CN109243541B - The analogy method and device of mass spectrum isotope fine structure and hyperfine structure - Google Patents
The analogy method and device of mass spectrum isotope fine structure and hyperfine structure Download PDFInfo
- Publication number
- CN109243541B CN109243541B CN201811080451.5A CN201811080451A CN109243541B CN 109243541 B CN109243541 B CN 109243541B CN 201811080451 A CN201811080451 A CN 201811080451A CN 109243541 B CN109243541 B CN 109243541B
- Authority
- CN
- China
- Prior art keywords
- vector
- isotope
- molecular formula
- fine structure
- quality
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses the analogy methods and device of a kind of mass spectrum isotope fine structure and hyperfine structure.Wherein, which calculates the isotope for the molecular formula that either element is constituted finely and hyperfine structure by isotope vector operation；Wherein, isotope vector is the combination of quality vector and abundance vector；Quality vector is arranged according to ascending or descending order, and abundance vector element and quality vector element correspond；Isotopic element cluster vector is established, the efficient calculation method of isotope fine structure is proposed, and gives the highly effective algorithm of specified mass-to-charge ratio isotope hyperfine structure, the efficient calculating of isotope fine structure and hyperfine structure is realized with unified algorithm；It was found that vector operation with " small change " method memory consumption is few, arithmetic speed is fast, computational accuracy is high, the isotope distribution that can be adapted for arbitrary element calculates, and supports customized isotope distribution.
Description
Technical field
The invention belongs to the data analysis field of high resolution mass spectrum more particularly to a kind of mass spectrum isotope fine structure and surpass
The analogy method and device of fine structure.
Background technique
The accurate and Fast simulation of isotope distribution is that parsing high resolution mass spectrum data and acquisition molecular composition and structure are believed
The key of breath.Isotope distribution can be divided into two levels: first is that the fine structure that common high-resolution mass spectrometer can be differentiated,
Its main feature is that the adjacent peak to deconvolute is spaced about 1Da；Second is that ultrahigh resolution Fourier's cyclotron resonance mass spectrum can be differentiated
Hyperfine structure, its main feature is that the peak to deconvolute forms " cluster ", it is peak-to-peak away from much smaller than 1Da in " cluster ".
Fine structure can regard the approximation of hyperfine structure at lower resolutions as.It can be proved that identity element
The molecular formula X of compositionn, the number at peak is in isotope fine structureWherein q indicates the stabilization natural isotope of X
Number.It is not difficult to find out that the peak number mesh of isotope fine structure is the high-order nonlinear function of atom number if q > 2.Therefore,
, complicated composition big for molecular weight or molecule containing more transition metal element, it is quick using computer and accurate simulation is same
The plain structure in position is always mass-spectrometry and the problem for calculating chemistry.
Currently, model molecule amount is big, the isotope structure of complicated composition or the molecule containing more transition metal element
Problem can be divided into two classes, and the first kind is to simulate fine isotope distribution by Fourier transformation or Polynomial Method；Second class
It is that isotope hyperfine structure is calculated based on the methods of multidimensional Fourier trans form, Dynamic Programming, transition tree, quality state classification.
But these mass spectrum isotope analogy methods there is problems at present:
First, the algorithm frame difference that isotope fine structure and hyperfine structure calculate far apart, calculating between the two
It is difficult effectively to switch；
Second, the arithmetic speed of the algorithm of existing isotope hyperfine structure is still relatively slow and memory source consumption compared with
Greatly.
Summary of the invention
In order to solve the deficiencies in the prior art, the first object of the present invention is to provide a kind of mass spectrum isotope fine structure
Analogy method is based on the operations such as vector operation and " small change " method, provides the unified computation model of isotope fine structure, make
The parsing of high resolution mass spectrum data is more succinct efficient and applied widely.
A kind of analogy method of mass spectrum isotope fine structure of the invention calculates any give by isotope vector operation
Determine the isotope fine structure of molecular formula；Wherein, isotope vector is the combination of quality vector and abundance vector；Quality vector is pressed
It is arranged according to ascending or descending order, abundance vector element and quality vector element correspond；The analogy method, comprising:
Step 1: seeking " small change " system D；Wherein, " small change " system D is one group of Positive Integer Set, member in Positive Integer Set
The number that element decomposes for each Elements Atom number in given molecular formula, Positive Integer Set interior element number correspondence are determined in molecular formula
The atom number of element；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: opened from 1
Begin to calculate using greedy algorithm respective element in given molecular formula is former up to the respective element atom number into given molecular formula
The number that sub- number is decomposed, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value；
Step 2: the atomicity of element each in given molecular formula being projected on " small change " system D, each element is obtained
" small change " of atomicity is grouped, and in " small change " grouping will there is different number of atomic group to be used as " cluster "；
Step 3: quality vector and abundance vector to each of each element " cluster " carry out regular operations；
Step 4: calculating the vector multiplications matrix and adduction matrix of " cluster " after each element regular operations, vector is multiplied
Product matrix and adduction matrix carry out convolution algorithm, obtain new quality vector and abundance vector, and then obtain the new of each element
Isotope finally obtains the isotope fine structure of all elements of given molecular formula.
Such as: " small change " system D=(1,2,5,10,20,50,100,200,500,1000,2000,5000,10000),
Or (1,4,9,11,26,38,44,100,400,900,1100,2600,3800,4400,10000), or (1,2,5,11,25,
42,103,164,212,484,733,1754,2730,6475,10000)。
It should be noted that " small change " system D is not limited to above-mentioned Positive Integer Set.
In the present invention, the isotope distribution spectrum of " cluster " of building can be naturally occurring, be also possible to artificial
Setting, using isotope vector operation operation, progressive alternate calculates the isotope fine structure of " cluster "；Small change " system D
The corresponding cluster of the corresponding atomicity of middle number is as preset parameter.
Further, when given molecular formula Xn is only made of a kind of element X, then isotope vector is quality vector and abundance
The sequence set of vector, by the isotopics with identical central quality；XnQuality sequence set be expressed as:
Wherein: each center mass is uh, the corresponding isotope sub-vector of center mass is [uhk], h and k are integers, in
Heart quality corresponds to the mass number at h-th of peak in isotope fine structure；[uhk] correspond to h-th of peak the hyperfine knot of isotope
All mass numbers in structure, i.e. fine structure abundance vector.
Further, in the step 4, the calculation formula of mass matrix in the fine structure of isotope are as follows:
Wherein, mαAnd mβIt is the quality vector for needing operation；
The calculation formula of abundance matrix in the fine structure of isotope are as follows:
Wherein, pαAnd pβIt is the abundance vector for needing operation.
The second object of the present invention is to provide a kind of analogy method of mass spectrum isotope hyperfine structure, is grasped based on vector
The operations such as work and " small change " method, provide the unified computation model of isotope hyperfine structure, make the solution of high resolution mass spectrum data
Analysis is more succinct efficient and applied widely.
A kind of analogy method of mass spectrum isotope hyperfine structure of the invention, comprising:
Using the analogy method of mass spectrum isotope fine structure described above, all elements of given molecular formula are obtained
Isotope fine structure；
When given molecular formula is only made of a kind of element, directly extract in the isotope fine structure of given molecular formula
The quality sub-vector sequence set and abundance sub-vector sequence set at h-th of peak, obtain the isotope superfinishing of given molecular formula
Fine texture；Wherein, h is given mass-to-charge ratio, is positive integer.
The present invention also provides the analogy methods of another mass spectrum isotope hyperfine structure comprising:
Using the analogy method of mass spectrum isotope fine structure described above, all elements of given molecular formula are obtained
Isotope fine structure；
When the number of independent element in given molecular formula is greater than 2, giving molecular formula is XaYbZc...；It then will be in molecular formula
All elements are divided into two major class, make its satisfaction:
Wherein, qiIt is element XiNatural stabilisation isotope quantity；I indicates molecular formula XaYbZc... middle element X, Y,
Z ... location；
Solve the minimum value of f (s)；Wherein s is element set；
Find out the corresponding h value of specified mass-to-charge ratio；And product vector fortune is carried out to the element in any two element set
It calculates, the hyperfine structure of h-th of peak position is calculated:
Wherein m and p respectively corresponds quality vector and abundance vector, and α and β are the position coordinates of element in matrix；H is given
Mass-to-charge ratio is positive integer.
Further, to the following operation of element in element set:
Wherein, vαAnd uβIt is the isotope vector for needing operation.
The third object of the present invention is to provide a kind of simulator of mass spectrum isotope fine structure.
A kind of simulator of mass spectrum isotope fine structure of the invention, including memory and first processor；
The first processor, is configured as: the isotope of any given molecular formula is calculated by isotope vector operation
Fine structure；Wherein, isotope vector is the combination of quality vector and abundance vector；Quality vector is arranged according to ascending or descending order
Column, abundance vector element and quality vector element correspond；
The first processor is additionally configured to execute following procedure:
Seek " small change " system D；Wherein, " small change " system D be one group of Positive Integer Set, Positive Integer Set interior element be to
Determine the number that each Elements Atom number is decomposed in molecular formula, Positive Integer Set interior element number correspondence determines element in molecular formula
Atom number；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: opened from 1
Begin to calculate using greedy algorithm respective element in given molecular formula is former up to the respective element atom number into given molecular formula
The number that sub- number is decomposed, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value；
The atomicity of element each in given molecular formula is projected on " small change " system D, each pantogen subnumber is obtained
" small change " grouping, and will " small change " grouping in have different number of atomic group conduct " cluster "；
Quality vector and abundance vector to each of each element " cluster " carry out regular operations；
The vector multiplications matrix of " cluster " and adduction matrix after each element regular operations are calculated, to vector multiplications matrix
Convolution algorithm is carried out with adduction matrix, obtains new quality vector and abundance vector, and then obtain the new isotope of each element,
Finally obtain the isotope fine structure of all elements of given molecular formula.
Further, the first processor, is also configured to
As given molecular formula XnIt is only made of a kind of element X, then isotope vector is the suitable of quality vector and abundance vector
Ordered sets, by the isotopics with identical central quality；XnQuality sequence set be expressed as:
Wherein: each center mass is uh, the corresponding isotope sub-vector of center mass is [uhk], h and k are integers, in
Heart quality corresponds to the mass number at h-th of peak in isotope fine structure；[uhk] correspond to h-th of peak the hyperfine knot of isotope
All mass numbers in structure, i.e. fine structure abundance vector.
Further, the first processor, is also configured to
The calculation formula of mass matrix in the fine structure of isotope are as follows:
Wherein, mαAnd mβIt is the quality vector for needing operation；
The calculation formula of abundance matrix in the fine structure of isotope are as follows:
Wherein, pαAnd pβIt is the abundance vector for needing operation.
The fourth object of the present invention is to provide a kind of simulator of mass spectrum isotope hyperfine structure.
A kind of simulator of mass spectrum isotope hyperfine structure of the invention, comprising:
The simulator of mass spectrum isotope fine structure described above；And
Second processor is configured as:
When given molecular formula is only made of a kind of element, directly extract in the isotope fine structure of given molecular formula
The quality sub-vector sequence set and abundance sub-vector sequence set at h-th of peak, obtain the isotope superfinishing of given molecular formula
Fine texture；Wherein, h is given mass-to-charge ratio, is positive integer.
The present invention also provides the simulators of another mass spectrum isotope hyperfine structure comprising:
The simulator of mass spectrum isotope fine structure described above；And
Second processor is configured as:
When the number of independent element in given molecular formula is greater than 2, giving molecular formula is XaYbZc...；It then will be in molecular formula
All elements are divided into two major class, make its satisfaction:
Wherein, qiIt is element XiNatural stabilisation isotope quantity；I indicates molecular formula XaYbZc... middle element X, Y,
Z ... location；
Solve the minimum value of f (s)；Wherein s is element set；
Find out the corresponding h value of specified mass-to-charge ratio；And product vector fortune is carried out to the element in any two element set
It calculates, the hyperfine structure of h-th of peak position is calculated:
Wherein m and p respectively corresponds quality vector and abundance vector, and α and β are the position coordinates of element in matrix；H is given
Mass-to-charge ratio is positive integer.
Compared with prior art, the beneficial effects of the present invention are:
(1) System of Logic of the invention is tight, and it is clearly clear to define；The present invention is based on isotope vector and vector operation,
Including vector regularization, vector adduction and product calculation and convolution algorithm；" small change " system optimization algorithm is introduced simultaneously
The speed of service exactly defines " small change " system D and it is calculated and evaluation method；
(2) present invention is using isotope sub-vector and the concept of vector ordered set, and obtains the isotope of the specified position h
Fine structure calculation method；
(3) present invention can calculate the isotope fine structure and hyperfine structure of any molecular formula, and computational accuracy is high,
Speed is exceedingly fast, and consumes that memory is few, and conventional method can only often calculate one in isotope fine structure or hyperfine structure
Kind, and computing resource consumption is big.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the molecular schematic diagram of people's flesh hemoglobin；
Fig. 2 is vector operation schematic diagram；
Fig. 3 (a) is the isotope fine structure of people's flesh hemoglobin；
Fig. 3 (b) is the isotope hyperfine structure of people's flesh hemoglobin；
Fig. 4 is the program flow diagram of calculating isotope distribution method of the invention；
Fig. 5 is a kind of analogy method flow chart of mass spectrum isotope fine structure of the invention.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
In the present invention, isotope vector multiplication is the inner product of vector A (m dimension) and vector B (n dimension), as a resultIsotope vector addition be the interior of vector A (m dimension) and vector B (n dimension) and, as a result
The regular operations of isotope vector are as follows: suitably increase element in isotopic mass vector and abundance vector, make every
Form between two continuous mass of poor quality is 1Da, and increased abundance vector element is zero；
The convolution algorithm of isotope vector are as follows:
ph=∑α, β ∈ { alpha+beta -1=h }pαβ, andWherein pαβAnd mαβRespectively isotope
(α, β) element numerical value, m in the matrix that abundance vector multiplication and quality vector add operation obtainhAnd phIt is new after convolution algorithm respectively
H-th of the quality elements and abundance element of isotope.
As shown in figure 5, a kind of analogy method of mass spectrum isotope fine structure of the invention, passes through isotope vector operation
Calculate the isotope fine structure of any given molecular formula；Wherein, isotope vector is the combination of quality vector and abundance vector；
Quality vector is arranged according to ascending or descending order, and abundance vector element and quality vector element correspond；The analogy method, packet
It includes:
Step 1: seeking " small change " system D；Wherein, " small change " system D is one group of Positive Integer Set, member in Positive Integer Set
The number that element decomposes for each Elements Atom number in given molecular formula, Positive Integer Set interior element number correspondence are determined in molecular formula
The atom number of element；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: opened from 1
Begin to calculate using greedy algorithm respective element in given molecular formula is former up to the respective element atom number into given molecular formula
The number that sub- number is decomposed, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value；
Such as: " small change " system D=(1,2,5,10,20,50,100,200,500,1000,2000,5000,10000),
Or (1,4,9,11,26,38,44,100,400,900,1100,2600,3800,4400,10000), or (1,2,5,11,25,
42,103,164,212,484,733,1754,2730,6475,10000)。
It should be noted that " small change " system D is not limited to above-mentioned Positive Integer Set.
Step 2: the atomicity of element each in given molecular formula being projected on " small change " system D, each element is obtained
" small change " of atomicity is grouped, and in " small change " grouping will there is different number of atomic group to be used as " cluster "；
Step 3: quality vector and abundance vector to each of each element " cluster " carry out regular operations；
Step 4: calculating the vector multiplications matrix and adduction matrix of " cluster " after each element regular operations, vector is multiplied
Product matrix and adduction matrix carry out convolution algorithm, obtain new quality vector and abundance vector, and then obtain the new of each element
Isotope finally obtains the isotope fine structure of all elements of given molecular formula.
In the step 4, the calculation formula of mass matrix in the fine structure of isotope are as follows:
Wherein, mαAnd mβIt is the quality vector for needing operation；
The calculation formula of abundance matrix in the fine structure of isotope are as follows:
Wherein, pαAnd pβIt is the abundance vector for needing operation.
In the present invention, the isotope distribution spectrum of " cluster " of building can be naturally occurring, be also possible to artificial
Setting, using isotope vector operation operation, progressive alternate calculates the isotope fine structure of " cluster "；Small change " system D
The corresponding cluster of the corresponding atomicity of middle number is as preset parameter.
Specifically, when given molecular formula Xn is only made of a kind of element X, then isotope vector is that quality vector and abundance are sweared
The sequence set of amount, by the isotopics with identical central quality；XnQuality sequence set be expressed as:
Wherein: each center mass is uh, the corresponding isotope sub-vector of center mass is [uhk], h and k are integers, in
Heart quality corresponds to the mass number at h-th of peak in isotope fine structure；[uhk] correspond to h-th of peak the hyperfine knot of isotope
All mass numbers in structure, i.e. fine structure abundance vector.
When given molecular formula is only made of a kind of element, directly extract in the isotope fine structure of given molecular formula
The quality sub-vector sequence set and abundance sub-vector sequence set at h-th of peak, obtain the isotope superfinishing of given molecular formula
Fine texture；Wherein, h is given mass-to-charge ratio, is positive integer.
When the number of independent element in given molecular formula is greater than 2, giving molecular formula is XaYbZc...；It then will be in molecular formula
All elements are divided into two major class, make its satisfaction:
Wherein, qiIt is element XiNatural stabilisation isotope quantity；I indicates molecular formula XaYbZc... middle element X, Y,
Z ... location；
Solve the minimum value of f (s)；Wherein s is element set；
Find out the corresponding h value of specified mass-to-charge ratio；And product vector fortune is carried out to the element in any two element set
It calculates, the hyperfine structure of h-th of peak position is calculated:
Wherein m and p respectively corresponds quality vector and abundance vector, and α and β are the position coordinates of element in matrix；H is given
Mass-to-charge ratio is positive integer.
In order to describe calculating process, the biomolecule containing carbon, hydrogen, nitrogen, oxygen and element sulphur is selected, as shown in table 1.
The stabilization natural isotope quality and its abundance of carbon, hydrogen, nitrogen, oxygen and element sulphur in 1 biomolecule of table
And with human muscle hemoglobin C as shown in Figure 1744H1224N210O222S5For be illustrated.
But the calculating process can be applied to containing any compound in addition to this five kinds of elements.It provides in molecule first
The isotope distribution of any isotope cluster or element clusters indicates are as follows:
Wherein M and P respectively corresponds quality and abundance vector ordered set, by vector u1,u2... and v1,v2... structure respectively
At；
Wherein vector u1,u2... it is respectively [u10,u11],[u20,u21,u22,...],...；
Vector v1,v2... it is respectively [v10,v11],[v20,v21,v22,...],...；
By u10,u20... and v10,v20... it waits items to extract, and according to the sequence permutation of vector ordered set, obtains
X containing n elementnQuality vector MXWith abundance vector PX；
MX(n)=[u10X(n),u20X(n),u30X(n),...]；
PX(n)=[v10X(n),v20X(n),v30X(n),...]；
Set " small change " system D；" small change " system D is one group of Positive Integer Set, and Positive Integer Set interior element is given point
The number that each Elements Atom number is decomposed in minor, the corresponding atom for determining element in molecular formula of Positive Integer Set interior element number
Number；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: opened from 1
Begin to calculate using greedy algorithm respective element in given molecular formula is former up to the respective element atom number into given molecular formula
The number that sub- number is decomposed, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value.
" small change " system D can also from D=(1,2,5,10,20,50,100,200,500,1000,2000,5000,
10000), (1,4,9,11,26,38,44,100,400,900,1100,2600,3800,4400,10000) and (1,2,5,11,
25,42,103,164,212,484,733,1754,2730,6475,10000) selection in.
To the X containing k atomk, " small change " system D is utilized, k is decomposed, is obtained:
K=∑ D (i)；
Wherein D (i) indicates i-th of element in " small change " system D；
According to the D (i) and D (j) value in k=∑ D (i), corresponding quality vector and abundance vector are obtained:
MD(i)=[u10D(i),u20D(i),u30D(i),...]；
PD(i)=[v10D(i),v20D(i),v30D(i),...]；
MD(j)=[u10D(j),u20D(j),u30D(j),...]；
PD(j)=[v10D(j),v20D(j),v30D(j),...]；
Vector sum and vector product are calculated using vector operation, as a result, as shown in Figure 2:
Convolution algorithm is carried out to two obtained matrixes, so that:
ph=∑α, β ∈ { alpha+beta -1=h }ναβ；
Wherein h is the element coordinate parameters of new vector, and m and p distinguish new quality vector and abundance vector, and α and β are matrixes
The position coordinates of middle element；
By operation above, C can be respectively obtained744,H1224,N210,O222, and S5The isotope of five element clusters is fine
Structure；C can successively further be obtained to this five element clusters progress regularization operations, vector operation, convolution algorithms744H1224,
C744H1224N210,C744H1224N210O222, and final molecular formula C744H1224N210O222S5Isotope fine structure, such as Fig. 3
(a) shown in；
Calculate C744,H1224,N210,O222, and S5Fine structure quality vector dimension, have following relationship:
It can be calculated:
DimC=745；DimH=1225；DimN=211；DimO=24976；DimS=56；
F (s) functional minimum value is found, corresponding set s is found out；It is calculated by optimization:
f(s)min=DimC×DimO+DimH×DimN×DimS=33081720；
Corresponding category set s={ C, O }；
Calculate separately s collection withCollect the isotope fine structure of " element clusters ", the isotope for obtaining two " element clusters " is fine
Structure XCOWith XHNS:
To progress regularization operation, and to vector operation operation, obtain:
Two formulas are the functions of h above, i.e., the function of specified mass-to-charge ratio m/z, therefore, for given mass-to-charge ratio, same to position
Plain hyperfine structure can be uniquely by mhCHNOSAnd phCHNOSIt determines；
By sequential operation as shown in Figure 4, human muscle hemoglobin C is obtained744H1224N210O222S5The isotope distribution of molecule
Situation.
In Fig. 4, IUPAC, International Union of Pure and Applied Chemistry are international
Purely with applied chemistry federation, and international theory (chemistry) and applied chemistry federation are translated, is one and is dedicated to promoting chemistry
One united organization of relevant non-government organization and the meeting of various countries' chemistry.It is famous with generally acknowledged chemical name authority.Name and
The committee, symbol branch can all modify IUPAC nomenclature every year, to make every effort to provide the accurate rule of Compound nomenclature.IUPAC
It is one of the member of International Science Council.
Above-mentioned human muscle hemoglobin C744H1224N210O222S5The isotope fine structure of molecule, as shown in Figure 3；Hyperfine structure
Shown in the calculated result such as Fig. 3 (b) at (the maximum peak of abundance in fine structure).By test, the time required to fine structure operation
It is 4.496 milliseconds, relative error is 1.698 × 10-4Ppb (1,000,000,000 points of ratios)；Hyperfine structure operation time is 161 milliseconds, phase
It is 0.009ppm (part per million) to error.The above test is in Intel Core i5-3210 CPU@2.50GHz, 8GB RAM
It is carried out on computer.
In the example of the application, by modes such as isotope vector calculus, " small change " system, sub-vector operations, simultaneously
The isotope fine structure and isotope hyperfine structure of human muscle hemoglobin are obtained, and arithmetic speed is fast, result is accurate, is same
The simulation of position element distribution provides an efficient calculation method.
Conventional method calculate isotope fine structure, such as Fourier transformation, although speed is higher with accuracy, method without
Method is generalized to the calculating of isotope hyperfine structure.Theoretically, C744H1224N210O222S5Isotope hyperfine structure in peak number mesh
About 2.69 × 1014It is a.Due to huge amount, Traditional calculating methods, which will obtain isotope hyperfine structure, inevitably to be needed
Long-time operation, and memory consumption is big.By testing many Typical molecular systems, speed of the invention is obviously good with accuracy
In existing model, and the calculation method of isotope fine structure and hyperfine structure is unified.
The present invention also provides for example a kind of simulators of mass spectrum isotope fine structure comprising at memory and first
Manage device；
The first processor, is configured as: the isotope of any given molecular formula is calculated by isotope vector operation
Fine structure；Wherein, isotope vector is the combination of quality vector and abundance vector；Quality vector is arranged according to ascending or descending order
Column, abundance vector element and quality vector element correspond；
The first processor is additionally configured to execute following procedure:
Seek " small change " system D；Wherein, " small change " system D be one group of Positive Integer Set, Positive Integer Set interior element be to
Determine the number that each Elements Atom number is decomposed in molecular formula, Positive Integer Set interior element number correspondence determines element in molecular formula
Atom number；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: opened from 1
Begin to calculate using greedy algorithm respective element in given molecular formula is former up to the respective element atom number into given molecular formula
The number that sub- number is decomposed, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value；
The atomicity of element each in given molecular formula is projected on " small change " system D, each pantogen subnumber is obtained
" small change " grouping, and will " small change " grouping in have different number of atomic group conduct " cluster "；
Quality vector and abundance vector to each of each element " cluster " carry out regular operations；
The vector multiplications matrix of " cluster " and adduction matrix after each element regular operations are calculated, to vector multiplications matrix
Convolution algorithm is carried out with adduction matrix, obtains new quality vector and abundance vector, and then obtain the new isotope of each element,
Finally obtain the isotope fine structure of all elements of given molecular formula.
Specifically, the first processor, is also configured to
As given molecular formula XnIt is only made of a kind of element X, then isotope vector is the suitable of quality vector and abundance vector
Ordered sets, by the isotopics with identical central quality；XnQuality sequence set be expressed as:
Wherein: each center mass is uh, the corresponding isotope sub-vector of center mass is [uhk], h and k are integers, in
Heart quality corresponds to the mass number at h-th of peak in isotope fine structure；[uhk] correspond to h-th of peak the hyperfine knot of isotope
All mass numbers in structure, i.e. fine structure abundance vector.
Specifically, the first processor, is also configured to
The calculation formula of mass matrix in the fine structure of isotope are as follows:
Wherein, mαAnd mβIt is the quality vector for needing operation；
The calculation formula of abundance matrix in the fine structure of isotope are as follows:
Wherein, pαAnd pβIt is the abundance vector for needing operation.
The present invention also provides a kind of simulators of mass spectrum isotope hyperfine structure.
A kind of simulator of mass spectrum isotope hyperfine structure of the invention, comprising:
The simulator of mass spectrum isotope fine structure described above；And
Second processor is configured as:
When given molecular formula is only made of a kind of element, directly extract in the isotope fine structure of given molecular formula
The quality sub-vector sequence set and abundance sub-vector sequence set at h-th of peak, obtain the isotope superfinishing of given molecular formula
Fine texture；Wherein, h is given mass-to-charge ratio, is positive integer.
The present invention also provides the simulators of another mass spectrum isotope hyperfine structure comprising:
The simulator of mass spectrum isotope fine structure described above；And
Second processor is configured as:
When the number of independent element in given molecular formula is greater than 2, giving molecular formula is XaYbZc...；It then will be in molecular formula
All elements are divided into two major class, make its satisfaction:
Wherein, qiIt is element XiNatural stabilisation isotope quantity；I indicates molecular formula XaYbZc... middle element X, Y,
Z ... location；
Solve the minimum value of f (s)；Wherein s is element set；
Find out the corresponding h value of specified mass-to-charge ratio；And product vector fortune is carried out to the element in any two element set
It calculates, the hyperfine structure of h-th of peak position is calculated:
Wherein m and p respectively corresponds quality vector and abundance vector, and α and β are the position coordinates of element in matrix；H is given
Mass-to-charge ratio is positive integer.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not protects model to the present invention
The limitation enclosed, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not
Need to make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (10)
1. a kind of analogy method of mass spectrum isotope fine structure, which is characterized in that calculated by isotope vector operation any
The isotope fine structure of given molecular formula；Wherein, isotope vector is the combination of quality vector and abundance vector；Quality vector
It is arranged according to ascending or descending order, abundance vector element and quality vector element correspond；The analogy method, comprising:
Step 1: seeking " small change " system D；Wherein, " small change " system D is one group of Positive Integer Set, and Positive Integer Set interior element is
The number that each Elements Atom number is decomposed in given molecular formula, Positive Integer Set interior element number correspondence determine element in molecular formula
Atom number；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: straight since 1
To the respective element atom number into given molecular formula, calculated using greedy algorithm by respective element atom in given molecular formula
The number that number decomposes, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value；
Step 2: the atomicity of element each in given molecular formula being projected on " small change " system D, each Elements Atom is obtained
Several " small change " groupings, and in " small change " grouping will there is different number of atomic group to be used as " cluster "；
Step 3: quality vector and abundance vector to each of each element " cluster " carry out regular operations；
Step 4: the vector multiplications matrix and adduction matrix of " cluster " after each element regular operations are calculated, to vector multiplications square
Battle array and adduction matrix carry out convolution algorithm, obtain new quality vector and abundance vector, and then obtain the new same position of each element
Element finally obtains the isotope fine structure of all elements of given molecular formula.
2. a kind of analogy method of mass spectrum isotope fine structure as described in claim 1, which is characterized in that when given molecule
Formula XnIt is only made of a kind of element X, then isotope vector is the sequence set of quality vector and abundance vector, by in identical
The isotopics of heart quality；XnQuality sequence set be expressed as:
Wherein: each center mass is uh, the corresponding isotope sub-vector of center mass is [uhk], h and k are integer, centroplasm
Amount corresponds to the mass number at h-th of peak in isotope fine structure；[uhk] correspond in the isotope hyperfine structure at h-th of peak
All mass numbers, i.e. fine structure abundance vector.
3. a kind of analogy method of mass spectrum isotope fine structure as described in claim 1, which is characterized in that in the step
In 4, the calculation formula of mass matrix in the fine structure of isotope are as follows:
Wherein, mαAnd mβIt is the quality vector for needing operation；
The calculation formula of abundance matrix in the fine structure of isotope are as follows:
Wherein, pαAnd pβIt is the abundance vector for needing operation.
4. a kind of analogy method of mass spectrum isotope hyperfine structure characterized by comprising
Using the analogy method of mass spectrum isotope fine structure as claimed in any one of claims 1-3, given molecule is obtained
The isotope fine structure of all elements of formula；
When given molecular formula is only made of a kind of element, h in the isotope fine structure of given molecular formula is directly extracted
The quality sub-vector sequence set and abundance sub-vector sequence at a peak are gathered, and the hyperfine knot of isotope of given molecular formula is obtained
Structure；Wherein, h is given mass-to-charge ratio, is positive integer.
5. a kind of analogy method of mass spectrum isotope hyperfine structure characterized by comprising
Using the analogy method of mass spectrum isotope fine structure as claimed in any one of claims 1-3, given molecule is obtained
The isotope fine structure of all elements of formula；
When the number of independent element in given molecular formula is greater than 2, giving molecular formula is XaYbZc...；To then own in molecular formula
Element is divided into two major class, makes its satisfaction:
Wherein, qiIt is element XiNatural stabilisation isotope quantity；I indicates molecular formula XaYbZc... middle element X, Y, Z ... institute
The position at place；
Solve the minimum value of f (s)；Wherein s is element set；
Find out the corresponding h value of specified mass-to-charge ratio；And product vector calculus, meter are carried out to the element in any two element set
Calculation obtains the hyperfine structure of h-th of peak position:
Wherein m and p respectively corresponds quality vector and abundance vector, and α and β are the position coordinates of element in matrix；H is given matter lotus
Than being positive integer.
6. a kind of analogy method of mass spectrum isotope hyperfine structure as described in right wants 5, which is characterized in that element set
The following operation of interior element:
Wherein, vαAnd uβIt is the isotope vector for needing operation.
7. a kind of simulator of mass spectrum isotope fine structure, which is characterized in that including memory and first processor；
The first processor, is configured as: the isotope for calculating any given molecular formula by isotope vector operation is fine
Structure；Wherein, isotope vector is the combination of quality vector and abundance vector；Quality vector is arranged according to ascending or descending order, rich
It spends vector element and quality vector element corresponds；
The first processor is additionally configured to execute following procedure:
Seek " small change " system D；Wherein, " small change " system D is one group of Positive Integer Set, and Positive Integer Set interior element is given point
The number that each Elements Atom number is decomposed in minor, the corresponding atom for determining element in molecular formula of Positive Integer Set interior element number
Number；
" small change " system D is to optimize by χ value and have the χ value less than preset threshold；The calculating process of χ value are as follows: straight since 1
To the respective element atom number into given molecular formula, calculated using greedy algorithm by respective element atom in given molecular formula
The number that number decomposes, the mean value for finally seeking all elements decomposition number in given molecular formula is χ value；
The atomicity of element each in given molecular formula is projected on " small change " system D, " looking for for each pantogen subnumber is obtained
Zero " grouping, and in " small change " grouping will there is different number of atomic group to be used as " cluster "；
Quality vector and abundance vector to each of each element " cluster " carry out regular operations；
Calculate the vector multiplications matrix of " cluster " and adduction matrix after each element regular operations, to vector multiplications matrix and plus
Convolution algorithm is carried out with matrix, obtains new quality vector and abundance vector, and then obtain the new isotope of each element, finally
Obtain the isotope fine structure of all elements of given molecular formula.
8. a kind of simulator of mass spectrum isotope fine structure as claimed in claim 7, which is characterized in that at described first
Device is managed, is also configured to
As given molecular formula XnIt is only made of a kind of element X, then isotope vector is the ordered set of quality vector and abundance vector
It closes, by the isotopics with identical central quality；XnQuality sequence set be expressed as:
Wherein: each center mass is uh, the corresponding isotope sub-vector of center mass is [uhk], h and k are integer, centroplasm
Amount corresponds to the mass number at h-th of peak in isotope fine structure；[uhk] correspond in the isotope hyperfine structure at h-th of peak
All mass numbers, i.e. fine structure abundance vector；
Or/and
The first processor, is also configured to
The calculation formula of mass matrix in the fine structure of isotope are as follows:
Wherein, mαAnd mβIt is the quality vector for needing operation；
The calculation formula of abundance matrix in the fine structure of isotope are as follows:
Wherein, pαAnd pβIt is the abundance vector for needing operation.
9. a kind of simulator of mass spectrum isotope hyperfine structure characterized by comprising
The simulator of mass spectrum isotope fine structure as described in any one of claim 7-8；And
Second processor is configured as:
When given molecular formula is only made of a kind of element, h in the isotope fine structure of given molecular formula is directly extracted
The quality sub-vector sequence set and abundance sub-vector sequence at a peak are gathered, and the hyperfine knot of isotope of given molecular formula is obtained
Structure；Wherein, h is given mass-to-charge ratio, is positive integer.
10. a kind of simulator of mass spectrum isotope hyperfine structure characterized by comprising
The simulator of mass spectrum isotope fine structure as described in any one of claim 7-8；And
Second processor is configured as:
When the number of independent element in given molecular formula is greater than 2, giving molecular formula is XaYbZc...；To then own in molecular formula
Element is divided into two major class, makes its satisfaction:
Wherein, qiIt is element XiNatural stabilisation isotope quantity；I indicates molecular formula XaYbZc... middle element X, Y, Z ... institute
The position at place；
Solve the minimum value of f (s)；Wherein s is element set；
Find out the corresponding h value of specified mass-to-charge ratio；And product vector calculus, meter are carried out to the element in any two element set
Calculation obtains the hyperfine structure of h-th of peak position:
Wherein m and p respectively corresponds quality vector and abundance vector, and α and β are the position coordinates of element in matrix；H is given matter lotus
Than being positive integer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811080451.5A CN109243541B (en) | 2018-09-17 | 2018-09-17 | The analogy method and device of mass spectrum isotope fine structure and hyperfine structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811080451.5A CN109243541B (en) | 2018-09-17 | 2018-09-17 | The analogy method and device of mass spectrum isotope fine structure and hyperfine structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109243541A CN109243541A (en) | 2019-01-18 |
| CN109243541B true CN109243541B (en) | 2019-05-21 |
Family
ID=65058632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811080451.5A Active CN109243541B (en) | 2018-09-17 | 2018-09-17 | The analogy method and device of mass spectrum isotope fine structure and hyperfine structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109243541B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102759592A (en) * | 2012-07-04 | 2012-10-31 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | Method for analyzing CO stable isotope mass number abundance ratio through chromatography-mass spectrometry |
| CN105718744A (en) * | 2016-01-25 | 2016-06-29 | 深圳大学 | Metabolic mass spectrum screening method and system based on the deep learning |
| WO2016209080A2 (en) * | 2015-06-24 | 2016-12-29 | Universiteit Leiden | Glycosylated metabolites. |
| US9746464B2 (en) * | 2002-10-03 | 2017-08-29 | Anderson Forschung Group, Llc. | High sensitivity quantitation of peptides by mass spectrometry |
| CN107112192A (en) * | 2014-11-27 | 2017-08-29 | 株式会社岛津制作所 | Fourier transform mass spectrography |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI603070B (en) * | 2011-01-03 | 2017-10-21 | 諾發測量儀器股份有限公司 | Method and system for use in measuring in complex patterned structures |
| JP5569761B1 (en) * | 2013-03-29 | 2014-08-13 | シャープ株式会社 | Analysis method |
| GB2531336B (en) * | 2014-10-17 | 2019-04-10 | Thermo Fisher Scient Bremen Gmbh | Method and apparatus for the analysis of molecules using mass spectrometry and optical spectroscopy |
| WO2018039144A1 (en) * | 2016-08-22 | 2018-03-01 | Global Medical Isotope Systems Llc | System and method for breeding tritium from lithium using a neutron generator |
| CN106959345A (en) * | 2017-03-27 | 2017-07-18 | 上海谱领生物科技有限公司 | A kind of full Isotopic Internal Standard mass spectrum quantitative approach of neurotransmitter metabolite |
-
2018
- 2018-09-17 CN CN201811080451.5A patent/CN109243541B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9746464B2 (en) * | 2002-10-03 | 2017-08-29 | Anderson Forschung Group, Llc. | High sensitivity quantitation of peptides by mass spectrometry |
| CN102759592A (en) * | 2012-07-04 | 2012-10-31 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | Method for analyzing CO stable isotope mass number abundance ratio through chromatography-mass spectrometry |
| CN107112192A (en) * | 2014-11-27 | 2017-08-29 | 株式会社岛津制作所 | Fourier transform mass spectrography |
| WO2016209080A2 (en) * | 2015-06-24 | 2016-12-29 | Universiteit Leiden | Glycosylated metabolites. |
| CN105718744A (en) * | 2016-01-25 | 2016-06-29 | 深圳大学 | Metabolic mass spectrum screening method and system based on the deep learning |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109243541A (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mavrotas et al. | An improved version of the augmented ε-constraint method (AUGMECON2) for finding the exact pareto set in multi-objective integer programming problems | |
| Gower et al. | Minimum spanning trees and single linkage cluster analysis | |
| Kim | Estimating classification error rate: Repeated cross-validation, repeated hold-out and bootstrap | |
| CN109632310A (en) | A kind of Method for Bearing Fault Diagnosis based on feature enhancing | |
| Schlier et al. | High-order symplectic integration: an assessment | |
| Larcher | Digital point sets: analysis and application | |
| CN104965821B (en) | A kind of data mask method and device | |
| CN107545509A (en) | A kind of group dividing method of more relation social networks | |
| CN109243541B (en) | The analogy method and device of mass spectrum isotope fine structure and hyperfine structure | |
| CN113496762B (en) | Biological gene sequence summary data generation method and system | |
| Leydesdorff | “Structuration” by intellectual organization: the configuration of knowledge in relations among structural components in networks of science | |
| CN104463802B (en) | Non-convex compressed sensing image reconstruction method based on variable scale over-complete dictionaries | |
| CN110188407A (en) | The determination method and device of fluid flow parameter in porous media | |
| Zhao et al. | Predicting power conversion efficiency of binary organic solar cells based on Y6 acceptor by machine learning | |
| Knüpfer et al. | Compressible memory data structures for event-based trace analysis | |
| Jabbari et al. | Spatio-temporal warping for myoelectric control: an offline, feasibility study | |
| Chen | Component reliability analysis of k-out-of-n systems with censored data | |
| Vallejo et al. | Characterization of the local instability in the Hénon–Heiles Hamiltonian | |
| Sciamarella et al. | Unveiling the topological structure of chaotic flows from data | |
| Kässinger et al. | Persival: Simulating complex 3d meshes on resource-constrained mobile ar devices using interpolation | |
| CN109768890B (en) | Symbolized directed weighted complex network building method based on STL decomposition method | |
| Xiao | Carleson embeddings for Sobolev spaces via heat equation | |
| CN106205572A (en) | Sequence of notes generates method and device | |
| Araujo et al. | The higher-order matching polynomial of a graph | |
| CN113033778B (en) | Buddha music generation method, device, equipment and storage medium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |