Drops of water-in-fluorocarbon emulsions have great potential for compartmentalizing both in vitro and in vivo biological systems; however, surfactants to stabilize such emulsions are scarce. Here we present a novel class of fluorosurfactants that we synthesize by coupling oligomeric perfluorinated polyethers (PFPE) with polyethyleneglycol (PEG). We demonstrate that these block copolymer surfactants stabilize water-in-fluorocarbon oil emulsions during all necessary steps of a drop-based experiment including drop formation, incubation, and reinjection into a second microfluidic device. Furthermore, we show that aqueous drops stabilized with these surfactants can be used for in vitro translation (IVT), as well as encapsulation and incubation of single cells. The compatability of this emulsion system with both biological systems and polydimethylsiloxane (PDMS) microfluidic devices makes these surfactants ideal for a broad range of high-throughput, drop-based applications.
We use microfluidic devices to encapsulate, incubate, and manipulate individual cells in picoliter aqueous drops in a carrier fluid at rates of up to several hundred Hz. We use a modular approach with individual devices for each function, thereby significantly increasing the robustness of our system and making it highly flexible and adaptable to a variety of cell-based assays. The small volumes of the drops enables the concentrations of secreted molecules to rapidly attain detectable levels. We show that single hybridoma cells in 33 pL drops secrete detectable concentrations of antibodies in only 6 h and remain fully viable. These devices hold the promise of developing microfluidic cell cytometers and cell sorters with much greater functionality, allowing assays to be performed on individual cells in their own microenvironment prior to analysis and sorting.
We present a simple microfluidic device that uses an array of well-defined chambers to immobilize thousands of femtoliter- to picoliter-scale aqueous drops suspended in inert carrier oil. This device enables timelapse studies of large numbers of individual drops, while simultaneously enabling subsequent drop recovery.
Cyanines derived from heptamethines were investigated in combination with iodonium salts as initiators of the radical polymerization of tripropylene glycol diacrylate and epoxides derived from bisphenol‐A‐diglycidylether. A new near‐infrared (NIR) LED prototype emitting at 805 nm with an exposure intensity of 1.2 W cm−2 facilitated initiation of both radical and cationic polymerization using sensitizers derived from cyanines. This new light‐emitting device has brought new insight into the photochemistry of cyanines with the general structure 1 because a combination of photonic and thermal processes strongly influences reaction pathways. In particular, cationic cyanines comprising a cyclopentene moiety and diphenylamino group in the center initiated the cationic polymerization of epoxides. Selective oxidation of this unit explains why specifically these derivatives may function as initiators for cationic polymerization. In contrast, when the diphenylamino group was replaced by a barbital group at the meso‐position cationic polymerization of epoxides was not initiated.
NIR-sensitized photoinduced atom-transfer radical polymerization (ATRP) is possible by using ppm of Cu II /tris(2pyridylmethyl)amine (TPMA) as the catalyst, apolymethine as the photosensitizer,a nd a-bromophenylacetate as the alkyl halide initiator.A mong the polymethines investigated with cationic, zwitterionic,o ra nionic structures,o nly the zwitterionic 2 exhibited sensitization activity under NIR light at room temperature resulting in the formation of polymers with controlled molecular weight characteristics and functionalities. The barbital group placed at the meso-position of 2 caused the activity in this photo-ATRP framework. The chain-end fidelity of the polymers was confirmed by chain extension and block copolymerization experiments.T he polymerization system exhibits high photostability under NIR light exposure and irradiation dependency as demonstrated by light on/off experiments.
Cyanines derived from heptamethines were mainly discussed regarding their functionalization to broaden the solubility in different surroundings exhibiting either hydrophilic or hydrophobic properties and to tailor made the ΔG
et photopysical properties with respect to absorption and fluorescence. Electrochemical properties were additionally considered for some selected examples. The cyanines chosen comprised as end groups either indolenine, benzo[e]- or benzo[cd]indolium pattern, which facilitated to shift the absorption between 750–1000 nm. This enabled their use in applications with light sources emitting in the near-infrared (NIR) region selected from high power LEDs or lasers with line-shaped focus. The absorbers considered were discussed regarding their function as sensitizer for applications related to Chemistry 4.0 standards. These were mainly photopolymer coatings, which can be found for applications in the graphic industry or to protect selected substrates. The huge release of heat on demand upon turning ON or OFF the NIR light source enables them for photothermal treatment in processes requesting heat to initiate either chemical (activated reactions) or physical (melting, evaporation) events.
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