Project description:A scaling theory is developed for selective adsorption of polymers induced by the strong binding between specific monomers and complementary surface adsorption sites. By "selective" we mean specific attraction between a subset of all monomers, called "sticky", and a subset of surface sites, called "adsorption sites". We demonstrate that, in addition to the expected dependence on the polymer volume fraction ?bulk in the bulk solution, selective adsorption strongly depends on the ratio between two characteristic length scales, the root-mean-square distance l between neighboring sticky monomers along the polymer, and the average distance d between neighboring surface adsorption sites. The role of the ratio l/d arises from the fact that a polymer needs to deform to enable the spatial commensurability between its sticky monomers and the surface adsorption sites for selective adsorption. We study strong selective adsorption of both telechelic polymers with two end monomers being sticky and multisticker polymers with many sticky monomers between sticky ends. For telechelic polymers, we identify four adsorption regimes at l/d < 1 that are characterized by the fraction of occupied adsorption sites and whether the dominant conformation of adsorbed chains is a single-end-adsorbed "mushroom" or double-end-adsorbed loop. For l/d > 1, we expect that the adsorption layer at exponentially low ?bulk consists of separated unstretched loops, while as ?bulk increases the layer crosses over to a brush of extended loops with a second layer of weakly overlapping tails. For multisticker chains, in the limit of exponentially low ?bulk, adsorbed polymers are well separated from each other. As l/d increases, the conformation of an individual polymer changes from a single-end-adsorbed "mushroom" to a random walk of loops. For high ?bulk, adsorbed polymers at small l/d are mushrooms that cover all the adsorption sites. At sufficiently large l/d, adsorbed multisticker polymers strongly overlap. We anticipate the formation of a self-similar carpet and with increasing l/d a two-layer structure with a brush of loops covered by a self-similar carpet. As l/d exceeds the threshold determined by the adsorption energy, the brush of loops under the carpet reaches a saturated state, resulting in a l/d-independent brush-under-carpet structure, which can also be applied to describe adsorbed multisticker polymers in nonselective adsorption where a sticker can strongly bind to any place on the adsorption surface. We examine the adsorbed amount ? of multisticker polymers in different regimes for selective adsorption. If the adsorbed multisticker polymers are nonoverlapping mushrooms, the adsorbed amount ? increases linearly with the surface density of adsorption sites ? ? 1/d(2). In the self-similar carpet regime, ? increases sublinearly as ?(0.15) in a good solvent, while only logarithmically in a theta solvent. Formation of a brush layer under the carpet contributes an additional adsorbed amount. This additional amount increases linearly with ? and eventually dominates the overall adsorbed amount ? before saturating at a plateau value controlled by the adsorption energy.
Project description:An iron(III) complex of tetradentate N,N'-disubstituted bis(aminophenoxide) (designated as salan, a saturated version of the corresponding salen ligand) with a sterically hindered organic base anchored on the ligand framework, can selectively mediate the conversion of carbonyl sulfide to sulfur-containing polymers by the copolymerization with epoxides. This single-site catalyst exhibits broad substrate scope, and the resultant copolymers have completely alternating structures. In addition, this catalyst is efficient in producing diblock copolymers, suggesting a living polymerization nature.
Project description:In this research, a novel, sulfamethazine, thermosensitive, molecularly-imprinted polymer (MIP) with an obvious core?shell structure for the enrichment of sulfamethazine (SMZ), which involved temperature sensitive monomer N-Isopropylacrylamide, functional monomer methacrylic acid and cross-linking agents ethyleneglycol dimethacrylate (EGDMA) and N,N'-methylenebisacrylamide, was successfully compounded using the surface polymerization method. To ensure the best experimental group, we designed and compared three groups of controlled experiments of MIPs with different crosslinking agents. When the adsorption temperature was almost the lower critical solution temperature (LCST) of Poly(N-Isopropylacrylamide), the preparative MIPs showed outstanding adsorption capacity and specific identification to sulfamethazine. Moreover, this allowed the MIPs to better facilitate by combining the template molecules, as well as optimizing the imprinting factor. In addition, after 80 min, the adsorption of the MIPs leveled off and remained constant, and the adsorption quantity reached (a maximum of) at 8.1 mg·g-1.
Project description:Five new pyran rings containing polyketides, penicipyrans A-E (1-5), together with the known pestapyrone A (6), were isolated from the saline soil-derived Penicillium raistrickii. Their structures were determined by interpretation of NMR and HRESIMS data. The absolute configurations of compounds 4 and 5 were established by the modified Mosher's method and single-crystal X-ray diffraction analysis, respectively. These compounds possessed high structural diversity including two ?-pyrones (1, 2), three isocoumarins (3, 4, 6), and one dihydropyran derivative (5). Among them, Compound 5 exhibited cytotoxicity against HL-60 and K562 cell lines with IC50 values of 4.4 and 8.5 ?M, respectively.
Project description:The first zeolite structure (ITQ-40) that contains double four (D4) and double three (D3) member ring secondary building units has been synthesized by introducing Ge and NH(4)F and working in concentrated synthesis gels. It is the first time that D3-Rs have been observed in a zeolite structure. As was previously analyzed [Brunner GO, Meier, WM (1989) Nature 337:146-147], such a structure has a very low framework density (10.1 T/1,000 A(3)). Indeed, ITQ-40 has the lowest framework density ever achieved in oxygen-containing zeolites. Furthermore, it contains large pore openings, i.e., 15-member rings parallel to the [001] hexagonal axis and 16-member ring channels perpendicular to this axis. The results presented here push ahead the possibilities of zeolites for uses in electronics, control delivery of drugs and chemicals, as well as for catalysis.
Project description:An efficient method for the asymmetric gold(I)-catalyzed preparation of medium sized rings has been developed. The method provides 7- to 9-membered rings in excellent yield. High enantioselectivities can be achieved for 7- and 8-membered ring products employing chiral gold(I) complexes. The results provide insight into the mechanism, showing the fluxional nature of gold(I)-stabilized vinyl carbenoid intermediates.
Project description:Antimony(III) is a rare element whose chemical and toxicological properties bear a resemblance to those of arsenic. As a result, the presence of Sb(III) in water might have adverse effects on human health and aquatic life. However, Sb(III) exists at very ultra-trace levels which may be difficult for direct quantification. Therefore, there is a need to develop efficient and reliable selective extraction and preconcentration of Sb(III) in water systems. Herein, a selective extraction and preconcentration of trace Sb(III) from environmental samples was achieved using ultrasound assisted magnetic solid-phase extraction (UA-MSPE) based on magnetic Sb(III) ion imprinted polymer-Fe3O4@SiO2@CNFs nanocomposite as an adsorbent. The amount of antimony in samples was determined using inductively coupled plasma optical emission spectrometry (ICP-OES). The UA-MSPE conditions were investigated using fractional factorial design and response surface methodology based on central composite design. The Sb(III)-IIP sorbent displayed excellent selectivity towards Sb(III) as compared to NIIP adsorbent. Under optimised conditions, the enrichment factor, limit of detection (LOD) and limit of quantification (LOQ) of UA-MSPE/ICP-OES for Sb(III) were 71.3, 0.13 µg L-1 and 0.44 µg L-1, respectively. The intra-day and inter-day precision expressed as relative standard deviations (%RSDs, n = 10 and n = 5) were 2.4 and 4.7, respectively. The proposed analytical method was applied in the determination of trace Sb(III) in environmental samples. Furthermore, the accuracy of the method was evaluated using spiked recovery experiments and the percentage recoveries ranged from 95-98.3%.
Project description:Gas-phase spectroscopic detection of tiny carbon clusters is a recent success story in the area of carbon cluster research. However, experimental production and isolation of these clusters are extremely difficult because of their high reactivity. One possibility to isolate the generated clusters would be to deposit them on graphene and to desorb them for subsequent use. One of the pertinent questions toward realizing this would be the energetics of the adsorption process. Therefore, in this work, the energetics for the adsorption of the monocyclic carbon rings (C n with n = 10, 12, 14, 16, 18, 20, and 22) on a graphene sheet are investigated using the analytical approaches, developed earlier by Hill and co-workers. The adsorption process here is driven by the noncovalent interactions between the carbon rings and the graphene sheet. The analyses of the interaction energies as a function of both the vertical distance Z and the rotational angle ϕ are performed in order to determine the preferred orientations, equilibrium positions, and binding energies for the adsorption of various carbon rings on graphene. We find that the preferred orientation of the rings with respect to the graphene sheet is the parallel orientation. The results from continuum, discrete-continuum, and discrete models are in good agreement. Further, computations using density functional theory and quantum mechanics/molecular mechanics approaches are performed, and comparisons of the computed energetics with the data from the models are reported. Finally, we highlight the scope and the limitations of the analytical models.
Project description:Utilizing human pluripotent stem cells (hPSCs) in cell-based therapy and drug discovery requires large-scale cell production. However, scaling up conventional adherent cultures presents challenges of maintaining a uniform high quality at low cost. In this regard, suspension cultures are a viable alternative, because they are scalable and do not require adhesion surfaces. 3D culture systems such as bioreactors can be exploited for large-scale production. However, the limitations of current suspension culture methods include spontaneous fusion between cell aggregates and suboptimal passaging methods by dissociation and reaggregation. 3D culture systems that dynamically stir carrier beads or cell aggregates should be refined to reduce shearing forces that damage hPSCs. Here, we report a simple 3D sphere culture system that incorporates mechanical passaging and functional polymers. This setup resolves major problems associated with suspension culture methods and dynamic stirring systems and may be optimal for applications involving large-scale hPSC production.
Project description:Owing to the growing hardware capabilities and the enhancing efficacy of computational methodologies, computational chemistry approaches have constantly become more important in the development of novel anticancer metallodrugs. Besides traditional Pt-based drugs, inorganic and organometallic complexes of other transition metals are showing increasing potential in the treatment of cancer. Among them, Au(I)- and Au(III)-based compounds are promising candidates due to the strong affinity of Au(I) cations to cysteine and selenocysteine side chains of the protein residues and to Au(III) complexes being more labile and prone to the reduction to either Au(I) or Au(0) in the physiological milieu. A correct prediction of metal complexes' properties and of their bonding interactions with potential ligands requires QM computations, usually at the ab initio or DFT level. However, MM, MD, and docking approaches can also give useful information on their binding site on large biomolecular targets, such as proteins or DNA, provided a careful parametrization of the metal force field is employed. In this review, we provide an overview of the recent computational studies of Au(I) and Au(III) antitumor compounds and of their interactions with biomolecular targets, such as sulfur- and selenium-containing enzymes, like glutathione reductases, glutathione peroxidase, glutathione-S-transferase, cysteine protease, thioredoxin reductase and poly (ADP-ribose) polymerase 1.