Multiphoton Lithography as a Promising Tool for Biomedical Applications

Multiphoton lithography (MPL) is a powerful and useful structuring tool capable of generating 2D and 3D arbitrary micro- and nanometer features of various materials with high spatial resolution down to nm-scale. This technology has received tremendous interest in tissue engineering and medical device manufacturing, due to its ability to print sophisticated structures, which is difficult to achieve through traditional printing methods. Thorough consideration of two-photon photoinitiators (PIs) and photoreactive biomaterials is key to the fabrication of such complex 3D micro- and nanostructures. In the current review, different types of two-photon PIs are discussed for their use in biomedical applications. Next, an overview of biomaterials (both natural and synthetic polymers) along with their crosslinking mechanisms is provided. Finally, biomedical applications exploiting MPL are presented, including photocleaving and photopatterning strategies, biomedical devices, tissue engineering, organoids, organ-on-chip, and photodynamic therapy. This review offers a helicopter view on the use of MPL technology in the biomedical field and defines the necessary considerations toward selection or design of PIs and photoreactive biomaterials to serve a multitude of biomedical applications.     

Selective Functionalization of 3D Matrices Via Multiphoton Grafting and Subsequent Click Chemistry

Grafting is a popular approach for adjusting the properties and functionalization of various surfaces. Conventional photoinduced grafting has been utilized on flat surfaces, porous monoliths, and hydrogels. By masking or illuminating only a portion of the sample, a certain degree of spatial and temporal control is possible, but the ability to use grafting to pattern in 3D is limited. Here, the laser‐induced photolysis of an aromatic azide compound is employed for true 3D photografting within a poly(ethylene glycol) (PEG)‐based matrix. Since the multiphoton interaction occurs only in a confined area within the laser focal spot, the localized immobilization of a selected molecule with high spatial resolution in 3D is possible. In contrast to the widely utilized chain‐growth polymerization‐based grafting, the approach is characterized by a single‐molecule insertion mechanism. Successful binding of the fluorophore is confirmed by laser scanning microscopy. To test for the presence of latent azides and to determine the suitability for additional postmodification with arbitrary functional groups, the sample is further subjected to copper‐catalyzed alkyne click‐reaction conditions. The described 3D photografting method is simple, highly efficient, and universal. The presented results demonstrate the great potential of multiphoton‐induced grafting for 3D site‐specific functionalization.     

Customizable and Reconfigurable Surface Properties of Printed Micro-objects by 3D Direct Laser Writing via Nitroxide Mediated Photopolymerization

Photoactivated Reversible Deactivation Radical Polymerization (RDRP) technologies have emerged very recently in the field of 3D printing systems especially at the macroscale in vat-photopolymerization-based processes such as digital light processing (DLP). Contrary to conventional free radical photopolymerization, photoRDRP in 3D printing leads to 3D objects with living character and thus confers them the unique ability to be post-modified after fabrication. While 3D direct laser writing (3D DLW) by two photon polymerization has become a standard for fabrication of complex 3D micro-objects, the use of RDRP and its associated benefits has so far been under-investigated at that scale. Herein, a photoresist suitable for 3D DLW based on nitroxide mediated photopolymerization (NMP2) is developed. The photopolymerization efficiency for fabrication of micro-structures and their subsequent post-modification are investigated regarding the laser power and the wavelength of excitation. Moreover, highly tunable, precise, and successive surface patterning of 2D and 3D multi-material microstructures are demonstrated thanks to the spatial and temporal control offered by the photo-induced post-modification. This work highlights new directions to be explored in order to accelerate the adoption of RDRP in 3D printing based on photopolymerization.     

多光子过程中光场的位相特性

本文应用Pegg-Barnett位相理论研究了光场在与原子的多光子相互作用过程中位相的几率分布,期待值和涨落等。     

355 nm激光作用下CH3I分子的多光子电离解离

利用飞行时间质谱仪在超声射流冷却条件下研究了CH3I分子在355 nm激光作用下的多光子电离解离机制.得到了分子的飞行时间质谱,质谱中有较强的H 、CH 3和I 信号,较弱的C ,CH 、CH 2和母体离子CH3I 信号,CH3I 的出现表明CH3I分子的多光子电离解离(MPID)属母体离子阶梯模式:CH3I分子由双光子共振激发到里德堡C态,处于该激发态的母体分子继续吸收光子上泵浦至电离态形成母体离子CH3I ,碎片离子可由母体离子解离形成.同时结合母体离子及碎片离子的出现势对CH3I分子的多光子电离解离通道进行分析,提出了可能的解离电离通道.     

真空态多光子Tavis－Cummings模型中辐射场的高阶压缩性质

本文研究了初始处于多原子压缩态的两个全同二能级原子小过多光子跃迁与真空态相互作用过程中场的高阶压缩。     

Tough,Resorbable Polycaprolactone-Based Bimodal Networks for Vat Polymerization 3D Printing

Vat polymerization allows for the accurate and fast fabrication of personalized implants and devices. While the technology advances rapidly and more materials become available, the fabrication of flexible yet tough resorbable materials for biomedical applications remains a challenge. Here, a formulation that can be 3D printed with high accuracy using vat polymerization, yielding materials that are tough, degradable, and non-toxic is presented. This unique combination of properties is obtained by combining a long-chain polycaprolactone macromonomer with a small molecule cross-linker. A wide range of properties is achieved by tuning the ratio of these components. The use of benzyl alcohol as a non-volatile, benign solvent enables fabrication on a low-cost desktop 3D printer, with an exposure time of 8 s per 50-micron layer. The 3D-printed networks are tough and elastic with a tensile strength of 11 MPa at 116% elongation at break. Cells attach and proliferate on the networks with a viability of >91%. The networks are fully degradable to soluble products. This new 3D printable material opens up a range of opportunities in biomedical engineering and personalized medicine.     

CH3I在532nm及455.5nm激光作用下多光子电离研究

本文利用飞行时间质谱仪研究了532nm和455.5nm激光作用下CH3I分子的多光子电离解离（MPID）。在532nm激光作用下，CH3I分子由双光子激发到A带的A2态，它的MPID属母体离子阶梯模式;在455.5nm激光作用下，CH3I分子由双光子激发到A带的3E态，它的MPID属中性碎片光电离模式。     

Si(CH_3)_4分子的多光子电离和解离研究

对Si(CH_3)_4分子在280.0nm波长的激光多光电子电离和解高产物离子的飞行时间质谱进行了测定,结果表明:Si(CH_3)_4分子解离和电离后的主要正离子产物为:Si(CH_3)_2~+、Si~+和CH_x~+(x=0,1,2,3)离子等。本文还讨论了不同激光功率下Si(CH_3)_4分子产生不同碎片产物离子的机理。     

Fabricating Tunable Superhydrophobic Surfaces Enabled by Surface-Initiated Emulsion Polymerization in Water

Fabricating controllable superhydrophobic surfaces remains challenging in various fields ranging from chemical industries to biomedical engineering. Conventional methods commonly require volatile organic solvents and the assistance of special surface deposition and modification equipment, which are detrimental to environment and limit their applications in micro-devices. Herein, an equipment-free method is reported to directly transform fluorinated monomer micro-droplets into hydrophobic polymer particles on flat substrate surfaces in water, simultaneously depositing hydrophobic coatings with tunable surface structures. The as-prepared surfaces show superior superhydrophobicity and great stability in extreme conditions (e.g., varying acidity, basicity, and heating conditions), and excellent anti-fouling property. Meanwhile, surface hydrophobicity can be manipulated by adjusting emulsion droplet number density and reaction time. Hence, superhydrophobic surfaces with tunable hydrophobicity gradients have been successfully fabricated in one pot. This study provides an equipment-free method to facilely fabricate controllable superhydrophobic surfaces, with great potential in the development of smart superhydrophobic materials in various engineering and industrial applications.     

在300um波段OCS分子的多光子电离谱

本文首次测定了ＯＣＳ分子在２９９～３０２ｕｍ波段的多光子电离谱。这一段的谱线被归属为Ｄ１Σ＋←Ｘ１Σ＋的跃迁。通过激光功率和离子信号强度的关系，认为ＯＣＳ分子多光子电高经历了（２＋１）三光子电离的过程。此外，还考察了ＯＣＳ的压力对离子信号强度的影响，并对此进行了讨论。     

在532nm激光作用下n—C4H9I的多光子离解过程质谱研究

报道了碘代正丁烷分子在５３２ｎｍ激光作用下的多光子电离（ＭＰＩ）质谱（ＭＳ）研究结果。（１）碎片离子主要由离子离解阶梯模式产生；波长不仅影响碘代正丁烷分子碎片离子产生模式，同时还影响其碎片离子的碎裂程度。（２）激光强度一般只影响分子离子及碎片离子的碎裂程度。     

原位聚合法制备BaTiO3厚膜的研究

研究了在BaTiO3水浆料中通过加入丙烯酰胺有机单体原位聚合形成聚丙烯酰胺的过程制备厚膜。生坯的柔韧性通过加入丙三醇作为增塑剂加以改善。实验结果表明，由于所制备浆料的均匀性好，这种由原位聚合形成的厚膜显微结构均匀，电性能优良。     

多光子过程的光强指数研究

本文讨论了三能级系统多光子过程的光强指数。给出了光强指数随激光光强变化关系图，并用此图对光强指数的过渡区进行了理论分析。结果表明，过渡区能向我们提供关于多光子过程的许多信息。同时，我们还用一些数值模拟计算，与文献（９）结果的比较，以及我们的实验结果来表明分析的合理性。     

依赖强度耦合的多光子Jaynes—Cummings模型场的位相特性

本文运用Pegg—Barnett位相理论,研究了依赖强度耦合的多光子Jaynes—Cummings模到场的位相特性,具体讨论了其位相概率分布、厄来位相算符的平均值以及位相的涨落。     

共振多光子电离探测芳香烃污染物对比实验研究

本文用两种不同的方法对同期制备的不同浓度的苯、甲苯、二甲苯及其混合气和摩托车尾气三类样品分别进行了对比实验,实验验证了多光子电离所得实验数据的可靠性及其测量精确性,同时可以看出多光子电离方法所具有的快速、实时在线和多组分同时探测的优越性。     

双频CO2 激光多光子离解分离硼同位素的研究

使用一种可调谐双频TEA CO2激光器输出的空间重叠的双频CO2激光对BCl3进行多光子离解，在没有聚焦的情况下照射反应池中BCl3和O2的混合气体150次，生成物（B2O3）中^10B的富集系数达到1．80。     

3D Printing of Multifunctional Hydrogels

3D printing technology has been widely explored for the rapid design and fabrication of hydrogels, as required by complicated soft structures and devices. Here, a new 3D printing method is presented based on the rheology modifier of Carbomer for direct ink writing of various functional hydrogels. Carbomer is shown to be highly efficient in providing ideal rheological behaviors for multifunctional hydrogel inks, including double network hydrogels, magnetic hydrogels, temperature‐sensitive hydrogels, and biogels, with a low dosage (at least 0.5% w/v) recorded. Besides the excellent printing performance, mechanical behaviors, and biocompatibility, the 3D printed multifunctional hydrogels enable various soft devices, including loadable webs, soft robots, 4D printed leaves, and hydrogel Petri dishes. Moreover, with its unprecedented capability, the Carbomer‐based 3D printing method opens new avenues for bioprinting manufacturing and integrated hydrogel devices.     

高功率激光作用下多光子激发Cs_2的新扩散带辐射

本文报告当λ＝１．０７５６ｍ的强激光作用于铯金属蒸气时，获得了从波长４１０ｎｍ到４７３ｎｍ的准连续的新的辐射带，它在４１２．７ｎｍ、４２１．５ｎｍ、４３３．１ｎｍ、４４５．２ｎｍ、４４６．６ｎｍ及４６０．６ｎｍ等处有较高的强度，初步分析表明这个准连续辐射带是来源于Ｃｓ２的新扩散带，这是迄今首次获得的Ｃｓ２的一个新的谱带实验结果。