A sulfated polysaccharide from Navicula incerta (SPNi) was extracted, and its physicochemical characteristics, antioxidant activity, and anti-hemolytic property were investigated. The polysaccharide yield was 4.8% (SPNi weight/biomass dry weight). Glucose, galactose, mannose, and xylose were the primary sugars. The sulfate content and Mw values were 0.46% and 45 kDa, respectively. The FT-IR spectrum showed characteristic bands at 3276,1079,1255, and 820 cm−1, related to -OH, C-O-C, S=O, and C-O-S stretching vibration. The 1H-NMR analysis revealed signals of anomeric protons, indicating the presence of CH2-O and CH-O groups. SPNi registered ferric-reducing antioxidant power (up to 1.47 µmol TE/g) and 54% anti-radical activity on ABTS+. This polysaccharide registered 90% hemolysis inhibition achieving integrity of the erythrocyte membrane. The results indicate that SPNi could be a candidate for biotechnology applications where antioxidant activity and hemolysis inhibition are required.
Citation: Ricardo I. González-Vega, Carmen L. Del-Toro-Sánchez, Ramón A. Moreno-Corral, José A. López-Elías, Aline Reyes-Díaz, Norma García-Lagunas, Elizabeth Carvajal-Millán, Diana Fimbres-Olivarría. Sulfated polysaccharide-rich extract from Navicula incerta: physicochemical characteristics, antioxidant activity, and anti-hemolytic property[J]. AIMS Bioengineering, 2022, 9(4): 364-382. doi: 10.3934/bioeng.2022027
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Abstract
A sulfated polysaccharide from Navicula incerta (SPNi) was extracted, and its physicochemical characteristics, antioxidant activity, and anti-hemolytic property were investigated. The polysaccharide yield was 4.8% (SPNi weight/biomass dry weight). Glucose, galactose, mannose, and xylose were the primary sugars. The sulfate content and Mw values were 0.46% and 45 kDa, respectively. The FT-IR spectrum showed characteristic bands at 3276,1079,1255, and 820 cm−1, related to -OH, C-O-C, S=O, and C-O-S stretching vibration. The 1H-NMR analysis revealed signals of anomeric protons, indicating the presence of CH2-O and CH-O groups. SPNi registered ferric-reducing antioxidant power (up to 1.47 µmol TE/g) and 54% anti-radical activity on ABTS+. This polysaccharide registered 90% hemolysis inhibition achieving integrity of the erythrocyte membrane. The results indicate that SPNi could be a candidate for biotechnology applications where antioxidant activity and hemolysis inhibition are required.
1.
Introduction
Grey system theory is a method for forecasting and analyzing small sample sequences. It was first put forward by Deng [1,2] and has been widely used in various fields. In order to enhance the adaptability of the prediction model, Deng proposed a single-variable grey prediction model GM(2,1), which stands for one variable and second-order differential equation. However, due to defects in the structure, the prediction effect is not ideal in some cases [21]. In order to improve the prediction accuracy of the model, scholars put forward some improved models based on the classical GM(2,1) model. Shen et al. [3] proposed a method to determine the system parameters using the least square method to reduce error. Zeng et al. [4] proposed a new parameter estimation to GM(2,1) model based on accumulating method which reduces the matrix calculation quantity. A new healthier model was obtained and the serious morbidity problem with a multiple transformation on the initial data was resolved. In [5], two improved models are proposed based on modeling and predicting on non-linear rolling motion by GM(2,1), which are grey cycle extension and grey neural network respectively based on error compensation. Li et al. [6] introduced the GM(2,1) model and its improved algorithm and prediction steps by Matlab. By analyzing the shortcomings of GM(2,1) model, an optimized SOGM(2,1) model was constructed in [7] and applied to the prediction of high-speed roadbed settlement with higher prediction accuracy. In [8], Zhou et al. focused on the two shortcomings of GM(2,1) model and proposed appropriate measures for improvement. Moreover Zhou improved the method, which was used in solving albino equations of the classical GM(2,1) model, to solve the same equations by Laplace transform and improve the prediction accuracy. In [9], based on the GM(2.1) model, the boundary conditions were improved, and the effectiveness of the improved method was verified with grey data.
In [10], Wu et al. first discussed using perturbation theory and the least square method to address a violation of the new information priority principle in grey system theory. Ihis introduced a new grey system model with fractional order accumulation that reflects new information priority better with smaller accumulation orders. In recent years, various grey prediction models based on fractional order accumulation have been proposed in [11,12,13,14,15]. In [12], Wu improved the GM(2,1) using fractional order AGO to achieve an accurate prediction. Based on the GM(2,1) model with fractional order accumulation, Zeng [15] gave two different ways to determine the time response parameters of the fractional order GM(2,1) model, which can be flexibly selected according to the specific results in practical application.
The B-spline method has been widely applied to derive numerical solutions of partial differential equations. In [16], a cubic monotonicity-preserving interpolation spline was proposed to reconstruct the background value. In [17], Chen and Zhu developed a new GM(1,1) model based on C1 monotonicity-preserving rational linear interpolation spline to provide a more reasonable method to calculate the background value. In [18], in order to improve the GM (1,1) model, a formula based on a C1 monotonicitypreserving piecewise rational quadratic interpolation spline for calculating background value was proposed.
In the classical GM2(2,1) model, the corresponding estimated function x(2)(t) has the property of convexity and C∞ continuity. The classical GM2(2,1) model use the piecewise linear polynomial interpolation Lk(t)=(k+1−t)x(2)(k)+(t−k)x(2)(k+1), k=1,2,…,n−1 as an approximate solution of x(2)(t) so as to estimate background values z(2)(k+1) and the derivative values dx(2)(t)dt|t=k+1 and dx(2)(t)dt|t=k. It is well known that the piecewise linear polynomial interpolation has convexity-preserving property, but it just has C0 continuity and only has O(h2) order of convergence. In estimating dx(2)(t)dt|t=1, the classical GM2(2,1) model simply sets x(2)(0)=0, whereas this will cause error in estimating dx(2)(t)dt|t=1.
The main contribution of this work is to use a C1 convexity-preserving rational quadratic interpolation spline given in [19] as approximate solution of x(2)(t) so as to estimate background values z(2)(k+1) and the derivative values dx(2)(t)dt|t=k+1 and dx(2)(t)dt|t=k, k=1,2,…,n−1 and thereby a new GM2(2,1) model is established. The rest of this paper is structured as follows. Section 2 recall the construction of the C1 convexity-preserving interpolation spline given in [19]. In section 3, on the basis of C1 convexity-preserving rational quadratic interpolation spline, a new GM2(2,1) model is constructed in detail. Several numerical examples are given in section 4. The conclusion is given in section 5.
2.
Classical GM2(2,1) model
In this subsection, we recall the classical GM2(2,1) model. Let an original non-negative and uniformly-spaced sequence be
From [10], by using the fractional order accumulation operator, we can also rewrite x(r)(k) as x(r)(k)=k∑i=1(k−i+r−1k−i)x(0)(i),k=1,2,…,n. Here, (mn):=m!(m−n)!n! and (0n):=1,(n+1n):=0. In the following discussion, we mainly focus on r=2.
From Eq (2.1), we can obtain 1-AGO sequence X(1) and 2-AGO sequence X(2) as follows
From Eq (2.2), we can see that the 2-AGO sequence X(2) has convexity property, that is x(1)(k+2)=x(2)(k+2)−x(2)(k+1)≥x(2)(k+1)−x(2)(k)=x(1)(k+1). Suppose that x(2)(t) meets the following second order grey forecasting differential equation
d2x(2)(t)dt2+a1dx(2)(t)dt+a2x(2)(t)=b,
(2.3)
where α=(a1,a2,b)T is the parameter in the model to be estimated.
The corresponding characteristic function of Eq (2.3) is r2+a1r+a2=0. Consider the case that Δ=a21−4a2>0, then the roots of the characteristic function are r1,2=−a1±√Δ2.
Thus, the solution of Eq (2.3) with the initial condition ˜x(2)(1)=x(2)(1),˜x(2)(n)=x(2)(n) is as follows
Therefore, to obtain the prediction model of the original data sequence, we need to identify the effect of α. For this purpose, we do the integral accumulation on both sides of Eq (2.3) in each interval [k,k+1],k=1,2,…,n−1, then we can get
Let background value be z(2)(k+1):=∫k+1kx(2)(t)dt. In order to calculate the background value z(2)(k+1), we need to integrate x(2)(t), which requires the value of α to be given in advance. However, the value of α needs to be determined from the Eq (2.4). Consequently, to estimate the value of α, we must use some methods to estimate the background values z(2)(k+1), k=1,2,⋯,n−1. In the classical GM2(2,1) model, for t∈[k,k+1],k=1,2,…,n−1, we use the piecewise linear polynomial interpolation Lk(t):=(k+1−t)x(2)(k)+(t−k)x(2)(k+1) as an approximate solution of x(2)(t), that is x(2)(t)≈Lk(t) for t∈[k,k+1],k=1,2,…,n−1. Then we get the estimated background values z(2)(k+1), k=1,2,…,n−1 as follows
For dx(2)(t)dt|t=1, by setting x(2)(0)=0, then we get dx(2)(t)dt|t=1≈x(2)(1)−x(2)(0)=x(2)(1).
For each interval [k,k+1], k=1,2,…,n−1, by substituting the estimated background values z(2)(k+1) given in Eq (2.5) and the approximate derivative values dx(2)(t)dt|t=k+1 and dx(2)(t)dt|t=k into Eq (2.4), we have
With the estimated parameter α=(a1,a2,b)T, we further get the solution ˜x(2)(t) of the second order grad forecasting differential equation given in (2.3) with the initial condition ˜x(2)(1)=x(2)(1),˜x(2)(n)=x(2)(n). Finally, we get the following classical GM2(2,1) prediction formula
Given convexity data set {(xk,yk)∈R2}nk=1 with Δ1<Δ2<…<Δn−1, where x1<x2<…<xn and Δk=[yk+1−yk]/[xk+1−xk],k=1,2,…,n−1. For x∈[xk,xk+1], k=1,2,…,n−1, Let hk=xk+1−xk,t=(x−xk)/hk,Ak=Δk−dk,Bk=dk+1−Δk, then the C1 convexity-preserving rational quadratic interpolation spline S(x) developed in [19] is as follows
From Eq (3.1), it is easy to check that S(x+k)=yk,S(x−k+1)=yk+1,S′(x+k)=dk,S′(x−k+1)=dk+1, k=1,2,…,n−1 which implies that S(x)∈C1[x1,xn]. For Δ1<Δ2<…<Δn−1, from [19], we see that S″(x)>0, which means that S(x) has convexity-preserving properties. Furthermore, let f(x)∈C3[x1,xn] be a given convex function with which S(x) is compared and yi=f(xi),i=1,2,…,n, from [19], we have f(x)−S(x)=O(h3), which indicates that interpolant has O(h3) convergence. Since the C1 convexity-preserving rational quadratic interpolation spline S(x) developed in [19] has many merits, in the following we shall use it as approximate solution of x(2)(t) so as to estimate background values z(2)(k+1) and the derivative values dx(2)(t)dt|t=k+1 and dx(2)(t)dt|t=k and a method for estimating dx(2)(t)dt|t=1 will be given.
4.
Establish new GM2(2,1) model
For the original non-negative sequence X(0)={x(0)(1),x(0)(2),…,x(0)(n)}, we first calculate its 1-AGO sequence X(1)={x(1)(1),x(1)(2),…,x(1)(n)}, 2-AGO sequence X(2)={x(2)(1),x(2)(2),…,x(2)(n)}. From the above discussion, the 2-AGO sequence X(2) is a convex data set. The corresponding estimated function x(2)(t) has the property of convexity and C∞ continuity. Thus, we consider to reconstruct x(2)(t) with the C1 convexity-preserving rational quadratic interpolation spline developed in [19]. For the convex 2-AGO sequence data set {(xk,x(2)(k))∈R2}nk=1 with xk=k, for each of the subintervals [k,k+1], by using the C1 convexity-preserving rational quadratic interpolation spline given in (3.1) as approximate solution of x(2)(t), t∈[k,k+1], k=1,2,…,n−1, we have
where the derivative values dk, k=1,2,…,n are given by Eq (4.2).
Then, by substituting the estimated background values z(2)(k+1)=∫k+1kx(2)(t)dt and the estimated the derivative values dx(2)(t)dt|t=k+1 and dx(2)(t)dt|t=k, k=1,2,…,n−1 into the grey differential Eq (2.4) and applying the following least square method to solve Eq (2.4), we get
with dk, k=1,2,…,n are given by Eq (4.2) and z(2)(k+1)=∫k+1kx(2)(t)dtk=1,2,…,n−1 are given by Eq (4.3).
With the estimated parameter α=(a1,a2,b)T given by (4.5), we further solve the second order grad forecasting differential equation given in (2.3) with the initial condition ˜x(2)(1)=x(2)(1),˜x(2)(n)=x(2)(n), whose solution is denoted as ˜x(2)(t). Finally, we get the following new GM2(2,1) grey prediction formula
Summarize the above discussion, we give the following algorithm for establish our new grey prediction equation.
Algorithm 1 New grey prediction model based on a C1 convexity-preserving rational quadratic interpolation spline
Input: original non-negative and uniformly-spaced sequence X(0)={x(0)(1),x(0)(2),…,x(0)(n)}.
Output:grey prediction formula ˜x(0)(k), k=1,2,….
1: Compute the 2-AGO sequence X(2)={x(2)(1),x(2)(2),…,x(2)(n)} by Eq (2.2);
2: Compute the estimated derivative values dk, k=1,2,…,n by Eq (4.2);
3: Compute the estimated background values z(2)(k+1), k=1,2,…,n−1 by Eq (4.3);
4: Compute the estimated model parameter α by Eq (4.5);
5: With the estimated parameter α=(a1,a2,b)T, solve the second order grad forecasting differential equation given in (2.3) with the initial condition ˜x(2)(1)=x(2)(1),˜x(2)(n)=x(2)(n) so as to get ˜x(2)(t).
6: Get the grey prediction formula ˜x(0)(k), k=1,2,… by Eq (4.6).
5.
Numerical examples
We shall give several examples to show that the new GM2(2,1) model based on C1 convexity-preserving rational quadratic interpolation spline has better predict accuracy than the classical GM(2,1) model and GM2(2,1) model, Zeng's GM2(2,1) model given in [15] and Xu and Dang's GM(2,1) model given in [7]. In the following examples, the relative error is computed by
ε=|˜x(0)(k)−x(0)(k)|x(0)(k)×100%,k=1,2,….
Example 1.We take the total water consumption of Beijing from 2003 to 2019 in [20] as an example. We compare our new GM2(2,1) model with the classical GM(2,1) model, the classical GM2(2,1) model and Zeng's GM2(2,1) model given in [15]. We use the data from 2003 to 2015 as the training data and the data from 2016 to 2019 as the testing data. Table 1 gives the numerical results. The results show that the new GM2(2,1) has improved prediction accuracy compared to the classical GM(2,1) model, the classical GM2(2,1) model and Zeng's GM2(2,1) model.
Example 2.We take the precipitation data of Xichang City from 1986 to 1990 in [20] as the second example. We use the data from 1986 to 1989 as the training data and the data in 1990 as the testing data. From the numerical results presented in Table 2, it can be seen that compared with the classical GM(2,1) model, the classical GM2 (2,1) model and Zeng's GM2 (2,1) model given in [15], our new GM2 (2.1) has the best performance.
Example 3.In this example, we consider the historical syphilis incidence data of China from 2000 to 2008 given in [22].We use the data from 2000 to 2005 as the training data and the data from 2006 to 2008 as the testing data. We compare our new GM2(2,1) model with the classical GM(2,1) model, the classical GM2(2,1) model and Zeng's GM2(2,1) model given in [15]. Table 3 gives the numerical results. From the results, compared with the classical GM(2,1) model, the classical GM2(2,1) model and Zeng's GM2(2,1) model, the new GM2(2,1) has better performance.
Example 4.We take the data of inbound tourists (in 10,000 people) in Beijing from 2012 to 2019 as an example. The data comes from the Beijing Statistical Yearbook in Beijing Municipal Bureau of Statistics and Survey Office of the National Bureau of Statistics in Beijing. The unit is 10,000 people. We use the data from 2012 to 2015 as the training data and the data from 2016 to 2019 as the testing data. We compare our new GM2(2,1) model with the classical GM(2,1) model, the classical GM2(2,1) model and Zeng's GM2(2,1) model given in [15]. Table 4 gives the numerical results. From the results, compared with the classical GM(2,1) model, the classical GM2(2,1) model and Zeng's GM2(2,1) model, the new GM2(2,1) has the best prediction accuracy.
Example 5.In this example, we consider the data of tourists staying overnight in Guangzhou (in 10,000 people) from 2010 to 2019, which is from the Guangzhou Statistical Yearbook of Guangzhou Municipal Bureau of Statistics.The data from 2010 to 2015 are taken as the training data and the data from 2016 to 2019 are used as the testing data. Best prediction accuracy using our new GM2(2,1) model can be founded from the numerical results presented in Table 5, compared with the classical GM(2,1) model, the classical GM2 (2,1) model and Xu and Dang's GM(2,1) model given in [7].
Example 6.We take the data on China's foreign exchange reserves (in trillion dollars) from 2010 to 2021. The data is from the China Statistical Yearbook of National Bureau of Statistics of China. We use the data from 2010 to 2018 as the training data and the data from 2019 to 2021 as the testing data. We compare our new GM2(2,1) model with the classical GM(2,1) model, the classical GM2(2,1) model and Xu and Dang's GM(2,1) model given in [7]. Table 6 gives the numerical results. From the results, compared with the classical GM(2,1) model, the classical GM2(2,1) model and Xu and Dang's GM(2,1) model, the new GM2(2,1) has the best prediction accuracy.
Example 7.We take the data of inbound tourists (in 10,000 people) in Zaozhuang from 2005 to 2019 as an example. The data comes from the Ministry of Culture And Tourism of the People's Republic of China. The unit is 10,000 people. We use the data from 2005 to 2017 as the training data and the data from 2018 to 2019 as the testing data. We compare the new GM2(2,1) model with the classical GM(2,1) model, the classical GM2(2,1) model and the OFOPGM model given in [23]. Table 7 gives the numerical results. From the results, the new GM2(2,1) model has better prediction accuracy.
According to the results of the above numerical examples1–6, the prediction accuracy of our new GM2(2,1) model is improved for all the numerical examples compared to the classical GM(2,1) model, the classical GM2(2,1) model, Zeng's GM2(2,1) model given in [15], Xu and Dang's GM(2,1) model given in [7] and the OFOPGM model given in [23]. There are different degrees of improvement for different data features. Based on the above data characteristics, we make the conclusion that the more convexity the original datas presents the higher the prediction accuracy of the new GM2(2,1) model, the better the actual prediction effect.
6.
Conclusions
Using the C1 convexity-preserving rational quadratic interpolation spline developed in [19] to estimate the background values and derivative values, we established a new GM2(2,1) model. Numerical examples show that the new GM2(2,1) model can improve the forecasting quality, especially in prediction reliability and this model performs better when the original data are presented with convexity in time series. There is a limitation in the new method: The computations concerning the background values and derivative values take more time than the methods included in classical GM2(2,1) model. Future work will concentrate on applying C1 convexity-preserving rational quadratic interpolation spline to establish a new GMr(2,1) model with fractional r.
Use of AI tools declaration
The author declares he has not used Artificial Intelligence (AI) tools in the creation of this article.
Acknowledgments
The research is supported by the National Natural Science Foundation of China (No. 61802129).
Conflict of interest
The author declares no conflict of interest.
Acknowledgments
This research received funding from CONACYT, grant number 319684. The authors are pleased to acknowledge the DICTUS, CIAD, DIPA, and DIPM spectroscopy laboratory of Universidad de Sonora for use of the facilities to characterize the material.
Conflict of interest
All authors declare no conflicts of interest in this paper.
Author contributions
Ricardo I. González-Vega: Conceptualization, methodology, formal analysis, investigation, writing—review and editing, visualization, supervision. Carmen L. Del-Toro-Sánchez: resources, writing—review and editing. Ramón A. Moreno-Corral: methodology, writing—review and editing. José A. López-Elías: resources, writing—review and editing. Aline Reyes-Díaz: methodology, writing—review and editing. Norma García-Lagunas: formal analysis, writing—review and editing. Elizabeth Carvajal-Millán: Supervision, Project administration, Funding acquisition, Conceptualization, Writing- Reviewing and Editing, Validation. Diana Fimbres-Olivarría: Conceptualization, methodology, investigation, writing—original draft preparation, writing—review and editing, visualization, supervision.
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Ricardo I. González-Vega, Carmen L. Del-Toro-Sánchez, Ramón A. Moreno-Corral, José A. López-Elías, Aline Reyes-Díaz, Norma García-Lagunas, Elizabeth Carvajal-Millán, Diana Fimbres-Olivarría. Sulfated polysaccharide-rich extract from Navicula incerta: physicochemical characteristics, antioxidant activity, and anti-hemolytic property[J]. AIMS Bioengineering, 2022, 9(4): 364-382. doi: 10.3934/bioeng.2022027
Ricardo I. González-Vega, Carmen L. Del-Toro-Sánchez, Ramón A. Moreno-Corral, José A. López-Elías, Aline Reyes-Díaz, Norma García-Lagunas, Elizabeth Carvajal-Millán, Diana Fimbres-Olivarría. Sulfated polysaccharide-rich extract from Navicula incerta: physicochemical characteristics, antioxidant activity, and anti-hemolytic property[J]. AIMS Bioengineering, 2022, 9(4): 364-382. doi: 10.3934/bioeng.2022027
Figure 1. FT-IR spectrum of SPNi. The principal absorption bands are indicated
Figure 2. 1H-NMR spectrum of extracellular sulfated polysaccharide from Navicula incerta in D2O solution. R-GP= Region of Glycoside Peaks. Glu: Glucose, Man: Mannose, Xyl: Xylose, Gal: Galactose, and Rha: Rhamnose
Figure 3. Antioxidant activity of SPNi. (A) Reducing power by FRAP at different times (min) expressed as µmol Trolox equivalent/g (µmol TE/g D.W.), (B) Free radical scavenging by ABTS·+ inhibition (%) assay and (C) Hemolysis inhibition (%) at different concentrations (mg/mL). Gallic acid (100 µg/mL) was used as standard in the ABTS inhibition assay. The control used in the hemolysis inhibition assay was a mixture of free radical generator AAPH and RBCs. The data represent the mean ± standard deviation. Different letters indicate significant differences (p ≤ 0.05)
Figure 4. Optical micrograph of (a) erythrocyte: negative control, (b) erythrocyte + AAPH radical: positive control and (c) erythrocyte + AAPH radical + SPNi: treatment. Magnification x100, scale bar 5 µm