A hmo concentrate syrup and a method of making the same

Abstract

The application provides an HMO concentrated liquid syrup and a preparation method thereof, and the preparation method comprises the following steps: concentrating an HMO fermentation liquid prepared by a microbial fermentation method to more than 60wt% after separation and purification, then cooling to -10-4 DEG C within 0.5-2h, maintaining stirring during the cooling process, and continuing to maintain stirring for 1-4h after cooling to the target temperature. Through the improvement of the preparation method, the stability of the high-concentration HMO concentrated liquid syrup under the refrigerated state can be realized.

Description

Technical Field

[0001] This invention relates to the field of food technology, and in particular to an HMO concentrate syrup and its preparation method. Background Technology

[0002] HMO (human milk oligosaccharides) is the third most abundant solid component in breast milk (after fat and lactose). It has functions such as regulating immunity, helping brain development, and regulating gut microbiota, which are beneficial to the growth and development of infants and young children.

[0003] To incorporate HMOs into nutritional compositions, particularly infant formula, synthetic HMOs are becoming increasingly popular. Currently, HMO products are commonly obtained through microbial conversion of lactose, followed by separation and purification using methods such as chromatography, nanofiltration, and / or electrodialysis. The final product is then dried using solvent crystallization drying, or by direct spray drying of the concentrate, vacuum drum dryer, fluidized bed drying, or other drying methods to obtain various crystalline or amorphous powders.

[0004] For downstream applications of dry-mixed products, powdered HMO has its advantages. However, for more downstream applications where the intermediate state is liquid, concentrated syrup is a more convenient and economical application form. Furthermore, the high concentration of syrup creates osmotic pressure that inhibits microbial growth. With proper sterilization before storage, liquid syrup can be stored for 6 to 12 months, offering convenient storage.

[0005] However, current HMO concentrate syrups, as shown in CN103797021B, are prone to crystallization due to their high concentration, resulting in poor storage stability. Therefore, stability issues are typically avoided by controlling the syrup concentration below 50%. Furthermore, the applicant's research revealed that while concentrates exceeding 50% can maintain complete dissolution in most processes, crystallization occurs after approximately seven days of refrigeration. Once crystal nuclei appear, the subsequent crystallization rate accelerates dramatically, producing large crystal clumps at the bottom. This phenomenon not only directly impacts the ease of storage and use of concentrates in northern regions but also places higher demands on transit times and increases costs for transportation across significant north-south meridians. Summary of the Invention

[0006] This invention provides an HMO concentrate syrup and its preparation method, which can prevent the concentrate syrup from forming large crystals under long-term refrigeration.

[0007] In a first aspect, the present invention provides a method for preparing HMO concentrate syrup.

[0008] The preparation method provided by the present invention includes: separating and purifying the HMO fermentation broth obtained by microbial fermentation and concentrating it to more than 60 wt%, then cooling it to -10 to 4°C within 0.5-2 h, maintaining stirring during the cooling process, and continuing to stir for 1-4 h after cooling to the target temperature.

[0009] More preferably, in some embodiments of the present invention, the preparation method includes: separating and purifying the HMO fermentation broth obtained by microbial fermentation and concentrating it to more than 60 wt%, and then cooling it to -10 to 4°C within 0.5-2 h;

[0010] After cooling to the target temperature, raise the temperature by 10-20℃ within 0.5-1h and maintain it for 0-1h, then cool it down to -10~4℃ within 0.5-2h.

[0011] Generally, as the temperature decreases, HMO syrup transitions from a stable state to a metastable state. In this state, the solution is easily stimulated to produce a small number of fine crystals. These crystals act as nuclei, causing the solute to aggregate and align around them. Under relatively stable external conditions, this leads to a crystallization process, often resulting in clumps of crystals at the bottom of the container. As the container volume increases, these clumps become more numerous and larger, becoming increasingly difficult to dissolve. This invention, however, involves rapid cooling during the preparation of the concentrate, causing the solution to enter an unstable state, resulting in a large amount of crystallization and a transition to a stable state. A subsequent moderate reheating and cooling process further controls the fineness and uniformity of the precipitated crystals. Simultaneously, due to the concentrate's inherent viscosity and the neutral, uncharged nature of HMO, the crystals remain non-clumping during subsequent low-temperature storage.

[0012] In some embodiments of the present invention, stirring is performed during the cooling process at a speed of 100-500 rpm.

[0013] In some embodiments of the present invention, the cooling step includes: first, rapidly reducing the temperature of the liquid to room temperature through a heat exchanger, and then cooling it to -10 to 4°C through a jacketed cooling element.

[0014] In some embodiments of the present invention, the HMO fermentation broth, after separation and purification, has a purity of over 95%. Preferably, the separation and purification steps involve the HMO fermentation broth sequentially undergoing sterilization treatment, decolorization treatment, ion exchange desalting treatment, and chromatographic separation.

[0015] In some embodiments of the present invention, the concentration is carried out in a falling film evaporator, a rotary evaporator or a multi-effect evaporator, preferably a falling film evaporator.

[0016] Preferably, before concentration, the liquid material is subjected to ultra-high temperature instantaneous sterilization.

[0017] In some embodiments of the present invention, the concentrated HMO fermentation broth after separation and purification is obtained by the following steps:

[0018] (1) The HMO fermentation broth (HMO mass concentration of about 5%) was filtered through a 200nm filter membrane to remove bacteria, resulting in sterile fermentation broth;

[0019] (2) Heat the sterile fermentation broth obtained in step (1) to 43°C; add activated carbon and stir, filter to remove activated carbon and protein, and obtain decolorized solution;

[0020] (3) The decolorized solution obtained in step (2) is sequentially adsorbed and desalted by cation exchange resin and anion exchange resin to obtain a desalted solution; the desalted solution is concentrated under reduced pressure to obtain a desalted concentrate.

[0021] (4) The desalting concentrate obtained in step (3) is separated by a styrene polymer gel column and eluted with pure water to obtain an eluent with a mass concentration of HMO of 5-20%. The eluent is then filtered and subjected to UHT.

[0022] (5) Concentrate the eluent obtained in step (4) to more than 60 wt%, and the temperature of the liquid after concentration is 60-70℃.

[0023] In the above technical solution, the HMO fermentation broth is preferably 2′-FL fermentation broth.

[0024] Secondly, the present invention provides an HMO concentrate syrup, wherein the mass concentration of HMO is above 70%, the HMO concentrate syrup does not contain genetically engineered microorganisms, nucleic acid molecules derived from genetically engineered microorganisms and proteins, or organic solvents, the purity of the HMO is at least 95%, and 90% of the crystals in the HMO concentrate have a particle size not greater than 150 micrometers; that is, the crystal particle size D90 in the concentrate is ≤150 micrometers.

[0025] The purity of the HMO is at least 95%, and "purity" refers to the weight of the HMO relative to the dry matter or solute in the HMO concentrate syrup.

[0026] Preferably, the optimized preparation method results in 90% of the crystals in the HMO concentrate having a particle size no larger than 80 micrometers. That is, the crystal particle size D90 in the concentrate is ≤80 micrometers.

[0027] As described in the background art, in the prior art, although HMO concentrate syrups with a concentration of more than 50% can maintain a completely dissolved state in most processes, crystallization will occur after about seven days of storage during refrigeration (around 0°C). Once crystal nuclei appear, the subsequent crystallization rate will accelerate dramatically, and large crystal blocks will be formed at the bottom. These crystal blocks are difficult to dissolve even by heating. This phenomenon occurs faster in concentrates with higher concentrations, and neutral oligosaccharides are more prone to this phenomenon than acidic oligosaccharides. Therefore, this limits the scope of application of HMO concentrate syrups and increases storage and transportation costs.

[0028] To address this issue, the present invention provides an HMO concentrate syrup that maintains excellent stability under refrigeration even at concentrations of 60% or higher, and even 70% or higher. Specifically, the HMO concentrate syrup, after being stored at 0°C for more than one month, can be completely reconstituted within 20 minutes when the temperature is raised to 30°C. This discovery fills a gap in the existing market.

[0029] In some embodiments of the present invention, the HMO is a fucoidan oligosaccharide, a sialic acid oligosaccharide, or an oligosaccharide formed from a core glycan structure that does not contain fucoidan or sialic acid groups.

[0030] In this invention, fucoidan oligosaccharides, also known as fucosylated oligosaccharides, refer to oligosaccharides containing fucose residues. Representative substances include 2′-fucosylated lactose and 3-fucosylated lactose.

[0031] 2′-Fucosyllactose (2′-FL) is a trisaccharide formed from fucose and lactose. Commercially available 2′-FL is typically prepared via microbial fermentation and has the same structure as 2′-fucosyllactose found in human milk.

[0032] 3-Fucosyllactose (3-FL) is a trisaccharide formed from fucose and lactose, and is an isomer of 2′-fucosyllactose. This substance can be prepared by microbial fermentation and has the same structure as 3-fucosyllactose found in human milk.

[0033] Sialoyl oligosaccharides, also known as sialylated oligosaccharides, refer to oligosaccharides containing sialic acid residues. Representative examples include 3′-sialyl lactose and 6′-sialyl lactose.

[0034] 3′-sialyllactose (3′-SL) is a structure formed by sialic acid and lactose, and is an isomer of 6′-sialyllactose. This substance is prepared by microbial fermentation and has the same structure as 3′-sialyllactose found in human milk.

[0035] 6′-sialyllactose (6′-SL) is a structure formed by sialic acid and lactose, and is an isomer of 3′-sialyllactose. This substance can be prepared by microbial fermentation and has the same structure as 6′-sialyllactose found in human milk.

[0036] Oligosaccharides formed without a core sugar chain structure containing fucose or sialic acid groups refer to oligosaccharides other than fucose-based and sialic acid-based oligosaccharides. Representative substances include lactosyl-N-tetrasaccharide or lactosyl-N-butose.

[0037] Lacto-N-tetraose (LNT) is a tetrasaccharide formed from galactose and glucose. It is a representative oligosaccharide with a core sugar chain as its basic structure and does not contain fucose or sialic acid groups. This substance can be prepared by microbial fermentation and has the same structure as lacto-N-tetraose found in human milk.

[0038] During the applicant's research, it was discovered that neutral oligosaccharides are more prone to the crystallization and clumping problems described in the invention compared to acidic oligosaccharides. Therefore, preferably, in some embodiments of the invention, the HMO is a neutral HMO.

[0039] In this invention, neutral HMO, or neutral oligosaccharide, refers to oligosaccharide that does not have a negative charge originating from a carboxylic acid group.

[0040] More preferably, the HMO is selected from one or more of 2'-fucosyllactose, 3-fucosyllactose, 2',3-difucosyllactose, lactosyl-N-triose II, lactosyl-N-butose, lactosyl-N-neotose, lactosyl-N-fucosylpentose I, lactosyl-N-neotose, lactosyl-N-fucosylpentose II, lactosyl-N-fucosylpentose III, lactosyl-N-fucosylpentose V, lactosyl-N-neotose V, lactose-N-difucosylhexose I, lactose-N-difucosylhexose II, 6'-galactosyllactose, 3'-galactosyllactose, lactosyl-N-hexose, and lactosyl-N-neotose.

[0041] Thirdly, the present invention provides a nutritional composition comprising the above-mentioned HMO concentrate syrup.

[0042] In this invention, the term "nutritional composition" refers to a composition that provides nutrition to the object. This nutritional composition is typically taken orally or intravenously, and it generally includes a lipid or fat source and a protein source.

[0043] Fourthly, the present invention provides a food product comprising the above-mentioned HMO concentrate syrup.

[0044] In this invention, the term "food" is intended to cover any consumable substance. Therefore, it can be a product intended for human consumption, particularly infant formula, follow-up formula, and foods for infants or young children such as baby cereals. In particular, the HMO concentrate syrup of this invention can be added to infant formula, dehydrated milk, or cereal mixtures.

[0045] This invention provides an HMO concentrate syrup and its preparation method. Through improvements in the preparation method, the stability of the high-concentration HMO concentrate syrup under refrigeration is achieved. This discovery overcomes the limitations of HMO concentrate syrup in terms of application scope and high storage and transportation costs, fills market gaps, and provides technical support for the development of more downstream products containing HMO. Detailed Implementation

[0046] The terms “comprising” or “including” in this invention are open-ended descriptions that include the specified ingredients or steps described, as well as other specified ingredients or steps that do not materially affect them.

[0047] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0048] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "specific implementation," or "some specific implementations," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0049] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0050] Where specific techniques or conditions are not specified in the examples, they shall be performed in accordance with the techniques or conditions described in the literature in this field, or in accordance with the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased through legitimate channels.

[0051] Example 1

[0052] This embodiment provides a 2′-fucosylated lactose concentrate, the preparation method of which is as follows:

[0053] (1) The 2′-fucosylated lactose fermentation broth (2′-fucosylated lactose content is 5%) was filtered through a 200nm filter membrane to remove bacteria, and sterile fermentation broth was obtained;

[0054] (2) Heat the sterile fermentation broth obtained in step (1) to 43°C; add activated carbon (the mass ratio of the amount of activated carbon added to the mass of the sterile fermentation broth is 6:100), stir, filter to remove activated carbon and protein, and obtain decolorized broth;

[0055] (3) The decolorized solution obtained in step (2) is sequentially adsorbed and desalted by cation exchange resin and anion exchange resin to obtain a desalted solution; the desalted solution is concentrated under reduced pressure to obtain a desalted concentrate.

[0056] The cation exchange resin is a strong acid styrene-based cation exchange resin 001X7 (Anhui Samsung Resin Co., Ltd.), and the anion exchange resin is a macroporous weakly basic anion exchange resin D315 with a polyacrylic acid skeleton (Anhui Samsung Resin Co., Ltd.).

[0057] The conductivity of the desalting solution is 8 μS / cm, and the mass concentration of 2′-fucosylated lactose in the desalting solution is 75 g / L;

[0058] The conductivity of the desalting concentrate is 8 μS / cm;

[0059] (4) The desalted concentrate obtained in step (3) is separated using a styrene polymer gel column and eluted with pure water to obtain an eluent; wherein, the column temperature of the chromatographic column is 55℃; the purity of 2′-fucosylated lactose in the eluent is 97%;

[0060] The eluent contains 10% 2′-fucosylated lactose by mass, and is filtered before UHT treatment.

[0061] (5) The eluent obtained in step (4) is concentrated in a falling film evaporator at 65°C under negative pressure until the mass content of 2′-fucosylated lactose is 70%; at this time, the temperature of the resulting liquid is 70°C.

[0062] (6) Cool the concentrated liquid to 4°C within 2 hours. Specifically, first, the liquid temperature is rapidly reduced to room temperature through a heat exchanger, and then cooled to 4°C through a jacketed cooling element (coolant temperature is -15°C). The stirring speed is 200 rpm during the cooling process.

[0063] (7) After cooling to 4℃, continue to keep warm and stir for 2 hours at a speed of 200 rpm to obtain 2′-fucosylated lactose concentrate. The crystal particle size D90 was measured to be 145 micrometers.

[0064] Example 2

[0065] This embodiment provides a 2′-fucosylated lactose concentrate, the preparation method of which is as follows:

[0066] (1) The 2′-fucosylated lactose fermentation broth (2′-fucosylated lactose content is 5%) was filtered through a 200nm filter membrane to remove bacteria, and sterile fermentation broth was obtained;

[0067] (2) Heat the sterile fermentation broth obtained in step (1) to 43°C; add activated carbon (the mass ratio of the amount of activated carbon added to the mass of the sterile fermentation broth is 6:100), stir, filter to remove activated carbon and protein, and obtain decolorized broth;

[0068] (3) The decolorized solution obtained in step (2) is sequentially adsorbed and desalted by cation exchange resin and anion exchange resin to obtain a desalted solution; the desalted solution is concentrated under reduced pressure to obtain a desalted concentrate.

[0069] The cation exchange resin is a strong acid styrene-based cation exchange resin 001X7 (Anhui Samsung Resin Co., Ltd.), and the anion exchange resin is a macroporous weakly basic anion exchange resin D315 with a polyacrylic acid skeleton (Anhui Samsung Resin Co., Ltd.).

[0070] The conductivity of the desalting solution is 8 μS / cm, and the mass concentration of 2′-fucosylated lactose in the desalting solution is 75 g / L;

[0071] The conductivity of the desalting concentrate is 8 μS / cm;

[0072] (4) The desalted concentrate obtained in step (3) is separated using a styrene polymer gel column and eluted with pure water to obtain an eluent; wherein, the column temperature of the chromatographic column is 55℃; the purity of 2′-fucosylated lactose in the eluent is 97%;

[0073] The eluent contains 20% 2′-fucosylated lactose by mass, and after filtration, it is subjected to UHT.

[0074] (5) The eluent obtained in step (4) is concentrated in a rotary evaporator under a negative pressure of -0.1 MPa until the mass content of 2′-fucosylated lactose is 75%, and the temperature of the resulting liquid is 65℃.

[0075] (6) Cool the concentrated liquid to 0°C within 2 hours. Specifically, first, the liquid temperature is rapidly reduced to room temperature through a heat exchanger, and then cooled to 0°C within 2 hours through a jacketed cooling element (coolant temperature is -15°C). The stirring speed is 200 rpm during the cooling process.

[0076] (7) After cooling down to 0℃, the temperature is raised to 10℃ within 1 hour, and then cooled down to 0℃ within 2 hours. During the cooling process, the stirring speed is 200 rpm to obtain a 2′-fucosylated lactose concentrate. The crystal particle size D90 is measured to be 55 micrometers.

[0077] Example 3

[0078] This embodiment provides a 2′-fucosylated lactose concentrate, the preparation method of which is as follows:

[0079] Steps (1) to (4) are the same as steps (1) to (4) in Example 2;

[0080] (5) The eluent obtained in step (4) is concentrated in a rotary evaporator under a negative pressure of -0.1 MPa until the mass content of 2′-fucosylated lactose is 75%, and the temperature of the resulting liquid is 60°C.

[0081] (6) Cool the concentrated liquid to 4°C within 1 hour. Specifically, first, the liquid temperature is rapidly reduced to room temperature through a heat exchanger, and then cooled to 4°C within 1 hour through a jacketed cooling element (coolant temperature is -15°C). The stirring speed is 200 rpm during the cooling process.

[0082] (7) After cooling down to 4°C, the temperature is raised to 15°C within 1 hour, and then cooled down to 4°C within 1 hour. During the cooling process, the stirring speed is 200 rpm to obtain a 2′-fucosylated lactose concentrate. The crystal particle size D90 is measured to be 68 micrometers.

[0083] Comparative Example 1

[0084] This comparative example provides a 2′-fucosylated lactose concentrate (concentration of 70%) prepared by a conventional method. That is, compared with Example 1, after obtaining the concentrate in step (5), there are no other process operations, and it is naturally cooled to room temperature.

[0085] Comparative Example 2

[0086] This comparative example provides a 2′-fucosylated lactose concentrate (concentration of 70%) prepared by a conventional method. That is, compared with Example 1, after obtaining the concentrate in step (5), it is allowed to cool naturally to room temperature and then placed in a non-rapidly cooled environment of 4°C for storage.

[0087] Effect Comparison

[0088] Take 1L of each of the 2′-fucosylated lactose concentrates obtained in each example and comparative example, place them in a glass jar and store at 0°C for two months.

[0089] 1. Observation revealed that there were no clumps of crystals at the bottom of the concentrates in Examples 1, 2, and 3. The small crystals at the bottom of Example 1 could be easily dispersed by shaking. Examples 2 and 3 were only cloudy in appearance.

[0090] In contrast, the concentrated solutions of Comparative Examples 1 and 2 showed that the crystals at the bottom were clumped together and could not be dispersed.

[0091] 2. Solubility

[0092] The concentrated solutions obtained in Examples 1, 2, and 3 were heated to 30°C in a water bath and kept for 10 minutes while being stirred at 50 rpm until they were completely dissolved.

[0093] The concentrates of Comparative Examples 1 and 2 could not be completely dissolved when heated in a water bath to 30°C for 20 minutes and stirred at 50 rpm. They were completely dissolved after stirring for 40 minutes.

[0094] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing HMO concentrate syrup, characterized in that, include: The HMO fermentation broth obtained by microbial fermentation was separated, purified, and concentrated to more than 60 wt%. Then, it was cooled to -10~4℃ within 0.5-2h, with stirring maintained during the cooling process. After cooling to the target temperature, stirring was continued for 1-4h.

2. The method for preparing HMO concentrate syrup according to claim 1, characterized in that, The preparation method includes: separating and purifying the HMO fermentation broth obtained by microbial fermentation, concentrating it to more than 60wt%, and then cooling it to -10~4℃ within 0.5-2h; After cooling to the target temperature, raise the temperature by 10-20℃ within 0.5-1h and maintain it for 0-1h, then cool it down to -10~4℃ within 0.5-2h.

3. The method for preparing HMO concentrate syrup according to claim 1 or 2, characterized in that, Stirring is performed during the cooling process at a speed of 100-500 rpm.

4. The method for preparing HMO concentrate syrup according to claim 1 or 2, characterized in that, The cooling process includes: first, rapidly reducing the temperature of the liquid to room temperature using a heat exchanger, and then cooling it to -10 to 4°C using a jacketed cooling element.

5. The method for preparing HMO concentrate syrup according to claim 1 or 2, characterized in that, The separation and purification steps involve sequentially subjecting the HMO fermentation broth to sterilization treatment, decolorization treatment, ion exchange desalting treatment, and chromatographic separation. After separation and purification, the purity of the HMO fermentation broth is above 95%.

6. The method for preparing HMO concentrate syrup according to claim 5, characterized in that, Before the concentration process, the liquid material is subjected to ultra-high temperature instantaneous sterilization.

7. The HMO concentrate syrup prepared by any one of claims 1-6, characterized in that, The HMO concentration is above 60%, the HMO concentrate syrup does not contain genetically engineered microorganisms, nucleic acid molecules of microorganisms and proteins derived from genetically engineered microorganisms, or organic solvents, the purity of the HMO is at least 95%, and 90% of the crystals in the HMO concentrate have a particle size of no more than 150 micrometers.

8. The HMO concentrate syrup according to claim 7, characterized in that, In the HMO concentrate, 90% of the crystals have a particle size of no more than 80 micrometers.

9. The HMO concentrate syrup according to claim 8, characterized in that, The HMO concentrate syrup can be completely reconstituted within 20 minutes when the temperature is raised to 30°C after being left at 0°C for more than one month, and the reconstitution process includes stirring.

10. The HMO concentrate syrup according to claim 8 or 9, characterized in that, The HMO is a fucoidan, a sialic acid oligosaccharide, or an oligosaccharide formed from a core glycan structure that does not contain fucoidan or sialic acid groups.

11. The HMO concentrate syrup according to claim 10, characterized in that, The HMO is a neutral HMO.

12. The HMO concentrate syrup according to claim 11, characterized in that, The HMO is selected from one or more of 2'-fucosylvose, 3'-fucosylvose, 2',3'-difucosylvose, lactosyl-N-triose II, lactosyl-N-butose, lactosyl-N-neotose, lactosyl-N-fucosylvose I, lactosyl-N-neotose, lactosyl-N-fucosylvose II, lactosyl-N-fucosylvose III, lactosyl-N-fucosylvose V, lactosyl-N-neotose V, lactosyl-N-difucosylvose I, lactosyl-N-difucosylvose II, 6'-galactosyllactose, 3'-galactosyllactose, lactosyl-N-hexose, and lactosyl-N-neotose.

13. A nutritional composition, characterized in that, Includes the HMO concentrate syrup according to any one of claims 7-12.

14. A food product, characterized in that, Includes the HMO concentrate syrup according to any one of claims 7-12.

15. The food product according to claim 14, characterized in that, The food in question is infant formula.