CN107367449B - Traceable PM2.5 particle composite material and preparation method thereof - Google Patents

Traceable PM2.5 particle composite material and preparation method thereof Download PDF

Info

Publication number
CN107367449B
CN107367449B CN201710629470.8A CN201710629470A CN107367449B CN 107367449 B CN107367449 B CN 107367449B CN 201710629470 A CN201710629470 A CN 201710629470A CN 107367449 B CN107367449 B CN 107367449B
Authority
CN
China
Prior art keywords
particles
traceable
composite material
haze
particle composite
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.)
Active
Application number
CN201710629470.8A
Other languages
Chinese (zh)
Other versions
CN107367449A (en
Inventor
孙康宁
葛平慧
李爱民
成圆
张书品
祁宇凡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong University
Original Assignee
Shandong University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shandong University filed Critical Shandong University
Priority to CN201710629470.8A priority Critical patent/CN107367449B/en
Publication of CN107367449A publication Critical patent/CN107367449A/en
Application granted granted Critical
Publication of CN107367449B publication Critical patent/CN107367449B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00Investigating characteristics of particles; Investigating permeability, pore-volume, or surface-area of porous materials
    • G01N15/06Investigating concentration of particle suspensions
    • G01N15/075

Abstract

The invention relates to a traceable PM2.5 particle composite material and a preparation method thereof, wherein PM2.5 particles collected in the atmosphere and nano luminescent particles are subjected to chemical crosslinking compounding to obtain the traceable PM2.5 particle composite material. The materials with the micro-nano structure have the performances of stable luminescence performance, tracer, high biological penetrability and the like, can be used as biological materials and functional materials for haze formation, hazard, defense simulation and pathological research, and are used in the related fields.

Description

Traceable PM2.5 particle composite material and preparation method thereof
Technical Field
The invention belongs to the field of biological materials, and particularly relates to a traceable haze particle composite material and a preparation method thereof, in particular to a method for chemically crosslinking PM2.5 particles by adopting a luminescent material to prepare traceable haze particles with high penetrating power for haze defense simulation and pathological research.
Background
With the rapid expansion of economic scale and the acceleration of urbanization process in China, atmospheric aerosol pollution is becoming more and more serious, visibility deterioration events caused by aerosol are more and more, and haze becomes one of important reasons for harming human public health, especially PM2.5 particles. NO in PM2.5 particles3-,SO4 2-,Cl-,NH4+,Na+The plasma concentration is higher than that of normal atmospheric particles, and the main pollutants are heavy metals such As As, Cr, PB, Ti and V, so that the plasma can damage human organs after entering a human body. Then what is the particular intrusion path of PM 2.5? How to protect against PM2.5 damage to human organs and systems? These problems have been of considerable concern. The key to the problem is to clearly mark and trace the route pattern of PM2.5 particle intrusion and egress from the body.
Upconversion luminescence refers to the process by which a material absorbs two or more photons of low energy (typically near infrared light) and emits photons of high energy (typically visible light). Long persistence luminescence, which means that the material still can emit light for a period of time after excitation is stopped, and the duration of light emission is from several seconds to several weeks. The up-conversion luminescence nano-particles and the near-infrared long-afterglow nano-particles are used as nano optical probes for in vivo imaging, which attracts people's extensive attention. This is because the upconversion luminescence imaging usually uses 980nm near-infrared light as an excitation light source, and the near-infrared long-afterglow imaging uses near-infrared light as an imaging signal. In the imaging process, no matter near infrared light is used as an excitation light source or an imaging signal, background interference (such as autofluorescence and the like) of organism tissues can be greatly reduced, so that the tissue penetration depth and sensitivity of biological imaging are remarkably improved.
At present, PM2.5 haze particles are complex in composition and have certain pathogenicity and toxicity, so that the process that PM2.5 haze particles invade a human body is generally researched by a mode material in the prior art, but the mode material is complex to prepare, low in simulation degree and limited in wide application, and therefore a simpler and efficient PM2.5 particle tracing method is urgently needed.
Disclosure of Invention
In order to overcome the defects, the invention provides a preparation method of a nano luminescent material and PM2.5 haze particle composite material, namely nano up-conversion or long afterglow luminescent material chemically crosslinking PM2.5 particles. When the particles enter lung tissues, the invasion process of PM2.5 particles to human bodies and the defense mechanism of human tissues to the PM2.5 particles are researched through marking and tracing the particles, and the results show that: the method can clearly mark and trace the route pattern of PM2.5 particle invasion and excretion from human bodies.
In order to achieve the purpose, the invention adopts the following technical scheme:
a traceable PM2.5 particulate composite comprising:
PM2.5 haze particles;
the nano inorganic luminescent particles coat the PM2.5 haze particles;
the traceable PM2.5 particle composite material is of a core-shell structure;
and the PM2.5 haze particles are subjected to soaking and drying treatment.
In order to solve the problems of complex preparation and low simulation degree of the existing mode material, the invention designs the luminous PM2.5 particles, and the nano up-conversion or long-afterglow luminous material is coated outside the luminous PM2.5 particles by utilizing the characteristics of irregular shape and easiness in pollutant loading of the particles to form the tracer. The method not only effectively ensures the integrity of the PM2.5 haze particle structure, but also greatly reduces the background interference of organism tissues in the process of PM2.5 particles invading human bodies, and obviously improves the tissue penetration depth and sensitivity of imaging.
Preferably, the mass fraction of the PM2.5 haze particles can be 0.1-99.9%.
The invention also provides a preparation method of the traceable PM2.5 particle composite material, which comprises the following steps:
collecting PM2.5 haze particles, soaking in an organic solvent, and freeze-drying for later use;
mixing and grinding the nano inorganic luminescent particles and the PM2.5 haze particles in the presence of a chemical cross-linking agent to obtain mixed particles, drying, and sintering at a low temperature to obtain the PM2.5 particle composite material capable of tracing.
In order to obtain a simple preparation method of a PM2.5 particle composite material with a better tracing effect, the invention carries out systematic research on the combination rule of PM2.5 particles and a nano inorganic luminescent material and the influence of the combination rule on the tracing effect under different combination modes, and finds that: the haze particles and the nano luminescent particles after freeze drying can form traceable PM2.5 particles with a shell surface coating structure through drying and low-temperature sintering under the action of a chemical crosslinking agent. The method has the advantages of easy control, simple and convenient process and the like, can regulate and control the size and the performance of the traceable PM2.5 particle composite material by controlling parameters such as the proportion and the like, and has better tracing effect.
Preferably, the nano-phosphor particles are ZnGa2O4:Cr3+Isometric afterglow luminescent material, NaYF4: Yb3+,Er3+Etc. up-converting the luminescent material.
Preferably, the mass ratio of the PM2.5 particles to the nano inorganic luminescent particles is 1000: 1-1: 1000.
Preferably, the organic solvent is an organic solvent containing a hydroxyl group such as ethanol or methanol.
Preferably, the chemical crosslinking agent is polyvinyl alcohol (PVA), cyclodextrin, paraffin and other bio-available organic plasticizers.
Preferably, the drying is freeze-drying, with the conditions: freezing at-200 deg.C, lyophilizing for 50h, and drying thoroughly.
The invention also provides traceable PM2.5 particulate composites prepared by any of the above methods.
According to the invention, luminescent nanoparticles and PM2.5 particles are chemically crosslinked, and a traceable PM2.5 particle composite material is prepared by compounding excellent luminescent properties such as high sensitivity and high stability of a luminescent nanomaterial and a biological tracing property with the PM2.5 particles, so that the traceable PM2.5 particles with controllable size, uniform compounding, stable property, traceable property and high biological penetrability are obtained, and the traceable PM2.5 particle is used for haze formation, hazard, defense simulation and pathological research.
The invention also provides application of any traceable PM2.5 particle composite material in haze particle tracing, haze formation, harm and defense simulation and pathological research.
As the intake is very small and mainly used for scientific research, the traceable PM2.5 particulate composite material of the present invention is of negligible harm to humans and animals. If necessary, it can be used only for labeling and tracing of cell culture.
The invention has the advantages of
(1) The invention provides a traceable PM2.5 particle composite material and a preparation method thereof, wherein nanometer up-conversion or long afterglow luminescent materials are adopted to chemically crosslink PM2.5 haze particles. The traceable PM2.5 particle composite material is prepared by the method. The invention designs a PM2.5 particle capable of photoluminescence, which has the capabilities of tracing and high penetration, can solve the tracing problem and explore the itinerant route of haze particles in an animal body, namely, the defense and invasion mechanism of biological tissues to the haze particles is directly observed by utilizing a PM2.5 particle composite material capable of tracing.
(2) In the invention, different luminescent materials are selected to prepare PM2.5 composite materials with different luminescent material performances and different tracing properties. PM2.5 composite materials with various PM2.5 contents and luminous brightness and capable of being traced are prepared by controlling different proportions of the luminescent materials and the haze particles. The mass fraction of PM2.5 in the traceable PM2.5 composite may be 0.1-99.9%.
(3) The preparation method is simple, high in luminous efficiency, strong in practicability and easy to popularize.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 shows PM2.5 and ZnGa of example 12O4:Cr3+And (3) a cross-linked composite structure.
FIG. 2 shows ZnGa of example 12O4:Cr3+Cubic phase particles coat PM2.5 particles to form a traceable PM2.5 particle composite material with a shell coating structure.
Fig. 3 is a graph of the photoluminescence performance of the traceable PM2.5 particle composite of example 1.
FIG. 4 is a graph of the afterglow performance of the traceable PM2.5 particulate composite of example 1.
FIG. 5 is a confocal microscope image of the traceable PM2.5 particle composite material of example 4.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
Example 1:
1) soaking a glass fiber filter membrane which is used for collecting PM2.5 haze particles by an atmosphere collector (MH1200, an atmospheric particulate matter sampler, SALTHENTIAN Instrument and Meter Co., Ltd.) in ethanol for 12h, taking out the filter membrane, placing an ethanol solution in which the PM2.5 particles are dissolved in a vacuum freeze drying oven (Scientz-ND, a freeze dryer, Ningbo New Ganoderma Biotech Co., Ltd.), setting the freezing temperature to-200 ℃, freeze-drying for 50h, and fully evaporating and drying to obtain treated PM2.5 particles;
2) ZnGa prepared by solid phase method2O4:Cr3+(according to patent CN201510650991.2), stirring, ultrasonically dissolving in water, standing for 24 hours, taking the suspension, and centrifuging at high speed by a centrifuge at the rotation speed of 10000rpm to obtain the near-infrared ultra-long afterglow luminescent ZnGa with the average particle size of less than 100nm2O4:Cr3+And (3) nanoparticles.
3) Taking ZnGa2O4:Cr3+0.02g of nano particles, 0.02g of treated PM2.5 particles and 0.25g of cyclodextrin are dissolved in 60ml of water together, the mixture is stirred vigorously in a three-neck flask under the protection of nitrogen until the mixture is completely dissolved, 1 mol/L NaOH is added to adjust the pH value to be 9-10, the obtained black solution is poured into the flask for ultrasonic reaction for 1 hour, and vacuum drying is carried out for 24 hours, so that dry particles are obtained;
4) sintering the dried particles obtained in the step 3) at 300 ℃ for 4h for degumming and volatilization, namely decomposing and volatilizing cyclodextrin to obtain a PM2.5 traceable particle composite material;
the structure of the particles after the crosslinking and the structure of the composite material were observed by a scanning electron microscope (SEM, TDC L S-4800, Toshiba, Japan) as shown in FIGS. 1 and 2, the structure of the composite particles was observed by X-ray spectroscopy (EDS, TDC L S-4800, Toshiba, Japan) and the photoluminescence properties of the composite material were analyzed by a fluorescence spectrophotometer (F-7000, 200-900nm, Hitachi, Japan) test as shown in FIG. 3 and the afterglow properties as shown in FIG. 4.
Example 2:
traceable PM2.5 particulate composites were prepared using the same method as in example 1, using 5% by mass polyvinyl alcohol instead of the cyclodextrin used.
The traceable PM2.5 particle composite material prepared in the embodiment is taken to represent the properties of the sample, and the detection result is similar to that of the embodiment 1.
Example 3:
using the same method as in example 1, a near-infrared long afterglow luminescent material Zn was used3Ga2Ge2O10:Cr3+(according to patent CN 103215041A) and PM2.5 particles are compounded to prepare a traceable PM2.5 particle composite material.
The traceable PM2.5 particle composite material prepared in the embodiment is taken to represent the properties of the sample, the detection result is similar to that of the embodiment 1, and the traceable PM2.5 particle composite material has better long afterglow performance.
Example 4:
using the same method as in example 1, NaYF, which is an up-conversion luminescent material, was used4:Yb3+,Er3+(according to patent CN105112056A) and PM2.5 particles to prepare traceable PM2.5 particle composite materials.
The traceable PM2.5 particle composite material prepared in the embodiment is taken to represent the properties of the sample, the detection result is similar to that of the embodiment 1, and the traceable PM2.5 particle composite material has up-conversion luminescence performance.
Example 5:
ZnGa was reacted by the same method as in example 12O4:Cr3+And haze particles are mixed according to the mass ratio of 10:1, and the PM2.5 particle composite material can be traced.
The traceable PM2.5 particle composite material prepared in the embodiment is taken to represent the properties of the sample, and the detection result is similar to that of the embodiment 1.
Example 6:
ZnGa was reacted by the same method as in example 12O4:Cr3+And haze particles are mixed according to the mass ratio of 20:1, and the PM2.5 particle composite material can be traced.
The traceable PM2.5 particle composite material prepared in the embodiment is taken to represent the properties of the sample, and the detection result is similar to that of the embodiment 1.
Example 7:
traceable PM2.5 particle composites were prepared using the same method as in example 4 and imaged with a confocal microscope equipped with a titanium gem pulsed laser (C L SM, AZ-C2)+Nikon corporation of Japan) observed that the composite material emitted 520-540nm visible light under 980nm near-infrared excitation, as shown in FIG. 5. It is inferred that when the composite material is used for cell culture and organism culture, it can be labeled and traced by a confocal microscope and a living body imager (DS-Ri1-U3 Digital Camera, Nikon corporation, Japan).
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (3)

1. A preparation method of a traceable PM2.5 particle composite material is characterized by comprising the following steps:
1) soaking a glass fiber filter membrane which collects PM2.5 haze particles by using an atmosphere collector in ethanol for 12 hours, taking out the filter membrane, placing an ethanol solution in which the PM2.5 particles are dissolved in a vacuum freeze drying box, setting the freezing temperature to be-200 ℃, freeze-drying for 50 hours, and fully evaporating and drying to obtain the treated PM2.5 particles;
2) ZnGa prepared by solid phase method2O4:Cr3+Stirring, dissolving in water after ultrasonic treatment, standing for 24 hours, taking the suspension, and centrifuging at high speed under the rotation speed of 10000rpm by using a centrifuge to obtain the near-infrared ultra-long afterglow luminescent ZnGa with the average particle size of less than 100nm2O4:Cr3+A nanoparticle;
3) taking ZnGa2O4:Cr3+0.02g of nano particles, 0.02g of treated PM2.5 particles and 0.25g of cyclodextrin are dissolved in 60ml of water together, the mixture is stirred vigorously in a three-neck flask under the protection of nitrogen until the mixture is completely dissolved, 1 mol/L NaOH is added to adjust the pH value to be 9-10, the obtained black solution is poured into the flask for ultrasonic reaction for 1 hour, and vacuum drying is carried out for 24 hours, so that dry particles are obtained;
4) sintering the dried particles obtained in the step 3) at 300 ℃ for 4h for degumming and volatilization, namely decomposing and volatilizing cyclodextrin to obtain the traceable PM2.5 particle composite material.
2. Traceable PM2.5 particulate composites made by the method of claim 1.
3. Use of the traceable PM2.5 particulate composite of claim 2 in haze particulate tracing and haze formation, hazard, defense simulation and pathology research.
CN201710629470.8A 2017-07-28 2017-07-28 Traceable PM2.5 particle composite material and preparation method thereof Active CN107367449B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710629470.8A CN107367449B (en) 2017-07-28 2017-07-28 Traceable PM2.5 particle composite material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710629470.8A CN107367449B (en) 2017-07-28 2017-07-28 Traceable PM2.5 particle composite material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107367449A CN107367449A (en) 2017-11-21
CN107367449B true CN107367449B (en) 2020-07-31

Family

ID=60308545

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710629470.8A Active CN107367449B (en) 2017-07-28 2017-07-28 Traceable PM2.5 particle composite material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107367449B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105548114A (en) * 2015-12-31 2016-05-04 北京大学 Method for analyzing atmospheric particulate matter toxicity online in real time
CN106191229A (en) * 2014-11-12 2016-12-07 韩国科学技术研究院 For to being exposed to microRNA that particulate matter 2.5 (PM2.5) differentiates and using this microRNA to carry out the method for distinguishing that reflects
CN106290272A (en) * 2016-07-25 2017-01-04 北京大学 A kind of method of real-time detection Atmospheric particulates bio-toxicity
CN106834429A (en) * 2015-12-07 2017-06-13 韩国科学技术研究院 For confirming less than the 2.5 microns whether exposed biomarkers of fine dust and utilizing its confirmation method
CN107219215A (en) * 2017-05-03 2017-09-29 河海大学 Organic pollution detection method of toxicity in Atmospheric particulates based on Luminous bacteria
CN107314955A (en) * 2017-07-03 2017-11-03 上海市浦东新区疾病预防控制中心 Judge the method for the bio-toxicity of PM2.5 fine particles

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013060568A (en) * 2011-09-15 2013-04-04 Tokai Univ Upconversion phosphor
US8999506B2 (en) * 2012-03-21 2015-04-07 The Hong Kong Polytechnic University Method of one-pot synthesis of water-soluble nanoparticles exhibiting up-conversion luminescence
JP2015178602A (en) * 2014-02-28 2015-10-08 積水化学工業株式会社 Up-conversion coated particle
CN105802627B (en) * 2016-04-29 2018-05-01 华南师范大学 Composite nano materials and its preparation of long afterglow are changed in a kind of near infrared light excitation
CN106433627A (en) * 2016-09-13 2017-02-22 山东大学 Cr<3+>-doped zinc gallate near-infrared long-afterglow luminescent nanoparticles and preparation method
CN106398694A (en) * 2016-09-13 2017-02-15 山东大学 Pb<2+>-doped ultraviolet long-afterglow luminescent material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106191229A (en) * 2014-11-12 2016-12-07 韩国科学技术研究院 For to being exposed to microRNA that particulate matter 2.5 (PM2.5) differentiates and using this microRNA to carry out the method for distinguishing that reflects
CN106834429A (en) * 2015-12-07 2017-06-13 韩国科学技术研究院 For confirming less than the 2.5 microns whether exposed biomarkers of fine dust and utilizing its confirmation method
CN105548114A (en) * 2015-12-31 2016-05-04 北京大学 Method for analyzing atmospheric particulate matter toxicity online in real time
CN106290272A (en) * 2016-07-25 2017-01-04 北京大学 A kind of method of real-time detection Atmospheric particulates bio-toxicity
CN107219215A (en) * 2017-05-03 2017-09-29 河海大学 Organic pollution detection method of toxicity in Atmospheric particulates based on Luminous bacteria
CN107314955A (en) * 2017-07-03 2017-11-03 上海市浦东新区疾病预防控制中心 Judge the method for the bio-toxicity of PM2.5 fine particles

Also Published As

Publication number Publication date
CN107367449A (en) 2017-11-21

Similar Documents

Publication Publication Date Title
Xue et al. A 980 nm laser-activated upconverted persistent probe for NIR-to-NIR rechargeable in vivo bioimaging
Chatterjee et al. Upconversion fluorescence imaging of cells and small animals using lanthanide doped nanocrystals
US20220001032A1 (en) Coated up-conversion nanoparticles
Liu et al. Simultaneous synthesis and amine-functionalization of single-phase BaYF 5: Yb/Er nanoprobe for dual-modal in vivo upconversion fluorescence and long-lasting X-ray computed tomography imaging
Singh Red and near infrared persistent luminescence nano-probes for bioimaging and targeting applications
Anilkumar et al. Toward quantitatively fluorescent carbon-based “quantum” dots
Hemmer et al. In vitro and in vivo investigations of upconversion and NIR emitting Gd 2 O 3: Er 3+, Yb 3+ nanostructures for biomedical applications
Yu et al. Luminescence enhancement of CaF 2: Nd 3+ nanoparticles in the second near-infrared window for in vivo imaging through Y 3+ doping
US20060269483A1 (en) SEM cathodoluminescent imaging using up-converting nanophosphors
CN108485097B (en) Long-afterglow luminescent nanoparticle labeled micro-plastic and preparation method and application thereof
CN113817469B (en) Ultra-bright monochromatic up-conversion nano probe for excitation/emission in biological window and preparation method and application thereof
Li et al. Preparation and upconversion luminescence cell imaging of O-carboxymethyl chitosan-functionalized NaYF 4: Yb 3+/Tm 3+/Er 3+ nanoparticles
CN108949151B (en) Up-conversion luminescence nano composite material with transition metal disulfide growing on surface, preparation method and application
Kang et al. SrAl12O19: Fe3+@ 3‐aminopropyl triethoxysilane: Ambient aqueous stable near‐infrared persistent luminescent nanocomposites
CN107367449B (en) Traceable PM2.5 particle composite material and preparation method thereof
CN108300460B (en) Nano sulfide near-infrared long-afterglow material and preparation and application thereof
Gherman et al. Pharmacokinetics evaluation of carbon nanotubes using FTIR analysis and histological analysis
CN108545950A (en) A kind of er-doped biological activity glass and preparation method thereof
CN108587102A (en) The micro- plastics of environment and preparation method of a kind of metal organic fluorescence cooperation substance markers and application
Parvin et al. Polyelectrolyte carbon quantum-dots: new player as a noninvasive imaging probe in Drosophila
CN105463616B (en) A kind of cadmium telluride quantum dot/polylactic acid nano fiber fluorescence probe preparation method to chloramphenicol detection
CN104031635B (en) The preparation method of the up/down conversion luminescence mesoporous nano material of rare earth compounding functionalization and bio-imaging application thereof
Jung et al. High selective fluorescence imaging of cesium distribution in Arabidopsis using a bis (trihydroxyphenyl)-appended fluorescent probe with a turn-on system
CN107216871B (en) A kind of preparation method of the water-solubility rare-earth up-conversion nano material of polyose modification
CN113201344B (en) Rare earth doped near infrared luminous hydrogel and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant