Non-Aqueous Poly(dimethylsiloxane) Organogel Sponges for Controlled Solvent Release: Synthesis, Characterization, and Application in the Cleaning of Artworks.

Polydimethylsiloxane (PDMS) organogel sponges were prepared and studied in order to understand the role of pore size in an elastomeric network on the ability to uptake and release organic solvents. PDMS organogel sponges have been produced according to sugar leaching techniques by adding two sugar templates of different forms and grain sizes (a sugar cube template and a powdered sugar template), in order to obtain materials differing in porosity, pore size distribution, and solvent absorption and liquid retention capability. These materials were compared to PDMS organogel slabs that do not contain pores. The sponges were characterized by Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and compared with PDMS slabs that do not contain pores. Scanning electron microscopy (SEM) provided information about their morphology. X-ray micro-tomography (XMT) allowed us to ascertain how the form of the sugar templating agent influences the porosity of the systems: when templated with sugar cubes, the porosity was 77% and the mean size of the pores was ca. 300 µm; when templated with powdered sugar, the porosity decreased to ca. 10% and the mean pore size was reduced to ca. 75 µm. These materials, porous organic polymers (POPs), can absorb many solvents in different proportions as a function of their polarity. Absorption capacity, as measured by swelling with eight solvents covering a wide range of polarities, was investigated. Rheology data established that solvent absorption did not have an appreciable impact on the gel-like properties of the sponges, suggesting their potential for applications in cultural heritage conservation. Application tests were conducted on the surfaces of two different lab mock-ups that simulate real painted works of art. They demonstrated further that PDMS sponges are a potential innovative support for controlled and selective cleaning of works of art surfaces.

1D Supramolecular Assemblies That Crystallize and Form Gels in Response to the Shape-Complementarity of Alcohols.

N-9-Fluorenylmethyloxycarbonyl (Fmoc)- and C-tertiary butyl (t-Bu)-protected glutamate (L-2), bearing a phenanthroline moiety at the side residue, forms 1D supramolecular assemblies via H-bonding as well as undergoing π-stacking interactions to afford crystals or gels that depend on the shape-complementarity of coexisting alcohols, as demonstrated by structural analyses on these assemblies by means of single-crystal X-ray diffractometry and supplemented with small- and wide-angle X-ray scattering data. Moreover, the rheological measurements on the gels help to define a model for when gels and crystals are expected and found. These observations and conclusions highlight an important, but not very appreciated, aspect of solute-solvent interactions within supramolecular assemblies that can allow the constituent-aggregating molecules in some systems to exhibit high selectivity toward the structures of their solvents. The consequences of this selectivity, as demonstrated here by single-crystal and powder X-ray diffraction data, can lead to self-assembled structures which alter completely the bulk phase properties and morphology of the materials. In that regard, rheological measurements have helped to develop a model to explain when gels and phase-separated mixtures of crystals and solvents are expected.

Dollars and Sense: The Business of Pediatric Surgery.

INTRODUCTION: This study evaluated North American pediatric surgeons' opinions and knowledge of business and economics in medicine and their perceptions of trends in their healthcare delivery environment. METHODS: We conducted an elective online survey of 1119 American Pediatric Surgical Association members. Over 8 mo, we iteratively developed the survey focused on four areas: opinion, knowledge, current practice environment, and trends in practice environment over the past 5 y. RESULTS: We received 227 (20.3%) complete surveys from pediatric surgeons. One hundred ninety four (85.5%) perceive healthcare as a business and most (85.9%) believe healthcare decisions may affect patients' out-of-pocket expenses. More than half (51.1%) of surgeons believe it has become more challenging to perform emergent cases and most believe staff quality has decreased for elective (56.4%) and emergent (63.0%) cases over the past 5 y. CONCLUSIONS: Pediatric surgeons recognize that medicine is a business and have concerns regarding the decreasing quality of operating room staff and the increasing difficulty providing surgical care over the last 5 y.

Ion-Transport Properties of Polydimethylsiloxane-Based Ionomers with Amidinium or Imidazolinium Alkyldithiocarbamate Pendant Groups in Low Dielectric Solvents or as Neat Liquids.

The ion transport properties of ionomers comprised of polydimethylsiloxanes with amidinium or imidazolinium attached side chains and alkyldithiocarbamate anions (where alkyl is hexyl or octadecyl) have been investigated in chloroform solutions principally and as neat liquids. The influence of modifying the molecular weights of the polydimethylsiloxanes, the frequency of their amidininium or imidazolinium side groups, and temperature on the conductivity have been explored. When a solvent more polar than chloroform, syn-tetrachloroethane, was employed, a large increase in the ionic conductivity was found despite there being an increase in the viscosity of the solution. At least in these two solvents, polarity is more important in determining the conductivity than the viscosity. When normalized for ion content, Walden plots of the ionomer solutions at different ionomer concentrations approached values found for 1 M aqueous KCl. As neat liquids, the amidinium and imidazolinium hexyldithiocarbamate ionomers exceeded the values associated with the "superionic" region of the Walden plot (i.e., above the conductivity values for 1 M aqueous KCl). As ion content and polymer molecular weight increased, larger decoupling between bulk viscosity and ionic conductivity was noted, probably as a result of changes in the dynamic fragility of the ionomers.

Effects of cyclic and acyclic amidine side-chains on the properties of polysiloxane ionomers constructed in situ from three uncharged components.

Ionomers, polysiloxanes with imidazolinium dithiocarbamate side chains, have been synthesized in situ from three uncharged components-a polysiloxane with imidazole side chains, CS2, and hexylamine or octadecylamine. Their structural and dynamic properties are compared over a temperature range of 0-50 °C with those of the analogous ionomers in which the polysiloxanes have amidinium side chains. The results, primarily from differential scanning calorimetry, powder X-ray diffraction measurements, and rheology show that the small structural (and smaller electronic) differences between the cyclic 5-membered ring imidazolinium and acyclic amidinium groups have marked effects on the bulk properties of the ionomers. These include their shear strengths and the manner in which the microcrystalline portions of the ionomers with dithiooctadecylcarbamate anions are packed. Thus, it is possible to finely tune the natures of the ionomers from one polysiloxane by changing temperature, the chain length of the alkylamine, and the nature of the base attached to the polysiloxane chain. Why these changes occur to the various properties is discussed.

Molecular and Aggregate Structural, Thermal, Mechanical and Photophysical Properties of Long-Chain Amide Gelators Containing an α-Diketo Group in the Presence or Absence of a Tertiary Amine Group.

Three structurally related gelators, each containing octadecyl chains, an α-diketo group at the 9,10 positions, and each with a different N-amide group-isobutyl (DIBA), isopentyl (DIPA) or N-(2-(dimethylamino)ethyl) (DMEA)-have been synthesized. Their neat structures as well as the thermal mechanical, and photophysical properties in their gel states with various liquids have been investigated. The gelator networks of DIBA and DIPA in octane, hexylbenzene and silicone oil consist of bundles of fibers. These gels are partially thixotropic and mechanically, thermally (to above their melting or silicone oil gelation temperatures), and photophysically stable. They are mechanically and thermally stronger than the gels formed with DMEA, the gelator with a tertiary amine group. The lone pair of electrons of the tertiary amine group leads to an intra-molecular or inter-molecular charge-transfer interaction, depending on whether the sample is a solution, sol, or gel. Neat, solid DMEA does not undergo the charge-transfer process because its amino and diketo groups are separated spatially by a large distance in the crystalline state and cannot diffuse into proximity. However, the solution of DIPA upon the addition of triethylamine becomes unstable over time at room temperature in the dark or (more rapidly) when irradiated, which initiates the aforementioned charge-transfer processes. The eventual reaction of the gelators in the presence of a tertiary amine group is ascribed to electron transfer from the lone-pair on nitrogen to an α-diketo group, followed by proton transfer to an oxygen atom on the anion radical of the α-diketo group from a methyl or methylene group attached to the nitrogen atom of the cation radical. Finally, the formation of an α-diketyl radical leads to irreversible electronic and structural changes that are observed over time.

Benzil Photoperoxidations in Polymer Films and Crosslinking by the Resultant Benzoyl Peroxides in Polystyrene and Other Polymers.

Benzil (BZ) can be converted almost quantitatively to benzoyl peroxide (BP) in aerated polymer films upon irradiation at >400 nm (i.e., the long-wavelength edge of the n→π* absorption band of BZ, where BP does not absorb). Here, we summarize results for the photoperoxidation of BZ structures with molecular oxygen, principally in glassy polymer matrices. Some of the polymers are doped directly with BZ or its derivatives, and others, contain covalently attached BZ pendant groups from which BP groups are derived. While the decomposition of low-molecular-weight BP doped into polymer films (such as those of polystyrene (PS)) results in a net decrease in polymer molecular weight, thermal decomposition of pendant BP groups is an efficient method for chain crosslinking. Crosslinking of PS films doped with a molecule containing two covalently linked BZ or BP groups proceeds in a similar fashion. Free radicals from the covalently attached BP allow grafting of new monomers, as well. Additionally, the use of radiation filtered through masks has been used to create patterns of polymers on solid surfaces. Crosslinking of photodegradable poly(phenyl vinyl ketone) with BP structures obtained by photoperoxidation of BZ structures for the preparation of photodegradable polymer networks is described as well. In sum, the use of BZ and BP and their derivatives offers simple and convenient routes for modifying polymer chains and, especially, for crosslinking them. Specific applications of each use and process are provided. Although applications with PS are featured here, the methodologies described are amenable to a wide variety of other polymers.

Thiol- and Disulfide-Based Stimulus-Responsive Soft Materials and Self-Assembling Systems.

Properties and applications of synthetic thiol- and disulfide-based materials, principally polymers, are reviewed. Emphasis is placed on soft and self-assembling materials in which interconversion of the thiol and disulfide groups initiates stimulus-responses and/or self-healing for biomedical and non-biomedical applications.

Luminescent Behavior of Gels and Sols Comprised of Molecular Gelators.

We present a brief review of some important conceptual and practical aspects for the design and properties of molecular luminescent gelators and their gels. Topics considered include structural and dynamic aspects of the gels, including factors important to their ability to emit radiation from electronically excited states.

NMR spectral fingerprint patterns as diagnostics for the unambiguous configurational analysis of the classic organo-gelator 1,3:2,4-dibenzylidene-d-sorbitol (DBS) and its derivatives.

On the basis of experimental data and density functional theory (DFT) chemical shift and scalar coupling predictions, simple spectral nuclear magnetic resonance (NMR) fingerprint patterns have been established for the determination of the configuration in 1,3:2,4-dibenzylidene-d-sorbitol (DBS), a classic low molecular weight gelator, and its derivatives. The results rigorously prove the orientation of the phenyl rings in DBS that had been previously assumed in the literature on the basis of thermodynamic arguments.

Multiple-State Emissions from Neat, Single-Component Molecular Solids: Suppression of Kasha's Rule.

Three rigid and structurally simple heterocyclic stilbene derivatives, (E)-3H,3'H-[1,1'-biisobenzofuranylidene]-3,3'-dione, (E)-3-(3-oxobenzo[c] thiophen-1(3H)-ylidene)isobenzofuran-1(3H)-one, and (E)-3H,3'H-[1,1'-bibenzo[c] thiophenylidene]-3,3'-dione, are found to fluoresce in their neat solid phases, from upper (S2 ) and lowest (S1 ) singlet excited states, even at room temperature in air. Photophysical studies, single-crystal structures, and theoretical calculations indicate that large energy gaps between S2 and S1 states (T2 and T1 states) as well as an abundance of intra and intermolecular hydrogen bonds suppress internal conversions of the upper excited states in the solids and make possible the fluorescence from S2 excited states (phosphorescence from T2 excited states). These results, including unprecedented fluorescence quantum yields (2.3-9.6 %) from the S2 states in the neat solids, establish a unique molecular skeleton for achieving multi-colored emissions from upper excited states by "suppressing" Kasha's rule.

Experimental and Theoretical Investigation of Excited-State Intramolecular Proton Transfer Processes of Benzothiazole Derivatives in Amino-polydimethylsiloxanes before and after Cross-Linking by CO2.

The changes in the ability of three fluorescent derivatives of 2-(2'-hydroxyphenyl)benzothiazole to undergo excited-state intramolecular proton transfer (ESIPT) processes have been correlated with the rheological properties of four amino-polydimethylsiloxanes with different molar masses and containing different amounts of monomer units with amino pendant groups, in the presence and absence of a cross-linking molecule, CO2. The changes lead to a variety of species (keto, enol, and enolate forms) in both the ground and excited states. Calculations using the density-functional theory/time-dependent density-functional theory method at the CAM-B3LYP/6-311++G(d,p) level helped to identify how ESIPT is involved in the formation of the intermediates. The results demonstrate that proton transfer in 2-(2'-hydroxyphenyl)benzothiazoles is a powerful tool to identify local changes in the viscosity and micropolarity of the environment that are attributed to the structural differences of the amino-polydimethylsiloxanes and their cross-linking.

Poly(vinyl alcohol)-induced thixotropy of an l-carnosine-based cytocompatible, tripeptidic hydrogel.

The generally poor mechanical stability of hydrogels limits their use as functional materials for many biomedical applications. In this work, a poly(vinyl alcohol) (PVA) embedded hybrid hydrogel of a ß-amino acid-containing Fmoc-protected tripeptide was produced at physiological pH (7.4) and room temperature. The hydrogel system was characterized by a number of techniques, including UV-vis, fluorescence, circular dichroism, FT-IR spectroscopy, electron microscopy, and rheology. While the tripeptide-based pure hydrogel was found to be unstable after ca. half an hour, addition of PVA, a water soluble polymer, increased the temporal and mechanical stability of the hydrogel. A rheological step-strain experiment demonstrates that the peptide-polymer hydrogel is thixotropic. Results from a fluorescence probe study and transmission electron microscopy reveal that addition of PVA increases both the fibre diameter and entanglement. Circular dichroism spectra of the hydrogels confirm the formation of aggregates with supramolecular chirality. The thixotropic nature of the hydrogel has been exploited to entrap and release doxorubicin, an anticancer drug, under physiological conditions. Furthermore, an MTT assay of the Fmoc-tripeptide using AH927 cells confirmed its cytocompatibility, which broadens the utility of the hybrid gel for biomedical applications.

Long Range Polymer Chain Dynamics of Highly Flexible Polysiloxane in Solution Probed by Pyrene Excimer Fluorescence.

A poly(dimethylsiloxane-co-(3-aminopropyl)methylsiloxane) polymer (PDMS with 20.3 mol % of (3-aminopropyl)methyl siloxane monomer) has been labeled randomly with 1-pyreneacetyl groups to generate a series of polysiloxanes (Py-PDMS) with pyrenyl contents ranging from 0.7 mol % to 5.2 mol % of the total number of structural units. The remainder of the amino groups were acetylated to avoid intra-chain quenching of the excited singlet states of pyrene via exciplex formation with free amino groups while allowing the formation of excimers to proceed. The fluorescence spectra and temporal decays of the Py-PDMS samples were acquired in tetrahydrofuran (THF), N,N-dimethylformamide (DMF), and dioxane. blob, the average rate constant for intra-chain pyrene excimer formation, was determined from the analysis of the fluorescence decays. blob was found to equal 1.16 (±0.13) × 108, 1.14 (±0.12) × 108, and 0.99 (±0.10) × 108 s-1 in THF, DMF, and dioxane, respectively, at room temperature. They are the largest values found to date for any polymeric backbone in these solvents. The qualitative relationship found here between blob and the chemical structures of the polymers indicates that the luminescence characteristics of randomly labeled polymers is a very useful method to probe the long range dynamics of chains of almost any polymer that is amenable to substitution by a lumophore.

Controlling Variables in Molecular Gel Science: How Can We Improve the State of the Art?

By design, no references are included in this article. It is intended to be a series of recommendations in which the focus is on lab practices for investigating substances rather than on the substances being investigated. Thus, it discusses some specific areas of concern identified by the author. Other scientists are encouraged to add to or amend the contents. This article should be read as a "living" document, like a blog in which many gel scientists work, over time, to achieve a consensus about reporting everything from acronyms and definitions to procedures and methods. For those entering the field and seeking compendia on the subject, the author suggests "Googling" the words "molecular gels" or "molecular gels books".

l-Carnosine-Derived Fmoc-Tripeptides Forming pH-Sensitive and Proteolytically Stable Supramolecular Hydrogels.

A series of ß-amino acid containing tripeptides has been designed and synthesized in order to develop oligopeptide-based, thermoreversible, pH-sensitive, and proteolytically stable hydrogels. The Fmoc [N-(fluorenyl-9-methoxycarbonyl)]-protected tripeptides were found to produce hydrogels in both pH 7 and 2 buffers at a very low concentration (<0.2% w/v). It has been shown that the Fmoc group plays an important role in the gelation process. Also a dependence of gelation ability on hydrophobicity of the side chain of the Fmoc-protected α-amino acid was observed. The effect of the addition of inorganic salts on the gelation process was investigated as well. Spectroscopic studies indicated formation of J-aggregates through π-π stacking interactions between Fmoc groups in solution as well as in the gel state. In the gel phase, these self-assembling tripeptides form long interconnected nanofibrils leading to the formation of 3-dimensional network structure. The hydrogels were characterized by various techniques, including field emission electron microscopy, transmission electron microscopy, atomic force microscopy, rheology, Fourier transform IR, circular dichroism (CD), and wide-angle X-ray diffraction (WAXD) spectroscopy. The CD studies and WAXD analyses show an antiparallel ß-sheet structure in the gel state. l-Phenylalanine and l-tyrosine containing tripeptides formed helical aggregates with handedness opposite to those containing l-valine and l-leucine residues. The mechanical stability of the hydrogels was found to depend on the hydrophobicity of the side chain of the tripeptide as well as on the pH of the solution. Also, the tripeptides exhibit in vitro proteolytic stability against proteinase K enzyme.

Molecular Nuances Governing the Self-Assembly of 1,3:2,4-Dibenzylidene-d-sorbitol.

1,3:2,4-Dibenzylidene-d-sorbitol (DBS) is the gold-standard for low-molecular-weight organogelators (LMOGs). DBS gels a wide array of solvents, as illustrated by the large Hansen sphere representing gels (2δd = 33.5 MPa1/2, δp = 7.5 MPa1/2, and δh = 8.7 MPa1/2; radius = 11.2 MPa1/2). Derivatives of DBS have been synthesized to isolate and determine molecular features essential for organogelation. In this work, π-π stacking and hydrogen bonding are the major noncovalent interactions examined. The importance of π-π stacking was studied using 1,3:2,4 dicyclohexanecarboxylidene-d-sorbitol (DCHS), which eliminates possible π-π stacking while still conserving the other structural aspects of DBS. The replacement of the benzyl groups with cyclohexyl groups led to a very a poor gelator; only one of the several solvents examined, carbon tetrachloride, formed a gel. 1,3:2,4-Diethylidene-d-sorbitol (DES), another DBS analogue incapable of π-π stacking but with very different polarity, gelated a large Hansen space (2δd = 34.0 MPa1/2, δp = 10.9 MPa1/2, and δh = 10.8 MPa1/2; radius = 9.2 MPa1/2). DES gels solvents with higher δp and δh values than DBS. To assess the role of hydrogen bonding, DBS was acetalated (A-DBS), and it was found that the Hansen space gelated by A-DBS shifted to less polar solvents with higher hydrogen-bonding Hansen solubility parameters (HSPs) (2δd = 33.8 MPa1/2, δp = 6.3 MPa1/2, and δh = 9.6 MPa1/2; radius = 11.1 MPa1/2) than for DBS. These systematic structural modifications are the first step in exploring how specific intermolecular features alter aspects of Hansen space corresponding to positive gelation outcomes.

Influence of Cations on the Fluorescence Quenching of an Ionic, Sterically Congested Pyrenyl Moiety by Iodide in Water.

Quenching of the excited singlet states of a water-soluble, sterically congested tetraarylpyrene, 1,3,6,8-tetrakis(2,6-dimethyl-4-(α-carboxy)methoxyphenyl)pyrene (Py4C), by a series of iodide salts has been investigated by steady-state and time-resolved fluorescence measurements. Access to the pyrenyl group of Py4C is restricted sterically as a result of the four flanking (2,6-dimethylphenoxy)acetic acid groups and the energy costs associated with their rotation. Deprotonation of the carboxylic acid groups of Py4C permits examination of ion-ion electrostatic interactions on the rates of quenching by iodide salts in which different steric and electrostatic factors are introduced by varying the cationic portions. At the same concentrations and with the same cations, chloride anions are ineffective quenchers. The quenching rate constants of Py4C by iodide are found to correlate linearly with the ionic radii of the cations and their enthalpies of hydration. These correlations are discussed in terms of the Hofmeister series. Furthermore, the results indicate that the cations that flank Py4C decrease the quenching efficiency of iodide through polarization and shielding effects (i.e., lowering the effective charge), which isolate to varying degrees the π-system. The effects of the different cations on quenching the fluorescence of a simpler and sterically unencumbered pyrenyl derivative, 1-pyrenylbutyric acid (PyBu), by iodide are much smaller. Overall, the results with Py4C indicate that the fluorescence quenching efficiency by iodide is influenced by direct interactions with the cations associated with the carboxylate groups of Py4C and not the solvation of water molecules. This observation is germane to a topic of current debate: Are the effects of the cations more closely related to bulk water properties or to direct ion-ion interactions? The conclusions obtained from these studies are applicable clearly to a wide variety of other systems in which ion pairing influences cooperative or inhibitory interactions.