Research data for "Bridging the gap between performance and biocompatibility: non-toxic, multifunctional aliphatic photoinitiators based on α-ketoesters for lithography-based manufacturing applications"

Context

This dataset was created from original work conducted in the framework of a PhD project and compiled in a publication ("Bridging the gap between performance and biocompatibility: non-toxic, multifunctional aliphatic photoinitiators based on α-ketoesters for lithography-based manufacturing applications"). It provides the raw data of the results presented and discussed therein.

Technical details

Microsoft Excel file “Raw Data_Photoinitiators”:

Tab 1 - Raw Data obtained for UV Vis measurements (KE1-4, BP)

Tab 2 – Evaluated Data obtained for Photo-DSC measurements of KE1-4 and BP+MDEA in various monomers using a 320-500 nm broadband UV lamp

Tab 3 – Evaluated Data obtained for Photo-DSC measurements of KE3 and co-initiators in various monomers using a 320-500 nm broadband UV lamp

Tab 4 – Evaluated Data obtained for Photo-DSC measurements of KE1-4 and BP+MDEA in various monomers using a 385 nm LED

Tab 5 – Raw Data obtained for Presto Blue Assay

Tab 6 – Raw Data obtained for Presto Blue Assay – Detailed evaluation of the cytotoxicity tests

Tab 7 – Raw Data of Plate Reader for Presto Blue Assay

Tab 8 – Raw Data obtained for the GPC measurements of KE4 and ethoxylated pentaerythritol

Tab 9 – Raw Data obtained for Photo-DSC measurements of KE1-4 and BP+MDEA in various monomers using a 320-500 nm broadband UV lamp

Tab 10 – Raw Data obtained for Photo-DSC measurements of KE3 and co-initiators in various monomers using a 320-500 nm broadband UV lamp

Tab 11 - Raw Data obtained for Photo-DSC measurements of KE1-4 and BP+MDEA in various monomers using a 385 nm LED

Tab 12 - Raw Data obtained for UV Vis measurements of IC2959

Tab 13 - Raw Data obtained for Photo-DSC measurements of KE3 and BP+MDEA in JRNIL cure and M286 resins

Tab 14 - Raw Data obtained for RT-NIR measurements of KE1-3, BP+MDEA and IC2959 in various monomers using a 320-500 nm broadband UV lamp

NMR file

‘1H KE2, ‘13C KE2', ‘1H KE3’, ‘13C KE3’ and ‘1H KE4’ folders:

NMR data obtained during all synthesis steps of KE2, KE3 and KE4.

A software to display NMR-spectra is needed, such as MestreNova or Topspin.

Compound descriptions

Compound descriptions in the files included herein adhere to the naming in the related publication referenced in the Related Works section, where all compounds are described in detail and drawn as structural formulas. In brief:

KE1: Ethyl pyruvate

KE2: 2-(Acetylcarbonyloxy)ethyl pyruvate

KE3: 2,2-Bis[(acetylcarbonyloxy)methyl]butyl pyruvate

KE4: Ethoxylated pentaerythritol tetrapyruvate

BP: Benzophenone

MDEA: Methyldiethanolamine

HDDA: Hexanedioldiacrylate

DMM: Dimethacrylate mixture (equimolar mixture of urethanedimethacrylate UDMA and decandioldimethacrylate D3MA)

PEGDA: Poly(ethylene glycol) diacrylate Mw ~700 g/mol, 50 wt% in water

EDB: Ethyl 4-dimethylaminobenzoate

PEG: Poly(ethylene glycol)

PPG: Poly(propylene glycol)

IC/IC2959: Irgacure 2959

Li-TPO: Lithium-phenyl-2,4,6-trimethylbenzoylphosphinat

DMEM: Dulbecco's Modified Eagle’s medium

FBS: Fetal bovine serum

JRNIL cure: Decandiol diacrylat

M286: Poly(ethylene glycol) diacrylate Mw ~700 g/mol, 50 wt% in water

Abstract (English)

Photoinitiators (PIs) represent the key molecules within a photopolymerizable resin, due to their ability to generate the initiating species. However, the majority of state-of-the-art PIs comprise aromatic chromophores, known to produce cytotoxic photoproducts, whose migration out of the cured resin poses both environmental and human health threats. Herein, we present a set of multifunctional, aliphatic free radical photoinitiators based on the α-ketoester moiety, which exhibit low cytotoxicity even after irradiation. By systematically increasing the number of PI moieties, purely aliphatic molecules comprised of up to four radical-generating units have been synthesized. High miscibility in both organic and water-based formulations, combined with excellent photoreactivity and no discoloration upon irradiation with broadband (320-500 nm) and LED (385 nm) light sources, are demonstrated. The developed α-ketoester derivatives outperform the benchmark Norrish Type II benzophenone/amine system and can be used for advanced applications, including UV-nanoimprint lithography as well as additive manufacturing technologies (DLP 3D printing).

## 背景

本数据集源自一项博士项目框架下的原创研究工作，并收录于一篇题为《弥合性能与生物相容性的鸿沟：面向光刻基制造应用的、基于α-酮酸酯的无毒多功能脂肪族光引发剂》的学术论文中，完整提供了该论文中呈现与讨论的各项结果的原始数据。

## 技术细节

Microsoft Excel文件"Raw Data_Photoinitiators"：

Tab 1 - 紫外-可见分光光度法（UV Vis）测量所得原始数据（对应KE1-4与二苯甲酮BP）

Tab 2 – 采用320-500 nm宽带紫外灯，在多种单体中对KE1-4以及BP+甲基二乙醇胺（MDEA）进行光差示扫描量热法（Photo-DSC）测量所得评估数据

Tab 3 – 采用320-500 nm宽带紫外灯，在多种单体中对KE3与助引发剂进行光差示扫描量热法（Photo-DSC）测量所得评估数据

Tab 4 – 采用385 nm LED光源，在多种单体中对KE1-4以及BP+MDEA进行光差示扫描量热法（Photo-DSC）测量所得评估数据

Tab 5 – Presto Blue细胞毒性检测法（Presto Blue Assay）原始数据

Tab 6 – Presto Blue细胞毒性检测法（Presto Blue Assay）原始数据——细胞毒性测试详细评估结果

Tab 7 – Presto Blue细胞毒性检测法（Presto Blue Assay）酶标仪检测原始数据

Tab 8 – 凝胶渗透色谱法（GPC）测量所得原始数据（对应KE4与乙氧基化季戊四醇）

Tab 9 – 采用320-500 nm宽带紫外灯，在多种单体中对KE1-4以及BP+MDEA进行光差示扫描量热法（Photo-DSC）测量所得原始数据

Tab 10 – 采用320-500 nm宽带紫外灯，在多种单体中对KE3与助引发剂进行光差示扫描量热法（Photo-DSC）测量所得原始数据

Tab 11 - 采用385 nm LED光源，在多种单体中对KE1-4以及BP+MDEA进行光差示扫描量热法（Photo-DSC）测量所得原始数据

Tab 12 - 紫外-可见分光光度法（UV Vis）测量所得IC2959原始数据

Tab 13 - 在JRNIL固化树脂与M286树脂中，对KE3与BP+MDEA进行光差示扫描量热法（Photo-DSC）测量所得原始数据

Tab 14 - 采用320-500 nm宽带紫外灯，在多种单体中对KE1-3、BP+MDEA与IC2959进行实时近红外光谱法（RT-NIR）测量所得原始数据

## 核磁共振波谱（NMR）文件

‘1H KE2’、‘13C KE2’、‘1H KE3’、‘13C KE3’及‘1H KE4’文件夹：
包含KE2、KE3与KE4全合成步骤中获得的核磁共振波谱数据。需使用MestreNova或Topspin等软件以查看核磁共振谱图。

## 化合物说明

本文所附文件中的化合物命名均遵循参考文献章节中相关学术论文的命名规则，所有化合物均有详细描述并附有结构式。简要说明如下：

KE1：丙酮酸乙酯（Ethyl pyruvate）

KE2：2-(乙酰羰氧基)乙基丙酮酸酯（2-(Acetylcarbonyloxy)ethyl pyruvate）

KE3：2,2-双[(乙酰羰氧基)甲基]丁基丙酮酸酯（2,2-Bis[(acetylcarbonyloxy)methyl]butyl pyruvate）

KE4：乙氧基化季戊四醇四丙酮酸酯（Ethoxylated pentaerythritol tetrapyruvate）

BP：二苯甲酮（Benzophenone）

MDEA：甲基二乙醇胺（Methyldiethanolamine）

HDDA：己二醇二丙烯酸酯（Hexanedioldiacrylate）

DMM：二甲基丙烯酸酯混合物（氨基甲酸酯二甲基丙烯酸酯UDMA与癸二醇二甲基丙烯酸酯D3MA的等摩尔混合物）

PEGDA：聚乙二醇二丙烯酸酯（分子量约700 g/mol，水溶液浓度50 wt%）

EDB：对二甲氨基苯甲酸乙酯（Ethyl 4-dimethylaminobenzoate）

PEG：聚乙二醇（Poly(ethylene glycol)）

PPG：聚丙二醇（Poly(propylene glycol)）

IC/IC2959：伊格库瑞2959（Irgacure 2959，光引发剂2959）

Li-TPO：苯基-2,4,6-三甲基苯甲酰基次膦酸锂（Lithium-phenyl-2,4,6-trimethylbenzoylphosphinat）

DMEM：达尔伯克改良伊格尔培养基（Dulbecco's Modified Eagle’s medium）

FBS：胎牛血清（Fetal bovine serum）

JRNIL cure：癸二醇二丙烯酸酯（Decandiol diacrylat）

M286：聚乙二醇二丙烯酸酯（分子量约700 g/mol，水溶液浓度50 wt%）

## 摘要

光引发剂（Photoinitiators, PIs）是光聚合树脂中的核心组分，因其可产生活性引发物种。然而，当前主流的光引发剂多含芳香发色团，其光解产物具有细胞毒性，且可从固化树脂中迁移出来，对环境与人体健康均构成威胁。本文报道了一系列基于α-酮酸酯结构的多功能脂肪族自由基型光引发剂，即使经辐照后仍表现出极低的细胞毒性。通过系统性增加光引发剂结构单元的数量，我们合成了最多含4个自由基生成单元的纯脂肪族分子。该类光引发剂在有机与水基配方中均具有优异的混溶性，同时展现出良好的光反应活性，经宽带（320-500 nm）与LED（385 nm）光源辐照后无变色现象。所开发的α-酮酸酯衍生物性能优于基准参比的诺里什II型二苯甲酮/胺体系，可应用于包括紫外纳米压印光刻以及增材制造技术（如DLP 3D打印）在内的高端场景。