a kind of sensor of non-intervention detection sweat gland perspiration ion situation
Technical field
The present invention relates to biochemical sensor field, relate to a kind of sensor of non-intervention detection sweat gland perspiration ion situation particularly.
Background technology
Autonomic nerve is an indispensable ingredient of intact nervous, and its fiber be distributed on skin distributes identical with sensory fiber, and anesthesia district is consistent with lossless district.The autonomic nerve fibers of domination sweat gland is mainly cholinergic nerve fibers.Xerosis cutis after nerve fiber damage in sensory deprivation district is lossless, along with the regeneration of nerve, perspires and increases gradually.Therefore check and secrete antiperspirant function, the degree of nerve injury and regeneration can be judged.
Mainly comprise about the inspection of secreting antiperspirant function in clinical at present and secrete the quantitative test of antiperspirant axon reflex, antiperspirant print test, temperature control perspire test etc., but mostly not easily to implement due to more complicated, method complex operation, apparatus expensive; Or affect by surrounding, temperature, be difficult to objective quantitative, and be not suitable for clinical research.Chinese patent (application number is 201120399122.4) a kind of sweat gland activity sensor and psychological tester; comprise power subsystem, protective resistance unit, parallel plate capacitor unit and voltage signal output unit; for carrying detection site between the two-plate of parallel plate capacitor unit, voltage signal output unit is used for according to parallel plate capacitor electric power output voltage signal.
Sympathetic nerve galvanic skin response (SSR) is that human body accepts to stimulate the rear skin reflex current potential occurred, it derives from the synchronous movement that sweat gland is brought out in sympathetic activities fiber release impulsion, belongs to and urges antiperspirant to move.Clinical discovery a lot of diabetics lower limb SSR abnormal rate is higher than upper limb, and the feature of Diabetic autonomic neuropathy is onset concealment, makes slow progress, the symptom of lower limb overweights upper limb, and occur prior to upper limb, sensory disturbance overweights the dyskinesia, and the abnormal rate of lower limb nerve conduction velocity is higher than upper limb.Autonomic nerve functional lesion may be similar to the feature that sensory nerve damages, or because lower limb conducting pathway is long, easily decay is relevant.SSR and the course of disease of diabetics are proportionate, and namely disease time is longer, and the sickness rate being associated with dysautonomia is also higher, and SSR is abnormal also more obvious.So SSR is a kind of method of quantitative check autonomic nervous function of sensitivity, be comparatively responsive atraumatic means to early diagnosis diabetics autonomic nerve functional lesion.But its state by environment and experimenter affects very large, reduces the degree of reliability of test result.
Therefore need to provide a kind of simple, hurtless measure and technological means and the equipment of the perspiration wicking problem of sweat gland can be detected fast.
Sweat gland spreads all over whole skin, and sweat gland secretion perspiration, is excreted to skin surface through conduit part, and energy moistening skin, discharge section water and ion, contribute to regulate body temperature and water salt balance.Sweat gland is divided into again apocrine gland and eccrine gland, and the distributed pole of eccrine gland is wide, and throughout whole body everywhere, sum about has 160 ~ 4,000,000 altogether, and different ethnic group and individual variation are very large.Eccrine gland have activeness sweat gland and inactivity sweat gland point, secretory activity is bullied the impact of gentle humidity, and juice is based on moisture.The secretion density of eccrine gland is different because of position, palm, and sole density is maximum, and be secondly forehead, the back of the hand, be extremity again, trunk is minimum.
Perspiration can be divided into inorganic constituents and organic principle two class, and inorganic constituents is the salt such as sodium chloride, calcium carbonate mainly.Maintain the salt balance in body and electric equilibrium, also have nerve impulse.In perspiration, calcium ion concentration is about 2.25 ~ 2.58mmol/l, and potassium concentration is about 3.5 ~ 5.5 mmol/l, and Na ion concentration is about 135 ~ 145mmol/l, and chlorine ion concentration is about 95 ~ 105mmol/l.
Chloride ion plays various physiological role.Have chloride channel in many cells, its primary responsibility controls transmembrane potential and the cell volume of stationary phase cells; In membranous system, the chloride ion in special neuron can regulate and control the effect of glycine and γ-aminobutyric acid, and chloride ion is also relevant with the acid-base balance maintained in blood.Chloride ion in body fluid and hydrogen ion concentration can not change because of the growth at age.Usually, people is the basic held stationary of body fluid chloride concentration after 20 years old, thus detects when can ensure Electrochemical Detection perspiration ion situation not by the restriction at age.
By electro-chemical test sweat gland perspiration ion situation, being the electrochemical appliance by being applied to epidermis, under specific voltage, producing electrochemical reaction.Apply a voltage being placed in the electrochemical appliance in epidermis, cation is adsorbed to negative electrode, anion is adsorbed to anode.
Under low dc voltage, fat deposit has very high electric capacity, and the ion in usual perspiration can not through organizing horny layer.Ion in perspiration is in this electric field, and the approach of unique movement is exactly the antiperspirant pipe of sweat gland, and thus when electro-chemical test perspiration ion, test result can not change with the change of external environment, thus can ensure feasibility and the concordance of detection.
Summary of the invention
The object of the present invention is to provide a kind of sensor of non-intervention detection sweat gland perspiration ion situation, use reverse ion method and electrochemical process principle, under applying specific voltage (0.5 ~ 12V) condition, accurately react physiological situation or health status by test perspiration chloride ion or hydrion situation.
For achieving the above object, solution of the present invention invents a kind of sensor of non-intervention detection sweat gland perspiration ion situation, specific as follows:
A first aspect of the present invention provides a kind of sensor being used for detection of skin sweat gland ion changed condition, comprise the electrochemical reaction situation active electrode pair being used for for a pair testing sweat gland perspiration ion, and be used for carrying out the electrochemical signals tested out active electrode the inert electrode pair of self-correcting for a pair, active electrode to inert electrode to being receive in parallel in outside measuring circuit.The anode of sensor is made up of an active electrode of homonymy and an inert electrode, and negative electrode is made up of an active electrode of opposite side and another one inert electrode.Sensor outside apply specific voltage condition under, active electrode can produce electrochemical reaction with the chloride ion in sweat gland perspiration or hydrion, and inert electrode can not produce electrochemical reaction with any ion of sweat gland perspiration.The signal of the active electrode perception of sensor is the mixed signal of the multi-signal comprising electrochemical reaction signal, the impact of the state of this signal tested person person self; For eliminating the effects of the act, inert electrode signal is adopted to carry out self-correcting to it.
Preferably, sensor rest is the position of experimenter's eccrine gland prosperity, and as the epidermis at the positions such as back, forehead, extremity, more preferably position is lower limb sole or upper limb palm.
Preferably, active electrode is nickel electrode or silver/silver chloride electrode etc., more preferably nickel electrode, is used for perception electrochemical reaction.
Preferably, inert electrode is copper electrode or Ti electrode etc., is more preferably intended for self-correcting electrode.
A second aspect of the present invention provides a kind of preparation method of the sensor being used for detection of skin sweat gland ion changed condition, comprises the preparation method controlling preparation method and inert electrode of active electrode.
Preferably, the processing method of nickel electrode and copper electrode can be the one of electrochemical polish, grinding and polishing, magnetic variation fluid polishing.
Further, nickel electrode surface electrochemistry polishing flow process is: sonochemistry oil removing → washing → pickling → washing → electrochemical degreasing → washing → pickling → washing → electrochemical polish → washing → washing → washing → oven dry.The technological parameter of electrochemical polish is as following table 1.
Table 1 nickel electrode electrochemical polishing process parameter
Raw material and operating condition |
Processing range |
Phosphoric acid |
65% |
Sulphuric acid |
15% |
Chromic anhydride |
6% |
Water |
14% |
Density |
1.74 |
Voltage |
12-18/V |
Cathode-current density |
30-40A/dm
2 |
Temperature |
Room temperature |
Time |
0.3-2min |
Cathode material |
Stereotype |
After electrochemical polish processing, surface roughness reaches 0.003 micron.
Further, copper electrode surface electrochemistry glossing flow process is: oil removing → copper polishing → cleaning → distilled water or the anti-copper discoloration agent → distilled water of washed with de-ionized water → leaching RT or washed with de-ionized water → centrifugal drying or compressed air dry up or dry (temperature 70 ~ 90 DEG C).The technological parameter of electrochemical polish is as following table 2.
Table 2 electrode electro Chemical glossing parameter
Raw material and operating condition |
Processing range |
Phosphoric acid |
800ml/L |
Additive A |
100ml/L |
Additive B |
100ml/L |
Temperature |
10-30℃ |
Anodic current density |
5-6A/dm
2 |
Voltage |
6-12V |
Time |
1-8min |
Negative electrode |
Rustless steel |
Further, nickel electrode surface grinding polishing process is corase grind, fine grinding, rough polishing, essence throwing.Lapping liquid is corundum lapping liquid, and milling time is respectively 40 minutes, 40 minutes, 30 minutes, 40 minutes.Carry out ultrasonic cleaning after grinding, dry, pack.
After above-mentioned grinding and polishing, nickel electrode surface roughness is 0.004 micron.
Further, copper electrode Surface Machining grinding and polishing operation is corase grind, fine grinding, rough polishing, essence throwing.Lapping liquid is corundum lapping liquid, and milling time is respectively 30 minutes, 20 minutes, 20 minutes, 40 minutes.Carry out ultrasonic cleaning after grinding, dry, pack.
The product of copper electrode after having to pass through the polishing of Passivation Treatment guarantee after polishing can not be oxidized.Passivation technology is as following table 3.
Table 3 copper electrode passivation technology parameter
Raw material and operating condition |
Processing range |
Copper imitates colour-changing agent |
50ml/L |
Water |
950ml/L |
Temperature |
Room temperature |
Time |
1-2min |
Preferably, can not there be any residual material except the material of electrode own on the nickel electrode after processing and copper electrode surface.
Preferably, choose purity be more than 99.5% nickel be preparation nickel electrode raw material.
Further, nickel electrode raw material nickel fractions is hard state, and hardness HV is greater than 180; Surface roughness is less than 0.01 micron, and sheet material flatness is less than 0.05 micron, and thickness deviation size is less than 0.05 micron.
Preferably, choosing purity is that the copper of more than 99.5% is as the raw material preparing copper electrode.
Further, the form of copper electrode raw material copper is hard state, and hardness HV is greater than 180; Surface roughness is less than 0.01 micron, and sheet material flatness is less than 0.05 micron, and sheet metal thickness tolerance dimension is less than 0.05 micron.
Preferably, the shape of nickel electrode and copper electrode can be sheet (block) shape, also can be cylindric, or semi-cylindrical etc.
Preferably, the Validity Test area of nickel electrode and copper electrode is all not less than 0.1cm
2, nickel electrode is not in contact with each other mutually with copper electrode, and nickel electrode becomes multiple proportion with the area of copper electrode, more preferably, and area equation.
Preferably, become minute surface with the nickel/copper electrode Surface Machining of epidermis location contacts, minute surface roughness Ra value is less than 0.006 micron, and Rz value is less than 0.01 micron.
The present invention uses reverse ion method and electrochemical process principle, adopts inert electrode to carry out the self-correcting of active electrode signal, environmental disturbances signal can be eliminated, and thus, ion concentration range that is highly sensitive, test is wide, and result is accurate.Meanwhile, what the present invention tested is perspiration ion change in sweat gland antiperspirant pipe, and the change of this ion is because the impact of patient self function (as the change of autonomic nerve, heart disease etc.) causes, and is non-mutability.Thus this sensor can be used for the disease detection relevant to autonomic nerve, heart etc.
Accompanying drawing explanation
Fig. 1 is sensor construction schematic diagram;
Fig. 2 is embodiment one sensor anode (or negative electrode) generalized section;
Fig. 3 is embodiment two sensor electrode generalized section;
Fig. 4 is embodiment three sensor electrode horizontal section schematic diagram;
Fig. 5 is embodiment three sensor anode generalized section
After Fig. 6 is through electrochemical polish, 50 times of figure are amplified on nickel electrode surface
Fig. 7 is that 150 times of figure are amplified on nickel electrode surface after grinding and polishing
In figure, 1 is sensor anode, and 2 is sensor cathode, and 1a is anode nickel electrode, and 1b is anode copper electrode, and 2a is cathode nickel electrode, and 2b is tough cathode electrode, and 3 is insulating bars.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is further illustrated.Explanation below adopts the mode exemplified, but protection scope of the present invention should not be limited to this.
Fig. 1 is following examples sensor construction schematic diagram: wherein 1 is anode, is made up of an active nickel electrode 1a and inertia copper electrode 1b; Wherein 2 is negative electrode, is made up of an active nickel electrode 2a and inertia copper electrode 2b.Wherein nickel electrode is connected with external measuring circuitry respectively by wire with copper electrode, and connected mode is parallel way.
Embodiment one:
Fig. 2 is the generalized section of the present embodiment sensor anode (or negative electrode).
The Validity Test area of nickel electrode and copper electrode is 200cm
2, shape is square, does not contact between nickel electrode with copper electrode.Nickel electrode surface roughness Ra value is 0.003 micron, Rz value 0.007 micron, and copper electrode surface roughness Ra value is 0.003 micron, Rz value 0.006 micron.
Embodiment two:
Fig. 3 is the present embodiment sensor electrode generalized section: wherein 1 is anode, is made up of an a semi-cylindrical active nickel electrode 1a and semi-cylindrical inertia copper electrode 1b; Wherein 2 is anode, is made up of an a semi-cylindrical active nickel electrode 2a and semi-cylindrical inertia copper electrode 2b; Wherein nickel electrode is connected with external measuring circuitry respectively by wire with copper electrode, and connected mode is parallel way.
The radius of nickel electrode and copper electrode is equal, is 20mm, and under the prerequisite ensureing effective test area, other radiuses also can be considered.Do not contact between nickel electrode with copper electrode.Nickel electrode surface roughness Ra value is 0.004 micron, and copper electrode surface roughness Ra value is 0.004 micron.
Embodiment three:
Fig. 4 is the present embodiment sensor electrode horizontal section schematic diagram.Wherein 3 is plastic cement insulating bars, the coated arc nickel sheet in outside as active nickel electrode and an arc copper sheet as copper electrode.Wherein nickel electrode is connected with external measuring circuitry respectively by wire with copper electrode, and connected mode is parallel way.The Validity Test area of nickel electrode and copper electrode is 100cm
2, do not contact between nickel electrode with copper electrode.Nickel electrode surface roughness Ra value is 0.004 micron, and copper electrode surface roughness Ra value is 0.004 micron.
Fig. 5 is the present embodiment sensor anode generalized section.
The sensor electrode processing method of above three embodiments adopts electrochemical polish method or grinding and polishing method.
Nickel electrode Surface Machining electrochemical polishing method: nickel material is 99.9% pure nickel plate, long 60mm, wide 50mm, thick 3mm, cold rolled plate material, and hardness HV is 220, surface roughness 0.01 micron, sheet material flatness 0.05 micron.The one side welding screw do not processed, thus shield electrode is to prevent from being corroded.Carry out electrochemical polish, work flow is as follows:
Sonochemistry oil removing → washing → pickling → washing → electrochemical degreasing → washing → pickling → washing → electrochemical polish → washing → washing → washing → oven dry.
The technological parameter of electrochemical polish is as follows:
Raw material and operating condition |
Processing range |
Phosphoric acid |
65% |
Sulphuric acid |
15% |
Chromic anhydride |
6% |
Water |
14% |
Density |
1.74 |
Voltage |
12-18/V |
Cathode-current density |
30-40A/dm
2 |
Temperature |
Room temperature |
Time |
0.3-2min |
Cathode material |
Stereotype |
After electrochemical polish processing, surface roughness reaches 0.003 micron, and Fig. 6 amplifies 50 times of nickel electrode exterior views after electrochemical polish.
Copper electrode Surface Machining electrochemical polishing method: copper product is 99.9% fine copper plate, long 60mm, wide 50mm, thick 3mm, cold rolled plate material, surface roughness 0.01 micron, sheet material flatness 0.05 micron.
Electrochemical polishing process flow process: oil removing → copper polishing → cleaning → distilled water or the anti-copper discoloration agent → distilled water of washed with de-ionized water → leaching RT or washed with de-ionized water → centrifugal drying or compressed air dry up or dry (temperature 70 ~ 90 DEG C), and electrochemical polishing process parameter is as follows.
Raw material and operating condition |
Processing range |
Phosphoric acid |
800ml/L |
Additive A |
100ml/L |
Additive B |
100ml/L |
Temperature |
10-30℃ |
Anodic current density |
5-6A/dm
2 |
Voltage |
6-12V |
Time |
1-8min |
Negative electrode |
Rustless steel |
Nickel electrode Surface Machining abrasive polishing method: nickel material is 99.9% pure nickel plate, long 120mm, wide 60mm, thick 3mm, cold rolled plate material, and hardness HV is 280, surface roughness 0.01 micron, sheet material flatness 0.06 micron.Grinding step is corase grind, fine grinding, rough polishing, essence throwing four procedures, and lapping liquid is corundum lapping liquid, and milling time is respectively 40 minutes, 40 minutes, 30 minutes, 40 minutes.Carry out ultrasonic cleaning after grinding, dry, pack.
After above-mentioned grinding and polishing, nickel electrode surface roughness is 0.004 micron.Fig. 7 amplifies 150 times of nickel electrode exterior views after grinding and polishing.
Copper electrode Surface Machining abrasive polishing method: copper product is 99.9% fine copper plate, long 120mm, wide 60mm, thick 3mm, cold rolled plate material, surface roughness 0.01 micron, sheet material flatness 0.05 micron.Grinding step is corase grind, fine grinding, rough polishing, essence throwing four procedures, and lapping liquid is corundum lapping liquid, and milling time is respectively 30 minutes, 20 minutes, 20 minutes, 40 minutes.Carry out ultrasonic cleaning after grinding, dry, pack.
The product of copper electrode after having to pass through the polishing of Passivation Treatment guarantee after polishing can not be oxidized.Passivation technology is as follows:
Raw material and operating condition |
Processing range |
Copper imitates colour-changing agent |
50ml/L |
Water |
950ml/L |
Temperature |
Room temperature |
Time |
1-2min |