Note: Descriptions are shown in the official language in which they were submitted.
CA 02278383 1999-07-21
STIMULATORS FOR LIVING ORGANISMS
RELATED APPLICATIONS
This application relates to my former USSR patent No. 1096919 "S", issued
February
8, 1984, and USSR patent No. 1614434"S", issued August 15,1990.
FIELDS OF INVENTION
This invention relates to the compositions and application of the chelate
complexes of the
bioactive metals with ethylenediamine-N,N'dicarbonic acid, oxyacids, like
tartaric acid,
citric acid, ascorbic acid and boric acid.
More particularly, the invention related to the improved method of preparing
soluble
complexes and compositions of the ethylenediamine-N, N'-disuccinate (edds), of
metal
ions of iron, zinc, manganese, magnesium, cobalt, copper and mixed complexes
of
aforenamed ions with edds and oxyacids of tartaric, citric and boric acids;
the application
of these complexes as environmental friendly microfertilizes and
biostimulators of
growth, seeds, flowers and fruits production, nectar productivity of green
plants, curing
agents for animals and poultry.
Further, the invention relates to the application of the compositions for the
green plants
and consists of the dilute solution of formulations treatment directly to the
foliage of
plants in open ground or in greenhouses once a fortnight or once a month,
depending of
the specific type of plants and including stimulating effects of complexes and
their
fragments on the processes of growth, nectar productivity, seeds/ fruits
formation. These
goals achieved by direct penetration of the complexes and their fragments
through the
foliage and promoting the chlorophyll formation and intensification of vital
activity of the
whole plants, as result of treatments.
The application of such types of complexes to the plants leads to the growing
of the
crops harvesting from 20 till 50 % and do not pollute the plant's tissues,
fruits, seeds and
environment with any toxic compounds.
Further, the invention deals with the application of iron, zinc, manganese and
magnesium compositions for curing the 1'' and 2'~ phases of chlorosis in
grapes, fruit
trees, flax, cucumbers and tomatoes in full and partly the 3'~ phase of
chlorosis.
Still further, the invention relates to the application of iron, cobalt,
copper and
magnesium complexes aforesaid ligands in veterinary and for prophylaxis of fur
animals, for pets and for poultry farming to cure such types of diseases, as
white-puffs,
stresses, to improve the quality of fur of animals, to increase the vital
activity of animals
and poultry.
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2
DESCRIPTION OF THE PRIOR ART
The shortage of the bioactive metals in the green plants leads to the
depressing of the
growth and finally to the decreasing of the crops harvesting of the main
agricultural
products. To overcome this effect, the greater amount of growth stimulators,
microelements and macrofertilizes are used in all branches of agriculture.
Basically, three
approaches are used now to reach the positive erects:
a. The increasing of the amount of conventional fertilizes and / or
preparation these
fertilizes in the more appropriate forms;
b. The application of microelements with the macrofertilizes in the forms of
inorganic
salts, some complex compounds of metals in different combinations;
c. The application of organic stimulators of plant growth, for example indole-
derivatives, to increase the rates of plant's growth and to increase the rates
of roots,
fruits formations.
All of them have some negative consequences. The increasing of the water-
soluble plant
nutrients in soils may cause phytotoxicity to the plants, increasing the cost
of agricultural
production and leads to the pollution of the soils and waters with the basic
phosphorus,
nitrogen, potassium compounds. That erecting to the main nutrition chains of
the nature
and makes dramatic changes in the environment. For the last decades a lot of
improvements were proposed to overcome the negative effects of overloading of
basic
fertilizes to the soils: preparing the granulated nutrients, coated nutrients,
normalizing the
amounts of fertilizes to the specific areas, using the microelements with the
basic
nutrients.
These microelements are the sufficient component of ferments producing by
plants and
play the key roles in vital processes. Application of the bioactive metal ions
provides the
increasing of growth and decreasing of macro-nutrients consumption, that in
turn depletes
the contamination and lowing the cost of agriproducts. This trend is the most
perspective
for the agriculture, but still demands the further improvements.
The application of the organic stimulators may effected to the genetic
structure and
mechanism of natural material and thus can lead to long-term negative effects
for the
customers of agricultural products.
Additionally, it may be taken in account the fourth way - genetic engineering
of new
types of plants, but it is out of our consideration.
Researchers for a long time have attempted to develop the most effective types
of
bioactive metals compositions. These compound should be soluble in the large
scale of
pH, must be effectively utilized by the plants and they should be accessible
and at
competitive prices.
One of the most appropriate compounds are so called complexonates- chelate
complexes
of metals. Well known ethylenediamine-N, N'-tetraacetates of metals are widely
used in
agriculture as microelements suppliers.
These chelates of bioactive metals are rather acceptable, as they are soluble
in the pH
range of 3 till 10, they can be produced easily and gave good results in
practice.
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Unfortunately, these compounds do not decompose in full under natural
conditions and
have a little stimulating effect, as the complexes are very firm.
Complexes of biometals with the aminoacids and some additives are too
expensive and
not demonstrated the perfect results.
Many of these shortcomings in the prior art were overcome in my former USSR
patent
No. 1096919 "S" , issued February 8, 1984, which discloses the synthesis and
application of the Fe-edds, Zn-edds and their different compositions as the
effective
microfertilizes and biostimulators of seed formation and nectar- production in
Lucerne.
My former USSR patent No. 1614434"S" issued August 15,1990, also deals with
the
stimulating effects of growth, seeds formation and nectar-productivity of
buckwheat
provided by iron- containing edds, tartaric acid complexes.
The methods described in my aforesaid USSR patents apply the particular
complexes to
some particular plants. The present invention now provides the whole lot of
edds-
oxyacids- bioactive metals complexes, their preparation and application for
the plants as
biostimulators and microfertiLizes.
SUMMARY OF THE INVENTION
Accordingly, this invention seeks to provide a new and improved method of
treatment of
plants to stimulate the growth, seeds and green masses production of the honey
planted
nectar-productive ( polygonum, clover), feeding ( Lucerne, rape, sweetclover,
cockshead
sainfoin) and technical (flax, hop) cultures.
Further, this invention seeks to provide the improved treatment of
floricuLtural plants
stimulating the increasing of the quantity and quality of flowers, providing
the thickening
of stems, curing completely the first and second phases of ferruginous and
magnesium
chlorosis.
Still further, thisinvention seeks to provide the improved method of treatment
of
horticultural and viticuLtural plants, stimulating the growth of quantity and
quality of
fruits and berries, curing the first, second and, partly, the third phases of
chlorosis.
Still further, this invention seeks to provide the increasing of growth and
amount of fruits
in vegetable's production in open ground and in greenhouses, by actively
stimulating the
vitality, chlorophyll content in leaves, curing completely the ferruginous and
magnesium
chlorosis.
Still further, this invention seeks to provide the curing of the white-puffs
in fur animals
and pets, increasing the hemoglobin content in blood and increasing the growth
rate and
quality of fur for animals, increasing the rate of growth and curing the
stresses for
poultry.
The present invention provides an improved and simplified method of
preparation of the
effective blends and formulations of bioactive chelate compositions directly
from the
tetrasodium/potassium salts of ethylenediamine-N,N'-disucarbonic acid,
oxyacids, like
tartaric, citric acids and boric acid and related metal salts.
The invention in one broad aspect provide a method of the treatment of green
plants to
stimulate the processes of growth and productivity of the plants and to
stimulate vital
activity of animals, comprising (a) applying the ethylenediamine-N,N'
disuccinic acid as
bioactive chelating agent for the microelements ( iron, zinc, cobalt, copper,
manganese,
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4
magnesium) and the oxyacids as the second ligands for complexes formation, (b)
applying of these monocomplexes and compositions of several metal complexes
for the
treatment of plants to stimulate the growth of productivity of aforenamed
plants in range
of 20 till 50%, for curing the first and second phases of chlorosis in full
and of curing
and stimulating of vital activity of animals and poultry.
DETAILED DESCRIPTION OF THE INVENTION
The improved method of the plant treatment started with the synthesis of
corresponding
chelate compounds which comprises a chemical reactions of relative metal salts
with the
ehtylenediamine-N,N'-disuccinic acid (edds) tetrasodium/tetrapotassium salts
Na4K4edds) in water solution ( and corresponding oxyacids).
The synthesis can be carried out in two steps:
a. Synthesis of sodium/potassium salt of edds performed by dissolving malefic
acid or
malefic anhydride in water in the ratio of l:l by weight foe malefic acid and
with the
ratio of 1:1.5 for malefic anhydride. To this solution the calculated amount
of sodium
potassium hydroxide have to be added slowly with the small portions to prevent
the
boiling and foaming of the reactive mass. To this solution the calculated
amount of
ethylenediamine (70% water solution or 60 % water solution) adding dropwise
under
active stirring and at the temperature of no more then 50-60 degrees Celsius,
till all
ethylendiamine would adding to reactive mass. Reactive vessel should be
provided
with the downward condenser and temperature control facilities. After addition
of all
ethylenediamine the temperature should be increased to 105-110 degrees of
Celsius
and the pH of the solution must be in the range of 10.5 till 11.5. The
reaction should
run for 20-24 hours at the temperature of 105-110 degrees Celsius and under
active
agitation.
After reaction completed the reactor cooled and thick slightly yellow solution
of edds
salt removed and precipitated with the adding hydrochloric acid at temperature
of 0-
15 degrees Celsius. After filtering and drying of the precipitation the white
powder of
edds ( 90-95% yield) obtained.
The calculated amount of edds putting in reaction with appropriate amount of
NaOH
or KOH to receive the tetra sodium/tetrapotassium salt of edds, in water
solution
containing double amount of water to compare with the summarizing weight of
reactives.
b. Metal nitrate or chloride salt dissolved in the minimum amount of the
water, enough
to receive the clear solution and start adding to the edds solution with the
small
portions controlling the pH of the solution after each addition of metal salt
solution.
At the end of eddition of the metal ions solution the pH of the blend should
not be
less then 4.9-5.5 and no more then 8Ø These concentrated solutions (may
contain the
solid particles) can be used directly, after chemical analysis, or can be
dryed under 90
degrees Celsius to obtain dry materials.
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To receive the complexes with two ligands, the monoligand complexes mixed with
the oxyacid in the ratio 1:1 in water solution and heating to 45-50 degrees of
centigrade, under agitation for 1-2 hours.
Then the complexes can be precipitated or used directly to obtain desirable
blends.
For the cases of Fe, Mn, Mg, Co, Cu ions, compounds in solid state and in
solution are
dimeric and containing 2-3 molecules of water. In the cases of complexes with
edds and
citic, tartaric acids complexes are monomeric and containing 1-2 molecules of
water
bounded to the active groups of ligands ( for Mn the structure is more
complicated).
For the treatment of plants, the following solutions have to be prepared by
diluting the
concentrate solutions, or by dissolving the solid compounds in the water to
obtain the
following concentrations:
Fe - edds 0.01- 0.20(mass % for individual
of Me) complex
Mn - edds 0.01- 0.10(mass % for individual
of Me) complex
Zn - edds 0.01- 0,25(mass % for individual
of Me) complex
Cu - edds 0.01- 0.10(mass % for individual
of Me) complex
Co - edds 0.005- 0.10(mass % for individual
of Me) complex
Mg - edds 0.05 - 0.20(mass % for individual
of me) complex
Fe - edds - oxyacid ( 1:1:1 ) 0.01 ( mass % of Fe) for mixed complex
Mn - edds - oxyacid ( 1:1:1 ) 0.01 ( mass % of Mn) for mixed complex
Fe - edds - boric acid ( 1:1:1 ) 0.01 ( mass % of Fe) for mixed complex
Co - edds - oxyacid ( 1:1:1 ) 0.005-0.01 ( mass % of Co) for mix complex
Cu - edds - oxyacid ( 1:1:1 ) 0.005-0.01 ( mass % of Cu) for mix complex
It has been found that the application of the dilute solutions of complexes
consisting with
the aforementioned bioactive metals and ethylenediamine-N,N'- disuccinic acid
and
tartaric, citric and boric acids for the plant treatment give the remarkable
results, and can
be carried out in following steps.
For the honey planted nectar productive ( polygonum, clover) feeding (
Lucerne, rape,
sweetclover, cockhead sainfoin ) technical ( hop, flax ) culture the
compositions of
monocomplexes of Fe-edds and Zn-edds in the ratio of 1: 0.5-1, compositions of
Fe-edds-
tartaric acid and Zn-edds with the ratio of 1: 0.5-l, monocomplex of manganese
and
monocomplex of magnesium { buckwheat) are used for spray-treatment within the
plants
bud formation period, as the diluted solution containing 0.01-0.2 percents of
each metal
in solution. The treatments should be done one or two times within the
interval of one
month. Treatments should be carried out at early morning, following by the
sunny, dry
day lasting for at least 8-12 hours. For this period the complexes are partly
utilized by
plants directly or decomposed to the bioactive fragments, which in turn are
actively
utilized by foliage. The consumption of the stimulators for these cultures is
2.5-3.0 kg per
hectare. The amount of spraying solutions is 800-1200 L per hectare.
The effect consists of increasing the both seed cropping harvest up to 40-50 %
and nectar
productivity up to the 100%.
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For viti- and horticultures the compositions of iron with the edds and citric
acid, iron
with the edds and tartaric acid and iron with the edds and boric acid, mixed
compositions
of iron, copper, zinc and cobalt with the edds in the ratio of 1: 0.2 : 0.1 :
0.05 are used to
increase the grapes and fruits crop harvesting up to the 30-40%, fruits and
grapes sugar
content up to the 20%.
These formulations also completely cures the first and second phases of
chlorosis and
reduce the effect of third phase of chlorosis as well.
The treatments performed by spraying the plants within the period of first
leaf appearance
and performed for two-three times with the interval of one month. The
consumption of
the complexes are 5- 10 kg per hectare. The amount of spraying solutions is
600-1200 L
per hectare.
The treatment can be carried out by root application method and in this case,
the
pronounced prolonged effect occurs: the crop harvest increased up to 20-25%
next year
without any treatment.
The consumption of the complexes for root treatment is 10-30 kg per hectare.
Complexes
can be introduce to the soil with the macro- fertilizes directly.
For the floriculture the compositions of iron edds and magnesium edds in the
ratio of
1:0.5, the compositions of iron, manganese, copper with the ethylenediamine-
N,N'-
disuccinic acid and citric acid ( 1:1 ) in the ratio of 1:0.2: 0.2 are
applying as quantity
increasing agents for decorative flowers ( roses, pink-flowers, herberas,
etc.) cultivated
both in greenhouses and in an open ground. These compositions can be applied
for spray-
treatment and for root-treatment, that enables to receive the stem thickening,
increasing
the amount of flower stems, to increase the elite product sorts up to 25-35 %.
The application should be done by treating the flowers once a month starting
from the
moment of bud formation for all period of growing the flowers.
The consumption of these compositions are 35-50 kg per hectare for greenhouses
treating performing all year round).
The amount of solution for spraying is 400-500 L per hectare per treatment.
In vegetable production the compositions of iron, zinc, cobalt and magnesium
with the
edds and iron with the edds and tartaric acid, iron with the edds and boric
acid are used to
increase the fruits crop harvesting in open ground and in greenhouses. The
methods of
treatments are the same as previously mentioned: spraying and root feeding. In
the event
of spraying, the dilute solution with the concemration of bioactive
compositions of 0.01-
0.15 mass percentage of each metal, spraying onto the foliage once a month.
It have been found, that the application of these compounds and compositions
increasing
the total crops harvest up to 30-35 %, stimulates the plant's vitality,
completely cures the
ferruginous and magnesium chlorosis. The shoot growth intensification is
attained in two-
three weeks.
The consumption of the compounds is 4-4.5 kg per hectare. The total amount of
solution
is 600-1200 liters per hectare.
The complexes of iron-edds and iron edds, citric acid, have been found to be
very
effective for the poultry farming as a hemoglobin level increasing agent,
which gives rise
to poultry resistance to diseases and stress situations. The method of
treatment is to add
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7
the complexes to the poultry food once a day through all period of growth. The
application of these compounds leads to the increasing the poultry weight up
to the 50-80
and reducing the broilers cramming time in 20-35 %.
The consumption of these complexes is 30-60 mg / kg per day.
There were no toxic effects occurred during the 3 years of testing period.
The compositions of 25-50% of iron edds, 10- 25 % of cobalt edds, 10-20 % of
copper
edds and 5-15 % of manganese edds complexes were used to treat the fur animals
grown
in cages. It was estimated, that this treatment completely exclude stress and
white-puff
development in animals, increasing the rate of fur growth, improves fur
quality. Special
effect were occurred, when the animals are fish fed.
The consumption of the compositions is 55-200 mg/kg per day. The compositions
should
be added to food or to water.
The effect of increasing the off springs up to 15-25 % occurred while treating
foxes,
sables and minks.
In the aforesaid discloser it is to be understood that the term "edds" is used
to define
either ethylenediamine-N,N"-disuccinic acid , or corresponding anion of this
acid.
The critical feature of these treatments, as stated hereinbefore, is the
application of
coordination compounds of iron, manganese, copper, cobalt, zinc and magnesium
with
ethylenediamine-N,N'-disuccinic acid and tartaric, citric and boric acids, as
the second
ligands, to increase the crops harvesting of seeds, fruits, green masses,
nectar production,
to cure chlorosis of the plants at first and second phases completely and the
third phase
partly, for prophylaxis and veterinary treatment of fur animals and some pets,
stimulating
agents in poultry farming.
PRESENTLY PREFERRED MODES OF OPERATIONS OF
INVEVTION
Having described the basic concepts of the instant invention, reference is now
made to
the following examples which illustrate the presently performed embodiments of
the
invention.
EXAMPLE 1
Application of Fe, Zn - edds complexes for the honey planted nectar-productive
plants of
Lucerne of Jigeva 118 sort.
During the bud formation period (May) the spraying of foliage of Lucerne was
performed
on the standard background. Thirty lots of 30 sq. m. were used for tests. Five
of them
were used as control lots. The non-root feeding by complex compositions were
performed according the scheme:
a. Control (water and basic agricultural background + inorganic salts of iron
sulfate and
zinc sulfate).
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b. Fe, Zn 0.01 ( mass% Fe) , )Ø 005
adds- ( mass % Zn)
c. Fe, Zn 0.05 ( mass% of each metal)
--adds-
d. Fe, Zn 0.10 ( mass% of each metal)
-edds-
e. Fe, Zn 0.15 ( mass% of each metal)
-edds-
f. Fe, Zn 0.20 ( mass% of each metal)
-adds-
The amount of solution for each lot was estimated as 25-30 liters per each
lot.
The effectiveness was estimated for nectar production, seed formation and the
amount of
green mass of plants
The results of seed cropping, nectar production and green mass harvesting
tests for
Lucerne are presented in the Table 1, 2.
Table 1. Seeds harvesting and green mass productivity of Lucerne of Jigeva
118.
Type of Content of Seeds harvestAdditional Green mass Additional
treatment mass% Fe; centners / increasing harvest increasing
(Zn) ha in % centn./ha in
a - 4.49 - 420.6 -
b 0.01' 0.005 6.21 38 481.3 14.5
c 0.05 each 6.07 34 492.0 17.0
d 0.10 each 6.70 49 532.8 27.0
a 0.15 each 6_.30 40 515.1 22.5
f _ _ 5.98 ~ 1 489.0 16.5
0.20 each
Calculations of seeds amounts were performed after threshing the full ripening
of
Lucerne.
Table 2. Nectar productivity in Lucerne of Jigeva 118.
Type Content Amount Amount % of Amount ProductiIncrease
of
treatmenof mass%of stemsof increasinof sugarson of of sugars
t Fe; (Zn)on squ.flowers g of in nectarsugars In %
in to
m. on stem flowersmg/flow.nectar control
in
k a
a - 176 246 - 0.204 88.0 -
b 0.01(0.00175 260 8 0.341 155.0 77
5
c 0.05 176 385 50 0.258 174.5 98
d 0.10 175 437 80 0.324 248.0 182
a 0.15 176 455 85 0.290 290.5 163
_
rf - ~ 0.20 I 175. 325 ~ 35. x.321 184.5 ( 109
- ~ I ~ --
~
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The determination of nectar in flowers were performed on the base of whole
removal of
nectar from flowers by washing with water and, consequently, determining the
glucose
fructose content by conventional methods.
EXAMPLE 2
The influence of stimulators was investigated for the pink-flowers and for
roses during 9
years and showed the excellent results. Table 3 presents some data of 3- years
cycle of
treated pink-flowers in greenhouses by the composition of Fe, Cu, Mn, Mg -
edds -
tartaric acid complexes and by non-root spraying- treatment with the 0.015%
solution for
the flowers ( Fe : Mn : Mg : Cu = 1 : 0.2 : 0.2 : 0.1 ).
Table 3. Application of bioactive complexes for the pink-flowers ( data for 1
sq. m.)
Type QualityAmount Amount Amount IncreaseIncreaseIncrease
of of of of steamsof of stemsof stemsof stems
test steams steams steams amount amount amount
1~ ear 2 ear 3 ear 1 ear 2 ear 3~ ear
Control extra 153 162 lb4 - - -
Treated e~ 165 ~ 179 - 182 12 - 17 18
~ _ I -.
1
At the Table 4, the results of application of the same compositions for the
roses in
greenhouses for 3-years cycle are presented.
Table 4. Data for the application of stimulators for the roses ( data for 1
sq. m. )
QualityAmount Amount Amount IncreaseIncreaseIncrease
of stemsof stemsof stemsof stemsof stemsof stemsof stems
amount amount amount
1~ ear 2 ear 3 ear 1~' ear 2n ear 3~ ear
Control e~ _ 69 - 71. _ _ 70 - - - _
_. __
Treated-~ e ~-97 101 - 102 I 2g--~ 30 32
-- I _ ~ -_..
These experiments were performed three times for 3-years cycles and gave the
similar
results (differences were 5-10% in amount of steams per square m).
It have been shown, that after treatment of flowers with the stimulators, the
amount of
extra quality stems increasing up to 25-40%.
EXAMPLE 3
For the experimental treatment, two areas of 50 hectares of viticulture of
"Sauvignon"
type were used Treatment were performed by non-root spraying with the amount
of
CA 02278383 1999-07-21
spraying solution of 400-600 liters of solution per hectare. Concentration of
the
stimulator was 0.015 % of Fe.
The first spraying was performed during the first leaves formation period, the
second - in
one month and the third- at the end of third month.
After the grapes ripened, the total crop harvesting were calculated and the
amount of
sugars in grapes were estimated.
It appeared that the application of the Fe-edds-tartaric acid formulations for
the grapes
gave the increase of crops in 30-40% and the increase in sugars content in 20-
25%.
EXAMPLE 4
Application of the magnesium complex of edds for the buckwheat.
Twenty four lots of buckwheat with the similar area and agricultural
background were
used for the tests.
Treatments were performed as non-root spraying of dilute solutions of
complexes and
sulfate of magnesium as control, during the vegetation period of buds
formation.
Treatments were done two times in a period of one month.
The following scheme of treatment were chosen:
a. Control 0.1% of sulfate of magnesium
b. Fe-edds 0.01 % solution ( Fe mass % )
c. Mg-edds 0.005 % solution ( Mg mass %)
d. Mg-edds 0.010 % solution ( Mg mass %)
e. Mg-edds 0.015 % solution ( Mg mass %)
The data are represented in the Table 3 and Table 4.
Table 3. The seeds crop of buckwheat after non-root treatment with the
stimulators.
Variants Crops harvest Addition to Addition to
in comrol control
cent/ha c/ha in
a 19.47 - -
b. 27.65 8.18 42
c. 30.72 11.25 58
d. 3 13.96 72
3.43
e. _ __ 68
32.70 T 13.23
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11
Table 4. The nectar productivity of buckwheat after complex's treatments.
Variants Amount Amount Amount ProductiviAddition Addition
of of of
plants flowers sugar ty of to controlto control,
on on in sugar
one sq. one plantnectar in nectarkghla
m. for
1 flower kg/ha
in m
a. 84 1098 0.124 114.4 - -
b. 84 1120 0.155 145.6 31.4 29
c. 84 1099 0.153 141.0 26.6 23
d. 84 1117 0.154 144.6 30 26
.2
~4 ~ 1057 j 0.169 ( 150.0 _ 31
~5.6
As it can be easily seen from the tables, non-root treatments of buckvvheat
gave the
increasing of the seeds crops harvesting up to the 70%, nectar productivity -
up to the 30
%, which are sufficient for this culture.
As will be apparent to one skilled in the art, various modification and,
consequently,
application can be made within the scope of the aforesaid description.
Suchmodifications
being within the ability of one skilled in the art form a part of the present
invention and
are embraced by the appended claims.
