes or glass Pasteur pipettes. Explaining the method for heating and pulling will sound more complicated than it actually is, just take a look at this short but on-point video:.
As you can see is not terribly complicated, and it can even be a nice experiment for undergraduate labs. Just be careful with the flame or other heating source that you use!
Avoid using open flames in the lab if you have alternatives. So, there are actual chambers designed for running TLC, and they are just great, such as these from Fischer:.
The beauty and simplicity of this technique is that you can use it in basically any situation! It is worth mentioning here that this is another key for a good eluent chamber: You need the atmosphere as saturated as possible.
This can be detrimental for the separation, so always ensure that your chamber is a reasonably closed system.
As you can see in the picture above, you can also put a piece of filter paper inside the chamber a while before eluting your TLC.
The solvent will ascend through the filter paper as well by the same principle than through the TLC , helping a lot in saturating the atmosphere inside the chamber with the eluent.
This will make the eluent go up the TLC plate in a much more even manner. Also, be patient, leave the eluent in the chamber with the filter paper for a while before eluting you plate!
Finally, the more practical low-cost alternative, in my opinion, is just using a glass tar with a screw cap, like the ones you get you jam, or other edible stuff in!
Silica gel SiO2 is slightly acidic, so certain compounds are quite sensitive to these acidic conditions. Many times this does the trick, but in other cases is not enough.
For those cases, there are alternative stationary phases such as neutral alumina Al2O3. Maybe your target compound does survive in alumina and you can use it for both TLC and flash column chromatography purification.
Typical silica gel stationary phases are very polar, and you elute the plate with a solvent systems that is much less polar than SiO2.
This works wonders form most typical organic compounds. For these cases, we can use reverse phase chromatography , in which the stationary phase is apolar it will retain polar compounds much less , and you will use polar solvents, such as MeOH, as eluent.
Very polar compounds, such as oligopeptides , can literally fly on reverse phase. But sometimes although very few times, we have to say they are the only way to go, so keep in mind that these alternatives exist!
Finally, I have to mention that simple filter paper can be used as stationary phase. Separations are going to be bad, and you will get poor visualization.
But if you have colored compounds, you can still see some separation. As a matter of fact, my first TLC experiment was just spotting a solution of spinach extract on filtering paper, and eluting it with acetone.
There is no use in running a TLC if you cannot see the spots of the different compounds on your mixture.
You can see the spots right as they elute up the plate! This is common with highly conjugated compounds such as polyaromatics, or polyenes , and with organometallic compounds, such as ferrocene derivatives.
These compounds are great because you can basically run TLCs and column chromatography purifications knowing at all times where your compounds are on the silica!
However, most organic compounds do not absorb visible light strongly enough. So you have to use a visualizing agent.
The most common one is just using an ultraviolet lamp. TLC stationary phases are prepared to make your compounds visible in certain UV wavelengths.
Most organic compounds, which have a minimum of conjugation will be observable in this manner.
Those are generally highly aliphatic compounds with little functional groups. Staining agents for TLC are basically solutions of one or more compounds in which we can dip the plates after elution.
It is worth keeping in mind that, even if your target compound s absorbs strongly UV or even visible light, it is recommended to stain the plate anyway, if you can.
This is because there might be other components of the mixture present as impurities which you cannot observe correctly under typical UV-Vis conditions.
So remember, even if your compound is visible at first sight, check also under UV light. And even if you can see everything under UV light, developing the plate with a general-purpose staining agent will almost never be overkill.
Now follows a list of the most typical staining agents, and how to prepare them. There are many others, some incredibly specific for certain types of compounds.
Many people use this vanillin solutions. It is really easy to prepare, and after heating, it is really sensitive to most functional groups.
The coolest thing is that many times, small changes in functionalities on organic compounds lead to a change in the color of the TLC plate after vanillin staining and heating.
This is really great if your starting material and product have a very close Rf. You can still differentiate them by the color! Specifically, it shows brightly most compounds with polar functional groups.
It might not be great for highly apolar compounds, such as simple alkenes or aromatics. The recipe for this stain is really easy: Weigh g of vanillin, dissolve it mL of ethanol, and add 2.
Stir and you are good to go! To use it just dip your eluted TLC plate, and heat up with a heating gun. This is another great general purpose stain.
It is my personal favorite, and it does color almost anything you can find in an organic chemistry lab. From polyaromatics to alcohols, going through alkenes, or simpler aliphatic compounds.
It gives you different blue-green shades, so it might not be the best for identifying different compounds with similar Rf, but for first choice, it will do great.
This staining solution is also extremely easy to prepare. You just need to dissolve around 5 g of phosphomolybdic acid buy the lesser quality one for this purpose!
This is the most classical one, probably the cheaper option, and it is also quite general. Basically it turns your TLC plate purple, and every compound that can potentially be oxidized will show up as a yellow spot.
You basically need to dissolve 1. Just be careful not to stain yourself with the mixture! It is a water based stain which makes your spots turn blue over a cool pale yellow background, after heating.
I have seen people use two different recipes. Dissolve 5 g of ammonium molybdate and 1 g of cerium sulfate OR 2 g of cerium ammonium sulfate into mL of water.
To this mixture, add 10 mL of concentrated sulfuric acid, and stir! There are many other staining agents, but they are usually more specific for certain types of compounds, and not the best ones to prepare or use routinely in the lab.
To anyone with a couple of years of experience in the lab, choosing the solvent combination for running a TLC or a column comes really easy.
Or at least a good starting point. But for beginners, it can be really overwhelming. After all, there are a lot of different functional groups, and A LOT of different combinations.
Not to mention the endless solvent combinations that you could imagine. That is the reason why it is extremely difficult to find a good guide out there to choosing the eluent for chromatography.
We wanted to get as close as possible to the best guide. And we came up with the following infographic for choosing solvents for TLC.
Keep in mind that of course this is an orientation and approximation, and there will always be compounds that behave weirdly. But we think that it will do the trick to for most situations, at least as a first shoot for a new reaction that you are running.
We have limited it to classical mixtures of apolar solvent hexane, pentane or cyclohexane and polar solvent ethyl acetate or diethyl ether , as a combination of these solvents will be usually enough to deal with most organic compounds.
Again, this is an approximation, and the values are not always additive. But if you have 3 alcohols, it is not certain that will work.
Maybe is enough. Or maybe not even , maybe you even need to add methanol. As you can imagine, the most polar group itself will often dictate the polarity of the entire molecule.
Then you change that methoxy group for an alcohol. For practical purposes, solvents such as pentane, hexane, heptane or cyclohexane are similar, polarity-wise.
The only problem with those two solvents is that are less volatile, and more difficult to get rid of. If you need a more volatile alternative, use pentane.
This should be used in cases where your target compound is relatively volatile and you cannot put it under high vacuum to remove the solvent completely.
In the polar component side, ethyl acetate and diethyl ether can be the main options. Diethyl ether is more volatile, so it should generally be avoided if possible, unless it gives you a much better separation or your target product is also volatile.
This can potentially lead to reproducibility issues. Compounds with basic or acidic sites, such as amines, amides basic or carboxylic acids acid , can sometimes stick to the silica gel of the stationary phase a little bit too much.
This results on very wide spots on TLC, and as a consequence, very broad bands in your flash column chromatography purifications.
This deactivates de acidic sites of the silica: Si—O—H bonds. By adding Et3N to your eluent, you remove all of them and your compound will elute freely!
Similarly, acidic compounds such as carboxylic acids can react with Si—O bonds in silica gel to give Si—O—H, which really makes them stick to the stationary phase.
This will make acidic compounds much more mobile through the TLC plate or column. We have already covered flash column chromatography in a previous section.
Running purifications is one of the main applications of thin layer chromatography. But we can actually apply TLC to run preparative-scale purification.
Well, preparative TLC is just a regular thin layer chromatography separation, but with a bigger plate!
They are usually made of glass coated with a thicker layer of silica gel. Then, instead of a single point spot, you apply the solution of your mixture in roughly 0.
For applying this solution, I usually use a 1 mL syringe with the thinest needle I can find. It has to be uniform and you need to be careful not to scrap the silica!
After drying it, you elute the plate in the appropriate solvent system carefully chosen by classical TLC , and the different compounds will get separated.
You obviously will need a bigger chamber. Afterwards, you just need to scrap off separately the bands that you are interested in. For this, visualize the plate under UV light, and mark with a pencil the bands you are interested in.
Then, scrap off the band, and just pass a polar solvent such as DCM through the silica gel with your product, so it gets dissolved.
Filter it off to get rid of the SiO2. All this being said, I will leave you with a short time-lapse video of how does running preparative thin layer chromatography go:.
TLC is a simple yet widely used technique. So in most reports and journals, you should provide information about TLC data for experimental procedures.
The very minimum is stating in which solvent mixture you have run the purification of each compound. The best way, is reporting retention factors Rf of your product in a certain solvent mixture.
For example, you report a procedure to make benzaldehyde. We will finish by gathering some tricks, tips and lab hacks for TLC.
You will definitely find something useful here! Two-dimensional thin layer chromatography or 2D TLC got me through my first year of grad school, when I had to work with a great deal of compounds that could potentially decompose during purification on silica gel.
We have covered this sand bed for TLC in our lab hacks post. If you have trouble leaving your plates standing vertically on your elution chamber, of if you want to run many plates on the same eluent at the same time… Get a big enough chamber, and make a bed with sea sand at the bottom about 2 cm is enough.
Then, put your eluent in the chamber covering just a bit above the sea sand, and stick all the TLCs you need on the sand! They will not fall, and you can elute many of them parallel to each other.
Letting your plate drawn will result in spot broadening and worse separations. Huge spots appear when you overload your TLC plate. Dilute more your sample before spotting.
Some compounds can decompose when passing through silica gel from TLC plates or columns. You can tell if a compound is stable by using 2D thin layer chromatography see above.
No, you should always spot the samples slightly above the level of eluent in your TLC chamber. Otherwise, you will dilute the spots and worsen your separation.
Spot both the starting material and the reaction mixture in your TLC. Also, make an additional spot with both starting material and reaction co-spot.
If the reaction is finished, you will see two different spots snowman shape in the co-spot, even if the Rf of both compounds is the same. The most important thing is to report the retention factor Rf in a certain eluent combination, of all the compounds that you have used.
An English-language version of the channel was originally launched in across Europe and was subsequently renamed Discovery Home and Leisure and later Discovery Real Time as part of Discovery's slate of themed channels.
On July 4, , a Dutch version was launched, time sharing with Animal Planet's standard definition feed. Animal Planet remained a hour service for high-definition viewers.
TLC became a hour channel on January 8, It is also available in HD. An Indian version was launched in under the jurisdiction of Discovery Channel.
It was relaunched as TLC on September 1, Available across sub-Saharan Africa on the DStv satellite service. From Wikipedia, the free encyclopedia. For other uses, see TLC.
Main article: List of programs broadcast by TLC. TV by the Numbers. Archived from the original on February 23, Retrieved March 14, August 15, San Diego Union-Tribune.
Archived from the original on September 10, Retrieved April 18, The New York Times. April 2, Washington Examiner. Retrieved The Inspiration Room.
Entertainment Weekly. Archived from the original on Deadline Hollywood. Retrieved March 2, Digital Spy. Daily Sabah. Archived from the original on October 11, Retrieved 23 August Retrieved 15 July Discovery, Inc.
Hendricks , the Company's Founder and Chairman. TLC original programming. Pimple Popper Dragnificent! Former TLC original programming.
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Ja ist es aller die Phantastik
Ich meine, dass es der falsche Weg ist.