Calibration of the complex matrix effects on the sampling of polycyclic aromatic hydrocarbons in milk samples using solid phase microextraction

Solid phase microextraction (SPME), a simple, fast and promising sampling technique, has been widely used for complex sample analysis. However, complex matrices could modify the absorption property of coatings as well as the uptake kinetics of analytes, eventually biasing the quantification results. In the current study, we demonstrated the feasibility of a developed calibration method for the analysis of polycyclic aromatic hydrocarbons (PAHs) in complex milk samples. Effects of the complex matrices on the SPME sampling process and the sampling conditions were investigated. Results showed that short exposure time (pre-equilibrium SPME, PE-SPME) could increase the lifetime of coatings, and the complex matrices in milk samples could significantly influence the sampling kinetics of SPME. In addition, the optimized sampling time, temperature and dilution factor for PAHs were 10 min, 85 °C and 20, respectively. The obtained LODs and LOQs of all the PAHs were 0.1–0.8 ng/mL and 1.4–4.7 ng/mL, respectively. Furthermore, the accuracy of the proposed PE-SPME method for milk sampling was validated by the recoveries of the studied compounds in two concentration levels, which ranged from 75% to 110% for all the compounds. Finally, the proposed method was applied to the screening of PAHs in milk samples.     

Laser Sculpting of Atomic sp,sp2, and sp3 Hybrid Orbitals

Atomic sp, sp², and sp³ hybrid orbitals were introduced by Linus Pauling to explain the nature of the chemical bond. Quantum dynamics simulations show that they can be sculpted by means of a selective series of coherent laser pulses, starting from the 1s orbital of the hydrogen atom. Laser hybridization generates atoms with state‐selective electric dipoles, opening up new possibilities for the study of chemical reaction dynamics and heterogeneous catalysis.     

Effective biosorption of U(VI) from aqueous solution using calcium alginate hydrogel beads grafted with amino-carbamate moieties

Journal of Radioanalytical and Nuclear Chemistry - The kinetics of Co ions sorption on CoTreat® was investigated in the 5–40 mg/L concentration range at a bulk temperature of...     

Preparation and controlled degradation of oxidized sodium alginate hydrogel

Degradation is often a critical property of materials utilized in tissue engineering. Although alginate, a naturally derived polysaccharide, is an attractive material due to its biocompatibility and ability to form hydrogels, its slow and uncontrollable degradation can be an undesirable feature. In this study, the degradation behavior of hydrogel based on oxidized sodium alginate (OSA) crosslinked with Ca²⁺ was studied in phosphate buffer solution (PBS, pH = 7.4) and Tris-(hydroxymethyl) aminomethane–HCl (Tris–HCl, pH = 7.4) at 37 °C. The degradation behavior of OSA hydrogels with different degrees of oxidation was evaluated as a function of degradation time by monitoring the changes of molecular weight and weight loss. It was found that the degradation behavior relied heavily on the degree of oxidation and the surrounding medium. This result indicates that the degradation rates of OSA hydrogels can be controlled by changing the degree of oxidation.     

1-[Ferrocenyl(hydroxy)methyl]-1,7-dicarba<Emphasis Type="Italic">-closo</Emphasis>-dodecaborane: Synthesis and X-ray crystal structure

The synthesis and molecular structure of the novel 1-[ferrocenyl(hydroxy)methyl]-1,7-dicarba-closo-dodecaborane (1) is described. Compound 1 was synthesized from reaction of m-carborane and ferrocene carboxaldehyde using n-butyllithium (n-BuLi) or tetrabutylammonium fluoride (TBAF) in THF in 45% and 36% yield, respectively. Compound 1 consists of a ferrocene molecule tethered to m-carborane through a methylhydroxy bridge. The crystal structure of 1 was determined by single crystal X-ray diffraction analysis. Crystal data: 1 [Fe(C₅H₅)(C₅H₄-CH₂O-1,7-C₂B₁₀H₁₂)], formula weight = 359.17, crystallized in orthorhombic system, space group Pna2 ₁ with a=19.698(4) ?, b=10.709(2) ?, c=8.520(2) ?, and V=1797.3(7) ?³ and Z=4. Refined to R ₁=0.043 for 4124 observed reflections with I/σ>2σ(I). The compound was crystallized as racemic twins in a ratio of 73(2)/27(2). The unsubstituted Cp ring was disordered and modeled as two conformations in a 53(3)/47(3) ratio. Intermolecular hydrogen bonding was observed from the hydrogen of the meta-carbon on the carborane cluster towards the hydroxyl oxygen.     

Crystal Structures of Diphosphinated Chromium Fischer Amino Carbenes

The crystal structures of four new diphosphinated chromium Fischer amino carbenes with the compositions fac-[(P-P)(CO)₃Cr=C(NR₂′)(R)] (R = Me, NR₂′ = pyrrolidino, P-P = dppe, 1; R = Me, NR₂′ = pyrrolidino, P-P = dppp, 2; R = Me, R′ = Me, P-P = dppe, 3; R = Me, R′ = Me, P-P = dppp, 4) have been determined at 243 K. Compound 1 crystallizes in the monoclinic system, space group P2₁ /n with a = 12.1597(11) Å, b = 20.1556(17) Å, c = 14.0557(12) Å, β = 114.163(3)°, V = 3143.0(5) Å³, and Z = 4. Compound 2 crystallizes in the triclinic system, space group P ? 1 with a = 7.4424(3) Å, b = 10.8830(5) Å, c = 20.6040(9) Å, α = 100.9880(10)°, β = 91.7650(10)°, γ = 97.6610(10)°, V = 1620.90(12) Å³, and Z = 2. Compound 3 crystallizes in the monoclinic system as a mono-solvate of d⁵-pyridine, space group P2₁ /c with a = 11.485(2) Å, b = 22.825(5) Å, c = 14.092(3) Å, β = 108.53(3)°, V = 3502.7(12) Å³, and Z = 4. Compound 4 crystallizes in the orthorhombic system, space group P2 ₁ 2 ₁ 2 ₁ with a = 8.359(3) Å, b = 15.364(6) Å, c = 23.784(9) Å, V = 3055(2) Å³, and Z = 4. Steric repulsions with the diphosphine ligand favor a conformation with the amino moiety directed away from the diphosphine backbone in 1–4.     

Polymer‐supported half‐titanocene catalysts for the syndiospecific polymerization of styrene

Monocyclopendienyltitanium trichloride (CpTiCl₃) was supported on polymer carriers with different hydroxyl contents, and the supported catalysts were used for styrene polymerization. The supported catalysts exhibited high activity even at low Al/Ti ratios and increased the molecular weight of the products, indicating that polymer carriers could stabilize the active sites. The polymers prepared with unsupported and supported catalysts were extracted with boiling n‐butanone and characterized by carbon nuclear magnetic resonance (¹³C NMR) and differential scanning calorimetry. The polymers obtained by supported catalysts had a high fraction of boiling n‐butanone‐insoluble part and high melting temperatures, but ¹³C NMR results showed that syndiotacticity decreased compared with that of polymers prepared with an unsupported catalyst. ESR study on the supported catalysts confirmed that the active sites supported on the carrier dropped into the solution and formed active sites the same as those in the unsupported system when they reacted with methylaluminoxane. ¹³C NMR analysis showed that the polymerization mechanism of the supported active sites was an active‐site controlled mechanism instead of a chain‐end controlled mechanism of the unsupported active sites. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 127–135, 2000     

The synthesis of a new cardiac sympathetic nerve imaging agent N-[11C]CH3-dopamine and biodistribution study

In this study, we synthesized and characterized N-[¹¹C]methyl-dopamine ([¹¹C]MDA) for cardiac sympathetic nerve imaging. [¹¹C]MDA was synthesized by direct N-methylation of dopamine with [¹¹C]methyl iodide and purified by semi-preparation reverse high pressure liquid chromatography (HPLC). The total synthesis time was 45 min including HPLC purification. The radiochemical yields of [¹¹C]MDA was 20 ± 3 %, without decay correction. The radiochemical purity was >98 % and the specific activity was about 50 GBq/mmol. The biological properties of [¹¹C]MDA were evaluated by biodistribution study in normal mice. PET imaging was performed in healthy Chinese mini-swines. Biodistribution study showed that [¹¹C]MDA had high myocardium uptake. PET/CT imaging showed [¹¹C]MDA had clear and symmetrical myocardium uptake, which was blocked obviously by injecting imipramine hydrochloride. [¹¹C]MDA would be a promising candidate of radiotracer for cardiac sympathetic nervous system imaging.     

Phase behavior of amphiphiles at liquid crystals/water interface: A coarse-grained molecular dynamics study

We present a coarse-grained molecular dynamics simulation study of phase behavior of amphiphilic monolayers at the liquid crystal （LC）/water interface. The results revealed that LCs at interface can influence the lateral ordering of amphiphiles. Particularly, the amphiphile tails along with perpendicularly penetrated LCs between tails undergo a two-dimension phase transition from liquid-expanded into a liquid-condensed phase as their area density at interface reaches 0.93. While, the liquid-condensed phase of the monolayer never appears at oil/water interface with isotropic shape oil particles. These findings reveal the penetration of anisotropic LC can promote ordered lateral organization of amphiphiles. Moreover, we find the phase transition point is shifted to lower surface coverage of amphiphiles when the LCs have larger affinity to the amphiphile tails.     

Sulfation behavior of white mud from paper manufacture as SO<Subscript>2</Subscript> sorbent at fluidized bed combustion temperatures

The calcination characteristics, sulfation conversion, and sulfation kinetics of a white mud from paper manufacture at fluidized bed combustion temperatures were investigated in a thermogravimetric analyzer. Also, the comparison between the white mud and the limestone in sulfation behavior and microstructure was made. Although the white mud and the limestone both contain lots of CaCO₃, they are different in the alkali metal ions content and microstructure. It results in a marked difference in sulfation behavior between the white mud and the limestone. The CaO derived from white mud achieves the maximum sulfation conversion of 83% at about 940 °C which is 1.7 times higher than that derived from limestone at about 880 °C. The shrinking unreacted core model is appropriate to analyze the sulfation kinetics of the white mud. The chemical reaction activation energy E _a and the activation energy for product layer diffusion E _p for the sulfation of the white mud are 44.94 and 55.61 kJ mol⁻¹, respectively. E _p for the limestone is 2.8 times greater than that for the white mud. The calcined white mud possesses higher surface area than the calcined limestone. Moreover, the calcined white mud has more abundant pores in 4–24 nm range which is almost optimum pore size for sulfation. It indicates that the microstructure of the white mud is beneficial for SO₂ removal.