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Claims  |
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We claim:
1. An optical sensor for a blood constituent of interest consisting
essentially of: a gas permeable, crosslinked silicone polymeric matrix
having therein at least one optical indicator consisting essentially of a
mixture of derivatives of a polynuclear aromatic compound, each of said
derivatives providing a portion of an optical signal in response to
excitation light when in the presence of a blood constituent of interest.
2. A sensor of claim 1 wherein:
said polynuclear aromatic compound is selected from the group consisting of
decacyclene, benzo-ghi-perylene and coronene.
3. A sensor of claim 1 wherein:
said polynuclear aromatic compound is decacyclene.
4. A sensor of claim 1 wherein said polynuclear aromatic compound is
derivatized with at least one material selected from the group consisting
of aliphatic hydrocarbons, cycloalkyl and cycloalkenyl hydrocarbons, alkyl
and alkenyl spiro hydrocarbons, aromatic hydrocarbons, aliphatic-aliphatic
ethers, aliphatic-aromatic ethers, aromatic-aromatic ethers,
aliphatic-aliphatic ketones, aliphatic-aromatic ketones and
aromatic-aromatic ketones; provided that said aliphatic groups are
selected from the group consisting of C.sub.1-C.sub.18 straight and
branched chain alkyl, alkenyl and alkynyl groups, and said aromatic groups
are selected from the group consisting of unsubstituted and substituted
aromatic groups where said substituents on said substituted aromatic
groups are selected from the group consisting of alkyl, alkenyl, fluoro
and chloro groups.
5. A sensor of claim 4 wherein:
said at least one material is selected from the group consisting of
aliphatic hydrocarbons, cycloalkyl and cycloalkenyl hydrocarbons, alkyl
and alkenyl spiro hydrocarbons, aromatic hydrocarbons and substituted
aromatic hydrocarbons; provided that said aliphatic groups are selected
from the group consisting of C.sub.1-C.sub.18 straight and branched chain
alkyl, alkenyl, and alkynyl groups, and said substituents on said
substituted aromatic groups are selected from the group consisting of
alkyl, alkenyl alkynyl, fluoro and chloro groups.
6. A sensor of claim 1 wherein:
said derivatives are non-polar derivatives.
7. A sensor of claim 1 wherein:
said mixture of derivatives of said polynuclear aromatic compound is a
mixture of t-butyl derivatives of said polynuclear aromatic compound.
8. A sensor of claim 7 wherein:
said polynuclear aromatic compound is decacyclene and said mixture is
soluble in hexane.
9. A sensor of claim 8 wherein:
said silicone polymeric matrix is a dimethylsiloxane polymeric matrix.
10. A sensor of claim 1 wherein:
said silicone polymeric matrix is selected from the group consisting of
dimethylsiloxane, diphenylsiloxane and dimethyldiphenylsiloxane.
11. A sensor of claim 1 wherein:
said mixture of derivatives of said polynuclear aromatic compound includes
at least three derivatives of said polynuclear aromatic compound.
12. A sensor of claim 1 wherein:
said mixture of derivatives of said polynuclear aromatic compound is
present in said silicone polymeric matrix in a concentration of at least
about 1.2 mg of said mixture per gram of said silicone polymeric matrix.
13. An optical sensor consisting essentially of:
a gas permeable, crosslinked dimethylsiloxane polymeric matrix having a
mixture of t-butyl derivatives of decacyclene present therein.
14. The sensor of claim 13 wherein:
said mixture of derivatives includes at least three of said derivatives and
is soluble in hexane.
15. The sensor of claim 13 wherein:
said mixture is present in an amount of least 1.2 mg of said mixture per
gram of said polymeric matrix.
16. An apparatus for measuring a blood constituent of interest consisting
essentially of:
an optical sensor consisting essentially of a gas permeable, crosslinked
silicone matrix having therein at least one optical indicator consisting
essentially of a mixture of derivatives of a polynuclear aromatic
compound, each of said derivatives providing a portion of an optical
signal in response to excitation light when exposed to a blood constituent
of interest, said matrix being permeable to such a blood constituent of
interest;
means for holding the optical sensor so that it can be exposed to blood;
and
optical fiber means for delivering excitation light to the optical sensor
so that the optical sensor can provide an optical signal indicative of a
characteristic of a constituent of interest and of transmitting such an
optical signal from the optical sensor.
17. The apparatus of claim 16 wherein:
said derivatives are hydrocarbon derivatives.
18. The apparatus of claim 16 wherein:
said at least one optical indicator consists essentially of a mixture of
derivatives of decacyclene.
19. The apparatus of claim 18 wherein:
said derivatives are t-butyl derivatives and said mixture is soluble in
hexane.
20. An optical sensor for a blood constituent of interest consisting
essentially of:
a gas permeable, crosslinked silicone polymeric matrix having at least one
optical indicator therein for providing an optical signal in response to
excitation light when in the presence of a blood constituent of interest,
said at least one optical indicator consisting essentially of a mixture of
derivatives of a polynuclear aromatic compound selected from the group
consisting of decacyclene, benzo-ghi-perylene and coronene.
21. A sensor of claim 20 wherein said polynuclear aromatic compound is
decacyclene.
22. A sensor of claim 21 wherein said derivatives are t-butyl derivatives.
23. A sensor of claim 22 wherein said silicone polymeric matrix is a
dimethylsiloxane polymeric matrix.
24. A sensor of claim 20 wherein said polynuclear aromatic compound is
benzo-ghi-perylene.
25. A sensor of claim 24 wherein said derivatives are t-butyl derivatives.
26. An optical sensor consisting essentially of a gas permeable,
crosslinked dimethylsiloxane polymeric matrix having an optical indicator
consisting essentially of a mixture of derivatives of a polynuclear
aromatic compound selected from the group consisting of decacyclene,
benzo-ghi-perylene and coronene dispersed therein, said optical indicator
being present in an amount of at least about 1.2 mg of said indicator per
gram of said dimethylsiloxane polymerix matrix.
27. An apparatus for measuring a blood constituent of interest consisting
essentially of:
an optical sensor consisting essentially of a gas permeable, crosslinked
silicone matrix having at least one optical indicator therein for
providing an optical signal in response to excitation light when exposed
to a blood constituent of interest, said at least one optical indicator
consisting essentially of a mixture of derivatives of a polynuclear
aromatic compound selected from the group consisting of decacyclene,
benzo-ghi-perylene and coronene, said matrix being permeable to such a
blood constituent of interest;
means for holding the optical sensor so that it can be exposed to blood;
and
optical fiber means for delivering excitation light to the optical sensor
so that the optical sensor can provide an optical sensor indicative of a
characteristic of a constituent of interest and for transmitting such an
optical signal from the optical sensor.
28. The apparatus of claim 27 wherein:
said at least one optical indicator consists essentially of derivatives of
decacyclene.
29. The apparatus of claim 28 wherein said derivatives are t-butyl
derivatives. |
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Claims |
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Description |
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BACKGROUND OF THE INVENTION
It is sometimes necessary or desirable for a physician to determine the
concentration of gases in blood. This can be accomplished utilizing an
optical sensor which contains an optical indicator responsive to the
constituent of interest. The optical sensor is exposed to the blood, and
excitation light is provided to the sensor so that the optical indicator
can provide an optical signal indicative of a characteristic of the
constituent of interest. For example, the optical indicator may fluoresce
and provide a fluorescent optical signal as described in Lubbers et al
U.S. Pat. No. RE31,897 or it may function on the principals of light
absorbance as described, for example, in Fostick U.S. Pat. No. 4,041,932.
The optical sensor may include a gas permeable polymeric matrix with the
optical indicator dispersed in the matrix. For accuracy of measurement, it
is important to have a strong optical signal. The intensity of the optical
signal is a function of the quantity of the optical indicator present in
the polymeric matrix which in turn depends upon the quantity of the
optical indicator that can be dissolved in the polymeric matrix during
manufacture of the sensor.
Unfortunately, the preferred optical indicators are not very soluble in
silicone polymers, the polymers of choice, and so less than the desired
quantity of the indicator is present in the matrix. For example,
decacyclene is a preferred fluorescent indicator for oxygen because it has
maximum sensitivity in the appropriate wavelength range. However,
decacyclene is not very soluble in silicone polymers. Silicone polymers
are the most suitable oxygen permeable matrix materials known to be
presently acceptable for use with blood. Accordingly, the problem cannot
be solved by selecting another polymeric matrix material.
It has been suggested by others that the solubility of decacyclene in a
silicone polymer might be increased by utilizing the hexa-t-butyl
derivative of decacyclene. However, contrary to this suggestion, we have
found that the use of hexa-t-butyl decacyclene as a substitute for
decacyclene does not, in fact, yield significant and reproducible
increases in the solubility in the silicone polymer.
SUMMARY OF THE INVENTION
This invention provides an optical sensor having a higher concentration of
the relevant optical indicator in a silicone matrix than has been possible
heretofore. Consequently, the optical sensor can provide an optical output
signal of higher intensity. The output signal may be fluorescent signal or
result from optical absorbance.
These desirable results are accomplished by enhancing the solubility of the
optical indicator in a silicone polymeric matrix. This, in turn, can be
accomplished by employing as the optical indicator an indicator which
consists essentially of a mixture of derivatives of a polynuclear aromatic
compound wherein the derivatizing groups are preferably non-polar. Of
course, the silicone polymeric matrix may also contain other optical
indicators, which are independent of this mixture of derivatives of the
polynuclear aromatic compound and additional additives provided for other
purposes.
The basic polynuclear aromatic compound suitable for derivation would be
any fluorescent or absorbance optical indicator of the polynuclear
aromatic class. If used as a fluorescence indicator, for all practical
purposes taking into consideration a reasonable cost which would be
affordable to hospitals, analytical laboratories and physicians for an
analyzing instrument for detecting and analyzing the fluorescent signal,
the basic polynuclear aromatic indicator will be chosen such that its
excitation wavelength is separated from its fluorescence wavlength by
about at least 40 nm (nanometers). Of course, if the analyzing
instrumentation costs are not a consideration, the spread between the
excitation wavelength and the fluorescence wavelength could be less than
40 nm. In any event, there should not be any overlap of the excitation
wavelength and the fluorescence wavelength.
Generally the basic polynuclear aromatic indicator suitable for derivation
would be chosen to have an excitation or absorbance wavelength of from
about 350 nm to about 450 nm and a fluorescence wavelength of from about
450 nm to about 600 nm.
Presently preferred for the polynuclear aromatic compound suitable for
derivation are decacyclene, benzo-ghi-perylene and coronene.
The polynuclear aromatic compound is derivatized with non-polar substituent
groups. Alkyl and aromatic hydrocarbons, ketones and ethers are preferred
as these substituents. Suitable for use as the substituent group for
derivation are aliphatic hydrocarbons, cycloalkyl and cycloalkenyl
hydrocarbons, bridge or spiro hydrocarbons, aromatic hydrocarbons and
substituted aromatic hydrocarbons, aliphatic-aliphatic ethers,
aliphatic-aromatic or substituted aromatic ethers, aromatic or substituted
aromatic-aromatic or substituted aromatic ethers, aliphatic-aliphatic
ketones, aliphatic-aromatic or substituted aromatic ketones and aromatic
or substituted aromatic-aromatic or substituted aromatic ketones where the
aliphatic groups are chosen from the group consisting of C.sub.1-C.sub.18
straight and branched chain alkyl, alkenyl and alkynyl hydrocarbons and
the substituent groups for the aromatic hydrocarbons are chosen from the
group consisting of alkyl, alkenyl, alkynyl, fluoro and chloro.
Thus a preferred group of said non-polar derivatives are chosen from the
group consisting of aliphatic hydrocarbons, cycloalkyl and cycloalkenyl
hydrocarbons, alkyl and alkenyl spiro hydrocarbons, aromatic hydrocarbons,
aliphatic-aliphatic ethers, aliphatic-aromatic ethers, aromatic-aromatic
ethers, aliphatic-aliphatic ketones, aliphatic-aromatic ketones and
aromatic-aromatic ketones where said aliphatic hydrocarbons, ethers and
ketones are C.sub.1-C.sub.18 straight and branched chain alkyl, alkenyl
and alkynyl hydrocarbons, ethers and ketones, respectively, and said
aromatic hydrocarbons, ethers and ketones are un-substituted and
substituted aromatic hydrocarbons are alkyl, alkenyl, alkynyl, fluoro and
chloro.
A more preferred group of said non-polar derivatives would be chosen from
the group consisting of aliphatic hydrocarbons, cycloakyl and cycloalkenyl
hydrocarbons, alkyl and alkenyl spiro hydrocarbons, aromatic hydrocarbons
and substituted aromatic hydrocarbons where said aliphatic hydrocarbons
are C.sub.1-C.sub.18 straight and branched chain alkyl, alkenyl and
alkynyl hydrocarbons and where said substituted aromatic hydrocarbons are
alkyl, alkenyl, alkynyl, fluoro and chloro substituted aromatic
hydrocarbons.
According to this invention, the precursor polynuclear aromatic compound is
derivatized to provide a mixture of a plurality of derivatives. For the
purposes of this specification, mixtures of derivatives are defined as
meaning multiples of the same substituent, multiples of different
substitutents and isomeric mixtures. As an example of multiples of the
same substitutent would be instances in which decacyclene is derivatized
with t-butyl groups to yield a mixture of hexa-t-butyl decacyclene,
penta-t-butyl decacyclene, decacyclene and tetra-t-butyl decacyclene shown
in scheme A. As an example of multiples of different substituents are
mixtures similar to those of the preceding sentence except two different
derviation groups are used as for instance the t-butyl group and the
isopentyl group. In addition multiple isomers of the same group can also
be formed. Examples of these would be the isomers of tri-t-butyl
decacyclene shown in scheme B and those of tetra-t-butyl decacyclene shown
in scheme C.
These mixtures are formed by reacting the basic polynuclear aromatic
compound with the precursor of the derivative group or groups in a manner
wherein there is incomplete substitution of all the possible substitution
sites on the basic polynuclear aromatic compound. This can generally be
accomplished by conducting an incomplete reaction. A first way of
achieving this result is by utilizing less than the amount of the
precursor of the derivative group which is necessary to completely
substitute the basic polynuclear aromatic compound. A further way is to
run the substitution reaction for a time period which is insufficient for
complete reaction, and an additional way is to run the reaction at a
depressed temperature so as to retard the rate of the reaction. In any
event the reaction will be conducted in such a manner that mixtures of
products of the substitution of the basic polynuclear aromatic compound
are obtained.
It has been found that by using mixtures of these derivatives of the
polynuclear aromatic compounds that the solubility of the polynuclear
aromatic compounds are greatly enhanced. For example, utilizing a mixture
of derivatized decacyclene, the solubility has been increased to about at
least two to ten fold as compared with the solubility of underivatized
decacyclene in the same silicone polymer. The results achieved with this
invention are synergistic in that the solubility of the mixtures of
derivatives of the polynuclear aromatic compounds in a silicone polymeric
matrix is much greater than the solubility of the individual compound in
the same polymeric matrix. The solubility of the compound is enhanced by
using mixtures of derivatives and/or isomers of the compound.
The reason why the mixtures of these derivatives enhances the solubility in
a silicone polymeric matrix is not known for certain. While we do not wish
to be bound by theory, it is believed that a pure compound has a higher
crystallization energy and it is further believed that the multiple
derivatives and/or isomers interfere with the fitting together of the
individual molecules in the crystal lattice structure. It is believed that
this is one contributing factor leading to the enhanced solubility.
A significant advantage of this invention is that each of the mixtures of
derivatives of the polynuclear aromatic compounds have similar optical
properties for providing an optical signal in response to excitation
light. For example, in the case of decacyclene, which is a fluorescent
indicator, each of the mixtures of derivatives thereof provided in
accordance with the teachings of this invention have similar excitation
and emission wavelengths. If this were not the case, the optical
properties of the sensor would tend to be much more varied.
Although various forms of silicone can be employed for the matrix, it is
important that the silicone have a high permeability to the gas of
interest so that the sensitivity of the optical indicator to the gas of
interest is optimized. For example, the silicone polymer may be
dimethylsiloxane, diphenylsiloxane, or a diphenyldimethylsiloxane
copolymer. Of this group, dimethylsiloxane is preferred because of its
high gas permeability. It is of course realized that other members of the
homologous series which include the before mentioned polymers might also
be used.
An optical sensor constructed in accordance with the teachings of this
invention has a higher concentration of the optical indicator in the
silicone polymeric matrix and as a result thereof, the optical output
signal obtainable from the optical indicator is also higher. For example,
using the mixtures of derivatives of polynuclear aromatic compounds of
this invention, up to five times more optical indicator can be dissolved
in a given weight of a silicone polymer as compared with utilizing any of
the individual compounds alone. Similarly, using the features of this
invention, the optical signal is up to about five times stronger as
compared with the optical signal generated from the individual compounds
in the silicone polymer.
The mixtures of derivatives of the polynuclear aromatic compounds can be
obtained using synthesizing procedures, such as a Friedel-Craft reaction.
The mixtures of the polynuclear aromatic compounds thus obtained can then
be dispersed in an uncured silicone as a powder or in a volatile solvent
such as methylene chloride or hexane. The solvent is then removed as for
instance by vacuum evaporation or the like. The uncured silicone having
the mixture of derivatives of the polynuclear aromatic compound dispersed
therein, is then crosslinked to form the optical sensor.
Solubility of the derivatives in the silicone polymer can be also be
enhanced by appropriately controlling the number and ratio of the
derivatives of the polynuclear aromatic compound in the mixture.
Heretofore utilizing only hexa-t-butyl decacyclene it was only possible to
obtain a concentration of the hexa-t-butyl decacyclene no greater than 0.5
mg per gram of dimethylsiloxane silicone polymer. Utilizing the teaching
of this invention, solubilities of at least 1.2 mg per gram of gas
permeable silicone polymer, such as dimethylsiloxane, can be achieved.
However, even greater solubilities of 4 to 5 mg per gram of silicone
polymer have been achieved. In this regard, for decacyclene, it is
preferred to utilize a mixture having at least three derivatives of the
basic decacyclene compound as determined by liquid chromatography. A
typical ratio for the three derivatives of decacyclene would be
approximately 51 to 45 to 3 as determined by liquid chromatography.
Typically, this ratio would have a solubility of about 4 mg per gram of
the silicone polymer.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of an optical sensor constructed in accordance
with the teachings of this invention.
FIG. 2 is an enlarged, fragmentary, sectional view taken generally along
line 2--2 of FIG. 1.
FIG. 3 is a schematic view partially in section showin an apparatus for
providing continuous monitoring of substances in the blood with such
apparatus incorporating the optical sensor of this invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows an optical sensor 11 which comprises a matrix 13 (FIG. 2) of a
silicone polymer and an optical indicator 15 dissolved in and carried by
the matrix. Although the matrix 13 can be of various sizes and
configurations, in the form shown in FIGS. 1-3, the matrix is in the form
of a thin, cylindrical membrane having relatively broad circular faces 17
and 19.
Although the sensor 11 may sense various blood constituents, such as oxygen
and carbon dioxide, in this embodiment, it is an oxygen sensor.
Accordingly, the matrix 13 is constructed of an oxygen permeable material,
such as a silicone polymer. Similarly, the optical indicator 15 must be
oxygen responsive and may be, for example, derivatives of decacyclene.
The optical sensor 11 can be used in various different ways to measure the
concentration of oxygen in blood or other substances. For example, the
optical sensor 11 may be suitably retained on a distal end of an optical
fiber 21 as by mechanical means (not shown), by adhesion of the silicone
of the sensor to the fiber and/or by use of an adhesive. The optical fiber
21 includes a core 23 and cladding 25 and an opaque overcoat 27 of
cellulose or other oxygen-permeable material covering the optical sensor
11 at a distal end portion of the optical fiber 21. The overcoat 27 may
also be used to retain or to assist in retaining the optical sensor 11 on
the optical fiber 21.
Although the optical sensor 11 could function on the principles of
absorbance, in this embodiment, the sensor is a fluorescent sensor.
Exciting light from a light source 29 is directed towards a half-silvered
mirror 31, and a component of the exciting light is reflected by the
mirror to a reference detector 33. The remainder of the exciting light
passes through the mirror 31 and through the optical fiber 21 to the
sensor 11. The reference detector 33 compensates for variations in
intensity of the light source 29.
The exciting light excites the fluorescence of the optical indicator 15. If
the optical sensor 11 is in the presence of oxygen gas, the optical
indicator 15 emits a fluorescent light signal at a different wavelength
from the exciting light of the source 29 with the intensity of the signal
depending on the concentration of the oxygen. The fluorescent signal
returns through the optical fiber 21 to the mirror 31 which reflects a
component of the fluorescent signal to a detector 35 which measures the
intensity of the fluorescent signal and correlates that to oxygen
concentration in the sample being tested.
The optical fiber 21 may be in the form of probe or catheter insertable
into a blood vessel of a patient to provide continuous on-line in vivo
monitoring of oxygen gas concentration in the blood. Alternatively, the
optical sensor 11 can be embodied in a flow-through housing as shown, for
example, in Heitzmann U.S. Pat. No. 4,557,900 to provide extracorporeal
blood gas monitoring.
EXAMPLES
Example 1
4.5 grams of decacyclene were added to a 500 cc. flask equipped with a
drying tube and a magnetic stirring rod. 450 mls of o-dichlorobenzene and
15 mls of t-butyl chloride were added. The reaction mixture was rapidly
stirred. Approximately 400 mg (weighed by difference) of aluminum chloride
was added to the reaction. Upon the addition of the aluminum chloride, the
color of the reaction mixture changed from brown to greenish brown. The
reaction was allowed to proceed overnight.
The reaction was quenched with 100 cc of a 3% sodium hydroxide solution.
The organic phase was separated and the aqueous phase was extracted with
dichloromethane. The combined organic phases were washed once with water
and the solvent was evaporated on a rotary evaporator under vacuum.
The crude reaction product was loaded onto a 4.times.24 inch chromatography
column containing 1100 grams of silica gel. Utilizing hexane as the mobile
phase, a yellow fluorescent eluent was collected. The solvent was
evaporated under vacuum to yield approximately 3.5 grams of crystals.
The crystals were extracted with 100 cc of hexane per 3 grams of crystals
by stirring at room temperature for 0.5 hours. The insoluble fractions
were removed by filtering, and the filtrate was evaporated to yield 1.5
grams of final product. HPLC was utilized to monitor the reaction, the
purification steps and the final product. The final product was shown by
HPLC to be a mixture of derivatives believed to be hexa-t-butyl
decacyclene, penta-t-butyl decacyclene and tetra-t-butyl decacyclene in a
ratio of 51 to 45 to 3, respectively, as determined by liquid
chromatography.
Example 2
In a like manner to Example 1, 1 gram of decacyclene was suspended in 40 cc
of o-dichlorobenzene. 2.0 grams of aluminum chloride followed by 4.0 grams
of chlorobenzyl chloride were added with stirring. The reaction mixture
was allowed to react for 40 minutes at ambient temperature and then was
quenched with dilute sodium hydroxide. The organic phase was washed once
with dilute sodium bicarbonate solution and then evaporated under vacuum
to yield a brownish oily suspension. This oil was purified on a silica gel
column using methylene chloride as the eluent to yield 0.5 grams of
yellowish brown crystals.
Example 3
In a like manner to Example 1, to 150 mg of benzo-ghi-perylene in 30 cc of
o-dichlorobenzene was added 0.15 grams of aluminum chloride and 0.5 grams
of t-butyl chloride. The reaction mixture was stirred for four hours and
quenched. The organic phase was evaporated and the residue passed through
a silica gel column to yield 125 mg of yellow crystals.
Example 4
In a like manner to Example 1, isopentyl chloride was reacted with
decacyclene.
Example 5
In a like manner to Example 1, 3-chloro-3-methylpentane was reacted with
decacyclene.
Example 6
In a like manner to Example 1, ethylbromide was reacted with decacyclene.
Example 7
In a like manner to Example 1, beta-chloro-p-fluoropropiophenone was
reacted with decacyclene to yield a fluorescent tar.
Example 8
In a like manner to Example 1, exonorborneol was reacted with decacyclene.
Example 9
In a like manner to Example 1, 2-chloroethylvinyl-ether was reacted with
decacyclene.
Example 10
In a like manner to Example 1, adamantylethanol was reacted with
decacyclene.
Example 11
In a like manner to Example 1, 1-adamantylmethanol was reacted with
decacyclene.
Example 12
In a like manner to Example 1, 2-chlorobutane was reacted with decacyclene.
Example 13
In a like manner to Example 1, 2-chloropropane was reacted with
decacyclene.
Example 14
In a like manner to Example 1, chlorocyclohexane was reacted with
decacyclene.
Example 15
In a like manner to Example 1, chloroethane was reacted with decacyclene.
Example 16
In a like manner to Example 1, equal mixtures of t-butyl chloride,
2-chloropropane, 2-chlorobutane and chlorocyclohexane were reacted with
decacyclene.
Example 17
In a like manner to Example 1, 1-chloro-hex-3-yne was reacted with
decacyclene.
Typically, utilizing t-butyl chloride for an example, for each 4.5 grams of
decacyclene, 8 to 20 grams of t-butyl chloride would be used, 0.2 to 0.6
grams of aluminum chloride would be used and 300 to 700 cc of
o-dichlorobenzene would be used.
In a like manner suitable mixtures of derivatives could be prepared
utilizing 2-chloroethylbenzene, 1-chlorooctadecane, 1-chlorododecane,
norbornylene, 2-chloroethylethylether, crotyl chloride, allyl chloride,
propargyl chloride, chloroacetophenone and chloroethylphenyl ketone by
reacting the same with a suitable polynuclear aromatic compound such as
decacyclene, benzo-ghi-perylene or coronene.
Example 18
300 mg of a mixture of t-butylated decacyclene derivatives were dissolved
in 15 cc of hexane to form a solution. The solution was mixed with 100
grams of vinyl terminated dimethylsilicone. The mixture was stirred until
a clear homogeneous solution was obtained. The solvent was removed under
vacuum. The residue was further cross linked to yield an optical sensor
having a mixture of derivatives of a polynuclear aromatic compound in a
silicone polymer matrix.
Example 19
A optical sensor was constructed as per Example 19 utilizing the mixture of
derivatives of Example 1. For this sensor 0.3 grams of the mixture of
derivatives of Example 1 were initially solubilized in 100 grams of the
dimethylsiloxane precursor. As a result, an optical sensor of the type
shown in FIG. 1 was produced. Exciting light at a wavelength of 400 nm was
directed at the optical sensor when the sensor was in the presence of
oxygen gas having a concentration of 74 mm Hg to provide a fluorescent
signal having a peak at a wavelength of 510 nm.
Although exemplary embodiments of the invention have been shown and
described, many changes, modification and substitutions may be made by one
having ordinary skill in the art without necessarily departing from the
spirit and scope of this invention.
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