Dynamic Liquid Surface Enhanced Raman Scattering Platform Based on Soft Tubular Microfluidics for Label-Free Cell Detection.

Cell detection is of great significance for biomedical research. Surface enhanced Raman scattering (SERS) has been widely applied to the detection of cells. However, there is still a lack of a general, low-cost, rapid, and sensitive SERS method for cell detection. Herein, a dynamic liquid SERS platform, which combines label-free SERS technique with soft tubular microfluidics for cell detection, is proposed. Compared with common static solid and static liquid measurement, the dynamic liquid SERS platform can present dynamical mixing, precise control of the mixing time, and continuous spectra collection. By characterizing the model molecules, the proposed dynamic liquid SERS platform has successfully demonstrated good stability and repeatability with 1.90% and 4.98% relative standard deviation (RSD), respectively. Three cell lines including one normal breast cell line (MCF-10A) and two breast cancer cell lines (MCF-7 and MDA-MB-231) were investigated in this platform. 270 cell spectra were selected as the training set for the classification of the models based on the K-Nearest Neighbor (K-NN) algorithm. In three independent experiments, three types of cells were identified by a test set containing 180 cell spectra with sensitivities above 83.3% and specificities above 91.6%. The accuracy was 94.1 ± 1.14% among three independent cell identifications. The dynamic liquid SERS platform has shown higher signal intensity, better repeatability, less pretreatment, and obtainment of more spectra with less time consumption. It will be a powerful detection tool in the area of cell research, clinical diagnosis, and food safety.

Honeycomb-Inspired Surface-Enhanced Raman Scattering Microarray for Large-Area Automated Testing of Urease in Saliva Samples.

Surface-enhanced Raman scattering (SERS) technology, as an important analytical tool, has been widely applied in the field of chemical and biomedical sensing. Automated testing is often combined with biochemical analysis technologies to shorten the detection time and minimize human error. The present SERS substrates for sample detection are time-consuming and subject to high human error, which are not conducive to the combination of SERS and automated testing. Here, a novel honeycomb-inspired SERS microarray is designed for large-area automated testing of urease in saliva samples to shorten the detection time and minimize human error. The honeycomb-inspired SERS microarray is decorated with hexagonal microwells and a homogeneous distribution of silver nanostars. Compared with the other four common SERS substrates, the optimal honeycomb-inspired SERS microarray exhibits the best SERS performance. The RSD of 100 SERS spectra continuously collected from saliva samples is 6.56%, and the time of one detection is reduced from 5 min to 10 s. There is a noteworthy linear relationship with a R2 of 0.982 between SERS intensity and urease concentration, indicating the quantitative detection capability of the urease activity in saliva samples. The honeycomb-inspired SERS microarray, combined with automated testing, provides a new way in which SERS technology can be widely used in biomedical applications.

Palladium-catalyzed asymmetric allylic 4-pyridinylation via electroreductive substitution reaction.

The enantioselective pyridinylation is important for providing chiral compounds bearing heterocycles of pharmaceutical interests. 4-CN-pyrinde is extensively applied in the radical pyridinylation reaction, however, its' enantioselective application is highly challenging. To achieve this goal, we propose an electrochemical catalytic activation of 4-CN-pyridine with a chiral transition metal complex instead of direct cathodic reduction. The chiral catalyst acts as the electron mediator and the transition metal catalysis in turn. The radical species from 4-CN-pyridine is captured via radical rebound by chiral catalyst, and undergoes enantioselective pyridinylation reaction. Here, we show the first method for catalytic asymmetric allylic 4-pyridinylation reactions using 4-CN-pyridine under electrochemical conditions.

Non-powered capillary force-driven stamped approach for directly printing nanomaterials aqueous solution on paper substrate.

The recent boom of nanomaterials printing in the fields of biomedical engineering, bioanalysis and flexible electronics has greatly stimulated researchers' interest in printing technologies. However, specifically formulated nanomaterial inks have limited the types of printable nanomaterials. Here, a unique non-powered capillary force-driven stamped (CFDS) approach, combining a 3D-printed stamper with a paper substrate, is developed for directly printing patterned nanomaterials aqueous solution. The CFDS approach has two processes, including the loading process in which the capillary force of the stamper channel is stronger than gravity, and the deposition process, in which the synergistic action of the capillary force of the paper fibre tubes and gravity is approximately 20 times the capillary force of the stamper channel. Four additive-free nanomaterial aqueous solutions, including nanowires, nanosheets, nanostars and nanogels, are used to print patterns, and show slight diffusion and desired uniformity with a diffusion rate and roundness of 1.12 and 0.78, respectively, demonstrating the feasibility of this approach. Four kinds of nanogel with different fluorescence labels are simultaneously printed to challenge the approach and demonstrate its flexibility and scalability. The resolution of the approach is 0.3 mm. Without any post-processing, the stamped paper substrates directly serve as paper-based surface enhanced Raman scattering substrates with an enhancement factor of 4 × 106 and as electrodes with a resistance of 0.74 Ω, demonstrating their multi-functionality. Due to its general, flexible and scalable applicability, this simple, low-cost and non-powered approach could be widely applied to the personalized printing of nanomaterials on paper substrates.