Asymmetric Benzotrithiophene-Based Hole Transporting Materials Provide High-Efficiency Perovskite Solar Cells.

In this study, we synthesized a series of small-molecule benzotrithiophenes (BTTs) and used them as hole transporting materials (HTMs) in perovskite solar cells (PSCs). The asymmetric benzo[2,1-b:-3,4-b':5,6-b″]trithiophene unit was used as the central core to which were appended various donor groups, namely, carbazole (BTT-CB), thieno thiophene (BTT-FT), triphenylamine (BTT-TPA), and bithiophene (BTT-TT). The extended aromatic core in the asymmetric BTT provided full planarity, thereby favoring intermolecular π-stacking and charge transport. The physical, optical, and electrical properties of these small-molecule HTMs are reported herein. BTT-TT displayed good crystallinity and superior hole mobility, when compared with those of the other three HTMs, and formed smooth and uniform surfaces when covering the perovskite active layer. Accordingly, among the devices prepared in this study, a PSC incorporating BTT-TT as the HTM achieved the highest power conversion efficiency (18.58%). Moreover, this BTT-TT-containing device exhibited good stability after storage for more than 700 h. Thus, asymmetric BTTs are promising candidate materials for use as small-molecule HTMs in PSCs.

Sulfonated Polyaniline as Zwitterionic and Conductive Interfaces for Anti-Biofouling on Open Electrode Surfaces in Electrodynamic Systems.

Electrodynamic systems for bioanalytical applications constantly suffer from biofouling due to electrical field-induced nonspecific bioadsorption on electrode surfaces. To minimize this issue, surface modification using anti-biofouling and conductive materials is necessary to not only protect the electrode surface from nonspecific bioadsorption but also maintain desired electrodynamic properties for electrode operation. In this study, we designed and prepared a conductive, zwitterionic, and self-doped sulfonated polyaniline (SPANI) coating on Au electrode surfaces for anti-biofouling applications. The zwitterionic coating was fabricated by electrochemical polymerization of aniline on the Au electrode surface functionalized with cysteamine (HS-CH2CH2-NH2) and then a post-polymerization treatment with fuming sulfuric acid. We found that the SPANI-coated electrodes exhibited an excellent anti-biofouling ability in dielectrophoresis (DEP) capturing-and-releasing processes, with a very low average residual mass rate of 1.44% for the SPANI-5s electrode, whereas electrodes modified with poly(ethylene glycol) (PEG) gave an average residual mass rate of 14.30%. Even under continuous operation for more than 1 h, the SPANI-5s electrode still showed stable anti-biofouling ability for an 11-cycle E. coli capturing-and-releasing DEP process, with the residual mass rate for all 11 cycles being kept at or below 2.18% to give an average residual mass rate of 1.62% with a standard deviation of 0.40%. This study demonstrates that electrodynamic systems with zwitterionic SPANI coated on open electrode surfaces can excellently function with decent conductance and anti-biofouling performance.

The 3 D Structure of Twisted Benzo[ghi]perylene-Triimide Dimer as a Non-Fullerene Acceptor for Inverted Perovskite Solar Cells.

Here, we introduced benzo[ghi]perylenetriimide (BPTI) derivatives including monomer and twisted dimer (t-BPTI) as an alternative electron-transport layer (ETL) material to replace the commonly used PC61 BM in inverted planar heterojunction perovskite solar cells (PSCs). Moreover, the double ETL was applied in our PSCs with structure of glass/ITO/PEDOT:PSS/perovskite/BPTI/C60 or PDI-C4/BCP/Al. The use of a double ETL structure can effectively eliminate the leakage current. The devices with the t-BPTI/C60 double ETL yield an average power conversion efficiency of 10.73 % and a maximum efficiency of 11.63 %. The device based on the complete non-fullerene electron acceptors of t-BPTI/PDI-C4 as double ETL achieved maximum efficiency of 10.0 %. Moreover, it was found that the utilization of alloy t-BPTI+BPTI as ETL can effectively reduce the hysteresis effect of PSCs. The results suggest that BPTI-based electron-transport materials are potential alternatives for widely used fullerene acceptors in PSCs.

Modified Separator Performing Dual Physical/Chemical Roles to Inhibit Polysulfide Shuttle Resulting in Ultrastable Li-S Batteries.

In this paper we describe a modified (AEG/CH) coated separator for Li-S batteries in which the shuttling phenomenon of the lithium polysulfides is restrained through two types of interactions: activated expanded graphite (AEG) flakes interacted physically with the lithium polysulfides, while chitosan (CH), used to bind the AEG flakes on the separator, interacted chemically through its abundance of amino and hydroxyl functional groups. Moreover, the AEG flakes facilitated ionic and electronic transfer during the redox reaction. Live H-cell discharging experiments revealed that the modified separator was effective at curbing polysulfide shuttling; moreover, X-ray photoelectron spectroscopy analysis of the cycled separator confirmed the presence of lithium polysulfides in the AEG/CH matrix. Using this dual functional interaction approach, the lifetime of the pure sulfur-based cathode was extended to 3000 cycles at 1C-rate (1C = 1670 mA/g), decreasing the decay rate to 0.021% per cycle, a value that is among the best reported to date. A flexible battery based on this modified separator exhibited stable performance and could turn on multiple light-emitting diodes. Such modified membranes with good mechanical strength, high electronic conductivity, and anti-self-discharging shield appear to be a scalable solution for future high-energy battery systems.

Continuous affinity-gradient nano-stationary phase served as a column for reversed-phase electrochromatography and matrix carrier in time-of-flight mass spectrometry for protein analysis.

This study developed an affinity-gradient nano-stationary phase (AG-NSP) for protein analysis using nanofluidic capillary electrochromatography (nano-CEC) conjugated with matrix assisted laser desorption ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). The AG-NSP can be used for protein pre-separation in nano-CEC and as a matrix carrier for protein analysis in MALDI-TOF-MS. A hydrophobicity gradient in AG-NSP was photochemically formed by grafting 4-azidoaniline hydrochloride on vertically arrayed multi-wall carbon nanotubes (MWCNTs) through gray-level exposure to UV light. The reversed-phase gradient stationary phase in AG-NSP was tailored according to the properties of the mobile phase gradient in capillary electrochromatography. As a result, the operation of the system is easily automated using a single buffer solution without the need for multiple solvents for elution. The use of nano-CEC with AG-NSP demonstrated excellent separation efficiency and high resolution for various types of DNA/protein/peptide. MALDI-TOF-MS analysis was then performed directly on the separated proteins and peptides on the chip. The proposed system was then used for the detection of three types of proteins with different molecular weights and PI values, including Cytochrome c (12,360, pI = 10), Lysozyme (14,300, pI = 11), and BSA (86,000, pI = 5)), and digested IgG fragments. The proposed system provided resolution of 1000 Da for the proteins in this study and the separation of digested IgG fragments at a low concentration of 1.2 pmol µL(-1).

Impact of pulse duration on localized single-cell nano-electroporation.

We introduce a localized single-cell membrane nano-electroporation with controllable sequential molecular delivery by millisecond to nanosecond electrical pulses. An intense electrical field was generated by a pair of transparent indium tin oxide (ITO)-based nano-electrodes, which was confined to a narrow region of the single-cell membrane surface near the nano-electrode edges (approximately 2 µm × 50 nm area), whereas the remaining area of the membrane was unaffected. Moreover, a 250 nm SiO2 passivation layer on top of the nano-electrode reduced not only the thermal effect on the cell membrane surface, but it also avoided the generation of ions during the experiment, resulting in the reduction of cell toxicity and a significant enhancement of cell viability. Our approach precisely delivers dyes, Quantum Dots (QDs) and plasmids, through a localized region of single HeLa cells by considerably enhanced electrophoresis and diffusion effects with different duration of the pulsing process. The smaller molecules took less time to deliver into a single cell with a single pulse, whereas larger biomolecules took longer time even for multiple numbers of long lasting pulses. The system not only generates sequential well-controlled nano-pores allowing for the rapid recovery of cell membranes, but it also provides spatial, temporal and qualitative dosage control to deliver biomolecules into localized single-cell levels, which can be potentially beneficial for single cell studies and therapeutic applications.

Highly conductive PEDOT:PSS treated with formic acid for ITO-free polymer solar cells.

We proposed a facile film treatment with formic acid to enhance the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) by 4 orders of magnitude. The effect of formic acid concentration on conductivity was investigated; conductivity increased fast with increasing concentration up to 10 M and then increased slightly, the highest conductivity being 2050 S cm(-1) using 26 M concentration. Formic acid treated PEDOT:PSS films also exhibited very high transmittances. The mechanism of conductivity enhancement was explored through SEM, AFM, and XPS. Formic acid with its high dielectric constant screens the charge between PEDOT and PSS bringing about phase separation between them. Increased carrier concentration, removal of PSS from the film, morphology, and conformation change with elongated and better connected PEDOT chains are the main mechanisms of conductivity enhancement. ITO-free polymer solar cells were also fabricated using PEDOT:PSS electrodes treated with different concentrations of formic acid and showed equal performance to that of ITO electrodes. The concentrated acid treatment did not impair the desirable film properties as well as stability and performance of the solar cells.

Delivery of molecules into cells using localized single cell electroporation on ITO micro-electrode based transparent chip.

Single cell electroporation is one of the nonviral method which successfully allows transfection of exogenous macromolecules into individual living cell. We present localized cell membrane electroporation at single-cell level by using indium tin oxide (ITO) based transparent micro-electrodes chip with inverted microscope. A focused ion beam (FIB) technique has been successfully deployed to fabricate transparent ITO micro-electrodes with submicron gaps, which can generate more intense electric field to produce very localized cell membrane electroporation. In our approach, we have successfully achieved 0.93 µm or smaller electroporation region on the cell surface to inject PI (Propidium Iodide) dye into the cell with 60 % cell viability. This experiments successfully demonstrate the cell self-recover process from the injected PI dye intensity variation. Our localized cell membrane electroporation technique (LSCMEP) not only generates reversible electroporation process but also it provides a clear optical path for potentially monitoring/tracking of drugs to deliver in single cell level.

Probing quenched dye fluorescence of Cy3-DNA-Au-nanoparticle hybrid conjugates using solution and array platforms.

Tuning the luminescence intensity of fluorophores using nanoparticles has shown great potential for the detection of inorganic metal ions, viruses, and proteins. The enhancement or quenching of a dye's fluorescence intensity is strongly dependent on the spatial separation of the dye from the nanoparticle surface. To extend luminescence probing from the solution platform to the solid-state platform, we explored and performed dye quenching assessment using an array format in this study. We report the distance-dependent fluorescence behavior of Au-DNA conjugates prepared by equilibrating phosphine-stabilized gold nanoparticles (AuNPs) of 10-nm size with the designed spacer ds-DNA consisting of thiol-modified target and Cy3-labeled complementary probe of different lengths (5-20 nm). The Cy3-labeled products were immobilized onto MPTMS (3-mercaptopropyltrimethoxysilane)-modified glass substrates and then excited with a 532-nm laser source. Quenching efficiency of AuNPs with increasing Au-to-dye distance was assessed using ligand exchange of the thiolated oligonucleotide by 2-mercaptoethanol (ME) to obtain free Cy3-DNA probe, thus eliminating nanoparticle effect on the dye's luminescence intensity. Effective exchange, revealed by UV-vis absorption and fluorescence profiles, was achieved in a few minutes. It was observed that fluorescence quenching of Au-DNA-Cy3 assessed using the array format was consistent with the result in solution phase for the conjugates with up to 10-nm Au-to-Cy3 separation distance.

Effective enhancement of fluorescence detection efficiency in protein microarray assays: application of a highly fluorinated organosilane as the blocking agent on the background surface by a facile vapor-phase deposition process.

Protein microarrays are emerging as an important enabling technology for the simultaneous investigation of complicated interactions among thousands of proteins. The solution-based blocking protocols commonly used in protein microarray assays often cause cross-contamination among probes and diminution of protein binding efficiency because of the spreading of blocking solution and the obstruction formed by the blocking molecules. In this paper, an alternative blocking process for protein microarray assays is proposed to obtain better performance by employing a vapor-phase deposition method to form self-assembled surface coatings using a highly fluorinated organosilane as the blocking agent on the background surfaces. Compared to conventional solution-based blocking processes, our experimental results showed that this vapor-phase process could shorten the blocking time from hours to less than 10 min, enhance the binding efficiency by up to 6 times, reduce the background noise by up to 16 times, and improve the S/N ratio by up to 64 times. This facile blocking process is compatible with current microarray assays using silica-based substrates and can be performed on many types of silane-modified surfaces.

Nanostructured pillars based on vertically aligned carbon nanotubes as the stationary phase in micro-CEC.

We present a micro-CEC chip carrying out a highly efficient separation of dsDNA fragments through vertically aligned multi-wall carbon nanotubes (MWCNTs) in a microchannel. The vertically aligned MWCNTs were grown directly in the microchannel to form straight nanopillar arrays as ordered and directional chromatographic supports. 1-Pyrenedodecanoic acid was employed for the surface modification of the MWCNTs' stationary phase to adsorb analytes by hydrophobic interactions. This device was used for separating dsDNA fragments of three different lengths (254, 360, and 572 bp), and fluorescence detection was employed to verify the electrokinetic transport in the MWCNT array. The micro-CEC separation of the three compounds was achieved in less than 300 s at a field strength of 66 V/cm due to superior laminar flow patterns and a lower flow resistance resulting from the vertically aligned MWCNTs being used as the stationary phase medium. In addition, a fivefold reduction of band broadening was obtained when the analyte was separated by the chromatographic MWCNT array channel instead of the CE channel. From all of the results, we suggest that an in situ grown and directional MWCNT array can potentially be useful for preparing more diversified forms of stationary phases for vertically efficient chip-based electrochromatography.

Flexible thin films of single-walled carbon nanotubes deposited on plastic substrates.

In the present study, an experimental procedure used to produce thin films of single-walled carbon nanotubes is described. The method was used to prepare solid-state thin films of single walled carbon nanotubes (SWNTs) for various types of studies, such as scanning electron microscopy (SEM) and electrical resistance characterization. In particular, a series of experiments were carried out and, for the first time, a simple and reliable method for removing surfactant (Triton X-100) was described. The scanning electron microscopy studies showed that the SWNTs were shortened after the sonication process used to prepare the SWNT aqueous dispersion in the presence of Triton X-100.

Interactions of ADP-stimulated human platelets with PEGylated polystyrene substrates prepared by surface amidation.

A study primarily focused on the interactions between ADP-stimulated human platelets and PEGylated polystyrene substrates is described in this paper. The platelet-surface interactions were investigated using colorimetric acid phosphatase assay. Two types of amine-containing polymeric hydrogel materials based on poly(ethylene glycol) (PEG), H(2)N-PEG-OCH(3) and H(2)N-PEG-NH(2), were used to PEGylate polystyrene surfaces derivatized with maleic anhydride by amidation at alkaline pH. In addition, comparative studies using surfaces non-covalently adsorbed by bovine serum albumin (BSA) or fibrinogen (Fg) were also conducted. The assay results showed that no significant platelet adhesion was observed when PEGylated surfaces or BSA-coated surfaces were exposed to unstimulated gel-filtered platelets (GFP). However, upon ADP-stimulation, platelet adhesion to the surfaces under investigation in this study all increased to varying degrees. Most importantly, the results showed that polystyrene surfaces PEGylated using H(2)N-PEG-NH(2) were most effective in resisting platelet adhesion when assays were performed using ADP-stimulated GFP. By PEGylating the surfaces of polystyrene microtiter wells via the amidation reaction described in this paper, it is demonstrated that (i) higher degree of surface PEGylation is favored at more alkaline pH and (ii) polystyrene substrates capable of more effectively resisting the adhesion of ADP-stimulated GFP can be obtained by the PEGylation reaction carried out at pH 9.1 using H(2)N-PEG-NH(2).

High-resolution chiral separation using microfluidics-based membrane chromatography.

A plastic microfluidic system, containing porous poly(vinylidene fluoride) (PVDF) membranes adsorbed with bovine serum albumin (BSA), is demonstrated for high resolution chiral separation of racemic tryptophan and thiopental mixtures. Microfluidic networks on poly(dimethylsiloxane) (PDMS) substrates are fabricated by capillary molding technique. This miniaturized chiral separation system consists of two layers of PVDF membranes which are sandwiched between two PDMS slabs containing microchannels facing the membranes. On-line adsorption of BSA onto the membranes is employed for the preparation of chiral stationary phase and the evaluation of solution conditions in an effort to achieve maximum protein adsorption. Variations in the mobile phase conditions, including solution pH and ammonium sulfate concentration, are studied for their effects on chiral separation. Based on the large surface area to volume ratio of porous membrane media, adsorbed BSA onto the PVDF membranes enables high resolution separation of racemic mixtures with sample consumption of sub-nanogram or less in the integrated microfluidic networks. In addition, the membrane pore diameter in the submicron range eliminates the constraints of diffusional mass-transfer resistance during protein adsorption and chiral chromatographic processes.