CN108072692A - A kind of portable drugs scene authentication equipment and method - Google Patents
A kind of portable drugs scene authentication equipment and method Download PDFInfo
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Abstract
本发明涉及一种便携式毒品现场鉴别设备及方法,设备包括控制模块、矩形离子阱质谱分析模块、数据采集与处理模块、谱图识别与报警模块和结果输出模块,毒品标样或实际样品经过鉴别设备之后产生电流信号,转变为电压信号,内部时钟输出时间信号;将电压信号转变为数字信号;提取时间信号和数字信号,进行归一化和基线校正处理;如果样品是毒品标样,生成标准谱库;如果样品是实际样品,生成样品谱图;将样品谱图与标准普库进行特征比对。本发明体积小、重量轻,无需复杂的前处理,液体样品或固体样品直接进行进样检测,实现检测结果的自动识别、报警及打印,单个样品检测及报警时间小于2s,适合毒品现场查缉与鉴别,具有非常广阔的应用前景。
The invention relates to a portable on-site drug identification device and method. The device includes a control module, a rectangular ion trap mass spectrometry module, a data acquisition and processing module, a spectrogram identification and alarm module, and a result output module. Drug standard samples or actual samples are identified The device then generates a current signal and converts it into a voltage signal, and the internal clock outputs a time signal; converts the voltage signal into a digital signal; extracts the time signal and digital signal, and performs normalization and baseline correction processing; if the sample is a drug standard sample, generate a standard Spectrum library; if the sample is an actual sample, generate a sample spectrum; compare the characteristics of the sample spectrum with the standard library. The invention is small in size and light in weight and does not require complex pretreatment. Liquid samples or solid samples are directly injected and tested to realize automatic identification, alarm and printing of test results. The detection and alarm time of a single sample is less than 2s, which is suitable for on-site investigation and detection of drugs. Identification has very broad application prospects.
Description
技术领域technical field
本发明涉及毒品现场检测设备领域,具体地说是一种便携式毒品现场鉴别设备及方法。The invention relates to the field of on-site drug detection equipment, in particular to a portable on-site drug identification device and method.
背景技术Background technique
毒品已成为危害社会的大毒瘤,毒品犯罪活动不但危害个人生命健康,更危害公共安全。我国在“十二五”期间禁毒工作的重点是“堵源截流”,但是每年依靠查缉设备查缉到的毒品仅占4%,远不能满足禁毒斗争的需要,研发高技术含量的毒品、易制毒化学品查缉、取证及鉴定的设备势在必行。Drugs have become a big cancer that endangers society. Drug crimes not only endanger personal life and health, but also endanger public safety. The focus of my country's anti-drug work during the "Twelfth Five-Year Plan" period is "blocking the source and intercepting the flow", but the drugs seized by inspection equipment each year account for only 4%, which is far from meeting the needs of the anti-drug struggle. Equipment for the detection, evidence collection and identification of toxic chemicals is imperative.
目前主要的毒品检测技术有X射线技术、生物技术、色质联用技术、毛细管电泳技术、中子及拉曼技术以及离子迁移谱技术。这些技术虽然在我国的禁毒工作中发挥着作用,但每种技术都有其自身的缺陷,如X射线技术,它仪器的体积庞大,只能应用于机场、火车站等特定场合;生物技术如缉毒犬,它的稳定性和可靠性较差;中子及拉曼技术的仪器较贵,使用成本高等。At present, the main drug detection technologies include X-ray technology, biotechnology, chromatography-mass spectrometry, capillary electrophoresis, neutron and Raman technology, and ion mobility spectrometry. Although these technologies are playing a role in my country's anti-drug work, each technology has its own defects, such as X-ray technology, whose instruments are bulky and can only be used in specific occasions such as airports and railway stations; biotechnology such as Anti-drug dogs, its stability and reliability are poor; neutron and Raman technology instruments are more expensive, and the cost of use is high.
发明内容Contents of the invention
本发明针对我国每年依靠毒品查缉仪器设备查缉到的毒品仅占毒品查缉总量的4%,禁毒仪器设备远不能满足当前禁毒斗争需要的实际情况,提出一种便携式毒品现场鉴别仪设备,用于毒品现场快速查缉与鉴定。The present invention aims at the fact that the drugs seized every year by relying on drug detection instruments and equipment in our country account for only 4% of the total amount of drugs seized, and the anti-drug equipment is far from meeting the needs of the current anti-drug struggle, and proposes a portable drug on-site identification device for Rapid detection and identification of narcotics on the spot.
本发明为实现上述目的所采用的技术方案是:The technical scheme that the present invention adopts for realizing the above object is:
该设备包括控制模块、矩形离子阱质谱分析模块、数据采集与处理模块、谱图识别与报警模块和结果输出模块;The device includes a control module, a rectangular ion trap mass spectrometry module, a data acquisition and processing module, a spectrum identification and alarm module, and a result output module;
控制模块通过导线和网线与矩形离子阱质谱分析模块进行通信,从而实现对矩形离子阱质谱分析模块的工作状态进行总体控制;The control module communicates with the rectangular ion trap mass spectrometry module through wires and network cables, so as to realize the overall control of the working state of the rectangular ion trap mass spectrometry module;
矩形离子阱质谱分析模块对毒品样品进行电离及质量分析,产生电信号,通过导线将电信号传输至数据采集与处理模块;The rectangular ion trap mass spectrometry module performs ionization and mass analysis on drug samples, generates electrical signals, and transmits the electrical signals to the data acquisition and processing module through wires;
数据采集与处理分析模块将电信号转化为数字信号,生成质谱数据,并将质谱数据通过COM接口反馈给控制模块,控制模块显示出质谱图;The data acquisition, processing and analysis module converts the electrical signal into a digital signal, generates mass spectrum data, and feeds the mass spectrum data back to the control module through the COM interface, and the control module displays the mass spectrum;
识别与报警模块从数据采集与处理分析模块获得质谱数据,与已建立的标准谱库中的数据进行对比,将比对结果反馈给控制模块在计算机上显示,并以代码形式下发给结果输出模块;The identification and alarm module obtains the mass spectrum data from the data acquisition and processing analysis module, compares it with the data in the established standard spectrum library, feeds back the comparison result to the control module for display on the computer, and sends it to the result output in the form of code module;
结果输出模块将鉴别结果代码转换为文字并打印输出。The result output module converts the identification result code into text and prints it out.
控制模块由集成电路板、嵌入式工业计算机和控制软件组成。其中,集成电路板由供电电源板、质谱控制板、高压电源板和射频放大器组成;嵌入式工业计算机配置有屏幕触摸功能,屏幕位于仪器正上方,采用翻折式开启设计。The control module is composed of integrated circuit board, embedded industrial computer and control software. Among them, the integrated circuit board is composed of a power supply board, a mass spectrometer control board, a high-voltage power supply board and a radio frequency amplifier; the embedded industrial computer is equipped with a screen touch function, and the screen is located directly above the instrument and adopts a flip-open design.
矩形离子阱质谱模块包括:热解析进样器、真空紫外灯电离腔、不连续大气压力接口(DAPI)、真空系统、矩形离子阱质量分析器和正离子探测器。其中,热解析进样器竖直放置,进样口朝向仪器正前方;进样器和真空紫外灯电离腔之间通过金属管道及卡套相连接,并且外部包裹石棉等保温材料进行保温;真空紫外灯与进样金属管道成90度放置,样品气态分子紧贴灯头进入电离腔;电离腔与真空系统之间通过不连续大气压力接口进行连接,不连续大气压力接口保持常闭状态,只有接受特定电压信号,接口才打开,离子进入真空系统,进而被矩形离子阱质量分析器分析,被正离子探测器检测,经数据采集及处理系统分析后得到质谱图。真空系统由真空腔体、80L或者60L的分子泵、8L的膜片泵以及微皮拉尼与冷阴极复合真空规组成;真空腔体位长方体,其尺寸为:14cm*11.5cm*6.6cm。The rectangular ion trap mass spectrometry module includes: thermal desorption sampler, vacuum ultraviolet lamp ionization chamber, discontinuous atmospheric pressure interface (DAPI), vacuum system, rectangular ion trap mass analyzer and positive ion detector. Among them, the thermal desorption sampler is placed vertically, and the sample inlet faces the front of the instrument; the sampler and the ionization chamber of the vacuum ultraviolet lamp are connected by metal pipes and ferrules, and are wrapped with asbestos and other thermal insulation materials for insulation; The ultraviolet lamp is placed at 90 degrees to the metal pipe for sampling, and the gaseous molecules of the sample enter the ionization chamber close to the lamp head; the ionization chamber and the vacuum system are connected through a discontinuous atmospheric pressure interface, and the discontinuous atmospheric pressure Only when the interface is opened with a specific voltage signal, the ions enter the vacuum system, and then are analyzed by the rectangular ion trap mass analyzer, detected by the positive ion detector, and the mass spectrum is obtained after being analyzed by the data acquisition and processing system. The vacuum system consists of a vacuum chamber, an 80L or 60L molecular pump, an 8L diaphragm pump, and a micro-Pirani and cold cathode composite vacuum gauge; the vacuum chamber is a cuboid, and its size is: 14cm*11.5cm*6.6cm.
所述特定电压信号为:脉冲施加的直流电压信号,幅值为24V,持续时间可根据需要在1ms至9s之间调节,一次质谱分析过程,该电压施加一次。The specific voltage signal is: a DC voltage signal applied by pulse, the amplitude is 24V, the duration can be adjusted between 1ms and 9s according to the needs, and the voltage is applied once during a mass spectrometry analysis process.
所述谱图识别与报警模块内嵌于质谱控制软件当中,由数据处理算法和毒品特征质谱峰识别数据库构成,毒品的特征质谱峰识别数据库是通过大量实验获得,并手动录入。The spectrum identification and alarm module is embedded in the mass spectrometry control software, and consists of a data processing algorithm and a drug characteristic mass spectrum peak identification database. The drug characteristic mass spectrum peak identification database is obtained through a large number of experiments and entered manually.
结果输出模块为打印机,用于将鉴别结果进行打印输出,打印纸可更换。The result output module is a printer, which is used to print out the identification results, and the printing paper can be replaced.
仪器的整体布局围绕真空系统展开。仪器结构分为上下两层,下层为分子泵、膜片泵、进样泵和散热风扇,上层主要为嵌入式工业计算机、进样器、电离腔、不连续大气压力接口和真空腔体;供电电源板位于仪器左侧下方,立式放置,质谱控制板和高压电源板叠加在一起位于仪器前侧,立式放置;射频放大器通过螺丝悬挂于真空腔体外壁上,位于仪器右后侧;打印机固定于仪器外壳上,位于计算机主板的上方。The overall layout of the instrument revolves around the vacuum system. The instrument structure is divided into upper and lower layers, the lower layer is molecular pump, diaphragm pump, sampling pump and cooling fan, the upper layer is mainly embedded industrial computer, sampler, ionization chamber, discontinuous atmospheric pressure interface and vacuum chamber; power supply The power supply board is located at the lower left side of the instrument and placed vertically. The mass spectrometer control board and the high-voltage power supply board are stacked together and located at the front of the instrument and placed vertically. The RF amplifier is suspended on the outer wall of the vacuum chamber by screws and is located at the right rear of the instrument. The printer It is fixed on the instrument case and located above the computer motherboard.
所述的供电电源板和质谱控制板之间通过485接口进行通信;质谱控制板和计算机之间通过网线接口进行通信。The power supply board and the mass spectrometer control board communicate through the 485 interface; the mass spectrometer control board communicates with the computer through the network cable interface.
所述的热解析进样器需要采样布和一路载气配合使用。采样布是用来承接液体或者固体样品,其材质为聚四氟乙烯,采样布的尺寸规格为105mm*28mm;载气是由进样泵抽取仪器周围空气,经干燥管净化后得到,载气流量通过气体流量调节阀进行调节,干燥管位于仪器左后侧,固定于底板;在载气管道中还有一个试剂分子添加装置,固定于进样器支架上,用以提供添加试剂分子辅助电离。The thermal analysis sampler needs to be used in conjunction with a sampling cloth and a path of carrier gas. The sampling cloth is used to accept liquid or solid samples. Its material is polytetrafluoroethylene. The size of the sampling cloth is 105mm*28mm. The flow rate is adjusted by the gas flow regulating valve. The drying tube is located on the left rear side of the instrument and fixed on the bottom plate; there is also a reagent molecule adding device in the carrier gas pipeline, which is fixed on the sampler bracket to provide auxiliary ionization for adding reagent molecules.
一种便携式毒品现场鉴别仪设备的鉴别方法,包括以下步骤:An identification method for a portable drug on-site identification device, comprising the following steps:
步骤1:毒品标样或实际样品经过矩形离子阱质谱分析模块之后产生电流信号,采集卡采集电流信号,经过IV转换将电流信号转变为电压信号,同时内部时钟输出一个时间信号,并存储于内存中;Step 1: The drug standard sample or actual sample generates a current signal after passing through the rectangular ion trap mass spectrometry module. The acquisition card collects the current signal, and converts the current signal into a voltage signal through IV conversion. At the same time, the internal clock outputs a time signal and stores it in the memory. middle;
步骤2:电压信号被D/A芯片接收,经过模数转换电路,将电压信号转变为数字信号,并存储于内存中;Step 2: The voltage signal is received by the D/A chip, through the analog-to-digital conversion circuit, the voltage signal is converted into a digital signal, and stored in the memory;
步骤3:数据采集与处理分析模块从内存中提取时间信号和数字信号,并进行归一化和基线校正处理;Step 3: The data acquisition and processing analysis module extracts the time signal and digital signal from the memory, and performs normalization and baseline correction processing;
步骤4:判断如果样品是毒品标样,则经过处理后的数据生成标准谱图,并归入标准普库,标准谱库可根据实际需求随时扩展;如果样品是实际样品则将处理后的数据生成样品谱图;Step 4: Judging that if the sample is a drug standard sample, the processed data will generate a standard spectrum and be included in the standard library. The standard library can be expanded at any time according to actual needs; if the sample is an actual sample, the processed data will be Generate a sample spectrum;
步骤5:样品谱图与标准普库进行特征比对,如果样品谱图的特征峰与标准普库中的某一标准样品的特征峰相同,则报警,否则显示未检出。Step 5: Compare the characteristics of the sample spectrum with the standard library. If the characteristic peak of the sample spectrum is the same as that of a standard sample in the standard library, an alarm will be issued, otherwise it will be displayed as not detected.
所述归一化过程为通过归一化运算,将质谱峰强度的绝对值变成相对值关系,即The normalization process is to change the absolute value of the mass spectrum peak intensity into a relative value relationship through a normalization operation, that is
Y={yi=f(N(x1,j),N(x2,j),...,N(xm,j))|xk,i∈Xk,i=1,2,...,n,k=1,2,...m}Y={y i =f(N(x 1, j ), N(x 2, j ),..., N(x m, j ))|x k, i ∈ X k, i = 1, 2 ,...,n,k=1,2,...m}
其中,Y为归一化运算的结果,xk,j为任取的量化值,Xk为样本区间,N(x)为归一化函数。Among them, Y is the result of the normalization operation, x k, j are arbitrary quantized values, X k is the sample interval, and N(x) is the normalization function.
所述基线校正处理过程为:采用非对称最小二乘法去除基线噪声使之更平滑The baseline correction process is: using the asymmetric least squares method to remove baseline noise to make it smoother
优化目标为:The optimization goal is:
argmin[∑iwi(yi-zi)2+λ∑i(Δ2zi)2] (1)argmin[∑ i w i (y i -z i ) 2 +λ∑ i (Δ 2 z i ) 2 ] (1)
公式(1)中,wi为权重因子,wi根据非对称的方式选择,当yi>zi时,wi=p,而yi<zi时,wi=1-p,p为拟合函数,yi为未知数,zi为样本平均值,Δ为二阶差分算子,λ是正则化参数(也叫折中因子);公式(1)中第一项表示拟合函数与原始数据的非对称拟合程度;第二项是为了保证拟合函数的光滑性,折中因子λ起到平衡非对称逼近程度和光滑性的作用;In formula (1), w i is the weight factor, and w i is selected in an asymmetric way. When y i > z i , w i = p, and when y i < z i , w i = 1-p, p is the fitting function, y i is the unknown, z i is the sample average value, Δ is the second-order difference operator, and λ is the regularization parameter (also called the compromise factor); the first item in formula (1) represents the fitting function The degree of asymmetric fit with the original data; the second item is to ensure the smoothness of the fitting function, and the compromise factor λ plays a role in balancing the degree of asymmetric approximation and smoothness;
最小化公式(1),可得:Minimizing formula (1), we can get:
(W+λDTD)z=Wy (2)(W+λD T D)z=W y (2)
公式(2)中,W是由权重因子w(本身为向量)组成的对角阵,即W=diag(w),D是z的二阶导数矩阵,即Dz=Δ2z,DT是指关于D的矩阵,z为估计的基线方程;In formula (2), W is a diagonal matrix composed of weight factor w (itself a vector), that is, W=diag(w), D is the second-order derivative matrix of z, that is, Dz=Δ 2 z, D T is refers to the matrix about D, z is the estimated baseline equation;
求解(2)得到估计的基线方程:Solve (2) to get the estimated baseline equation:
z=(W+λDTD)-1Wy (3)z=(W+λD T D) -1 W y (3)
公式(3)中,In formula (3),
所述特征比对为:The feature comparison is:
对比标准样品或实际样品中的有效组分对应的分子离子峰及其特征碎片离子峰位置,如果实际样品的质谱峰与标准谱库中的至少一个标准毒品的谱峰位置相同,则认为样品中含有与其相同种类的毒品。Compare the molecular ion peak and its characteristic fragment ion peak position corresponding to the effective component in the standard sample or the actual sample. If the mass spectrum peak of the actual sample is the same as the peak position of at least one standard drug in the standard library, it is considered that the Contains the same type of drug as it.
标准谱图为:毒品标样经该毒品现场鉴别仪分析后生成的质谱图,对于同一台毒品鉴别仪来说,一个毒品标样对应一张标准谱图。The standard spectrum is: the mass spectrum generated after the drug standard sample is analyzed by the drug on-site identification instrument. For the same drug identification instrument, one drug standard sample corresponds to one standard spectrum.
本发明具有以下有益效果及优点:The present invention has the following beneficial effects and advantages:
1.本发明突出的优点是:以矩形离子阱质谱为检测核心,灵敏度高,稳定性强,且定性检测准确度高;1. The outstanding advantages of the present invention are: using the rectangular ion trap mass spectrometer as the detection core, it has high sensitivity, strong stability, and high qualitative detection accuracy;
2.本发明集毒品检测、鉴别、报警与一体;2. The present invention integrates drug detection, identification, and alarm;
3.本发明体积小、重量轻,可置于行李箱中,便于携带和运输;3. The invention is small in size and light in weight, can be placed in a suitcase, and is easy to carry and transport;
4.本发明无需复杂样品前处理,可直接分析固体和液体样品;4. The present invention does not require complex sample pretreatment, and can directly analyze solid and liquid samples;
5.本发明该发明分析检测速度快,体积小、重量轻,可以实现毒品的现场快速检测、鉴别及自动报警,样品检测及报警时间小于2s;5. The present invention has fast analysis and detection speed, small size and light weight, and can realize on-site rapid detection, identification and automatic alarm of drugs, and the sample detection and alarm time is less than 2s;
6.本发明配备触摸屏,无需额外鼠标键盘等输入设备。6. The present invention is equipped with a touch screen, without additional input devices such as mouse and keyboard.
附图说明Description of drawings
图1为本发明的毒品现场鉴别仪设备功能框图;Fig. 1 is a functional block diagram of the drug on-the-spot identification device of the present invention;
图2为本发明的毒品现场鉴别仪设备结构示意图;Fig. 2 is a schematic diagram of the device structure of the on-site drug identification device of the present invention;
图3为本发明的毒品现场鉴别仪结构及工作流程图;Fig. 3 is the structure and work flow diagram of the on-the-spot drug identification device of the present invention;
图4为本发明的毒品现场鉴别仪鉴别样品流程图。Fig. 4 is a flow chart of identifying samples by the on-site narcotics identification device of the present invention.
其中,1-嵌入式工业计算机、2-供电电源板、3-质谱控制、4-射频放大器、5-热解析进样器、6-真空紫外灯电离腔、7-不连续大气压力接口(DAPI)、8-矩形离子阱质量分析系统、9-真空泵系统、10-散热风扇、11供电电源板12-打印机、13-干燥管、14-试剂分子添加装置。Among them, 1-embedded industrial computer, 2-power supply board, 3-mass spectrometer control, 4-radio frequency amplifier, 5-thermal desorption sampler, 6-vacuum ultraviolet lamp ionization chamber, 7-discontinuous atmospheric pressure interface (DAPI ), 8-rectangular ion trap mass analysis system, 9-vacuum pump system, 10-cooling fan, 11 power supply board, 12-printer, 13-drying tube, 14-reagent molecule adding device.
具体实施方式Detailed ways
下面结合附图及实施例对本发明做进一步的详细说明。The present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.
为了使本发明的内容更加清楚和易懂,下面结合具体实施例和附图对本发明的内容进行详细描绘。In order to make the content of the present invention clearer and easier to understand, the content of the present invention will be described in detail below in conjunction with specific embodiments and accompanying drawings.
仪器的功能框架示意图如图1所示。该仪器设备包括:控制模块I、矩形离子阱质谱分析模块II、数据采集与处理模块III、谱图识别与报警模块IV和结果输出模块V。其中,控制模块I通过导线和网线与矩形离子阱质谱分析模块II块进行通信,从而实现对矩形离子阱质谱分析模块II的工作状态进行总体控制;The schematic diagram of the functional framework of the instrument is shown in Figure 1. The instrument includes: a control module I, a rectangular ion trap mass spectrometry module II, a data acquisition and processing module III, a spectrum identification and alarm module IV, and a result output module V. Among them, the control module I communicates with the rectangular ion trap mass spectrometry module II through wires and network cables, so as to realize the overall control of the working state of the rectangular ion trap mass spectrometry module II;
矩形离子阱质谱分析模块II对毒品样品进行电离及质量分析,产生电信号,通过导线将电信号传输至数据采集与处理模块III;Rectangular ion trap mass spectrometry module II conducts ionization and mass analysis on drug samples, generates electrical signals, and transmits the electrical signals to data acquisition and processing module III through wires;
数据采集与处理模块III将电信号转化为数字信号,生成质谱数据,并将质谱数据通过COM接口反馈给控制模块I,控制模块I通过计算机绘制并显示质谱图;The data acquisition and processing module III converts the electrical signal into a digital signal, generates mass spectrum data, and feeds the mass spectrum data back to the control module I through the COM interface, and the control module I draws and displays the mass spectrum through the computer;
谱图识别与报警模块IV从数据采集与处理模块III获得质谱数据,与已建立的标准谱库中的数据进行对比,将比对结果反馈给控制模块I在计算机上显示,并以代码形式下发给结果输出模块V;The spectrum identification and alarm module IV obtains mass spectrum data from the data acquisition and processing module III, compares it with the data in the established standard spectrum library, and feeds back the comparison results to the control module I for display on the computer, and downloads the data in the form of code Send to the result output module V;
结果输出模块V将鉴别结果代码转换为文字并打印输出。The result output module V converts the identification result code into text and prints it out.
控制模块I由集成电路板、嵌入式工业计算机1和控制软件组成。其中,集成电路板由供电电源板2、质谱控制3和射频放大器4组成;嵌入式工业计算机配置有屏幕触摸功能,屏幕位于仪器正上方,采用翻折式开启设计。Control module 1 is made up of integrated circuit board, embedded industrial computer 1 and control software. Among them, the integrated circuit board is composed of power supply board 2, mass spectrometer control 3 and radio frequency amplifier 4; the embedded industrial computer is equipped with a screen touch function, and the screen is located directly above the instrument, and adopts a foldable opening design.
矩形离子阱质谱模块II包括:热解析进样器5、真空紫外灯电离腔6、不连续大气压力接口(DAPI)7、矩形离子阱质量分析系统8。其中,热解析进样器5竖直放置,进样口朝向仪器正前方;进样器5和真空紫外灯电离腔6之间通过金属管道及卡套相连接,并且外部包裹石棉等保温材料进行保温;真空紫外灯与进样金属管道垂直放置,样品气态分子紧贴灯头进入电离腔6;电离腔与真空系统之间通过不连续大气压力接口7进行连接,不连续大气压力接口保持常闭状态,只有接受特定电压信号,接口才打开,离子进入真空系统,进而被矩形离子阱质量分析器分析,被正离子探测器检测,经数据采集及处理模块III分析后得到质谱图。真空系统由真空腔体、80L或者60L的分子泵、8L的膜片泵以和微皮拉尼与冷阴极复合真空规组成;真空腔体为长方体,其尺寸为:14cm*11.5cm*6.6cm。Rectangular ion trap mass spectrometry module II includes: thermal desorption sample injector 5 , vacuum ultraviolet lamp ionization chamber 6 , discontinuous atmospheric pressure interface (DAPI) 7 , and rectangular ion trap mass analysis system 8 . Among them, the thermal desorption sampler 5 is placed vertically, and the sample inlet faces the front of the instrument; the sampler 5 and the ionization chamber 6 of the vacuum ultraviolet lamp are connected through metal pipes and ferrules, and are wrapped with asbestos and other thermal insulation materials for Heat preservation; the vacuum ultraviolet lamp is placed vertically with the metal pipe for sampling, and the gaseous molecules of the sample enter the ionization chamber 6 close to the lamp head; the ionization chamber and the vacuum system are connected through the discontinuous atmospheric pressure interface 7, and the discontinuous atmospheric pressure interface is kept in a normally closed state , only when a specific voltage signal is received, the interface is opened, ions enter the vacuum system, and then are analyzed by the rectangular ion trap mass analyzer, detected by the positive ion detector, and the mass spectrum is obtained after analysis by the data acquisition and processing module III. The vacuum system consists of a vacuum chamber, an 80L or 60L molecular pump, an 8L diaphragm pump, and a composite vacuum gauge with micro-Pirani and cold cathode; the vacuum chamber is a cuboid, and its size is: 14cm*11.5cm*6.6cm .
所述谱图识别与报警模块IV内嵌于质谱控制软件当中,由数据处理算法和毒品特征质谱峰识别数据库构成,毒品的特征质谱峰识别数据库是通过大量实验获得,并手动录入。The spectrum recognition and alarm module IV is embedded in the mass spectrometry control software, and is composed of a data processing algorithm and a drug characteristic mass spectrum peak recognition database. The drug characteristic mass spectrum peak recognition database is obtained through a large number of experiments and entered manually.
结果输出模块,主要部件为微型打印机,用于将鉴别结果进行打印输出,打印纸可更换。The result output module, the main part is a micro-printer, which is used to print out the identification results, and the printing paper can be replaced.
仪器的整体布局围绕真空系统展开。仪器结构分为上下两层,下层为真空泵系统9和散热风扇10,上层主要为嵌入式工业计算机1、进样器5、电离腔6、不连续大气压力接口7和真空腔体8;供电电源板11位于仪器左侧下方,立式放置,质谱控制板和高压电源板3叠加在一起位于仪器前侧,立式放置;射频放大器通过螺丝悬挂于真空腔体外壁上,位于仪器右后侧;打印机12固定于仪器外壳上,位于计算机主板的上方。The overall layout of the instrument revolves around the vacuum system. The instrument structure is divided into upper and lower layers, the lower layer is the vacuum pump system 9 and cooling fan 10, the upper layer is mainly embedded industrial computer 1, sample injector 5, ionization chamber 6, discontinuous atmospheric pressure interface 7 and vacuum chamber 8; power supply The board 11 is located on the lower left side of the instrument, placed vertically, and the mass spectrometer control board and the high-voltage power supply board 3 are stacked together and located on the front side of the instrument, placed vertically; the radio frequency amplifier is suspended on the outer wall of the vacuum chamber by screws, and is located on the right rear side of the instrument; Printer 12 is fixed on the instrument shell, is positioned at the top of computer motherboard.
所述的供电电源板和质谱控制板之间通过485接口进行通信;质谱控制板和计算机之间通过网线接口进行通信。The power supply board and the mass spectrometer control board communicate through the 485 interface; the mass spectrometer control board communicates with the computer through the network cable interface.
所述的热解析进样器需要采样布和一路载气配合使用。采样布是用来承接液体或者固体样品,其材质为聚四氟乙烯,采样布的尺寸规格为105mm*28mm;载气是由进样泵抽取仪器周围空气,经干燥管13净化后得到,载气流量通过气体流量调节阀进行调节,干燥管13位于仪器左后侧,固定于底板;在载气管道中还有一个试剂分子添加装置14,固定于进样器支架上,用以提供添加试剂分子辅助电离。The thermal analysis sampler needs to be used in conjunction with a sampling cloth and a path of carrier gas. The sampling cloth is used to accept liquid or solid samples, and its material is polytetrafluoroethylene. The size of the sampling cloth is 105mm*28mm; The gas flow is adjusted by the gas flow regulating valve. The drying tube 13 is located on the left rear side of the instrument and is fixed on the bottom plate; there is also a reagent molecule adding device 14 in the carrier gas pipeline, which is fixed on the sampler bracket to provide reagent molecules. Auxiliary ionization.
实施例1Example 1
图1给出了毒品现场鉴别仪设备的功能框架示意图。从图中可以看出:该仪器设备包括:控制模块I、矩形离子阱质谱分析模块II、数据采集与处理模块III、谱图识别与报警模块IV和结果输出模块V。Figure 1 shows a schematic diagram of the functional framework of the on-the-spot drug identification device. It can be seen from the figure that the instrument includes: control module I, rectangular ion trap mass spectrometry module II, data acquisition and processing module III, spectrum identification and alarm module IV and result output module V.
实施例2Example 2
图2给出了毒品现场鉴别仪设备结构示意图。如图2所示,优选的,仪器的整体布局围绕真空系统展开。仪器结构布局分为上下两层,下层为真空泵系统9和散热风扇10,上层主要为嵌入式工业计算机1、进样器5、电离腔6、不连续大气压力接口7和真空腔体8;供电电源板11位于仪器左侧下方,立式放置,质谱控制板和高压电源板3叠加在一起位于仪器前侧,立式放置;射频放大器通过螺丝悬挂于真空腔体外壁上,位于仪器右后侧;打印机12固定于仪器外壳上,位于计算机主板的上方。Figure 2 shows a schematic diagram of the equipment structure of the on-the-spot drug identification device. As shown in Figure 2, preferably, the overall layout of the instrument is developed around the vacuum system. The structure layout of the instrument is divided into upper and lower layers, the lower layer is the vacuum pump system 9 and cooling fan 10, the upper layer is mainly embedded industrial computer 1, sample injector 5, ionization chamber 6, discontinuous atmospheric pressure interface 7 and vacuum chamber 8; power supply The power supply board 11 is located at the lower left side of the instrument, placed vertically, the mass spectrometer control board and the high-voltage power supply board 3 are stacked together and located at the front side of the instrument, placed vertically; the RF amplifier is hung on the outer wall of the vacuum chamber by screws, and is located at the right rear side of the instrument ; The printer 12 is fixed on the instrument shell and is located above the computer motherboard.
矩形离子阱质谱模块II包括:热解析进样器5、真空紫外灯电离腔6、不连续大气压力接口(DAPI)7、矩形离子阱质量分析系统8。其中,热解析进样器5竖直放置,进样口朝向仪器正前方;进样器5和真空紫外灯电离腔6之间通过金属管道及卡套相连接,并且外部包裹石棉等保温材料进行保温;真空紫外灯与进样金属管道成90度放置,样品气态分子紧贴灯头进入电离腔6;电离腔与真空系统之间通过不连续大气压力接口7进行连接。热解析进样器需要采样布和一路载气配合使用,载气是由进样泵抽取仪器周围空气,经干燥管13净化后得到。Rectangular ion trap mass spectrometry module II includes: thermal desorption sample injector 5 , vacuum ultraviolet lamp ionization chamber 6 , discontinuous atmospheric pressure interface (DAPI) 7 , and rectangular ion trap mass analysis system 8 . Among them, the thermal desorption sampler 5 is placed vertically, and the sample inlet faces the front of the instrument; the sampler 5 and the ionization chamber 6 of the vacuum ultraviolet lamp are connected through metal pipes and ferrules, and are wrapped with asbestos and other thermal insulation materials for Heat preservation; the vacuum ultraviolet lamp is placed at 90 degrees to the sample metal pipe, and the gaseous molecules of the sample enter the ionization chamber 6 close to the lamp head; the ionization chamber and the vacuum system are connected through a discontinuous atmospheric pressure interface 7. The thermal analysis sampler requires a sampling cloth and a carrier gas to be used together. The carrier gas is obtained from the air around the instrument extracted by the sample pump and purified by the drying tube 13.
如图3所示为本发明的毒品现场鉴别仪结构及工作流程图。As shown in Fig. 3, it is the structure and working flow chart of the on-the-spot drug identification device of the present invention.
毒品现场鉴别仪结构及工作流程描述:Description of the structure and working process of the drug scene identification device:
液体样品使用微量进样针取一定的体积,点于采样试纸特定位置;固体样品用采样试纸的特定位置轻轻擦拭,将采样试纸插入进样器的进样口。For liquid samples, use a micro-sampling needle to take a certain volume, and point it on a specific position of the sampling test paper; for solid samples, gently wipe the specific position of the sampling test paper, and insert the sampling test paper into the sampling port of the injector.
进样器由机械锁止机构、加热块和载气组成。机械锁止机构用于锁止采样试纸,其开关由光电感应控制;加热块用于液体和固体样品的热解析(使样品从液态或者固态变成气态);载气用于载带气态样品离开进样器,进入电离腔。The injector consists of a mechanical locking mechanism, heating block and carrier gas. The mechanical locking mechanism is used to lock the sampling test paper, and its switch is controlled by photoelectric induction; the heating block is used for thermal analysis of liquid and solid samples (making the sample change from liquid or solid to gas); the carrier gas is used to carry the gaseous sample away The injector, into the ionization chamber.
进样器的出口通过四氟导管与电离腔体相连接,电离腔体为一圆柱体结构,圆柱体的左端固定有一个射频VUV灯,用来产生光子使样品电离,圆柱体的另一端通过金属毛细管与非连续大气压接口(DAPI)的一端相连。气态样品在电离腔中发生一系列反应,反应的类型可以是直接光电离反应、质子转移反应、电荷转移反应中的一种或几种,最后产生样品离子。The outlet of the sampler is connected to the ionization chamber through the tetrafluoro tube. The ionization chamber is a cylindrical structure. A radio frequency VUV lamp is fixed on the left end of the cylinder to generate photons to ionize the sample. The other end of the cylinder passes through A metal capillary was connected to one end of the Discontinuous Atmospheric Pressure Interface (DAPI). The gaseous sample undergoes a series of reactions in the ionization chamber. The type of reaction can be one or more of direct photoionization reaction, proton transfer reaction, and charge transfer reaction, and finally generate sample ions.
非连续大气压接口(DAPI)的另一端通过金属毛细管与真空腔体密封连接,非连续大气压接口作为离子传输的开关,只有接受到控制系统下发的命令时才打开,打开时样品离子从电离腔进入真空腔内。(DAPI用时打开,不用时关闭可以减小真空系统进气量,减轻泵组压力,便于仪器小型化。)The other end of the discontinuous atmospheric pressure interface (DAPI) is sealed and connected to the vacuum chamber through a metal capillary. The discontinuous atmospheric pressure interface is used as a switch for ion transmission. into the vacuum chamber. (Open when DAPI is in use, and close when not in use can reduce the air intake of the vacuum system, reduce the pressure of the pump set, and facilitate the miniaturization of the instrument.)
进入真空腔内的离子立即被矩形离子阱质量分析器捕获,通过扫描施加在离子阱上的射频电压,使离子有序的从离子阱质量分析器中排出;The ions entering the vacuum chamber are immediately captured by the rectangular ion trap mass analyzer, and the ions are discharged from the ion trap mass analyzer in an orderly manner by scanning the RF voltage applied to the ion trap;
从离子阱中排出的离子直接打到离子探测器的接收极上被转换成电信号(离子探测器的作用就是将离子转变为电信号),电信号被信号处理系统采集,并被转化为数字信号生成质谱数据。The ions discharged from the ion trap directly hit the receiving electrode of the ion detector and are converted into electrical signals (the function of the ion detector is to convert ions into electrical signals), and the electrical signals are collected by the signal processing system and converted into digital The signal generates mass spectral data.
生成的质谱数据一方面由计算机直接绘图通过显示器显示,另一方面被谱图识别与报警模块提取,与已建立的标准谱库中的数据进行比对(比对的对象是样品离子的特征m/z谱峰),将比对结果(即检测结果)以文字形式通过计算机显示器显示,并可由打印机打印。On the one hand, the generated mass spectrum data is directly drawn by the computer and displayed on the display, on the other hand, it is extracted by the spectrum identification and alarm module, and compared with the data in the established standard spectrum library (the object of comparison is the characteristic m of the sample ion. /z spectral peak), the comparison result (that is, the detection result) will be displayed in text form on the computer monitor, and can be printed by the printer.
如图4所示为本发明的毒品现场鉴别仪鉴别样品流程图。Fig. 4 is a flow chart of identifying samples by the on-site narcotics identification device of the present invention.
一种便携式毒品现场鉴别仪设备的鉴别方法,包括以下步骤:An identification method for a portable drug on-site identification device, comprising the following steps:
步骤1:毒品标样或实际样品经过矩形离子阱质谱分析模块之后产生电流信号,采集卡采集电流信号,经过IV转换将电流信号转变为电压信号,同时内部时钟输出一个时间信号,并存储于内存中;Step 1: The drug standard sample or actual sample generates a current signal after passing through the rectangular ion trap mass spectrometry module. The acquisition card collects the current signal, and converts the current signal into a voltage signal through IV conversion. At the same time, the internal clock outputs a time signal and stores it in the memory. middle;
步骤2:电压信号被D/A芯片接收,经过模数转换电路,将电压信号转变为数字信号,并存储于内存中;Step 2: The voltage signal is received by the D/A chip, through the analog-to-digital conversion circuit, the voltage signal is converted into a digital signal, and stored in the memory;
步骤3:数据采集与处理分析模块从内存中提取时间信号和数字信号,并进行归一化和基线校正处理;Step 3: The data acquisition and processing analysis module extracts the time signal and digital signal from the memory, and performs normalization and baseline correction processing;
步骤4:判断如果样品是毒品标样,则经过处理后的数据生成标准谱图,并归入标准普库,标准谱库可根据实际需求随时扩展;如果样品是实际样品则将处理后的数据生成样品谱图;Step 4: Judging that if the sample is a drug standard sample, the processed data will generate a standard spectrum and be included in the standard library. The standard library can be expanded at any time according to actual needs; if the sample is an actual sample, the processed data will be Generate a sample spectrum;
步骤5:样品谱图与标准普库进行特征比对,如果样品谱图的特征峰与标准普库中的某一标准样品的特征峰相同,则报警,否则显示未检出。Step 5: Compare the characteristics of the sample spectrum with the standard library. If the characteristic peak of the sample spectrum is the same as that of a standard sample in the standard library, an alarm will be issued, otherwise it will be displayed as not detected.
所述归一化过程为通过归一化运算,将质谱峰强度的绝对值变成相对值关系,即The normalization process is to change the absolute value of the mass spectrum peak intensity into a relative value relationship through a normalization operation, that is
Y={yi=f(N(x1,j),N(x2,j),...,N(xm,j))|xk,j∈Xk,i=1,2,...,n,k=1,2,...m}Y={y i =f(N(x 1, j ), N(x 2, j ),..., N(x m, j ))|x k, j ∈ X k, i = 1, 2 ,...,n,k=1,2,...m}
其中,Y为归一化运算的结果,xk,j为任取的量化值,Xk为样本区间,N(x)为归一化函数。Among them, Y is the result of the normalization operation, x k, j are arbitrary quantized values, X k is the sample interval, and N(x) is the normalization function.
所述基线校正处理过程为:采用非对称最小二乘法去除基线噪声使之更平滑The baseline correction process is: using the asymmetric least squares method to remove baseline noise to make it smoother
优化目标为:The optimization goal is:
argmin[∑iwi(yi-zi)2+λ∑i(Δ2zi)2] (1)argmin[∑ i w i (y i -z i ) 2 +λ∑ i (Δ 2 z i ) 2 ] (1)
公式(1)中,wi为权重因子,wi根据非对称的方式选择,当yi>zi时,wi=p,而yi<zi时,wi=1-p,p为拟合函数,yi为未知数,zi为样本平均值,Δ为二阶差分算子,λ是正则化参数(也叫折中因子);公式(1)中第一项表示拟合函数与原始数据的非对称拟合程度;第二项是为了保证拟合函数的光滑性,折中因子λ起到平衡非对称逼近程度和光滑性的作用;In formula (1), w i is the weight factor, and w i is selected in an asymmetric way. When y i > z i , w i = p, and when y i < z i , w i = 1-p, p is the fitting function, y i is the unknown, z i is the sample average value, Δ is the second-order difference operator, and λ is the regularization parameter (also called the compromise factor); the first item in formula (1) represents the fitting function The degree of asymmetric fit with the original data; the second item is to ensure the smoothness of the fitting function, and the compromise factor λ plays a role in balancing the degree of asymmetric approximation and smoothness;
最小化公式(1),可得:Minimizing formula (1), we can get:
(W+λDTD)z=Wy (2)(W+λD T D)z=W y (2)
公式(2)中,W是由权重因子w(本身为向量)组成的对角阵,即W=diag(w),D是z的二阶导数矩阵,即Dz=Δ2z,DT是指关于D的矩阵,z为估计的基线方程;In formula (2), W is a diagonal matrix composed of weight factor w (itself a vector), that is, W=diag(w), D is the second-order derivative matrix of z, that is, Dz=Δ 2 z, D T is refers to the matrix about D, z is the estimated baseline equation;
求解(2)得到估计的基线方程:Solve (2) to get the estimated baseline equation:
z=(W+λDTD)-1Wy (3)z=(W+λD T D) -1 W y (3)
所述特征比对为:The feature comparison is:
对比标准样品或实际样品中的有效组分对应的分子离子峰及其特征碎片离子峰位置,如果实际样品的质谱峰与标准谱库中的至少一个标准毒品的谱峰位置相同,则认为样品中含有与其相同种类的毒品。Compare the molecular ion peak and its characteristic fragment ion peak position corresponding to the effective component in the standard sample or the actual sample. If the mass spectrum peak of the actual sample is the same as the peak position of at least one standard drug in the standard library, it is considered that the Contains the same type of drug as it.
虽然本发明已以较佳的实施实例披露如上,然而上述实施实例并非用以限定本发明。因此,凡是为脱离本发明技术方案的内容,根据本发明的技术使之对以上实施实例做的任何修改、等同变化及修饰,均仍属本发明技术方案保护的范围。Although the present invention has been disclosed above with preferred implementation examples, the above implementation examples are not intended to limit the present invention. Therefore, any modifications, equivalent changes and modifications made to the above implementation examples according to the technology of the present invention in order to depart from the content of the technical solution of the present invention still belong to the scope of protection of the technical solution of the present invention.
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