Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/62—Plasma-deposition of organic layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/34—Applying different liquids or other fluent materials simultaneously

Definitions

• the invention relates to a thin film coating method with minimal adhesion to biological species.
• Implants, catheters, intraocular lenses or more generally all bio-systems (bio-components) require non-adherent surfaces to the biological material (non-fouling) such as proteins, lipids or cells.
• the reactions to a solid-liquid interface are generally complex, multiple and specific to the nature of the species in the presence.
• the reactions lead to a localized biological disturbance of the host medium characterized by the formation of an interfacial layer between the foreign object (the implant, the catheter, the intraocular lens) and the medium of the host. welcome (the body, the eye). Controlling the activity of this interface layer is necessary for the balance of compatible conditions between matter and living (bio compatibility).
• the constituent materials of the various bio-systems are generally chosen for their mechanical, optical, or electrical properties but are mostly not or not very biocompatible.
• Their deposition can be carried out, as described for example in the international patent application WO 03/090939, by plasma using a precursor comprising the -COOH group, which can be written in the form X-COOH.
• WO 03/090939 also describes the use of a precursor comprising a carbonyl group, the -OH functionality being brought by a donor gas such as water.
• a donor gas such as water.
• the materials obtained are no longer crosslinked: they have poor mechanical and chemical resistance. It is also limited in this process on the choice of the precursor and therefore the final matrix, and therefore on the properties other than non-adhesion.
• polyethylene oxide / polyethylene glycol coatings which is the reference biocompatible material. It can be deposited in thin film by plasma or by grafting or by different chemical processes in the liquid phase.
• PEO-like is a polyethylene oxide having a composition slightly different from the polyethylene oxide obtained by liquid phase synthesis. But, again, the major problem encountered is the need to maintain the starting functionality (usually ethylene oxide EO (-CH2-CH2-O) n ). This constraint requires, in this case also, to use very low power plasmas leading to the production of deposits, certainly biocompatible, but, again, not or very little crosslinked. Furthermore, there is known a process for etching organic materials in which the water is injected into a plasma (EJ Tonnis & al.
• the present invention solves this problem by allowing the functionalization in situ, that is to say during the production of the coating, of any type of matrix. It thus becomes possible to choose a material for its properties, for example optical, and to add a non-fouling feature.
• the invention relates to a process for functionalizing a thin film being grown by -COOH functions for, in particular, the production of non-adherent surface or minimal adhesion to the biological material, (non-fouling).
• the invention provides a thin-film coating method with minimal adhesion to biological species of the type comprising the deposition of a thin film with -COOH function, comprising a step of chemical vapor phase decomposition.
• a carbon precursor comprising neither carbonyl group nor carboxyl group, in the presence of water.
• Said step of chemical vapor phase decomposition may be activated by plasma, and / or by heat input, and / or by addition of waves and / or radiation, preferably by plasma.
• the chemical decomposition is preferably activated by plasma as an energy carrier.
• This plasma can for example be of the radiofrequency, low frequency, ECR (Electron Cyclic Resonance), ICP (Inductively Coupled Plasma), DBD (Dielectric Barrier Discharge) type.
• ECR Electrode Cyclic Resonance
• ICP Inductively Coupled Plasma
• DBD Dielectric Barrier Discharge
• heat and / or of waves and / or radiation, and / or of several of these energy sources, possibly in combination with the plasma, is also part of the invention.
• the carbon precursor is a precursor of a hydrophobic material such as a fluorocarbon or organosilicon or mixtures thereof.
• the precursor of the hydrophobic material is C 4 F 8 or C 2 F 4 or hexamethyldisiloxane or mixtures thereof.
• the carbon precursor is a precursor of hydrophilic material such as a hydrocarbon.
• the precursor of hydrophilic material is C 2 H 2 or C 9 H 10 or mixtures thereof
• FIG. 1 schematically represents an example of a device for implementing the method of the invention
• FIG. 2 represents the infrared spectrum of a polytetrafluoroethylene-like (PTFE-like) film obtained from C 4 F 8 without functionalization
• FIG. 3 represents the infrared spectrum of a PTFE-like film obtained from C 4 F 8 according to the method of the invention
• FIG. 4 represents the infrared spectrum of an amorphous carbon film ( ⁇ -CH), that is to say hydrophilic, without functionalization, obtained from C 9 H 0
• FIG. 5 represents the infrared spectrum of an ⁇ -CH film obtained from C 9 H 10 according to the process of the invention
• FIG. 6 represents the infrared spectrum of a polymethyldisiloxane-like (PDMS-like) film obtained from hexamethyldisiloxane, without functionalization
• FIG. 7 represents the infrared spectrum of a PDMS-like film obtained from hexamethyldisiloxane according to the method of the invention
• FIG. 8 is a schematic representation of a passive microfluidic valve according to one embodiment. of the invention.
• the gaseous mixture is entrained by a suitable carrier gas such as, for example, helium, argon or hydrogen or mixtures thereof.
• the method of the invention makes it possible to obtain a film made of a material chosen for its properties, for example mechanical, optical or electrical properties, and to add thereto -COOH functionalities, while the film is being grown.
• the precursor contains carbon and that water is introduced into the enclosure.
• the method of the invention allows to work at higher powers, plasma, when the plasma is used as a source of energy.
• the precursor is any precursor containing carbon. It can be chosen to create a hydrophilic or hydrophobic coating film. By choosing a precursor of a hydrophilic material, a hydrophilic coating film will be obtained. Among the precursors of hydrophilic material, mention may be made of hydrocarbons.
• a precursor of hydrophobic material such as a fluorocarbon, preferably C 4 F 8 or C 2 F 4, is used .
• hydrophobic film it is also possible to use an organosilicon such as, for example, hexamethyldisiloxane (HMDSO) as a precursor material.
• organosilicon such as, for example, hexamethyldisiloxane (HMDSO) as a precursor material.
• the invention allows the deposition of a film having the desired mechanical, electrical and / or optical characteristics, and a minimal adhesion to biological species, in particular, on all types of implanted biological systems, d. on the one hand, and on all types of fluid systems for biological applications, on the other hand.
• Non-exhaustive examples include the treatment of intraocular implants, catheters, the treatment of channels of microfluidic systems (s) such as lab-on-chips or MEMS (Micro Electro Mechanical System),
• s microfluidic systems
• MEMS Micro Electro Mechanical System
• the method of the invention it is possible, for example, to render the inside of a channel non-adherent to the biological material.
• the channel may be selected as hydrophilic or hydrophobic. This advantage is particularly interesting in the context of the realization of passive valves as will be explained in the examples. In order to better understand the invention, we will now give several examples of implementation and realization.
• the invention consists in injecting, in a closed enclosure, denoted 7 in FIG. 1, kept under vacuum thanks to the vacuum pump (not shown) connected to the pipe denoted 6 in FIG. 1, on the one hand the precursor (s) of the end materials of the coating, in gaseous form, through the pipe marked 2 in Figure 1, and, on the other hand, water vapor, through the pipe denoted 1 in Figure 1.
• the pipes 1 and 2 are connected to a perforated pipe 3 denoted in FIG. 1 which allows the transport of the precursor (s) and the water vapor inside the enclosure 7.
• the sample to be coated, denoted by 8 FIG. 1 is placed on the sample holder marked 5 in FIG. 1, and the precursor (s) and the water are decomposed by plasma at the level of the chemical reaction zone, denoted 9 in FIG. 1, and the reaction products are deposited. on the sample 8.
• This process allows in situ formation during growth of the carboxylic acid film and its incorporation into the growing layer.
• a PTFE-like layer functionalized by the method of the invention is deposited on a silicon substrate.
• the operating conditions for the deposition and growth of the layer are as follows: Precursor: C 4 F 8
• a silicon substrate was coated with a layer obtained from the same precursor C 4 F 8 , without addition of water, under the same conditions.
• the coating obtained is not functionalized with COOH groups, this spectrum showing only the absorption peaks of the fluorocarbon matrix.
• the minimal adhesion property with respect to the biological species of these two layers was analyzed by protein labeling with Cy3 and Cy5 fluorophores of antigen, cell lysate, serum and biopsy.
• the results of this study clearly show that the layer functionalized by the process of the invention has a minimal adhesion towards the biological species while the non-functionalized layer has a high adhesion.
• contact angle measurements were made on both surfaces. The contact angle for the non-functionalized surface is 110 ° and for the functionalized surface is 105 °.
• This example shows that it is possible to achieve a hydrophobic surface with minimal adhesion to biological species.
• FIG. 4 The infrared spectrum of the deposit obtained without the addition of water is represented in FIG. 4.
• the layer obtained is not functionalized with -COOH groups whereas, as seen in FIG. which represents the layer obtained with the method of the invention, the latter is functionalized.
• the contact angle measurements made on these two surfaces give, for the surface obtained according to the method of the invention a contact angle of 32 ° and, for the non-functionalized surface, a contact angle of 28 °.
• a PDMS-like layer was deposited on a silicon substrate by the method of the invention.
• the precursor used is hexamethyldisiloxane (HMDSO): - Plasma power: 100 W
• Flow rate of the precursor HMDSO 60 cm 3 / min - Flow of H 2 O: 10 cm 3 / min Time: 2 mn Pressure: 1 mb.
• a layer was deposited in the same way on a silicon substrate. However, in this case, water was not injected into the plasma enclosure.
• the infrared spectrum of the layer obtained by the method without injection of water is shown in FIG. 6. It clearly shows that the layer has not been functionalized by the -COOH groups.
• the invention allows the deposition of a film with minimal adherence to biological species on all types of implanted biological systems on the one hand, and fluid systems for biological applications on the other hand.
• the microfluidic system channels (s) such as lab-on-chips or MEMS may be coated with a layer of material that is not adherent to the biological material, but also this layer may be rendered hydrophilic or hydrophobic.
• FIG. 8 represents a passive micro-fluidic valve, which comprises a first channel denoted 9 and a second channel denoted 10 in FIG. 8.
• the wall, denoted 12 in FIG. 8, of the channel 9 is coated with a hydrophilic deposit with -COOH functionality, while the wall, denoted 11 in Figure 8, the channel 10, is coated with a material -COOH hydrophobic functionality.
• the coating with a hydrophobic material of the wall 11 of the channel 10 makes it possible to prevent the rise of the fluid, flowing in the channel 9 in the direction of the arrow denoted F1 in FIG. 8, towards the channel 10, in which the fluid circulates in the the direction of the arrow marked F2 in Figure 8.

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• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Plasma & Fusion (AREA)
• Chemical Vapour Deposition (AREA)
• Materials For Medical Uses (AREA)

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• 2006
  • 2006-11-28 FR FR0610384A patent/FR2909013B1/fr not_active Expired - Fee Related
• 2007
  • 2007-11-06 EP EP07870244A patent/EP2131965A2/de not_active Withdrawn
  • 2007-11-06 US US12/516,459 patent/US20100028526A1/en not_active Abandoned
  • 2007-11-06 WO PCT/FR2007/001825 patent/WO2008068401A2/fr not_active Ceased

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