CN104327042B - A kind of formaldehyde quick detection reagent and preparation method and application - Google Patents
A kind of formaldehyde quick detection reagent and preparation method and application Download PDFInfo
- Publication number
- CN104327042B CN104327042B CN201410500026.2A CN201410500026A CN104327042B CN 104327042 B CN104327042 B CN 104327042B CN 201410500026 A CN201410500026 A CN 201410500026A CN 104327042 B CN104327042 B CN 104327042B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde
- pyridine
- amino
- quick detection
- detection reagent
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Immunology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a kind of formaldehyde quick detection reagent and preparation method and application, the chemical name of a kind of formaldehyde quick detection reagent provided by the present invention is 2 amido 3 (3 amido 1H benzo [d] imidazoles) pyridines, chemical structural formula shown in formula I:The preparation method of described reagent comprises the steps: step 1: will react 6 hours synthetic intermediates 3 in 200 DEG C of oil baths of mixture of nicotiamide and Ammonium sulfamate；Step 2: intermediate 3 is temperature rising reflux 4 hours in sour environment, after being cooled to room temperature, pH is adjusted to 7～8 and obtains intermediate 2；Step 3: intermediate 2 and two hydrochloric acid 1,2,4 triaminobenzene reactions obtain target product, the reagent prepared according to the method described above can reliably detect the concentration of formaldehyde, the present invention has the advantages that synthetic route is simple, with low cost, process is convenient, applicable production application, probe response speed are fast, highly sensitive, and the present invention can realize the quick detection quantitative, highly sensitive of environment and formaldehyde in food.
Description
Technical field
The invention belongs to technical field of analytical chemistry, be specifically related to a kind of formaldehyde testing reagent and preparation method thereof and answer
With, particularly to a kind of formaldehyde quick detection reagent and preparation method and application.
Background technology
Formaldehyde is a kind of important Organic Ingredients, is mainly used in plastics industry (such as phenolic resin processed, urea-formaldehyde plastics-electricity
Beautiful), synthetic fibers (such as synthesis vinylon-polyvinyl formal), leather industry, medicine, dyestuff etc..Textile adds in production
Use the N-methylol compound containing formaldehyde as resin finishing agent during work, the elasticity of fabric can be increased, improve wrinkle
Property, the use cationic resin containing formaldehyde is to improve dyefastness, but these easily cause formaldehyde in textile residue problem.
Formaldehyde can also be directly used as sterilization, sterilization, preservative.Because of ordering about of economic interests, some lawless persons are with formaldehyde as food
Additive, as water-soaked food add formaldehyde with coagulated protein, anticorrosion, improve outward appearance, increase mouthfeel, in inebriant add formaldehyde
Preventing muddiness, increase transparency etc., these all can cause the severe contamination of food, damages health.Formaldehyde is protoplasmic poison
, can there is the serious stimulation of respiratory tract and edema, Eye irritation, headache with protein bound, high concentration in material when sucking.Skin is straight
Connect Formaldehyde Exposed and can cause allergic dermatitis, mottle, necrosis, when sucking high-concentration formaldehyde, bronchial asthma can be induced.High concentration
Formaldehyde or a kind of genotoxicity material, may cause gene mutation.Laboratory animal laboratory high concentration suck in the case of,
Rhinopharyngeal neoplasm can be caused.Long Term Contact low concentration formaldehyde steam, can have the symptom such as headache, weakness.External report 14%～
Occur after worker exposure's formaldehyde of 16% gastricism, excitement, tremble, visual disorder.0.2-0.7mg/ is reached at concentration of formaldehyde
m3Workshop in, the workman that works long hours have loss of appetite, lose weight, weak, headache, the phenomenon such as cardiopalmus and insomnia.
Exactly because formaldehyde has sterilization, sterilization, preservative efficacy, so can be used in by some lawless person people are improper
In food manufacturing.Common problematic food is dried bean, rice flour and the food such as Gaster Bovis seu Bubali that floods, chicken claw etc..Health in 2011
In cloth promulgated by the ministries or commissions of the Central Government " food additive use standard ", formaldehyde etc. has logged out food additive list.Environmental Protection Agency USA is built
The formaldehyde Acceptable Daily Intake (ADI) of view is per kilogram of body weight 0.2 milligram.Take in a small amount of formaldehyde, health is not resulted in
Acute impact.The formaldehyde of excess intake then may cause general acidosis, and has the situation of gastrointestinal hemorrhage.Although no
Enough evidences show can cause human canceration, but has confirmed that formaldehyde can be carcinogenic in animal in the world.It is eaten for a long time containing excess first
The food of aldehyde, it may appear that the symptom such as dizziness, headache, weak, drowsiness, loss of appetite, visual deterioration.
The detection of PARA FORMALDEHYDE PRILLS(91,95) at present mainly has spectrophotography, electrochemical process, chromatography etc., but these analysis means are all
There is certain limitation, such as: detect formaldehyde, selectivity and highly sensitive by chromatography, but sample treatment is complicated, during test
Between long.And the method for most commonly seen detection formaldehyde is acetylacetone method, national standard ISO14184, GB/T29121-1998.
Its principle be utilize formaldehyde and acetylacetone,2,4-pentanedione and ammonia to generate yellow compound diacetyl dihydro lutidine after, carry out under 412nm
Spectrophotometry.This method advantage is easy and simple to handle, stable performance, and error is little, is not disturbed by acetaldehyde, and colored solutions can
Stable existence 12h.But it is relatively low that the shortcoming of maximum is sensitivity, concentration limit is 0.25mg/L, is only applicable to more highly concentrated
The mensuration of degree formaldehyde；And the reaction of this method is relatively slow, needs about 60min.Therefore, development one is simply, detect easily and fast
Formaldehyde and the high method of detection sensitivity are the most necessary.
Summary of the invention
Present invention aim at a kind of reagent by change in fluorescence Rapid Detection of Formaldehyde and preparation method thereof being provided and answering
With, thus realize highly sensitive, detect the formaldehyde in environment, food simply, easily and fast.
A kind of formaldehyde quick detection reagent that the present invention provides, its chemical name is: 2-amido-3-(3-amido-1H-benzene
And [d] imidazoles)-pyridine, its chemical structural formula is:
The preparation method of described a kind of formaldehyde quick detection reagent comprises the following steps: step 1: synthesis 2-(3-pyridine)
Pyrido [2,3-d] pyrimidine: obtain as after reaction is fully cured for 6 hours in oil bath after nicotiamide and Ammonium sulfamate are mixed
To 2-(3-pyridine) pyrido [2, the 3-d] pyrimidine as shown in Formula II；
Step 2: synthesis 2-amino-3-pyridine carboxaldehyde: by phonetic for product 2-obtained above (3-pyridine) pyrido [2,3-d]
The hydrochloric acid solution temperature rising reflux of pyridine and 2mol/L 4 hours, is cooled to room temperature, with 10mol/L sodium hydroxide solution regulation pH to 7～
8 obtain the 2-amino-3-pyridine carboxaldehyde as shown in formula III；
Step 3: synthesis 2-amido-3-(3-amido-1H-benzo [d] imidazoles)-pyridine: ar gas environment, ethanol as solvent,
PH is neutral, slowly drips in the mixture of 2-amino-3-pyridine carboxaldehyde to sodium sulfite, two hydrochloric acid 1,2,4-triaminobenzenes
Adding formaldehyde, temperature rising reflux obtains target product 2-amido-3-(3-amido-1H-benzo [d] imidazoles)-pyridine in four hours.
In described preparation method step 1, the temperature of oil bath is to be first to heat to 150 DEG C, temperature is slowly increased to the most again
200 DEG C, at a temperature of this, keep reaction 6 hours.
In described preparation method step 1, the mol ratio of nicotiamide and Ammonium sulfamate is 1: 1.5, two hydrochloric acid in step 3
1,2,4-triaminobenzene is 1: 1 with the mol ratio of 2-amino-3-pyridine carboxaldehyde.
Further object is that the using method providing this reagent at detection formaldehyde.This using method former
Reason is: by reagent of the present invention (probe) and formaldehyde molecule phase separation so that probe molecule generation Excited state proton trans fer, probe is sent out
Light changes, the most luminous in visible region, sends strong blue light in visible region, make probe by the most luminous after effect
Becoming the strongest blue light, naked eyes readily identify.Preferred concentration is 1 × 10-5M, preferred solvent water/ethanol=99: 1；This use
Method comprises the steps:
Step 1: measure certain density formalin, is formulated as the formaldehyde titer of 1200 μ g/mL；
Step 2: the formaldehyde titer compound concentration respectively of the 1200 μ g/mL that use previous step obtains is 0 μ g/mL, 15 μ
The formaldehyde liquid to be measured of g/mL, 30 μ g/mL, 100 μ g/mL and 200 μ g/mL；
Step 3: take appropriate five kinds of formaldehyde liquid to be measured respectively in test tube, and be separately added into appropriate probe molecule solutions, shake
Dynamic test tube so that it is mix homogeneously；
Step 4: place 30 minutes under room temperature, measure its fluorescence spectrum；
Step 5: map with the fluorescent emission intensity at 505nm, obtain concentration of formaldehyde numerical value to be measured.
Compared with prior art, the method have the advantages that
1, formaldehyde quick detection reagent synthetic route of the present invention is simple, with low cost, and it is convenient to process, and is suitable for reality
Production application.
2, formaldehyde quick detection reagent probe response speed of the present invention is fast, can detect in 2 minutes, sensitive
Degree height；The quick detection quantitative, highly sensitive of environment, formaldehyde in food can be realized.
Accompanying drawing explanation
Fig. 1 is the proton nmr spectra of intermediate 2-amino-3-pyridine carboxaldehyde.
Fig. 2 is the carbon-13 nmr spectra of intermediate 2-amino-3-pyridine carboxaldehyde.
Fig. 3 is the hydrogen nuclear magnetic resonance of compound 2-amido-3-(3-amido-1H-benzo [d] the imidazoles)-pyridine of the present invention
Spectrum.
Fig. 4 is the nuclear magnetic resonance, NMR carbon of compound 2-amido-3-(3-amido-1H-benzo [d] the imidazoles)-pyridine of the present invention
Spectrum.
Fig. 5 is the photo before and after the portable UV illumination of 365nm penetrates the compound Formaldehyde Exposed of the lower present invention.
Fig. 6 is the compound of present invention 505nm maximum fluorescence intensity and concentration of formaldehyde graph of a relation in aqueous phase.
Fig. 7 is the compound of the present invention fluorescence response curve to variable concentrations formaldehyde under 400nm exciting light.
Fig. 8 is that after the compound of the present invention adds formaldehyde at 505nm under 400nm exciting light, fluorescence intensity changes over
Curve chart.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is elaborated.
Embodiment 1: the preparation of compound of the present invention
The compound of the present invention following synthetic route of employing:
1) synthesis 2-(3-pyridine) pyrido [2,3-d] pyrimidine
Weigh nicotiamide (9.12g, 0.075mol) respectively and Ammonium sulfamate (13.07g, 0.113mol) is placed in 50mL's
In there-necked flask, oil bath is heated to 150 DEG C, the most again temperature increases to 200 DEG C slowly, keeps reaction 6 little at such a temperature
Time, then until reaction liquid is fully cured.After question response solidification, stop heating, after being cooled to room temperature, add appropriate
Water, then sucking filtration, rinse filter cake several times with water, then washs with ether, vacuum drying, obtain product 2-(3-pyridine) pyrido [2,
3-d] pyrimidine.
2) synthesis 2-amino-3-pyridine carboxaldehyde
The HCl solution of preparation 2mol/L.Transfer to dried sample, in the single port bottle of 50mL, be subsequently adding about 30mL
The HCl solution of 2mol/L, temperature rising reflux 4 hours, be cooled to room temperature.PH to 7～8 is reconciled by the NaOH solution of 10mol/L.Second
Ether extracts 5 times, and Anhydrous potassium carbonate is dried, and rotation is evaporated off solvent, obtains yellow solid.Through column chromatography for separation (VDCM/VEIOH=30:
1), cold drying obtains light yellow sterling 2-amino-3-pyridine carboxaldehyde, productivity: 30%.
It is characterized as below:1H-NMR: δH(400MHz；CDCl3；Me4Si) 6.743 (m, 3H), 7.810 (m, 1H), 8.267 (m,
1H), 9.864 (s, 1H).13C-NMR: δC(100Hz, CDCl3): 112.91,113.81,144.18,154.75,158.37,
192.67. decomposition temperature: 68～70 DEG C.2-amino-3-pyridine carboxaldehyde1H-NMR collection of illustrative plates as it is shown in figure 1, its13C-NMR such as Fig. 2
Shown in.
3) synthesis 2-amido-3-(3-amido-1H-benzo [d] imidazoles)-pyridine
Sodium sulfite (0.867g, 0.08mol) is placed in the there-necked flask of 50mL, is subsequently adding the anhydrous second of 10mL
Alcohol, ultrasonic makes it pulverize.Weigh two hydrochloric acid 1,2,4-triaminobenzene (0.317g, 0.003mol), add in above-mentioned reaction bulb, take out
Gas three times, argon shield, regulation pH is to neutral.Claim compound 2 (0.362g, 0.003mol), shift with after anhydrous alcohol solution
To constant pressure funnel, it is transferred quickly in there-necked flask, is slowly added dropwise aldehyde.It is warming up to backflow, stopped reaction after 4h.Sucking filtration,
With absolute ethanol washing, filtrate decompression rotation is steamed, and obtains light yellow solid.Column chromatography for separation (ethyl acetate/triethylamine=1: 1) obtains
Product 1, vacuum drying, productivity: 86.7%.
It is characterized as below: HRMS (EI) calcd.for C12H12N5[M+1], 226.1093；Found, 226.1091.1H
NMR: δH(400MHz, CDCl3, Me4Si): 3.25 (s, 2H), 6.70 (m, 3H), 7.12 (s, 2H), 7.56 (m, 1H), 7.77 (d,
1H), 8.14 (d, 1H), and 9.47 (s, 1H).Compound1H NMR is shown in Fig. 3, its13C-NMR is shown in Fig. 4.
Embodiment 2: the experiment of compound test formaldehyde of the present invention
The aqueous solution of the compound present invention prepared is water white transparency not luminescent solution, sends strong after formaldehyde being detected
Strong blue-fluorescence, has before and after the portable UV illumination at 365nm penetrates the compound Formaldehyde Exposed of the lower present invention as shown in Figure 5
Change significantly.(concentration of compound is 1.0 × 10 to the aqueous solution of the compounds of this invention as shown in Figure 6-5M, water: ethanol=
99: 1) under 400nm illumination, at 505nm, maximum fluorescence intensity and concentration of formaldehyde present good linear relationship.According to this relation
Figure, be can be inferred that the concentration of formaldehyde by 505nm maximum fluorescence intensity.Fig. 7 is that (concentration of compound is the compounds of this invention
1.0×10-5M, water: ethanol=99: 1) under 400nm exciting light to variable concentrations formaldehyde (concentration 0-200 × 10-6M) fluorescence
Response curve, will become apparent from its aqueous solution Fluorescence Increasing of the increase along with concentration of formaldehyde in figure.Fig. 8 is that the compounds of this invention is (dense
Degree 1.0 × 10-5M) (concentration is 1.0 × 10 to add formaldehyde under 400nm exciting light at 505nm-5M) fluorescence intensity is in time afterwards
Change curve.Just great changes have taken place, close to saturated in 5 minutes in 30 seconds for its fluorescence as seen from Figure 8.Utilize the present invention
Detection method can be readily available concentration of formaldehyde by maximum fluorescence intensity at 505nm.Detection side according to the present invention
Method the most successfully detects the content of formaldehyde of the products such as shredded squid, seasoned, dried bean, dry Stichopus japonicus.
Claims (6)
1. a formaldehyde quick detection reagent, its feature exists: its chemical name is: 2-amino-3-(5-amino-1H-benzo [d]
Imidazoles)-pyridine, its chemical structural formula is:
The preparation method of a kind of formaldehyde quick detection reagent the most as claimed in claim 1, it is characterised in that: preparation method includes
Following steps:
Step 1: synthesis 2-(3-pyridine) pyrido [2,3-d] pyrimidine: as oil bath after nicotiamide and Ammonium sulfamate are mixed
Middle reaction obtains 2-(3-pyridine) pyrido [2,3-d] pyrimidine after within 6 hours, being fully cured；
Step 2: synthesis 2-amino-3-pyridine carboxaldehyde: by product 2-obtained above (3-pyridine) pyrido [2,3-d] pyrimidine with
The hydrochloric acid solution temperature rising reflux of 2mol/L 4 hours, is cooled to room temperature, obtains with 10mol/L sodium hydroxide solution regulation pH to 7～8
To 2-amino-3-pyridine carboxaldehyde；
Step 3: synthesis 2-amino-3-(5-amino-1H-benzo [d] imidazoles)-pyridine: ar gas environment, ethanol as solvent, pH is
Neutrality, is slowly added dropwise first in sodium sulfite, two hydrochloric acid 1,2, the 4-triaminobenzenes mixture with 2-amino-3-pyridine carboxaldehyde
Aldehyde, temperature rising reflux obtains target product 2-amino-3-(5-amino-1H-benzo [d] imidazoles)-pyridine in four hours.
The preparation method of a kind of formaldehyde quick detection reagent the most as claimed in claim 2, it is characterised in that: described preparation side
In method step 1, the temperature of oil bath is to be first to heat to 150 DEG C, the most again temperature is slowly increased to 200 DEG C, keeps reaction at a temperature of this
6 hours.
The preparation method of a kind of formaldehyde quick detection reagent the most as claimed in claim 2, it is characterised in that: described preparation side
In method step 1, the mol ratio of nicotiamide and Ammonium sulfamate is 1: 1.5, two hydrochloric acid 1,2,4-triaminobenzenes and 2-ammonia in step 3
The mol ratio of base-3-pyridine carboxaldehyde is 1: 1.
The using method of a kind of formaldehyde quick detection reagent the most as claimed in claim 1, it is characterised in that: its using method
Comprise the steps:
Step 1: measure certain density formalin, is formulated as the formaldehyde titer of 1200 μ g/mL；
Step 2: the formaldehyde titer compound concentration respectively of the 1200 μ g/mL that use previous step obtains is 0 μ g/mL, 15 μ g/
The formaldehyde liquid to be measured of mL, 30 μ g/mL, 100 μ g/mL and 200 μ g/mL；
Step 3: take appropriate five kinds of formaldehyde liquid to be measured respectively in test tube, and be separately added into appropriate probe molecule solutions, shake examination
Pipe so that it is mix homogeneously；
Step 4: place 30 minutes under room temperature, measure its fluorescence spectrum；
Step 5: map with the fluorescent emission intensity at 505nm, obtain concentration of formaldehyde numerical value to be measured.
The purposes of a kind of formaldehyde quick detection reagent the most as claimed in claim 1, it is characterised in that: it can apply to formaldehyde
Qualitative or quantitative detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410500026.2A CN104327042B (en) | 2014-09-26 | 2014-09-26 | A kind of formaldehyde quick detection reagent and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410500026.2A CN104327042B (en) | 2014-09-26 | 2014-09-26 | A kind of formaldehyde quick detection reagent and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104327042A CN104327042A (en) | 2015-02-04 |
| CN104327042B true CN104327042B (en) | 2016-11-02 |
Family
ID=52401862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410500026.2A Expired - Fee Related CN104327042B (en) | 2014-09-26 | 2014-09-26 | A kind of formaldehyde quick detection reagent and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104327042B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106092977B (en) * | 2016-05-27 | 2019-05-24 | 中山永恒检测科技有限公司 | Sensor for detecting formaldehyde and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634900A (en) * | 2004-10-21 | 2005-07-06 | 复旦大学 | Method for preparing 3-methyl-2-benzothiazolinone hydrazone and its hydrochloride |
| KR20110075573A (en) * | 2009-12-28 | 2011-07-06 | 한국세라믹기술원 | Reversible formaldehyde detection sensor and manufacturing method thereof |
| CN103570678A (en) * | 2013-11-01 | 2014-02-12 | 山西大学 | 2-quinolinone compound and preparation method and application thereof |
-
2014
- 2014-09-26 CN CN201410500026.2A patent/CN104327042B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634900A (en) * | 2004-10-21 | 2005-07-06 | 复旦大学 | Method for preparing 3-methyl-2-benzothiazolinone hydrazone and its hydrochloride |
| KR20110075573A (en) * | 2009-12-28 | 2011-07-06 | 한국세라믹기술원 | Reversible formaldehyde detection sensor and manufacturing method thereof |
| CN103570678A (en) * | 2013-11-01 | 2014-02-12 | 山西大学 | 2-quinolinone compound and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 快速分光光度法检测肉类食品中痕量甲醛的研究;唐尧基等;《山东科技大学学报自然科学版》;20110630;第30卷(第3期);75-78 * |
| 掺甲醛牛乳快速检测试纸的研制;王志琴等;《动物医学进展》;20111231;第32卷(第7期);61-65 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104327042A (en) | 2015-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Eu3+ doped bismuth metal-organic frameworks with ultrahigh fluorescence quantum yield and act as ratiometric turn-on sensor for histidine detection | |
| Sharma et al. | Selective recognition of fluoride ions through fluorimetric and colorimetric response of a first mesitylene based dipodal sensor 15employing thiosemicarbazones | |
| CN105669644B (en) | A kind of benzimidazole quinoline, preparation method and applications | |
| CN105085413B (en) | Tetrahydroquinazoline-2-schiff base compounds as well as synthesis method and application thereof | |
| CN106632084B (en) | Isolonglifolane ketone group hexahydro quinazoline -2- amine Schiff bases zinc ion fluorescent and its preparation method and application | |
| CN109535147B (en) | Formaldehyde fluorescent probe with rapid response and preparation method and application thereof | |
| CN108120750B (en) | A kind of preparation method and application of zearalanol optical electro-chemistry sensor | |
| CN103288726B (en) | Long chain quinoline hydrazone gel factor, metal gel preparation thereof an application thereof for detecting cyanide ions | |
| Jindal et al. | Selective sensing of aliphatic biogenic polyamines by a zwitterionic Cd-MOF based on bisimidazole tetracarboxylic acid linker | |
| WO2014115176A4 (en) | A novel aza bodipy compound for the selective detection of nitrite ions in water and a process for preparation thereof | |
| CN108658838B (en) | Heptamethine indocyanine-based formaldehyde fluorescent probe and preparation method and use method thereof | |
| CN109096183A (en) | A kind of pyridines Bis-quaternary Ammonium Salt Surfactant and its preparation method and application | |
| Zhao et al. | A hydrostable samarium (iii)-MOF sensor for the sensitive and selective detection of tryptophan based on a “dual antenna effect” | |
| CN104327042B (en) | A kind of formaldehyde quick detection reagent and preparation method and application | |
| Hu et al. | A highly efficient and selective probe for F− detection based on 1H-imidazo [4, 5-b] phenazine derivative | |
| Rao et al. | Pyridine-hydrazone-controlled cyanide detection in aqueous media and solid-state: tuning the excited-state intramolecular proton transfer (ESIPT) fluorescence modulated by intramolecular NH⋯ Br hydrogen bonding | |
| CN105403612A (en) | Method for rapidly detecting pesticide residue based on plant esterase | |
| Khanmohammadi et al. | A catalyst-free approach to a novel imidazo [4, 5-f][1, 10] phenanthroline ligand and its corresponding ruthenium (II) complex: Insights into their applications in colorimetric anion sensing | |
| CN102809598B (en) | Thermal polymerization preparation method for electrochemical sensor for rapidly detecting epigallocatechin-3-gallate (EGCG) | |
| CN109270259A (en) | A kind of endotoxic method of detection | |
| CN103044406B (en) | Coumarin derivatives and preparation method thereof and the application in detection cyanide ion | |
| CN106749142B (en) | A kind of SO32-/HSO3-Detection reagent and its synthetic method and application | |
| CN109694706A (en) | A kind of half flower cyanines class SO of cyanofuran32-Ratiometric fluorescent probe and its application | |
| CN110790942A (en) | Synthesis method and application of rare earth luminescent Eu-MOF material | |
| CN107793440A (en) | Fluorescence porous material, synthetic method and its application |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161102 Termination date: 20170926 |