Connecting Molecular and Supramolecular Shapeshifting by the Ostwald's Nucleation Stages of a Star Giant Molecule.

The shapeshifting behavior for synthetic matters was found at either the molecular or supramolecular level, but the connection between shapeshifting at the two hierarchical levels remains missing. In this study, an 8-arm star giant molecule, NPOSS, was synthesized to connect the molecular and supramolecular shapeshifting. Controlling the conditions of bulk self-assembly allowed us to bring NPOSS into three different Ostwald's stages of nucleation. The high conformational flexibility of NPOSS facilitates molecular shapeshifting and allows NPOSS to take the discotic, rod-like and star-like geometries in different Ostwald's stages. Simultaneous changes in the supramolecular scaffolds were observed as the discotic, rod-like and star-like NPOSS molecules self-assembled into the supramolecular scaffolds of 1D columns, 2D lamellae, and 3D networks, respectively. These changes in the hierarchical structures also affect the CO2 affinity of NPOSS. Therefore, the connection between the molecular/supramolecular shapeshifting and the structure-driven property changes of NPOSS were established by taking advantage of the high conformational freedom of the 8-arm star giant molecule and its diverse self-assembly pathways leading to the different Ostwald's stages.

Materials Engineering of Violin Soundboards by Stradivari and Guarneri.

We investigated the material properties of Cremonese soundboards using a wide range of spectroscopic, microscopic, and chemical techniques. We found similar types of spruce in Cremonese soundboards as in modern instruments, but Cremonese spruces exhibit unnatural elemental compositions and oxidation patterns that suggest artificial manipulation. Combining analytical data and historical information, we may deduce the minerals being added and their potential functions-borax and metal sulfates for fungal suppression, table salt for moisture control, alum for molecular crosslinking, and potash or quicklime for alkaline treatment. The overall purpose may have been wood preservation or acoustic tuning. Hemicellulose fragmentation and altered cellulose nanostructures are observed in heavily treated Stradivari specimens, which show diminished second-harmonic generation signals. Guarneri's practice of crosslinking wood fibers via aluminum coordination may also affect mechanical and acoustic properties. Our data suggest that old masters undertook materials engineering experiments to produce soundboards with unique properties.

Importance of Internal Porosity for Glucan Adsorption in Mesoporous Carbon Materials.

To better understand the adsorption of long-chain poly(1 → 4)-ß-D-glucans on carbon surfaces as well as interactions responsible for this adsorption, we use a comparative study involving mesoporous carbon-silica composite materials that have been etched to varying degrees and all-atom molecular dynamics simulations. The materials synthesized as part of this etching study consist of an as-synthesized composite material (MCN-MSN), MCN-MSN-0.5 (composite materials consisting of 50% carbon by mass), MCN-MSN-0.3 (composite materials consisting of 70% carbon by mass), and MCN, in which silica etching was conducted using an aqueous ethanolic solution of either NaOH or HF. Data for the adsorption of long-chain glucans to these materials from concentrated aqueous HCl (37 wt %) solution demonstrate a direct relationship between the amount of ß-glu adsorption and the magnitude of exposed carbon mesopore surface area, which systematically increases and is also accompanied by an increase in the mesopore size during silica etching. This demonstrates ß-glu adsorption as occurring on internal carbon mesopores rather than exclusively on the external carbon surface. These experimental data on adsorption were corroborated by molecular dynamics (MD) simulations of ß-glu adsorption to a graphene bilayer separated by a distance of 3.2 nm, chosen to correspond to the carbon mesopore diameter of the experimental system. Simulation results using a variety of ß-glu solvent systems demonstrate the rapid adsorption of a ß-glu strand on the graphitic carbon surface via axial coupling and are consistent with experimentally observed trends in fast adsorption kinetics. Solvent-mediated effects such as small-scale hydrophobicity and preferential interactions with ions are shown to play important roles in modulating glucan adsorption to carbon surfaces, whereas experimental data on hydrophobically modified silica demonstrate that hydrophobicity in and of itself is insufficient to cause ß-glu adsorption from concentrated aqueous HCl solution.

Weak-acid sites catalyze the hydrolysis of crystalline cellulose to glucose in water: importance of post-synthetic functionalization of the carbon surface.

The direct hydrolysis of crystalline cellulose to glucose in water without prior pretreatment enables the transformation of biomass into fuels and chemicals. To understand which features of a solid catalyst are most important for this transformation, the nanoporous carbon material MSC-30 was post-synthetically functionalized by oxidation. The most active catalyst depolymerized crystalline cellulose without prior pretreatment in water, providing glucose in an unprecedented 70 % yield. In comparison, virtually no reaction was observed with MSC-30, even when the reaction was conducted in aqueous solution at pH 2. As no direct correlations between the activity of this solid-solid reaction and internal-site characteristics, such as the ß-glu adsorption capacity and the rate of catalytic hydrolysis of adsorbed ß-glu strands, were observed, contacts of the external surface with the cellulose crystal are thought to be key for the overall efficiency.

Understanding the intermediates and carbon dioxide adsorption of potassium chloride-incorporated graphitic carbon nitride with tailoring melamine and urea as precursors.

In this study, we demonstrated the synthesis of potassium chloride (KCl)-incorporated graphitic carbon nitride, (g-C3N4, CN) with varying amounts of N-vacancies and pyridinic-N as well as enhanced Lewis basicity, via a single-step thermal polymerization by tailoring the precursors of melamine and urea for carbon oxide (CO2) capture. Melamine, as a precursor, undergoes a phase transformation into melam and triazine-rich g-C3N4, whereas the addition of urea polymerizes the mixture to form melem and heptazine-rich g-C3N4 (CN11). Owing to the abundance of pyridinic-N and the high surface area, CN11 adsorbed higher amounts of CO2 (44.52 µmol m-2 at 25 °C and 1 bar of CO2) than those reported for other template-free carbon materials. Spectroscopic analysis revealed that the enhanced CO2 adsorption is due to the presence of pyridinic-N and Lewis basic sites on the surface. The intermediates of CO2adsorption, including carbonate and bicarbonate species, attached to the CN samples were identified using in-situ Fourier-transform infrared spectroscopy (FTIR). This work provides insights into the mechanism of CO2 adsorption by comparing the structural features of the synthesized KCl-incorporated g-C3N4 samples. CN11, with an excellent CO2 uptake capacity, is viewed as a promising candidate for CO2 capture and storage.

Glucan adsorption on mesoporous carbon nanoparticles: effect of chain length and internal surface.

The adsorption of cellulose-derived long-chain (longer than ten glucose repeat units on size) glucans onto carbon-based acid catalysts for hydrolysis has long been hypothesized; however, to date, there is no information on whether such adsorption can occur and how glucan chain length influences adsorption. Herein, in this manuscript, we first describe how glucan chain length influences adsorption energetics, and use this to understand the adsorption of long-chain glucans onto mesoporous carbon nanoparticles (MCN) from a concentrated acid solution, and the effect of mesoporosity on this process. Our results conclusively demonstrate that mesoporous carbon nanoparticle (MCN) materials adsorb long-chain glucans from concentrated acid hydrolyzate in amounts of up to 30% by mass (303 mg/g of MCN), in a manner that causes preferential adsorption of longer-chain glucans of up to 40 glucose repeat units and, quite unexpectedly, fast adsorption equilibration times of less than 4 min. In contrast, graphite-type carbon nanopowders (CNP) that lack internal mesoporosity adsorb glucans in amounts less than 1% by mass (7.7 mg/g of CNP), under similar conditions. This inefficiency of glucan adsorption on CNP might be attributed to the lack of internal mesoporosity, since the CNP actually possesses greater external surface area relative to MCN. A systematic study of adsorption of glucans in the series glucose to cellotetraose on MCN shows a monotonically decreasing free energy of adsorption upon increasing the glucan chain length. The free energy of adsorption decreases by at least 0.4 kcal/mol with each additional glucose unit in this series, and these energetics are consistent with CH-π interactions providing a significant energetic contribution for adsorption, similar to previous observations in glycoproteins. HPLC of hydrolyzed fragments in solution, (13)C Bloch decay NMR spectroscopy, and GPC provide material balance closure of adsorbed glucan coverages on MCN materials. The latter and MALDI-TOF-MS provide direct evidence for adsorption of long-chain glucans on the MCN surface, which have a radius of gyration larger than the pore radius of the MCN material.

Chromatic Fulleropyrrolidine as Long-Lived Metal-Free Catalyst for CO2 Photoreduction Reaction.

Conversion of CO2 into carbonaceous fuels with the aid of solar energy has been an important research subject for decades. Owing to their excellent electron-accepting capacities, fullerene derivatives have been extensively used as n-type semiconductors. This work reports that the fulleropyrrolidine functionalized with 4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole, abbreviated as DTBT-C60 , could efficiently catalyze the photoreduction of CO2 to CO. The novel C60 -chromophore dyad structure facilitated better usage of solar light and effective dissociation of excitons. Consequently, the DTBT-C60 exhibited a promising CO yield of 144 µmol gcat -1 under AM1.5G solar illumination for 24 h. Moreover, the isotope experiments demonstrated that water molecules could function as an electron source to reactivate DTBT-C60 . Impressively, DTBT-C60 exhibited an extremely durable catalytic activity for more than one week, facilitating the practical application of photochemical CO2 reaction.

Naphthalene Diimide-Based Donor-Acceptor-Donor Small Molecules as Metal-Free Organocatalysts for Photocatalytic CO2 Reaction.

The application of organic small molecules as metal-free photocatalysts for light-driven photoreduction of carbon dioxide (CO2) has seldom been explored. This work developed four naphthalene diimide (NDI)-derived donor-acceptor-donor small molecules with different numbers of thiophene units, namely, NDI-2T, NDI-TT, NDI-4T, and NDI-6T, as metal-free photocatalysts to catalyze the reduction of CO2 under irradiation with an air mass 1.5G solar simulator at one-sun intensity. The structure-property relationship was investigated by exploring the effects of the electron-donating ability of the donor units on the optical properties, redox potential, electron-hole distribution, and exciton lifetime. NDI-6T exhibited the most red-shifted absorption, longest exciton lifetime, and strongest electron-hole separation. However, the large upshift in oxidation potential because of the elevated electron-donating ability of the hexathiophene unit significantly reduced the driving force for catalyst regeneration, leading to poor catalytic performance. Alternatively, NDI-4T possessed proper redox potentials, reduced charge-transfer resistance, and excellent photocurrent intensity; therefore, it effectively converted CO2 to a single product of CO in the presence of water as an electron donor without a sacrificial reagent or cocatalyst with a product yield of 168.6 µmol gcat-1 24 h-1, which was considerably higher than those of NDI-TT (111.9 µmol gcat-1 24 h-1), NDI-2T (88.4 µmol gcat-1 24 h-1), and NDI-6T (40.5 µmol gcat-1 24 h-1). This study provides a practical guideline for the molecular design of conjugated organic molecules as promising photocatalysts for CO2 photoreduction.

Hydrophobic Copper Catalysts Derived from Copper Phyllosilicates in the Hydrogenation of Levulinic Acid to γ-Valerolactone.

A reduction-silylation-reduction method was developed to synthesize hydrophobic Cu catalysts derived from Cu phyllosilicates (CuPS). Triethoxy(octyl)silane (OTS) was used as the coupling agent. The OTS-grafted, reduced CuPS catalysts were applied in the hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL). The most promising catalyst was synthesized by reducing CuPS at a high temperature (350 °C for 3 h), followed by OTS grafting, and then by repeating the previous reduction step. High LA conversion (95.7%), GVL yield (85.2%), and stability (3 cycles with a 7.5% loss of initial activity) were obtained at a mild reaction condition (130 °C with a H2 pressure of 12 bar). A high reduction temperature not only leads to a low oxidation state of Cu species but also suppresses the formation of silylation-induced acids. Moreover, the intrinsic activity of a reduced CuPS catalyst was nearly intact after subjecting to silylation and the second reduction treatment.

KSCN-induced Interfacial Dipole in Black TiO2 for Enhanced Photocatalytic CO2 Reduction.

Tuning the electronic band structure of black titania to improve photocatalytic performance through conventional band engineering methods has been challenging because of the defect-induced charge carrier and trapping sites. In this study, KSCN-modified hydrogenated nickel nanocluster-modified black TiO2 (SCN-H-Ni-TiO2) exhibits enhanced photocatalytic CO2 reduction due to the interfacial dipole effect. Upon combining the experimental and theoretical simulation approach, the presence of an electrostatic interfacial dipole associated with chemisorption of SCN has dramatic effects on the photocatalyst band structure in SCN-H-Ni-TiO2. An interfacial dipole possesses a more negative zeta potential shift of the isoelectric point from 5.20 to 3.20, which will accelerate the charge carrier separation and electron transfer process. Thiocyanate ion passivation on black TiO2 demonstrated an increased work function around 0.60 eV, which was induced by the interracial dipole effect. Overall, the SCN-H-Ni-TiO2 photocatalyst showed an enhanced CO2 reduction to solar fuel yield by 2.80 times higher than H-Ni-TiO2 and retained around 88% product formation yield after 40 h.

Carbon-doped SnS2 nanostructure as a high-efficiency solar fuel catalyst under visible light.

Photocatalytic formation of hydrocarbons using solar energy via artificial photosynthesis is a highly desirable renewable-energy source for replacing conventional fossil fuels. Using an L-cysteine-based hydrothermal process, here we synthesize a carbon-doped SnS2 (SnS2-C) metal dichalcogenide nanostructure, which exhibits a highly active and selective photocatalytic conversion of CO2 to hydrocarbons under visible-light. The interstitial carbon doping induced microstrain in the SnS2 lattice, resulting in different photophysical properties as compared with undoped SnS2. This SnS2-C photocatalyst significantly enhances the CO2 reduction activity under visible light, attaining a photochemical quantum efficiency of above 0.7%. The SnS2-C photocatalyst represents an important contribution towards high quantum efficiency artificial photosynthesis based on gas phase photocatalytic CO2 reduction under visible light, where the in situ carbon-doped SnS2 nanostructure improves the stability and the light harvesting and charge separation efficiency, and significantly enhances the photocatalytic activity.

Ordered mesoporous polymer-silica hybrid nanoparticles as vehicles for the intracellular controlled release of macromolecules.

A two-dimensional hexagonal ordered mesoporous polymer-silica hybrid nanoparticle (PSN) material was synthesized by polymerization of acrylate monomers on the surface of SBA-15 mesoporous silica nanoparticles. The structure of the PSN material was analyzed using a series of different techniques, including transmission electron microscopy, powder X-ray diffraction, and N(2) sorption analysis. These structurally ordered mesoporous polymer-silica hybrid nanoparticles were used for the controlled release of membrane-impermeable macromolecules inside eukaryotic cells. The cellular uptake efficiency and biocompatibility of PSN with human cervical cancer cells (HeLa) were investigated. Our results show that the inhibitory concentration (IC(50)) of PSN is very high (>100 µg/mL per million cells), while the median effective concentration for the uptake (EC(50)) of PSN is low (EC(50) = 4.4 µg/mL), indicating that PSNs are fairly biocompatible and easily up-taken in vitro. A membrane-impermeable macromolecule, 40 kDa FITC-Dextran, was loaded into the mesopores of PSNs at low pH. We demonstrated that the PSN material could indeed serve as a transmembrane carrier for the controlled release of FITC-Dextran at the pH level inside live HeLa cells. We believe that further developments of this PSN material will lead to a new generation of nanodevices for intracellular controlled delivery applications.

Structurally ordered mesoporous carbon nanoparticles as transmembrane delivery vehicle in human cancer cells.

A structurally ordered, CMK-1 type mesoporous carbon nanoparticle (MCN) material was successfully synthesized by using a MCM-48 type mesoporous silica nanoparticle as template. The structure of MCN was analyzed by a series of different techniques, including the scanning and transmission electron microscopy, powder X-ray diffraction, and N2 sorption analysis. To the best of our knowledge, no study has been reported prior to our investigation on the utilization of these structurally ordered mesoporous carbon nanoparticles for the delivery of membrane impermeable chemical agents inside of eukaryotic cells. The cellular uptake efficiency and biocompatibility of MCN with human cervical cancer cells (HeLa) were investigated. Our results show that the inhibitory concentration (IC50) value of MCN is very high (>50 microg/mL per million cells) indicating that MCN is fairly biocompatible in vitro. Also, a membrane impermeable fluorescence dye, Fura-2, was loaded to the mesoporous matrix of MCN. We demonstrated that the MCN material could indeed serve as a transmembrane carrier for delivering Fura-2 through the cell membrane to release these molecules inside of live HeLa cells. We envision that further developments of this MCN material will lead to a new generation of nanodevices for transmembrane delivery and intracellular release applications.