Abstrict Disclosed are a novel desiccant containing a non-reducing anhydrous
trehalose as an effective ingredient; a dehydration of hydrous matters,
e.g. food products, pharmaceuticals and cosmetics, therewith; and
dehydrated products obtained by the dehydration. Such hydrous matters
are dehydrated without causing alteration or deterioration by incorporating
anhydrous trehalose into the hydrous matters to convert the anhydrous
trehalose into hydrous crystalline trehalose. The anhydrous trehalose
are anhydrous crystalline trehalose and hydrous amorphous trehalose.
Claims We claim:
1. In a desiccant comprising a saccharide as an the dessicant ingredient
and an inert diluent, the improvement wherein said saccharide is
selected from the group consisting of anhydrous crystalline trehalose,
anhydrous amorphous trehalose and mixtures thereof, which anhydrous
trehalose has substantially no reducing activity and which is converted
into hydrous crystalline trehalose upon absorbing moisture, and
wherein said anhydrous crystalline trehalose is obtained by:
providing a syrupy aqueous solution of trehalose with a moisture
content lower than 10 w/w %;
maintaining said syrupy aqueous solution of trehalose at a temperature
in the range of 50.degree.-160.degree. C. in the presence of a seed
crystal in order to crystallize anhydrous crystalline trehalose;
and
recovering the resultant anhydrous crystalline trehalose; and
said anhydrous amorphous trehalose is obtained by drying a syrupy
aqueous solution of trehalose or a hydrous crystalline trehalose,
and recovering the resultant anhydrous amorphous trehalose.
2. A method for dehydrating a hydrous matter comprising adding
from 0.01 to 200 parts by weight of anhydrous trehalose to one part
by weight of a hydrous matter to convert said anhydrous trehalose
into hydrous crystalline trehalose, thereby dehydrating said hydrous
matter, wherein said anhydrous trehalose is selected from the group
consisting of anhydrous crystalline trehalose, anhydrous amorphous
trehalose, and mixtures thereof;
wherein said anhydrous crystalline trehalose is obtained by:
providing a syrupy aqueous solution of trehalose with a moisture
content lower than 10 w/w %;
maintaining said syrupy aqueous solution of trehalose at a temperature
in the range of 50.degree.-160.degree. C. in the presence of a seed
crystal in order to crystallize anhydrous crystalline trehalose;
and
recovering the resultant anhydrous crystalline trehalose; and
said anhydrous amorphous trehalose is obtained by drying a syrupy
aqueous solution of trehalose or a hydrous crystalline trehalose,
and recovering the resultant anhydrous amorphous trehalose.
3. The method of claim 2 wherein said hydrous matter contains at
least one member selected from the group consisting of gelatinized
starch, alcohols, oil-soluble substances and biologically active
substances.
4. The method of claim 2 wherein said anhydrous trehalose entraps
about 10 w/w % moisture from said hydrous matter.
Description FIELD OF THE INVENTION
The present invention relates to a desiccant comprising anhydrous
trehalose as an effective ingredient, as well as to a method for
dehydrating hydrous matters with said desiccant and to dehydrated
products obtainable by the method.
DEFINITION
Throughout the specification, the wording "w/w %" will
be abbreviated as "%", unless specified otherwise.
BACKGROUND OF THE INVENTION
As disclosed by the present inventors in Japanese Patent Laid-Open
Nos.136240/87 152536/87 and 152537/87 conventional dehydration
methods using anhydrous saccharides are those wherein a dehydrating
activity is utilized, said activity being exerted by allowing an
anhydrous saccharide to absorb moisture from a hydrous matter to
convert the anhydrous saccharide into a hydrous crystalline form.
Unlike heat drying, these methods require no heating conditions
and have a merit of converting hydrous matters into dehydrated products
without deterioration or degeneration of their quality.
It was found that among the above-mentioned methods the method
using anhydrous aldohexoses such as anhydrous glucose or galactose
as disclosed in Japanese Patent Laid-Open No.152536/87 attains
a satisfiable dehydration of a relatively-large amount of water
and readily induces the maillard reaction because such an anhydrous
aldohexose has a reducing property and a relatively-high reactivity
to substances such as amino acids or peptides; and because of these,
there exists an anxiety about the stability of the resultant dehydrated
product. It was also found that anhydrous aldohexoses are not convertible
into hydrous crystalline aldohexoses even at an elevated humid condition,
and only exert a poor dehydrating-activity. It was found that in
case of using anhydrous maltose as disclosed in Japanese Patent
Laid-Open No. 136240/87 and in case of using anhydrous paratinose
as disclosed in Japanese Patent Laid-Open No. 152537/87 there
still remains an anxiety about a long-term stability of the resultant
dehydrated product because anhydrous maltose and anhydrous paratinose,
even if they have a relatively-low reducing activity, are basically
reducing sugars. It was also found that the amount of moisture absorbed
by anhydrous maltose or anhydrous paratinose is relatively low,
i.e. about 5 w/w % with respect to the amount of the anhydrous maltose
or the anhydrous paratinose, and because of this such saccharides
have a demerit that it should be used as a desiccant in a relatively-large
amount.
It may be speculated that anhydrous non-reducing glycosylfructosides
such as anhydrous raffinose, anhydrous erlose and anhydrous melezitose
as disclosed in Japanese Patent Laid-Open No. 152537/87 have no
reducing activity and do not react with amino acids and peptides,
and this imparts them a satisfactory shelf-life without inducing
the maillard reaction. Anhydrous glycosylfructosides, however, have
a fructoside bond with a relatively-low acid tolerance in their
molecules, and this may lead to an estimation that the anhydrous
glycosylfructosides are not necessarily suitable as a desiccant
for acid hydrous matters. In this case, there still remains an anxiety
about stability in the resultant dehydrated products.
SUMMARY OF THE INVENTION
In order to overcome these demerits of conventional dehydration
methods using saccharides, the present inventors have screened natural
non-reducing anhydrous saccharides and studied to establish a desiccant
with a satisfiable dehydrating activity, as well as its uses.
As a result, the present inventors found that among the non-reducing
anhydrous saccharides as tested anhydrous trehalose (throughout
the specification, ".alpha., .alpha.-trehalose" and ".alpha.,.beta.-trehalose"
are designated as "trehalose" and "neotrehalose"
respectively) dehydrates a relatively-large amount of water and
exerts a strong dehydrating activity, and that the resultant dehydrated
products prepared with the anhydrous trehalose are extremely stable.
These render the anhydrous trehalose useful as a desiccant in a
variety of fields. In other words, the present inventors found that
when anhydrous trehalose is incorporated into hydrous matters such
as hydrous food-products and hydrous pharmaceuticals, the anhydrous
trehalose is converted into hydrous crystalline trehalose which
absorbs a relatively-large amount of water in the hydrous matters
and exerts as a desiccant a strong dehydrating-activity. The anhydrous
trehalose is used in a variety of hydrous matters including hydrous
acidic matters. The present inventors also confirmed that anhydrous
trehalose is used in the preparation of dehydrated products such
as dehydrated food products with a satisfactory taste and quality,
as well as dehydrated pharmaceuticals with a relatively-high activity
and stability. Thus, the present inventors accomplished this invention.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
FIG. 1 shows a powder x-ray diffraction figure of hydrous crystalline
trehalose.
FIG. 2 shows a powder x-ray diffraction figure of anhydrous crystalline
trehalose.
FIG. 3 shows a powder x-ray diffraction figure of anhydrous amorphous
trehalose.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present inventors screened desiccants using non-reducing saccharides
and chose as the desiccant anhydrous trehalose which had not been
deemed useful for that purpose. The present inventors first accomplished
the dehydration method for a hydrous matter by incorporating anhydrous
trehalose thereinto.
The dehydration method according to the present invention can be
arbitrarily used to dehydrate hydrous matters, especially, those
which contain free water different from a bonded water such as water
incorporated in a crystalline structure. For example, the present
method can be advantageously used to decrease the moisture content
in atmosphere of a moistureproof package enclosing a dehydrated
food product, as well as to decrease the moisture content in a variety
of hydrous matters such as food products, pharmaceuticals, cosmetics,
chemicals for industrial uses, and their materials or intermediates.
The present inventors found that when anhydrous trehalose is incorporated
into the above-mentioned hydrous matters, it entraps about 10 w/w
% moisture from the hydrous matters in hydrous crystalline trehalose,
which is 2-fold higher than that attained with anhydrous maltose,
and substantially eliminates the moisture from the hydrous matters
or even brings them to dryness.
It was also found that the relative humidity in a moistureproof
package enclosing a dehydrated food product, for example, "ajitsuke-nori"
(seasoned laver) and cookie, is extremely decreased by placing in
the moistureproof package a small moisture-permeable paper-bag injected
with anhydrous trehalose, whereby the quality of the dehydrated
food product or powdery product is stabilized over a relatively-long
period of time.
Since anhydrous trehalose neither becomes sticky nor oozes during
or after conversion into hydrous crystalline trehalose, dehydrated
food products and moistureproof packages are free from staining.
Anhydrous trehalose prevents the solidification of powdery products
and their adhesion to moistureproof packages. In addition, trehalose
per se causes no side effect because it is a non-toxic and harmless
natural-sweetener.
According to the present invention, high-quality food products
with a substantially-decreased moisture in the form of, for example,
massecuite or powder, can be readily prepared by incorporating anhydrous
trehalose into food products with a relatively-high moisture content
in liquid or paste form, for example, brandy, vinegar, royal jelly,
fresh cream and mayonnaise to convert the anhydrous trehalose into
hydrous crystalline trehalose.
The dehydration method according to the present invention is characterized
in that it utilizes a stable non-reducing saccharide, i.e. anhydrous
trehalose, and requires no heat treatment such as heat drying, whereby
a relatively-high moisture content food product in liquid or paste
form is readily converted into a dehydrated product with a decreased
moisture and a satisfiable flavor and taste without alternating
or deteriorating the food product.
It was found that dehydrated food products in which anhydrous trehalose
has been partially converted into hydrous crystalline trehalose,
i.e. dehydrated food products containing anhydrous trehalose are
obtainable by adding an excessive amount of anhydrous trehalose
to material food products in an amount of which exceeds the moisture
content in the food products; and that when the dehydrated food
products is injected into moistureproof packages the moisture in
the packages are entrapped by the anhydrous trehalose for its conversion
into hydrous crystalline trehalose, whereby the relative humidity
in the packages is decreased by a large margin and the atmosphere
in the packages is kept at a relatively-high dryness. As a result,
it was found that the dehydrated food products obtained by the present
invention are prevented from bacterial contamination, as well as
alteration or deterioration such as hydrolysis, souring and browning,
and because of this the products with a satisfactory quality and
taste are stably retained for a relatively-long period of time.
In the preparation of dehydrated pharmaceuticals with a high quality
and a substantially-decreased moisture level, for example, those
in the form of massecuite and powder are readily prepared by incorporating
anhydrous trehalose into pharmaceuticals in liquid form such as
those containing lymphokines and antibiotics, as well as those in
paste form such as ginseng extract and snapping turtle extract,
to convert the anhydrous trehalose into hydrous crystalline trehalose.
The preparations can provide a high quality and stable dehydrated-pharmaceuticals
because they do not require severe conditions such as heat drying,
and because the anhydrous trehalose acts as a desiccant and stabilizer.
Conventional stabilizers such as water-soluble high molecular-weight
substances substantially do not waste energy for their drying so
that they can be favorably added to the dehydrated pharmaceuticals
to improve their qualities and stabilities.
The present invention can be advantageously practiced in the preparations
of solid pharmaceuticals by placing a prescribed amount of anhydrous
trehalose, for example, in a vial; adding to the vial an aqueous
solution containing a biologically active substance such as a lymphokine
or a hormone in an amount of which is slightly-lower than the moisture
content required for the complete conversion of the anhydrous trehalose
into hydrous crystalline trehalose; and cap sealing the vial.
In this case, it was found that the anhydrous trehalose dehydrates
the aqueous solution containing a biologically active substance,
and dehumidifies the atmosphere in the vial.
It was also found that as a consequence the present invention facilitates
the preparation of dehydrated solid pharmaceuticals, and still that
the solid pharmaceuticals retain their high-quality over a relatively-long
period of time and readily dissolve in water on use.
High quality and stable solid pharmaceuticals can be advantageously
prepared by mixing a prescribed amount of anhydrous trehalose while
a prescribed amount of an aqueous solution containing a biologically
active substance, placing the resultant powdery product in a container,
and sealing the container. If necessary, the powdery product can
be suitably formed into a granule or a tablet in usual manner.
As described above, unlike conventional desiccants such as a silica
gel and a calcium oxide, the present desiccant using anhydrous trehalose
is edible, and, therefore it is assimilable and alimentary in the
body. It also acts as a stabilizer for biologically active substances.
The present inventors studied on the preparation of anhydrous trehalose,
especially, the preparation of a powdery anhydrous trehalose.
The anhydrous trehaloses suitably used in the invention are, for
example, anhydrous crystalline trehalose and anhydrous amorphous
trehalose.
In Journal of the Chemical Society, pp.3489-3490 (1965), G. Birch
reported a preparation of anhydrous crystalline trehalose by crystallizing
it in pyridine. The preparation is, however, expensive because it
requires an excessive amount of pyridine as a solvent, and not satisfiable
in view of the food sanitation.
In view of the prior art, the present inventors studied the preparation
of a powdery anhydrous crystalline trehalose and established the
preparation thereof, e.g. a preparation which comprises providing
an aqueous solution in which a commercially available hydrous trehalose
has been dissolved or providing an aqueous trehalose solution prepared
by extracting trehalose from yeasts and purifying the resultant
extract in accordance with a method as described by M. Hayashibe
and K. Aso in Hakko-Kyokai-shi, Vol. 17 pp. 106-115 (1959); preparing
such an aqueous solution into a syrup with a relatively-high concentration
and a moisture content lower than about 10%, preferably, 2.0% or
higher but lower than 9.5%; keeping the syrup in the presence of
a seed crystal at a temperature of 50.degree.-160.degree. C. to
crystallize anhydrous crystalline trehalose; and pulverizing the
resultant crystal.
The pulverizing methods usable in the invention are suitably chosen
from conventional methods such as a block pulverization, extruding
granulation, fluidized-bed granulation and spray-drying. The anhydrous
amorphous trehaloses usable in the invention can be prepared from
a commercially-available hydrous crystalline trehalose or a concentrated
solution of a high-purity trehalose extracted and purified from
yeasts.
In the case of using hydrous crystalline trehalose as a material
for anhydrous trehalose, the hydrous crystalline trehalose is dissolved
in water, dried in vacuo or at an atmospheric pressure and at a
temperature of about 100.degree.-160.degree. C., and pulverized
to obtain anhydrous trehalose. In the case of using an aqueous solution
of a high-purity trehalose as a material for anhydrous trehalose,
for example, an about 70-90% trehalose syrup can be advantageously
dried in vacuo or at an atmospheric pressure, and pulverized into
anhydrous trehalose. Alternatively, an about 60-85% trehalose syrup
can be advantageously subjected to a spray-drying such as a high-pressure
nozzle method and a rotating disk method to directly obtain a powdery
anhydrous trehalose.
The powdery anhydrous trehaloses usable in the invention are non-reducing
saccharide powders in white having (i) a satisfactorily high-quality
and low-sweetness; (ii) a relatively-low moisture content or substantially
anhydrous, usually, 3% or lower, preferably, 2% or lower on the
Karl Fischer's method; and (iii) a substantial free-flowing ability
which may be varied dependently on their particle size and shape.
The anhydrous trehalose as referred to in the invention includes
any substantially anhydrous trehalose as long as it absorbs moisture
and converts into hydrous crystalline trehalose to exert a strong
dehydrating activity. In order to augment the effect of anhydrous
trehalose as a desiccant, trehalose can be formulated to coexist
in a powdery anhydrous amorphous trehalose the lowest possible amount
of hydrous crystalline trehalose as a seed crystal, usually, in
an amount lower than 5%, preferably, lower than one %, whereby the
conversion rate of anhydrous trehalose into hydrous crystalline
trehalose is improved.
It was found that the powdery anhydrous trehalose thus obtained
acts as a desiccant with a strong dehydrating activity against hydrous
matters in a manner such that it entraps and fixes the moisture
contained in hydrous matters such as food products, pharmaceuticals,
cosmetics and industrial chemicals when incorporated into the hydrous
matters.
The present desiccant can be advantageously used to dehumidify
and dry the atmosphere in a moistureproof package, as well as to
prepare a high-quality dehydrated product in massecuite or powder
form from a hydrous matter which is susceptible to alteration and
deterioration during heat drying- or vacuum drying-step, as well
as from those which are substantially difficult to dry.
The present desiccant can be suitably used to dehumidify and dry
hydrous matters. For example, it can be used to prevent "ajitsuke-nori"
and cookies from absorbing moisture, or advantageously incorporated
into powdery products which readily absorb moisture to form solid
products, for example, ready-mixed powders such as those of purine
and hot cake; powdery seasonings such as salt, sugar, powdered soy
sauce, powdered "miso" (soybean paste), powdered "sushi-su"
(a vinegar), powdered "dashi-no-moto", powdery mixed seasoning,
powdered paprika, powdered garlic, powdered cinnamon, powdered nutmeg,
powdered pepper and powdered sage; and other powdery products such
as powdered yeast extract, powered milk, powdered yogurt, powdered
cheese, powdered juice, powdered herb, powdered vitamin, granulated
soup, granulated bouillon, fish flour, blood meal, bone meal, powdered
agent of lactic acid bacteria, powdered enzyme and granulated digestive;
followed by placing the resultant dehydrated product into a package,
whereby (i) the relative humidity within the package is decreased,
and (ii) the resultant product is prevented from solidification
and adhesion to the package, and satisfactorily retains its quality
for a relatively-long period of time.
The desiccant according to the present invention can be suitably
used to dehydrate hydrous matters such as organs, tissues, cells,
homogenates, extracts and components derived from animals, plants
and microorganisms, as well as preparations therefrom.
When a hydrous matter is a food product, or its materials or intermediates
exist in liquid or paste form, a stable and tasty dehydrated food
product can be readily prepared according to the invention. Examples
of such a hydrous matter are agricultural products such as fresh
fruit, juice, vegetable extract, soybean milk, sesame paste, nut
paste, "nama-an" (unsweetened bean jam), gelatinized starch
paste and wheat flour; marine products such as sea urchin paste,
oyster extract and sardine paste; poultry and livestock products
such as fresh egg, lecithin, milk, whey, fresh cream, yogurt, butter
and cheese; hydrous seasonings such as maple syrup, honey, "miso"
(soybean paste), soy sauce, mayonnaise, dressing, bonito extract,
meat extract, tangle extract, chicken extract, beef extract, yeast
extract, mushroom extract, licorice extract, stevia extract, enzymatically
processed product thereof and seasoning liquid for pickles; liquors
such as Japanese sake, wine, brandy, whisky and medical liqueur;
soft drinks such as a tea, green tea and coffee; hydrous spices
such as those extracted from peppermint, "wasabi" (Japanese
horseradish), garlic, mustard, "sansho" (Japanese pepper
tree), cinnamon, sage, laurel, pepper and citrus fruit; hydrous
coloring agents such as those extracted from madder, annatto (Bixa
oreliana), turmeric, paprika, red beet, safflower, cape jasmine,
saffron and extract from microorganism of the genus Monascus; hydrous
emulsifiers such as a fatty acid sugar ester, glycerine, fatty acid
ester and sorbitan fatty acid ester; and preservatives in liquid
or paste form such as a smoke solution and a fermented solution.
The dehydrated products obtained in this way, for example, a powdered
agricultural- or poultry-product, powdered oil and fat, powdery
flavor and powdery coloring agent can be conveniently used, for
example, as a natural bulk flavor excellent in taste and flavor,
in various food products, for example, seasonings such as a mayonnaise
and soup stock; confectioneries such as a hard candy and cake; and
materials for food products such as a hot cake mix and instant juice.
When a hydrous matter is a pharmaceutical, or its material or intermediate,
it can be readily prepared into a stable and highly-active pharmaceutical
according to the present invention without inactivating the effective
ingredients. Examples of such a hydrous matter are a solution containing
lymphokine such as an .alpha.-, .beta.- .gamma.-interferon, tumor
necrosis factor-.alpha. (TNF-.alpha.), tumor necrosis factor-.beta.
(TNF-.beta.), macrophage migration inhibitory factor, colony-stimulating
factor, transfer factor and interleukin 2; a solution containing
hormone such as insulin, growth hormone, prolactin, erythropoietin
and follicle-stimulating hormone; a solution containing a biological
preparation such as BCG vaccine, Japanese encephalitis vaccine,
measles vaccine, live polio vaccine, smallpox vaccine, tetanus toxoid,
Trimeresurus antitoxin and human immunoglobulin; a solution containing
an antibiotic such as penicillin, erythromycin, chloramphenicol,
tetracycline, streptomycin and kanamycin sulfate; a solution containing
a vitamin such as thiamine, riboflavin, L-ascorbic acid, liver oil,
carotenoid, ergosterol and tocopherol; a solution containing an
enzyme such as lipase, elastase, urokinase, protease, .beta.-amylase,
isoamylase, glucanase and lactase; an extract such as ginseng extract,
snapping turtle extract, chlorella extract, aloe extract and propolls
extract; a paste of cell or minute infectious agent such as those
of virus, lactic acid bacterium and yeast; and a liquid or paste
such as royal jelly.
In order to dehydrate hydrous matters such as a cosmetic and its
materials or intermediates, a high-quality cosmetic can be readily
prepared by dehydrating a hydrous matter such as a fresh egg, lecithin,
fresh cream, honey, licorice extract, flavor, coloring agent or
an enzyme similarly as in the cases of food products and pharmaceuticals.
The cosmetic thus obtained can be advantageously used as a skin-
or hair-treatment, as well as a hair restorer. When a dehydrated
product is of an enzyme, it can be advantageously used as a therapeutic
agent, digestive and enzymatic detergent, as well as a catalyst
for the preparations of food products, pharmaceuticals and industrial
materials.
Any conventional method such as mixing, kneading, dissolving, permeating,
soaking, sprinkling, coating, spraying, crystallizing and injecting
can be suitably employed as a method to incorporate anhydrous trehalose
into hydrous matters before the completion of the processings of
the objective dehydrated products.
Although the amount of anhydrous trehalose to be incorporated into
a hydrous matter is varied depending on the moisture content and
property of the hydrous matter, it is generally 0.01-200 parts by
weight, desirably, 0.01-50 parts by weight to one part by weight
of the hydrous matter. If necessary, the anhydrous trehalose may
be incorporated into a hydrous matter after the hydrous matter has
been partially dehydrated or concentrated by conventional method.
In such a case, in order to improve the quality of the objective
dehydrated-products such as food products, pharmaceuticals and cosmetics,
an adequate flavor-imparting agent, coloring agent, taste-imparting
agent, stabilizer and/or filler can be suitably used in combination
with the anhydrous trehalose.
Examples of such a stabilizer are water-soluble polymers which
have been hardly deemed to be dehydrated, and not limited to a relatively-low
molecular-weight compound such as an antioxidant because the present
method for dehydration employs anhydrous trehalose with a strong
dehydrating activity. Examples of such a water-soluble polymer suitably
used as a stabilizer in the invention are soluble starch, dextrin,
pullulan, elsinan, dextran, xanthan gum, gum arabic, locust bean
gum, guar gum, tragacanth gum, carboxymethyl starch, hydroxyethyl
cellulose, pectin, agar, gelatin, albumin and casein.
When such a water-soluble polymer is used as a stabilizer, a dehydrated
food product containing microcrystals of hydrous crystalline trehalose
can be prepared by first dissolving a water-soluble polymer to homogeneity
in a hydrous matter in liquid or paste form, then incorporating
anhydrous trehalose to homogeneity into the resultant solution by
a method such as mixing or kneading.
The product thus obtained retains the flavor and effective components
of the material hydrous matter because the flavor and effective
components are coated with a membrane of the above-mentioned water-soluble
polymer, or enclosed in a microcapsule surrounded by the membrane
together with the microcrystals of hydrous crystalline trehalose.
Because of this, the flavor and effective components are prevented
from volatilization and deterioration, and stably retained in the
microcapsule. If necessary, cyclodextrins, which form an inclusion
complex with the flavor and the effective components, can be suitably
used as a water-soluble polymer in combination with the anhydrous
trehalose.
The cyclodextrins usable in the invention are not restricted to
those with the highest possible purity, and may be those with a
relatively-low purity which can be hardly dried and pulverized.
For example, syrups of a partial starch hydrolyzate containing cyclodextrins
together with a large amount of maltodextrins can be favorably used.
The methods to prepare dehydrated products usable in the present
invention, especially, those to prepare powdery products are varied.
For example, dehydrated products or powdery products can be prepared
by a method comprising homogeneously mixing a hydrous matter having
a relatively-high moisture content such as food products, pharmaceuticals,
cosmetics and their materials or intermediates with anhydrous trehalose
to obtain a mixture having a moisture content of about 40% or lower,
preferably, 10-30%; placing the mixture in a container; allowing
the container to stand at about 10.degree.-50.degree. C., e.g. at
an ambient temperature, for about 0.1-5 days to solidify the mixture
while the anhydrous trehalose is permitted to convert to hydrous
crystalline trehalose; and cutting or pulverizing the resultant
solid product. If necessary, a drying step and/or a classification
step may be added to the cutting or pulverizing step. Furthermore,
powdery products can be directly obtained by subjecting a mixture
of a hydrous matter and anhydrous trehalose onto a spray-drying,
etc.
Such a powdery product can be also prepared by a method (I) comprising
spraying a prescribed amount of a hydrous matter in liquid or paste
form to anhydrous trehalose in a state of flux, granulating the
resultant mixture while the hydrous matter is in contact with the
anhydrous trehalose, and, if necessary further ageing the resultant
granule at a temperature of about 30.degree.-60.degree. C. for about
0.1-10 hours to convert the anhydrous trehalose into hydrous crystalline
trehalose; and a method (II) comprising mixing or kneading anhydrous
trehalose with a hydrous matter in liquid or paste form, and spraying
the resultant mixture instantly or after the initiation of the conversion
of the anhydrous trehalose into hydrous crystalline trehalose. If
necessary, the powdery product thus obtained may be further aged
similarly as in method (I) to convert the anhydrous trehalose into
hydrous crystalline trehalose. Methods (I) and (II) can be suitably
employed in the invention as a mass production of a powdery dehydrated-product.
In the case of such a spray-drying, it can be advantageously practiced
to coexist with anhydrous trehalose the lowest possible level of
hydrous crystalline trehalose as a seed crystal in order to promote
the conversion of the anhydrous trehalose into hydrous crystalline
trehalose, whereby the ageing period of time is satisfactorily shortened
or the ageing step can be even eliminated. The powdery dehydrated-product
thus obtained can be used alone, and, if necessary it can be formed
into a product in liquid or paste form in combination with a filler,
excipient, binder and/or stabilizer, and freely formed into a granule,
tablet, capsule, rod, plate or cube.
Sugar-coating products can be advantageously prepared by coating
a core or a center, for example, a food product such as a peanut,
almond or candy, or a pharmaceutical intermediate in the form of
a granule or a crude tablet, with an aqueous solution containing
about 60-90% of anhydrous trehalose, preferably, a solution containing
anhydrous trehalose together with an adequate amount of a binder
such as a water-soluble polymer to crystallize hydrous crystalline
trehalose on the core.
Generally, starch requires a relatively-large amount of moisture
in order to Sweiland gelantinize. For this reason, gelatinized starch
is highly susceptible to bacterial contamination. Anhydrous trehalose
can be favorably used as a desiccant for dehydrating such a gelatinized
starch. For example, "gyuhi" (a gelatinized starch in
paste form) is prevented from bacterial contamination by incorporating
anhydrous trehalose into the gelatinized starch to convert the anhydrous
trehalose into hydrous crystalline trehalose, whereby the moisture
in the gelatinized starch is substantially decreased.
Anhydrous trehalose readily disperses homogeneously into gelatinized
starch and acts as a retrogradation-preventing agent, and because
of this anhydrous trehalose satisfactorily prolongs the shelf life
of a variety of processed food products containing gelatinized starch.
Anhydrous trehalose can be used as a food preservative, stabilizer
and quality-improving agent in hydrous food products having a relatively-high
moisture content such as a peeled banana, orange, sliced steamed-potato,
opened horse-mackerel, Pacific saury, raw noodle, boiled noodle
and bean-jam cake by sprinkling anhydrous crystalline trehalose
as an anhydrous trehalose over the surface of the hydrous food products
to convert the anhydrous crystalline trehalose into hydrous crystalline
trehalose, whereby the moisture on the surface of the hydrous food
products is substantially decreased, and their qualities and shelf
lives are satisfactorily improved and prolonged. In this case, when
a more prolonged shelf life is required, the anhydrous crystalline
trehalose can be suitably used in combination with lactic acid,
citric acid and/or ethanol; and, if necessary the resultant dehydrated
products may be subjected to a vacuum package, a gas flush package
or a cold storage.
Anhydrous trehalose has a relatively-high affinity for alcohols.
This property renders anhydrous trehalose useful as a desiccant
to remove moisture contained in alcohols such as methanol, ethanol,
butanol, propylene glycol, glycerin and polyethylene glycol, as
well as in alcohol-soluble substances.
For example, dehydrated liquors in massecuite or powdery form,
which retain the effective ingredients and flavors of liquors, can
be prepared by dehydrating with anhydrous trehalose liquors such
as "sake" (Japanese rice wine), "shochu" (low-class
distilled spirits), wine, brandy, whisky and vodka. The powdery
dehydrated-liquors thus obtained can be used in confectioneries
and ready-mix powders, or used by dissolving them in water prior
to their use.
In this case, anhydrous trehalose can exert a satisfactory effect
as a desiccant and stabilizer, as well as a mild sweetener, filler
and adequate viscosity-imparting agent.
Effective elements such as iodine can be stably retained by mixing
an alcohol-soluble substance such as iodine with anhydrous trehalose,
and mixing the resultant mixture with an aqueous solution containing
a water-soluble high molecular-weight substance to convert the anhydrous
trehalose into hydrous crystalline trehalose. Thus, an ointment
in massecuite form having an adequate viscosity, extensibility and
adhesiveness can be favorably prepared.
Dehydrated products, for example, powdery food products such as
those of oils and fats, seasonings, flavors and color-imparting
agents; powdery cosmetics; and powdery pharmaceuticals such as those
of vitamins and hormones can be favorably prepared by incorporating
anhydrous trehalose into their material products to convert it into
hydrous crystalline trehalose while impregnating or mixing the anhydrous
trehalose with a latex, an emulsified product or a hydrous oil-soluble
substance.
In this case, anhydrous trehalose acts as a desiccant, and the
converted hydrous crystalline trehalose acts as a stabilizer, preservative,
filler and carrier.
Anhydrous trehalose can be suitably used in food products containing
oil-soluble substances such as a chocolate and cream filling which
are apt to be readily damaged by moisture. In this case, anhydrous
trehalose is used as a desiccant, as well as an agent for improving
the processibility, flavor and meltability in the mouth. The dehydrated
food products thus obtained has a relatively-long shelf-life.
As described above, the present invention was made based on the
findings that anhydrous trehalose strongly dehydrates hydrous matters,
and that the resultant dehydrated products have a satisfiable stability.
By using the anhydrous trehalose as a desiccant, high-quality food
products and cosmetics with a decreased moisture-content can be
favorably prepared without deteriorating or losing their flavors
and tastes; and high-quality pharmaceuticals and cosmetics with
a decreased moisture-content can be favorably prepared without decomposing
or losing their effective ingredients or activities.
In addition to the aforementioned specific properties, anhydrous
trehalose as a natural sweetener is readily assimilated and utilized
by the body without fear of causing cariogenicity and increasing
the blood cholesterol-level, and has substantially the same level
of nutritive value as maltooligosaccharides. Anhydrous trehalose
has a mild sweetness, body-imparting ability, gloss-imparting ability,
viscosity-imparting ability and moisture-retaining ability, and
these render it advantageously useful in food products, pharmaceuticals
and cosmetics.
The followings are illustrative of additional uses of anhydrous
trehalose:
Anhydrous trehalose can be used as a seasoning with a strong dehydrating
activity. If necessary, it can be used together with one or more
other sweeteners, for example, powdered syrup, glucose, isomerized
sugar, sucrose, maltose, honey, maple sugar, sorbitol, maltitol,
dihydrocharcone, stevioside, .alpha.-glycosyl stevioside, sweet
substance derived from Momordica grosvenori Swingle, glycyrrhizin,
thaumatin, L-aspartyl L-phenylalanine methyl ester, saccharin, glycine
and alanine; and/or a filler such as dextrin, starch and lactose.
Anhydrous trehalose, a non-reducing saccharide, has features: (i)
it has the inherent mild sweetness of trehalose; (ii) it well harmonizes
with other materials having sour-, acid-, salty-, bitter-, astringent-
and delicious-tastes, and (iii) it is highly acid- and heat-resistant.
Thus, anhydrous trehalose can be favorably used in food products
in general as a desiccant, as well as a sweetener, taste-improving
agent and quality-improving agent.
Anhydrous trehalose is used as a desiccant, sweetener, taste-improving
agent and quality-improving agent in seasonings such as soy sauce,
powdered soy sauce, "miso", "funmatsu-miso"
(a powdered miso), "moromi" (a refined sake), "hishio"
(a refined soy sauce), "furikake" (a seasoned fish meal),
mayonnaise, dressing, vinegar, "sanbai-zu" (a sauce of
sugar, soy sauce and vinegar), "funmatsu-sushi-su" (powdered
vinegar for sushi), "chuka-no-moto" (an instant mix for
Chinese dish), "tentsuyu" (a sauce for Japanese deep-fat
fried food), "mentsuyu" (a sauce for Japanese vermicelli),
sauce, catsup, "yakiniku-no-tare" (a sauce for Japanese
grilled meat), curry roux, instant stew mix, instant soup mix, "dashi-no-moto"
(an instant stock mix), mixed seasoning, "mirin" (a sweet
sake), "shin-mirin" (a synthetic mirin), table sugar and
coffee sugar.
Also, anhydrous trehalose can be freely used for dehydrating "wagashi"
(Japanese cakes) such as "senbei" (a rice cracker), "arare-mochi"
(a rice-cake cube), "okoshi" (a millet-and-rice cake),
"gyuhi" (a rice paste), "mochi" (a rice paste),
"manju" (a bun with a bean-jam), "uiro" (a sweet
rice jelly), "an" (a bean jam), "Uokan" (a sweet
jelly of beans), "mizu-Uokan" (a soft adzuki-bean jelly),
"kingUoku" (a kind of yokan), jelly, pao de Castella and
"amedama" (a Japanese toffee); confectioneries such as
bakery products such as bun, biscuit, cracker, cookie, pie, pudding,
butter cream, custard cream, cream puff, waffle, sponge cake, doughnut,
chocolate, chewing gum, caramel and candy; frozen desserts such
as ice cream and sherbet; syrups such as "kajitsu-no-syrup-zuke"
(a preserved fruit) and "korimitsu" (a sugar syrup for
shaved ice); pastes such as flour paste, peanut paste and fruit
paste; processed fruits and vegetables such as jam, marmalade, "syrup-zuke"
(fruit pickles) and "toka" (conserves); pickles and pickled
products such as "fukujin-zuke" (red colored radish pickles),
"bettara-zuke" (a kind of whole fresh radish pickles),
"senmai-zuke" (a kind of sliced fresh radish pickles)
and "rakkyo-zuke" (pickled shallots); premixes for pickles
and pickled products such as "takuan-zuke-no-moto" (a
premix for pickled radish) and "hakusai-zuke-no-moto"
(a premix for fresh white rape pickles); meat products such as ham
and sausage; fish meat products such as fish ham, fish sausage,
"kamaboko" (a steamed fish paste), "chikuwa"
(a kind of fish paste) and "tenpura" (a Japanese deep-fat
fried fish paste); "chinmi" (relish) such as "uni-no-shiokara"
(salted guts of sea urchin), "ika-no-shiokara" (salted
guts of squid), "su-konbu" (processed tangle), "saki-surume"
(dried squid strips), "fugu-no-mirin-boshi" (a dried mirin-seasoned
swellfish), and mashed and seasoned food of cod, sea bream and shrimp;
"tsukudani" (foods boiled down in soy sauce) such as those
of laver, edible wild plants, dried squid, fish and shellfish; daily
dishes such as "nimame" (cooked beans), potato salad and
"konbu-maki" (a tangle roll); milk products; canned and
bottled products such as those of meat, fish meat, fruit and vegetable;
alcoholic beverages such as synthetic sake, "zozyo-shu",
fruit wine and liquors; soft drinks such as coffee, cocoa, juice,
carbonated beverage, sour milk beverage and beverage containing
a lactic acid bacterium; instant food products such as instant pudding
mix, instant hot cake mix, juice power, instant coffee, "sokuseki-shiruco"
(an instant mix of adzuki-bean soup with rice cake) and instant
soup mix; as well as for sweetening the aforementioned food products
and improving their tastes and qualities.
The following experiments explain the present invention in detail:
EXPERIMENT 1
Comparison of Dehydrating Activities of Non-reducing Saccharides
and Stabilities of Dehydrated Products Prepared Therewith
Non-reducing saccharides used in this experiment were sucrose,
anhydrous crystalline trehalose, anhydrous amorphous trehalose,
hydrous crystalline trehalose, anhydrous amorphous neotrehalose,
hydrous crystalline neotrehalose, hydrous amorphous erlose, hydrous
crystalline erlose, anhydrous amorphous raffinose, hydrous crystalline
raffinose, anhydrous amorphous melezitose and hydrous crystalline
melezitose. The sucrose, hydrous crystalline trehalose, hydrous
crystalline erlose, hydrous crystalline raffinose and hydrous crystalline
melezitose were the grades of commercially available reagents. The
anhydrous crystalline trehalose and anhydrous amorphous trehalose
were respectively prepared by the methods in Examples for reference
1 and 3. The anhydrous crystalline neotrehalose was prepared by
the method in Experiment 2 as disclosed in Japanese Patent Laid-Open
No. 179490/92. The anhydrous amorphous neotrehalose, anhydrous
amorphous erlose, anhydrous amorphous raffinose and anhydrous amorphous
melezitose were respectively prepared by dissolving each of them
in water, and drying the resultant solution in vacuo at an ambient
temperature.
The non-reducing saccharides were studied on their dehydrating
activities. A mixture, obtained by mixing 2 parts by weight of a
plain yogurt with 8 parts by weight of one of the non-reducing saccharides,
was placed in a container and allowed to stand at 25.degree. C.
overnight, followed by observing the macroscopic change of the resultant
mixture. The dehydrating activities of the non-reducing saccharides
were graded into 3 ranks, i.e. "High" meaning that it
formed a complete solidification; "Low", that it formed
an incomplete solidification; and "Non", that it showed
no substantial change.
The completely solidified-products were studied on their stabilities:
Each product was pulverized by a cutter to obtain a powdery product
which was then granulated to give a granular size of about 100-150.mu.m.
Thirty g aliquots of the granules were placed in plastic petri-dishes,
and allowed to stand at 37.degree. C. and a relative humidity of
70% for 2 weeks, followed by comparing the degree of color of the
resultant product. The degree of color was defined as a difference
between the absorbances at the wave lengths of 420nm and 720nm determined
in a 10-cm cell with a supernatant prepared from a 30 w/v suspension
of each solidified product. The stabilities of the dehydrated products
were graded into the following ranks: "Superior" meaning
that it showed a degree lower than 0.1; "Middle", that
it showed a degree of 0.1 or higher but lower than 0.2; and "Inferior",
that it showed a degree of 0.2 or higher.
The results were as shown in Table 1.
TABLE 1 __________________________________________________________________________
Stability of Dehydrating dehydrated Saccharide Macroscopic Change
activity product Judgement __________________________________________________________________________
Sucrose Unchanged Non -- Control Anhydrous crystalline Completely
solidified High Superior Present invention trehalose Anhydrous amorphous
Completely solidified High Superior Present invention trehalose
Hydrous crystalline Unchanged Non -- Control trehalose Anhydrous
amorphous Incompletely solidified Low -- Control neotrehalose Hydrous
crystalline Unchanged Non -- Control neotrehalose Anhydrous amorphous
Completely solidified High Inferior Control erlose Hydrous crystalline
Unchanged Non -- Control erlose Anhydrous amorphous Completely solidified
High Inferior Control raffinose Hydrous crystalline Unchanged Non
-- Control raffinose Anhydrous amorphous Incompletely solidified
Low -- Control melezitose Hydrous crystalline Unchanged Non -- Control
melezitose __________________________________________________________________________
Note: In the Table, the symbol "--" means that the stability
test of a mixture could not be done because of its incomplete solidification.
As evident from the results in Table 1 it was revealed that the
anhydrous crystalline trehalose and the anhydrous amorphous trehalose
had a strong dehydrating activity, and the dehydrated products prepared
therewith had a satisfactorily-high stability. Thus, anhydrous trehalose
can be advantageously used as a desiccant.
EXPERIMENT 2
Dehydration by Anhydrous Trehalose
The dehydrating activities of archydious crystalline trehalose
and anhydrous amorphous trehalose as an anhydrous trehalose were
studied, i.e. the levels of their dehydrating activities and their
dehydrating moisture-levels were studied in detail. As a control,
hydrous crystalline trehalose was used. The procedure of this experiment
was as follows: Each anhydrous trehalose obtained by the method
in Experiment 1 was prepared into a powdery product having a grain
size of about 100-150.mu.m. One g of the powdery product was placed
in a plastic petri-dish having a diameter of 5cm, and allowed to
stand at 25.degree. C. and a relative humidity of 70%, followed
by measuring the moisture content (%) of the resultant product at
a prescribed time-interval. The results were as shown in Table 2.
TABLE 2 ______________________________________ Time Trehalose 0
4 8 24 72 ______________________________________ Anhydrous crystalline
0.32 6.42 8.35 9.65 9.80 trehalose Anhydrous amorphous 0.83 8.20
9.57 9.80 9.80 trehalose Hydrous crystalline 9.57 9.60 9.62 9.64
9.70 trehalose ______________________________________
As evident from the results in Table 2 it was revealed that the
anhydrous trehaloses exerted a strong dehydrating activity, i.e.
they entrapped moisture in the atmosphere in an amount of about
10% by weight of the anhydrous trehaloses, on a dry solid basis
(d.s.b.). The anhydrous trehaloses were studied on their x-ray powder
diffraction figures at a prescribed time-interval to reveal that
they entrapped moisture and converted into hydrous crystalline trehaloses,
and that the resultant products equilibrated and stabilized when
absorbed about 10% moisture. An x-ray diffraction figure of hydrous
crystalline trehalose was as shown in FIG. 1.
Similarly as above, the anhydrous trehaloses were allowed to stand
at 25.degree. C. and a relative humidity of about 90%, followed
by measuring the moisture contents (%) of the resultant products
at a prescribed time-interval. Similarly as in the above, the anhydrous
trehaloses were converted into hydrous crystalline trehalose and
equilibrated when absorbed about 10% moisture. In this case, the
resultant products retained their powdery forms and no phenomenon
such as sticking and flowing was observed.
Based on these properties, it was revealed that anhydrous trehalose
can be advantageously used as a desiccant for food products, pharmaceuticals,
cosmetics and their materials or intermediates.
EXPERIMENT 3
Comparison of Dynamics of Anhydrous Trehalose and Hydrous Crystalline
Trehalose Against Gelatinized Starch
Four parts by weight of powdery glutinous rice was suspended in
6 parts by weight of water, and the suspension was poured onto a
wet close covered over the inside surface of a wooden container,
and steamed up at 105.degree. C. for 10 minutes to obtain a gelatinized
starch. To the gelatinized starch was added 7 parts by weight of
hydrous crystalline trehalose or anhydrous crystalline trehalose
prepared by the method in Example for reference 1 and the resultant
was mixed by a mixer until it showed homogeneity. Thereafter, the
resultant mixture was sufficiently kneaded with 2 parts by weight
of a starch hydrolyzate, formed, and mildly dried with a 40.degree.
C. hot-air for 2 hours to obtain "gyuhi" (a rice paste).
When the product prepared with anhydrous- or hydrous-crystalline
trehalose was allowed to stand at 25.degree. C. without packaging,
a colony of a black mold was observed in the product with hydrous
crystalline trehalose after 15 days of its processing, while no
bacterial contamination was observed in the product with anhydrous
crystalline trehalose even after 30 days of its processing.
The product with anhydrous crystalline trehalose after 30 days
of its processing was cut into sections, and the sections were observed
to find that the texture near the surface of the product exhibited
only a slight solidification and had a crystalline trehalose, while
the inner texture exhibited the same level of satisfiable semi-transparency,
gloss and viscosity as the product immediately after its processing.
An x-ray diffraction figure revealed that the crystalline trehalose
was hydrous crystalline trehalose which had been converted from
anhydrous crystalline trehalose.
As a result, it was revealed that anhydrous trehalose acts as a
desiccant for gelatinized starch and prevents bacterial contamination,
as well as the retrogradation of gelatinized starch. Anhydrous trehalose
having these satisfiable properties can be favorably used in a variety
of products prepared with gelatinized starch such as "gyuhi"
and flour paste.
The preparation of powdery anhydrous trehalose according to the
invention are described in the following Examples for reference:
Example for Reference 1
Hydrous crystalline trehalose was dissolved by heating in a small
amount of water, and the resultant aqueous solution was placed in
a vessel and boiled down in vacuo to obtain a syrup with a moisture
content of 5.0%. The syrup was transferred to a crystallizer, mixed
with one % by weight of anhydrous crystalline trehalose as a seed
crystal against the syrup, d.s.b., and allowed to crystallize trehalose
at 120.degree. C. for 5 minutes under stirring conditions. The resultant
massecuite was transferred to an aluminum container and aged at
100.degree. C. for 6 hours to form a block.
The resultant block was pulverized by a cutter into a powdery product
which was then subjected to a fluidized-bed drying to obtain an
anhydrous crystalline trehalose with a moisture content of 0.32%
in the yield of about 87% against the material hydrous crystalline
trehalose, d.s.b. The powder x-ray diffraction figure of the anhydrous
crystalline trehalose was as shown in FIG. 2.
The product can be favorably used as a desiccant for hydrous matters
such as food products, pharmaceuticals, cosmetics and their materials
or intermediates, as well as a white powdery sweetener with a mild
sweetness.
Example for Reference 2
An aqueous solution of a high-purity trehalose was placed in a
vessel and boiled down in vacuo to obtain a syrup with a moisture
content of 4.0%, which was then mixed with 5% by weight of anhydrous
crystalline trehalose as a seed crystal against the syrup, d.s.b.,
and allowed to crystallize trehalose at 95.degree. C. under stirring
conditions. The resultant crystal was granulated by a granulator,
aged, dried and pulverized by a pulverizer to obtain a powdery anhydrous
crystalline trehalose with a moisture content of 0.53% in the yield
of about 95% against the material trehalose, d.s.b.
Similarly as the powdery anhydrous crystalline trehalose obtained
by the method in Example for reference 1 the product can be favorably
used as a desiccant, as well as a sweetener for a variety of hydrous
matters.
Example for Reference 3
Hydrous crystalline trehalose was completely dissolved in water
at an ambient temperature, and the resultant aqueous solution was
dried in vacuo at 60.degree. C. for 24 hours. The resultant dehydrated
product was pulverized by a pulverizer to obtain an anhydrous amorphous
trehalose with a moisture content of 0.83% in the yield of about
89% against the material hydrous crystalline trehalose, d.s.b. The
powder x-ray diffraction figure of the anhydrous amorphous trehalose
was as shown in FIG. 3.
Similarly as the powdery anhydrous crystalline trehalose obtained
by the method in Example for reference 1 the product can be favorably
used as a sweetener, as well as a desiccant for a variety of hydrous
matters.
The examples and advantageous effects of the present invention
are disclosed hereinafter:
EXAMPLE 1
Desiccant
Twenty g aliquots of an anhydrous crystalline trehalose, obtained
by the method in Example for reference 1 were injected into moisture-permeable
small paper-bags to obtain a desiccant. The product can be favorably
used as a desiccant to dehydrate the atmosphere in a moistureproof
package injected with a dehydrated food product such as a cookie
or a toasted and seasoned laver. Dehydrated- and oily-food products
can be stably stored by using the product in combination with an
oxygen scavenger.
EXAMPLE 2
"Soboro-gyuhi" (a Starch Paste)
Four parts by weight of a powdery glutinous rice was suspended
in 6 parts by weight of water, and the resultant suspension was
poured onto a wet cloth covered over the inside surface of a wooden
container, steamed at 100.degree. C. for 20 minutes, mixed with
one part by weight of sucrose and 7 parts by weight of an anhydrous
crystalline trehalose obtained by the method in Example for reference
1 and further sufficiently mixed with 2 parts by weight of a starch
hydrolyzate. The resultant mixture was formed and allowed to stand
at an ambient temperature for 16 hours to convert the anhydrous
trehalose into hydrous crystalline trehalose on the surface of the
resultant product, which was then mildly rolled to form cracks on
its surface to obtain the captioned product. The product had a satisfiable
flavor and retained its high quality for a relatively-long period
of time without substantial bacterial contamination.
EXAMPLE 3
Confectionery Made of Sweet Potato
A sweet potato was sliced into thin pieces about 1-cm thick, and
the pieces were steamed, cooled at ambient temperature, and dehydrated
by dusting over them with an anhydrous crystalline trehalose prepared
by the method in Example for reference 1 to convert the anhydrous
crystalline trehalose into hydrous crystalline trehalose. Thus,
the captioned product, having hydrous crystalline trehalose adhered
on its surface, was prepared. The product had a satisfactory flavor
and stability.
EXAMPLE 4
Brandy Powder
Ten parts by weight of pullulan was dissolved in 2 parts by weight
of a brandy, and the resultant solution was mixed with 8 parts by
weight of an anhydrous crystalline trehalose obtained by the method
in Example for reference 2. The resultant mixture was transferred
to a container, and allowed to stand for 2 days to form a block
while allowing the anhydrous crystalline trehalose to convert to
hydrous crystalline trehalose. The block was pulverized by a pulverizer
and classified to obtain a brandy powder with a satisfactory flavor.
The product is a flavored powder having an adequate sweetness and
a sufficient brandy-flavor, and you can enjoy it in your mouth.
The product can be favorably used as a flavor-imparting agent for
tea, as well as a material for confectioneries such as a premix
powder and candy. The product can be favorably formed into a granule
or a tablet by a granulator or a tabletting machine.
EXAMPLE 5
"Miso" Powder
Two parts by weight of "akamiso" (a kind of miso) was
mixed with 5 parts by weight of an anhydrous crystalline trehalose
prepared by the method in Example for reference 2 and the resultant
mixture was poured onto a metal plate provided with semispheric
depressions, allowed to stand at an ambient temperature overnight
to solidify the mixture in the depressions. The solidified products
in the depressions were removed therefrom to obtain solid products,
about 4 g each, which were then subjected to a pulverizer to obtain
the captioned product. The product can be favorably used as a seasoning
in an instant noodle and instant soup. When the product is formed
into a solid product, it can be used as a solid seasoning or a miso
confectionery.
EXAMPLE 6
Soy Sauce Powder
A mixture, consisting of 0.02 parts by weight of a commercially
available hydrous crystalline trehalose and 4 parts by weight of
an anhydrous crystalline trehalose prepared by the method in Example
for reference 3 was sprayed with "usukuchi-shoyu" (a
less-colored soy sauce) to give the final content of one part by
weight while the mixture was moving on a conveyer belt, transferred
to an ageing tower, and allowed to stand at 30.degree. C. overnight
to covert the anhydrous trehalose into hydrous crystalline trehalose.
Thus, the captioned product was obtained. The product can be favorably
used as a seasoning for an instant noodle or an instant soup.
EXAMPLE 7
Egg-yolk Powder
An egg yolk prepared from a fresh egg was sterilized at 60.degree.-64.degree.
C. by a plate-type heat sterilizer to obtain a liquid egg yolk.
To one part by weight of the liquid egg yolk was added 4 parts by
weight of an anhydrous crystalline trehalose prepared by the method
in Example for reference 1 and, similarly as in Example 4 the resultant
mixture was formed into a block which was then pulverized into an
egg-yolk powder. The product can be favorably used as a material
for confectioneries such as premix powders, ice products and emulsifiers,
as well as baby foods and therapeutic nutrients such as intubation
foods and orally administrable fluid-foods. The product can be favorably
used as a skin refiner and a hair restorer.
EXAMPLE 8
Yogurt Powder
Two parts by weight of plain yogurt was mixed with 8 parts by weight
of an anhydrous crystalline trehalose prepared by the method in
Example for reference 1 and, similarly as in Example 4 the resultant
mixture was formed into a block which was then pulverized into a
yogurt powder. The product had a satisfactory flavor and stably
retained lactic acid bacteria alive for a relatively-long period
of time. The product can be favorably used as a material for confectioneries
such as premix powders, ice products, emulsifiers and baby foods,
as well as therapeutic nutrients such as intubation foods and orally-administrable
fluidfoods. The product can be favorably incorporated into margarine,
whipped cream, spread, cheese cake and jelly to obtain a product
having a yogurt-like flavor. The product can be formed by a granulator
or a tabletting machine into a preparation of lactic acid bacteria
which can be favorably used as an agent for intestinal disorder.
EXAMPLE 9
Hot Cake Mix
A hot cake mix was obtained by mixing 200 parts by weight of a
wheat flour with 60 parts by weight of an egg yolk powder prepared
by the method in Example 7 25 parts by weight of butter, 10 parts
by weight of sugar, 12 parts by weight of a baking powder and 0.5
parts by weight of salt. The product can be readily cooked into
a hot cake having a satisfiable flavor by mixing the product with
water or milk and baking the resultant mixture.
EXAMPLE 10
Ginseng Extract Powder
A half part by weight of ginseng extract was kneaded with 1.5 parts
by weight of an anhydrous crystalline trehalose prepared by the
method in Example for reference 2 and, similarly as in Example
4 the resultant mixture was formed into a block and pulverized to
obtain the captioned product. The product was subjected to a granulator
together with adequate amounts of powdery vitamins B1 and B2 to
obtain a granular ginseng extract containing vitamins. The product
can be favorably used as a fatigue-removing agent, restorative and
tonic.
EXAMPLE 11
Solid Preparation for Fluid Food
A composition consisting of 500 parts by weight of an anhydrous
crystalline trehalose prepared by the method in Example for reference
2 270 parts by weight of an egg yolk powder prepared by the method
in Example 7 209 parts by weight of a defatted milk, 4.4 parts
by weight of sodium chloride, 1.85 parts by weight of potassium
chloride, 0.01 part by weight of thiamine, 0.1 part by weight of
sodium L-ascorbate, 0.6 parts by weight of vitamin-E acetate and
0.04 parts by weight of nicotinic acid amide was prepared, and 25
g aliquots of the composition were injected into small moistureproof
aluminum bags, and heat sealed to obtain the captioned product.
The product, wherein the moisture content in the atmosphere of
the bag is decreased, does not require cold storage and has a satisfactory
stability for a relatively-long period of time even at an ambient
temperature. The solubility and dispersibility in water are satisfactory.
In use, one bag of the product is dissolved in about 150-300ml water
into a fluid food prior to oral administration to the body or intubation
into the nasal cavity, stomach and intestine.
EXAMPLE 12
Solid Pharmaceutical Preparation
New born hamsters were injected with an antiserum prepared from
rabbits by conventional method in order to reduce their immunoreaction,
subcutaneously transplanted with BALL-1 cells, and fed for 3 weeks
in usual manner. Subcutaneously-formed tumors in the hamsters were
extracted and cut into pieces which were then dispersed and suspended
in physiological saline. The resultant cells were washed with RPMI
1640 medium (pH 7.2) free of serum, resuspened in a fresh preparation
of the same medium to give a concentration of about 2.times.10.sup.6
cells/ml, and kept at 35.degree. C.
To the cell suspension was added 200 IU/ml human interferon-.alpha.,
incubated for about 2 hours, mixed with about 300HA (hemagglutination
titer)/ml of Sendai virus (HVJ), and further incubated for 20 hours
to induce human interferon-.alpha.. The resultant culture was centrifuged
at about 1000 .times.g and about 4.degree. C. to remove sediment.
The supernatant thus obtained was membrane filtered, and the resultant
filtrate was fed to a column of an immobilized anti-interferon-.alpha.
antibody. The column was fed with a buffer to remove a non-adsorbed
fraction, followed by eluting an adsorbed fraction from the column
and concentrating the fraction into a solution of about 0.01 w/v
% human interferon-.alpha. having a specific activity of about 2.times.10.sup.8
IU/mg protein in the yield of about 4 ml per hamster.
Six g aliquots of a pyrogen-free anhydrous crystalline trehalose,
prepared by the method in Example for reference 1 were placed in
100-ml moistureproof plastic bottles, and injected with 0.2 ml aliquots
of the solution containing about 4.times.10.sup.6 IU of human interferon-.alpha.,
followed by aseptically capping the bottles with rubber stoppers
and cap-sealing them. Thus, the captioned product was obtained.
According to the preparation, a solution containing human interferon-.alpha.
is simply dehydrated only by contacting it with a powdery anhydrous
trehalose so that none of treatment, apparatus and energy requisite
for general lyophilization are required, and the human interferon-.alpha.
is effectively stabilized.
The product readily dissolves in water, and this renders it advantageously
useful in an injection for an instillation or an intramuscular injection
as an agent for anti-susceptive diseases which can be prevented
and/or treated with human interferon-.alpha., for example, an anti-virus
agent, anti-tumor agent and agent of anti-rheumatism. The product
can be suitably used as an internal medicine, as well as an agent
for oral cavity. The product can be also used as a diagnostic reagent.
EXAMPLE 13
Solid Pharmaceutical Preparation
A seed culture of BALL-1 cell derived from human lymphoblastoid
was inoculated into Eagle's minimum essential medium (pH 7.4) supplemented
with 20% fetal calf serum, and subjected to a suspension culture
in vitro at 37.degree. C. in the usual manner. The resultant cells
were washed with serum-free Eagle's minimum essential medium (pH
7.4), and resuspended in a fresh preparation of the same medium
to give a concentration of about 1.times.10.sup.7 cells/ml. To the
cell suspension was added about 1000 HA/ml of HVJ, and incubated
at 38.degree. C. for one day to induce human tumor necrosis factor-.alpha.
(hTNF-.alpha.). The resultant culture was centrifuged at about 1000
.times.g and 4.degree. C. to obtain a supernatant which was then
dialyzed against a physiological saline (pH 7.2) containing 0.01M
phosphate buffer for 15 hours, and membrane filtered. The filtrate
thus obtained was fed to a column of an anti-interferon antibody,
and a non-adsorbed fraction was recovered and purified on an affinity
chromatography using a column of an anti-tumor necrosis factor-a
monoclonal antibody, followed by concentrating the resultant into
a 0.01 w/v % solution of hTNF-.alpha. having a specific activity
of about 2.times.10.sup.6 JRU (Japan reference unit)/mg protein.
The yield of hTNF-.alpha. was about 5.times.10.sup.4 JRU per one
L of the cell culture.
Ten g aliquots of an anhydrous crystalline trehalose, prepared
by the method in Example for reference 1 were injected into 100-ml
vials which were then injected with 0.5 ml aliquots of the solution
containing about 1.times.10.sup.5 JRU of hTNF-.alpha., aseptically
capped with rubber stoppers, and cap sealed to obtain the captioned
product. Since a solution containing hTNF-.alpha. is dehydrated
by a powdery anhydrous trehalose in the above-mentioned preparation,
no treatment such as a lyophilization is required and hTNF-.alpha.
is effectively stabilized.
The product readily dissolves in water, and this renders it advantageously
useful in an injection for instillation or an intramuscular injection
as an agent for anti-susceptive diseases which can be prevented
and/or treated with hTNF-.alpha., for example, an anti-virus agent,
anti-tumor agent, agent of anti-ascites and agent of anti-immunopathy.
The product can be suitably used as an internal medicine, as well
as an agent for oral cavity. The product can be also used as a diagnostic
reagent.
EXAMPLE 14
Ointment for Treating Skin Trauma
Three parts by weight of iodine was dissolved in 450 parts by weight
of an anhydrous crystalline trehalose prepared by the method in
Example for reference 2 and the solution was admixed with 50 parts
by weight of methanol. The resultant solution was admixed with 200
parts by weight of 10% aqueous pullulan solution and 50 parts by
weight of hydrous maltose, and the resultant mixture was allowed
to stand at an ambient temperature overnight to convert the anhydrous
trehalose into hydrous crystalline trehalose. Thus, an ointment
for treating skin trauma having a satisfactory extensibility and
adhesion was obtained.
The product heals trauma such as an ulcer caused by a cut, abrasion,
burn and dermatophytosis. The product exerts the inherent bactericidal
activity of iodine, and acts as a nutrient-supplementing agent for
living cells because it contains trehalose. Thus, the product shortens
a period required for such a treatment and heals a wounded part
thoroughly.
As described above, the present invention relates to a desiccant
comprising a non-reducing anhydrous trehalose as an effective ingredient.
The desiccant can be suitably used to decrease the moisture content
in atmosphere of a moistureproof package injected with a dehydrated
food product, as well as to decrease the moisture content in a hydrous
matter such as food products, pharmaceuticals, cosmetics, products
of chemical engineering, and their materials or intermediates. The
method according to the present invention, which contains a step
of dehydrating a hydrous matter by incorporating anhydrous trehalose
into the hydrous matter to convert the anhydrous trehalose into
hydrous crystalline trehalose, attains a substantial decrease of
the moisture content in the hydrous matter, and does not require
severe conditions such as heat drying. Thus, high-quality dehydrated
products are readily prepared by the present invention without deteriorating
the quality of hydrous matters such as food products which readily
lose their flavors and tastes, as well as pharmaceuticals which
are susceptible to decomposition and reduction of their effective
components. The dehydrated products thus obtained have a relatively-high
stability and a relatively-long shelf-life because they are prevented
from bacterial contamination, as well as deterioration and alteration
such as hydrolysis, acidification and browning.
While a preferred embodiment of the invention has been illustrative
purpose only, and it is to be understood that changes and variations
may be made without departing from the spirit or scope of the following
claims. |