Note: Descriptions are shown in the official language in which they were submitted.
CA 02512254 2005-07-15
COMPOSITIONS WITH CYCLOPROPENES AND METAL-COMPLEXING
AGENTS
BACKGROUND:
Ethylene can cause the premature death of plants or plant parts including, for
example, flowers, leaves, fruits, and vegetables through binding with certain
receptors
in the plant. Ethylene also promotes leaf yellowing and stunted growth as well
as
premature fruit, flower, and leaf drop. Cyclopropenes (i.e., substituted and
unsubstituted cyclopropene and its derivatives) are effective agents for
blocking the
effects of ethylene. Some useful methods of delivering cyclopropenes to plants
or
plant parts include forming a mixture that includes one or more cyclopropenes
and
water. However, in some of such mixtures, the activity of the cyclopropenes in
the
mixture is reduced. US 2003/0224939 discloses the use of permeabilizing agents
to
improve the permeability of the cell walls of plants to certain specific plant
growth
regulators. It is desired to provide improved compositions that contain
cyclopropenes
and that improve the activity of cyclopropenes in mixtures that contain water
and one
or more such improved compositions; it is also desired to improve the
effectiveness
of blocking the effects of ethylene by cyclopropenes that are delivered to
plants or
plant parts by methods that use such compositions.
STATEMENT OF THE INVENTION:
In the present invention, there is provided a composition comprising
(a) one or more cyclopropenes of the formula
/CH
R-C//
cH2
wherein said R is hydrogen or a substituted or unsubstituted alkyl, alkenyl,
alkynyl, cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the
substituents, when present, are independently halogen, alkoxy, or substituted
or
unsubstituted phenoxy; and,
(b) one or more metal-complexing agents.
DETAILED DESCRIPTION:
CA 02512254 2005-07-15
2
As used herein, all percentages are percent by weight and all parts are parts
by
weight, unless otherwise specified, and are inclusive and combinable. All
ratios are
by weight and all ratio ranges are inclusive and combinable. All molar ranges
are
inclusive and combinable.
As used herein, the term "alkyl" means straight chain, branched chain , or
cyclic (C~-CZO) radicals which include, for example, methyl, ethyl, n-propyl,
isopropyl, 1-ethylpropyl, n-butyl, tert-butyl, isobutyl, 2,2-dimethylpropyl,
pentyl,
octyl, and decyl. The terms "alkenyl" and "alkynyl" mean (C3-CZO) alkenyl and
(C3-
CZO) alkynyl groups such as, for example, 2-propenyl, 2-butenyl, 3-butenyl, 2-
methyl-
2-propenyl, and 2-propynyl. The term "cycloalkylalkyl" means a (Ci-C~5) alkyl
group substituted with a (C~-C7) cycloalkyl group such as, for example
cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, and cyclopentylethyl.
The
term "haloalkyl" means an alkyl radical wherein one or more of the hydrogen
atoms
have been replaced by a halogen atom. The term "halogen" means one or more of
fluorine, chlorine, bromine, and iodine.
The practice of the present invention involves the use of one or more
cyclopropenes. As used herein, "cyclopropene" means any compound with the
formula
/CH
R //C
cH2
where R is hydrogen or a substituted or unsubstituted alkyl, alkenyl, alkynyl,
cycloalkyl, cycloalkylalkyl, phenyl, or naphthyl group; wherein the
substituents, when
present, are independently halogen, alkoxy, or substituted or unsubstituted
phenoxy.
As used herein, when the compound of the above structure when R is a hydrogen
is
meant, the phrase "unsubstituted cyclopropene" will be used.
In some embodiments, R has no double bond. Independently, in some
embodiments, R has no triple bond. Independently, in some embodiments, there
is no
halogen atom substituent on R. Independently, in some embodiments, R has no
substituents that are ionic. Independently, in some embodiments, R is not
capable of
generating oxygen compounds.
CA 02512254 2005-07-15
3
In some embodiments of the invention, R is (CI-CIO) alkyl. In some
embodiments, R is (CI-Cg) alkyl, or (CI-C4) alkyl, or methyl. When R is
methyl, the
cyclopropene is known herein as "1-MCP."
The cyclopropenes applicable to this invention are known materials, which
may be prepared by any method. Some suitable methods of preparation of
cyclopropenes are the processes disclosed in U. S. Patents No. 5,518,988 and
6,017,849.
The amount of cyclopropene in compositions of the present invention may
vary widely, depending on the type of composition and the intended method of
use.
In some embodiments, the amount of cyclopropene, based on. the total weight of
the
composition, is 4% by weight or less; or 1% by weight or less; or 0.5% by
weight or
less; or 0.05% by weight or less. Independently, in some embodiments, the
amount
of cyclopropene, based on the total weight of the composition, is O.OOOOOI %
by
weight or more; or 0.00001 % by weight or more; or 0.0001 % by weight or more;
or
0.001 % by weight or more.
Among embodiments in which the composition of the present invention
includes water, the amount of cyclopropene may, in some embodiments that
include
water, be characterized as parts per million (i.e., parts by weight of
cyclopropene per
1,000,000 parts by weight of water, "ppm") or as parts per billion (i.e.,
parts by weight
of cyclopropene per 1,000,000,000 parts by weight of water, "ppb"). In some
embodiments that include water, the amount of cyclopropene is 1 ppb or more;
or 10
ppb or more; or 100 ppb or more. Independently, in some embodiments that
include
water, the amount of cyclopropene is 10,000 ppm or less; or 1,000 ppm or less.
The practice of the present invention involves the use of one or more metal-
complexing agents. A metal-complexing agent is a compound that contains one or
more electron-donor atoms capable of forming coordinate bonds with a metal
atoms.
Some metal-complexing agents are chelating agents. As used herein, a
"chelating
agent" is a compound that contains two or more electron-donor atoms that are
capable
of forming coordinate bonds with a metal atom, and a single molecule of the
chelating
agent is capable of forming two or more coordinate bonds with a single metal
atom.
Suitable chelating agents include, for example, organic and inorganic
chelating
agents. Among the suitable inorganic chelating agents are, for example,
phosphates
such as, for example, tetrasodium pyrophosphate, sodium tripolyphosphate, and
hexametaphosphoric acid. Among the suitable organic chelating agents are those
with
CA 02512254 2005-07-15
4
macrocyclic structures and non-macrocyclic structures. Among the suitable
macrocyclic organic chelating agents are, for example, porphine compounds,
cyclic
polyethers (also called crown ethers), and macrocyclic compounds with both
nitrogen
and oxygen atoms.
Some suitable organic chelating agents that have non-macrocyclic structures
are, for example, aminocarboxylic acids, 1,3-diketones, hydroxycarboxylic
acids,
polyamines, aminoalcohols, aromatic heterocyclic bases, phenol, aminophenols,
oximes, Shiff bases, sulfur compounds, and mixtures thereof. In some
embodiments,
the chelating agent includes one or more aminocarboxylic acids, one or more
hydroxycarboxylic acids, one or more oximes, or a mixture thereof. Some
suitable
aminocarboxylic acids include, for example, ethylenediaminetetraacetic acid
(EDTA),
hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid
(NTA), N-
dihydroxyethylglycine (2-HxG), ethylenebis(hydroxyphenylglycine) (EHPG), and
mixtures thereof. Some suitable hydroxycarboxylic acids include, for example,
tartaric acid, citric acid, gluconic acid, 5-sulfoslicylic acid, and mixtures
thereof.
Some suitable oximes include, for example, dimethylglyoxime, salicylaldoxime,
and
mixtures thereof. In some embodiments, EDTA is used.
Some additional suitable chelating agents are polymeric. Some suitable
polymeric chelating agents include, for example, polyethyleneimines,
polymethacryloylacetones, poly(acrylic acid), and poly(methacrylic acid).
Poly(acrylic acid) is used in some embodiments.
Some suitable metal-complexing agents that are not chelating agents are, for
example, alkaline carbonates, such as, for example, sodium carbonate.
Metal-complexing agents may be present in neutral form or in the form of one
or more salts. Mixtures of suitable metal-complexing agents are also suitable.
In some embodiments, the composition of the present invention includes
water. Independently, the composition of the present invention, whether or not
it
contains water, may, in some embodiments, be used in methods that include
admixing
the composition of the present invention with water. Whether the water is
included in
the composition of the present invention or the water is mixed with the
composition of
the present invention, the water that is used may suitably come from any
source.
Suitable water may be, for example, purified or unpurified. Suitable purified
water
may be, for example, deionized or distilled or both. Suitable unpurified water
may be
CA 02512254 2005-07-15
from any source, including, for example, municipal water supplies, wells,
streams,
other natural sources, irrigation ditches, or any combination thereof.
In some embodiments in which water is used, the water contains one or more
metal ions, such as, for example, iron ions, copper ions, other metal ions, or
mixtures
S thereof. In some embodiments, the water contains 0.1 ppm or more of one or
more
metal ions.
While the present invention is not limited to any particular mechanism, it is
contemplated that metal ions, in some cases, interact with cyclopropene in a
way that
reduces the activity of cyclopropene. In such cases, it is further
contemplated that a
metal-complexing agent may interact with metal ion in a way the reduces the
interaction between metal ion and cyclopropene, thus preserving the activity
of
cyclopropene.
The amount of metal-complexing agent used in the present invention also may
vary widely. In some embodiments, the amount of metal-complexing agent will be
adjusted to be sufficient to complex the amount of metal ion that is present
or
expected to encounter. Metal-complexing agent might, for example, encounter
metal
ion in the composition of the present invention, in the admixture formed when
the
composition of the present invention is admixed with water, or both. For
example, in
some embodiments, if a relatively efficient chelating agent is used as a metal-
complexing agent (i.e., a chelating agent that will form a complex with all or
nearly
all the metal ions in the water), the ratio of moles of chelating agent to
moles of metal
ion will be 0.1 or greater; or 0,2 or greater; or 0.5 or greater; or 0.8 or
greater.
Among such embodiments that use a relatively efficient chelating agent, the
ratio of
moles of chelating agent to moles of metal ion will be 2 or less; or 1.5 or
less; or 1.1
or less.
Independently, in some embodiments, the amount of metal-complexing agent
is, based on the total weight of the composition, 25% by weight or Iess; or
10% by
weight or less; or 1 % by weight or less. Independently, in some embodiments,
the
amount of metal-complexing agent is, based on the total weight of the
composition,
0.00001 % or more; or 0.0001 % or more; or 0.01 % or more.
Independently, in some of the embodiments in which the composition of the
present invention includes water, the amount of metal-complexing agent can
usefully
be determined by the molar concentration of metal-complexing agent in the
water. In
some embodiments, the concentration of metal-complexing agent is 0.00001 mM
(i.e.,
CA 02512254 2005-07-15
6
mini-Molar) or greater; or 0.0001 mM or greater; or 0.001 or greater; or 0.01
or
greater; or 0.1 or greater. Independently, in some embodiments, the
concentration of
metal-complexing agent is 100 mM or less; or 10 mM or less; or 1 mM or less.
In some embodiments, the composition includes at least one molecular
encapsulating agent. Useful molecular encapsulating agents include, for
example,
organic and inorganic molecular encapsulating agents. Suitable organic
molecular
encapsulating agents include, for example, substituted cyclodextrins,
unsubstituted
cyclodextrins, and crown ethers. Suitable inorganic molecular encapsulating
agents
include, for example, zeolites. Mixtures of suitable molecular encapsulating
agents
are also suitable. In some embodiments of the invention, the encapsulating
agent is
a-cyclodextrin ("oc-CD"), (3-cyclodextrin, y-cyclodextrin, or a mixture
thereof. In
another embodiment of the invention, particularly when the cyclopropene is 1-
methylcyclopropene, the encapsulating agent is a-cyclodextrin. The preferred
encapsulating agent will vary depending upon the size of the R group. However,
as
one skilled in the art will appreciate, any cyclodextrin or mixture of
cyclodextrins,
cyclodextrin polymers, modified cyclodextrins, or mixtures thereof can also be
utilized pursuant to the present invention. Cyclodextrins are available from
Wacker
Biochem Inc., Adrian, MI or Cerestar USA, Hammond, IN, as well as other
vendors.
Among embodiments of the present invention in which a molecular
encapsulating agent is used, it is contemplated that, in some embodiments, the
composition includes at least one molecular encapsulating agent that
encapsulates one
or more cyclopropenes. A cyclopropene or substituted cyclopropene molecule
encapsulated in a molecule of a molecular encapsulating agent is known herein
as a
"cyclopropene molecular encapsulating agent complex." The cyclopropene
molecular
encapsulation agent complexes, when used in the present invention, can be
prepared
by any means. In one method of preparation, for example, such complexes are
prepared by contacting the cyclopropene with a solution or slurry of the
molecular
encapsulation agent and then isolating the complex, again using general
processes
disclosed in U. S. Patent No. 6,017,849. In the case of 1-MCP, the 1-MCP gas
is
bubbled through a solution of a-cyclodextrin in water, from which the complex
first
precipitates and is then isolated by filtration.
Among embodiments of the present invention in which a molecular
encapsulating agent is used, in some of such embodiments, the amount of
molecular
CA 02512254 2005-07-15
7
encapsulating agent can usefully be characterized by the ratio of moles of
molecular
encapsulating agent to moles of cyclopropene. In some of such embodiments, the
ratio of moles of molecular encapsulating agent to moles of cyclopropene is
0.1 or
larger; or 0.2 or larger; or 0.5 or larger; or 0.9 or larger. Independently,
in some of
such embodiments, the ratio of moles of molecular encapsulating agent to moles
of
cyclopropene is 2 or lower; or 1.5 or lower.
It is sometimes desirable to include in the composition one or more adjuvants,
such as, for example, extenders, pigments, fillers, binders, plasticizers,
lubricants,
surfactants, wetting agents, spreading agents, dispersing agents, stickers,
adhesives,
defoamers, thickeners, transport agents, and emulsifying agents. Some of such
adjuvants commonly used in the art can be found in the John W. McCutcheon,
Inc.
publication Detergents arid Emulsifiers, Annual, Allured Publishing Company,
Ridgewood, New Jersey, U.S.A. In some embodiments, the composition includes
one
or more surfactants. In some embodiments, the compositions includes one or
more
anionic surfactants. Independently, in some embodiments, the composition
includes
one or more alkyl alcohols. In some embodiments, the composition includes one
or
more alkyl alcohols where the alkyl group has 6 or fewer carbon atoms, or 3 or
fewer
carbon atoms.
One useful method of assessing the usefulness of compositions is the activity
of the composition. As used herein, "activity" of a cyclopropene means the
concentration of pure cyclopropene that is available to be used. For example,
in
general, if a reagent is mixed with a composition containing cyclopropene, and
that
reagent reacts with some or all of the cyclopropene, or that reagent complexes
with
some or all of the cyclopropene in a way that makes some or all of the
cyclopropene
undetectable or unavailable for useful purposes, that reagent is said to
reduce the
activity of the cyclopropene. One method of measuring the activity of a
composition
of the present invention is by analyzing the cyclopropene concentration in the
headspace above a sample of the composition, for example by using the
headspace
measurement method defined herein below. Another method of measuring the
activity of a composition of the present invention is by testing the
effectiveness of the
composition in treating plants, using methods, for example, like the tomato
epinasty
test defined herein below.
The ingredients of the present invention may be admixed by any means, in any
order. In some embodiments in which the composition of the present invention
CA 02512254 2005-07-15
includes water, the metal-complexing agent is admixed with the water before
the
water and the cyclopropene come into contact. In some of such embodiments, the
metal-complexing agent and the cyclopropene contact the water at the same
time. In
some of such embodiments, the cyclopropene and the water come into contact
with
each other before the metal-complexing agent is admixed with the water; such
embodiments are contemplated to be useful as long as the cyclopropene has some
useful level of activity at the time when the metal-complexing agent is
admixed with
the water. Also contemplated are embodiments in which metal-complexing agent
is
admixed with cyclopropene to form a composition of the present invention; such
a
composition of the present invention may, if desired, then be admixed with
water.
Among embodiments in which a molecular encapsulating agent is used, the
ingredients may be admixed by any means, in any order. In some embodiments, a
cyclopropene molecular encapsulating agent complex is made. In some
embodiments, a cyclopropene molecular encapsulating agent complex is admixed
with water, and the metal-complexing agent is added simultaneously or
subsequently.
In some embodiments, a cyclopropene molecular encapsulating agent complex is
admixed with an admixture of water and metal-complexing agent. In some
embodiments, cyclopropene molecular encapsulating agent complex and metal-
complexing agent are admixed to form a composition of the present invention;
such a
composition of the present invention may, if desired then be admixed with
water.
It is contemplated that combinations of the above embodiments are also
possible; for example, some metal-complexing agent could be admixed with
cyclopropene (with or without the presence of molecular encapsulating agent),
while
further metal-complexing agent could be admixed with water, and then the two
admixtures could be admixed with each other.
It is further contemplated that the composition of the present invention may
be
in contact with water for a short time or a long time. For example, one
embodiment is
contemplated in which gaseous cyclopropene that is not highly soluble in water
could
be bubbled through water that contains metal-complexing agent. For another
example, an embodiment is contemplated in which a cyclopropene molecular
encapsulating agent complex is admixed with water that contains metal-
complexing
agent, and the admixture is then stored for a relatively long time.
CA 02512254 2005-07-15
9
It is to be understood that adjuvants, if used, may be added to any of the
above
admixtures or to other admixtures of ingredients or to a composition of the
present
invention.
For one example, in some embodiments, a composition of the present
invention is made by admixing cyclopropene molecular encapsulating agent
complex,
metal-complexing agent, optionally one or more fillers, and, optionally other
ingredients; such a composition could be, in some embodiments, stored and used
at a
later time. It is contemplated that such compositions of the present invention
have
little or no water. Depending on the choice of fillers, other ingredients, or
both, it is
contemplated that such compositions of the present invention could be a
liquid,
dispersion, paste, solid, powder, or combination thereof. It is contemplated
that it
may, in some cases, be desirable to use such a composition by admixing it with
water
and contacting the admixture to one or more plants or plant parts.
For an additional example, in some embodiments, an admixture of water and
cyclopropene molecular encapsulating agent complex could made and stored; and
when it is desired to use the composition, the powder and the admixture of
water and
metal-complexing agent could be admixed.
For another example, in some embodiments, an admixture is made of
cyclopropene molecular encapsulating agent complex, metal-complexing agent,
water, and at least one adjuvant selected from surfactants, alcohols, or a
mixture
thereof. Such an admixture could be stored for relatively long times before
use; such
admixtures are contemplated to be most useful in cases where the concentration
of
cyclopropene molecular encapsulating agent complex in water is relatively low.
In
some of such embodiments, the adjuvants used include at least one anionic
surfactant
or at least one alkyl alcohol or a mixture thereof.
In some embodiments, a composition of the present invention is used to treat
plants or plant parts. Such treatment may be conducted by any method that
allows
cyclopropene to contact the plants or plant parts. Plant parts include any
part of a
plant, including, for example, flowers, blooms, seeds, cuttings, roots, bulbs,
fruits,
vegetables, leaves, and combinations thereof. In some embodiments, a
composition
of the present invention is used to treat one or more of blooms, fruits, and
vegetables.
In some embodiments, the cyclopropene leaves the composition of the present
invention and diffuses through air or other gas phase to contact the plant or
plant part.
In some embodiments, the composition of the present invention contacts the
plant;
CA 02512254 2005-07-15
such contact may be accomplished by any method. Some examples of methods of
contact are, for example, spraying, foaming, fogging, pouring, brushing,
dipping,
similar methods, and combinations thereof. In some embodiments, spraying or
dipping or both is used.
5
EXAMPLES
In the following examples, the examples marked with "(C)" are comparative
examples.
C~clopropene Headspace Measurement
Method:
A composition containing water and cyclopropene was sealed
in a bottle
equipped with a septum in a
manner that leaves a portion
of the volume of the bottle
filled with gas; a portion of
the headspace was analyzed
for cyclopropene at 1 hour
after injection. The analysis
method was gas chromatography
using the following
parameters:
Instrument: Hewlett Packard (Agilent Technologies)
6890
Detector: Flame Ionization
Detector Temperature: 150 deg. C
Air Flow Rate: 450 ml/min.
Hydrogen Flow Rate: 40 ml/min.
Make up Gas Flow Rate: 25 ml/min.
Column: Chrompack CP-PoraPlot Q-HT
Dimensions: 10 m x 0.32 mm
i.d.
Film Thickness: 10 microns
Carrier Gas: Helium
Flow Rate: 2.5 ml/min
Column Head Pressure: 6 psi
Injection Port Temperature: 150 deg. C
Initial Temperature: 35 deg. C
Initial Time: 0.5 min.
Program Rate 1: 20 deg. C / min.
Final Temperature: 250 deg. C
CA 02512254 2005-07-15
11
Final Time: 6.5 min.
Injection Volume: 1 ml
Injector: Manual/Splitless (1 ml inlet glass liner)
Cyclopropene Release Measurement
The release of cyclopropene from a mixture of water and cyclopropene was
measured as follows. A sample of cyclopropene molecular encapsulating agent
complex (0.02 g of complex containing 0.14% by weight, based on the weight of
the
complex, cyclopropene) was sealed into a bottle ( 122 ml volume) fitted with a
septum, water (3m1) was injected into the bottle, and the concentration of
cyclopropene in the headspace was measured as described herein above.
From the measure concentration of cyclopropene in the headspace and the
amount of cyclopropene added to the bottle, the fraction of the total amount
of
cyclopropene in the bottle that resides in the headspace can be calculated and
reported
as a percentage based on the amount of cyclopropene added to the bottle.
Example 1: Results of Cyclo~ropene Release Measurements
Samples were prepared as described in the Release Measurement Method
described above, using 1-MCP and a-CD. Five different sources of water were
used:
two different tap waters, two different deionized waters, and filtered water
(purified
with a MilIiQTM purification system from Millipore). No metal-complexing agent
was included. Results were as follows:
Water Source % Release of 1-MCP
~
tap #1 (C) 60
tap #2 (C) 13
deionized #1 100
(C)
deionized #2 60
(C)
filtered (C) 100
Some sources of water reduce the activity of 1-MCP.
Example 2: Addition of Citric Acid
CA 02512254 2005-07-15
12
The results for tap #2 of Example 1 were repeated, with the difference that
citric acid was first added to the water. Results were as follows:
Concentration of
Citric
Acid (milliMolar) % Release of 1-MCP
100 92
100
1 63
The presence of citric acid improves the °~o release dramatically,
compared to the 13%
5 that occurred with no citric acid (Example 1 ).
Example 3: Addition of Sodium Salt of EDTA
The procedures of Example 2 were repeated using the sodium salt of EDTA
instead of citric acid. Results were as follows:
Concentration of Sodium
Salt
of EDTA (milliMolar) % Release of 1-MCP
10 100
1 100
0.1 100
0.01 100
0.001 100
0.0001 100
0.00001 87
The presence of sodium salt of EDTA improves the % release dramatically,
compared
to the 13% that occurred with no citric acid (Example 1).
Example 4: Effect of Added Copper Ion
The procedures of Example 1 were repeated. In this case, the water was
deionized water #1 with added copper ion (added in the form of cupric
sulfate). The
results were as follows:
Concentration of Concentration of Sodium
Conger Ions (harts her Salt of EDTA (milliMolar) % Release of 1-MCP
CA 02512254 2005-07-15
13
million
0 (C) 0 100
(C) 0 10
5 (C) 0 36
1 (C) 0 54
5 11 100
5 11~1~ 37
Note (1): sodium salt of EDTA was added 2 hours after 1-MCP a-CD complex was
admixed with water, and headspace was measured 1 hour later.
Presence of copper ions without sodium salt of EDTA causes reduction in
activity of
5 1-MCP; sodium salt of EDTA, when added to the water before the 1-MCP a-CD
complex was added to the water, maintains the full activity of the 1-MCP;
sodium
salt of EDTA, when added to water 2 hours after the 1-MCP a-CD complex was
added to the water, fails to maintain the activity of the 1-MCP.
10 Example 5: Further Metal-complexin~ agents:
The experiments of Example 4 were repeated, using 5 ppm (parts per million)
of copper ion in every sample, and various types arid amounts of metal-
complexing
agents, and the results were as follows. Concentration of meta-complexing
agent is
shown in mM (milliMolar):
Concentration of Metal-% Release of
Metal-Complexin~ AgentComnlexin~ Agent (mM) 1-MCP
tetrasodium pyrophosphate1 42
tetrasodium pyrophosphate5 39
tetrasodiurn pyrophosphate10 54
sodium carbonate 1 61
sodium carbonate 5 68
sodium carbonate 10 71
nitrilotriacetic acid 1 97
nitrilotriacetic acid 5 100
nitrilotriacetic acid 10 95
CA 02512254 2005-07-15
14
Tartaric acid 1 99
Tartaric acid 5 8S
Tartaric acid 10 92
Poly(acrylic acid)~2> 0.1 20
Poly(acrylic acid)~2~ 0.5 60
Poly(aerylic acid)~2> 1 54
note (2): molecular weight 2000.
All of the metal-complexing agents, if used in sufficient quantity, maintain
the
activity of 1-MCP as compared to the control sample from Example 4 (deionized
water with 5 ppm copper ion and no metal-complexing agent), which had 1-MPC
release of 36%.
Example 6: Tomato Epinasty Testing:
Tomato epinasty tests were performed as follows:
Tomatoes (Rutgers 39 Variety Harris Seeds No 885 Lot 37729-A3) were
grown in 21/2" square pots filled with a commercial potting mix. Two seeds
were
place in each pot. Plants that had expanded first true leaves and were between
3 and 5
inches high were used for the tomato epinasty test.
To conduct the assay, the plants were sprayed to run off with the test 1- MCP
foliar spray and allowed to dry for 4 hours in sunlight These operations were
performed in a ventilated area away from the plants growing in the greenhouse
so
there would not be any unintended treatment to growing plants destined for
later
experiments.
The 1-MCP treated plants and both treated and untreated controls were placed
into an SLX controlled-atmosphere shipping box and sealed. To the box,
ethylene
was injected through a septum, which gave a concentration of 14 ppm. The
plants
were held sealed for 12-14 hours in the dark with ethylene in the atmosphere.
At the
end of ethylene treatment, the box was opened and scored for epinasty. Scoring
for
epinasty was accomplished by using the following scoring system for each pot.
1. 0% no epinasty (100% control)
2. 20% A couple leaves show some drooping (80% control)
CA 02512254 2005-07-15
3. 50% Plants show 50% of full response. Not all leaves need to
show effect. (50% control)
4. 80% Almost all leaves drooping and some show underside of
leaf exposed on top. (20% control)
5 5. 100% Leaves completely drooping and the underside of the leaf
exposed from above. (0% control)
The score of each pot is recorded. The average of 6 or 8 pots is averaged to
get a score. The percentage improvement is calculated by interpolating the
percentage improvement from the control water (i.e., no additives) 1-MCP
treatment.
10 Tomato epinasty tests were conducted using a formulation that
included water; a 1-MCP a-CD complex that contained 0.14% 1-MCP by weight,
based on the weight of the 1-MCP a-CD complex; and sodium salt of EDTA. The
amount of 1-MCP a-CD complex was chosen so that the formulation had 140 ppb of
1-MCP. The amount of sodium salt of EDTA varied, as shown in the table below.
15 Also included in the formulation were an anionic surfactant (0.1 % by
weight based on
the weight of the formulation), isopropanol ( 1 % by weight based on the
weight of the
formulation), and a spray oil (1% by weight based on the weight of the
formulation).
Results were as follows:
1-MCP Concen- EDTA % Control
of
Water Source tration (ppb) Concentration Epinasty
(mM)
De-ionized water 0 0 0
(C)
De-ionized water 140 0 100
(C)
Well Water (C) 140 0 0
Well Water 140 0.003 80
deionized water alone does not control epinasty; deionized water with 1-MCP
does
control epinasty; well water with 1-MCP does not control epinasty; well water
with
1-MCP and sodium salt of EDTA (a composition of the present invention) does
control epinasty.
