Photoinitiated Free Radical Polymerization Research Articles

Exploring the role of SAP chemical composition in the internal curing of high-performance cementitious materials

This study investigates the impact of the chemical composition of superabsorbent polymers (SAPs) on their effectiveness in internal curing within high-performance cementitious materials. Although the use of commercial SAPs in cementitious systems has been widely researched, there is still no consensus on how different SAP structures influence material properties. For the first time, this research employs photoinitiated free radical polymerization technology to synthesize three structurally distinct SAPs: SAP with sulfonic acid groups (PAMPS), SAP with amide groups (PAM), and SAP with carboxyl groups (PAAs). The effects of these SAPs on the cement hydration process and microstructure were examined by analyzing their water absorption behavior in cement filtrate. The residual cation content on the SAP surface was evaluated using EDS, while XRD and TGA were used to study how SAP structure affects cement hydration products. Furthermore, the impact of these SAPs on the strength and autogenous shrinkage of the material was investigated. The results indicate that PAMPS, with its sulfonic acid groups, exhibited stable water absorption performance in the alkaline cement environment, promoting hydration reactions and increasing the formation of needle-shaped C-S-H. This stability contributed to mitigating the negative effects on mechanical properties. While the inclusion of SAPs generally reduced the strength of the cement matrix, PAMPS was the most effective in mitigating autogenous shrinkage, achieving a shrinkage mitigation efficiency of 86 %. These findings highlight the importance of SAP chemical structure in influencing cement hydration and material performance, offering insights for the development of effective internal curing agents to enhance high-performance concrete.

Impact of UV Light Exposure During Printing on Thermomechanical Properties of 3D-Printed Polyurethane-Based Orthodontic Aligners

Aim: Polyurethane-based aligners, created through photoinitiated free-radical polymerization, have been the subject of numerous studies focusing solely on their mechanical properties. In contrast, we investigate their thermomechanical properties, which are crucial for their efficacy. This paper aims to investigate the effects of different UV light exposure durations on the complex modulus of elasticity, tan delta, glass transition temperature, and the degree of conversion (DC). Methods: Aligners were printed using Tera Harz TC-85 and NextDent Ortho Flex resin with specific exposure times (2, 2.4, 3, 4, and 4.5 s for Tera Harz; 5, 6, 7, and 8 s for NextDent) and processed per manufacturer guidelines. The degree of conversion was analyzed using Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy, while Dynamic Mechanical Analysis (DMA) characterized the mechanical properties (complex modulus and tan delta) and the glass transition. Results: Tera Harz TC-85 showed a higher degree of conversion (90.29–94.54%), suggesting fewer residual monomers, which is potentially healthier for patients. However, its lower glass transition temperature (35.60–38.74 °C) might cause it to become rubbery in the mouth. NextDent Orto Flex, with a higher storage modulus (641.85–794.55 MPa) and Tg (49.36–50.98 °C), offers greater rigidity and stability at higher temperatures (greater than temperature in the oral cavity), ideal for orthodontic forces, though its lower degree of conversion raises health concerns. Conclusions: Tera Harz TC 85 generally achieves higher DC and more stable polymerization across different UV exposure times than NextDent Orto Flex. Optimal polymerization times significantly impact both the mechanical and thermal properties of these dental resins, with NextDent showing optimal properties at 7 s and Tera Harz benefiting from both very short and extended exposure times.

Rapid synthesis of solid polycarboxylate superplasticizers via photoinitiated radical polymerization

The synthesis and performance optimization of solid polycarboxylate superplasticizers (PCEs) present significant challenges. In our study, a rapid synthesis of a solid polycarboxylate superplasticizer (IPCE10) was achieved using photoinitiated free radical polymerization. IPCE10 exhibited good dispersibility and improved compressive strength in concrete. Dynamic light scattering tests and molecular dynamics simulations demonstrated that the adsorption conformation of IPCE10 on the calcium silicate hydrate surface was relatively dispersed, with a thicker adsorption layer. This indicates that IPCE10 has stronger steric hindrance, resulting in superior dispersibility. Additionally, density functional theory calculations of the reaction energy barriers for radical generation by photoinitiated and azo-initiated monomers revealed that the energy barrier in the photoinitiated system was significantly lower than that in the azo-initiated system, indicating that photoinitiated polymerization is more feasible. This study proposes a simple and rapid method for the preparation of solid polycarboxylate superplasticizers, providing valuable insights for the development of high-value-added construction materials.

Digital Light Processing of Thermoresponsive Hydrogels from Polyproline-Based Star Polypeptides.

The first report of star poly(L-proline) crosslinkers is disclosed for digital light processing 3D printing of thermoresponsive hydrogels. Through chain end functionalization of star poly(L-proline)s with methacryloyl groups, access to high-resolution defined 3D hydrogel structures via digital light processing is achieved through photoinitiated free radical polymerization. Changing the poly(L-proline) molecular weight has a direct influence on both thermoresponsiveness and printability, while shape-morphing behavior can be induced thermally.

Rapid photo-crosslinking, highly conductive, and anti-freezing acrylamide-based hydrogels applied for ECG sensors

In recent years, ionic conductive hydrogels have attracted significant attention in the wearable sensors field due to their simplified preparation process, cost- effectiveness, and high conductivity. However, a large amount of water in traditional hydrogels inevitably condense into ice at low temperatures and make them lose various properties in their practical applications. Hence, this study proposes a method to rapidly synthesized a water/glycerol binary anti-freezing hydrogel only in 10 s through photo-initiated free-radical polymerization. The introduction of LiCl into the crosslinked network composed of acrylamide (AAm) and poly (ethylene glycol) diacrylate (PEGDA) regulated the ionic conductivity of the hydrogel. The hydrogel exhibits a fracture strain of 1062.1 %, a tensile strength of 31 kPa, and an adhesive strength of 6.49 kPa. The synergistic effects of glycerol and LiCl imparted excellent anti-freezing properties (−60 °C). The three-dimensional network structure of the hydrogel facilitates ion transport, exhibiting superior conductivity (30.25 S/m), maintaining high conductivity capability of 1.46 S/m even at a low temperature of −55 °C. Notably, the hydrogel demonstrates prolonged durability and stability in real-time human motion monitoring applications while concurrently exhibiting remarkable sensitivity as an ECG sensor. Hence, this as-prepared hydrogel can adapt to extreme environments and deliver comprehensive performance as an ECG sensor.

Tough and self-adhesive zwitterionic hydrogels with mechano-responsive release of bFGF for tympanic membrane repair

The tympanic membrane (TM) is constantly in a state of vibrating. However, there is currently a lack of drug-delivery scaffolds suitable for the dynamic environment of TM perforation. In this study, a mechano-responsive tough hydrogel was developed. It consists of basic fibroblast growth factor (bFGF)-loaded sodium alginate (SA) microspheres, polysulfobetaine methacrylate (polySBMA), and gelatin methacrylate (GelMA). This hydrogel was designed to serve as a TM scaffold to promote perforation healing under dynamic conditions. bFGF was encapsulated in SA microspheres, which were then incorporated into polySBMA-GelMA hydrogels through photo-initiated free radical polymerization. The mechanical properties, tissue adhesiveness, swelling properties, and degradation of the hydrogels were evaluated before and after microsphere incorporation. It was observed that incorporating bFGF-loaded SA microspheres did not significantly impact the adhesion and degradation mechanisms of the hydrogel. The compressive strength and tensile strength of the microsphere-incorporated hydrogel were up to 6.6 MPa and 64.1 kPa, respectively, suitable for a TM scaffold. The release behavior of bFGF from the hydrogel could be controlled by vibration stimulation without significantly affecting the hydrogel's mechanical properties, indicating a mechano-responsive nature of the hydrogel. The in vitro cytotoxicity assay demonstrated that the hydrogels showed no cytotoxic effects. Moreover, cell culture assays demonstrated that vibration stimulation could enhance the release of bFGF, significantly promoting cell proliferation and migration. The results demonstrate the significant potential of the mechano-responsive hydrogel as a scaffold for repairing TM perforations.

Photoredox dual catalysis using stimulus-responsive fluoresceins for colorimetric detection of Hg(II) ions

We demonstrate photoredox dual catalysis using fluorescein derivatives and apply it to polymerization-based signal amplification (PBA) under the irradiation of visible light. The mechanism of the photoredox dual catalysis is elucidated using electron paramagnetic resonance (EPR) and UV–Vis spectroscopies. We applied the photoredox dual catalysis to amplify and readout the signal of Hg(II) ions with the unaided eye through photoinitiated free-radical polymerization. Although PBA offers a reliable and rapid colorimetric method for analyte detection, its sensitivity remains a challenge compared with fluorescence detection. To address this issue, we designed a dual system involving activatable fluoresceins that selectively react to external stimuli, followed by their action as photoredox catalysts/initiators. As a proof-of-concept, we employed fluorescin (rFL) and eosin hydrazide (EYHZ) as light- and Hg(II) ion-responsive probes, respectively. This dual system selectively initiated the polymerization of poly(ethylene glycol) diacrylate (PEGDA) in the presence of Hg(II) ions under visible light. Remarkably, this photoredox dual catalysis approach allowed the unaided eye to detect of Hg(II) ions as low as 90 nM in aqueous solution, demonstrating its potential for sensitive and versatile sensing applications.

Light-mediated intracellular polymerization.

The synthesis of synthetic intracellular polymers offers groundbreaking possibilities in cellular biology and medical research, allowing for novel experiments in drug delivery, bioimaging and targeted cancer therapies. These macromolecules, composed of biocompatible monomers, are pivotal in manipulating cellular functions and pathways due to their bioavailability, cytocompatibility and distinct chemical properties. This protocol details two innovative methods for intracellular polymerization. The first one uses 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone (Irgacure 2959) as a photoinitiator for free radical polymerization under UV light (365 nm, 5 mW/cm2). The second method employs photoinduced electron transfer-reversible addition-fragmentation chain-transfer polymerization with visible light (470 nm, 100 mW/cm2). We further elaborate on isolating these intracellular polymers by streptavidin/biotin interaction or immobilized metal ion affinity chromatography for polymers tagged with biotin or histidine. The entire process, from polymerization to isolation, takes ~48 h. Moreover, the intracellular polymers thus generated demonstrate significant potential in enhancing actin polymerization, in bioimaging applications and as a novel avenue in cancer treatment strategies. The protocol extends to animal models, providing a comprehensive approach from cellular to systemic applications. Users are advised to have a basic understanding of organic synthesis and cell biology techniques.

Triblock polymer PDMAEMA-co-PNIPAM-co-PMPC to deliver siKRAS for gene therapy in pancreatic cancer

Mutant KRAS sustained KRAS-GTP conformation and activated downstream signaling in pancreatic cancer. Inhibition of KRAS expression has been widely utilized for gene therapy of pancreatic cancer. In this study, a triblock cationic polymer, PDMAEMA-co-PNIPAM-co-PMPC (PDNM), was designed and synthesized as a gene carrier through photoinitiated free radical polymerization. The PDNM/siKRAS delivery system exhibited efficient cellular uptake and low bio-toxicity, as confirmed by fluorescence microscopy and flow cytometry. In vitro experiments using AsPC-1 cells showed that the nanoparticle transfection with PDNM/siKRAS demonstrated favorable anti-tumor effect, including enhanced apoptosis, inhibition of mitosis by arresting the cell cycle at the S phase, reduced Ki67 expression, and impaired cell migration ability. The anti-tumor effect was achieved primarily through KRAS inhibition and caspase 3 activation following siKRAS transfection. Additionally, in vivo experiments showed that the PDNM/siKRAS nanoparticles resulted in reduced tumor volumes and decreased Ki67 expression without apparent impairment of other organs. Notably, the transfection of nanoparticles in patient-derived organoids also demonstrated a similar inhibitory effect. Overall, PDNM holds promise as a potential carrier for siKRAS delivery and gene therapy, both in experimental and clinical applications.

Optical Fiber-Based Polymer Microcantilever for Chemical Sensing: A Through-Fiber Fabrication Scheme.

Fiber optics offer an emerging platform for chemical and biological sensors when engineered with appropriate materials. However, the large aspect ratio makes the optical fiber a rather challenging substrate for standard microfabrication techniques. In this work, the cleaved end of an optical fiber is used as a fabrication platform for cantilever sensors based on functional polymers. The through-fiber fabrication process is triggered by photo-initiated free-radical polymerization and results in a high-aspect-ratio polymer beam in a single step. The dynamic mode application of these cantilevers is first demonstrated in air. These cantilevers are then tuned for sensing applications, including humidity and chemical sensing based on molecularly imprinted polymers.

ACTIVE-BAPO - A Versatile Transfer Agent for Photoactive Bis(acyl)phosphane Oxide Units.

A N-hydroxy succinimide (NHS) ester substituted bis(acyl)phosphane oxide (ACTIVE-BAPO) was prepared by phospha-Michael addition and used for an easy one-step BAPO ligation with substrates containing primary amino groups, such as amino acids, proteins, and poly(amidoamine) (PAMAM) dendrimers. Thereby, a range of new molecular and polymeric photoinitators was obtained. Real-time photo-rheology experiments demonstrated the outstanding efficiency of the PAMAM BAPOs as photoinitiators for free radical polymerization. Remarkably, it is found that PAMAM BAPOs also act as crosslinking agents to convert monofunctional methacrylate monomers into thermosetting networks without any further additives. Depending on the number of the attached BAPOs, thermosets with a different degree of crosslinking and swelling capability in water were obtained.

Zwitterionic poly(sulfobetaine methacrylate)-based hydrogel coating for drinking water distribution systems to inhibit adhesion of waterborne bacteria.

Presence of biofilms in drinking water distribution systems (DWDS) can be a nuisance, leading to several operational and maintenance issues (i.e., increased secondary disinfectants demand, pipe damage or increased flow resistance), and so far, no single control practice was found to be sufficiently effective. Here, we propose poly (sulfobetaine methacrylate) (P(SBMA))-based hydrogel coating application as a biofilm control strategy in DWDS. The P(SBMA) coating was synthetized through photoinitiated free radical polymerization on polydimethylsiloxane with different combinations of SBMA as a monomer, and N, N'-methylenebis (acrylamide) (BIS) as a cross-linker. The most stable coating in terms of its mechanical properties was obtained using 20% SBMA with a 20:1 SBMA:BIS ratio. The coating was characterized using Scanning Electron Microscopy, Energy Dispersive X-Ray Spectroscopy, and water contact angle measurements. The anti-adhesive performance of the coating was evaluated in a parallel-plate flow chamber system against adhesion of four bacterial strains representing genera commonly identified in DWDS biofilm communities, Sphingomonas and Pseudomonas. The selected strains exhibited varying adhesion behaviors in terms of attachment density and bacteria distribution on the surface. Despite these differences, after 4h, presence of the P(SBMA)-based hydrogel coating significantly reduced the number of adhering bacteria by 97%, 94%, 98% and 99%, for Sphingomonas Sph5, Sphingomonas Sph10, Pseudomonas extremorientalis and Pseudomonas aeruginosa, respectively, compared to non-coated surfaces. These findings motivate further research into a potential application of a hydrogel anti-adhesive coating as a localized biofilm control strategy in DWDS, especially on materials known to promote excessive biofilm growth.

Tannin coordinated nanozyme composite-based hybrid hydrogel eye drops for prophylactic treatment of multidrug-resistant Pseudomonas aeruginosa keratitis

Pseudomonas aeruginosa infection is a severe acute suppurative ulcer that engulfs virtually the entire tissue in a short period and leads to devastating destruction. Antibiotic therapy is a common approach for the prophylaxis and treatment of P. aeruginosa infection. However, it is often associated with serious side effects, complications, and multidrug resistance. Therefore, it has been a long-standing challenge to explore safe and effective methods for controlling P. aeruginosa infection. Herein, tannin-coordinated nanozyme composite-based hybrid hydrogels (TCNH) are developed and characterized for the prophylactic treatment of P. aeruginosa and multidrug-resistant P. aeruginosa infections using mouse keratitis as the animal model. The TCNH eye drops are constructed by photoinitiated free radical polymerization of acetylated gelatin solution containing self-synthesized tannin-coordinated Co3O4/Ag nanozyme composite. The as-prepared TCNH displays good dispersibility, peroxidase-like activity and in vitro/in vivo biocompatibility. The nanozyme composite in TCNH seems to penetrate the interior of bacteria and exhibited significant broad-spectrum antibacterial activity owing to its intrinsic and nanozymic catalytic properties. Furthermore, TCNH eye drops can be successfully applied to treat P. aeruginosa and multidrug-resistant P. aeruginosa keratitis. The findings of this study reveal the potential of tannin-coordinated nanozyme composite-based hybrid hydrogel eye drops for treating infectious diseases.Graphical

Zwitterionic liquid hydrogel sustained-release strategy for high-performance nanofiltration membrane

Controlling the diffusion of amine monomers plays a crucial role in fabricating well-defined architecture and high-performance nanofiltration (NF) membranes through interfacial polymerization (IP). Herein, a sustained-release strategy was proposed to regulate the interfacial polymerization through a zwitterionic liquid hydrogel transition layer. The hydrogel (Gel) was fabricated via in-situ one-step UV photo-initiated free-radical polymerization between 1-vinyl-3-ethylimidazolium chloride ([VEIm][Cl]) and 3-sulfopropyl methacrylate potassium salt (SMP) on the polyethersulfone (PES) substrate. The polyamide (PA) layer was then formed on the Gel layer by mitigating the diffusion of amine monomers. Low-field time-domain nuclear magnetic resonance (TD NMR) analysis demonstrated that the Gel layer significantly enhanced the water-absorbing capacity of the composite membrane. Positron annihilation lifetime spectroscopy (PALS) also confirmed the Gel-PA composite membrane possessed enlarged free volumes. The obtained Gel-PA composite membrane displayed a permeance of 13.22 L m−2 h−1 bar−1, a high Na2SO4 rejection of 98.23 %, a favorable NaCl/Na2SO4 selectivity of 49.75, outstanding long-term operational stability, and membrane antifouling properties. This sustained-release strategy provides a facile and feasible approach to controlling the IP process and obtaining high-performance nanofiltration membranes.

PH and Reduction Dual-Responsive Nanogels as Smart Nanocarriers to Resist Doxorubicin Aggregation.

The use of smart nanocarriers that can modulate therapeutic release aided by biological cues can prevent undesirable cytotoxicity caused by the premature release of cytotoxic drugs during nanocarrier circulation. In this report, degradable nanocarriers based on pH/reduction dual-responsive nanogels were synthesized to encapsulate doxorubicin hydrochloride (DOX) and specifically boost the release of DOX in conditions characteristic of the cancer microenvironment. Nanogels containing anionic monomer 2-carboxyethyl acrylate (CEA) and N,N′-bis(acryloyl)cystamine (CBA) as a degradable crosslinker have been successfully synthesized via photoinitiated free radical polymerization. The loading process was conducted after polymerization by taking advantage of the electrostatic interaction between the negatively charged nanogels and the positively charged DOX. In this case, a high drug loading capacity (DLC) of up to 27.89% was achieved. The entrapment of DOX into a nanogel network could prevent DOX from aggregating in biological media at DOX concentrations up to ~160 µg/mL. Anionic nanogels had an average hydrodynamic diameter (dH) of around 90 nm with a negative zeta (ζ) potential of around −25 mV, making them suitable for targeting cancer tissue via the enhanced permeation effect. DOX-loaded nanogels formed a stable dispersion in different biological media, including serum-enriched cell media. In the presence of glutathione (GSH) and reduced pH, drug release was enhanced, which proves dual responsivity. An in vitro study using the HCT 116 colon cancer cell line demonstrated the enhanced cytotoxic effect of the NG-CBA/DOX-1 nanogel compared to free DOX. Taken together, pH/reduction dual-responsive nanogels show promise as drug delivery systems for anticancer therapy.

Synthesis and Characterization of Polymeric Blends Containing Polysulfone Based on Cyclic Bisphenol.

The elaboration of the composition and methods of preparation of new types of materials is an important issue from the plastics industry’s point of view. The paper presents the polysulfone synthesis based on 4,4′-cyclohexylidenebisphenol (bisphenol Z). This compound was used (in an amount of 5 or 10 wt.% sample) for the synthesis and characterization of new polymeric blends based on the two different acrylic resins (EB-150 and EB-600) and the active solvent N-vinyl-2-pyrrolidone (NVP). The weight ratio of the used resin to solvent was 1:2; 1:1 or 2:1. These new materials were obtained applying the photoinitiated free radical polymerization with 2,2-dimethoxy-2-phenyloacetophenone as a photoinitiator used in an amount of 1 wt.%. Six polymeric blends and six copolymers without polysulfone were cured by this method. By means of ATR/FT-IR (Attenuated Total Reflection–Fourier Transform Infrared) spectroscopy the chemical structure of the synthesized polysulfone was proved. The effect of the presence of the polysulfone presence on the thermal properties of the obtained blends was analyzed by means of thermogravimetry and differential thermogravimetry (TG/DTG), as well as differential scanning calorimetry (DSC). Moreover, the dynamic mechanical studies (DMA) of these materials were also carried out, demonstrating which of the materials showed the influence of the percentage of polysulfone on the selected properties in the blended- and parent-copolymers samples.

Effect of poly(ethylene glycol) methacrylate on the ophthalmic properties of silicone hydrogel contact lenses

In this study, silicone hydrogels were synthesized via the photoinitiated free radical polymerization of 3-(methacryloyloxy)propyltris(trimethylsiloxy) silane (TRIS), 1-vinyl-2-pyrrolidinone (NVP), methacrylic acid (MAA), and poly(ethylene glycol) methacrylate (PEGMA), with ethylene glycol dimethacrylate (EGDMA) as the cross-linker and 2-hydroxy-2-methylbenzene acetone (D-1173) as the photoinitiator. The equilibrium water content (EWC) and oxygen permeability (Dk) of the synthesized silicone hydrogel polymers were linearly proportional to the hydrophilic PEGMA content. The high PEGMA content of the polymers led to a higher EWC, lower Dk, and lower contact angle. The highest Dk value of the soft lens was 73 barrers, which corresponded with the lowest EWC (31 %) value of the hydrogel without PEGMA. The stiffness of the hydrogel decreased with increasing PEGMA content. The silicone hydrogel adsorbed low amounts of lysozymes and human serum albumin (HSA) due to the anti-fouling properties of PEG moiety. In addition, the synthesized silicone hydrogels were non-cytotoxic as determined by an in vitro L929 fibroblast assay. Therefore, the TRIS-NVP-MAA-PEGMA hydrogel can be potentially used as a contact lens material with adjustable EWC, Dk, and low protein adsorption.

Free-Radical Photopolymerization for Curing Products for Refinish Coatings Market.

Even though there are many photocurable compositions that are cured by cationic photopolymerization mechanisms, UV curing generally consists of the formation of cross-linking covalent bonds between a resin and monomers via a photoinitiated free radical polymerization reaction, obtaining a three-dimensional polymer network. One of its many applications is in the refinish coatings market, where putties, primers and clear coats can be cured faster and more efficiently than with traditional curing. All these products contain the same essential components, which are resin, monomers and photoinitiators, the latter being the source of free radicals. They may also include additives used to achieve a certain consistency, but always taking into account the avoidance of damage to the UV curing—for example, by removing light from the innermost layers. Surface curing also has its challenges since it can be easily inhibited by oxygen, although this can be solved by adding scavengers such as amines or thiols, able to react with the otherwise inactive peroxy radicals and continue the propagation of the polymerization reaction. In this review article, we cover a broad analysis from the organic point of view to the industrial applications of this line of research, with a wide current and future range of uses.

Zwitter-ionic monolith-based spintip column coupled with Evosep One liquid chromatography for high-throughput proteomic analysis

A high-throughput proteomic workflow with good sensitivity and reproducibility is highly demanding for proteomic studies of large clinical cohorts. We present a workflow that seamlessly integrates the zwitter-ionic monolith-based spintip (ZIM-Tip) with the Evosep One liquid chromatography system to address this challenge. Disposable ZIM-Tips were prepared with satisfying permeability based on photo-initiated free radical polymerization. Sample preparation steps, including ion-exchange-based protein concentration, reduction, alkylation, and enzymatic digestion, were processed on the ZIM-Tips in 2 h with about 10% sample loss. The peptides recovered from ZIM-Tips were directly loaded on Evotips for desalting and proteomic data acquisition. In one-hour high performance liquid chromatography-MS/MS run, more than 4000 proteins were consistently identified from 1 µg of cell lysate using timsTOF Pro-mass spectrometer in data-dependent acquisition mode (DDA). At least 20 samples with protein amount of 1 µg could be processed each day. Good intra- and inter-day precision in quantification were demonstrated with median coefficient of variation (CV) values of less than 20% and 30%, respectively. The average Pearson correlation coefficients of each two sets of samples are 0.934 and 0.901, respectively. Collectively, the ZIM-Tip technology offers an useful solution for clinical cohort studies with demand for large sample amounts and low sample input while maintaining in-depth proteome coverage.

A Water Soluble, Low Migration, and Visible Light Photoinitiator by Thioxanthone‐Functionalization of Poly(ethylene glycol)‐Containing Poly(β‐amino ester)

AbstractA novel photoinitiator (PI) is described here for low ecological impact, p(PEGDA575‐TX): It is water soluble, polymerizable, thioxanthone (TX) functional, and is a one‐component poly(ethylene glycol)‐based poly(β‐amino ester). The PI is synthesized in one step via classical aza‐Michael addition reaction between poly(ethylene glycol) diacrylate (Mn = 575 D) and amine functionalized TX (2‐(2‐aminoethoxy)‐9H‐thioxanthen‐9‐one). It absorbs at ≈ 404 nm (ε = 14 000–44 309) in water and can photodecompose with or without additives such as ethyl 4‐(dimethylamino)benzoate (EDB) and bis‐(4‐tert‐butylphenyl)‐iodonium hexafluorophosphate (Iod). Although it is an effective one‐component visible light PI for free radical polymerization of di‐ and tri(meth)acrylates, EDB or Iod will be favorable for synergistic effect. p(PEGDA575‐TX) has higher initiating reactivity, reducing ability of oxygen inhibition and migration stability compared to TX, which make it environmental friendly.