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Preventing Enzymatic browning in apples


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#1 SaRaRa

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Posted 08 January 2009 - 08:09 AM

Hello again!

I am studing the prevention of enzymatic browning in osmotically dehydrated apples using a sugar solution + calcium chloride. Can anyone give me more info / some sources about the mechanism of prevention of Calcium Chloride? I 've got some having more is always better nay? :P


Cheers!


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#2 Hongyun

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Posted 11 January 2009 - 05:35 AM

Hi sarara,

I think the use of CaCl2 is to make to create a film coating on the apple slices so as to prevent direct contact with oxygen.

I also found a summarized mechanism of browning by PPO as follows:

"Enzymatic browning is the discoloration that results when monophenolic compounds of plants or shellfish, in the presence of atmospheric oxygen and poly phenol oxidase (PPO), are hydroxylated to ortho phenols, and the latter are oxidized to ortho quinines. The quinine condenses and reacts nonenzymatically with other phenolic compounds to produce dark brown, black or red pigment of intermediate structure."

Taken from a patent by ADVANCED BIOCHEMICALS LIMITED.

Besides the use of CaCl2, there are other ways as describe in this pdf.

Hope these information gives extra boost to your new project! :smile:


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#3 SaRaRa

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Posted 12 January 2009 - 06:59 AM

Thank you for your answer Hongyun! :D

I already have those information. I just need to find out more about how calcium chloride really works! What I found so far is that it has been found that the chloride anion plays an active role in the inhibition of browning and not the calcium cation. However calcium appears to act as a firming agent by limiting both the deterioration of cell structure and hence browning and development of fungal deterioration. This has been shown both in the whole apple and in slices.

So I am trying to focus more on chemistry mechanisms and additional information on the above!

Thank you though!


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#4 a_andhika

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Posted 17 January 2009 - 02:08 PM

Dear SaRaRa,

I see your topic is quite interesting. I have some trouble too with enzymatic browning in my factory. We facing an enzymatic browning on one of our material, which is Garlic Flakes. Its get browned during our storage. Do you have any information regarding garlics? Or perhaps from Hongyun?

BTW, I found these articles, a bit technical and quite amuse me :w00t: , but I hope they might help you.

http://www.wipo.int/...mp;DISPLAY=DESC

Regards,


Arya

PS: I found this one too, its a 4M size :yeahrite: , so I couldnt attach it:
http://postharvest.u...les/234-390.pdf

Attached Files


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#5 SaRaRa

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Posted 17 January 2009 - 03:46 PM

wow! Thank you! Those are VERY useful links! I am grateful!
Well I don't know much about garlic and I also don't know how you process the garlic in your factory. I suppose that you are dehydrating them after cutting and blanching them. With a quick search I found some general information (below). Nothing directly related with color formation though... If you do cut, blanch and dehydrate them then I suppose that the enzyme responsible for the enzymic browning is not totally deactivated during blanching. Do you dip them in any solution? Unfortunately I am not aware of the chemical composition of garlic or the enzymes that are responsible for enzymatic browning in garlic. I suppose it could be polyphenoloxidase as well but I am not sure.


The following refer to drying processing:

Organoleptic quality is severely affected during drying since color and flavor are the most important sensory attributes of dried foods. The development of color due to enzymatic and non-enzymatic browning is one of the major problems that occurs during the processing and storage of dehydrated foods. Browning reactions also produce off-flavor development and loss of nutritional value. Enzymatic browning is due to the effect of enzymes that catalyze the hydroxylation and oxidation of phenolic compounds. Nonenzymatic browning is a Maillard reaction involving amino groups and reducing sugas that result in brown polymeric pigments. The rates of both types are strongly influenced by composition, temperature, water activity and pH.
The development of color in different foods has been extensively studied. Although several mathematical models have been proposed, in most cases a zero-order reaction with or without an induction period or a first-order reaction has been found to describe the kinetics of browning. The effects of temperature and moisture content on the reaction rate constant for color changes in onion and garlic that follow pseudo first-order kinetics are shown in Figure 11-3.

Figure 11-3 (page 139).

Chemical and thermal treatments such as sulfating or blanching are used to control enzymatic browning by enzyme inactivation in fruits and vegetables. However, thermal treatment is not recommended in products such as onion and garlic where some desirable enzymatic reactions involved in the production of the characteristic flavor and pungency are required. The enzyme inactivation reactions and loss of pungency can be modeled by first-order kinetics.
Since the stability of pigments in foods is affected by many factors, their degradation follows complex mechanisms which do not follow the same kinetics. However, most important degradation reactions such as chlorophyll, anthocyanins and carotenoids have been reported to follow pseudo first-order kinetics (Crapiste, 2000).

Dehydration technology:
(step 4) Cutting and rinsing:
Based on product requirements, raw materials can be cut into definite shape and size to facilitate dehydration. In general, vegetables are cut into slices, strips, dices and shreds, either mechanically or by hand. For some vegetables such as scallions and garlic, cutting has to be accompanied by continious rinsing to remove the colloidal liquid (cytoplasm) due to cutting to facilitate dehydration and provide products with good color and appearance.

(step 6) Color protection:
For vegetable products that change color easily, the addition of harmless color protectants such as sodium bicarbonate or citric acid (in the blanching water) may be permitted. The residual liquid on the vegetable must be removed by centrifuge (Cai et al., 2003).

G.H. Crapiste, Qualite Changes in Foods During Drying, Trends in Food Engineering, E. Lozano, Cristina Anon, CRC Press, 2000.

Tongyi Cai, Fang Chen and Jinghua Qi, Dehydrated Oriental Mushrooms, Leafy Vegetables and Food Preparation Herbs and Condiments, Handbook of Vegetable preservation and Processing, Yiu H. Hui, Sue Ghazala, Dee M. Graham, K. D. Murrell, Wai-Kit Nip, CRC Press, 2003.



I will search more when I 'll have more time!
Thank you again for your help!

Cheers!


Edited by SaRaRa, 17 January 2009 - 04:00 PM.

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#6 Hongyun

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Posted 18 January 2009 - 05:06 PM

Good links, Arya! :thumbup:

Helps me understand better. :smarty:

As for the garlic browning issue, I'm sorry. Am unable to provide useful details to you...

Though it is probably due to Maillard reaction (Amadori's Rearrangement) as per Sarara's findings. (due to fructosyl arginine? hydroxymethylfurfural?)

Maillard reaction is very complex with alot of unknown results and can occur even at room temperature. It takes an experienced reaction flavorist to understand which conditions will lead to which reactions. I believe you have someone with that experience in your company to help you out?


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#7 a_andhika

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Posted 20 January 2009 - 06:55 AM

Dear Sarara and Hongyun,

Thank you very much for your posts. This "elite" level conversation force me to cover my lackness by doin' some research again. But yet, I think I havent told you my exact matters (my bad...).

Actually, I am not a supllier of garlic flakes. I am using it to make end product such as roasted garlic powder and roasted garlic granules.

As for the powder, we havent found any serious difficulties. It roasted on 120 - 130C at 25 - 30 minutes. We can get various product characters by adjust the setting. I am not sayin its easy, but it relatively can be controlled with well. So the colour changing (I assume because of browning) during the storage (20-25C, RH max. 65%) wont be a significant trouble for us.

The real trouble is when we have to produce granules. The setting for granule is 100 - 110C at 5-7 minutes. We dont expect the colour was too dark, but we hope the roasted flavor may come up. During the storage, our garlic flakes is turn out into slighltly dark brown, which has the same colour as the roasted one (with granule setting). If we directly grind it into granules (without roasting), the granules were condensed (caking). I assume because the moisture content is still high.

So for the solution, we reduce the temp. setting into 90C for granules. It works, the result is fine, and the moisture is meet the standard, so as the micro content. But this solution is only for a short-therm. I need a better solution to save our stocks (which is quite large) at this time. Coz the browning reaction is still continued, and were running out of time...

Anyway, I've found some literatures, maybe I can share it to my supplier. Hope worthful for you too:
http://www.ieindia.o...6/june06ag1.pdf
http://www.freepaten...amp;stemming=on

I found some aother sources, but unfortunately I cant access it without spend any money.. (hehe..)

Regards,


Arya


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#8 SaRaRa

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Posted 20 January 2009 - 04:34 PM

Hello again,

"Like other vegetables, processing of garlic (crushing, chopping, drying etc) accelerates surface enzymatic and non-enzymatic browning, moisture and flavour losses, or microbial spoilage. These deteriorations result in a poor quality product with a short shelf life. The incorporation of anti-browning agents to the garlic cloves by the vacuum impregnation (VI) technique could retard deteriorating reactions in garlic."

I found this in this pdf file: Impregnation Parameters of Garlic Cloves

You can check this out too: Postharvest Technology of Horticultural crops

Hope its useful!


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#9 SaRaRa

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Posted 20 January 2009 - 08:42 PM

I also found something regarding onion flakes but I am not sure if it works for garlic as well:

"The effect of onion storage on the color of onion flakes stored for 15 months has also been examined. Flakes made from onions stored at higher temperatures were lighter in color, a finding attributed to the lower reducing-sugar content of bulbs stored under these conditions (Fenwick and Hanley, 1990)."

Oh... wait a sec... I just saw that there are some interesting parts about garlic on this paragraph.

"Both dehydrated onion and garlic are prone to discoloration. Darkening is associated with nonenzymic Malliard reactions and may be prevented by reducing processing temperatures. The use of sulfur dioxide has been suggested but significantly reduced garlic pungency and biological activity. A green discoloration associated with the maceration of garlic tissue may be minimized if dormant tissue is processed and this has been recently reexamined by Lukes. Much more significant however is the development of a pink discoloration during onion processing (Fenwick and Hanley, 1990)."

Check it out: Dehydrated Onion and Garlic


Reference:

G. R. Fenwick and A. B. Hanley, Processing of Alliums; Use in Food Manufacture, Onions and Allied Crops: Volume III, Biochemistry, Food Science and Minor Crops, CRC Press, 1990.


Edited by SaRaRa, 20 January 2009 - 08:44 PM.

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#10 AS NUR

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Posted 21 January 2009 - 02:03 AM

thanks sarara, hongyun and Arya

you are give me the deepest knowledge on browning reaction..
Actually i have some problem s with browning, we can decide the browning caused by temp. and time.. and I think my problems is not bigger like arya problems... So we just control our temp. and time to avoid browning products..


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#11 SaRaRa

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Posted 21 January 2009 - 11:22 AM

Hello AS NUR!

You are also selling processed garlic products?

By the way I found here a way to produce garlic powder. Maybe it could be helpful to compare methods. And here is a way to produce garlic flakes (and it also has some info about storage... and unfortunately the most important information are not available).

Here are a little more info about garlic powder. Also here. And here.

Cheers!


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#12 AS NUR

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Posted 22 January 2009 - 01:10 AM

no sarara.. but you make me motre understand to see browning problems in other product (garlic powder)..

We produce Non dairy Creamer, the production process are we mix ingredient to make liquid feed (wet mix) and after that spray it to make powders..

2 years ago we found the wet mix if we stay the product more than 4 hours at ± 65oC.. so we have to control the process less then 4 hour at 65oC.. and until now the process can run well...


BTW thanks for the links sarara...


Edited by AS NUR, 22 January 2009 - 01:12 AM.

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#13 a_andhika

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Posted 22 January 2009 - 01:37 AM

Dear Sarara,

Thank you very much for your kind attention to my problems. I guess now we have some inputs to our supplier to develop their resistance to browning. And its proven that the factor of storage time and condition truly affecting the browning reaction. I think we need to set the planning and inventory control with more carefully right now. Thanks again.

Regards,


Arya

PS: Even if most of our queries is answered, I think this topic is still widely opened. Since so many mysteries on the browning reaction. Interesting:)


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#14 Charles.C

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Posted 22 January 2009 - 02:33 AM

Dear All,

This must be the first contender for the "deepest" thread of the year 2009 award :thumbup: :biggrin:

Rgds / Charles.C


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Kind Regards,

 

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#15 SaRaRa

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Posted 22 January 2009 - 10:17 AM

I am glad my help proved useful! :D

I didn't know what non dairy creamers were until now.

"Non-dairy creamers are substances which are intended to substitutes for milk or cream as an additive for coffee, or other beverages; they do not contain lactose, and are therefore not considered dairy products. Non-dairy creamers typically contain sodium caseinate, and a milk protein (casein) derivative that does not contain lactose. Other common ingredients include corn syrup and vegetable juice solids. Some creamers are based on soy candels rather than on milk fat (www.wikipedia.com, 2009)."

So I suppose that the main cause of this is caused mainly from maillard reaction id est a reaction between reducing sugars and aminoacids.

Here is a nice tv show that explains quick and fast what non enzymatic browning is (maillard reaction and caramellization):

The Maillard Reaction

In non dairy creamers there is absence of lactose but I suppose that you probably use other ingredients as well that might contain some sugars. But for the reaction to take place there are some factors that play some important role:

"High temperature, low moisture levels (low moisture levels are mainly necessary because water boils into steam at 212 Fahrenheit (100 Celsius), whereas the Maillard reaction happens noticeably around 310 Fahrenheit (155 Celsius): by the time something is in fact browning, all the water is vaporized), and alkaline conditions all promote the Maillard reaction.

The rate of Maillard reactions increases as the water activity increases, reaching a maximum at water activities in the range of 0.6 to 0.7 (www.wikipedia.com, 2009)." You can see the different reaction rates in foods as a function of water activity in the following Figure.

http://www.landfood.ubc.ca/courses/fnh/301/brown/brown-02.gifPosted Image

(
www.landfood.ubc.ca, 2009).

However, as the Maillard reaction produces water, further increases in water activity may inhibit Maillard reactions.


"Pentose sugars react more than hexoses, which react more than disaccharides. Different amino acids produce different amounts of browning (www.wikipedia.com, 2009)."

I dont know if you use Sodium Caseinate but I found that it can be used in foodstuff also for browning. You see that in this chart. So if indeed your product contains sodium caseinate it could be one of the reasons for browning. Here is a chart of a sodium caseinate product of an american company that contains the physcal properties, a typical microbiological analysis, a typical chemical analysis and the typical aminoacid content of their product. I thought it could be useful.

Cheers!


Edited by SaRaRa, 22 January 2009 - 10:18 AM.

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#16 Hongyun

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Posted 22 January 2009 - 02:29 PM

Interesting links and reading material! :thumbup:

It's a wonder how a simple question on apple browning can lead to so many other issues!

Sarara, I hope you post more technical questions in this forum and generate more discussions! I sure had fun reading them. :biggrin:

@Arya, sorry to hear your dilemma. As suggested by other literature, your supplier may need to add sulfide compounds to slow down the browning while taking care of the permitted levels in your country. And you probably need to store your future garlic raw materials somewhere cool to prolong the shelf life.


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#17 SaRaRa

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Posted 22 January 2009 - 04:11 PM

Hey! Thanx Hongyun! I always enjoy discussing stuff especially with people all around the world! :thumbup:

Well, this forum is dedicated mainly in HACCP and ISO issues... things that I am not very familiar with... yet! :rolleyes:

My main interest is in chocolate industrial manufacture, oenology :drunk: , general food chemistry, molecular gastronomy (I love cooking ^_^ ) and biotechnology issues (even though I don't know much about it yet - I need to study more!).

I 'll be happy to discuss related issues in other posts!

Cheers!


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#18 AS NUR

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Posted 23 January 2009 - 01:39 AM

yes sarara.. your right.. the browning of NDC caused by maillard reaction.. because that contain t protein (Amino acids) and sugar.. plus temperature and time, the reaction of maillard became faster...
so i just control the temp. and time in wet mix.. but at the end product.. i just control temp. of storage ( ± 30oC, Rh ± 60) and we use multiple layer paper bag to protect the product...


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#19 Hongyun

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Posted 23 January 2009 - 01:53 AM

Sarara,

Like you, I'm not well verse in the world of HACCP and ISO related stuffs, but am interested in other food related technology.

Thanks to the moderators for adding this Food Technology forum as there wasn't one few yrs ago. :smile:

AS NUR,

Besides reducing temperature while spraying, you can also shorten the spray dry time by playing around with the solid contents (SC) of the liquid feed. The higher the SC, the faster the spraying will finish before 4 hrs.

Or you can try increasing your inlet temp and feed rate, while reducing your outlet temp to prevent burnt product.


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#20 AS NUR

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Posted 23 January 2009 - 08:07 AM

yes.. hongyun.. that what we are doing now.. i

and FYI.. what i mean control the temp. is temperature wet mix product before spray drying... usually for one batch we need ± 2 hours and the temp. ± 65oC... so .. we just control that wet mix not exceed 4 hours stay in tank and the temp. stay at ± 65oC...

rgds

AS Nur

NOTE : yes this sub forum interested me


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#21 SaRaRa

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Posted 11 February 2009 - 11:16 PM

Hello again!

The following have to do with Michaelis-Menten kinetics...

In my research I also measured the absorption at 420 nm of PPO (polyphenoloxidase) of apple slices osmotically dehydrated (for 4 hours with gentle agitation at 30 C) in the presence of different inhibitors (plain maltose 62 brix, maltose + ascorbic acid and maltose + calcium chloride at different concentrations).

I collected all the data via software and now I am processing them (yeh.. plain Excel but it works fine!). What I noticed is that for calcium chloride concentrations the Vmax (maximum velocity of the reaction of PPO with the catehol substrate 0,2 M - pH 6.5) and Km (concentration of catehol that is equal with the concentration at which the maximum velocity is half) values are negative... And the "sectors" of time at which I am working with ARE linear (absorption with time)... but still... negative values. Anyone encountered such a problem before? Any suggestions why this happens? I guess I need to run some tests again...


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#22 a_andhika

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Posted 12 February 2009 - 10:46 AM

Dear Sarara,

I must say that your question is bring some old college memories to me... Lets see... What about the Vmax and Km value of the 2 other inhibitors? Do they have some correlation? Do the consentrations among those inhibitors are different? Which concentration that gives negative value for the CaCl2?

Big sorry if I am wrong, does a negative value means a reverse reaction (not inhibiting)? Or, well what I know this one goes for the acceleration, but negative value may also indicating a slowing down reaction, perhaps?

I am have some interest to know your calculation. Do you mind to share it to us? PDF is fine to me.


Regards,


Arya


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#23 SaRaRa

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Posted 01 March 2009 - 12:16 AM

Well I am not sure if I can publish my results here. I will ask my teacher and let you know about this.

Thank you for you interest though.


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#24 a_andhika

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Posted 02 March 2009 - 11:36 AM

Dear Sarara,

Sure, take it easy. I wont ask for the detail, but your previous post seems touching my "old memories"... This kinetics matters really give some tough but exciting moment at that old time.. ;) Just a sample would be fine, not your own research. I know I can give you some troubles if you publishing that in here...


Regards,


Arya


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#25 SaRaRa

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Posted 01 July 2009 - 08:54 PM

The following concerns carrots but the process is similar to the one that I conducted and I am just adding this for encyclopedic reasons :P

Optimization of osmotic dehydration process of carrot cubes in sucrose solution


Edited by SaRaRa, 01 July 2009 - 08:58 PM.

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