CN105879111A - Novel construction method of biodegradable porous PHBV/PPC (poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate) composite scaffold - Google Patents
Novel construction method of biodegradable porous PHBV/PPC (poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate) composite scaffold Download PDFInfo
- Publication number
- CN105879111A CN105879111A CN201410814153.XA CN201410814153A CN105879111A CN 105879111 A CN105879111 A CN 105879111A CN 201410814153 A CN201410814153 A CN 201410814153A CN 105879111 A CN105879111 A CN 105879111A
- Authority
- CN
- China
- Prior art keywords
- ppc
- phbv
- poly
- gma
- dcp
- 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.)
- Pending
Links
Landscapes
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a construction method of a poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate (PHBV-PPC) porous scaffold by virtue of a reactive melt blending-ultrasonic particulate leaching-alkali treatment technology. The construction method comprises the following steps: mixing MA (1-2%), DCP (0.1-0.5%) and the PPC at 130-160 DEG C by 30rpm, so that MA-terminated PPC (MA-PPC) is obtained; mixing the PHBV with GMA (1-15%) and DCP (0.1-0.5%) at 165-175 DEG C, so that GMA-modified PHBV is obtained; and conducting reactive blending and ultrasonic particulate leaching on the MA-PPC, the GMA-modified PHBV and NaCl at 165-175 DEG C, soaking in 1-2mol/L of NaOH for 60-120min, washing in water and freeze-drying. The constructed scaffold, applied to tissue repair, is expected to achieve popularization and application in the fields of bio-medical materials and ecological environmental protection.
Description
Technical field
The present invention relates to the construction method of a kind of complete biodegradable porous poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV)/poly (propylene carbonate) (PPC) compound rest, it is specifically related to a kind of PHBV/PPC compound rest method built based on the reactive ultrasonic leaching of melt blending-particle-alkali treatment technology, belong to Biodegradable material field, be applied to packaging for foodstuff, medical apparatus and instruments, medicament slow release or field of tissue engineering technology.
Background technology
Organizational project is the external reconfiguration technique of live organism, is to repair or substitute the impaired or available strategy of pathological tissues.Use suitable support fast proliferating cells and to keep the biological activity of bioactive molecule be the great challenge of field of tissue engineering technology.From molecular level, cellular level, gene level multipolarity build can mediate cell growth, inducing cell specific differentiation, maintain cell phenotype, there is the functional type support of good biocompatibility, biological degradability, excellent mechanical performance, become the focus of imitation biochemistry design in recent years.
Poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV) is that microorganism is in carbon source excess, when nitrogen source, phosphorus source lack, it is accumulated in its internal thermoplastic aliphatic's polyester participating in cellular metabolism as nutrition and energy storage material, is the most potential biomedical material of organizational project and medicament slow release field in recent years.Its natural avirulence, the piezoelectricity of imitative bone, excellent biocompatibility and without significantly degrading acidity, slowly degradation rate and controlled mechanical property and to the medical treatment of cell or nutritive value, it is used for field of tissue engineering technology and forms cytoskeleton, excite tissue regeneration and functional rehabilitation.But, PHBV degree of crystallinity is higher, and spherulite size is relatively big, causes material fragility relatively big, and hydrophilic is poor, and its hydrophobicity and fragility are to limit it to apply the most challenging key scientific problems and bottleneck difficult point in vivo.
Poly (propylene carbonate) (PPC) is by carbon dioxide (CO2) and " two-way " environmental type high polymer of catalyzing and synthesizing of expoxy propane (PO), its production process consumes CO2, the CO in environment is fixed and circulated to building-up process2, this not only reduces the dependence to oil, and because of the CO of high added value2Fix and reduce greenhouse effect, become the research topic gained great popularity in recent years.The pliability of PPC is allowed in organizational project obtain first-stage success, it is blended, with poly-(3-hydroxybutyrate ester-3-hydroxycaproic ester) (PHBHHx), the support processed, mechanical property and wettability are obviously improved (L Zhang, Z H Zheng, J Xi, Y Gao, Q Ao, Y D Gong, N M Zhao, X F Zhang, European Polymer Journal 43 (2007) 2975-2986).
PHBV with PPC is blended, in the case of not affecting degradation property, the physical property of controlled material because of mutual supplement with each other's advantages, the combination property of material can be made to be optimized.The spherulite growth rate (S W Peng, Y X An, C Chen, B Fei, Y G Zhuang, L S Dong, Journal of Applied Polymer Science 90 (2003) 4054-4060) of PHBV is reduced as Dong Li pine group adds PPC；Chen Long group uses polarizing microscope (PLM) to observe crystal habit (L Chen, M F Zhu, the L Y Song of PHBV in blend, H Yu, Y Zhang, Y Chen, H J Adler, Macromolecular Symposia 210 (2004) 241-250)；The PHBV/PPC blend film that Wang Shufang group is prepared with solution casting method, improve heat stability and biological degradability (the J Tao of PPC, C J Song, M F Cao, D Hu, L Liu, N Liu, S F Wang, Polymer Degradation and Stability 94 (2009) 575-583).But, both components are the most miscible, easily occur to be separated and make mechanical property undesirable.And reactively blending method is by component functional group coupling in situ on boundary, form block or graft copolymer, it is achieved the increasing reaction of blend, solve the available strategy being separated between component.
Introduce the functional groups such as amino, epoxy radicals, maleic anhydride (MA), HEMA (HEMA), collagen, chitosan to PHBV surface or biomacromolecule covalency is fixed, the reactions such as ester exchange, grafting, depolymerization and repolymerization can occur, it is thus achieved that the polymer of excellent performance and blend.Wherein the hydrolyzate maleic acid of MA is identical with the structure of internal TCA cycle intermediate's Fumaric acid, and it is difficult to homopolymerization, beneficially cell adhesion and propagation, can safety applications in internal surface modification.Glycidyl methacrylate (GMA) is as a bifunctional monomer, and its unsaturated group is applicable to free radical grafting, and epoxy radicals has higher reactivity to electrophilic and nucleophilic group such as carboxyl, hydroxyl or amido.Foxtail millet case fibre (CSF) is grafted PHA (PHA-g-GMA) reactively blending with GMA, inoculation fibroblast (FB) is bred performance afterwards and is better than PHA (C S Wu, H T Liao, Polymer Degradation and Stability 99 (2014) 274-282).
Alkali treatment technology is the new surface modifications method improving polymer surfaces wettability and viscosity proposed in recent years.The PHBHHx surface processed with sodium hydroxide (NaOH), blood compatibility more excellent (F Shen, E L Zhang, Z J Wei, Materials Science and Engineering C 30 (2010) 369-375).Use electrostatic spinning, solution-cast/particle leaching, 3-D deposition, Thermal inactive, the selective laser sintering etc. can machining support, but the organic solvent used may cause internal fibrosis and the immunoreation with surrounding tissue, the mechanical property causing support is unsatisfactory, more cannot solve porogen residue problem.
The present invention passes through MOLECULE DESIGN and structural characterization, use the PHBV melt blending of PPC Yu the GMA grafting with MA end-blocking, by the coupling of functional group between component, allotment PHBV physical property, with the reactive ultrasonic leaching of melt blending-particle-alkali treatment technology new approaches, under the conditions of organic solvent-free, improved mechanical property and the surface hydrophilicity of PHBV/PPC co-mixing system by Interfacial compatibilization technology and basic hydrolysis technology, build high performance PHBV/PPC porous compound support frame.At present with PHBV/PPC as matrix, prepare the method for tissue engineering bracket do not have similar or similar patent or document to report both at home and abroad by reactive melt blending-particle leaching-alkali treatment technology of overfulfiling a production target.
Summary of the invention
It is an object of the invention to PHBV and PPC with good biocompatibility and biological degradability as matrix, use the reactive ultrasonic leaching of melt blending-particle-alkali treatment technology to provide the construction method of a kind of PHBV/PPC porous compound support frame.The compound rest obtained makes the mechanical property of PPC and PHBV obtain complementation, improves the fragility of PHBV, makes degradation property be regulated and controled.Construction method technique is simple, and environmental pollution is little.
The purpose of the present invention is realized by techniques below scheme:
Poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV)/poly (propylene carbonate) (PPC) compound rest that a kind of reacted ultrasonic leaching of property melt blending-particle-alkali treatment technology builds, being in terms of 100% by the gross mass of described support, the most each component and mass percent are as follows: poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) 20～80%；Poly (propylene carbonate) (PPC) 20～80%.
The preparation method of poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) of the present invention (PHBV)/poly (propylene carbonate) (PPC) compound rest is as follows:
(1) with cumyl peroxide (DCP) as initiator, by MA (1～2%), DCP (0.1～0.5%) with PPC at 30rpm, mixing in the Haake mixer of 130～160 DEG C, obtains the PPC (MA-PPC) of MA end-blocking；
(2) PHBV with GMA (1～15%), DCP (0.1～0.5%) 165～175 DEG C are mixed, obtain GMA modification PHBV, by MA-PPC (20～80%) and GMA modification PHBV (20～80%), porogen NaCl 165～175 DEG C of reactive melt blendings.Wherein (MA-PPC+GMA modification PHBV) quality: NaCl mass=10～50%: 50～90%.Blend is in blocks through hot press hot pressing, cold moudling.
(3) blended product being dipped in distilled water, ultrasonic removing water-soluble component in the 37 DEG C of water-baths of the ultrasonic percolation of particle, the quality of weighing support is to being not changed in, to determine the complete dissolution of salt ion.
(4) support after processing further is dipped in 1～2mol/LNaOH solution 60～120min, is washed to neutrality, lyophilization.
The principle of the present invention is: the PPC of MA end-blocking can be converted into carboxyl in the polymer melt course of processing under wet environment, improves the heat stability of PPC, the degraded of suppression PPC or solution slide fastener behavior.On GMA grafting PHBV, epoxy radicals and carboxyl situ-formed graft on MA end-blocking PPC, can stop crosslinking and degradation reaction between PHBV and PPC, improve heat stability and two group partition inter-capacitives of PHBV, improve the toughness of PHBV.
The invention have the advantage that the inventive method technique is simple, equipment is common.Technique only have mixing, hot pressing, ultrasonic, wash, soaking step；The equipment used is the most common Haake mixer, hot press, cleaning device of overfulfiling a production target, and is particularly suitable for industrialized production.
The raw material that the method for the present invention is used is simple and easy to get.PHBV and PPC is the most common biological degradation plastics, it is easy to bought.PHBV is provided by Hangzhou Tian An Biological Co., Ltd., and PPC is presented by Inner Mongol Meng Xi new and high technology company limited.The blend being obtained by the present invention can be with complete biodegradable, and environmental pollution is little.
Compared with domestic and international prior art, the invention has the beneficial effects as follows:
(1) poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV)/poly (propylene carbonate) (PPC) compound rest of the present invention makes poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) and the mechanical property of poly (propylene carbonate) obtain complementation, improving the fragility of poly-(beta-hydroxy-butanoic acid-valerate), degradation property is adjustable.
(2) present invention uses the reactive ultrasonic leaching of melt blending increase-volume-particle-alkali treatment method to build PHBV/PPC compound rest, improved mechanical property and the surface hydrophilicity of PHBV/PPC co-mixing system by Interfacial compatibilization technology and basic hydrolysis technology under the conditions of organic solvent-free, be conducive to medical application, technology environmental protection, and method the most easily realizes.
Accompanying drawing explanation
Accompanying drawing is the stereoscan photograph that HepG-2 cell adheres to 8h on support.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further described, but embodiment is merely to illustrate, and is not limiting as the scope of invention.
Embodiment 1:
By MA, DCP and PPC mixing in 30rpm, the Haake mixer of 160 DEG C, obtain the PPC (MA-PPC) of maleic anhydride end-blocking；PHBV with GMA (5%), DCP (0.5%) 165 DEG C are mixed, obtain GMA modification PHBV, by MA-PPC (10%) and GMA modification PHBV (10%), (80%) 165 DEG C of reactive melt blending of porogen NaCl, hot pressing is in blocks, cold moudling.Blended product being dipped in distilled water, in 37 DEG C of water-baths, removes water-soluble component through the ultrasonic percolation of particle, weighing the quality of support until being not changed in, to determine the complete dissolution of salt ion.Through 2mol/L NaOH solution immersion treatment 90min after, being washed to neutrality, lyophilization, obtain porous PHBV/PPC compound rest, porosity reaches 71.34%.Hepatoma carcinoma cell being fixed on support, scanning electron microscope (SEM) observation of cell adheres to growth conditions (as shown in drawings) at material surface.Cell adhesion condition on composite interstitial substance is good.Cell is gradually grown in hole, and form is rounded and similar round, and this support has good biocompatibility, and this has potential theory value and application prospect to In vivo study and the clinical practice of reconstruction.
Embodiment 2:
By MA, DCP and PPC mixing in 30rpm, the Haake mixer of 160 DEG C, obtain the PPC (MA-PPC) of MA end-blocking；PHBV with GMA (5%), DCP (0.5%) 165 DEG C are mixed, obtain GMA modification PHBV, by MA-PPC (3%) and PHBV-GMA graft (7% part), (90%) 165 DEG C of reactive melt blending of porogen NaCl, hot pressing is in blocks, cold moudling.Blended product being dipped in distilled water, through the ultrasonic percolation of particle ultrasonic removing water-soluble component in 37 DEG C of water-baths, weighing the quality of support until being not changed in, to determine the complete dissolution of salt ion.Through 2mol/L NaOH solution immersion treatment 90min after, it is washed to neutrality, lyophilization, obtaining porous PHBV/PPC compound rest, porosity reaches 82.79%, and the external degradation cycle is suitable, good mechanical performance, can be used for tissue carrier material, as tissue repair and reconstruction.
Embodiment 3:
By MA, DCP and PPC mixing in 30rpm, the Haake mixer of 160 DEG C, obtain the PPC (MA-PPC) of MA end-blocking；PHBV with GMA (5%), DCP (0.5%) 165 DEG C are mixed, obtain GMA modification PHBV, by MA-PPC (7%) and PHBV-GMA graft (3%), (90%) 165 DEG C of reactive melt blending of porogen NaCl, hot pressing is in blocks, cold moudling.Blended product being dipped in distilled water, through the ultrasonic percolation of particle ultrasonic removing water-soluble component in 37 DEG C of water-baths, weighing the quality of support until being not changed in, to determine the complete dissolution of salt ion.Through 2mol/L NaOH solution immersion treatment 90min after, it is washed to neutrality, lyophilization, obtaining porous PHBV/PPC compound rest, porosity reaches 82.9%, and the external degradation cycle is suitable, good mechanical performance, can be used for tissue carrier material, as tissue repair and reconstruction.
Claims (4)
1. one kind poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV) and the reactively blending thing of poly (propylene carbonate) (PPC), it is characterised in that this is blended
The component of thing mainly includes poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV), poly (propylene carbonate) (PPC), various auxiliary agents.
Copolymer the most according to claim 1, it is characterised in that the component of described blend, its percentage by weight is:
1) poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV) 20～80%；
2) poly (propylene carbonate) (PPC) 20～80%；
3) end-capping reagent maleic anhydride (MA): PPC mass ratio is 0.2～5%: 95～99.8%, preferably 1～2%: 98～99%；
4) initiator cumyl peroxide (DCP) 0.1～0.5%；
5) modifying agent glycidyl methacrylate (GMA) 1～15%；
6) porogen sodium chloride nacl: (MA-PPC+GMA modification PHBV) mass ratio is 50～90%: 10～50%.
3. the preparation method of poly-(3-hydroxybutyrate ester-3-hydroxyl valerate) (PHBV)/poly (propylene carbonate) (PPC) compound rest, it is characterised in that
1) with cumyl peroxide (DCP) as initiator, by MA (1～2%), DCP (0.1～0.5%) with PPC at 30rpm, 130～160 DEG C
Mixing in Haake mixer, obtains the PPC (MA-PPC) of MA end-blocking；
2) PHBV with GMA (1～15%), DCP (0.1～0.5%) 165～175 DEG C are mixed, obtain GMA modification PHBV, by MA-PPC with
GMA modification PHBV, porogen NaCl 165～175 DEG C of reactive melt blendings.Blend is in blocks through hot press hot pressing, cold moudling.
3) blended product is dipped in distilled water, ultrasonic removing water-soluble component in the 37 DEG C of water-baths of the ultrasonic percolation of particle, weighs the quality of support
To being not changed in, to determine the complete dissolution of salt ion.
4) support after processing further is dipped in 1～2mol/LNaOH solution 60～120min, is washed to neutrality, is frozen in dry.
Method the most according to claim 3, it is characterised in that step 2) in GMA modification PHBV Yu MA end-blocking PPC mixed in mixer
The conjunction time is 1～20min, preferably 5～10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410814153.XA CN105879111A (en) | 2014-12-24 | 2014-12-24 | Novel construction method of biodegradable porous PHBV/PPC (poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate) composite scaffold |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410814153.XA CN105879111A (en) | 2014-12-24 | 2014-12-24 | Novel construction method of biodegradable porous PHBV/PPC (poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate) composite scaffold |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105879111A true CN105879111A (en) | 2016-08-24 |
Family
ID=56700449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410814153.XA Pending CN105879111A (en) | 2014-12-24 | 2014-12-24 | Novel construction method of biodegradable porous PHBV/PPC (poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate) composite scaffold |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105879111A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327141A (en) * | 2019-07-22 | 2019-10-15 | 上海交通大学医学院附属仁济医院 | Degradable Colon and rectum internal bypass device and preparation method thereof |
| CN110420356A (en) * | 2019-08-09 | 2019-11-08 | 福州大学 | A kind of Dual-functional integrated bone-cartilage complex tissue engineering rack for osteosarcoma clinical treatment |
| CN113604020A (en) * | 2021-09-09 | 2021-11-05 | 福州大学 | Preparation method of high-toughness polylactic acid |
| CN113731192A (en) * | 2021-08-25 | 2021-12-03 | 中海油节能环保服务有限公司 | Hydrophilic ultrafiltration membrane for oil-water separation and preparation method thereof |
| CN113846423A (en) * | 2021-10-15 | 2021-12-28 | 嘉兴学院 | Preparation method of biological full-degradable composite fiber membrane |
| WO2023104073A1 (en) * | 2021-12-08 | 2023-06-15 | 山东联欣环保科技有限公司 | Degradable composite polymer having high ductility, and preparation method therefor |
| WO2024173526A1 (en) * | 2023-02-15 | 2024-08-22 | Danimer Ipco, Llc | Mitigation of poly(hydroxyalkanote) degradation in polymeric compositions |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566672A (en) * | 2016-01-20 | 2016-05-11 | 中国科学院长春应用化学研究所 | Method for preparing porous material by compounding polymeric resin with fibers |
-
2014
- 2014-12-24 CN CN201410814153.XA patent/CN105879111A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566672A (en) * | 2016-01-20 | 2016-05-11 | 中国科学院长春应用化学研究所 | Method for preparing porous material by compounding polymeric resin with fibers |
Non-Patent Citations (4)
| Title |
|---|
| FENG SHEN等: ""In vitro blood compatibility of poly (hydroxybutyrate-co-hydroxyhexanoate)and the influence of surface modification by alkali treatment"", 《MATERIALS SCIENCE AND ENGINEERING C》 * |
| J. LI等: ""Preparation, Thermal Properties, and Morphology of Graft Copolymers in Reactive Blends of PHBV and PPC"", 《POLYMER COMPOSITES》 * |
| 李静: ""生物降解PHBV/PPC 反应共混物中接枝产物的研究"", 《天津科技大学学报》 * |
| 李静等: ""聚酯基复合支架的构建、理化特性及体外生物相容性初探"", 《2013年全国高分子学术论文报告会论文摘要集》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327141A (en) * | 2019-07-22 | 2019-10-15 | 上海交通大学医学院附属仁济医院 | Degradable Colon and rectum internal bypass device and preparation method thereof |
| CN110420356A (en) * | 2019-08-09 | 2019-11-08 | 福州大学 | A kind of Dual-functional integrated bone-cartilage complex tissue engineering rack for osteosarcoma clinical treatment |
| CN113731192A (en) * | 2021-08-25 | 2021-12-03 | 中海油节能环保服务有限公司 | Hydrophilic ultrafiltration membrane for oil-water separation and preparation method thereof |
| CN113604020A (en) * | 2021-09-09 | 2021-11-05 | 福州大学 | Preparation method of high-toughness polylactic acid |
| CN113604020B (en) * | 2021-09-09 | 2022-06-14 | 福州大学 | Preparation method of high-toughness polylactic acid |
| CN113846423A (en) * | 2021-10-15 | 2021-12-28 | 嘉兴学院 | Preparation method of biological full-degradable composite fiber membrane |
| CN113846423B (en) * | 2021-10-15 | 2023-02-28 | 嘉兴学院 | Preparation method of biological full-degradable composite fiber membrane |
| WO2023104073A1 (en) * | 2021-12-08 | 2023-06-15 | 山东联欣环保科技有限公司 | Degradable composite polymer having high ductility, and preparation method therefor |
| WO2024173526A1 (en) * | 2023-02-15 | 2024-08-22 | Danimer Ipco, Llc | Mitigation of poly(hydroxyalkanote) degradation in polymeric compositions |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105879111A (en) | Novel construction method of biodegradable porous PHBV/PPC (poly (3-hydrobutyrate-3-hydroxyvalerate)/polypropylene carbonate) composite scaffold | |
| Donato et al. | Keratin associations with synthetic, biosynthetic and natural polymers: An extensive review | |
| Zhang et al. | Starch-based rehealable and degradable bioplastic enabled by dynamic imine chemistry | |
| CN108047465B (en) | Methacrylate gelatin/chitosan interpenetrating network hydrogel, preparation method and application | |
| Shi et al. | Three‐dimensional printing alginate/gelatin scaffolds as dermal substitutes for skin tissue engineering | |
| Prabhakaran et al. | Electrospun composite scaffolds containing poly (octanediol‐co‐citrate) for cardiac tissue engineering | |
| CN112759774B (en) | Mechanically-enhanced gelatin frozen hydrogel and preparation method and application thereof | |
| Khoramgah et al. | Freeze-dried multiscale porous nanofibrous three dimensional scaffolds for bone regenerations | |
| CN111729129B (en) | Fine manufacturing of light-operated hybrid cross-linked degradable scaffold and application of light-operated hybrid cross-linked degradable scaffold in bone tissue engineering | |
| Yan et al. | Cellulose/microalgae composite films prepared in ionic liquids | |
| Li et al. | Reinforced mechanical properties and tunable biodegradability in nanoporous cellulose gels: poly (l-lactide-co-caprolactone) nanocomposites | |
| Imre et al. | From natural resources to functional polymeric biomaterials | |
| Hsieh et al. | Characterization and cell culture of a grafted chitosan scaffold for tissue engineering | |
| Maleki et al. | Green semi-IPN hydrogels by direct utilization of crude wood hydrolysates | |
| CN104927319A (en) | Preparation method of novel hydroxyapatite graft polylactic acid | |
| Ciarfaglia et al. | Nanocellulose and elastin act as plasticizers of electrospun bioinspired scaffolds | |
| Yang et al. | An eco-friendly wood adhesive based on waterborne polyurethane grafted with gelatin derived from chromium shavings waste | |
| Yang et al. | A natural polymer-based hydrogel with shape controllability and high toughness and its application to efficient osteochondral regeneration | |
| Ke et al. | Thermal and in vitro degradation properties of the NH2-containing PHBV films | |
| CN107715181A (en) | A kind of preparation method of biodegradable organization engineering skin support | |
| Xia et al. | Tough and strong all-biomass plastics from agricultural and forest wastes via constructing an aggregate of hydrogen-bonding networks | |
| Guan et al. | Poly (propylene fumarate)-Based Adhesives with a Transformable Adhesion Force for Suture-Free Fixation of Soft Tissue Wounds | |
| Liu et al. | Hydrophilic and Biodegradable PBAT Copolyesters Prepared from Chemically Recycled Resources | |
| CN104327293A (en) | Composite film material based on polymer PRGD and preparation method of composite film material | |
| Fonseca et al. | Atom-economical, one-pot, self-initiated photopolymerization of lactose methacrylate for biobased hydrogels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160824 |
|
| RJ01 | Rejection of invention patent application after publication |