the present invention provides an electrolyte gel based on a crosslinked natural gum as the thickening agent . the preferred gums are guar gum and locust bean gum . structurally , the useful natural gums are high polymeric saccharides comprised of hexose , pentose or uronic acid groups linked together . one feature of the natural gums is their ready availability and low cost . a feature of guar gum is that it can be obtained in a rather pure state without extensive processing . guar gum in its natural state is relatively pure , having very few impurities such as sulphur ( sometimes found in agar ) or extraneous ions ( as found in many of the less pure gums ). a useful practical feature of guar gum gels is that they can be produced at room temperature or at only slightly raised temperature due to the fact that guar gum powder mixes well with room temperature water unlike synthetic gels such as polyvinyl alcohol which requires heating and more complicated production techniques . in addition , the natural ph of guar gum gels of this invention is approximately 7 - 8 . 5 , which is an excellent ph range for a composition to be used against the skin since it is close to the physiological ph . gels of the prior art have been neutralized or buffered in order to achieve an acceptable ph . natural gums are polysaccharides obtained from natural substances . for example , guar gum is a polysaccharide obtained from the seeds of the guar plant . the structure of guar gum , as illustrated below , is that of a chain mannose sacharide polymer with repeating single - unit galactose branches , referred to as galactomannan . ## str1 ## guar gum is available in anionic , cationic and nonionic forms . the nonionic type has been found most suitable for use with ag / agcl electrodes and is preferred for use with sensitive biomonitoring electrodes . applicant has surprisingly found that gels made from a hydroxy - propylated nonionic guar gum , sold by the stein hall co . under the trademark jaguar ® hp - 11 , are stable to concentrations of chloride ion greater than 10 percent by weight . thus , this guar gum gel can be successfully utilized where the transmission of high currents is desired ( i . e ., high salt concentrations are required ) without breakdown of the gel &# 39 ; s cohesive structure . however , in applications where the electrodes are to contact the skin for periods longer than an hour , lower concentrations , 0 . 1 - 5 percent by weight , of chloride ion are preferred . the lower concentrations of chloride are also preferred for electrodes which have been gelled and stored a long time prior to use in order to avoid corrosion effects on other parts of the electrode . both anionic and cationic guars are also useful as conductive gels . anionic guar , sold by the stein hall co . under the trademark jaguar ® cmhp , and cationic guar , sold by the stein hall co . under the trademark jaguar ® c - 13 , have been successfully tested . additionally , even a food - grade guar has been used successfully . gels made from these gums are of different viscosities and achieve peak viscosity at different times than do gels made from nonionic guar gum . mixtures of crosslinkable natural gums with other thickeners are also within the scope of the present invention . for example , the addition of polyvinyl alcohol ( pva ) to guar gum increases the cohesive strength of the final gel , and decreases its cold flow . this formulation is not particularly advantageous for biomonitoring electrodes , but can be valuable in electrodes where the gel is under high compressive loads , such as in electrosurgery or in transcutaneous nerve stimulation . other thickeners which can be mixed with the crosslinkable natural gums include hydroxyethyl cellulose , and hydroxypropyl methyl cellulose . examples of other natural gums which can be mixed with the crosslinkable natural gums of the present invention include gum arabic , sodium alginate and gum tragacanth . the gels of the present invention have increased internal cohesiveness and are able to be easily removed from surfaces with which they come in contact due to their crosslinked nature . the preferred crosslinking agent is borate ion , supplied by potassium tetraborate or sodium tetraborate . borate ion reacts effectively with the preferred gums , guar gum and locust bean gum , to form stable gels . in addition compositions crosslinked with borate are acceptable for contact with human skin . the exact nature of the crosslinking of guar gum with borate ion is not well understood . a degree of ester formation between the borate anions and the hydroxyl groups of the gums is possible . the formation of coordinate bonds would also account for the observed crosslinking effect . it is noted that polysaccharides with cis - hydroxyl groups on adjacent chains , such as guar gum and locust bean gum , are those most usefully crosslinked by borate ions for purposes of this invention . that is , gels made with polysaccharides having cis - hydroxyl groups exhibit the greatest degree of crosslinking ( e . g ., the stiffest gel is produced ) for given concentrations of gum and borate . it is possible that borate ion reacts with polysaccharides containing cis - hydroxyl groups to form bridges between adjacent cis - polyhydroxy moieties on different polymeric molecules . other crosslinking agents useful in the gels of the present invention include salts , such as ferric chloride , calcium chloride and the acetates of the multivalent cations of lead , chromium or nickel . those skilled in the art will recognize that by careful manipulation of reaction conditions , e . g ., temperature , ph , agitation , time of reaction , etc ., a degree of crosslinking can be achieved in the gel without the use of these crosslinking agents . such crosslinking can be detected by viscosity changes or by gel formations . however , the difficulty in preparing a stable medically - acceptable gel makes the above means of crosslinking less desirable than the borate - guar system . the preferred embodiment of the present invention includes within the crosslinked gum , any salt suitable to act as a conductor for the passage of electric current from an electrode to the body of a patient . however , crosslinked gums containing no salt are also contemplated since the gels of the present invention are aqueous in major portions and can conduct a current when subjected to high voltages . the preferred salts are chlorides , particularly those of sodium or potassium , since these are the most compatible with the normal electrolytes within the body . the chlorides are particularly preferred for use with the very sensitive ag / agcl ( silver / silver chloride ) electrodes , as they take part in the cell reaction and contribute to the proper functioning of the electrode . as previously mentioned the ag / agcl electrodes are particularly well suited for measuring minute electrical bio - events . the electrolyte concentration is important as it affects both current carrying capacity and skin irritation . for monitoring purposes , where electrodes may be worn for days at a time , it is desirable to keep the salt concentration below about 3 %. higher salt concentrations become irritating to the skin when in contact for prolonged periods and may cause serious lesions in the most severe cases . for short - term use as in cardiac stress testing , electrotherapy or electrosurgery , where the total contact time may be less than one hour , much higher salt concentrations can be used . the low electrical resistance necessary for the above - mentioned uses can only be exhibited by gels with high concentrations of electrolyte . a surprising feature of the crosslinked gels of the present invention are their stability even in the presence of saturated sodium chloride , approximately 25 percent by weight . thus , the present invention provides a gel which is stable in the presence of essentially any salt concentration desired . electrode storage time is another factor in the determination of electrolyte type and concentration . lower salt concentrations are preferred when electrodes are to be stored a long time between manufacture and use . salt solutions of sodium chloride and potassium chloride are corrosive to ferrous metals , with the result that gels high in concentrations of these salts may corrode the electrodes when in contact with the electrodes over a sufficiently long period of time . where storage periods are long and higher salt concentrations are desired , salts less corrosive than sodium chloride or potassium chloride , such as sodium citrate , should be used . the choice of electrolyte is also affected by electrode composition . where electrodes made of aluminum , stainless steel or german silver ( a silver - white alloy of copper , zinc and nickel ) are employed for biomonitoring purposes spurious signals or electrical noise are commonly experienced . such signals are thought to be generated by chemical reactions taking place between the electrode and corrosive conductive salts , such as sodium chloride . potassium citrate can be substituted for more corrosive salts , in order to reduce electrical noise . another aspect of the present invention may include the presence of humectants , plasticizers , and wetting agents in the crosslinked gel . humectants increase the ability of the gel to resist drying out when exposed to the atmosphere or to conditions of low humidity . plasticizers add smoothness and increased pliability to the gel . wetting agents permit the gel powder to disperse in water in a homogeneous and lump - free manner . 1 , 3 - butylene glycol , tetrahydrofurfuryl alcohol and dipropylene glycol are known plasticizers and humectants . diethylene glycol and glycerol have been commonly utilized as humectants . however , glycerol competes with guar gum for borate , and can interfere with proper gel formation by inhibiting crosslinking if present in sufficient quantity . propylene glycol can function in the gels of the present invention as a humectant , a plasticizer and a wetting agent for guar gum powder during manufacture . the gels of the present invention may also contain preservatives to prevent bacterial growth during storage and use . the parabens , e . g ., methyl and propyl - p - hydroxy - benzoates , are well - accepted preservatives for use in medicinal preparations . preferred components and concentrations for the gels of the present invention follow . all percentages are given in percents by weight . ______________________________________component percent by weight______________________________________guar gum ( sold by the stein hall 1 to 5 % co . under the trademarkjaguar ® hp - 11 ) nacl 0 . 8 to 25 % potassium tetraborate 0 . 05 to 3 . 0 %( k . sub . 2 b . sub . 4 o . sub . 7 . 5h . sub . 2 o ) propylene glycol 5 to 50 % propyl - p - hydroxy benzoate 0 . 01 to 0 . 05 %( propylparaben ) methyl - p - hydroxybenzoate 0 . 01 to 0 . 9 %( methylparaben ) water to 100 % ______________________________________ raising the amount of guar gum increases the viscosity of the gel , and conversely lowering the amount of guar gum decreases the viscosity of the gel . raising the chloride ion concentration increases the electrical conductivity of the gel and decreases the gel - skin impedance , and conversely lowering the chloride ion concentration decreases the electrical conductivity of the gel and increases gel - skin impedance . raising the borate ion concentration increases the degree of crosslinking and the stiffness of the gel , and conversely lowering the borate ion concentration decreases the degree of crosslinking and thus the stiffness of the gel . raising the amount of propylene glycol , a humectant , increases the ability of the gel to resist drying out . an especially preferred composition for use in the practice of the present invention , particularly with a biomonitoring electrode , is the following : ______________________________________component percent by weight______________________________________guar gum ( hp - 11 , stein hall & amp ; co .) 2 . 0nacl 2 . 4propylene glycol 15 . 0methyl - p - hydroxy benzoate 0 . 1propyl - p - hydroxy benzoate 0 . 02potassium tetraborate 0 . 57water to 100______________________________________ this composition has excellent electrical properties in addition to a useful combination of physical properties . the gel makes good contact with both skin and electrode , is stable with regard to moisture loss ( a major factor affecting shelf - life and useful life on patient ), and possesses excellent cohesive strength . the following examples further illustrate the present invention . in these examples , all parts and percents are by weight , unless otherwise indicated . approximately 300 ml of distilled water is heated in a 600 ml beaker to a temperature of 60 °- 75 ° c . and 9 . 9 gm of sodium chloride is added to the heated water with stirring until dissolved . in a separate vessel , 0 . 16 gm of propyl - p - hydroxy benzoate and 0 . 8 gm of methyl - p - hydroxy benzoate are mixed well with 80 . 0 gm of propylene glycol until dissolved . to this mixture 6 . 4 gm of guar gum powder ( commercially available as jaguar ® hp - 11 from the stein hall co .) is added slowly with constant stirring until homogeneously dispersed . the dispersion of guar gum in paraben / propylene glycol solution is added slowly to the aqueous sodium chloride solution with vigorous stirring , e . g ., with a high shear mixer ( homo - mixer commercially available from gifford wood , inc ., hudson , n . y .). vigorous mixing is continued and the temperature is maintained at about 60 °- 75 ° c . until the mixture is smooth and the guar gum is completely dissolved ( about 10 - 20 minutes ). the resultant mixture is a homogenous , viscous solution . the heat source is removed and vigorous mixing is continued while 20 ml of a 10 % w / v solution of potassium tetraborate is slowly added . the stirring is discontinued and the mixture is allowed to cool to room temperature . following the procedure of example 1 gels were prepared having the following compositions : ______________________________________ amount amount potassium amountexample gum tetraborate nacl / kcl * number gum (% by wt .) (% by wt .) (% by wt . ) ______________________________________2 guar 1 . 6 0 . 5 2 . 4 ( jaguar ® cmhp ) 3 guar 1 . 6 0 . 5 2 . 4 ( jaguar ® c - 13 ) 4 locust bean 1 . 6 0 . 375 2 . 45 guar 1 . 6 0 . 583 2 . 4 ( jaguar ® hp - 11 ) 6 guar 1 . 6 0 . 5 30 . 0 * ( jaguar ® c - 13 ) 7 guar 1 . 6 0 . 5 30 . 0 * ( jaguar hp - 11 ) ______________________________________ examples 6 and 7 illustrate that a gel can be made according to the present invention which can accomodate high salt concentrations . approximately 300 ml of distilled water is heated in a 600 ml beaker to a temperature of 60 °- 75 ° c . 9 . 9 gm of sodium chloride , 0 . 16 gm of propyl - p - hydroxy benzoate and 6 . 4 gm of guar gum powder ( commercially available as jaguar ® a2s from the stein hall co .) are added to the water and the mixture is stirred vigorously , e . g ., with a homo - mixer , until a homogeneous mixture is obtained ( 15 - 20 minutes ). the heat source is removed and , using moderate stirring ( e . g ., with a propeller - type stirrer ), a 10 % w / v solution of potassium tetraborate , and propylene glycol are slowly added in alternate aliquots over a period of about 5 - 10 minutes as follows : 1 . 2 - 5 ml 10 % w / v solution of potassium tetraborate ( until gelation starts ). thereafter 2 ml aliquots of the 10 % potassium tetraborate solution are alternated with 10 gm aliquots of propylene glycol until a total of 20 ml of the potassium tetraborate solution and 80 gms of propylene glycol have been added . upon cooling , a gel of this invention is obtained . following the procedure of example 8 a gel was prepared having the following composition : ______________________________________ amount potassium amountexample amount gum tetraborate naclnumber gum (% by wt .) (% by wt .) (% by wt . ) ______________________________________9 guar 1 . 6 0 . 25 2 . 4 ( jaguar ® a - 40 -( f )) ______________________________________ the following table ( table i ) is a list of the physical properties of the gels of examples ( 1 - 9 ). table i__________________________________________________________________________ electrical amount amount ph of resistivity viscosity ( poise ) example gum potassium crosslinked ohm - cm nacl / kcl * at shear ratenumbergum (% by wt .) tetraborate gel at 10 khz (% by wt .) 0 . 025 / sec . 0 . 1 / sec . __________________________________________________________________________1 guar ( hp - 11 ) 1 . 6 0 . 50 7 . 66 42 . 8 2 . 4 11 . 8 × 10 . sup . 3 5 . 2 × 10 . sup . 32 guar ( cmhp ) 1 . 6 0 . 50 7 . 70 44 . 0 2 . 4 12 . 0 × 10 . sup . 3 5 . 5 × 10 . sup . 33 guar ( c - 13 ) 1 . 6 0 . 50 7 . 66 43 . 7 2 . 4 20 . 0 × 10 . sup . 3 9 . 6 × 10 . sup . 34 locust bean 1 . 6 0 . 375 7 . 65 42 . 8 2 . 4 20 . 0 × 10 . sup . 3 -- 5 guar ( hp - 11 ) 1 . 6 0 . 583 7 . 6 18 . 4 6 . 4 9 . 2 × 10 . sup . 3 -- 6 guar ( c - 13 ) 1 . 6 0 . 5 7 . 6 6 . 8 30 . 0 * -- -- 7 guar ( hp - 11 ) 1 . 6 0 . 5 7 . 8 5 . 4 30 . 0 * -- -- 8 guar ( a2s ) 1 . 6 0 . 50 7 . 35 41 . 5 2 . 4 2 . 0 × 10 . sup . 3 1 . 7 × 10 . sup . 39 guar ( a40f ) 1 . 6 0 . 25 7 . 60 43 . 8 2 . 4 11 . 7 × 10 . sup . 3 8 . 3 × 10 . sup . 3__________________________________________________________________________ the viscosities of the gels of examples 6 and 7 were not measured since these gels were prepared to show high salt concentration capability . electrical resistivity was measured using a plastic cell of approximately 3 c . c . volume . the cell consisted of two circular platinized platinum electrodes approximately 0 . 7 cm in diameter , which faced each other and were approximately 0 . 8 cm . apart . the cell constant ( k cell ) was calculated according to known experimental technique ( see american society of testing materials standards , report number d202 - 77 , part 39 , section 48 , pp . 73 , 1978 annual ) and found to be equal to 1 . 39 at 10 khz ( sinusoidal signal ). resistivity measurements were taken at 10 khz ( sinusoidal signal ) using a hewlett packard model 4800 a vector impedance meter . a 10 khz frequency was chosen to minimize electrode polarization effects . the cell was filled with the appropriate gel and its measured resistance ( rm ) was obtained . resistivity ( ρ ) is given in ohm - cm by the equation all viscosity measurements were made using a mechanical spectrometer ( model rms - 7200 made by rheometrics , inc .) and according to the instrument instruction manual , using a 72 mm diameter cone and plate , a 0 . 04 radian angle and a 0 . 05 mm gap . all measurements were made at room temperature ( 18 25 ° c .). a 1 . 6 % by weight solution of jaguar ® hp - 11 in distilled water was prepared . to a 40 c . c . sample of the guar gum solution approximately 1 c . c . of a 10 % by weight solution of fecl 3 in water was added with stirring . to this a concentrated solution of potassium hydroxide was added dropwise and the ph of the mixture was monitored . when the ph rose to an alkaline ph of about 11 . 2 , from a starting ph of about 2 . 25 , a crosslinked , cohesive , non - sticky gel was obtained . a 1 . 6 % by weight solution of jaguar ® cmhp in distilled water was prepared . to a 20 gm sample of the guar gum solution , 15 drops of a 10 % by weight solution of chromium acetate was added with stirring . a concentrated solution of potassium hydroxide was then added dropwise to the mixture with stirring and the ph was monitored . at an alkaline ph of above about 9 , an excellent crosslinked gel of the present invention was obtained . subsequently 20 drops of a saturated solution of potassium chloride was mixed with the gel . the gel remained crosslinked , cohesive and non - sticky .
a cohesive nonsticky electrically conductive gel is disclosed , for facilitating low resistance contact between a metal electrode and a biological body . the gel comprises an aqueous solution of up to saturated concentrations of ionized salts as the conducting agent , a natural gum capable of crosslinking , and a crosslinking material which provides the electrically conductive gel with sufficient internal strength to remain cohesive without reinforcement . the gel has good electrical characteristics and improved physical properties which prevent the gel from leaving a messy residue on the skin of the patient or on the electrode .