Strong Ligand Control for Noble Metal Nanostructures.

ConspectusNanosynthesis is the art of creating nanostructures, with on-demand synthesis as the ultimate goal. Noble metal nanoparticles have wide applications, but the available synthetic methods are still limited, often giving nanospheres and symmetrical nanocrystals. The fundamental reason is that the conventional weak ligands are too labile to influence the materials deposition, so the equivalent facets always grow equivalently. Considering that the ligands are the main synthetic handles in colloidal synthesis, our group has been exploring strong ligands for new growth modes, giving a variety of sophisticated nanostructures. The model studies often involve metal deposition on seeds functionalized with a certain strong ligand, so that the uneven distribution of the surface ligands could guide the subsequent deposition.In this Account, we focus on the design principles underlying the new growth modes, summarizing our efforts in this area along with relevant literature works. The basics of ligand control are first revisited. Then, the four major growth modes are summarized as follows: (1) The curvature effects would divert the materials deposition away from the high-curvature tips when the ligands are insufficient. With ligands fully covering the seeds, the sparser ligand packing at the tips would then promote the initial nucleation thereon. (2) The strong ligands may get trapped under the incoming metal layer, thus modulating the interfacial energy of the core-shell interface. The evidence for embedded ligands is discussed, along with examples of Janus nanostructures arising from the synthetic control, including metal-metal, metal-semiconductor, and metal-C60 systems using a variety of ligands. (3) Active surface growth is an unusual mode with divergent growth rates, so that part of the emerging surface is inhibited, and the growth is focused onto a few active sites. With seeds attached to oxide substrates, the selective deposition at the metal-substrate interface produces ultrathin nanowires. The synthesis can be generally applied to grow Au, Ag, Pd, Pt, and hybrid nanowires, with straight, spiral, or helical structures, and even rapid alteration of segments via electrochemical methods. In contrast, active surface growth for colloidal nanoparticles has to be more carefully controlled. The rich growth phenomena are discussed, highlighting the role of strong ligands, the control of deposition rates, the chiral induction, and the evidence for the active sites. (4) An active site with sparse ligands could also be exploited in etching, where the freshly exposed surface would promote further etching. The result is an unusual sharpening etching mode, in contrast to the conventional rounding mode for minimized surface energy.Colloidal nanosynthesis holds great promise for scalable on-demand synthesis, providing the crucial nanomaterials for future explorations. The strong ligands have delivered powerful synthetic controls, which could be further enhanced with in-depth studies on growth mechanisms and synthetic strategies, as well as functions and properties.

Liquid-on-solid heterogeneous nucleation for a general synthesis of yolk-shell nanostructures.

Liquid-on-solid heterogeneous nucleation on solid nanoparticle seeds was achieved. Syrup solutions from a solute-induced phase separation (SIPS) process were heterogeneously nucleated on nanoparticle seeds to form syrup domains, similar to the "seeded growth" method in classical nanosynthesis. The selective inhibition of homogeneous nucleation was also confirmed and exploited for a high-purity synthesis, showing similarity between nanoscale droplets and particles. The seeded-growth of syrup could serve as a general and robust method to one-step fabricate yolk-shell nanostructures, with efficient loading of the dissolved substances.

Inorganic-organic coprecipitation: spontaneous formation of enclosed and porous silica compartments with enriched biopolymers.

We show that it is possible to spontaneously form all-enclosed compartments with microporous shells and enriched biopolymers via simple coprecipitation of silica and biopolymers. The reaction involves mild conditions and tolerates the random mixing of multiple reagents. Such a synthetic advance points to a new direction for resolving the chicken-egg dilemma of how the early life forms were hosted: without a physical barrier it would be difficult to maintain organized reactions, but without organized reactions, it would be difficult to create a cell membrane. In our synthesis, the divalent cation Ca2+ plays a critical role in the co-precipitation and in creating hollow compartments after simple dilution with water. The precursor of silica, poly(silicic acid), is a negatively charged, cross-linked polymer. It could be co-precipitated with negatively charged biopolymers such as DNA and proteins, whereas the remaining silica precursor forms a conformal and microporous shell on the surface of the initial precipitate. After etching, the biopolymers are retained inside the hollow compartments. The fact that multiple favorable conditions are easily brought together in enclosed compartments opens new possibilities in theorizing the host of early life forms.

mRNA Translation Is Dynamically Regulated to Instruct Stem Cell Fate.

Stem cells preserve tissue homeostasis by replacing the cells lost through damage or natural turnover. Thus, stem cells and their daughters can adopt two identities, characterized by different programs of gene expression and metabolic activity. The composition and regulation of these programs have been extensively studied, particularly by identifying transcription factor networks that define cellular identity and the epigenetic changes that underlie the progressive restriction in gene expression potential. However, there is increasing evidence that post-transcriptional mechanisms influence gene expression in stem cells and their progeny, in particular through the control of mRNA translation. Here, we review the described roles of translational regulation in controlling all aspects of stem cell biology, from the decision to enter or exit quiescence to maintaining self-renewal and promoting differentiation. We focus on mechanisms controlling global translation rates in cells, mTOR signaling, eIF2ɑ phosphorylation, and ribosome biogenesis and how they allow stem cells to rapidly change their gene expression in response to tissue needs or environmental changes. These studies emphasize that translation acts as an additional layer of control in regulating gene expression in stem cells and that understanding this regulation is critical to gaining a full understanding of the mechanisms that underlie fate decisions in stem cells.

Germ cells commit somatic stem cells to differentiation following priming by PI3K/Tor activity in the Drosophila testis.

How and when potential becomes restricted in differentiating stem cell daughters is poorly understood. While it is thought that signals from the niche are actively required to prevent differentiation, another model proposes that stem cells can reversibly transit between multiple states, some of which are primed, but not committed, to differentiate. In the Drosophila testis, somatic cyst stem cells (CySCs) generate cyst cells, which encapsulate the germline to support its development. We find that CySCs are maintained independently of niche self-renewal signals if activity of the PI3K/Tor pathway is inhibited. Conversely, PI3K/Tor is not sufficient alone to drive differentiation, suggesting that it acts to license cells for differentiation. Indeed, we find that the germline is required for differentiation of CySCs in response to PI3K/Tor elevation, indicating that final commitment to differentiation involves several steps and intercellular communication. We propose that CySC daughter cells are plastic, that their fate depends on the availability of neighbouring germ cells, and that PI3K/Tor acts to induce a primed state for CySC daughters to enable coordinated differentiation with the germline.

Liquid Nanoparticles: Manipulating the Nucleation and Growth of Nanoscale Droplets.

By manipulating the nucleation and growth of solid materials, the synthesis of various sophisticated nanostructures has been achieved. Similar methodology, if applied to liquids, could enable the mass-production and control of ultra-small droplets at the scale of nanoparticles (10-18  L or below). It would be highly desirable since droplets play a fundamental role in numerous applications. Here we present a general strategy to synthesize and manipulate nanoscale droplets, similar to what has been done to solid nanoparticles in classic solution-synthesis. It was achieved by a solute-induced phase separation which initiates the nucleation of droplets from a homogeneous solution. These liquid nanoparticles have great potentials to be manipulated like their solid counterparts, borrowing from the vast methodologies of nanoparticle synthesis, such as burst nucleation, seeded growth, and co-precipitation. Liquid nanoparticles also serve as a general synthetic platform, to fabricate nanoreactors, drug-loaded carriers, and other hollow nanostructures with a variety of shell materials.

Mutation in ε-Sarcoglycan Induces a Myoclonus-Dystonia Syndrome-Like Movement Disorder in Mice.

Myoclonus dystonia syndrome (MDS) is an inherited movement disorder, and most MDS-related mutations have so far been found in the ε-sarcoglycan (SGCE) coding gene. By generating SGCE-knockout (KO) and human 237 C > T mutation knock-in (KI) mice, we showed here that both KO and KI mice exerted typical movement defects similar to those of MDS patients. SGCE promoted filopodia development in vitro and inhibited excitatory synapse formation both in vivo and in vitro. Loss of function of SGCE leading to excessive excitatory synapses that may ultimately contribute to MDS pathology. Indeed, using a zebrafish MDS model, we found that among 1700 screened chemical compounds, Vigabatrin was the most potent in readily reversing MDS symptoms of mouse disease models. Our study strengthens the notion that mutations of SGCE lead to MDS and most likely, SGCE functions to brake synaptogenesis in the CNS.

Precise Dimerization of Hollow Fullerene Compartments.

Controlled docking, merging, and welding of hollow structures at the nanoscale are essential in constructing sophisticated hollow systems in ways similar to plumbing and biosystems. To this end, regioselectivity is an important milestone demanding new tools. We bring the steric effect, a powerful regioselective method in organic reactions, to the nanoscale. By tuning the exposed liquid area of Janus nanobowls, the sterics of the merging m-xylene liquid template can be precisely modulated, giving high-purity dimers (93.6%) and tetramers (80.6%) in one step. The shape uniformity of the nanobowls, the precise percentage of the exposed liquid, and, most importantly, the error correction in merging liquid domains are the critical factors leading to the precise regioselectivity. We believe that the development of a new regioselective tool and the understanding in docking and welding hollow structures would expand the horizon of nanoscience, opening new possibilities for designing sophisticated nanosystems.

On demand synthesis of hollow fullerene nanostructures.

Hollow nanostructures are widely used in chemistry, materials, bioscience, and medicine, but their fabrication remains a great challenge. In particular, there is no effective strategy for their assembly and interconnection. We bring pottery, the oldest and simplest method of fabricating hollow containers, into the nanoscale. By exploiting the liquid nature of the xylene template, fullerene hollow nanostructures of tailored shapes, such as bowls, bottles, and cucurbits, are readily synthesized. The liquid templates permit stepwise and versatile manipulation and hence, modular assembly of nodes and junctions leads to interconnected hollow systems. As a proof-of-concept, we create multi-compartment nano-containers, with different nanoparticles isolated in the separate pockets. This methodology expands the synthetic freedom for hollow nanostructures, building a bridge from isolated hollow units to interconnected hollow systems.

Few-mode multicore fiber enabled integrated Mach-Zehnder interferometers for temperature and strain discrimination.

We proposed and experimentally demonstrated paralleled Mach-Zehnder interferometers (MZIs) in few-mode multicore fiber (FM-MCF) for temperature and strain discriminative sensing. A section of FM-MCF is sandwich-spliced between two single-mode multicore fiber (SM-MCF) with a rotational offset. The arbitrarily controlled angular misalignment generates intentional intermodal interferences in outer cores of the FM-MCF thus multiple MZI structures are implemented. Experimental results show that the temperature sensitivities are 105.8 pm/°C and 223.6 pm/°C for two outer cores, strain sensitivity is 13.96 pm/µÎµ for the outer core 1 and 11.7 pm/µÎµ for the outer core 2, respectively. Due to the low condition number of the cross coefficient matrix dependent on the temperature and strain response indexes, the temperature-strain cross sensitivity can be efficiently eliminated. In addition, the structure's fabrication process is simple, cost effective, and repeatable. The sensing structure can be applied to a wide range of measurements and is expected to develop potentials by building a higher dimensional matrix with more cores.

Directional torsion and temperature discrimination based on a multicore fiber with a helical structure.

We propose and experimentally demonstrate a directional torsion sensor based on a Mach-Zehnder interferometer formed in a multicore fiber (MCF) with a ~570-µm-long helical structure (HS). The HS was fabricated into the MCF by simply pre-twisting and then heating with a CO2 laser splicing system. This device shows the capability of directional torsion measurement from -17.094 rad/m to 15.669 rad/m with the sensitivity of ~0.118 nm/(rad/m). Moreover, since the multiple interferences respond differently to torsion and temperature simultaneously, the temperature cross-sensitivity of the proposed sensor can be eliminated effectively. Besides, the sensor owns other merits such as easy fabrication and good mechanical robustness.

Few-mode optical fiber based simultaneously distributed curvature and temperature sensing.

The few-mode fiber (FMF) based Brillouin sensing operated in quasi-single mode (QSM) has been reported to achieve the distributed curvature measurement by monitoring the bend-induced strain variation. However, its practicality is limited by the inherent temperature-strain cross-sensitivity of Brillouin sensors. Here we proposed and experimentally demonstrated an approach for simultaneously distributed curvature and temperature sensing, which exploits a hybrid QSM operated Raman-Brillouin system in FMFs. Thanks to the larger spot size of the fundamental mode in the FMF, the Brillouin frequency shift change of the FMF is used for curvature estimation while the temperature variation is alleviated through Raman signals with the enhanced signal-to-noise ratio (SNR). Within 2 minutes measuring time, a 1.5 m spatial resolution is achieved along a 2 km FMF. The worst resolution of the square of fiber curvature is 0.333 cm-2 while the temperature resolution is 1.301 °C at the end of fiber.

Highly sensitive strain sensor based on helical structure combined with Mach-Zehnder interferometer in multicore fiber.

Optical fiber sensors for strain measurement have been playing important roles in structural health monitoring for buildings, tunnels, pipelines, aircrafts, and so on. A highly sensitive strain sensor based on helical structures (HSs) assisted Mach-Zehnder interference in an all-solid heterogeneous multicore fiber (MCF) is proposed and experimentally demonstrated. Due to the HSs, a maximum strain sensitivity as high as -61.8 pm/µÎµ was experimentally achieved. This is the highest sensitivity among interferometer-based strain sensors reported so far, to the best of our knowledge. Moreover, the proposed sensor has the ability to discriminate axial strain and temperature, and offers several advantages such as repeatability of fabrication, robust structure and compact size, which further benefits its practical sensing applications.

Heterogeneous all-solid multicore fiber based multipath Michelson interferometer for high temperature sensing.

A compact high temperature sensor utilizing a multipath Michelson interferometer (MI) structure based on weak coupling multicore fiber (MCF) is proposed and experimentally demonstrated. The device is fabricated by program-controlled tapering the spliced region between single mode fiber (SMF) and a segment of MCF. After that, a spherical reflective structure is formed by arc-fusion splicing the end face of MCF. Theoretical analysis has been implemented for this specific multipath MI structure; beam propagation method based simulation and corresponding experiments were performed to investigate the effect of taper and spherical end face on system's performance. Benefiting from the multipath interferences and heterogeneous structure between the center core and surrounding cores of the all-solid MCF, an enhanced temperature sensitivity of 165 pm/°C up to 900°C and a high-quality interference spectrum with 25 dB fringe visibility were achieved.

Few-mode fiber based distributed curvature sensor through quasi-single-mode Brillouin frequency shift.

We proposed and demonstrated a few-mode fiber (FMF) based optical-fiber sensor for distributed curvature measurement through quasi-single-mode Brillouin frequency shift (BFS). By central-alignment splicing FMF and single-mode fiber (SMF) with a fusion taper, a SMF-components-compatible distributed curvature sensor based on FMF is realized using the conventional Brillouin optical time-domain analysis system. The distributed BFS change induced by bending in FMF has been theoretically and experimentally investigated. The precise BFS response to the curvature along the fiber link has been calibrated. A proof-of-concept experiment is implemented to validate its effectiveness in distributed curvature measurement.

3-{[Bis(pyridin-2-ylmeth-yl)amino]-meth-yl}-2-hy-droxy-5-methyl-benz-aldehyde.

In the title compound, C(21)H(21)N(3)O(2), the pyridine rings and the benzene ring lie in a propeller arrangement around the central tertiary amine N atom. The dihedral angles formed by the benzene ring with the pyridine rings are 61.0 (3) and 49.6 (3)°, while the dihedral angle between the pyridine rings is 69.7 (3)°. The mol-ecular conformation is stabilized by intramolecular bifurcated O-H⋯N hydrogen bonds. In the crystal, inversion dimers are formed via pairs of C-H⋯N hydrogen bonds.