Three-dimensional scaffold structures with selectively functionalized polymer systems, their use and process for their manufacture

Patent metadata

Field	Value
Publication number	US-11851674-B2
Application number	US-201916683954-A
Country	US
Kind code	B2
Filing date	Nov 14, 2019
Priority date	Nov 14, 2018
Publication date	Dec 26, 2023
Grant date	Dec 26, 2023

Abstract

A three-dimensional scaffold structure and a process for its manufacture. The scaffold structure has a polymer system obtainable by photostructuring a starting material containing precursor molecules or inorganic polymers thereof having an organically polymerizable radical with at least one C═C double bond, an inorganically polymerizable silane-based radical and a functional group or derivative thereof.

First claim

The invention claimed is:

1. A three-dimensional scaffold structure, comprising:
scaffold structure parts made of a polymer system and fluid-filled open spaces between said scaffold structure parts with a minimum extent of 50 nm in each spatial direction;
the scaffold structure configured to be filled with water as a fluid to consist of at least 50 percent by volume of water at room temperature;
said polymer system is obtained by treating a starting material with electromagnetic radiation that is locally targeted to form the scaffold structure having open spaces, said starting material containing precursor molecules of formula (I) or partially condensated species thereof:

wherein the radicals and the indices have the following meaning:
B is a straight-chain or branched or cyclic organic radical having at least one C═C double bond and 4 to 100 carbon atoms;
X is hydrogen, halogen, hydroxy, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR 4 2 ;
R is alkyl, alkenyl, aryl, alkylaryl or arylalkyl;
R 2 is OH, COOH, NR 4 2 , NR 4 2 H + or SH or a derivative thereof;
R 4 is hydrogen, alkyl, aryl or alkylaryl;
R Rg is the backbone of a straight-chain or branched hydrocarbon bonded to the Si atom, where the backbone may be interrupted by heteroatoms or heteroatom-containing groups;
a=1, 2 or 3;
b=0, 1 or 2;
a+b=3; and
c=1, 2, 3 or 4.

2. The three-dimensional scaffold structure according to claim 1 , wherein the precursor molecules of formula (I) have a structure of formula (II):

wherein the radicals and indices have the following meaning:
B, X, R, R 2 , R 4 , a, b, a+b and c have the meaning as in formula (I);
R 1 and R 3 are, independently of one another, alkylene, arylene or alkylenearylene each having 1 to 20 carbon atoms, wherein it is possible that these radicals are interrupted by O, S, NR or NH;
A is O, S or NH for d=1 and Z=CO; or A is O, S, NH or COO for d=1;
Z is CHR 4 ; or A is O, S, NH or COO for d=0; and
e=0 or 1.

3. The three-dimensional scaffold structure according to claim 1 , wherein:
said polymer system is based on at least one first type of precursor molecules of formula (I) or partially condensated species thereof and at least one second type of precursor molecules or partially condensated species thereof, wherein the second type differs from the first type at least or exclusively in that R 2 is hydrogen; or
said polymer system is based on at least two types of precursor molecules or partially condensated species thereof which differ at least or exclusively in the group R 2 .

4. The three-dimensional scaffold structure according to claim 3 , wherein the difference is that R 2 is OH, COOH, NR 4 2 , NR 4 2 H + or SH in one type of precursor molecule and R 2 is a derivative of R 2 of the first type in the other type of precursor molecule.

5. The three-dimensional scaffold structure according to claim 1 , wherein the derivative of R 2 is derived from a biofunctional molecule or from a spacer having a bound biofunctional molecule.

6. The three-dimensional scaffold structure according to claim 1 , wherein the polymer system contains nanoparticles.

7. The three-dimensional scaffold structure according to claim 1 , wherein said polymer systems are produced from a single type of precursor molecule, except that the precursor molecules may differ in the presence or type of derivatization at R 2 or in both.

8. The three-dimensional scaffold structure according to claim 1 , comprising at least a first structural unit of a first thickness in a range from 10 μm to 100 mm and second structural units of a second thickness in a range from 100 nm to 1000 μm each branching off from the first structural unit, the second thickness at the branches being at most half the first thickness.

9. The three-dimensional scaffold structure according to claim 1 configured for interaction with biological cells in vitro or for medical use in vivo.

10. A method for fabricating a three-dimensional scaffold structure according to claim 1 , the method comprising the steps of:
(a) providing a photostructurable source material described in claim 1 ,
(b) photostructuring the starting material provided in step (a) to form the three-dimensional scaffold structure; and
(c) removing unreacted starting material.

11. The method according to claim 10 , which comprises performing steps (a) to (c) in a first pass with a first position of photostructuring and performing a second pass of steps (a) to (c) with a second position of photostructuring different from the first position to form two partial structures of the three-dimensional scaffold structure.

12. The method according to claim 11 , wherein the starting materials of the first pass differ from the starting materials of the second pass in at least one characteristic selected from the group consisting of the type of precursor molecule of formula (I) or an inorganic polymer thereof; the proportion of the precursor molecule of formula (I) or an inorganic polymer thereof in the total photostructurable compounds; the proportion of a precursor molecule corresponding, with the exception of R 2 =H, to the precursor molecule used of formula (I); the nanoparticle content; a proportion of the precursor molecule of formula (I) in which R 2 is a derivative; and a nature of the derivative of R 2 .

13. The method according to claim 11 , wherein only a single type of precursor molecule of formula (I) or an inorganic polymer thereof is used except that the precursor molecules may differ in the presence or type of derivatization at R 2 or in both, and wherein the type is the same or different in both passes.

Assignees

• Fraunhofer Ges Forschung
• Fraunhofer Gesllschaft Zur Foerderung Der Angewandten Forschung E V

Inventors

• Wolter Herbert
• Nique Somchith
• Hasselmann Sebastian
• Kopittke Caroline
• Heinrich Doris
• Schwaiger Johannes

Classifications

• C12N5/0068 Primary

  General culture methods using substrates (for specific animal cell type C12N5/06) · CPC title

• C08F122/10

  Esters · CPC title

• C08F230/085 Primary

  the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B33Y80/00

  Products made by additive manufacturing · CPC title