CN102707012A - Narrow band thin-layer chromatographic sheet and preparation method thereof - Google Patents
Narrow band thin-layer chromatographic sheet and preparation method thereof Download PDFInfo
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- CN102707012A CN102707012A CN2012101467623A CN201210146762A CN102707012A CN 102707012 A CN102707012 A CN 102707012A CN 2012101467623 A CN2012101467623 A CN 2012101467623A CN 201210146762 A CN201210146762 A CN 201210146762A CN 102707012 A CN102707012 A CN 102707012A
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Abstract
The invention relates to a narrow band thin-layer chromatographic sheet which comprises a base plate. A straight groove is arranged on the chromatograph base plate, a fixed phase is precipitated in the straight groove, and fixed phase substances are selected from silver iodide, barium fluoride, calcium fluoride, silver bromide or zinc sulfide. The fixed phase of the chromatographic sheet is small in consumption, the cost is low, the detection sensitivity is high, the plating time is short, and the usage is convenient.
Description
Technical field
The present invention relates to thin-layer chromatography and infrared spectrum technology used in conjunction, be specifically related to can with arrowband thin-layer chromatography of red spectrum coupling and preparation method thereof.
Background technology
Thin-layer chromatography is a kind of quick, easy, efficient, economic, widely used chromatogram analysis method, on the different components of separating mixture, huge advantage is arranged, but to there are not certain limitation in the detecting of principal component, evaluation aspect after separating; And infrared spectrum energy helps the identification organo-functional group, by finger-print and huge ir data storehouse, the not principal component after the thin-layer chromatography separation is identified.Both couplings will greatly improve the analytic ability to complex mixture, be one and will have wide application prospect, worth analysis of Development technology, thereby receive much concern.
As far back as the sixties in last century, reported in literature, for example R.N.McCoy have just been seen in the coupling work of thin-layer chromatography and infrared spectrum; E.C.Fiebig, technique for obtaining infrared spectra of microgram amounts of compounds separated by thin layer chromatography, Anal.Chem.; 37,593-595,1965 with Priscilla A.Sturm; R.M.Parkhurst, W.A.Skinner, Quantitative Determination of Individual Tocopherols by Thin Layer Chromatographic Separation and Spectrophotometry; Anal.Chem.; 38,1244,1966.Mainly be the component transfer earlier after with the method that solvent elution shifts thin-layer chromatography being separated at that time, carry out infrared microscopy again and detect.Complicated operating process is loaded down with trivial details, and has brought sample loss, impurity to introduce equivalent risk.
Consider this limitation; 1975; Percival and Griffiths are with passing through the base plate of the silver chloride film of infrared light as thin layer plate; With silica gel, the aluminium oxide phase that fixes, first the sample strip through Thin-layer separation is carried out examination of infrared spectrum, started the beginning of thin-layer chromatography-infrared spectrum coupling in site measurement method.
Afterwards; Fuller and Griffiths, Zuher replace the transmitted infrared light spectrum to carry out thin-layer chromatography-infrared spectrum coupling in site measurement with diffuse reflectance IR; But because of traditional TLCP stationary phase silica gel, aluminium oxide etc. stronger to the background absorption of mid-infrared light; The not detection of principal component after having a strong impact on thin-layer chromatography and separating, this method slower development.
Last century the nineties; Danielson proposes to carry out thin-layer chromatography with the more weak zirconia of infrared absorption as stationary phase to be separated; To alleviate the interference of stationary phase], this method has significantly improved the sensitivity of thin-layer chromatography-infrared spectrum, but because zirconium matrix contains a certain amount of planar water; Can produce very strong background absorption, still have adverse effect detecting effect.Therefore the in-situ method development of carrying out thin-layer chromatography-infrared spectrum coupling receives great restriction, and afterwards, this method almost is absorbed in dead state.
In order to give full play to the advantage of in-situ method thin-layer chromatography and infrared spectrum coupling, on the basis of theory, we attempt seeking do not absorb mid-infrared light material as stationary phase, fundamentally solve because of the thin-layer chromatography stationary phase and absorb influence infrared detection.
In previous work, we adopt " sedimentation volatility process " to prepare smooth TLCP, referring to one Chinese patent application CN201010118502.6.But the thin layer plate that this patent provides has following shortcoming:
(1) adopt in the process of " sedimentation volatility process " preparation thin layer plate, the consumption of stationary phase is big.When suspension being poured in the container into sedimentation, the full wafer TLCP all is fixed and covers mutually.Because the stationary phase consumption is big, as far as expensive stationary phase, the cost problem will certainly restrict its application in thin-layer chromatography and infrared spectrum coupling;
(2) component after thin layer plate separates, the infrared spectrum detection limit is lower.Because of the thickness of thin layer plate is very little, have only about 20 μ m, can only a point sample.Under the very little situation of point sample; Because thin-layer chromatography separates the diffusion of back spot, influences such as hangover are found when sample concentration is lower than 0.5% in the experiment; Component after thin-layer chromatography separates just can not be arrived by infrared light detection, and this weakness has also influenced the development of thin-layer chromatography and infrared spectrum;
(3) preparation time of thin layer plate is long.In the preparation process, a small amount of stationary phase must be disperseed by a large amount of dispersing liquids (like water or ethanol), and is few like the consumption of dispersing liquid, the uneven distribution of the TLCP of then making and easy of crack.When room temperature was lower, the ethanol of adding volatilizees fully needed about three days time.To a certain extent, the long extensive use that can influence it of thin layer plate preparation time.In addition, the use of a large amount of separatory possibly come pollution problem and potential safety hazard at large-scale production process from now on.
In order to promote thin-layer chromatography and infrared spectrum coupling technique, reduce cost, improve detection sensitivity, reduce the making sheet time, improve application flexibility, also need further improve chromatosheet.
Summary of the invention
In order to address the above problem, the inventor has carried out research with keen determination, and the result finds: through on substrate, offering straight grooves; Through subsidence style stationary phase is fallen in the groove, obtain the arrowband TLCP, when using this arrowband thin-layer chromatography that sample is carried out the thin-layer chromatography separation; The transverse dispersion of sample on chromatosheet is suppressed, and the sample point after the separation obviously reduces, and can detect the sample of 0.1% concentration; Can directly be used for infrared spectrum and detect, thereby accomplish the present invention.
The object of the present invention is to provide a kind of arrowband TLCP, it comprises substrate, on chromatographic substrate, offers straight grooves, and wherein sedimentation has stationary phase, and wherein, the stationary phase material is selected from: silver iodide, barium fluoride, calcium fluoride, silver bromide or zinc sulphide.
Another object of the present invention is to provide the preparation method of a kind of arrowband TLCP, this method comprises:
(1) the stationary phase material is ground to form fine powder,
(2) the stationary phase fine powder is mixed with dispersion liquid, under the ultrasound wave effect, forms suspending liquid,
(3) suspending liquid is dosed in the straight grooves of offering on the chromatographic substrate, treats promptly to obtain the arrowband TLCP after the dispersion liquid volatilization.
Arrowband provided by the invention TLCP has the following advantages:
(1) the stationary phase consumption is few, and cost is low;
(2) through deepening the thickness that depth of groove improves the arrowband TLCP, can improve the point sample number of times, and because the chromatosheet narrow width, under the restriction of groove two side, the transverse dispersion of sample is suppressed effectively, detection sensitivity significantly improves;
(3) the making sheet time is very short;
(4) thus the arrowband TLCP is effectively protected by the chromatographic substrate support, be not easy breakage, deposit and facility safe in utilization;
(5) sample is after arrowband thin-layer chromatography plate development separates, because the transverse dispersion of sample is suppressed, thereby distributes in the sample sets, is convenient to follow-up infrared detection.
Description of drawings
Fig. 1 a is illustrated in the synoptic diagram of gained arrowband TLCP in the embodiment of the invention 1.
Fig. 1 b is illustrated in the synoptic diagram of arrowband TLCP according to the preferred embodiment of the present invention
Fig. 2 is illustrated in the embodiment of the invention 2 synoptic diagram of arrowband TLCP after the sample separation.
Fig. 3 is illustrated in the infrared spectrogram of rhodamine sample in the embodiment of the invention 2.
Wherein a is the transmitted infrared light spectrum of rhodamine B
B is the reflection absorption ftir spectroscopy of 1% rhodamine B
Infrared spectrogram after Fig. 4 illustrates bromcresol green in embodiments of the present invention and rhodamine B separates.
Wherein, wherein a is the transmitted infrared light spectrum of rhodamine B,
B is the reflection absorption ftir spectroscopy of 0.5% rhodamine B,
C is the reflection absorption ftir spectroscopy of 0.2% rhodamine B,
D is the reflection absorption ftir spectroscopy of 0.1% rhodamine B,
Embodiment
Describe the present invention below, characteristics of the present invention and advantage will become more explicit along with these descriptions.
According to an aspect of the present invention, a kind of arrowband TLCP is provided, it comprises substrate, on substrate, offers straight grooves, and wherein sedimentation has stationary phase, and wherein, the stationary phase material is selected from: silver iodide, barium fluoride, calcium fluoride, silver bromide or zinc sulphide.
In arrowband according to the present invention TLCP,, can use thin-layer chromatography substrate commonly used, like glass plate, quartz glass plate, sheet metal as substrate.
On a substrate, can offer several straight grooves in order to preparation arrowband TLCP.
For the straight grooves of on substrate, offering, the not special restriction of its size.But; Taking all factors into consideration cost, separating effect, detection sensitivity and do not influencing under the situation of aspects such as infrared spectrum detection, the width of preferred straight grooves is 0.1-1.5mm, preferably about 1mm; The degree of depth of preferred straight grooves is 50-500 μ m, preferably about 100-120 μ m.
Very narrow in view of recess width, the width of the arrowband TLCP that forms thus is also very narrow, and utensil that point sample is used such as diameter capillaceous maybe be greater than the width of arrowband TLCP, so point sample can be had any problem.In preferred embodiments, the width of groove one end end can suitably increase, and for example uses diameter capillaceous greater than point sample, guarantees that the arrowband TLCP one end width that forms uses diameter capillaceous greater than point sample, so that point sample.Thus, not only can be so that point sample, and; Because groove remainder width is less than this end width; Then sample makes transverse dispersion further be suppressed owing to the chromatosheet width diminishes when being launched forward by the end, thereby further improves detection sensitivity and accuracy.
In arrowband according to the present invention TLCP; As stationary phase; Can use the material that is selected from silver iodide, barium fluoride, calcium fluoride, silver bromide and the zinc sulphide etc., preferably use silver iodide, this is because silver iodide almost do not absorb infrared light; And absorb water hardly, very little to the influence of infrared spectrometry.Under the situation that absorbs small amount of moisture, can remove adsorbed moisture through heating, can eliminate influence like this to infrared spectrometry.
In order further to avoid substrate, in preferred embodiment, on the groove of substrate, infrared light reflecting film is set, for example silver or golden to the influence that infrared spectrum detects.Infrared light reflecting film can not given unnecessary details at this through known method settings such as plating, coating, depositions.The emission infrared light can not avoided the absorption of substrate to infrared light thus fully because infrared light reflecting film does not absorb infrared light, guarantees that infrared detection result's accuracy is higher.
According to a further aspect in the invention, the preparation method of a kind of arrowband TLCP is provided, this method comprises:
(1) the stationary phase material is ground to form fine powder,
(2) the stationary phase fine powder is mixed with dispersion liquid, under the ultrasound wave effect, forms suspending liquid,
(3) suspending liquid is dosed in the straight grooves of offering on the chromatographic substrate, treats promptly to obtain the arrowband TLCP after the dispersion liquid volatilization.
In arrowband TLCP preparation method according to the present invention,, can use ethanol, water as dispersion liquid.
In arrowband TLCP preparation method according to the present invention, ultrasound wave helps to form at short notice uniform suspending liquid.
In arrowband TLCP preparation method according to the present invention, after dispersion liquid volatilization, in order to obtain smooth arrowband TLCP, preferably with groove surfaces floating/push away flat.
Adopt " sedimentation volatility process " preparation thin layer plate, adding ethanol is more before, and volatilization needs about three day time fully, and among the preparation method of the present invention, dispersion liquid such as ethanol volatilize fully only to be needed about 0.5h.
In addition, the inventive method has reduced the consumption of stationary phase.Under the situation of same consumption stationary phase, adopt " sedimentation volatility process " can only prepare a TLCP before, and can obtain five arrowband TLCPs through preparation method of the present invention.In every block of thin layer plate on average, it is original 1/5th that the silver iodide consumption is reduced to, and for expensive stationary phase such as silver iodide, can significantly reduce cost.
Embodiment
On the flass plate, offer two straight grooves, recess width is that 1mm, the degree of depth are about 110 μ m, and 3.0g silver iodide nano particle is joined in the mortar, fully grinds; Add 15ml ethanol gradually, change in 30 * 60 the measuring cup sonicated 2min over to; Form denseer suspension, leave standstill 2min after, the upper strata suspension is transferred to another measuring cup; Suspension is joined in the groove of flass plate, treats ethanol volatilization back (about 20min), with the same direction in microslide edge in the surperficial horizontal sliding of thin layer plate; Remove and remain near the silver iodide of groove, make the arrowband TLCP of surfacing, as shown in Figure 1.
Adopt " sedimentation volatility process " preparation thin layer plate, adding ethanol is more before, and volatilization needs about three day time fully, only needs about 0.5h and implement this preparation method; On the other hand, reduced the consumption of stationary phase, in working, the 3.0g silver iodide can only prepare three blocks of thin layer plates before, and the 3.0g silver iodide but can prepare 15 blocks of thin layer plates now.Average to every block of thin layer plate, it is original 1/5th that the silver iodide consumption is reduced to, and to this expensive stationary phase of silver iodide, the minimizing of consumption has very big benefit to its widespread use undoubtedly.
The thin-layer chromatography of embodiment 2 arrowband TLCPs-infrared spectrum is used
Take by weighing 0.1g rhodamine B and 0.1g bromcresol green respectively in measuring cup, add the 10ml absolute ethyl alcohol respectively, be mixed with the pure article solution of the bromcresol green of 1% the pure article solution of rhodamine B and 1%; Be mixed with 0.5%, 0.2%, 0.1% rhodamine B and bromcresol green mixed solution more respectively.
At first with the pure article point sample of 1% rhodamine B, measure reflection absorption ftir spectroscopy, secondly use 0.5%, 0.2%, 0.1% biased sample point sample respectively, developping agent is V
Ethanol: V
Ethyl acetate: V
Ammoniacal liquor=25:15:1, after the expansion, the separating fully of bromcresol green and rhodamine B, it is as shown in Figure 2 to separate arrowband, back TLCP, and visible, the sample point after the separation is less, and sample room separates fully.
Thin layer plate after separating in 120 ℃ of oven dry 2h, is cooled to room temperature, carries out In-situ Infrared and detect, the result is shown among Fig. 3.Can know by Fig. 3, at 4000-800cm
-1The reflection absorption ftir spectroscopy of the pure article of interior rhodamine B and its transmitted infrared light spectrum basically identical explains that silver iodide are the infrared detection that the thin layer plate of stationary phase does not influence sample.
The thin-layer chromatography of embodiment 3 arrowband TLCPs-infrared spectrum is used
According to implement in 2 same method and carry out thin-layer chromatography-infrared spectrum and detect, difference only is that sample is bromcresol green and rhodamine B potpourri, sample concentration is 0.5%.
The infrared spectrum that separates the back sample is illustrated among Fig. 4.
The thin-layer chromatography of embodiment 4 arrowband TLCPs-infrared spectrum is used
According to implement in 2 same method and carry out thin-layer chromatography-infrared spectrum and detect, difference only is bromcresol green and rhodamine B potpourri, sample concentration is 0.2%.
The infrared spectrum that separates the back sample is illustrated among Fig. 4.
The thin-layer chromatography of embodiment 5 arrowband TLCPs-infrared spectrum is used
According to implement in 2 same method and carry out thin-layer chromatography-infrared spectrum and detect, difference only is bromcresol green and rhodamine B potpourri, sample concentration is 0.1%.
The infrared spectrum that separates the back sample is illustrated among Fig. 4.
Can know that by Fig. 4 when sample concentration was reduced to 0.1%, the reflection absorption ftir spectroscopy of rhodamine B was at 2300-800cm
-1Interior and transmitted infrared light is composed still basically identical.
More than through embodiment and embodiment the present invention is described in detail, but these embodiment only are illustrative, scope of the present invention are not constituted any restriction.It will be appreciated by those skilled in the art that under the situation that does not exceed spirit and scope of the invention can carry out replacement, modification or the improvement of multiple equivalence to technical scheme of the present invention and embodiment thereof, these all should fall in the scope of the present invention.Scope of the present invention is as the criterion with appended claims.
All documents of mentioning in the literary composition are incorporated herein by reference at this in full.
Claims (7)
1. arrowband TLCP, it comprises substrate, on chromatographic substrate, offers straight grooves, and wherein sedimentation has stationary phase, and wherein, the stationary phase material is selected from: silver iodide, barium fluoride, calcium fluoride, silver bromide or zinc sulphide.
2. arrowband according to claim 1 TLCP, wherein, substrate can be glass plate, quartz glass plate or sheet metal.
3. arrowband according to claim 1 TLCP wherein, is provided with infrared light reflecting film on the groove of substrate.
4. according to each described arrowband TLCP among the claim 1-3, wherein, groove one side end width is bigger than the width of groove remainder, and correspondingly, stationary phase one end width is bigger than stationary phase remainder width on the arrowband TLCP.
5. the preparation method of an arrowband TLCP, this method comprises:
(1) the stationary phase material is ground to form fine powder;
(2) the stationary phase fine powder is mixed with dispersion liquid, under the ultrasound wave effect, form suspending liquid;
(3) suspending liquid is dosed in the straight grooves of offering on the chromatographic substrate, treats promptly to obtain the arrowband TLCP after the dispersion liquid volatilization.
6. method according to claim 4, wherein, dispersion liquid is an ethanol.
7. according to each described arrowband TLCP application in thin-layer chromatography-infrared spectrum coupling technique among the claim 1-4.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104655787A (en) * | 2015-01-26 | 2015-05-27 | 北京大学 | Narrow-band spiral chromatographic sheet and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2192876A1 (en) * | 1972-07-21 | 1974-02-15 | Zeiss Jena Veb Carl | Frame for several chromatograms of differing dimensions - slotted to support rods or plates carrying thin layer or paper media |
| JPH03165260A (en) * | 1989-11-22 | 1991-07-17 | Nissha Printing Co Ltd | Plate for thin-layer chromatography and production thereof |
| CN2515676Y (en) * | 2001-12-19 | 2002-10-09 | 胡滨 | Multiple-grooved chromatographic thin plate |
| CN102192968A (en) * | 2010-03-05 | 2011-09-21 | 北京大学 | Thin-layer chromatographic plate and TLC (thin-layer chromatography)-infrared spectrography coupled combined method using same |
-
2012
- 2012-05-11 CN CN201210146762.3A patent/CN102707012B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2192876A1 (en) * | 1972-07-21 | 1974-02-15 | Zeiss Jena Veb Carl | Frame for several chromatograms of differing dimensions - slotted to support rods or plates carrying thin layer or paper media |
| JPH03165260A (en) * | 1989-11-22 | 1991-07-17 | Nissha Printing Co Ltd | Plate for thin-layer chromatography and production thereof |
| CN2515676Y (en) * | 2001-12-19 | 2002-10-09 | 胡滨 | Multiple-grooved chromatographic thin plate |
| CN102192968A (en) * | 2010-03-05 | 2011-09-21 | 北京大学 | Thin-layer chromatographic plate and TLC (thin-layer chromatography)-infrared spectrography coupled combined method using same |
Non-Patent Citations (2)
| Title |
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| 刘元瑞 等: "制备薄层色谱联合FTIR检测中药制剂中添加化学药品方法的研究", 《中国药学杂志》 * |
| 刘溪 等: "使用氟化钡作为固定相的薄层色谱-红外光谱联用研究", 《光谱学与光谱分析》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104655787A (en) * | 2015-01-26 | 2015-05-27 | 北京大学 | Narrow-band spiral chromatographic sheet and preparation method thereof |
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