CN108187615A - Carbon monoxide releasable material based on carbon nanotube and preparation method thereof - Google Patents

Carbon monoxide releasable material based on carbon nanotube and preparation method thereof Download PDF

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CN108187615A
CN108187615A CN201711457046.6A CN201711457046A CN108187615A CN 108187615 A CN108187615 A CN 108187615A CN 201711457046 A CN201711457046 A CN 201711457046A CN 108187615 A CN108187615 A CN 108187615A
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carbon nanotube
carbon monoxide
carbon
releasable material
preparation
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CN108187615B (en
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张伟强
李晶晶
张晓�
刘晓
张霞丽
谢遵园
张国防
高子伟
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Shaanxi Normal University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B01J20/205—Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating

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Abstract

The invention discloses a kind of carbon monoxide releasable material based on carbon nanotube and preparation method thereof, which is made of nano-carbon tube load ruthenium guide structure [CORM 2], and feature is can the infrared light radiation sustained release carbon monoxide of significant response.The material preparation method that the present invention uses is simple, is produced on a large scale.Myoglobins immunization experiment is found, the releasable material photoresponse is sensitive, it can be stabilized under physiological environment in vitro, its carrier carbon nano tube structure can effectively adsorb the heavy metal ion generated after release, so as to reduce heavy metal ion residual for the genotoxic potential in organism, critical material is provided for carbon monoxide therapeutic treatment.

Description

Carbon monoxide releasable material based on carbon nanotube and preparation method thereof
Technical field
The invention belongs to carbon monoxide releasable material technical fields, and in particular to utilize sound after a kind of excitation near infrared light The carbon nanotube of great specific surface area should and with absorption heavy metal ability is controlled release carrier, prepares and synthesizes a kind of safety, nothing Poison, the carbon monoxide releasable material that therapeutic dose can be carried.
Background technology
In recent years, endogenous CO physiological activity and treatment use research were achieved and were developed on a large scale very much.CO painstaking effort enlargement of pipe, Therapeutic effect is notable in the pre-clinical assays such as organ transplant, antipyretic and anti-inflammatory.However, CO is gas molecule, it is difficult to accurately control Its dosage is transmitted to organ or tissue where pathogeny；CO can strongly be combined with hemoglobin simultaneously, and the CO of high concentration causes tissue Anoxic leads to advanced bio body hypoxia death.Therefore, for patient and medical staff, treatment ten is carried out using gas CO Divide danger, it is difficult to carry out clinical treatment application.
In recent years, in order to solve the problems, such as gas CO in treatment invocation procedure, CO transmission materials are come into being.This A little CO transmission materials can carry a certain amount of carbonyl metal compound, and under environmental stimuli, for example, solvent auxiliary, enzymatic with And chemical reaction etc. starts CO releases.Light is to allow that people to go to determine that its CO is released as the advantage of external signal excitation CO releases Put position and time.Light excitation CO release tech starts applied to various macromolecular carriers, with covalently bonded together in nano particle And protein surface, realize therapeutic CO transmission applications research.For example, azido functionalization SiO2Nano-particle is carrier, can With [Mn (CO)3(tpm)]+Covalent bonding forms the nanoparticle of ultraviolet light response manganese tricarbonyl functionalization；Polyethylene glycol amino Graphite alkene (aPEG (NH2)8- GO) and manganese carbonyl carbon monoxide-releasing molecules (MnCO), MnCO-GO can be effectively improved to infrared Light has response；Luminescent nanoparticle is used as core, cladding amphipathic nature polyalcohol (polyethylene glycol phosphatide) can activate 3-Mn (bpy)(PPh3)2(CO)2Respond near infrared light release CO；Polyethylene glycol amination prussian blue nano particle (NH2-PEG6000- NH2- PB NPs) it can be coordinated by active site-CN and carbonyl iron, the CO releasable materials responded near infrared light can be formed.This The appearance of a little photosensitive CO releasable materials realizes the controllable sustained-release of CO to a certain extent, but its optical Response is weak, particularly infrared Optical Response is poor, and molten release of metal can generate toxicity after release.
Invention content
The technical problems to be solved by the invention are to overcome existing carbon monoxide releasable material infrared light rdaiation response poor And there are the shortcomings that toxic heavy metal residual, provide a kind of carbon monoxide releasable material based on carbon nanotube, carbon nanotubes tool There is the infrared optical response that unique optical characteristics can effectively improve ruthenium, being simultaneously functionalized carbon nanotubes can effectively combine Metal ion inhibits the molten of metal to release, so as to reduce the bio-toxicity of entire material.
The carbon monoxide releasable material based on carbon nanotube is prepared by following methods used by solving above-mentioned technical problem It obtains：
By [Ru (CO)3Cl2]2(CORM-2) be dissolved in dimethyl sulfoxide or tetrahydrofuran, add in carbon nanotube, CORM-2 with The mass ratio of carbon nanotube is 1:3~2:1, be stored at room temperature to dimethyl sulfoxide or tetrahydrofuran and volatilize completely, with dimethyl sulfoxide or Tetrahydrofuran washs, dry with absolute ethyl alcohol centrifuge washing, obtains the carbon monoxide releasable material based on carbon nanotube.
In above-mentioned preparation method, preferably [Ru (CO)3Cl2]2Mass ratio with carbon nanotube is 1:2~2:1.
In above-mentioned preparation method, the carbon nanotube and quality-volume ratio of dimethyl sulfoxide or tetrahydrofuran are preferably 50mg:6~18mL.
The present invention is to be controllable with infrared optical response and to carbon nanotube of the heavy metal material with certain adsorptivity Discharge carrier, load ruthenium carbonyl species Ru (CO)3Cl2[Ru (CO)3Cl2]2, obtain a kind of carbon monoxide based on carbon nanotube Releasable material.Preparation method of the present invention is simple, and the carbon monoxide releasable material being prepared can effectively control the release of CO, no It can only achieve the purpose that transmit CO, and utilize the suction-operated of carbon nanotube absorption ruthenium carbonyl compound during CO is conveyed The heavy metal ion generated after kind release reduces the residual of heavy metal ion in vivo, realizes that biosystem CO delays safely Effect release remains heavy metal ion, simultaneously because carbon nanotube is only after solving the problems, such as transition metal carbonyl compound release Special optical property so that prepared carbon monoxide releasable material can effectively be sustained CO near infrared light region.
Description of the drawings
Fig. 1 is the infrared spectrogram of the carbon monoxide releasable material based on carbon nanotube prepared by embodiment 1.
Fig. 2 is the TEM light field figures of the carbon monoxide releasable material based on carbon nanotube prepared by embodiment 1.
Fig. 3 is the TEM details in a play not acted out on stage, but told through dialogues figures of the carbon monoxide releasable material based on carbon nanotube prepared by embodiment 1.
Fig. 4 is the XRD diagram of the carbon monoxide releasable material based on carbon nanotube prepared by embodiment 1.
Fig. 5 is the kinetic release curves of the carbon monoxide releasable material based on carbon nanotube prepared by embodiment 1.
Fig. 6 is the kinetic release curves of the carbon monoxide releasable material based on carbon nanotube prepared by embodiment 2.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to These embodiments.
Embodiment 1
It weighs 50mg CORM-2 to be dissolved in 6mL dimethyl sulfoxides, addition 100mg carbon nanotubes, magnetic agitation 3h, room temperature is quiet It puts to dimethyl sulfoxide and volatilizees completely, washed once with dimethyl sulfoxide, centrifuge, washed twice with absolute ethyl alcohol, centrifuge, it is dry, it obtains Carbon monoxide releasable material (CO-CNTs) based on carbon nanotube.
Resulting materials carry out infrared, transmission and XRD characterization, the result is shown in Figure 1~4.2375.39cm in Fig. 1-1With 2341.55cm-1Corresponding to three carbonyl peaks on CORM-2 molecules, Fig. 2 can be clearly apparent the CORM-2 loaded in carbon nanotube Molecule, the light tone dot in Fig. 3 are CORM-2 molecules, it is also clear that the CORM-2 loaded in carbon nanotube points Son, 14 ° in Fig. 4 with lattice peak that 15 ° of two spikes are CORM-2.
It is computed learning, the CO-CNTs materials of 1mg the present embodiment can carry 0.164mg carbon monoxide.The present embodiment is made Standby CO-CNTs materials are sustained carbon monoxide in vitro under the Infrared irradiation of 800nm under environment, burst size is shown in Fig. 5.By For Fig. 5 as it can be seen that when sample concentration is 0.6mg/ μ L, release CO amounts are 10.82369 μm of ol/L (26.8 μ L)；Sample concentration is During 1.2mg/ μ L, release CO amounts are 14.96933 μm of ol/L (36.74 μ L)；When sample concentration is 1.8mg/ μ L, CO is discharged It measures as 13.73106 μm of ol/L (33.70 μ L).
Embodiment 2
It weighs 100mg CORM-2 to be dissolved in 12mL tetrahydrofurans, addition 50mg carbon nanotubes, magnetic agitation 3h, room temperature is quiet It puts to tetrahydrofuran and volatilizees completely, washed once with tetrahydrofuran, centrifuge, washed twice with absolute ethyl alcohol, centrifuge, it is dry, it obtains Carbon monoxide releasable material (CO-CNTs) based on carbon nanotube.
As seen from Figure 6, when the CO-CNTs material concentrations prepared by the present embodiment are 0.6mg/ μ L, release CO amounts are 9.64753μmol/L(23.68μL)；It is 10.47938 μm of ol/L (25.72 μ L) that it, which discharges CO amounts, during a concentration of 1.2mg/ μ L；It is dense It is 22.87949 μm of ol/L (56.15 μ L) that it, which discharges CO amounts, when spending for 1.8mg/ μ L.

Claims (4)

1. a kind of preparation method of the carbon monoxide releasable material based on carbon nanotube, it is characterised in that：By [Ru (CO)3Cl2]2 It is dissolved in dimethyl sulfoxide or tetrahydrofuran, adds in carbon nanotube, [Ru (CO)3Cl2]2Mass ratio with carbon nanotube is 1:3~2: 1, be stored at room temperature to dimethyl sulfoxide or tetrahydrofuran and volatilize completely, washed with dimethyl sulfoxide or tetrahydrofuran, with absolute ethyl alcohol from The heart washs, dry, obtains the carbon monoxide releasable material based on carbon nanotube.
2. the preparation method of the carbon monoxide releasable material according to claim 1 based on carbon nanotube, it is characterised in that： [the Ru (CO)3Cl2]2Mass ratio with carbon nanotube is 1:2~2:1.
3. the preparation method of the carbon monoxide releasable material according to claim 1 based on carbon nanotube, it is characterised in that： The carbon nanotube is 50mg with quality-volume ratio of dimethyl sulfoxide or tetrahydrofuran:6~18mL.
4. the carbon monoxide releasable material based on carbon nanotube prepared by claims 1 to 3 any one method.
CN201711457046.6A 2017-12-28 2017-12-28 Carbon monoxide release material based on carbon nano tube and preparation method thereof Active CN108187615B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1561207A (en) * 2001-05-15 2005-01-05 北威克公园医学研究所 Therapeutic delivery of carbon monoxide
CN103920456A (en) * 2014-03-25 2014-07-16 陕西师范大学 Natural clay based carbon monoxide release material and preparation method thereof
JP2015105208A (en) * 2013-11-29 2015-06-08 日本ゼオン株式会社 Carbon nanotube and dispersion liquid thereof, and self-supporting film and composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1561207A (en) * 2001-05-15 2005-01-05 北威克公园医学研究所 Therapeutic delivery of carbon monoxide
JP2015105208A (en) * 2013-11-29 2015-06-08 日本ゼオン株式会社 Carbon nanotube and dispersion liquid thereof, and self-supporting film and composite material
CN103920456A (en) * 2014-03-25 2014-07-16 陕西师范大学 Natural clay based carbon monoxide release material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HENDRIK ULBRICHT等: "Thermal desorption of gases and solvents from graphite and carbon nanotube surfaces", 《CARBON》 *
周金梅 等: "多壁碳纳米管的纯化及其表面含氧基团的表征", 《物理化学学报》 *

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