阅读说明：本技术 一种施加电场作用的dsc热分析方法 (A kind of DSC heat analysis method applying electric field action ) 是由 钟力生 宋晓源 高景晖 于钦学 于 2019-08-08 设计创作，主要内容包括：公开了一种施加电场作用的DSC热分析方法,所述方法包括以下步骤：步骤1、在差示扫描量热仪的实验舱中将微电极坩埚和参比坩埚放在对应传感器上,微电极坩埚的电极引线与信号发生器接通,并设置好待输出的信号参数,放置被测试样品于微电极坩埚中的电极缝隙之间,盖上微电极坩埚盖并关闭实验舱；步骤2、在变温阶段测量被测试样品在电场作用下的DSC曲线,在复温阶段测量样品无电场作用下的DSC曲线；步骤3、结合电介质和热力学的相关理论,对DSC曲线进行分析并计算得到被测试样品的电场强度和变温至复温过程中的物相转化率。(Disclose a kind of DSC heat analysis method for applying electric field action, the described method comprises the following steps: microelectrode crucible and reference crucible are placed in respective sensor by step 1 in the Laboratory Module of differential scanning calorimeter, the contact conductor and signal generator of microelectrode crucible are connected, and set signal parameter to be output, tested sample is placed between the electrode gap in microelectrode crucible, microelectrode crucible cover is covered and closes Laboratory Module；Step 2 is tested DSC curve of the sample under electric field action in alternating temperature phase measuring, the DSC curve in the case where rewarming phase measuring sample is without electric field action；Step 3, in conjunction with dielectric and thermodynamic (al) correlation theory, to DSC curve analyzed and be calculated tested sample electric field strength and alternating temperature to rewarming during object inversion of phases rate.)

1. a kind of DSC heat analysis method for applying electric field action, the described method comprises the following steps:

Step 1 places microelectrode crucible, reference crucible and tested sample in the Laboratory Module of differential scanning calorimeter, wherein Microelectrode crucible is used to apply electric field to tested sample；Reference crucible is used to not apply tested sample electric field as ginseng According to；

Step 2 presets measurement temperature in a computer, and for controlling the temperature change in differential scanning calorimeter, measurement is tested Test agent is applied under electric field action and when reference crucible is without the freezing applied under electric field action outside and rewarming in the outer of microelectrode crucible DSC curve；The computer is connected with differential scanning calorimeter, is used for transmission signal and records experimental result；

Step 3, the electric field strength for being analyzed to obtain tested sample to DSC curve mutually turn with the object during alternating temperature to rewarming Rate, for analyzing different electric pulse field parameters for being tested the influence that ice crystal is formed in sample.

2. the method for claim 1, wherein preferred, 2 plate electrodes built in the microelectrode crucible in the step 1 are used In generating electric field, it is used to store tested sample there are gap between electrode；Electrode in tested sample and microelectrode crucible Surface is bonded completely；The electrode is connected by contact conductor with signal generator；Signal generator presets signal to be output Parameter applies electric field to tested sample for providing electric signal.

3. the method for claim 1, wherein the computer in the step 2 respectively with differential scanning calorimeter and from It is pressurized liquid nitrogen container to be connected, be used for from liquid nitrogen container is pressurized to cooling down in the Laboratory Module of differential scanning calorimeter.

4. the method for claim 1, wherein the microelectrode crucible in the step 1 and reference crucible are placed on differential It scans in calorimeter on corresponding sensor, sensor is used to detect the heat that sample is tested in microelectrode crucible and reference crucible Rheology is simultaneously converted into electric signal and exports to computer；The microelectrode crucible is bonded completely with sensor.

5. the method for claim 1, wherein the default measurement temperature in step 2 computer includes the alternating temperature stage With the rewarming stage, at the alternating temperature stage, the output channel of differential scanning calorimeter open signal generator, applies tested sample It is powered on field action；The output channel of differential scanning calorimeter shutdown signal generator at the rewarming stage is tested sample in nothing Natural rewarming under electric field action is applied outside.

6. being the method for claim 1, wherein tested object inversion of phases of sample during alternating temperature in the step 3 Rate η are as follows:

Wherein, Δ Q_ERefer to that tested sample applies alternating temperature under electric field action outside and phase transition is inhaled when rewarming under no electric field action The heat received or released, Δ Q_ORefer to tested sample alternating temperature and phase transition is absorbed or released when rewarming under no electric field action Heat.

7. method as claimed in claim 6, wherein be tested sample in the object inversion of phases rate η and apply under electric field action outside Alternating temperature and the heat Δ Q that phase transition is absorbed or released when rewarming under no electric field action_EIt is by applying electricity during alternating temperature The corresponding DSC curve of sample phase transition obtains in the rewarming dsc measurement of field, it may be assumed that

Wherein, β is heating rate, T₁、T₂The lowest temperature and temperature upper limit respectively integrated,For measured by DSC curve Heat flow rate.

8. method as claimed in claim 6, wherein be tested sample in the object inversion of phases rate η and become under no electric field action The heat Δ Q that phase transition is absorbed or released when temperature and rewarming_OBe by during alternating temperature without the rewarming dsc measurement for outside applying electric field In the corresponding DSC curve of sample phase transition obtain, it may be assumed that

Wherein, β is heating rate, T₁、T₂The lowest temperature and temperature upper limit respectively integrated,For measured by DSC curve Heat flow rate.

9. method according to claim 2, wherein by the output voltage and microelectrode crucible of the signal generator Electrode spacing calculates the electric field strength E of tested sample, it may be assumed that

Wherein, V is the output voltage of signal generator, and d is electrode spacing in microelectrode crucible.

10. a kind of method as described in any one of claim 1-9 claim is in the application of biomaterial low temperature preservation field.

Technical field

The present invention relates to thermal analysis system fields, more particularly, to a kind of DSC heat analysis method for applying electric field action.

Background technique

Biological dielectric is the important research direction of electromagnetism and biomaterial interdisciplinary field, dielectric to biology Research helps to deepen people to the understanding to interact between electromagnetism and biomaterial, is conducive to that it is pushed widely to answer With.How the major issue that biomaterial cryo-conservation technology faces at present avoids biomaterial from meeting in temperature-fall period The low temperature injury received, the main reason for leading to its low temperature injury are that water contained in biological tissue crystallizes generation in refrigerating process Ice crystal causes the chemical damage as caused by cell dehydration or punctures caused physical damnification by ice crystal by cell membrane.Therefore, it avoids The low temperature injury of biomaterial is mainly the crystallization for inhibiting water in biological tissue in temperature-fall period.

Currently, common biomaterial Cryopreservation mainly has fast cooling method, cryoprotective agent method or two is added Person combines.However, fast cooling method is only applicable to the preservation of the biomaterial of small volume, when the biomaterial that needs save Volume is larger, and material internal can not reach consistent rate of temperature fall due to the influence of heat transfer with material surface；And add low temperature Protective agent is not only complicated for operation, and is difficult to clean off after material rewarming, in addition, part cryoprotective agent is toxic to biomaterial Effect, application scenarios are limited.

Since hydrone is polar molecule, dipole polarization can be generated under the action of electromagnetic field outside by applying, the polarity effect meeting The balance of water cluster is interfered, and then influences the liquid-solid phase-change characteristic of hydrone.Studies have shown that applying the suitable electromagnetism of condition outside The enough crystallizations for inhibiting Water Proton molecule to a certain extent of field energy, to reduce damage of the cryogenic freezing to biomaterial Degree.

The correlative study of biomaterial cryogenic freezing is mainly realized by microscopic observation at this stage.Microscopic observation Experimental result have the characteristics that more simple and clear, but there are still following three aspects problems: first is that observing samples need to be thin slice The virtual condition of biomaterial is not inconsistent in shape, with practical application；Second is that most salt ion and ice crystal be it is colourless, this is Finer microscopic observation adds difficulty；Third is that the interpretation of result of microscopic observation generally requires to identify by subjectivity, do not unite One method is not easy to carry out more precise and tiny quantitative calculating and depth Analysis on Mechanism.

Traditional measurement and outer Effect study of the mode for biomaterial for applying electric field of verifying, often can only be cold by comparing The difference of biomaterial character is further analyzed after the difference of the ice crystal form of water or rewarming in Dong Hou biological tissue, is not easy to Record in real time.Differential scanning calorimetry (DSC=Differential Scanning Calorimetry) can be by measuring quilt The relationship between sample and the hot-fluid and temperature of reference substance is passed in and out when test sample heating, cooling or constant temperature, wherein measuring signal The variation that energy is absorbed or released to be tested sample, is indicated with milliwatt (mW).In addition, DSC can also be used in detection heat absorption and put Fuel factor, measurement peak area (enthalpy of transition and reaction enthalpy), measurement characterize temperature and the SPECIFIC HEAT CAPACITY at peak or other effects etc..

Differential scanning calorimeter is the principle based on DSC and designs and be applied to the relevant temperature of measurement material internal heat deflection The instrument of degree and hot-fluid relationship, when measurement, differential scanning calorimeter can generate DSC curve, can accurately be recorded by DSC curve Changes of heat flux of the biomaterial in cryogenic freezing and rewarming, and then quantitatively calculate and applied outside different under the conditions of certain temperature Influence of the electric pulse field parameter to the object inversion of phases rate of material.During cryogenic freezing, by the electricity of electrolyte solution in biological tissue Fuel factor caused by leading will be shifted up DSC baseline, and sample liquid-solid phase change moment, which can discharge a large amount of latent heat, causes test liquid temperature to be returned It rises, so that dsc measurement curve occurs that the heat release ring for calculating latent heat of phase change cannot be integrated.Therefore, in temperature-fall period, data are not Reference data can be objectively used as very much.If sample liquid-solid phase transformation crystallization mode difference when freezing, solid-liquid is corresponded under the conditions of rewarming The latent heat of phase change and transformation temperature of phase transition process can also show difference.

Consider that above-mentioned factor, the present invention are led to using electric field action effect is applied outside evaluating without the rewarming DSC data for applying electric field outside Cross in crucible embed electrode mode, when having electric field action using differential scanning calorimeter Simultaneous Monitoring biomaterial freezing and Changes of heat flux when rewarming, it is outer under the conditions of calculating certain temperature to apply electric field in conjunction with dielectric and thermodynamics correlation theory and model To the object inversion of phases rate of material, the Different Effects that different electric pulse field parameters forms ice crystal in biomaterial are compared, are further visited Study carefully and apply electric pulse field parameter outside difference to the difference of material object inversion of phases rate, provides reason to apply electric field raising cryogenic freezing preservation efficiency outside Test basis is referred to, to realize that the cryo-conservation of large volume biological tissue lays the foundation.

Disclosed above- mentioned information are used only for enhancing the understanding to background of the present invention in the background section, it is thus possible to Information comprising not constituting the prior art known to a person of ordinary skill in the art in home.

Summary of the invention

In view of the above problems, it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind The DSC heat analysis method for applying electric field action passes through differential scanning calorimeter in conjunction with dielectric and thermodynamic (al) correlation theory Changes of heat flux of the electric field for biomaterial freezing and rewarming when is applied outside real-time monitoring and generates DSC curve, calculates different electricity Field parameters disclose ice crystal in electric fields on biological material refrigerating process and are formed and growth to the influence difference of material object inversion of phases rate The mechanism of action, and then seek and apply electric pulse field parameter outside best, effectively inhibit the damage of biological tissue caused by ice crystal, improves low temperature Save efficiency.

The purpose of the present invention is achieved by the following technical programs.

A kind of DSC heat analysis method applying electric field action, the described method comprises the following steps:

Step 1 places microelectrode crucible, reference crucible and tested sample in the Laboratory Module of differential scanning calorimeter, Wherein microelectrode crucible is used to apply electric field to tested sample；Reference crucible is not for applying electric field conduct to tested sample Reference；

Step 2 presets measurement temperature in a computer, for controlling the temperature change in differential scanning calorimeter, measures Tested sample microelectrode crucible it is outer apply under electric field action and in reference crucible without the freezing applied under electric field action outside and multiple DSC curve when warm；The computer is connected with differential scanning calorimeter, is used for transmission signal and records experimental result；

Step 3, in conjunction with dielectric and thermodynamic (al) correlation theory and analysis method, to DSC curve analyzed to obtain by The electric field strength of test sample and the object inversion of phases rate during alternating temperature to rewarming, for analyzing different electric pulse field parameters for tested The influence that ice crystal is formed in test agent.

The present invention also provides the methods described in one kind to apply the DSC heat analysis method of electric field action in biomaterial low temperature The application of preservation field.

Compared with prior art, the beneficial effects of the present invention are:

(1) present invention has electric field using differential scanning calorimeter Simultaneous Monitoring by way of embedding electrode in crucible Biomaterial freezing and changes of heat flux when rewarming and DSC curve is generated when effect, in conjunction with dielectric and thermodynamics correlation theory With model, calculates outside under condition of different temperatures and apply electric field to the influence difference of material object inversion of phases rate, compare different electric pulse field parameters To the Different Effects that ice crystal in biomaterial is formed, for apply outside electric field improve cryogenic freezing save efficiency provide it is theoretical and test according to According to；

(2) this invention is easy to operate, and calculated result is accurate, and has repeatability, and saves process to material at low temperature The formation mechenism of middle ice crystal, which provides, new researchs and analyses method.

The above description is only an overview of the technical scheme of the present invention, in order to make technological means of the invention clearer Understand, reach the degree that those skilled in the art can be implemented in accordance with the contents of the specification, and in order to allow the present invention Above and other objects, features and advantages can be more clearly understood, illustrated below with a specific embodiment of the invention Explanation.

Detailed description of the invention

By reading the detailed description in hereafter preferred embodiment, various other advantages and benefits of the present invention It will become apparent to those of ordinary skill in the art.Figure of description only for the purpose of illustrating preferred embodiments, And it is not to be construed as limiting the invention.It should be evident that drawings discussed below is only some embodiments of the present invention, For those of ordinary skill in the art, without creative efforts, it can also be obtained according to these attached drawings Other attached drawings.And throughout the drawings, identical component is presented with like reference characters.

In the accompanying drawings:

Fig. 1 is the DSC heat analysis method flow chart of the application electric field action of one embodiment of the invention；

Fig. 2 be according to an embodiment of the present invention under different current field conditions pure water freezing after rewarming DSC curve；

Fig. 3 be according to an embodiment of the present invention under different current field conditions physiological saline freezing after rewarming DSC curve；

Fig. 4 is the DSC electrode system schematic diagram that one kind that one embodiment of the invention is achieved can apply electric field.

Below in conjunction with drawings and examples, the present invention will be further explained.

Specific embodiment

The specific embodiment that the present invention will be described in more detail below with reference to accompanying drawings.Although being shown in attached drawing of the invention Specific embodiment, it being understood, however, that may be realized in various forms the present invention without that should be limited by embodiments set forth here System.It is to be able to thoroughly understand the present invention on the contrary, providing these embodiments, and can be complete by the scope of the present invention Be communicated to those skilled in the art.

It should be noted that having used some vocabulary in the specification and claims to censure specific components.Ability Field technique personnel it would be appreciated that, technical staff may call the same component with different nouns.This specification and right It is required that not in such a way that the difference of noun is as component is distinguished, but with the difference of component functionally as differentiation Criterion."comprising" or " comprising " as mentioned throughout the specification and claims are an open language, therefore should be solved It is interpreted into " including but not limited to ".Specification subsequent descriptions are to implement better embodiment of the invention, and the description is to say For the purpose of the rule of bright book, the range that is not intended to limit the invention.Protection scope of the present invention is wanted when depending on appended right It asks subject to institute's defender.

In order to facilitate understanding of embodiments of the present invention, further by taking specific embodiment as an example below in conjunction with attached drawing to be solved Explanation is released, and each attached drawing does not constitute the restriction to the embodiment of the present invention.

In order to better understand, Fig. 1 is the DSC heat analysis method according to an embodiment of the invention for applying electric field action A kind of flow chart, DSC heat analysis method applying electric field action, the described method comprises the following steps:

Step 1 places microelectrode crucible, reference crucible and tested sample in the Laboratory Module of differential scanning calorimeter, Wherein microelectrode crucible is used to apply electric field to tested sample；Reference crucible is not for applying electric field conduct to tested sample Reference；

Step 2 presets measurement temperature in a computer, for controlling the temperature change in differential scanning calorimeter, measures Tested sample microelectrode crucible it is outer apply under electric field action and in reference crucible without the freezing applied under electric field action outside and multiple DSC curve when warm；The computer is connected with differential scanning calorimeter, is used for transmission signal and records experimental result；

Step 3, in conjunction with dielectric and thermodynamic (al) correlation theory and analysis method, to DSC curve analyzed to obtain by The electric field strength of test sample and the object inversion of phases rate during alternating temperature to rewarming, for analyzing different electric pulse field parameters for tested The influence that ice crystal is formed in test agent.

On the one hand, the present invention has by way of embedding electrode in crucible using differential scanning calorimeter Simultaneous Monitoring Biomaterial freezing and changes of heat flux when rewarming and DSC curve is generated when electric field action, in conjunction with dielectric and thermodynamic (al) phase Theoretical and model and method of chemical phase analysis are closed, calculates outside under condition of different temperatures and applies electric field to material object inversion of phases rate Difference is influenced, the Different Effects that different electric pulse field parameters form ice crystal in biomaterial are compared, improves low temperature cold to apply electric field outside Freeze and efficiency offer theory and test basis are provided；

On the other hand, this invention is easy to operate, and calculated result is accurate, and has repeatability, and protects to material at low temperature The formation mechenism of ice crystal, which provides, during depositing new researchs and analyses method.

In a preferred embodiment, 2 plate electrodes built in the microelectrode crucible in step 1, there are gaps between electrode For storing tested sample；Tested sample is bonded completely with the electrode surface in microelectrode crucible；The electrode passes through electricity Pole lead is connected with signal generator；Signal generator presets signal parameter to be output, for providing electric signal so as to quilt Test sample applies electric field, and the insulating properties for reviewing and validate contact conductor with multimeter is good, excludes signal generator and differential Scan the short circuit problem between calorimeter.

In a preferred embodiment, the microelectrode crucible in step 1 and reference crucible are placed on differential scanning calorimetry In instrument on corresponding sensor, sensor, which is used to detect in microelectrode crucible and reference crucible, is tested the changes of heat flux of sample simultaneously Electric signal is converted into export to computer；The microelectrode crucible is bonded completely with sensor.

In a preferred embodiment, the computer in step 2 is pressurized liquid nitrogen with differential scanning calorimeter and certainly respectively Tank is connected, described to be used for from pressurization liquid nitrogen container to cooling down in the Laboratory Module of differential scanning calorimeter.

In a preferred embodiment, the tested sample in verification step 1 and the electrode surface in microelectrode crucible Completely after fitting, covers microelectrode crucible cover and close differential scanning calorimeter Laboratory Module.

In a preferred embodiment, it includes alternating temperature stage and rewarming rank that measurement temperature is preset in the computer of step 2 Section, the output channel of differential scanning calorimeter open signal generator at the alternating temperature stage apply electric field to tested sample and make With；The output channel of differential scanning calorimeter shutdown signal generator at the rewarming stage, tested sample are applying electric field without outer Lower nature rewarming is acted on, DSC curve is generated.

In a preferred embodiment, object inversion of phases rate η of sample during alternating temperature is tested in step 3 are as follows:

Wherein, Δ Q_ERefer to that tested sample applies alternating temperature under electric field action outside and object phase turns when rewarming under no electric field action Become the heat for absorbing or releasing, Δ Q_oRefer to tested sample alternating temperature and phase transition is absorbed or put when rewarming under no electric field action Heat out.

ΔQ_EIt is bent by applying the corresponding DSC of the sample phase transition in the rewarming dsc measurement of electric field during alternating temperature Line obtains, it may be assumed that

Wherein, β is heating rate, T₁、T₂The lowest temperature and temperature upper limit respectively integrated,It is surveyed by DSC curve The heat flow rate obtained.

ΔQ_oBe by during alternating temperature without the corresponding DSC of the sample phase transition in the rewarming dsc measurement for outside applying electric field Curve obtains, it may be assumed that

Wherein, β is heating rate, T₁、T₂The lowest temperature and temperature upper limit respectively integrated,It is surveyed by DSC curve The heat flow rate obtained.

In a preferred embodiment, pass through the electrode spacing in the output voltage of signal generator and microelectrode crucible Calculate the electric field strength E of tested sample, it may be assumed that

Wherein, V is the output voltage of signal generator, and d is electrode spacing in microelectrode crucible.

In the present embodiment, comprising temperature control program in the computer that is connected with differential scanning calorimeter, described program is set It is set to three phases.Stage one: setting initial temperature as 4 DEG C, and is kept for 2 minutes；Stage two: cooled down with the rate of 3 DEG C/min To -60 DEG C；Stage three: it is kept for 3 minutes at -60 DEG C；Stage four: 10 DEG C are warming up to the rate of 3 DEG C/min.

In the present embodiment, before the experiment, microelectrode crucible need to be tested for the property, the purpose of performance test be for It keeps stablizing within the scope of temperature involved by guaranteeing it during the experiment, avoids the occurrence of physical conversion or chemical reaction and interfere Experimentation and interpretation of result.

Embodiments of the present invention and effect are illustrated below by 2 embodiments.