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The hexameric assemblies of resorcinarenes and pyrogallolarenes are fascinating structures that can serve as nanoreactors in which new chemistry and catalysis occur. Recently, it was suggested based on SANS or SAXS that

The observed induction time for seeded gypsum crystallization was investigated with respect to gypsum particle seed size and mass loading. The induction time was significantly shortened in the pres...

Bis-resorcin[4]arene 2 connected by its lower rims was synthesized via click chemistry and found, by diffusion NMR, to self-assemble quantitatively, despite the different alternatives, into hexameric capsules reminiscent of the well-characterized hexameric capsule of resorcin[4]arene 1. The hexameric capsules of the flexible bis-resorcin[4]arene 2 prevail in apolar organic solvents and can, as expected, encapsulate quite well ammonium salts, demonstrating that spontaneous self-assembly into hexameric capsules is a general characteristic of such systems.

© 2016 American Chemical Society. Engineered nanomaterials (ENMs) are increasingly entering the environment with uncertain consequences including potential ecological effects. Various research communities view differently whether ecotoxicological testing of ENMs should be conducted using environmentally relevant concentrations - where observing outcomes is difficult - versus higher ENM doses, where responses are observable. What exposure conditions are typically used in assessing ENM hazards to populations? What conditions are used to test ecosystem-scale hazards? What is known regarding actual ENMs in the environment, via measurements or modeling simulations? How should exposure conditions, ENM transformation, dose, and body burden be used in interpreting biological and computational findings for assessing risks? These questions were addressed in the context of this critical review. As a result, three main recommendations emerged. First, researchers should improve ecotoxicology of ENMs by choosing test end points, duration, and study conditions - including ENM test concentrations - that align with realistic exposure scenarios. Second, testing should proceed via tiers with iterative feedback that informs experiments at other levels of biological organization. Finally, environmental realism in ENM hazard assessments should involve greater coordination among ENM quantitative analysts, exposure modelers, and ecotoxicologists, across government, industry, and academia.

Tetraalkylammonium salts were found, contrary to literature reports, to be encapsulated into hexameric capsules of pyrogallol[4]arene in benzene solution. The guest affinity depended on the length of the alkyl chain, the counteranion, the solvent used, the ammonium concentration, and most importantly, the pyrogallol[4]arene to ammonium salt ratio. At high ammonium salt to pyrogallol[4]arene ratios no encapsulation was observed, presumably since the high salt destabilized the formed hexamers.

A compartmental multimedia model was developed to enable evaluation of the dynamic environmental multimedia mass distribution and concentrations of engineered nanomaterials (ENMs). The approach considers the environment as a collection of compartments, linked via fundamental environmental intermedia transport processes. Model simulations for various environmental scenarios indicated that ENM accumulation in the sediment increased significantly with increased ENMs attachment to suspended solids in water. Atmospheric dry and wet depositions can be important pathways for ENMs input to the terrestrial environment in the absence of direct and distributed ENM release to soil. Increased ENM concentration in water due to atmospheric deposition (wet and dry) is expected as direct ENM release to water diminishes. However, for soluble ENMs dissolution can be the dominant pathway for suspended ENM removal from water even compared to advection. Mass accumulation in the multimedia environment for the evaluated ENMs (metal, metal oxides, carbon nanotubes (CNT), nanoclays) was mostly in the soil and sediment. The present modeling approach, as illustrated via different test cases, is suited for "what if" first tier analyses to assess the multimedia mass distribution of ENMs and associated potential exposure concentrations.

Sensor fault detection and isolation (SFDI) approaches, based on support vector regression (SVR) plant sensor models and self-organizing-map (SOM) analysis, were investigated for application to reverse osmosis (RO) desalination plant operation. SFDI-SVR and SFDI-SOM were assessed using operational data from a small spiral-wound RO pilot plant and synthetic faulty data generated as perturbations relative to normal plant operational data. SFDI-SVR was achieved without false negative (FN) detections for sensor deviations of ≳|10%| and FN detections of, at the most, ≲|5%|, and for sensor deviations of ≳|4%| at sensor fault detection (FD) thresholds of up to ∼|4%|. False positive (FP) detections were almost invariant, with respect to sensor FD, being ≲|5%| for sensor deviations of ≳|5%|. Corrections of faulty sensor readings were within SVR model accuracy (AARE < 1%) for SFDI-SVR and ≲|5%| for SFDI-SOM. Although SFDI-SOM has lower detection accuracy, it requires a single overall plant model (or SOM), while providing pictorial representation of plant operation and depiction of faulty operational trajectories.

A novel model-based control system for the operation of a spiral-wound RO membrane desalination system was developed with a focus on maintaining energy-optimal operation. The control scheme utilized an operational model for spiral-wound RO desalting with a supervisory controller providing real-time updates of membrane permeability and the appropriate feed pressure set-points for maintaining the target permeate productivity at the lowest feasible specific energy consumption. System RO feed pressure and flow rates were controlled by a lower-level RO controller through adjustment of the RO high pressure feed pump, variable frequency drive, and RO concentrate valve. Seawater desalination tests with an RO plant, capable of permeate productivity up to 18 000 gallons/day, demonstrated effective self-adaptive energy-optimal operation, subject to feed salinity fluctuations, constraints imposed by the system’s physical limitations (i.e., minimum and maximum feasible operational pressures and flow rates), and the th...

Because a variety of human-related activities, engineer-ed nanoparticles (ENMs) may be released to various environmental media and may cross environmental boundaries, and thus will be found in most media. Therefore, the potential environmental impacts of ENMs must be assessed from a multimedia perspective and with an integrated risk management approach that considers rapid developments and increasing use of new nanomaterials. Accordingly, this Account presents a rational process for the integration of in silico ENM toxicity and fate and transport analyses for environmental impact assessment. This approach requires knowledge of ENM toxicity and environmental exposure concentrations. Considering the large number of current different types of ENMs and that those numbers are likely to increase, there is an urgent need to accelerate the evaluation of their toxicity and the assessment of their potential distribution in the environment. Developments in high throughput screening (HTS) are now enabling the rapid generation of large data sets for ENM toxicity assessment. However, these analyses require the establishment of reliable toxicity metrics, especially when HTS includes data from multiple assays, cell lines, or organisms. Establishing toxicity metrics with HTS data requires advanced data processing techniques in order to clearly identify significant biological effects associated with exposure to ENMs. HTS data can form the basis for developing and validating in silico toxicity models (e.g., quantitative structure-activity relationships) and for generating data-driven hypotheses to aid in establishing and/or validating possible toxicity mechanisms. To correlate the toxicity of ENMs with their physicochemical properties, researchers will need to develop quantitative structure-activity relationships for nanomaterials (i.e., nano-SARs). However, as nano-SARs are applied in regulatory applications, researchers must consider their applicability and the acceptance level of false positive relative to false negative predictions and the reliability of toxicity data. To establish the environmental impact of ENMs identified as toxic, researchers will need to estimate the potential level of environmental exposure concentration of ENMs in the various media such as air, water, soil, and vegetation. When environmental monitoring data are not available, models of ENMs fate and transport (at various levels of complexity) serve as alternative approaches for estimating exposure concentrations. Risk management decisions regarding the manufacturing, use, and environmental regulations of ENMs would clearly benefit from both the assessment of potential ENMs exposure concentrations and suitable toxicity metrics. The decision process should consider the totality of available information: quantitative and qualitative data and the analysis of nanomaterials toxicity, and fate and transport behavior in the environment. Effective decision-making to address the potential impacts of nanomaterials will require considerations of the relevant environmental, ecological, technological, economic, and sociopolitical factors affecting the complete lifecycle of nanomaterials, while accounting for data and modeling uncertainties. Accordingly, researchers will need to establish standardized data management and analysis tools through nanoinformatics as a basis for the development of rational decision tools.

A constant-number direct simulation Monte Carlo (DSMC) model was developed for the analysis of nanoparticle (NP) agglomeration in aqueous suspensions. The modeling approach, based on the "particles in a box" simulation method, considered both particle agglomeration and gravitational settling. Particle-particle agglomeration probability was determined based on the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory and considerations of the collision frequency as impacted by Brownian motion. Model predictions were in reasonable agreement with respect to the particle size distribution and average agglomerate size when compared with dynamic light scattering (DLS) measurements for aqueous TiO(2), CeO(2), and C(60) nanoparticle suspensions over a wide range of pH (3-10) and ionic strength (0.01-156 mM). Simulations also demonstrated, in quantitative agreement with DLS measurements, that nanoparticle agglomerate size increased both with ionic strength and as the solution pH approached the isoelectric point (IEP). The present work suggests that the DSMC modeling approach, along with future use of an extended DLVO theory, has the potential for becoming a practical environmental analysis tool for predicting the agglomeration behavior of aqueous nanoparticle suspensions.

Most in vitro toxicity studies on engineered nanomaterials (ENMs) use transformed rather than primary cells for logistical reasons. However, primary cells may provide a more appropriate connection to in vivo toxicity because these cells maintain their phenotypic fidelity and are also capable of differentiating into lineages that may be differently affected by potentially hazardous ENM. Few studies to date have focused on the role of cellular differentiation in determining ENM toxicity. We compared the response of undifferentiated and differentiated primary human bronchial epithelial cells (NHBE) to cationic mesoporous silica nanoparticles (MSNP) that are coated with polyethyleneimine (PEI) since this polymer is known to exert differential cytotoxicity depending on its molecular weight and cationic density. The attachment of cationic PEI polymers to the MSNP surface was used to assess these materials' toxicological potential in undifferentiated and differentiated human bronchial epithelial cells (NHBE), using of a multi-parametric assay that screens for an integrated set of sub-lethal and lethal response outcomes. MSNP coated with high molecular weight (10 and 25 kD) polymers were more toxic in differentiated cells than particles coated with shorter length polymers. The increased susceptibility of the differentiated cells is in agreement with more abundant expression of a proteoglycan, syndecan-1, which contains copious heparin sulfate side chains. Pre-treatment with heparinase to remove the negatively charged sulfates decreased MSNP-PEI binding to the cell surface and lowered the cytotoxic potential of the cationic particles. These data demonstrate the importance of studying cellular differentiation as an important variable in the response of primary cells to toxic ENM properties.

The response of a murine macrophage cell line exposed to a library of seven metal and metal oxide nanoparticles was evaluated via High Throughput Screening (HTS) assay employing luciferase-reporters for ten independent toxicity-related signaling pathways. Similarities of toxicity response among the nanoparticles were identified via Self-Organizing Map (SOM) analysis. This analysis, applied to the HTS data, quantified the significance of the signaling pathway responses (SPRs) of the cell population exposed to nanomaterials relative to a population of untreated cells, using the Strictly Standardized Mean Difference (SSMD). Given the high dimensionality of the data and relatively small dataset the validity of the SOM clusters was established via a consensus clustering technique. Analysis of the SPR signatures revealed two cluster groups corresponding to (i) sub-lethal pro-inflammatory responses to Al2O3, Au, Ag, SiO2 nanoparticles possibly related to ROS generation, and (ii) lethal genotoxic responses due to exposure to ZnO and Pt nanoparticles at a concentration range of 25 μg/mL-100 μg/mL at 12 h exposure. In addition to identifying and visualizing clusters and quantifying similarity measures, the SOM approach can aid in developing predictive quantitative-structure relations; however, this would require significantly larger datasets generated from combinatorial libraries of engineered nanoparticles.

This work focuses on the design and implementation of a nonlinear model-based control system on an experimental reverse-osmosis (RO) membrane water desalination system to address large set-point changes and variations in feedwater salinity. A dynamic nonlinear lumped-parameter model is derived using first-principles, and its parameters are computed from experimental data to minimize the error between model predictions and experimental RO system response. This model then is used as the basis for the design of a nonlinear control system, using geometric control techniques. The nonlinear control system is implemented on the experimental RO system, and its set-point tracking and disturbance rejection capabilities are successfully evaluated.

The potential impact of coagulants on mineral scaling in reverse osmosis (RO) feed treatment of brackish water was assessed experimentally, with respect to calcium sulfate and barium sulfate scalin...

Polymer layer growth by free radical graft polymerization (FRGP) and controlled nitroxide-mediated graft polymerization (NMGP) of polystyrene was achieved by atmospheric pressure hydrogen plasma surface activation of silicon. Kinetic polystyrene layer growth by atmospheric pressure plasma-induced FRGP (APPI-FRGP) exhibited a maximum surface-grafted layer thickness (125 A after 20 h) at an initial monomer concentration of [M] 0 = 2.62 M at 85 degrees C. Increasing both the reaction temperature ( T = 100 degrees C) and initial monomer concentration ([M] 0 = 4.36 M) led to an increased initial film growth rate but a reduced polymer layer thickness, due to uncontrolled thermal initiation and polymer grafting from solution. Controlled atmospheric pressure plasma-induced NMGP (APPI-NMGP), using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), exhibited a linear increase in grafted polystyrene layer growth with time due to controlled surface graft polymerization as well as reduced uncontrolled solution polymerization and polymer grafting, resulting in a polymer layer thickness of 285 A after 60 h at [TEMPO] = 10 mM, [M] 0 = 4.36 M, and T = 120 degrees C. Atomic force microscopy (AFM) surface analysis demonstrated that polystyrene-grafted surfaces created by APPI-NMGP exhibited a high surface density of spatially homogeneous polymer features with a low root-mean-square (RMS) surface roughness ( R rms = 0.36 nm), similar to that of the native silicon surface ( R rms = 0.21 nm). In contrast, polymer films created by APPI-FRGP at [M] 0 = 2.62 M demonstrated an increase in polymer film surface roughness observed at reaction temperatures of 85 degrees C ( R rms = 0.55 nm) and 100 degrees C ( R rms = 1.70 nm). The present study concluded that the current approach to APPI controlled radical polymerization may be used to achieve a grafted polymer layer with a lower surface roughness and a higher fractional coverage of surface-grafted polymers compared to both conventional FRGP and APPI-FRGP.

Advances in highly permeable reverse osmosis (RO) membranes have enabled desalting operations, in which it is practically feasible for the applied pressure to approach the osmotic pressure of the exit brine stream. However, energy cost remains a major contributor to the total cost of water produced by RO membrane desalination. Reduction of the overall cost of water production represents a major challenge and, in the present work, various elements of water production cost are evaluated from the viewpoint of optimization, with respect to various costs (energy, membrane area and permeability, brine management, and pressure drop), as well as the important thermodynamic cross-flow constraint, utilization of energy recovery devices, and operational feed and permeate flow rate constraints. More specifically, in the present study, an approach to the optimization of product water recovery at pressures that approach the osmotic pressure of the exit brine stream is presented via several simple RO process models that...

Model-based control and monitoring such as feed-forward/feedback control, fault detection and isolation (FDI), and fault-tolerant control (FTC) techniques that utilize Lyapunov-based control laws are implemented on a high recovery reverse osmosis desalination plant model. A detailed mathematical model of a high recovery reverse osmosis plant is developed. This model incorporates the large spatial variations of concentration and flow rate that occur in membrane units during high recovery operation. Bounded nonlinear feedback and feed-forward controllers are developed and applied to this system. The application of these controllers with FDI and FTC is demonstrated in the context of a high recovery reverse osmosis process simulation. The first set of simulations demonstrates the ability to compensate for the effects of large time-varying disturbances in the feed concentration on specific process outputs with and without feed-forward control. The second set of simulations demonstrates the ability of FDI and F...

[reaction: see text] Bimetallic alkylzinc calixarene inclusion complexes were prepared and used in the ring-opening polymerization of L-lactide. Polymers with high molecular weight and a low degree of polydispersity were obtained. 1H NMR and diffusion NMR experiments suggest that a single-site mechanism is operative.

Diffusion NMR and, more recently, diffusion ordered spectroscopy (DOSY) are gaining popularity as efficient tools for the characterization of supramolecular systems in solution. Here, using diffusion NMR of hydrogen-bond molecular capsules, we demonstrate that the use of different diffusion sequences may have a dramatic effect on exchanging peaks. In fact, we found that the signal decay of the water peak in [(1a)(6)(H(2)O)(8)] is monoexponential in the pulsed gradient spin-echo (PGSE) and stimulated echo (PGSTE) sequences and biexponential in the longitudinal eddy current delay (LED) and the bipolar longitudinal eddy current delay (BPLED) sequences, routinely used in modern DOSY experiments. By performing these diffusion measurements on molecular capsules, in which water is not part of the molecular capsules, we demonstrate that this phenomenon is observed only for water molecules that exchange between two sites that differ considerably in their diffusion coefficients. Degeneration of the LED or the BPLED sequences into PGSTE-type sequences by shortening the te period resulted in the disappearance of the extra slow diffusing component. The origin, as well as the implications of the different results obtained from conventional diffusion sequences, such as the PGSE and PGSTE as compared with the LED and BPLED sequences generally used in DOSY experiments, are briefly discussed.

Pharmacokinetic studies of soybean isoflavones have shown that following oral ingestion, the two major isoflavones, daidzin and genistin, are hydrolyzed in the intestine, rapidly absorbed into the peripheral circulation, and eliminated from the body with a terminal half-life of 7-8 h. These characteristics make maintenance of steady-state plasma isoflavone concentrations difficult to attain unless there is repeated daily ingestion of foods or supplements containing isoflavones. In an attempt to sustain more constant plasma isoflavone concentrations, a new slow-release formulation of a soybean isoflavone extract was prepared by microencapsulation with a mixture of hydroxypropylcellulose and ethylcellulose to alter its dissolution characteristics. In vitro experiments confirmed slow aqueous dissolution of isoflavones from this formulation when compared with the conventional isoflavone extract. The pharmacokinetics of this slow-release isoflavone extract was studied in 10 healthy postmenopausal women after oral administration of a single capsule containing the equivalent of 22.3 mg of genistein and 7.47 mg of daidzein expressed as aglycons. A comparison of the key pharmacokinetic parameters obtained in this study with those established in extensive studies performed previously in this laboratory indicated that the mean residence time of genistein and daidzein increased 2-fold with microencapsulation. These findings are indicative of a decreased rate of absorption, consistent with the observed slow in vitro dissolution rate. These findings show that it is feasible to employ polymer matrices that slow the aqueous dissolution for preparing sustained-release formulations of soy isoflavones. Further studies to optimize such formulations are warranted.

In the present study, we applied for the first time (31)P diffusion NMR to resolve different species obtained by the addition of organophosphorus compounds (OP) such as diisopropyl phosphorofluoridate (DFP) or 1-pyrenebutyl phosphorodichloridate (PBPDC) to alpha-chymotrypsin (Cht). (31)P diffusion NMR was used since the products of these reactions constitute a mixture of OP-covalent conjugates of the enzyme and OP-containing hydrolysis products that have noninformative (1)H NMR spectra. It was shown that the peak, attributed to the covalent native diisopropylphosphoryl-Cht (DIP-Cht) conjugate by chemical shift considerations, has a greater diffusion coefficient (D = (0.65 +/- 0.01) x 10(-5) cm(2) s(-1)) than expected from its molecular mass (approximately 25 kDa). This peak was therefore suggested to consist of at least two superimposed signals of diisopropyl phosphoryl (DIP) pools of high and low molecular weights that happen to have the same chemical shift. This conclusion was substantiated by the use of DMSO-d(6) that separated the overlapping signals. Diffusion measurements performed on the extensively dialyzed and unfolded DIP-Cht conjugate still resulted in a high diffusion coefficient ((0.30 +/- 0.05) x 10(-5) cm(2) s(-1)) relative to the assumed molecular mass. This observation was attributed to a dynamic dealkylation at the OP moiety (i.e., aging) that occurred during the relatively long diffusion measurements, where DIP-Cht was converted to the corresponding monoisopropyl phosphoryl Cht (MIP-Cht) conjugate. Homogeneous aged forms of OP-Cht were obtained by use of DFP and heat-induced dealkylation of DIP-Cht, and by PBPDC that provided the aged form via the hydrolysis of a P-Cl bond (PBP-Cht). The thermally stable aged conjugates enabled a reliable determination of the diffusion coefficients over several days of data acquisition, and the values found were (0.052 +/- 0.002) x 10(-5) cm(2) s(-1) and (0.054 +/-0.004) x 10(-5) cm(2) s(-1) for the MIP-Cht and the PBP-Cht adducts, respectively, values in the range expected for a species with a molecular weight of 25 kDa. The advantages and limitations of (31)P diffusion NMR in corroborating the type of species that prevail in such systems are briefly discussed.

In the present study, we used diffusion NMR to probe the structures and characteristics of the products obtained from the self-assembly of resorcin[4]arenes 1a and 1b and pyrogallol[4]arenes 2a and 2b in CDCl(3) solutions. It was found that all four molecules self-assemble into hexameric capsules. The hexameric capsules of pyrogallol[4]arenes 2a and 2b were found to be more stable than the capsules of resorcin[4]arenes 1a and 1b in polar media. We also studied the role of water molecules in the self-assembly of the different capsules and found that water molecules are part of the hexameric capsules of resorcin[4]arenes 1a and 1b but not in the capsules of pyrogallol[4]arenes 2a and 2b. It was found that the self-assembly process between the resorcin[4]arenes and pyrogallol[4]arenes proceeds with self-recognition. When mixing two macrocycles of different types in a chloroform solution, no heterohexamers are formed, only the capsule constructed from the same macrocycle is detected. However, when two resorcin[4]arenes (i.e., 1a and 1b) or two pyrogallol[4]arenes (i.e., 2a and 2b) are mixed, heterohexamers are formed over time. In addition, we found that resorcin[4]arenes and pyrogallol[4]arenes differ significantly in their guest affinity. The capsules of 1a and 1b can accommodate both the tertiary alkylamines and their respective ammonium salts, while the capsules of 2a and 2b encapsulate only the neutral tertiary alkylamines.

[reaction: see text] NMR diffusion measurements were used to characterize the self-assembled molecular capsule of pyrogallolarene 2c in CDCl(3) solutions. The results were compared with the characteristics of the hexameric capsule of 1b. Although both 2c and 1b self-assemble into hexameric capsules, the role of water in these capsules is rather different. It was also found that the capsule of 2c is more stable in polar media than that of 1b.

The interactions of 1,4-diaminobutane (1), 1,6-diaminohexane (2), 1,8-diaminooctane (3), 1,10-diaminodecane (4), and 1,12-diaminododecane (5) with alpha-cyclodextrin (alpha-CD) were studied in aqueous solutions by NMR diffusion measurements before and after protonation. The correlation between the association constant and the length of the alkyl chain of the diamine unit was studied. The assumption that protonation on the amino groups can be used as a stopper and, as a result, to convert the pseudorotaxanes into rotaxanes was tested. In addition, other factors that can affect the pseudorotaxane stability, such as the effects of temperature, were tested. On the basis of these measurements, the following conclusions could be reached: (1) The association constant increases with the increase in the alkyl chain length. (2) For the salts (2b-5b), both in neutral and in acidic solutions, the binding constants increase as the number of CH(2) units increases. (3) The association constants of the complexes of the diaminoalkane salts and alpha-CD are lower than those of the corresponding neutral diaminoalkanes. (4) This difference between the binding constants of the diaminoalkanes and their respective salts decreases as the chain length increases. (5) By examining the effects of temperature on the (1)H NMR spectra, it was found that after addition of DCl the energy barrier for the threading-dethreading process of the salt of 5a is larger than that for the salt of 4a.

Anhydrous silylation of vinyltrimethoxysilane (VTMS) onto silica and zirconia substrates was investigated experimentally to demonstrate and quantify the effects of surface water on multilayer silylation. Silylation coverage was controlled by the availability of surface water, which is consumed in multilayer silylation reactions. Silylation coverage increased with surface water coverage, reaching a maximum at approximately two monolayers of water. The subsequent decline in silylation coverage is attributed to the formation of bulk polysilanes and the decreased accessibility of the water-bearing surface to the hydrophobic VTMS molecules. Atomic force microscopy images revealed a nanometer-scale clusterlike surface morphology consistent with the formation of bonded polysilanes. The present study suggests that multilayered silylated surfaces can be prepared reproducibly. Such surfaces could prove useful in applications that require a high concentration of surface active groups such as in ceramic membrane modi...

The ligands 2,9-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-1,10-phenanthroline (6), 6' ',6' "-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl)]-2' ',2' "-bipyridine (2), 5,5'-bis[(6-methyl-2,2'-bipyridin-6'yl)methyleneoxymethylenyl]-2, 2'-bithiophene (7), and 6,6'-bis[(6-methyl-2, 2'-bipyridin-6'-yl)methyleneoxymethylenyl]-2,2'-biphenyl (8) and their respective homo- and heteroleptic double-stranded copper(I) complexes were prepared and characterized in order to estimate the importance of self-recognition in the self-assembly processes of double-stranded copper complexes. The homoleptic double-stranded copper complexes of 2, 6, 7, and 8 were characterized by NMR, FAB-MS, and electrochemistry. It was found that 6 and 2 each form a single double-stranded helicate having the structure of [(L)(2)Cu(3)](3+) (L = 2 or 6), 7 forms two double-stranded [(7)(2)Cu(3)](3+) complexes, and 8 results in a mixture of at least two [(8)(2)Cu(2)](2+) complexes. The potential shift, DeltaE degrees (,) of the Cu(+)/Cu(2+) redox process of these complexes reflects the binding affinity of the different binding sites to the copper cation. The electrochemical data show that the central units have a higher affinity to Cu(+) as compared to the off-center binding sites. NMR was used to determine the actual complex composition obtained from different mixtures of 2, 6, or 7 with Cu(+). Interestingly, we have found that, although 6, 2, and 7 each form homoleptic double-stranded complexes, no heteroleptic double-stranded copper complexes were formed from the mixtures of 7 with either 6 or 2. However, when mixtures of 6 and 2 are used, helicate distributions seem to follow simple statistics. These results are discussed in terms of the relative importance of self-recognition in the self-assembly of double-stranded helicates.

The C(1)-symmetrical complex [Ru(bpy)(2)(ieil)][PF(6)](2) exhibits unique electrochemical and photophysical properties, and forms discrete dimers in solution and in the solid state held by weak pi-pi stacking interactions via its isoeilatin ligand, preferentially from one of its faces and in a specific orientation.

A modified expression for the change in chemical potential of a solvent, in a polymer network, due to isotropic swelling was obtained by substituting a non-Gaussian chain length probability distribution in Flory's statistical analysis of rubber elasticity. The affine non-Gaussian expression for the free energy change due to elastic deformation was compared to both the traditional Flory and the James-Guth phantom network expressions for the free energy change due to elastic deformation using available experimental data for the swelling of highly cross-linked polymeric resins. Among the different models for the elastic contribution to the free energy change resulting from isotropic swelling, the non-Gaussian elasticity expression was found to be as good as, or slightly better than the Flory expression, and clearly superior to the James-Guth phantom network expression. Both of the two different expressions used to represent the free energy of mixing, the Flory-Huggins expression and a modified version of the quasi-chemical mixing expression, were found to be equally successful when describing the isotropic swelling of cross-linked polymeric resins

A screening-level methodology was developed for the evaluation of solute affinity for polymers that are candidate sorption resins. In this approach novel grafted polymer-silica resins were synthesized to produce poly(vinylpyrrolidone)-silica (PVP-Si) and poly(vinyl acetate)-silica (PVAc-Si) resins. The polymer-silica resins along with a number of commercially available polymer resins were used to evaluate the aqueous-phase adsorption of phenol, tetrachloroethene (PCE), trichloroethene (TCE), and chloroform. The polymer-grafted silicas were able to selectively remove pollutants from water with a covalently bonded polymer layer that has a high affinity for the target pollutant. The PVAc-silica resin had a sorption capacity for TCE and ChCl 3 as high as commercial poly(styrene) resin XAD-4; the PVP-Si resin had a sorption capacity for phenol higher than a commercial poly(vinylpyridine) resin (Reillex 425). PCE adsorption onto the PVAc-silica was comparable to the commercial poly(methacrylate) and poly(vinylpyridine) resins but less than the poly(styrene) resin. The results show that the Hildebrand solubility parameter along with the dipole moment of the polymer functional groups can be used for an initial screening-level assessment of polymer-solute affinity

We have extend the preliminary study of Chaimberg et al. (1989) on the graft copolymerization of vinylpyrrolidone to a wider range of reaction temperatures and initial monomer concentrations. In addition, we report on an experimental procedure for detaching the graft polymerized PVP chains from the substrate surface. The average molecular weigth of the degrafted polymer was determined by way of HPLC-SEC using a novel PVP-silica matrix separation material.

Numerous investigations regarding atmospheric H{sub 2}O{sub 2} have been conducted during the 1980s; nevertheless, the distribution pattern of H{sub 2}O{sub 2} and its formation, decomposition, and deposition processes still are not clearly understood. In this article, the authors summarize previous investigators' findings concerning the levels of H{sub 2}O{sub 2} in the gas and aqueous phases at various locations in the world. They also review and evaluate previous studies on factors affecting the formation of gaseous H{sub 2}O{sub 2}. Additionally, they review studies on the decomposition and deposition of atmospheric H{sub 2}O{sub 2}, including its gas-phase and aqueous-phase reactions, to evaluate the role of H{sub 2}O{sub 2} as an oxidizer of sulfur dioxide (SO{sub 2}) in the atmosphere. Finally, they suggest that although H{sub 2}O{sub 2} may be the dominant oxidant of atmospheric SO{sub 2} to sulfate, the limited amount of field data currently available on the temporal and geographic concentration and distribution of H{sub 2}O{sub 2} hinders the identification of major factors affecting the formation of atmospheric H{sub 2}O{sub 2}.

A screening-level spatial-multimedia-compartmental (SMCM) approach to modeling the fate and transport of volatile organic pollutants in regional environments is presented. The SMCM approach, which makes use of both uniform (i.e., well-mixed) and nonuniform (one-dimensional) compartments, incorporates a variety of transport phenomena associated with pollutant transport such as dry deposition, rain scavenging, runoff, infiltration, soil drying, and pollutant diffusion and convection in the vadose zone. The multimedia distributions of trichloroethylene, tetrachloroethylene, and 1,1,1-trichloroethane in the Los Angeles area, and tetrachloroethylene in the San Diego area, were explored by using the SMCM model. The predicted concentrations were found to be in reasonable agreement with the available field data. The study suggests that the SMCM approach is useful and efficient for rapid screening-level analysis of the steady-state or dynamic multimedia distribution of chemical pollutants.

A new computational model for free-radical polymerization reactions was developed. The model algorithm is based on the use of an implicit numerical technique to solve for the coupled monomer and total growing polymer concentration differential equations. Determination of the monomer and total growing polymer concentrations ensures that conservation of mass is maintained without the need to solve the large number of differential equations associated with the growing polymer concentrations for each individual chain length. Acceleration of the numerical calculations was achieved by lumping the growing polymer chains into distinct groups. The proposed numerical scheme generates the monomer conversion and a complete molecular weight distribution (MWD) of the growing and dead polymer chains. The current formulation allows for the incorporation of nonidealities, such as the onset of gelation and chain-length-dependent reaction rate coefficients

The adsorption of the EPA priority pollutants trichloroethene (TCE) and chloroform (CHCl 3 ) from aqueous solutions onto activated carbon and macroporous polymeric resins was investigated over a wide concentration range. Over much of the concentration range studied, activated carbon adsorbed more TCE and CHCl 3 on a weight basis and on a surface area basis than did the polymer resins. At concentrations greater than 1000 μg/L, the adsorption capacity, on a surface area basis, for the different resins and for activated carbon was similar. The adsorption isotherms were fitted by the empirical Freundlich isotherm and the semiempirical isotherm of Jossens et al. The affinity of the solutes for the different resins was qualitatively described by a simple Hildebrand solubility parameter correlation

NMR experiments demonstrate that, although 2b and 3b form hexameric capsules in chloroform solutions and despite the very similar building units of these hexamers, 3b encapsulates only the noncharged trialkylamines while 2b can encapsulate both the noncharged trialkylamines and the respective ammonium salts obtained by the addition of DCl. In fact, it was found that protonation that forms in situ the ammonium salt ejects the guest from the hexameric capsule of 3b. This is a general observation as it was found for guests containing alkyl chains of four, five, six, and eight carbons.

NMR diffusion measurements provide unequivocal proof that the resorcinarene 1b self-assembles spontaneously into a stable hexamer capsule in chloroform solution by encapsulating several chloroform molecules, which occupy different chemical positions. Although the affinity of tetrahexylammonium bromide (2a) toward the cavity of the hexamer is much higher than that of the chloroform molecules, it was found that the same amount of DMSO is needed to disrupt the two hexamers, thus suggesting similar stabilities for these two supramolecular capsules.

Reduction par Li et Na de benzo [c] cinnoline, dibenzo [a,c] phenazine et de derives de la quinoxaline. Obtention de dianions. Spectres RMN de 1 H et 13 C

Polystyrene adsorbe dans le toluene et le cyclohexane et polyacrylamide en solution aqueuse de NaCl

Un systeme a six compartiments (air, sol, eau, biota, solides en suspension, sediment) est utilise pour etudier le transport du trichloroethylene dans l'environnement