Tailorable and Biocompatible Supramolecular-Based Hydrogels Featuring two Dynamic Covalent Chemistries.

Dynamic covalent chemistry (DCC) has proven to be a valuable tool in creating fascinating molecules, structures, and emergent properties in fully synthetic systems. Here we report a system that uses two dynamic covalent bonds in tandem, namely disulfides and hydrazones, for the formation of hydrogels containing biologically relevant ligands. The reversibility of disulfide bonds allows fiber formation upon oxidation of dithiol-peptide building block, while the reaction between NH-NH2 functionalized C-terminus and aldehyde cross-linkers results in a gel. The same bond-forming reaction was exploited for the "decoration" of the supramolecular assemblies by cell-adhesion-promoting sequences (RGD and LDV). Fast triggered gelation, cytocompatibility and ability to "on-demand" chemically customize fibrillar scaffold offer potential for applying these systems as a bioactive platform for cell culture and tissue engineering.

Thiol-free self-assembled oligoethylene glycols enable robust air-stable molecular electronics.

Self-assembled monolayers (SAMs) are widely used to engineer the surface properties of metals. The relatively simple and versatile chemistry of metal-thiolate bonds makes thiolate SAMs the preferred option in a range of applications, yet fragility and a tendency to oxidize in air limit their long-term use. Here, we report the formation of thiol-free self-assembled mono- and bilayers of glycol ethers, which bind to the surface of coinage metals through the spontaneous chemisorption of glycol ether-functionalized fullerenes. As-prepared assemblies are bilayers presenting fullerene cages at both the substrate and ambient interface. Subsequent exposure to functionalized glycol ethers displaces the topmost layer of glycol ether-functionalized fullerenes, and the resulting assemblies expose functional groups to the ambient interface. These layers exhibit the key properties of thiolate SAMs, yet they are stable to ambient conditions for several weeks, as shown by the performance of tunnelling junctions formed from SAMs of alkyl-functionalized glycol ethers. Glycol ether-functionalized spiropyrans incorporated into mixed monolayers lead to reversible, light-driven conductance switching. Self-assemblies of glycol ethers are drop-in replacements for thiolate SAMs that retain all of their useful properties while avoiding the drawbacks of metal-thiolate bonds.

Fullerenes Enhance Self-Assembly and Electron Injection of Photosystem I in Biophotovoltaic Devices.

This paper describes the fabrication of microfluidic devices with a focus on controlling the orientation of photosystem I (PSI) complexes, which directly affects the performance of biophotovoltaic devices by maximizing the efficiency of the extraction of electron/hole pairs from the complexes. The surface chemistry of the electrode on which the complexes assemble plays a critical role in their orientation. We compared the degree of orientation on self-assembled monolayers of phenyl-C61-butyric acid and a custom peptide on nanostructured gold electrodes. Biophotovoltaic devices fabricated with the C61 fulleroid exhibit significantly improved performance and reproducibility compared to those utilizing the peptide, yielding a 1.6-fold increase in efficiency. In addition, the C61-based devices were more stable under continuous illumination. Our findings show that fulleroids, which are well-known acceptor materials in organic photovoltaic devices, facilitate the extraction of electrons from PSI complexes without sacrificing control over the orientation of the complexes, highlighting this combination of traditional organic semiconductors with biomolecules as a viable approach to coopting natural photosynthetic systems for use in solar cells.

Down-Regulation of Nfatc1 Suppresses Proliferation, Migration, Invasion, and Warburg Effect in Prostate Cancer Cells.

BACKGROUND Prostate cancer (PCa), accounting for 28% of all male cancer cases, is the second leading cause of cancer-related death among men. NFATc1, belonging to the NFAT family, is overexpressed in PCa and is correlated with the risk of recurrence after radical prostatectomy. MATERIAL AND METHODS In the present study, the expression of NFATc, c-myc, and PKM2 in PCa cells was regulated by lentiviruses and then detected by real-time PCR and Western blot analysis. Further, proliferation, invasion, and migration assays were performed. The glucose consumption and lactate production were assessed by biochemical detection. RESULTS We found that NFATc1 down-regulation significantly suppressed the proliferation and Warburg effect of PCa cells, concurrent with a decrease of c-myc and PKM2 expression. Likewise, the abilities of migration and invasion were also inhibited in NFATc1-silenced PCa cells. In addition, NFATc1 down-regulation-induced inhibition of cell proliferation, migration, invasion, and Warburg effect were counteracted by up-regulation of c-myc or PKM2. The expression of PKM2 was positively regulated by NFATc1 and c-myc expression. CONCLUSIONS These results indicate that NFATc1 down-regulation can suppress the proliferation, Warburg effect, and migration and invasion abilities of PCa cells, probably by regulating c-myc and PKM2 expression. NFATc1 may be a potential therapeutic target for PCa and could be used as a diagnosis or prognosis indicator of PCa.

In-Place Modulation of Rectification in Tunneling Junctions Comprising Self-Assembled Monolayers.

This paper describes tunneling junctions comprising self-assembled monolayers that can be converted between resistor and diode functionality in-place. The rectification ratio is affected by the hydration of densely packed carboxylic acid groups at the interface between the top-contact and the monolayer. We studied this process by treatment with water and a water scavenger using three different top-contacts, eutectic Ga-In (EGaIn), conducting-probe atomic force microscopy (CP-AFM), and reduced graphene oxide (rGO), demonstrating that the phenomena is molecular in nature and is not platform-speciffc. We propose a mechanism in which the tunneling junctions convert to diode behavior through the lowering of the LUMO, which is suffcient to bring it close to resonance at positive bias, potentially assisted by a Stark shift. This shift in energy is supported by calculations and a change in polarization observed by X-ray photoelectron spectroscopy and Kelvin probe measurements. We demonstrate light-driven modulation using spiropyran as a photoacid, suggesting that any chemical process that is coupled to the release of small molecules that can tightly bind carboxylic acid groups can be used as an external stimulus to modulate rectification. The ability to convert a tunneling junction reversibly between a diode and a resistor via an effect that is intrinsic to the molecules in the junction extends the possible applications of Molecular Electronics to reconfigurable circuits and other new functionalities that do not have direct analogs in conventional semiconductor devices.

Tunneling Probability Increases with Distance in Junctions Comprising Self-Assembled Monolayers of Oligothiophenes.

Molecular tunneling junctions should enable the tailoring of charge-transport at the quantum level through synthetic chemistry but are hindered by the dominance of the electrodes. We show that the frontier orbitals of molecules can be decoupled from the electrodes, preserving their relative energies in self-assembled monolayers even when a top-contact is applied. This decoupling leads to the remarkable observation of tunneling probabilities that increase with distance in a series of oligothiophenes, which we explain using a two-barrier tunneling model. This model is generalizable to any conjugated oligomers for which the frontier orbital gap can be determined and predicts that the molecular orbitals that dominate tunneling charge-transport can be positioned via molecular design rather than by domination of Fermi-level pinning arising from strong hybridization. The ability to preserve the electronic structure of molecules in tunneling junctions facilitates the application of well-established synthetic design rules to tailor the properties of molecular-electronic devices.

Enhancing the Conductivity and Thermoelectric Performance of Semicrystalline Conducting Polymers through Controlled Tie Chain Incorporation.

Conjugated polymers are promising materials for thermoelectric applications, however, at present few effective and well-understood strategies exist to further advance their thermoelectric performance. Here a new model system is reported for a better understanding of the key factors governing their thermoelectric properties: aligned, ribbon-phase poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT) doped by ion-exchange doping. Using a range of microstructural and spectroscopic methods, the effect of controlled incorporation of tie-chains between the crystalline domains is studied through blending of high and low molecular weight chains. The tie chains provide efficient transport pathways between crystalline domains and lead to significantly enhanced electrical conductivity of 4810 S cm-1, which is not accompanied by a reduction in Seebeck coefficient or a large increase in thermal conductivity. Respectable power factors of 173 µW m-1 K-2 are demonstrated in this model system. The approach is generally applicable to a wide range of semicrystalline conjugated polymers and could provide an effective pathway for further enhancing their thermoelectric properties and overcome traditional trade-offs in optimization of thermoelectric performance.

Printable logic circuits comprising self-assembled protein complexes.

This paper describes the fabrication of digital logic circuits comprising resistors and diodes made from protein complexes and wired together using printed liquid metal electrodes. These resistors and diodes exhibit temperature-independent charge-transport over a distance of approximately 10 nm and require no encapsulation or special handling. The function of the protein complexes is determined entirely by self-assembly. When induced to self-assembly into anisotropic monolayers, the collective action of the aligned dipole moments increases the electrical conductivity of the ensemble in one direction and decreases it in the other. When induced to self-assemble into isotropic monolayers, the dipole moments are randomized and the electrical conductivity is approximately equal in both directions. We demonstrate the robustness and utility of these all-protein logic circuits by constructing pulse modulators based on AND and OR logic gates that function nearly identically to simulated circuits. These results show that digital circuits with useful functionality can be derived from readily obtainable biomolecules using simple, straightforward fabrication techniques that exploit molecular self-assembly, realizing one of the primary goals of molecular electronics.

In Operando Modulation of Rectification in Molecular Tunneling Junctions Comprising Reconfigurable Molecular Self-Assemblies.

The reconfiguration of molecular tunneling junctions during operation via the self-assembly of bilayers of glycol ethers is described. Well-established functional groups are used to modulate the magnitude and direction of rectification in assembled tunneling junctions by exposing them to solutions containing different glycol ethers. Variable-temperature measurements confirm that rectification occurs by the expected bias-dependent tunneling-hopping mechanism for these functional groups and that glycol ethers, besides being an unusually efficient tunneling medium, behave similarly to alkanes. Memory bits are fabricated from crossbar junctions prepared by injecting eutectic Ga-In (EGaIn) into microfluidic channels. The states of two 8-bit registers were set by trains of droplets such that they are able to perform logical AND operations on bit strings encoded into chemical packets that alter the composition of the crossbar junctions through self-assembly to effect memristor-like properties. This proof-of-concept work demonstrates the potential for fieldable devices based on molecular tunneling junctions comprising self-assembled monolayers and bilayers.

Controlling n-Type Molecular Doping via Regiochemistry and Polarity of Pendant Groups on Low Band Gap Donor-Acceptor Copolymers.

We demonstrate the impact of the type and position of pendant groups on the n-doping of low-band gap donor-acceptor (D-A) copolymers. Polar glycol ether groups simultaneously increase the electron affinities of D-A copolymers and improve the host/dopant miscibility compared to nonpolar alkyl groups, improving the doping efficiency by a factor of over 40. The bulk mobility of the doped films increases with the fraction of polar groups, leading to a best conductivity of 0.08 S cm-1 and power factor (PF) of 0.24 µW m-1 K-2 in the doped copolymer with the polar pendant groups on both the D and A moieties. We used spatially resolved absorption spectroscopy to relate commensurate morphological changes to the dispersion of dopants and to the relative local doping efficiency, demonstrating a direct relationship between the morphology of the polymer phase, the solvation of the molecular dopant, and the electrical properties of doped films. Our work offers fundamental new insights into the influence of the physical properties of pendant chains on the molecular doping process, which should be generalizable to any molecularly doped polymer films.

Amphipathic Side Chain of a Conjugated Polymer Optimizes Dopant Location toward Efficient N-Type Organic Thermoelectrics.

There is no molecular strategy for selectively increasing the Seebeck coefficient without reducing the electrical conductivity for organic thermoelectrics. Here, it is reported that the use of amphipathic side chains in an n-type donor-acceptor copolymer can selectively increase the Seebeck coefficient and thus increase the power factor by a factor of ≈5. The amphipathic side chain contains an alkyl chain segment as a spacer between the polymer backbone and an ethylene glycol type chain segment. The use of this alkyl spacer does not only reduce the energetic disorder in the conjugated polymer film but can also properly control the dopant sites away from the backbone, which minimizes the adverse influence of counterions. As confirmed by kinetic Monte Carlo simulations with the host-dopant distance as the only variable, a reduced Coulombic interaction resulting from a larger host-dopant distance contributes to a higher Seebeck coefficient for a given electrical conductivity. Finally, an optimized power factor of 18 µW m-1 K-2 is achieved in the doped polymer film. This work provides a facile molecular strategy for selectively improving the Seebeck coefficient and opens up a new route for optimizing the dopant location toward realizing better n-type polymeric thermoelectrics.

Biosynthesis of selenium nanoparticles and their effect on changes in urinary nanocrystallites in calcium oxalate stone formation.

Plant bio constituents have the ability to prepare nanoparticles, and usually, plant polyphenols are tested to reduce sodium selenite to selenium nanoparticles (SeNPs). In this work, we showed the biosynthesis of SeNPs using Ocimum tenuiflorum leaf extract. The as obtained SeNPs were in the size range of 15-20 nm and spherical in shape. Also, TEM microscopic images represented the aggregation of crystal structures as extracellular deposits. Moreover, scanning electron microscopy was performed to examine the chemical transition of calcium oxalate (CaC2O4) crystal's shape and structure due to the influence of SeNPs. SeNPs inhibited the aggregation and growth of CaC2O4 monohydrate crystals and hence the prepared SeNPs could have important prospects in medical and pharmaceutical applications as a potential inhibitor of CaC2O4 urinary stones.

Solid-State Protein Junctions: Cross- Laboratory Study Shows Preservation of Mechanism at Varying Electronic Coupling.

Successful integration of proteins in solid-state electronics requires contacting them in a non-invasive fashion, with a solid conducting surface for immobilization as one such contact. The contacts can affect and even dominate the measured electronic transport. Often substrates, substrate treatments, protein immobilization, and device geometries differ between laboratories. Thus the question arises how far results from different laboratories and platforms are comparable and how to distinguish genuine protein electronic transport properties from platform-induced ones. We report a systematic comparison of electronic transport measurements between different laboratories, using all commonly used large-area schemes to contact a set of three proteins of largely different types. Altogether we study eight different combinations of molecular junction configurations, designed so that Ageoof junctions varies from 105 to 10-3 µm2. Although for the same protein, measured with similar device geometry, results compare reasonably well, there are significant differences in current densities (an intensive variable) between different device geometries. Likely, these originate in the critical contact-protein coupling (∼contact resistance), in addition to the actual number of proteins involved, because the effective junction contact area depends on the nanometric roughness of the electrodes and at times, even the proteins may increase this roughness. On the positive side, our results show that understanding what controls the coupling can make the coupling a design knob. In terms of extensive variables, such as temperature, our comparison unanimously shows the transport to be independent of temperature for all studied configurations and proteins. Our study places coupling and lack of temperature activation as key aspects to be considered in both modeling and practice of protein electronic transport experiments.

N-type organic thermoelectrics: demonstration of ZT > 0.3.

The 'phonon-glass electron-crystal' concept has triggered most of the progress that has been achieved in inorganic thermoelectrics in the past two decades. Organic thermoelectric materials, unlike their inorganic counterparts, exhibit molecular diversity, flexible mechanical properties and easy fabrication, and are mostly 'phonon glasses'. However, the thermoelectric performances of these organic materials are largely limited by low molecular order and they are therefore far from being 'electron crystals'. Here, we report a molecularly n-doped fullerene derivative with meticulous design of the side chain that approaches an organic 'PGEC' thermoelectric material. This thermoelectric material exhibits an excellent electrical conductivity of >10 S cm-1 and an ultralow thermal conductivity of <0.1 Wm-1K-1, leading to the best figure of merit ZT = 0.34 (at 120 °C) among all reported single-host n-type organic thermoelectric materials. The key factor to achieving the record performance is to use 'arm-shaped' double-triethylene-glycol-type side chains, which not only offer excellent doping efficiency (~60%) but also induce a disorder-to-order transition upon thermal annealing. This study illustrates the vast potential of organic semiconductors as thermoelectric materials.

Systematic experimental study of quantum interference effects in anthraquinoid molecular wires.

In order to translate molecular properties in molecular-electronic devices, it is necessary to create design principles that can be used to achieve better structure-function control oriented toward device fabrication. In molecular tunneling junctions, cross-conjugation tends to give rise to destructive quantum interference effects that can be tuned by changing the electronic properties of the molecules. We performed a systematic study of the tunneling charge-transport properties of a series of compounds characterized by an identical cross-conjugated anthraquinoid molecular skeleton but bearing different substituents at the 9 and 10 positions that affect the energies and localization of their frontier orbitals. We compared the experimental results across three different experimental platforms in both single-molecule and large-area junctions and found a general agreement. Combined with theoretical models, these results separate the intrinsic properties of the molecules from platform-specific effects. This work is a step towards explicit synthetic control over tunneling charge transport targeted at specific functionality in (proto-)devices.

Self-assembled monolayers of polyoxovanadates with phthalocyaninato lanthanide moieties on gold surfaces.

The two first representatives of phthalocyaninato (Pc) lanthanide-ligated polyoxovanadate cages {[V12O32(Cl)](LnPc)n}n-5 (n = 1 or 2, Ln = Yb3+) were synthesised and fully characterised. These magnetic complexes form two-dimensional self-assembled monolayers exhibiting electrical conductivity on gold substrate surfaces, as assessed by using an EGaIn tip.

Correction: Systematic experimental study of quantum interference effects in anthraquinoid molecular wires.

[This corrects the article DOI: 10.1039/C8NA00223A.].

1,8-diiodooctane acts as a photo-acid in organic solar cells.

The last decade saw myriad new donor polymers, among which benzodithiophene-co-thienothiophene polymers are attractive due to their relatively high power conversion efficiency in bulk heterojunction solar cells. We examine the effect of UV-light on the stability of these polymers. The relationship between the polymer chemical structure and the UV-stability of the cells is explored on the one hand, and on the other hand, the effect of additives on their UV-stability: 1,8-diiodooctane against 1-chloronaphthalene in the cells and 1,8-octanedithiol in solution. For example, PBDTTT-E with 18% efficiency loss is more stable than PBDTTT-ET with 36% loss throughout the exposure. While 1,8-diiodooctane acts as photo-acid and leads to accelerated degradation of the solar cells, 1-chloronaphthalene does not. Acidity is known to be detrimental to the efficiency and stability of organic solar cells. The degradation is initiated upon UV-irradiation by the cleavage of the side chains, resulting in more electron traps and by the formation of iodine, dissolved HI and carbon-centered radicals from 1,8-diiodooctane as revealed by 1H NMR spectrum. The 1,8-octanedithiol spectra do not show such species. Finally, the mechanisms behind the effect of 1,8-diiodooctane are explained, paving the way for the design of new, efficient as well as stable materials and additives.

Conductive Self-Assembled Monolayers of Paramagnetic {CoII Co 4 III } and { Co 4 II Co 2 III } Coordination Clusters on Gold Surfaces.

Two polynuclear cobalt(II,III) complexes, [Co5(N3)4(N-n-bda)4(bza·SMe)2] (1) and [Co6(N3)4(N-n-bda)2(bza·SMe)5(MeOH)4]Cl (2), where Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H2bda = N-n-butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound 1 exhibits an unusual, approximately C 2-symmetric {CoII Co 4 III } core of two isosceles Co3 triangles with perpendicularly oriented planes, sharing a central, high-spin CoII ion residing in a distorted tetrahedral coordination environment. This central CoII ion is connected to four outer, octahedrally coordinated low-spin CoIII ions via oxo bridges. Compound 2 comprises a semi-circular { Co 4 II Co 2 III } motif of four non-interacting high-spin CoII and two low-spin CoIII centers in octahedral coordination environments. Self-assembled monolayers (SAMs) of 1 and 2 were physisorbed on template-stripped gold surfaces contacted by an eutectic gallium-indium (EGaIn) tip. The acquired current density-voltage (I-V) data revealed that the cobalt-based SAMs are more electrically robust than those of the previously reported dinuclear {CuIILnIII} complexes with Ln = Gd, Tb, Dy, or Y (Schmitz et al., 2018a). In addition, between 170 and 220°C, the neutral, mixed-valence compound 1 undergoes a redox modification, yielding a {Co5}-based coordination cluster (1-A) with five non-interacting, high-spin octahedral CoII centers as indicated by SQUID magnetometry analysis in combination with X-ray photoelectron spectroscopy and infrared spectroscopy. Solvothermal treatment of 1 results in a high-nuclearity coordination cluster, [Co10(N3)2(N-n-bda)6(bza·SMe)6] (3), containing 10 virtually non-interacting high-spin CoII centers.