NL2033634B1 - Zinc-based hybrid material for blue light emission and preparation method thereof - Google Patents
Zinc-based hybrid material for blue light emission and preparation method thereof Download PDFInfo
- Publication number
- NL2033634B1 NL2033634B1 NL2033634A NL2033634A NL2033634B1 NL 2033634 B1 NL2033634 B1 NL 2033634B1 NL 2033634 A NL2033634 A NL 2033634A NL 2033634 A NL2033634 A NL 2033634A NL 2033634 B1 NL2033634 B1 NL 2033634B1
- Authority
- NL
- Netherlands
- Prior art keywords
- blue light
- zinc
- based hybrid
- light emission
- hybrid material
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 61
- 239000011701 zinc Substances 0.000 title claims abstract description 58
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 9
- XZGLNCKSNVGDNX-UHFFFAOYSA-N 5-methyl-2h-tetrazole Chemical compound CC=1N=NNN=1 XZGLNCKSNVGDNX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- SQASHPHWVSAHDM-UHFFFAOYSA-N 4h-benzotriazole-5-carboxylic acid Chemical compound C1C(C(=O)O)=CC=C2N=NN=C21 SQASHPHWVSAHDM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 230000005284 excitation Effects 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 229910052762 osmium Inorganic materials 0.000 description 7
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 229910052741 iridium Inorganic materials 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GUOVBFFLXKJFEE-UHFFFAOYSA-N 2h-benzotriazole-5-carboxylic acid Chemical compound C1=C(C(=O)O)C=CC2=NNN=C21 GUOVBFFLXKJFEE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005564 crystal structure determination Methods 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- -1 iridi- um Chemical compound 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Luminescent Compositions (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
A Zinc—based hybrid material for blue light emission and a preparation method, thereof. The zinc—based, hybrid, material for blue light emission has a molecular formula of C8HL5N4bZn, and is a molecular crystal material. The preparation method comprises the following steps: a. dissolving organic compounds benzotriazole—5— formic acid, 5—methyl tetrazole and Zn(OAc)z4H20 into N, N— dimethylformamide to obtain a mixed solution; b. carrying out thermostatic reaction on the mixed solution in a hydrothermal reaction kettle at 90—130%I for 1—96 h, taking out the product, separating a solid, and washing the solid, with N, N— dimethylformamide for multiple times to obtain the Zinc—based hybrid material for blue light emission. The prepared zinc—based hybrid material for blue light emission is simple and convenient to synthesize, easy to implement, high in yield and high in repeatability. The Zinc—based hybrid material for blue light emission has good luminous brightness and luminous efficiency, and blue light properties.
Description
ZINC-BASED HYBRID MATERIAL FOR BLUE LIGHT EMISSION AND PREPARATION
METHOD THERECE
The present disclosure relates to a zinc-based hybrid materi- al for blue light emission and a preparation method thereof, be- longs to the technical field of synthesis of new luminescent mate- rials.
For a long time, the research on metal blue light materials mainly focuses on the transition metals of the sixth period, among which the research on noble metal blue light materials such as ru- thenium, osmium, iridium and platinum is the most extensive. The main reason is that the noble metal materials such as ruthenium, osmium, iridium, and platinum can utilize the energy of all sin- glet and triplet states under the heavy atom effect and strong spin-orbit coupling, thereby improving the luminous efficiency.
However, the noble metals such as ruthenium, osmium, iridium, platinum are scare in the earth's crust and are difficult to mine.
Therefore, the cost of synthesizing noble metal blue light materi- als such as ruthenium, osmium, iridium, and platinum is high. In addition, noble metals such as ruthenium, osmium, iridium, and platinum are usually highly toxic, which can cause serious envi- ronmental pollution problems in both synthesis and application, restricting the large-scale application of this series of blue- light materials. Therefore, it is necessary to find other alterna- tive metals for the preparation of blue light materials.
Compared with noble metals such as ruthenium, osmium, iridi- um, and platinum in the sixth period, the metal zinc in the fourth period has the characteristics of abundant resources and low price. In addition, metal zinc exhibits good luminescent proper- ties due to its d°? electronic configuration, and the constructed metal complex materials show great application prospects in light- emitting devices, optical sensors, etc., which is also one of rea-
sons for zinc to become the research hotspot in the field of coor- dination chemistry.
However, there are few reports on the blue-light materials constructed with metal zinc. At present, there is no published re- port on the application of benzotriazole-5-formic acid and 5- methyltetrazole to design and synthesize zinc-based blue light ma- terials.
An object of the present disclosure is to provide a zinc- based hybrid material for blue light emission and a preparation method thereof, to solve the shortcomings of high use cost and un- friendly environment of existing noble metal blue light emitting materials such as ruthenium, osmium, iridium and platinum.
The present disclosure adopts the following technical solu- tions: a zinc-based hybrid material for blue light emission is provided, the molecular formula of the zinc-based hybrid material is CsHa,sN50:2n, in accordance with Fig. 1.
The zinc-based hybrid material is a molecular crystal materi- al, and is crystallized in a Pnma space group in an orthorhombic system and, and the lattice parameters are as follows: o=90°,
B=90°, y=90°, and the crystal volume is Zz=4.
The zinc-based hybrid material can emit blue light under 295 nm ultraviolet excitation, and the CIE coordinates of the blue light are (0.1454, 0.1312), which are close to the CIE coordinates (0.14, 0.08) of saturated blue light, and therefore, the zinc- based hybrid material can be used in the field of blue light emit- ting materials.
The present disclosure provides a method for preparing the zinc-based hybrid material for blue light emission, and the method comprises the following steps: {1) dissolving organic compounds benzotriazole-5-formic acid, 5-methyl tetrazole and Zn{(OAc}:.4H;0 into N, N-dimethylformamide to obtain a mixed solution; (2) carrying out thermostatic reaction on the mixed solution in a hydrothermal reaction kettle at 90-130°C for 1-96 h, taking out the product, separating a solid, and washing the solid with N,
N-dimethylformamide for multiple times to obtain the zinc-based hybrid material for blue light emission.
The mole ratio of benzotriazole-5-formic acid to 5-methyl te- trazole to Zn (OAc), 4H,O to N-dimethylformamide is 1: 2: 2: 322.
The present disclosure has the following beneficial effects: the prepared zinc-based hybrid material for blue light emission is simple and convenient to synthesize, easy to implement, high in yield and high in repeatability. The zinc-based hybrid material for blue light emission has good luminous brightness and luminous efficiency, can replace the noble metal blue light emitting mate- rials, and can be applied on a large scale. The zinc-based hybrid material for blue light emission has a good blue light emitting characteristic, the CIE coordinates of the blue light are (0.1454, 0.1312), which are close to the CIE coordinates (0.14, 0.08) of the saturated blue light, and therefore, the zinc-based hybrid ma- terial can be applied to the field of blue light emitting materi- als.
FIG. 1 is a crystal structure diagram of a zinc-based hybrid material for blue light emission;
FIG. 2 is an X-ray powder diffraction pattern of a zinc-based hybrid material for blue light emission;
FIG. 3 is a fluorescence spectrogram of a zinc-based hybrid material for blue light emission;
FIG. 4 is a CIE chromaticity diagram of a zinc-based hybrid material for blue light emission.
This example provided a method for preparing the zinc-based hybrid material for blue light emission, comprising the following steps: mix the zinc acetate in N,N-dimethylformamide solution with a concentration of 0.1lmol/L benzotriazole-5-carboxylic acid in N,N- dimethylformamide solution with a concentration of 0.05 mol/L, and 5-methyltetrazole with 0.1mol/L and sonicate for 10 min; place the mixed solution into a closed hydrothermal reaction kettle, react at a constant temperature of 90 °C for 24 h, take out the product, separate the solid, and wash the solid with N,N-dimethylformamide for 3 times, to obtain the zinc-based hybrid material for blue light emission.
The properties of a zinc-based hybrid material for blue light emission prepared in this example were characterized as follows: {1} Structure determination of zinc-based hybrid material for blue light emission in this example:
A Supernova type X-ray single crystal diffractometer was adopted for crystal structure determination; Mo-Ko rays subjected to graphite monochromatization were used as an incident radiation source; diffraction points were collected in a scanning manner; lattice parameters were obtained through least square correction; a crystal structure was obtained from a difference value Fourier electron density map by using an SHELXL-97 direct method, and cor- rected by Lorentz and a polarization effect. All H atoms were syn- thesized by difference value Fourier and were determined by calcu- lation of ideal positions. Detailed crystal determination data were shown in Table 1.
Table 1 Crystallographic data of zinc-based hybrid material for blue light emission
Lattice parameters a=9.7411(3}À, b=21.6398(7)A, c=
TTT se
FIG. 1 was a crystal structure of the zinc-based hybrid mate- rial for blue light emission. As shown in the figure, the minimum asymmetric structural unit contained one Zn®% ion, one benzotria-
zole-5-formic acid and half 5-methyl tetrazole, wherein the Zn ion adopted a four-coordination tetrahedral coordination mode and was respectively coordinated with one oxygen atom from three ben- zotriazole-5-formic acids, two nitrogen atoms and one nitrogen at- 5 om of one 5-methyl tetrazole. (2) Phase purity test of zinc-based hybrid material for blue light emission:
An x-ray powder diffraction pattern of the zinc-based hybrid material for blue light emission was tested in a room temperature environment. As shown in FIG. 2, compared with a simulated pattern of the zinc-based hybrid material, the tested powder diffraction pattern had the advantages that positions and shapes of the peaks could be well matched except that the intensities of certain peaks were slightly different, so that the zinc-based hybrid material for blue light emission had relatively high phase purity. (3) Characterization of fluorescent properties of the zinc- based hybrid material for blue light emission:
A method for determining fluorescent data in this example comprised the following step: determine the solid fluorescence property of the zinc-based hybrid material for blue light emission under a condition of 295 nm excitation wavelength by adopting Edinburgh FLS920 at room tem- perature.
As shown in FIG. 3, the zinc-based hybrid material for blue light emission had one fluorescence spectrum characteristic peak at 352 nm under the condition of 295 nm ultraviolet excitation at room temperature, and the characteristic peak was m*>n and/or n*-n transition from a ligand, which was a transfer of effective energy from the ligand to Zn“ ion.
As shown in FIG. 4, the CIE coordinates corresponding to the fluorescence spectrum of the zinc-based hybrid material for blue light emission were (0.1454, 0.1312), and were in a blue light re- gion, and close to the CIE coordinates (0.14, 0.08) of the satu- rated blue light, and therefore, the zinc-based hybrid material f£ could be applied to the field of blue light emitting materials.
Claims (5)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111545811.6A CN114149453B (en) | 2021-12-16 | 2021-12-16 | Zinc-based hybrid material for blue light emission and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| NL2033634A NL2033634A (en) | 2023-06-28 |
| NL2033634B1 true NL2033634B1 (en) | 2023-09-20 |
Family
ID=80451268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL2033634A NL2033634B1 (en) | 2021-12-16 | 2022-11-28 | Zinc-based hybrid material for blue light emission and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN114149453B (en) |
| NL (1) | NL2033634B1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101463253B (en) * | 2009-01-12 | 2012-03-07 | 太原理工大学 | White light electroluminescent organic material based on 8-hydroxyquinoline |
| CN103524539B (en) * | 2013-10-08 | 2015-09-30 | 重庆师范大学 | Luminescent material Zn (phen) (HL) 2and preparation method thereof |
| CN104152140B (en) * | 2014-08-01 | 2016-04-20 | 宁波大学 | A kind of blue fluorescent material and preparation method thereof |
| CN107523291B (en) * | 2017-09-08 | 2019-08-23 | 湖南科技大学 | It is a kind of while identifying phosphate radical and the fluorescence probe complex of copper ion, preparation method and application in water body |
-
2021
- 2021-12-16 CN CN202111545811.6A patent/CN114149453B/en active Active
-
2022
- 2022-11-28 NL NL2033634A patent/NL2033634B1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| CN114149453A (en) | 2022-03-08 |
| CN114149453B (en) | 2023-07-28 |
| NL2033634A (en) | 2023-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | A new strategy for achieving white-light emission of lanthanide complexes: effective control of energy transfer from blue-emissive fluorophore to Eu (III) centres | |
| CN107722047A (en) | A kind of double-core Rare Earth Europium Complex luminescent material and its preparation method and application | |
| CN113683642B (en) | Zero-dimensional organic-inorganic hybrid metal halides (TMA) 2 SbCl 5 DMF material and preparation method and application thereof | |
| CN106995696A (en) | A kind of zinc-base luminescent metal organic framework material and its preparation method and application | |
| CN105924469A (en) | Crystalline benzimidazolyl quinoline cuprous complex luminescent material | |
| Liu et al. | Excitation-dependent tunable white light of ns2 ions doped Rb2SnCl6 vacancy ordered double perovskite | |
| NL2033634B1 (en) | Zinc-based hybrid material for blue light emission and preparation method thereof | |
| CN104194774B (en) | One class antimonio fluorescent material and preparation method thereof | |
| CN109734733A (en) | A kind of fluorescence Zn complex and its application | |
| CN110078933A (en) | Novel coordination polymer crystalline material and preparation method thereof and fluorescent applications | |
| CN105884829A (en) | CuIN2P cuprous complex light-emitting material based on benzoxazolyl pyridine | |
| CN112479893A (en) | Preparation method of novel metal halide perovskite with temperature-variable fluorescent property | |
| CN105694868B (en) | Benzimidazolyl-quinoline cuprous complex light-emitting material | |
| CN109749740B (en) | Photoluminescent material, preparation method and application thereof | |
| CN110551292A (en) | preparation method of rare earth luminescent material with adjustable light color | |
| CN105669721A (en) | Two-dimensional zinc coordination polymer of triazole heterocycle, preparation method and application thereof | |
| CN105837568A (en) | Fluorenyl-[beta]-carboline compound, application thereof as organic light-emitting material and aggregation-induced emission enhancement material, and preparation method of the compound | |
| CN114605659A (en) | Cd-MOF material with double-spiral structure and preparation method and application thereof | |
| CN108822051A (en) | The synthetic method and application of Zn (II) complex of fluorescent type three-dimensional | |
| CN104861961B (en) | CuIN2P tetrahedral coordination cuprous complex luminous material | |
| Wei et al. | Synthesis, structure, and photoelectric properties of a novel zero-dimensional organic-inorganic hybrid perovskite (C6H9N2) 2MnI4 | |
| CN116769181A (en) | Zinc-based molecular crystal blue-green light material and preparation method thereof | |
| CN105713022A (en) | Benzimidazolyl quinoline cuprous complex orange phosphorescent material | |
| CN106967119B (en) | A kind of copper cluster compound, preparation method and application | |
| CN106432325B (en) | A kind of non-linear optical crystal material of yellow photoluminescence and its preparation and application |