WO2020029622A1 - 一种基于顺磁位移的磁纳米粒子浓度与温度测量方法 - Google Patents
一种基于顺磁位移的磁纳米粒子浓度与温度测量方法 Download PDFInfo
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- the present invention relates to the technical field of nanomaterial testing, and in particular to a method for magnetic nanoparticle concentration and temperature based on paramagnetic shift.
- Temperature is an important characteristic of life activities. In medical treatment, many diseases can be treated by changing the temperature. For non-invasive visual temperature measurement of living bodies, it is not only required that the temperature measurement is accurate, but also that the temperature probe is accurately positioned. Magnetic resonance imaging temperature measurement is a promising temperature measurement method among a variety of non-invasive temperature measurement methods. However, it is mainly based on the current sensitivity of the relevant parameters of nuclear magnetic resonance imaging. The principle determines the measurement results. Affected by some temperature-related parameters in human tissues, such as the presence of fat will cause errors in temperature estimation, and even in the same tissue, changes in temperature sensitivity coefficient caused by changes in tissue structure will cause changes in temperature values to appear non-uniform Linear. So far, the spatial resolution of MRI is 1mm, and the temperature measurement accuracy of MRI is 1 ° C.
- Magnetic nanoparticles such as iron oxide nanoparticles, as a substance with non-toxic performance to living organisms, provide a possible solution for visualizing temperature measurement inside a living body based on its temperature sensitivity.
- temperature measurement and concentration imaging based on magnetic nanoparticles are in There are still challenges in high-precision measurement and high spatial resolution imaging.
- the detection capability of NMR spectrometers reaches the ppm level. Therefore, a temperature measurement method that can combine the temperature measurement principle of magnetic nanoparticles with the principle of nuclear magnetic resonance spectroscopy is pursued in order to achieve high-precision visual temperature measurement in vivo.
- the purpose of the present invention is to provide a method and method for the concentration and temperature of magnetic nanoparticles based on paramagnetic displacement, which can effectively achieve the concentration information of magnetic nanoparticles and high-precision temperature measurement by acquiring the magnetic resonance paramagnetic displacement of a magnetic nano sample.
- a method for magnetic nanoparticle concentration and temperature based on paramagnetic shift includes the following steps:
- M s is the saturation magnetization of the magnetic nano-particles
- N is the concentration of the magnetic nano-sample
- V is the volume of the magnetic nano-particles
- H is the strength of the excitation magnetic field
- k is the Boltzmann constant
- T is the temperature
- the step (3) substitutes the chemical shifts ⁇ R and ⁇ S of the pure reagent and the experimental reagent into the formula
- the resonance frequencies ⁇ R and ⁇ S of pure reagents and experimental reagents are obtained by solving, and ⁇ 0 is the resonance frequency of the internal standard magnetic field of the nuclear magnetic resonance equipment tetramethylsilane under the uniform magnetic field of the equipment.
- step (6) is specifically:
- NMR equipment is used to measure the concentration and temperature of magnetic nanoparticles by measuring the chemical shift of a liquid sample containing paramagnetic particles, effectively achieving high-precision concentration and temperature measurement.
- Paramagnetic magnetic nanoparticles are added to the NMR sample reagent, and the paramagnetic shift of the sample is obtained by NMR.
- the paramagnetic shift is used to obtain the resonance frequency, and the magnetic susceptibility is obtained according to the relationship between the resonance frequency and the magnetic susceptibility of the magnetic nanoparticles.
- the concentration information and temperature information of the sample are further decomposed based on the relationship between the magnetic susceptibility of the magnetic nanoparticles and the concentration and temperature.
- the present invention uses nuclear magnetic resonance paramagnetic displacement information to achieve magnetic nanoparticle concentration and temperature measurement, which can effectively achieve magnetic nanosample concentration information measurement and high-precision magnetic nanoparticle temperature measurement. Judging from the simulation data, the use of paramagnetic displacement information can effectively achieve the concentration measurement and high-precision temperature measurement of magnetic nanoparticle samples.
- FIG. 1 is a flowchart of a method of the present invention
- FIG. 2 is a simulation diagram of the change in the NMR paramagnetic displacement of a magnetic nano-sample with the same concentration at different magnetic fields at 200 Gs, 300 Gs, and 400 Gs with temperature;
- Figure 3 is a simulation diagram of the change in the magnetic resonance paramagnetic displacement of a magnetic nano-sample with magnetic field at 200 Gs, 300 Gs, and 400 Gs at the same temperature as a function of concentration;
- Figure 4 shows the concentration and temperature results of magnetic nano-samples obtained by inversion of standard temperature and magnetic field at 200Gs, 300Gs, and 400Gs, respectively;
- FIG. 5 is a simulation diagram of concentration and temperature errors obtained by inversion of the magnetic field at 200Gs, 300Gs, and 400Gs, respectively.
- the present invention provides a method for the concentration and temperature of magnetic nanoparticles based on paramagnetic shift, including the following steps:
- a nuclear magnetic resonance device with a uniform magnetic field strength of H 0 was used to detect pure reagents and experimental reagents with magnetic nanoparticles added to obtain chemical shift information ⁇ R and ⁇ S , where the chemical shift ⁇ R of pure reagents is used as a reference value. .
- the nuclear magnetic resonance equipment can use the existing nuclear magnetic resonance spectrometer with a measurement accuracy of up to ppm level.
- the current nuclear magnetic resonance spectrometer with a measurement accuracy of up to ppm level is used as a measurement method, it is possible to achieve higher precision magnetic nanoparticle concentration and temperature measurement .
- TMS tetramethylsilane
- ⁇ R and ⁇ S are the magnetic susceptibility of magnetic nanoparticles.
- M s is the saturation magnetization of the magnetic nano-particles
- N is the concentration of the magnetic nano-sample
- V is the volume of the magnetic nano-particles
- H is the strength of the excitation magnetic field
- k is the Boltzmann constant
- T is the temperature.
- the NMR paramagnetic displacement of magnetic nanoparticles containing magnetic nanoparticles under 200Gs, 300Gs, and 400Gs static magnetic field strengths were simulated as a function of temperature.
- the results of the change in paramagnetic displacement of the same concentration sample with temperature under different magnetic field intensities are shown in FIG. 2; the results of the change in nuclear magnetic resonance paramagnetic displacement of magnetic nano-samples at the same temperature with concentration are shown in FIG. 3.
- Fig. 4 reflects the temperature information of the standard temperature and the 10 nm magnetic nanoparticles decomposed under the static magnetic fields of 200Gs, 300Gs, and 400Gs respectively.
- the concentration obtained by the inversion is 0.1009mmol, and the simulation setting is 0.1mmol.
- Figure 5 reflects the temperature measurement error of the 10 nm magnetic nanoparticles that were reversely resolved under the static magnetic fields of 200 Gs, 300 Gs, and 400 Gs, respectively.
- the simulation results prove that the magnetic resonance paramagnetic shift of magnetic nanoparticles can effectively measure the concentration and temperature of magnetic nanoparticles.
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Abstract
一种基于顺磁位移的磁纳米粒子浓度与温度测量方法,利用核磁共振设备通过测量含顺磁性颗粒的液体样品化学位移来进行磁纳米粒子浓度及温度测量,有效实现高测量精度的浓度与温度测量。在核磁共振样品试剂中添加顺磁性磁纳米粒子,通过核磁共振得到样品的顺磁位移。利用顺磁位移获取共振频率,依照共振频率与磁纳米粒子磁化率的关系获取磁化率,进一步根据磁纳米粒子磁化率与浓度、温度的关系反解样品浓度信息及温度信息。从仿真数据来看,利用顺磁位移信息可以有效地实现磁纳米粒子样品的浓度测量以及高精度温度测量。
Description
本发明涉及纳米材料测试技术领域,具体涉及一一种基于顺磁位移的磁纳米粒子浓度与温度方法。
温度是生命活动的重要表征,在医学治疗时,许多疾病可以通过改变温度从而得到治疗。针对活体的非侵入式可视化温度测量,不仅仅要求温度测量准确,还要求温度探针需要准确定位。磁共振成像测温是目前的多种无创测温方法中较为具有前景的一种温度测量方法,然而其主要是基于目前核磁共振成像的相关参数具有温度敏感性,其原理决定了其测量结果会受到人体组织内一些与温度相关的参数的影响,例如脂肪的存在会造成造成温度估计的误差,而即便同一组织,组织结构的变化引起的温度敏感系数的变化也会造成温度数值的变化呈现非线性。到目前为止,核磁共振成像的空间分辨率在1mm,核磁共振成像测温精度在1℃。
近年来,基于磁纳米颗粒磁温特性的温度测量方法以及磁纳米粒子成像得到了快速的发展。2005年。B.Gleich和J.Weizenencker利用直流梯度磁场进行空间编码,通过检测磁纳米粒子在交流磁场和梯度场作用下的磁化响应信号首次实现磁纳米粒子成像,2009年,John.B.Weaver首次提出利用磁纳米粒子进行温度估计的方法,2011年刘文中等人通过测量直流磁场下磁纳米粒子的磁化率倒数实现了温度的测量。2012年及2013年刘文中等人分辨实现了交流磁场激励下基于磁纳米粒子磁化强度的温度测量以及三角波激励下基于磁纳米粒子磁化强度的温度测量。
磁纳米粒子例如氧化铁纳米粒子作为一种具有对生物无毒表现的物质,基于其温度敏感性,为实现活体内部可视化温度测量提供了可能方案,但基于磁纳米粒子的温度测量与浓度成像在高精度测量以及高空间分辨率 成像方面尚面临挑战,而目前核磁共振波谱仪探测能力达到ppm级。因此寻求一种能够将磁纳米粒子的测温原理与核磁共振波谱仪的原理相结合的温度测量方法,以追求实现在体高精度可视化温度测量。
[发明内容]
本发明的目的在于提供一种基于顺磁位移的磁纳米粒子浓度与温度方法,能够通过获取磁纳米样品核磁共振顺磁位移来有效实现磁纳米粒子的浓度信息以及高精度温度测量。
一种基于顺磁位移的磁纳米粒子浓度与温度方法,包括如下步骤:
(1)将磁纳米样品添加入待测实验试剂中;
(2)将未含磁纳米粒子的纯试剂和含磁纳米粒子的实验试剂和放入均匀磁场磁场强度为H
0的核磁共振设备中,分别检测得到纯试剂和实验试剂的共振吸收峰的位移,即化学位移δ
R和δ
S;
(3)分别依据纯试剂和实验试剂的化学位移δ
R和δ
S,求解得到纯试剂和实验试剂的共振频率υ
R和υ
S;
(6)改变磁场磁场强度H
0,按照步骤(2)-(5)的方式构建多个磁 纳米粒子在静磁场激励下其磁化强度与温度敏感特性方程式,联立获取磁纳米粒子浓度N及温度T。
进一步地,所述步骤(6)具体为:
其中,x=NM
s,y=M
sV/kT;
利用设置n个不同的激励磁场H
i和测量得到的与其对应的磁化率χ
si,即可构建n个关于温度的非线性方程组
本发明的技术效果体现在:
利用核磁共振设备通过测量含顺磁性颗粒的液体样品化学位移来进行磁纳米粒子浓度及温度测量,有效实现高测量精度的浓度与温度测量。在核磁共振样品试剂中添加顺磁性磁纳米粒子,通过核磁共振得到样品的顺磁位移。利用顺磁位移获取共振频率,依照共振频率与磁纳米粒子磁化率的关系获取磁化率,进一步根据磁纳米粒子磁化率与浓度、温度的关系反解样品浓度信息及温度信息。本发明利用核磁共振顺磁位移信息实现磁纳米粒子浓度与温度测量,能够有效实现磁纳米样品浓度信息测量以及高精度的磁纳米粒子温度测量。从仿真数据来看,利用顺磁位移信息可以有效地实现磁纳米粒子样品的浓度测量以及高精度温度测量。
图1为本发明方法流程图;
图2为磁场分别在200Gs、300Gs和400Gs下,同一浓度的磁纳米样品的核磁共振顺磁位移位移随温度变化仿真图;
图3为磁场分别在200Gs、300Gs和400Gs下,同一温度下的磁纳米样品的核磁共振顺磁位移位移随浓度变化仿真图;
图4为标准温度以及磁场分别在200Gs、300Gs和400Gs下反演得到的磁纳米样品浓度和温度结果图;
图5为磁场分别在200Gs、300Gs和400Gs下的反演得到的浓度和温度误差仿真图。
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
如图1所示,本发明提供了一种基于顺磁位移的磁纳米粒子浓度与温度方法,包括如下步骤:
(1)选取粒径合适、浓度合适的磁纳米液体样品,将磁纳米样品添加入待测实验试剂中。前期对于不同浓度的含磁纳米粒子的试剂进行测量,以选取浓度尽可能高的、同时不会严重破坏核磁共振设备空间磁场均匀性的磁纳米粒子试剂。
(2)将未含磁纳米粒子的试剂和含磁纳米粒子的实验试剂和放入均匀磁场磁场强度为H
0的核磁共振设备中,分别检测得到纯试剂和实验试剂的共振吸收峰的位移,即化学位移δ
R和δ
S。
采用匀磁场磁场强度为H
0的核磁共振设备,对于纯试剂和添加了磁纳米粒子的实验试剂分别进行检测获取化学位移信息δ
R和δ
S,其中纯试剂化学位移δ
R是作为一个参考值。
核磁共振设备可采用现有测量精度高达ppm级的核磁共振波谱仪,由于利用的目前测量精度高达ppm级的核磁共振波谱仪作为测量手段,因此能够实现更高精度的磁纳米粒子浓度与温度测量。
依据样品的化学位移δ与核磁共振设备的频率υ
0,依据化学位移的计算公式
可以分别求解得到纯试剂和实验试剂的共振频率υ
R和υ
S,则实际在测温工程中使用的是由于磁纳米粒子造成的共振频率的改变量△υ=υ
S-υ
R,其中υ
0为核磁共振设备内标物四甲基硅烷(TMS)在该设备均匀磁场下的共振频率。
(4)将纯试剂和实验试剂的共振频率υ
R和υ
S带入
χ
S为磁纳米粒子磁化率,α的值通常由样品的几何形状、样品管与外界磁场的相对方向共同决定:当样品方向与磁场方向垂直时,α=2π;当样品方向与磁场方向平行时,α=0。
对郎之万函数进行展开,则可以得到
其中,x=NM
s,y=M
sV/kT。
利用设置不同的激励磁场H
i和测量得到的与其对应的磁化率χ
mi,即可构构建关于温度的非线性方程组
仿真实例(浓度、温度求解):
1.仿真模型与测试说明:
为了研究基于顺磁位移的磁纳米粒子测温方法可行性,仿真分别在200Gs、300Gs、400Gs静磁场强度下含磁纳米粒子的核磁共振顺磁位移随温度变化的情况,温度T从300K开始到330K均匀变化,共计30个温度点;磁纳米粒子个数N0=1mmol,浓度N变化从0.1N0均匀变化到0.7N0,共计7个浓度点。
仿真设定用TMS作为核磁标准物质,核磁共振样品与磁场方向平行,即α=0。磁纳米粒子的相关仿真参数为:磁纳米粒子粒径d=10nm,饱和磁化强度Ms=314400A/m,k=1.38*10^(-23)。得到的不同磁场强度下同一浓度的样品顺磁位移随温度变化的结果如图2所示;同一温度的磁纳米样品的核磁共振顺磁位移位移随浓度变化结果如图3所示。
依据温度、浓度求解步骤反解出来的在0.1mmol浓度下温度信息如图4 所示,温度误差如图5所示。
2.仿真试验结果:
图4反映了标准温度以及反解出的10nm的磁纳米粒子在分别在200Gs、300Gs、400Gs静磁场下的温度信息,反演得到的浓度为0.1009mmol,仿真设定为0.1mmol。
图5反映了反解出的10nm的磁纳米粒子在分别在200Gs、300Gs、400Gs静磁场下的温度测量误差。
从结果可以看出,当静磁场强度在200Gs时,温度测量误差在0.15K以内。然而随着静磁场强度的增大,温度测量误差增大。出现这种现象的原因,一方面是磁纳米粒子的磁化率—温度曲线本身存在这磁场调制特性,这使得在不同激励磁场下,曲线存在有一定的平移现象,且该平移量与激励磁场的轻度有关;另一方面是郎之万函数的泰勒展开式的截断误差逐渐增加。
仿真结果证明,利用磁纳米粒子的核磁共振顺磁位移,能够有效实现磁纳米粒子的浓度与温度测量。
Claims (3)
- 一种基于顺磁位移的磁纳米粒子浓度与温度方法,其特征在于,包括如下步骤:(1)将磁纳米样品添加入待测实验试剂中;(2)将未含磁纳米粒子的纯试剂和含磁纳米粒子的实验试剂和放入均匀磁场磁场强度为H 0的核磁共振设备中,分别检测得到纯试剂和实验试剂的共振吸收峰的位移,即化学位移δ R和δ S;(3)分别依据纯试剂和实验试剂的化学位移δ R和δ S,求解得到纯试剂和实验试剂的共振频率υ R和υ S;(6)改变磁场磁场强度H 0,按照步骤(2)-(5)的方式构建多个磁纳米粒子在静磁场激励下其磁化强度与温度敏感特性方程式,联立获取磁纳米粒子浓度N及温度T。
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| CN117973272A (zh) * | 2024-04-02 | 2024-05-03 | 中国石油大学(华东) | 一种纳米流体改变非均质多孔介质润湿性的预测方法 |
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| CN108663391B (zh) * | 2018-08-10 | 2019-12-20 | 华中科技大学 | 一种基于顺磁位移的磁纳米粒子浓度与温度测定方法 |
| CN110179463B (zh) * | 2019-04-03 | 2020-06-02 | 华中科技大学 | 一种磁纳米粒子的温度与浓度成像方法 |
| CN110687152B (zh) * | 2019-09-24 | 2021-02-05 | 华中科技大学 | 一种监控活动对象活跃度和温度的磁学方法及装置 |
| CN112539853B (zh) * | 2020-11-04 | 2022-03-29 | 华中科技大学 | 一种基于电子顺磁共振的磁纳米粒子温度测量方法 |
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| CN113932939B (zh) * | 2021-09-26 | 2023-07-21 | 郑州轻工业大学 | 基于扫场法的铁磁共振测温方法 |
| CN114112097B (zh) * | 2021-12-08 | 2023-03-31 | 华中科技大学 | 基于电子顺磁共振积分谱半高宽的磁纳米粒子测温方法 |
| CN119310124B (zh) * | 2024-11-06 | 2025-12-05 | 武汉纺织大学 | 一种基于核磁共振波谱半高宽的磁纳米粒子质量浓度计算方法 |
| CN119223825B (zh) * | 2024-11-21 | 2026-02-17 | 武汉纺织大学 | 一种基于核磁共振波谱化学位移的磁纳米粒子质量浓度测量方法 |
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