Great little berries that have a unique taste, almost like currant mixed with strawberry.
I first tried eating them right out of the bag thinking they were like raisins but they are not!!! Be careful of your dental work if you do this! Later after reading about them online, you want to soak them in water overnight to soften them up.
However if you intend to use these in oatmeal and you cook your oats in an instant pot, add them dry and you will have luscious goji berries with your oatmeal. Rolled oats and quick cooking steel cut only take three minutes in the instant pot. Add the goji berries along with the oats, without extra water, and the berries will be plump and juicy after natural pressure release.
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There were no significant differences in this parameter between 10 and 20 min of micronization. For the longest time (20 MRP), the share of red color a* was highest in the micronized samples, and the share of yellow color b* was highest in the micronized samples (20 MRP). Previous research [ 28 ] has shown that the micronization method affects the color of spinach stems and leaves. In comparison to the control sample and dry micronization, wet micronization produced a darker color.
The color results revealed that the color of the raspberry powders after micronization differed marginally, but this difference was significant, particularly in the case of the L* and b* parameters. The control (CRP) sample had the lightest color (L* = 49.2), and the longest micronized sample (20 MRP) had the darkest color (L* = 48.3) ( ).
In other studies in which superfine grinding of apple pomace [ 31 ] or herbal plant [ 32 ] was used, similarly to our tests, a significant reduction in particle size was observed. In these tests, the control apple pomace had a d50 particle size below 326 μm, and fine grinding reduced the d50 particle size parameter below 51.5 μm. In our research, at 10 and 20 min of micronization (10 MRP; 20 MRP), we obtained much lower dimensions of d50, i.e., 25 and 10.5 μm. This was due to different characteristics of the raw material. Here, we micronized raspberry pomace after removing the seeds. For cryogrinding buckwheat hulls [ 33 ], the d50 was below 15.1 μm. Micronization of oat husks [ 34 ] helped to obtain d50 dimensions below 15.5 μm.
The investigation demonstrated that, as expected, the micronization process with the utilized ball mill induced considerable changes in the particle size distribution of the studied samples ( ). The mean particle size (D[4;3]) was equal to 277 μm for the control sample (CRP). After 10 min (10 MRP) of micronization, this value dropped to 29.8 μm, and after 20 min of micronization (20 MRP) to 11 μm. More than 90% of the particles (d90) in the control sample (CRP) had dimensions below 578 μm. In the sample with 10 min of micronization, this parameter was 59.4 μm, and with 20 min of micronization, only 19.2 μm. The particle sizes for the 50% share (d50) were less than 225 μm for CRP, 25 μm for 10 MRP, and 10.5 μm for 20 MRP.
At the next stage of the study, spectroscopic ATR-FTIR measurements were also performed ( ), which assessed the impact of the sample treatment employed to facilitate more effective micronization. The results obtained from the spectral analysis in the infrared range might suggest that changes occur at the molecular level in the chemical structure of the raspberry samples in question.
presents all the characteristic bands present in the obtained spectra and correlates them with specific vibrations of their respective functional groups, based on a detailed literature review [31,32,33,35,36,37,38,39,40,41] as well as on the careful structural analysis of the molecules present in our samples.
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The infrared spectra recorded for the analyzed raspberry byproduct contain clear bands that can be fairly accurately associated with identifiable vibrations of particular functional groups that are characteristic of ingredients present in products rich in polysaccharides and similar nutrients [31,32,33,38].
Starting from the highest wave numbers, we first observed characteristic, wide bands that are present in the range from approx. 2500 to 3600 cm−1. The maximum of these bands, located at ~3300 cm−1, is typical of the vibrations of asymmetric bonds induced by the stretching vibrations of the hydroxy -OH groups, which are characteristic of polysaccharide molecules that are predominant in the analyzed samples [38,41]. Moreover, the groups are involved in the formation of hydrogen bonds between smaller units of polysaccharide molecules. Notably, the band corresponding to the stretching vibrations of the -OH groups enhances the stretching vibrations of the C-H groups [36,41]. There are two very sharp bands present in this region, with wave numbers of 2914 and 2848 cm−1, that are particularly characteristic of asymmetric and symmetric stretching vibrations in the CH2 groups present in this type of food sample. The highest intensity of this particular band, similar to the band corresponding to the -OH vibrations, could be observed in the sample subjected to micronization for 20 min, with a lower value registered for the sample micronized for 10 min and the lowest for the control.
Next, we proceed to the analysis of the essential group of vibrations known as the fingerprint region. The first two key bands corresponded to vibrations with the maxima at 1720 and 1632 cm−1, respectively. The former was associated with the characteristic stretching vibrations of the carbonyl group ν(C=O) [38] found in the molecules of simple sugars present in the samples. The latter band with the maximum at approx. 1630 cm−1 [37,38] corresponded to the deformation vibrations characteristic of water molecules, δ(-OH). During the micronization process, the relation between the two bands was noticeably altered. In the control, the respective ratio of the 1632/1720 bands was: 0.94, whereas in the sample subjected to 20 min., micronization increased to as much as 1.04. This pair of bands can therefore be treated as an excellent spectroscopic marker for the processing treatment in question.
Furthermore, the bands observed in the region from 1550 to 900 cm−1 corresponded to the strong vibrations of the C-O, C-C, C-O-H, and C-O-C groups, various oligomolecules or polysaccharides [32,33]. Even though the spectra recorded in this region seemed similar in terms of shape, two significant changes ought to be noted. Firstly, there was a change in the shape and increase in the intensity of the band with the maximum at 1540 cm−1, characteristic of ν(C=C) vibrations. Secondly, we observed changes in terms of the intensity and, most importantly, the shape of the bands with the maximum at 1326 cm−1, characteristic of δ(C-H) vibrations and potentially enhanced by δ(O-H) vibrations in the molecules of poly- and oligosaccharides that were the primary ingredients of the analyzed samples. While other vibrations in this region retained their original shapes, their intensity was significantly increased with the growing duration of the micronization process. On addition, the intensity of the bands with the maximum at 1412 cm−1 was characteristic of δ(C-H) vibrations. Next, we observed an increase in intensity of the vibrations with the maxima at 1360, 1222, and 1144 cm−1. These are characteristic of the vibrations of, respectively, δ(-OH in plane), δ(CH2) groups, and δ(C-H) groups, as well as of the stretching vibrations in the C-O-C system found in oligo- and polysaccharides present in raspberries. We also observed increased intensity of the bands, with the main maximum at 1019 cm−1. The bands in this spectral region are primarily associated with C-O and C-O-C stretching vibrations in polysaccharide molecules. The highest intensity of these vibrations was observed in the samples subjected to 20 min processing.
The last spectral “fingerprint” region below 930 cm−1 corresponds primarily to the crystalline regions and indicates conformational changes occurring in the analyzed material through possible changes to the β-1,4-glycoside bonds in polysaccharide molecules [38]. As we know, a fingerprint region is a spectral infrared range where each organic compound produces its unique absorption band. Such bands provide information as to the presence of various functional groups found in the given analyzed sample. As can be seen in our results, in the discussed case, the region below 930 cm−1 was characterized by a relatively low intensity of the bands with the maxima at ~891, 808, 774, or 580 cm−1. Apart from intensity variations, no particularly significant changes were observed here. Nonetheless, the changes in vibration intensity observed in this region, particularly in samples subjected to micronization, clearly indicate effects on the bonds between individual units in polysaccharide molecules [31,32,33].
To briefly recapitulate the already discussed results obtained from the spectral FTIR measurements, the observed discrepancies in terms of band intensity and, in some cases, slight shifts thereof indicate that the mechanical strength of finely ground material had a significant impact in the molecular properties of the analyzed samples. Firstly, the method of micronization employed for the raspberry byproduct samples resulted in cleaving the intramolecular hydrogen bonds in cellulose, hemicellulose, and polysaccharides predominantly present in the samples in question, likely leading to an increase in their content of amorphic cellulose and simple saccharides [31,32,33]. This was evidenced mainly by the changes in the intensity of bands characteristic of the stretching vibrations of the -OH group and the altered ratio of the 1720/1632 cm−1 bands, but also by the increased intensity of bands such as those with maxima at 1326, 1222, or 1019 cm−1. As follows from the literature data, mechanical strength usually cleaves only the amorphic region on the ordered surface in a crystalline substance [31,32,33]. Due to the same, the stiff and ordered structure of cellulose was slightly deteriorated by very fine grinding. All the mentioned shifts were related to the cleavage of hydrogen bonds present in the polymer chain during the grinding process. Additional cleavage of bonds and structural changes occurring in the polysaccharides were also facilitated by the observed increase in sample temperature during the micronization process. However, the observed spectral changes also clearly indicated that very fine grinding had no effect on the primary functional groups in cellulose, and the observed discrepancies were associated mainly with modifications to polysaccharide chains. This observation was further corroborated by the vibrations recorded below 930 cm−1, where the only effects noted related to band intensity. The bands in this region are characteristic of the vibrations on β-1,4-glycoside bonds, as already discussed above. As for the registered changes in the intensity of said vibrations, they evidence the same susceptibility to factors related to the micronization of the tested raspberry samples.
As evidenced by the above, the use of FTIR spectroscopy allowed us to identify the bands of marker changes characterizing the micronization process employed. The presented results may allow for better optimization of the process in the course of future research with a view of obtaining even higher-quality products.
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