CN1621487A - Porphyrin platinum complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing - Google Patents
Porphyrin platinum complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing Download PDFInfo
- Publication number
- CN1621487A CN1621487A CN 200410011163 CN200410011163A CN1621487A CN 1621487 A CN1621487 A CN 1621487A CN 200410011163 CN200410011163 CN 200410011163 CN 200410011163 A CN200410011163 A CN 200410011163A CN 1621487 A CN1621487 A CN 1621487A
- Authority
- CN
- China
- Prior art keywords
- oxygen
- molecular sieve
- luminous intensity
- weight ratio
- nitrogen
- 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.)
- Granted
Links
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 124
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000001301 oxygen Substances 0.000 title claims abstract description 123
- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000013335 mesoporous material Substances 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- -1 porphyrin platinum complexes Chemical class 0.000 claims description 3
- 244000178870 Lavandula angustifolia Species 0.000 claims description 2
- 235000010663 Lavandula angustifolia Nutrition 0.000 claims description 2
- 235000011194 food seasoning agent Nutrition 0.000 claims description 2
- 238000009415 formwork Methods 0.000 claims description 2
- 239000001102 lavandula vera Substances 0.000 claims description 2
- 235000018219 lavender Nutrition 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 abstract description 19
- 238000005406 washing Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000012265 solid product Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 108
- 229910052757 nitrogen Inorganic materials 0.000 description 54
- 238000011084 recovery Methods 0.000 description 21
- 229960001701 chloroform Drugs 0.000 description 19
- 230000005284 excitation Effects 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 9
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 9
- 244000038561 Modiola caroliniana Species 0.000 description 9
- 235000010703 Modiola caroliniana Nutrition 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 241001104043 Syringa Species 0.000 description 6
- 235000004338 Syringa vulgaris Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 102220500397 Neutral and basic amino acid transport protein rBAT_M41T_mutation Human genes 0.000 description 1
- NPRDEIDCAUHOJU-UHFFFAOYSA-N [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical class [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NPRDEIDCAUHOJU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000027734 detection of oxygen Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009711 regulatory function Effects 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The present invention relates to one kind of composite light emitting materials comprising compound formed with porphyrin ligand and metal platinum and inorganic mesoporous molecular sieve, and the application of these materials in oxygen sensing. Through dispersing and dissolving the mesoporous molecular sieve with the organic template agent eliminated in solvent; adding the compound formed with porphyrin ligand and metal platinum into the solution with the weight ratio between the compound and the mesoporous molecular sieve being 1-8 to 100; stirring to react for 1 hr; filtering; washing the solid product with the solvent the same as that in the mother liquid for 3-6 times and naturally drying in the air, the composite light emitting materials may be prepared. The materials are light purple and can emit light with peak wavelength of 630-680 nm under the irradiation of ultraviolet lamp.
Description
Technical field
The present invention relates to a class composite luminescent material and an application thereof, be specifically related to luminescent material that title complex that porphyrin part and metal platinum form is compounded to form with inorganic mesoporous molecular sieve and these materials in the application aspect the oxygen sensor.
Background technology
Embedded photoluminescent material and oxygen molecule effect can cause the variation of the luminous behaviors such as luminous intensity, spectrum and lifetime of excited state of light emitting molecule.This character is used to research and develop oxygen sensor in large quantities, and research fields such as medical diagnosis, industrial detection, environment protection, biological chemistry are all had very important meaning.This technology causes that because of it has characteristics such as rapid sensitive, nondestructive, relatively cheap, easy handling people favor more and more.Especially in the nearly more than ten years, relevant research is reported in a large number.Thereby light emitting molecules such as metal porphyrins have photochemistry, optical physics and thermostability that strong visible spectrum becomes reconciled and the long hair light life-span of excited state, big characteristics such as Stokes displacement to become the focus of research.
People such as Sang-Kyung Lee and Ichiro Okura have reported in 1997 five fluorine substituted-phenyl porphyrin platinum have been contained in preparation oxygen sensor material in the polystyrene, its selectivity numerical value I
0/ I
100(I herein,
0And I
100Represent 100N respectively
2And 100%O
2Luminous intensity under existing) greater than 3, the time of response was 18 seconds, and the recovery time is 1 minute (Sang-Kyung Lee, Ichiro Okura, Analytical Communications, 1997,34,85).In the same year, they also mix octaethylporphyrin platinum and sol-gel mutually and obtain the oxygen sensor material, and its selectivity numerical value is greater than 8, and the time of response was 5 seconds, recovery time is 10 seconds (Sang-Kyung Lee, Ichiro Okura, Analyst, 1997 .122,81).People such as Yutaka Amao in 2000 are in [5-(1-carboxyl decyl-4-pyridyl)-10,15, the 20-trimethylphenyl] porphyrin platinum is adsorbed on the alumina plate and forms the oxygen sensor film, and its selectivity numerical value is less than 18.3, and the time of response was 26 seconds, recovery time is (Yutaka Amao in 131 seconds, Kiyoko Miyakawab, Ichiro Okurab, J.Mater.Chem.2000,10,305).People such as M.C.Tedford in 2004 are doped to octaethylporphyrin platinum and make the oxygen sensor film in a kind of fluorinated polymer and be used for measuring oxygen, but its performance is not desirable especially, oxygen selectivity numerical value I
0/ I
100Have only 1.8 (R.N.Gillanders, M.C.Tedford, P.J.Crilly, R.T.Bailey, Analytica Chimica Acta2004,502,1).
As can be seen, a kind of performance quality of oxygen sensor material not only depends on porphyrin compound, and closely related with selected carrier from above-mentioned report.Carrier commonly used at present has silicon rubber, organic polymer material (as: polyvinyl chloride (PVC), polystyrene (PST), polycarbonate (PC) and polymethylmethacrylate (PMMA)) and sol-gel (sol-gel) material etc., but the effect that obtains is not very desirable.Therefore the novel carriers of seeking a kind of excellent property becomes one of key issue that further develops high-performance oxygen sensor material and device.For this reason, we adopt mesopore molecular sieve to carry out relevant research as new carrier.
Synthetic (C.T.Kresge, M.E.Leonowicz, W.J.Roth, J.C.Vartuli, J.S.Beck, Nature, 1992,359,710 of the reported first M41S of U.S. Mobil company series mesopore molecular sieve in 1992; J.S.Beck, J.C.Vartuli, W.J.Roth, M.E.Leonowicz, C.T.Kresge, K.D.Schmitt, C.T.-W.Chu, D.H.Olson, E.W.Sheppard, S.B.McCullen, J.B.Higgins, J.L.Schlenker, J.Am.Chem.Soc.1992,114,10834.), with regard to present synthetic mesopore molecular sieve, can be divided into six classes: MCM-41, MCM-48, MCM-50 by structure, SBA-1, SBA-2, MSU-n.Mesopore molecular sieve has very large voidage, very high specific surface, in order and the adjustable pore passage structure in aperture and have characteristics such as surface, modifiable duct.Luminous sensing function group of molecules is installed in the mesopore molecular sieve duct, by the suitable regulatory function molecule volume and the ratio of mesopore molecular sieve channel diameter, molecule that some volumes are less such as oxygen molecule are free to cause by the mesopore orbit that contains functional molecular the variation of light emitting molecule luminescent properties, thereby make assembly have the oxygen sensor performance.Because the selectivity of mesopore orbit itself can improve the selectivity of former functional molecular, and the bigger specific surface area of mesopore molecular sieve can make functional molecular reach the high dispersing state, thus the sensitivity of raising functional molecular.Therefore adopting mesopore molecular sieve to do carrier is the performance that can improve transmitter.We are assembled into the oxygen sensor that has obtained better performances in the mesopore molecular sieve with two kinds of metal platinum porphyrin compounds.
Summary of the invention
The purpose of this invention is to provide a class composite luminescent material, the optical physics performance of these materials (mainly comprising luminous intensity, luminous peak position) is very sensitive to oxygen, is adapted to the preparation of oxygen sensor device.
Find that after deliberation the title complex that porphyrin part and metal platinum form can be assembled in the duct of mesopore molecular sieve, and form composite luminescent material, their luminescent properties is very responsive to oxygen.Of the present invention to as if will be assembled in the duct of mesopore molecular sieve suc as formula the porphyrin platinum luminescent ligand compound shown in (I), (II), a class composite luminescent material of acquisition, these composite luminescent materials can be used for the preparation of oxygen sensor device.
Mesopore molecular sieve is the inorganic carrier that a class is made of silicon-dioxide, comprises MCM-41, MCM-48 and SBA-15 etc. as the mesopore molecular sieve bag of carrier.Pore passage structure among MCM-41 and the SBA-15 is six sides to be arranged, and is isolated mutually between the duct, and the duct radius ratio MCM-41 of SBA-15 is big.Pore passage structure among the MCM-48 is a cube arrangement, connects mutually between the duct.Title complex (I), (II) are the luminous cooperation of porphyrin platinum.MCM-41, MCM-48 and SBA-15 can be powder, spherical, fibrous or sheet.
After being assembled in the mesopore molecular sieve, title complex (I), (II) can obtain the mixture of mesopore molecular sieve/porphyrin platinum complex.Be fixed in the duct of mesopore molecular sieve after title complex (I), (II) are assembled in the mesopore molecular sieve, water or organic solvent can not be dissolved out title complex (I), (II).The characteristics of luminescence of composite materials of the present invention has the oxygen sensor performance, is applicable to preparation oxygen sensor device.Advantage of the present invention is that the preparation method is simple, sensitivity and selectivity height, stable performance.
Used title complex (I), (II) can be undertaken by reaction pattern 1 among the present invention, concrete experiment condition reference literature (P.Hambright, E.B.Fieischer, Inorg.Chem.1970,9,1757; R.F.Pasternack, P.R.Huber, P.Boyd, G.Engasser, L.Francesoni, J.Am.Chem.Soc.1972,4511; I.A.Blinova, V.V.Vasil ' ev, Russ.J.Phys.Chem.1995,69,995).
Used inorganic carrier mesoporous material MCM-41, MCM-48 and SBA-15 can obtain (C.T.Kresge, M.E.Leonowicz, W.J.Roth, J. C.Vartuli, J.S.Beck, Nature, 1992,359,710 according to literature method; J.S.BecK, J. C.Vartuli, J.Roth, M.E.Leonowicz, C.T.Kresge, K.D.Schmitt, C.T.-W.Chu, D.h.Olson, E.W.Sheppard, S.B.McCullen, J.B.Higgins, J.L.Shlenker, J.Am.Chem.Soc.1992,114,10834; D.Zhao, Q. Huo, J.Feng, B.F.Chmelka, G.D.Stucky, J.Am.Chem.Soc.1998,120,6024.).
Reaction pattern 1
Title complex (I), (II) assembling in mesoporous material prepares the technical process of composite luminescent material and is: with (550 ℃ of heating in the air, 6 hours) the method mesoporous material that will remove organic formwork agent be distributed in the kind solvent, this kind solvent can be with title complex (I), (II) dissolving is (according to the difference of title complex, can be water, ethanol, chloroform etc.), then with an amount of porphyrin platinum complex (I), (II) be added in the above-mentioned solution, the part by weight scope of title complex and mesopore molecular sieve is controlled between 1: 100～8: 100, adding title complex afterreaction system at room temperature stirred 1 hour, filter then, with with the identical solvent wash solid of mother liquor 3～6 times, seasoning promptly obtains promptly to obtain the luminescent material that is compounded to form with inorganic mesoporous molecular sieve by porphyrin platinum complex of the present invention under the air at room temperature, the prepared matrix material that goes out is lavender, have the characteristics of luminescence under ultra violet lamp, its luminous peak position is at 630～680nm.
This material can be used for the assembling of oxygen sensor device, especially for the on-chip active coating of oxygen sensor device sensing.For example material of the present invention is fixed on the substrate of printing opacity or is coated with that to invest blue light inorganic or Organic Light Emitting Diode is surperficial, and then mix photorectifier and carry out signal detection, can prepare the oxygen sensor device.
Description of drawings
Fig. 1: the oxygen sensor optical device structural representation of using organic materials of the present invention.
The application of matrix material in the oxygen sensor device that the present invention is combined to form by title complex (I), (II) and mesoporous material now is described in conjunction with the accompanying drawings.Object of the present invention can be used for preparing the oxygen sensor device, and has the active coating of one or more compound formation of the present invention on the sensing substrate in device.The luminosity of active coating is very sensitive to oxygen.The basic structure of this type of luminescent device as shown in Figure 1, this device is made of photodiode 1, spectral filter 2, sensing substrate 3, pneumatic outlet 4, gas inlet 5, spectral filter 6, lens 7 and photodiode 8.Wherein sensing substrate 3 is cores of this device, matrix material of the present invention is attached to the surface on the black hard substrate (can be metal or plastic material), the incident light of photodiode 1 is on spectral filter 2 is got to active coating on the sensing substrate 3, luminophore in the active coating is excited and luminous, and the light that sends is mapped on the photodiode 8 (being signal detector) by spectral filter 6 and lens 7; Pneumatic outlet 4, gas inlet 5 are entrance and exits of detected gas.In detected gas oxygen content not simultaneously, detected luminous intensity difference can analyze the content of oxygen in the detected gas by the luminous intensity variations of luminophore in the observation active coating.This device can be used the analysis and the detection of oxygen composition in the gas.
Embodiment
Further illustrate the preparation and the application of The compounds of this invention below by embodiment, rather than will limit the present invention with these embodiment.
Embodiment 1: assembly I/gMCM-41's (weight ratio is 2: 100) is synthetic
Take by weighing mauve I 2mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the MCM-41 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain little purplish assembly I/gMCM-41 (weight ratio is 2: 100).
Embodiment 2: assembly I/gMCM-41's (weight ratio is 4: 100) is synthetic
Take by weighing mauve I 4mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the MCM-41 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain purplish assembly I/gMCM-41 (weight ratio is 4: 100).
Embodiment 3: assembly I/gMCM-41's (weight ratio is 8: 100) is synthetic
Take by weighing mauve I 8mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the MCM-41 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain lilac assembly I/gMCM-41 (weight ratio is 8: 100).
Embodiment 4: assembly I/gMCM-48's (weight ratio is 2: 100) is synthetic
Take by weighing mauve I 2mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the MCM-48 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain little purplish assembly I/gMCM-48 (weight ratio is 2: 100).
Embodiment 5: assembly I/gMCM-48's (weight ratio is 4: 100) is synthetic
Take by weighing mauve I 4mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the MCM-48 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain purplish assembly I/gMCM-48 (weight ratio is 4: 100).
Embodiment 6: assembly I/gMCM-48's (weight ratio is 8: 100) is synthetic
Take by weighing mauve I 8mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the MCM-48 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain lilac assembly I/gMCM-48 (weight ratio is 8: 100).
Embodiment 7: assembly I/gSBA-15's (weight ratio is 2: 100) is synthetic
Take by weighing mauve (I) 2mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the SBA-15 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain little purplish assembly I/gSBA-15 (weight ratio is 2: 100).
Embodiment 8: assembly I/gSBA-15's (weight ratio is 4: 100) is synthetic
Take by weighing mauve I 4mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the SBA-15 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain purplish assembly I/gSBA-15 (weight ratio is 4: 100).
Embodiment 9: assembly I/gSBA-15's (weight ratio is 8: 100) is synthetic
Take by weighing mauve I 8mg and place the 50ml beaker, add the trichloromethane of about 8ml, shake up, form red clear solution.To wherein adding the SBA-15 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, wash 3 times with chloroform soln, colourless until filtrate.Dry under the room temperature, obtain lilac assembly I/gSBA-15 (weight ratio is 8: 100).
Embodiment 10: assembly II/gMCM-41's (weight ratio is 1: 100) is synthetic
Take by weighing atropurpureus II 1mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the MCM-41 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain little purplish assembly II/gMCM-41 (weight ratio is 1: 100).
Embodiment 11: assembly II/gMCM-41's (weight ratio is 2: 100) is synthetic
Take by weighing atropurpureus II 2mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the MCM-41 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain purplish assembly II/gMCM-41 (weight ratio is 2: 100).
Embodiment 12: assembly II/gMCM-41's (weight ratio is 4: 100) is synthetic
Take by weighing atropurpureus II 4mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the MCM-41 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain lilac assembly II/gMCM-41 (weight ratio is 4: 100).
Embodiment 13: assembly II/gMCM-48's (weight ratio is 1: 100) is synthetic
Take by weighing atropurpureus II 1mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the MCM-48 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain little purplish assembly II/gMCM-48 (weight ratio is 1: 100).
Embodiment 14: assembly II/gMCM-48's (weight ratio is 2: 100) is synthetic
Take by weighing atropurpureus II 2mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the MCM-48 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain purplish assembly II/gMCM-48 (weight ratio is 2: 100).
Embodiment 15: assembly II/gMCM-48's (weight ratio is 4: 100) is synthetic
Take by weighing atropurpureus II 4mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the MCM-48 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain lilac assembly II/gMCM-48 (weight ratio is 4: 100).
Embodiment 16: assembly II/gSBA-15's (weight ratio is 1: 100) is synthetic
Take by weighing atropurpureus II 1mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the SBA-15 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain little purplish assembly II/gSBA-15 (weight ratio is 1: 100).
Embodiment 17: assembly II/gSBA-15's (weight ratio is 2: 100) is synthetic
Take by weighing atropurpureus II 2mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the SBA-15 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain purplish assembly II/gSBA-15 (weight ratio is 2: 100).
Embodiment 18: assembly II/gSBA-15's (weight ratio is 4: 100) is synthetic
Take by weighing atropurpureus II 4mg and place the 50ml beaker, add the distilled water of about 8ml, shake up, form red clear solution.To wherein adding the SBA-15 that the 100mg roast is crossed, stir and left standstill 40 minutes after 1 hour again.Solution is filtered, with distillation washing 3 times, colourless until filtrate.Dry under the room temperature, obtain lilac assembly II/gSBA-15 (weight ratio is 4: 100).
The oxygen sensor character of embodiment 19:I/gMCM-41 (weight ratio is 2: 100)
On the sensing substrate of I/gMCM-41, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 640nm, I
0/ I
100=5.51 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.75s, descend 95% o'clock required time), the recovery time is 204s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 20:I/gMCM-41 (weight ratio is 4: 100)
On the sensing substrate of I/gMCM-41, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 643nm, I
0/ I
100=7.00 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.5s, descend 95% o'clock required time), the recovery time is 220.12s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 21:I/gMCM-41 (weight ratio is 8: 100)
On the sensing substrate of I/gMCM-41, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 645nm, I
0/ I
100=3.07 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.375s, descend 95% o'clock required time), recovery time is 235.56s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 22:I/gMCM-48 (weight ratio is 2: 100)
On the sensing substrate of I/gMCM-48, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 648nm, I
0/ I
100=8.59 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.29s, descend 95% o'clock required time), the recovery time is 15.6s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 23:I/gMCM-48 (weight ratio is 4: 100)
On the sensing substrate of I/gMCM-48, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 649nm, I
0/ I
100=8.82 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.21s, descend 95% o'clock required time), the recovery time is 14.69s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 24:I/gMCM-48 (weight ratio is 8: 100)
On the sensing substrate of I/gMCM-48, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 651nm, I
0/ I
100=7.56 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.25s, descend 95% o'clock required time), recovery time is 257.84s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 25:I/gSBA-15 (weight ratio is 2: 100)
On the sensing substrate of I/gSBA-15, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 646nm, I
0/ I
100=5.34 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.83s, descend 95% o'clock required time), the recovery time is 118.6s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 26:I/gSBA-15 (weight ratio is 4: 100)
On the sensing substrate of I/gSBA-15, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 648nm, I
0/ I
100=5.86 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.75s, descend 95% o'clock required time), the recovery time is 94.5s (glimmering intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 27:I/gSBA-15 (weight ratio is 8: 100)
On the sensing substrate of I/gSBA-15, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 650nm, I
0/ I
100=4.87 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.77s, descend 95% o'clock required time), recovery time is 158.75s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 28:II/gMCM-41 (weight ratio is 1: 100)
On the sensing substrate of II/gMCM-41, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 665nm, I
0/ I
100=17.27 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.29s, descend 95% o'clock required time), recovery time is 106.56s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 29:II/gMCM-41 (weight ratio is 2: 100)
On the sensing substrate of II/gMCM-41, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 668nm, I
0/ I
100=29.47 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.33s, descend 95% o'clock required time), the recovery time is 26.62s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 30:II/gMCM-41 (weight ratio is 4: 100)
On the sensing substrate of II/gMCM-41, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 673nm, I
0/ I
100=23.53 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.36s, descend 95% o'clock required time), the recovery time is 29.58s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 31:II/gMCM-48 (weight ratio is 1: 100)
On the sensing substrate of II/gMCM-48, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 670nm, I
0/ I
100=12.62 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.146s, descend 95% o'clock required time), recovery time is 134.03s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 32:II/gMCM-48 (weight ratio is 2: 100)
On the sensing substrate of II/gMCM-48, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 668nm, I
0/ I
100=12.57 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.4s, descend 95% o'clock required time), the recovery time is 20.67s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 33:II/gMCM-48 (weight ratio is 4: 100)
On the sensing substrate of II/gMCM-48, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 667nm, I
0/ I
100=10.49 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.42s, descend 95% o'clock required time), the recovery time is 21.7s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 34:II/gSBA-15 (weight ratio is 1: 100)
On the sensing substrate of II/gSBA-15, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 670nm, I
0/ I
100=10.36 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.25s, descend 95% o'clock required time), the recovery time is 156.3s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 35:II/gSBA-15 (weight ratio is 2: 100)
On the sensing substrate of II/gSBA-15, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 671nm, I
0/ I
100=11.63 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.33s, descend 95% o'clock required time), the recovery time is 41.7s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
The oxygen sensor character of embodiment 36:II/gSBA-15 (weight ratio is 4: 100)
On the sensing substrate of II/gSBA-15, observe its variations in light under different oxygen concentrations attached to device shown in the accompanying drawing 1.With 400nm is excitation wavelength, and the luminous peak position of sample is 671nm, I
0/ I
100=9.56 (I
0The luminous intensity that records when being 100% nitrogen, I
100The luminous intensity that records when being 100% oxygen), the cancellation time is that (luminous intensity is changed to 100% oxygen by 100% nitrogen to 0.37s, descend 95% o'clock required time), the recovery time is 45.87s (luminous intensity is changed to 100% nitrogen by 100% oxygen, rises 95% o'clock required time).
Claims (6)
1, composite luminescent material, it is characterized in that by following method preparation: the meso-porous molecular sieve material dispersing and dissolving that will remove organic formwork agent is in solvent, be added in the above-mentioned solution with porphyrin platinum complex (I) or (II) then, the weight ratio of title complex and mesopore molecular sieve is 1: 100～8: 100, adding title complex afterreaction system at room temperature stirred 1 hour, filter then, use again with the identical solvent wash solid of mother liquor 3～6 times, seasoning promptly obtains the luminescent material that is compounded to form with inorganic mesoporous molecular sieve by porphyrin platinum complex of the present invention under the air, the prepared matrix material that goes out is lavender, under ultra violet lamp, has the characteristics of luminescence, its luminous peak position is at 630～680nm, porphyrin platinum complex (I) or (II) be adsorbed on securely in the duct of mesoporous material, solvent can not be with porphyrin platinum complexes (I) or (II) are dissolved out.
2, composite luminescent material as claimed in claim 1 is characterized in that: solvent is water, ethanol or chloroform.
3, composite luminescent material as claimed in claim 1 is characterized in that: meso-porous molecular sieve material is MCM-41, MCM-48 or SBA-15.
4, claim 1, the application of 2 or 3 described composite luminescent materials aspect the oxygen sensor material.
5, claim 1, the application of 2 or 3 described composite luminescent materials aspect preparation oxygen sensor device.
6, claim 1, the application of 2 or 3 described composite luminescent materials aspect preparation oxygen sensor device sensing substrate active coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011163 CN1274782C (en) | 2004-10-19 | 2004-10-19 | Porphyrin platinum complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011163 CN1274782C (en) | 2004-10-19 | 2004-10-19 | Porphyrin platinum complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1621487A true CN1621487A (en) | 2005-06-01 |
| CN1274782C CN1274782C (en) | 2006-09-13 |
Family
ID=34763187
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410011163 Expired - Fee Related CN1274782C (en) | 2004-10-19 | 2004-10-19 | Porphyrin platinum complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274782C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448254A (en) * | 2014-10-21 | 2015-03-25 | 南京邮电大学 | Phosphorescence conjugated polyelectrolyte photoelectric material containing porphyrin platinum complex as well as preparation method and application of phosphorescence conjugated polyelectrolyte photoelectric material |
| CN108101916A (en) * | 2017-12-25 | 2018-06-01 | 南京邮电大学 | A kind of preparation and application of water-soluble porphyrin complex |
-
2004
- 2004-10-19 CN CN 200410011163 patent/CN1274782C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448254A (en) * | 2014-10-21 | 2015-03-25 | 南京邮电大学 | Phosphorescence conjugated polyelectrolyte photoelectric material containing porphyrin platinum complex as well as preparation method and application of phosphorescence conjugated polyelectrolyte photoelectric material |
| CN108101916A (en) * | 2017-12-25 | 2018-06-01 | 南京邮电大学 | A kind of preparation and application of water-soluble porphyrin complex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1274782C (en) | 2006-09-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sanchez et al. | Design and properties of hybrid organic–inorganic nanocomposites for photonics | |
| Li et al. | Supersensitive detection of explosives by recyclable AIE luminogen-functionalized mesoporous materials | |
| CN112226231B (en) | Multicolor fluorescent carbon quantum dot and preparation method and application thereof | |
| CN109749091B (en) | Sky blue fluorescent cadmium organic ring supramolecules and preparation method and application thereof | |
| CN103257127B (en) | It is a kind of that to improve fluorescent indicator molecule dispersed and prepare the method for oxygen sensitive fluorescent screen in organic silica gel | |
| CN101870866A (en) | Preparation method of inverse opal structure fluorescent thin film for detecting ultra-trace TNT (Trinitrotoluene) steam | |
| CN112010869B (en) | Light capture system and preparation method and application thereof | |
| An et al. | Solid-state carbon dots with tunable fluorescence via surface substitution: effect of alkyl moieties on fluorescence characteristics | |
| CN110243889A (en) | Based on CsPbBr3Molecular engram optical electro-chemistry sensor of/GO isotype heterostructure and its preparation method and application | |
| CN109679109A (en) | A kind of orange organic supermolecular polymer and the preparation method and application thereof | |
| CN103540318B (en) | Preparation method of rare earth complex grafted luminescent titanium dioxide mesoporous microsphere | |
| Klimant et al. | Novel metal—organic ruthenium (II) diimin complexes for use as longwave excitable luminescent oxygen probes | |
| Wang et al. | RhB-encapsulated metal-organic cage as a dual-emission fluorescence sensor for detection of malachite green and glycine | |
| CN1274782C (en) | Porphyrin platinum complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing | |
| CN102020872A (en) | Composite fluorescent dye, base material containing same and preparation methods thereof | |
| Chen et al. | Enantioselective recognition based on aggregation-induced emission | |
| Lin et al. | Recent Advances in triplet–triplet annihilation upconversion for bioimaging and biosensing | |
| CN1274781C (en) | Ruthenium complex/mesoporous molecular sieve composite luminescent material and its application on oxygen sensing | |
| CN105255484B (en) | A kind of SrAl for detection of organic phosphorus pesticide2B2O7:Eu3+The preparation method of fluorescence probe | |
| CN111072717A (en) | Preparation method of organic-inorganic hybrid perovskite material with good stability in water | |
| CN113444518B (en) | Energy transfer system based on cyanostyrene and preparation method and application thereof | |
| CN100347545C (en) | Method of preoceeding qualitative and/or quantitative analysis against target substance in sample and its detecting device | |
| He et al. | Eu3+ functionalized Gd-BTC: Turn-off fluorescent switch for selectively detecting acetone and Fe3+ | |
| CN102995154A (en) | Preparation method of rare earth fluorescence micro-nano fiber array | |
| CN114891029B (en) | Cd (cadmium sulfide) 2+ Base coordination compound SUST-WJ-12, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JILIN OPTICAL AND ELECTRONIC MATERIALS CO., LTD. Free format text: FORMER OWNER: JILIN UNIVERSITY Effective date: 20101112 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130023 NO.10, QIANWEI ROAD, CHAOYANG DISTRICT, CHANGCHUN CITY, JILIN PROVINCE TO: 130012 NO.5299, FANRONG ROAD, NEW AND HIGH TECHNOLOGY ZONE, CHANGCHUN CITY, JILIN PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20101112 Address after: 130012 No. 5299 prosperity Road, hi tech Zone, Jilin, Changchun Patentee after: JILIN OPTICAL AND ELECTRONIC MATERIALS Co.,Ltd. Address before: 130023, Jilin, Changchun, Chaoyang District, 10 avant-garde Road Patentee before: Jilin University |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060913 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |