On the potential use of two-photon polymerization to 3D print chromatographic packed bed supports

The continuous quest for chromatographic supports offering kinetic performance properties superior to that of the packed bed of spheres has pushed the field to consider alternative formats such as for example monolithic and pillar array columns. This quest seems bound to culminate in the use of 3D printing technology, as this intrinsically offers the possibility to produce supports with a perfect uniformity and with a size and shape that is fully optimized for the chromatographic separation process. However, to be competitive with the current state-of-the-art, structures with sub-micron feature sizes are required. The present contribution therefore investigates the use of the 3D printing technology with the highest possible resolution available today, i.e., two-photon polymerization (2PP). It is shown that 2PP printing is capable of achieving the required ≤ 1 µm printing resolution. Depending on the laser scan speed, the lower limit through-pore size for a tetrahedral skeleton monolith with a theoretical 80% external porosity was found to be at 800 nm, when printing at a scan speed of 50 mm/s with a laser power of 10%. For a scan speed of 10 mm/s, the minimal through-pore size dropped to 500 nm. However, this very high resolution comes at the cost of excessively long printing times. The total printing time for a column volume equivalent to that of a typical nano-LC column (75 µm i.d. cylindrical tube with length L = 15 cm) has been determined to correspond to 330 and 470 h for the 50 mm/s and the 10 mm/s scan speed respectively. Other issues remaining to be solved are the need to clad the printed skeleton with a suitable mesoporous layer for chromatographic retention and the need to add a top-wall to the printed channels after the removal of the non-polymerized resin. It is therefore concluded that 2PP printing is not ready yet to replace the existing column fabrication methods.