A magnetic sorbent was fabricated by coating the magnetized graphene oxide with polystyrene (PS) to obtain a sorbent of the type GO-Fe3O4@PS. The chemical composition and morphology of the sorbent were characterized. The sorbent was employed for the enrichment of polycyclic aromatic hydrocarbons (PAHs) from water samples. Various parameters affecting the enrichment were investigated. The PAHs were then quantified by gas chromatography with flame ionization detection. Linear responses were found in the range of 0.03–100 ng mL?1 for naphthalene and 2-methylnaphthalene, and of 0.01–100 ng mL?1 for fluorene and anthracene. The detection limits (at an S/N ratio of 3) range between 3 and 10 pg mL?1. The relative standard deviations (RSDs) for five replicates at three concentration levels (0.05, 5 and 50 ng mL?1) of analytes ranged from 4.9 to 7.4%. The method was applied to the analysis of spiked real water samples. Relative recoveries are between 95.8 and 99.5%, and RSD% are <8.4%.
Graphical abstract A magnetic sorbent was fabricated by polystyrene coated on the magnetic graphene oxide for the extraction and preconcentration of PAHs in water samples prior to their determination by gas chromatography with flame ionization detection.
A new method for multi-component synthesis of 1,4-dihydropyridine derivatives (1,4-DHPs) in the presence of meglumine supported on multiwalled carbon nanotubes (MWCNTs@meglumine) as a new heterogeneous, highly efficient and reusable catalyst was investigated. The reaction was performed under ultrasonic irradiation in EtOH at room temperature. A new, highly efficient heterogeneous catalyst, short reaction times, high to excellent yield of products, and safe and clean conditions are the advantages of the presented method. 相似文献
Erigeroside was extracted from Satureja khuzistanica Jamzad (Marzeh Khuzistani in Persian, family of lamiaceae), and (1)H, (13)C, (13)C{(1)H}, (1)H-(1)H COSY, HMQC and J-HMBC were obtained to identify this compound and determine a complete set of J-coupling constants ((1)J(C-H), (2)J(C-H), (3)J(C-H) and (3)J(H-H)) values within the exocyclic hydroxymethyl group (CH(2)OH) and anomeric center. In parallel, density functional theory (DFT) using B3LYP functional and split-valance 6-311++G** basis set has been used to optimized the structures and conformers of erigeroside. In all calculations solvent effects were considered using a polarized continuum (overlapping spheres) model (PCM). The dependencies of (1)J, (2)J and (3)J involving (1)H and (13)C on the C(5')-C(6') (omega), C(6')-O(6') (theta) and C(1')-O(1') (phi) torsion angles in erigeroside were computed using DFT method. Complete hyper surfaces for (1)J(C1',H1'), (2)J(C5',H6'R), (2)J(C5',H6'S), (2)J(C6',H5'), (3)J(C4',H6'R), (3)J(C4',H6'S) and (2)J(H6'R-H5'S) as well as (3)J(H5',H6'R) were obtained and used to derive Karplus equations to correlate these couplings to omega, theta and phi. These calculated J-couplings are in agreement with experimental values. These results confirm the reliability of DFT calculated coupling constants in aqueous solution. 相似文献
We present a supramolecular approach to catalyzing photochemical CO2 reduction through second-sphere porosity and charge effects. An iron porphyrin box ( PB ) bearing 24 cationic groups, FePB-2(P) , was made via post-synthetic modification of an alkyne-functionalized supramolecular synthon. FePB-2(P) promotes the photochemical CO2 reduction reaction (CO2RR) with 97 % selectivity for CO product, achieving turnover numbers (TON) exceeding 7000 and initial turnover frequencies (TOFmax) reaching 1400 min−1. The cooperativity between porosity and charge results in a 41-fold increase in activity relative to the parent Fe tetraphenylporphyrin ( FeTPP ) catalyst, which is far greater than analogs that augment catalysis through porosity ( FePB-3(N ), 4-fold increase) or charge (Fe p-tetramethylanilinium porphyrin ( Fe-p-TMA ), 6-fold increase) alone. This work establishes that synergistic pendants in the secondary coordination sphere can be leveraged as a design element to augment catalysis at primary active sites within confined spaces. 相似文献
In this study density functional theory (DFT) calculations at B3LYP/6-31G(d), B3LYP/6-31+G(d) and B3LYP/6-311+G(2df,2p) levels for geometry optimization and total energy calculation were applied for investigation of the important energy-minimum conformations and transition-state of 1,2-, 1,3-, and 1,4-dithiepanes. Moreover, ab initio calculations at HF/6-31G(d) level of theory for geometry optimization and MP2/6-311G(d)//HF/ 6-31G(d) level for a single-point total energy calculation were reported for different conformers. The obtained results reveal that, the twist-chair conformer is a global minimum for all of these compounds. Also, two local minimum were found in each case, which are twisted-chair and twisted-boat conformers. The boat and chair geometries are transition states. The minimum energy conformation of 1,2-dithiepane is more stable than the lowest energy forms of 1,3-dithiepane and 1,4-dithiepane. Furthermore, the anomeric effect was investigated for 1,3-dithiepane by the natural bond orbital method. The computational results of this study shows that all conformers of 1,3-dithiepane have a hypercojugation system. Finally, the 13C NMR chemical shifts for the conformers of 1,4-dithiepane were calculated, which have good correlation with their experimental values. 相似文献
Let X be an irreducible projective variety over an algebraically closed field of characteristic zero. For ≥ 3, if every (r−2)-plane
, where the xi are generic points, also meets X in a point xr different from x1,..., xr−1, then X is contained in a linear subspace L such that codimLX ≥ r − 2. In this paper, our purpose is to present another derivation of this result for r = 3 and then to introduce a generalization to nonequidimensional varieties. For the sake of clarity, we shall reformulate
our problem as follows. Let Z be an equidimensional variety (maybe singular and/or reducible) of dimension n, other than a linear space, embedded into ℙr, where r ≥ n + 1. The variety of trisecant lines of Z, say V1,3(Z), has dimension strictly less than 2n, unless Z is included in an (n + 1)-dimensional linear space and has degree at least 3, in which case dim V1,3(Z) = 2n. This also implies that if dim V1,3(Z) = 2n, then Z can be embedded in ℙn + 1. Then we inquire the more general case, where Z is not required to be equidimensional. In that case, let Z be a possibly singular variety of dimension n, which may be neither irreducible nor equidimensional, embedded into ℙr, where r ≥ n + 1, and let Y be a proper subvariety of dimension k ≥ 1. Consider now S being a component of maximal dimension of the closure of
. We show that S has dimension strictly less than n + k, unless the union of lines in S has dimension n + 1, in which case dim S = n + k. In the latter case, if the dimension of the space is strictly greater than n + 1, then the union of lines in S cannot cover the whole space. This is the main result of our paper. We also introduce some examples showing that our bound
is strict.
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Translated from Fundamentalnaya i Prikladnaya Matematika, Vol. 12, No. 2, pp. 71–87, 2006. 相似文献
Metal catalyzed polymerizations are among the most important chemical reactions, accounting for the production of about 400 million tons per year of polymeric materials, 50 % of which are polyolefins. The CIRCC research units at the University of Salerno, founded by the late Professor Adolfo Zambelli, a coworker of Giulio Natta and a pioneer in the studies of stereospecific polymerization catalysts, has a consolidated expertise in this field. Although often considered a “mature” area of research, olefin polymerization catalysis continues to drive great interest of both industrial and academic scientists. On the other hand, strong political and economic pressure toward the development of “green” and possibly biodegradable alternatives to olefin-based polymers stimulated our group to direct increasing research efforts in the area of sustainable polymers. In this perspective, we focus on the most recent work from the CIRCC research units involved in homogeneous catalysis for polymerization of a variety of monomers, with the aim to address how the concepts and the expertise developed for olefin polymerization can be applied to the development of different metal-catalyzed polymerizations and copolymerizations. Of course, although the results are discussed in the frame of the most important literature contributions, a comprehensive review of such a wide and diversified topic is out of the scope of the paper. References to reviews covering the different types of metal catalyzed polymerizations are provided in each chapter. 相似文献
A facile method was developed for the synthesis of β-azido alcohols and β-nitro alcohols in the presence of a novel nano-Fe3O4-copoly[(styrene/acrylic acid)/grafted ethylene oxide (nano-Fe3O4-PS-Co-[PAA-g-PEG]) as a phase-transfer catalyst in water. The catalyst was characterized with IR, SEM, and TGA. This procedure offers several advantages, including excellent regioselectivity, high yields, short reaction times, a recyclable catalyst, easy separation of the catalyst through an external magnet, and easy workup. 相似文献
In the present work, an automated on-line electrochemically controlled in-tube solid-phase microextraction (EC-in-tube SPME) coupled with HPLC-UV was developed for the selective extraction and preconcentration of indomethacin as a model analyte in biological samples. Applying an electrical potential can improve the extraction efficiency and provide more convenient manipulation of different properties of the extraction system including selectivity, clean-up, rate, and efficiency. For more enhancement of the selectivity and applicability of this method, a novel molecularly imprinted polymer coated tube was prepared and applied for extraction of indomethacin. For this purpose, nanostructured copolymer coating consisting of polypyrrole doped with ethylene glycol dimethacrylate was prepared on the inner surface of a stainless-steel tube by electrochemical synthesis. The characteristics and application of the tubes were investigated. Electron microscopy provided a cross linked porous surface and the average thickness of the MIP coating was 45 μm. Compared with the non-imprinted polymer coated tubes, the special selectivity for indomethacin was discovered with the molecularly imprinted coated tube. Moreover, stable and reproducible responses were obtained without being considerably influenced by interferences commonly existing in biological samples. Under the optimal conditions, the limits of detection were in the range of 0.07–2.0 μg L−1 in different matrices. This method showed good linearity for indomethacin in the range of 0.1–200 μg L−1, with coefficients of determination better than 0.996. The inter- and intra-assay precisions (RSD%, n = 3) were respectively in the range of 3.5–8.4% and 2.3–7.6% at three concentration levels of 7, 70 and 150 μg L−1. The results showed that the proposed method can be successfully applied for selective analysis of indomethacin in biological samples. 相似文献