Remembering the Work of Phillip L. Geissler: A Coda to His Scientific Trajectory.

Phillip L. Geissler made important contributions to the statistical mechanics of biological polymers, heterogeneous materials, and chemical dynamics in aqueous environments. He devised analytical and computational methods that revealed the underlying organization of complex systems at the frontiers of biology, chemistry, and materials science. In this retrospective we celebrate his work at these frontiers.

Porous PVDF as effective sonic wave driven nanogenerators.

Piezomaterials are known to display enhanced energy conversion efficiency at nanoscale due to geometrical effect and improved mechanical properties. Although piezoelectric nanowires have been the most widely and dominantly researched structure for this application, there only exist a limited number of piezomaterials that can be easily manufactured into nanowires, thus, developing effective and reliable means of preparing nanostructures from a wide variety of piezomaterials is essential for the advancement of self-powered nanotechnology. In this study, we present nanoporous arrays of polyvinylidene fluoride (PVDF), fabricated by a lithography-free, template-assisted preparation method, as an effective alternative to nanowires for robust piezoelectric nanogenerators. We further demonstrate that our porous PVDF nanogenerators produce the rectified power density of 0.17 mW/cm3 with the piezoelectric potential and the piezoelectric current enhanced to be 5.2 times and 6 times those from bulk PVDF film nanogenerators under the same sonic-input.

Self-assembly of magnetic nanoparticles in evaporating solution.

When deposited from an evaporating solution onto a substrate, even nondescript nanoparticles can organize into intricate spatial patterns. Here we show that a simple but long-ranged anisotropy in nanoparticles' interactions can greatly enrich this scenario. In experiments with colloidal Co nanocrystals, which bear a substantial magnetic dipole, we observe assemblies quite distinct from those formed by nonmagnetic particles. Reflecting the strongly nonequilibrium nature of this process, nanocrystal aggregates also differ substantially from expected low-energy arrangements. Using coarse-grained computer simulations of dipolar nanoparticles, we have identified several dynamical mechanisms from which such unusual morphologies can arise. For particles with modest dipole moments, transient connections between growing domains frustrate phase separation into sparse and dense regions on the substrate. Characteristic length scales of the resulting cellular networks depend non-monotonically on the depth of quenches we use to mimic the effects of solvent evaporation. For particles with strong dipole moments, chain-like aggregates formed at early times serve as the agents of assembly at larger scales. Their effective interactions drive the formation of layered loop structures similar to those observed in experiments.

Breakdown of chiral recognition of amino acids in reduced dimensions.

The homochirality of amino acids in living organisms is one of the great mysteries in the phenomena of life. To understand the chiral recognition of amino acids, we have used scanning tunnelling microscopy to investigate the self-assembly of molecules of the amino acid tryptophan (Trp) on Au(111). Earlier experiments showed only homochiral configurations in the self-assembly of amino acids, despite using a mixture of the two opposite enantiomers. In our study, we demonstrate that heterochiral configurations can be favored energetically when L- and D-Trp molecules are mixed to form self-assembly on the Au surface. Using density functional theory calculations, we show that the indole side chain strongly interacts with the Au surface, which reduces the system effectively to two-dimension, with chiral recognition disabled. Our study provides important insight into the recognition of the chirality of amino acid molecules in life.

4-O-Carboxymethylascochlorin Inhibits Expression Levels of on Inflammation-Related Cytokines and Matrix Metalloproteinase-9 Through NF-κB/MAPK/TLR4 Signaling Pathway in LPS-Activated RAW264.7 Cells.

Toll-like receptor 4 (TLR4) and matrix metalloproteinase-9 (MMP-9) are known to play important roles in inflammatory diseases such as arteriosclerosis and plaque instability. The purpose of this study was to perform the effect of 4-O-carboxymethylascochlorin (AS-6) on MMP-9 expression in lipopolysaccharide (LPS)-induced murine macrophages and signaling pathway involved in its anti-inflammatory effect. Effect of AS-6 on MAPK/NF-κB/TLR4 signaling pathway in LPS-activated murine macrophages was examined using ELISA, Western blotting, reverse transcription polymerase chain reaction (RT-PCR) and fluorescence immunoassay. MMP-9 enzyme activity was examined by gelatin zymography. AS-6 significantly suppressed MMP-9 and MAPK/NF-κB expression levels in LPS-stimulated murine macrophages. Expression levels of inducible nitric oxide synthase (iNOS), COX2, MMP-9, JNK, ERK, p38 phosphorylation, and NF-κB stimulated by LPS were also decreased by AS-6. Moreover, AS-6 suppressed TLR4 expression and dysregulated LPS-induced activators of transcription signaling pathway. The results of this study showed that AS-6 can inhibit LPS-stimulated inflammatory response by suppressing TLR4/MAPK/NF-κB signals, suggesting that AS-6 can be used to induce the stability of atherosclerotic plaque and prevent inflammatory diseases in an in vitro model.

Exposure to Hyperchloremia Is Associated with Poor Early Recovery of Kidney Graft Function after Living-Donor Kidney Transplantation: A Propensity Score-Matching Analysis.

The effects of hyperchloremia on kidney grafts have not been investigated in patients undergoing living-donor kidney transplantation (LDKT). In this study, data from 200 adult patients undergoing elective LDKT between January 2016 and December 2017 were analyzed after propensity score (PS) matching. The patients were allocated to hyperchloremia and non-hyperchloremia groups according to the occurrence of hyperchloremia (i.e., ≥110 mEq/L) immediately after surgery. Poor early graft recovery was defined as estimated glomerular filtration rate (eGFR) < 60 mL/min/1.73 m2 during the first 48 hours after surgery. After PS matching, no significant differences in perioperative recipient or donor graft parameters were observed between groups. Although the total amount of crystalloid fluid infused during surgery did not differ between groups, the proportions of main crystalloid fluid type used (i.e., 0.9% normal saline vs. Plasma Solution-A) did. The eGFR increased gradually during postoperative day (POD) 2 in both groups. However, the proportion of patients with eGFR > 60 mL/min/1.73 m2 on POD 2 was higher in the non-hyperchloremia group than in the hyperchloremia group. In this PS-adjusted analysis, hyperchloremia was significantly associated with poor graft recovery on POD 2. In conclusion, exposure to hyperchloremia may have a negative impact on early graft recovery in LDKT.

Unraveling the Structural and Electronic Properties of Graphene/Ge(110).

The direct growth of graphene on a semiconducting substrate opens a new avenue for future graphene-based applications. Understanding the structural and electronic properties of the graphene on a semiconducting surface is key for realizing such structures; however, these properties are poorly understood thus far. Here, we provide insight into the structural and electronic properties of graphene grown directly on a Ge(110) substrate. Our scanning tunneling microscopy (STM) study reveals that overlaying graphene on Ge(110) promotes the formation of a new Ge surface reconstruction, i.e., a (6 × 2) superstructure, which has been never observed for a bare Ge(110) surface. The electronic properties of the system exhibit the characteristics of both graphene and Ge. The differential conductance (d I/d V) spectrum from a scanning tunneling spectroscopy (STS) study bears a parabolic structure, corresponding to a reduction in the graphene Fermi velocity, exhibiting additional peaks stemming from the p-orbitals of Ge. The density functional theory (DFT) calculations confirm the existence of surface states due to the p-orbitals of Ge.

Nanoscale control of phonon excitations in graphene.

Phonons, which are collective excitations in a lattice of atoms or molecules, play a major role in determining various physical properties of condensed matter, such as thermal and electrical conductivities. In particular, phonons in graphene interact strongly with electrons; however, unlike in usual metals, these interactions between phonons and massless Dirac fermions appear to mirror the rather complicated physics of those between light and relativistic electrons. Therefore, a fundamental understanding of the underlying physics through systematic studies of phonon interactions and excitations in graphene is crucial for realising graphene-based devices. In this study, we demonstrate that the local phonon properties of graphene can be controlled at the nanoscale by tuning the interaction strength between graphene and an underlying Pt substrate. Using scanning probe methods, we determine that the reduced interaction due to embedded Ar atoms facilitates electron-phonon excitations, further influencing phonon-assisted inelastic electron tunnelling.

Surface energy-mediated construction of anisotropic semiconductor wires with selective crystallographic polarity.

ZnO is a wide band-gap semiconductor with piezoelectric properties suitable for opto-electronics, sensors, and as an electrode material. Controlling the shape and crystallography of any semiconducting nanomaterial is a key step towards extending their use in applications. Whilst anisotropic ZnO wires have been routinely fabricated, precise control over the specific surface facets and tailoring of polar and non-polar growth directions still requires significant refinement. Manipulating the surface energy of crystal facets is a generic approach for the rational design and growth of one-dimensional (1D) building blocks. Although the surface energy is one basic factor for governing crystal nucleation and growth of anisotropic 1D structures, structural control based on surface energy minimization has not been yet demonstrated. Here, we report an electronic configuration scheme to rationally modulate surface electrostatic energies for crystallographic-selective growth of ZnO wires. The facets and orientations of ZnO wires are transformed between hexagonal and rectangular/diamond cross-sections with polar and non-polar growth directions, exhibiting different optical and piezoelectrical properties. Our novel synthetic route for ZnO wire fabrication provides new opportunities for future opto-electronics, piezoelectronics, and electronics, with new topological properties.

Heterogeneous stacking of nanodot monolayers by dry pick-and-place transfer and its applications in quantum dot light-emitting diodes.

Layered assembly structures composed of nanomaterials, such as nanocrystals, have attracted considerable attention as promising candidates for new functional devices whose optical, electromagnetic and electronic behaviours are determined by the spatial arrangement of component elements. However, difficulties in handling each constituent layer in a material-specific manner limit the 3D integration of disparate nanomaterials into the appropriate heterogeneous electronics. Here we report a pick-and-place transfer method that enables the transfer of large-area nanodot assemblies. This solvent-free transfer utilizes a lifting layer and allows for the reliable transfer of a quantum dot (QD) monolayer, enabling layer-by-layer design. With the controlled multistacking of different bandgap QD layers, we are able to probe the interlayer energy transfer among different QD monolayers. By controlling the emission spectrum through such designed monolayer stacking, we have achieved white emission with stable optoelectronic properties, the closest to pure white among the QD light-emitting diodes reported so far.