A New Material Based on Clay and its Successful Application to Fix the Glucose

Introduction

There are a wide variety of argillaceous rocks, depending on their structure and mineralogical composition, of which only few are used in medical therapy¹. Each of these clays can, very often, shows some specific therapeutic virtues.Although they present in general a number of similar properties that characterize them.

The montmorillonitestudied in the present work are of colloidal clays ², which received multiple applications, dueto their high exchange capacity and swelling as well as their rheological properties (thixotropy) ³. They are therefore used in various fields such as drilling, foundry, ceramics, pharmacy, … etc.

In the present studywe aimed to use a material and a compensating cationin which the retention of glucose is the most important (KSF-Fe²⁺). The kinetics of contact between  clayand solutions of glucose was investigated to search for an optimal time giving a better retention. In this article, the results obtained by the combined use of X-ray diffraction, IR, thermal analysis and Mossbauer spectroscopy are described. These analyses were carried out with the objective of determining the state of the iron in montmorillonite structure, and to characterize the interaction between montmorillonite exchanged By ferrous ions and glucose.

Experimental section

Preparation of the adsorbents

All experiments in this work were carried out on a same bacthof montmorillonite KSF supplied by Aldrich.It is a commercial montmorillonite, calcium-rich form of gray powder.
The mass ratios of oxides of the elements forming this clay are given in Table 1.

Table 1: Chemical composition (in wt%) of montmorillonite KSF⁴

Oxide	Al2O3	SiO2	Na2O	MgO	P2O5	K2O	CaO	TiO2	MnO	Fe2O3
٪	14.93	69.31	0.14	2.19	0.09	1.17	2.08	0.44	0.01	3.97

 

The  exchange by Fe²⁺

The cation exchange Fe²⁺was selected based on its capacity to form a complex with glucose.
In order to investigate the potential fixation of glucose, three materials referenced as FM₃, FM₈ and FM₁₁wereprepared and subjected to a cation exchange with ferrous ions by varying the exchange time asindicated in following chart (Fig.1).The studied materials were then characterized.

Figure 1: chart represents the exchange of KSF by ferrous ions Click here to View figure

 

Determination of glucose

The determination of glucose was achieved by an enzymaticmethod reaction, as described previously ^5,6. The assessmentswere performed using a spectrophotometer (Shimadzu Corporation, Japan 1200 UV). The peak wavelengths were obtained directly by an automatic scanning between 200 to 800 nm.

Principle

Glucose is oxidised to gluconic acid and hydrogen peroxide in the presence of glucose oxidase. Hydrogen peroxide further reacts with phenol and 4-aminoantipyrine by the catalytic action of peroxidase to form a red colouredquinoneimine dye complex. Intensity of the colour

formed is directly proportional to the amount of glucose present in the sample^7,8,9.

 

 

Procedure

Wavelength: 505 nm

Temperature: 37°C

Light path: 1cm

Addition Sequence	Blank(ml)            Standard                      Test
Glucose Reagent (L1)	1(ml)                         1(ml)              1(ml)
Distilled water	1(µl)                        –                                        –
Glucose standard	–                                  1(µl)                                 –
Sample	–                                –                                1(µl)

 

Mix well and incubate at 37°C for 10 mins,

Measure absorbance of the Standard (Abs.S) and Test Sample (Abs.T)

Calculations

Abs.T

Total Glucose in mg/dl =  ————  x 100

Abs.S

Cinétique adsorption

It was necessary to follow the kinetics of the adsorption of glucose to determine the conditions for maximal binding. For this, three suspensions containing 250ml of glucose solution at 2 g/l and 1.5g FM₃,FM₈ and FM₁₁, were kept under stirring followed by a centrifugation at 4500rpm/min then assayed as described above.

Results and discussion

Adsorption kinetics

As shown in the (Fig 2), the maximum adsorption rate for the three materials used ( FM₃, FM₈, and FM₁₁) are 23.5%, 40.5% and 29.5%, respectively.

Figure 2: The % rate  of the adsorption of glucose  by the studied materials: FM3,FM11, FM8 Click here to View figure

 

Interestingly,  the FM₈ material, prepared using Fe(II) exchanged montmorillonite KSF for an exchange time of 8 hours gives an adsorption rate of 40.5% glucose, which is much higher when compared to those obtained with the other two materials (FM₃ and FM₁₁).

Characterization by XRD

Powder pattern where recorded on a PHILIPS X’Pert MPD θ-θ diffractometer equipped with the X’Celerator detector with Cu Kα radiation (λ = 1.5418 Å) and nickel filter »The different results regarding the XRDcharacterization of the studied samples
are summarized in the Fig.3. Examination of this recorded diffractogram and peak list show that the basic structure of the aluminosilicates is maintained and the values of angle  are bandsq2 Characteristics of montmorionite. It seems clearly that the distance d₀₀₁ of exchanged montmrillonite by ions ferrous  affected a slight change in the inter-fowl distanceafter the fixation of glucose.

Figure 3: X-ray powder patterns of the studied samples FM8 and FM8-G  Click here to View figure

 

Characterization by IR

The use of infrared spectroscopy allows determininginformation about the different absorption bands existing in the material FM₈-G. The IRTF spectrum examination (Fig. 4) shows the following bands: An intense strip at 3450 cm ^-1 and a strip at about 1630 cm ^-1; Are relative to the modes of vibration of the water molecules adsorbed in the inter-sheet           space ^10,11,12, the bands located around 1050 cm ^-1 and 910 cm ^-1 and 840 cm ^-1 are assigned respectively to the “Elongation of the Si-O bond; The deformation of the Al-Al-OH bond and the deformation of the Al-Mg-OH bond, the band located around 780 cm^-1 is due to the elongation vibration of the bond Si-O bond^13,14, we noticed an appearance of new band at 1150cm^-1 correspond tonC-O and Another band located around 1420 cm ^-1 is assigned d CH₂+d OCH+dCCH.

This result could confirm that the fixation of glucose was achieved successfully.

Figure 4: Infrared spectrum of FM8-G  Click here to View figure

 

Thermal gravimctric analysis 

The process of weight loss can be devised two stapes the firstweight loss observed Around 100 °C is attributed to the desorption of water ( with may be physical or chemical adsorption on the interpaticle surface of two samples (FM₈ and FM₈-G), the second stap from 560 to 600 °C with the main weight loss  can correspond to the weight loss caused by breaking the Calcite¹⁵. In the sample  FM₈-Gthere is a loss of weight around 350°C and 410 °C corresponds to the decomposition of the glucose.

Figure 5: Thermal gravimetricanalysis  ofstudied samples FM8 and FM8-G  Click here to View figure

 

Mossbauer analysis

A typical Mossbauer spectrum of FM₈ is shownin(Fig. 6), whereas the computer-fitted parametersfor the sample studied are given in Table 3.

Iron is present in 5 forms, 2 Fe²⁺ kinds (15%) and 3 types of Fe³⁺ (85%)

Figure 6: Room temperature Mossbauer spectrum of FM8 sample. Click here to View figure

 

Table 3: Mossbauer parameters at room temperature of FM₈

FM8	IS, mm/s			QS, mm/s			LW, mm/s			Contribution %
Comp1	1.09	±	0.02	2.00	±	0.03	0.32	±	0.03	13	±	5
Comp2	1.06	±	-1.00	2.82	±	-1.00	0.23	±	-1.00	2	±	-1
Comp3	0.36	±	0.00	1.21	±	0.01	0.30	±	0.02	38	±	5
Comp4	0.36	±	0.01	0.68		0.07	0.56	±	0.06	34	±	7
Comp5	0.44	±	0.01	0.22	±	0.03	0.31	±	0.08	12	±	4

 

Conclusion

This study describes the preparation of a  new material based on clay: montmorillonite Fe²⁺ shows a high percentages of glucose capture.

The results showed an important adsorption of glucose (around 40,5%) with compensating cation (Fe (II) – KSF) at 8 hours where the exchange of montmorillonite KSF with ferrous ions. ), this sample is identified as FM_8.

The use of infrared spectroscopy allows determining informations about the different absorption bands existing, appearance of new band at 1150cm^-1 correspond to nC-O and Another band located around 1420 cm -1  is assigned d CH₂+d OCH+dCCH.

The t Thermogravimetric analysismakes it possible to follow the loss of mass of the sample as a function of the temperature, In the sample  FM₈-Gthere is a loss of weight around 350°C,380°C and 410 °C corresponds to the decomposition of the glucose

Mossbauer spectroscopy were carried out  the state of oxidation of ferrous ions in montmorillonite structure.

This result could confirm that the fixation of glucose was achieved successfully.

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