Optimizing separation conditions for polycyclic aromatic hydrocarbons in micellar electrokinetic chromatography

We report the separation of polycyclic aromatic hydrocarbons (PAHs) using 0.1% poly(ethylene oxide) (PEO) in micellar electrokinetic chromatography (MEKC). In the presence of PEO, adsorption of PAHs on the capillary wall was reduced, leading to better resolution and reproducibility. Effects of tetrapentylammonium iodide (TPAI), dextran sulfate (DS), methanol, and sodium lauryl sulfate (SDS) on the separation of PAHs were elucidated. In terms of resolution and speed, DS, compared to TPAI, is a better additive for separation of PAHs. When using 0.1% PEO solution containing 45% methanol, 50 mM SDS, and 0.02% DS, separation of 10 PAHs containing 2 to 5 benzene rings was accomplished in less than 12 min at 15 kV in a commercial CE system. The method has also been tested for separating seven PAHs with high quantum yields when excited at 325 nm using a He-Cd laser. Unfortunately, separation of the seven PAHs was not achieved and sensitivity diminished under the same conditions. To optimize sensitivity, resolution and speed, a stepwise technique in MEKC has been proposed. The seven PAHs were resolved in 35 min at 15 kV when separation was performed in 0.1% PEO solution containing 35 mM SDS, 40% methanol and 0.02% DS for 2 min, and subsequently in 0.1% PEO solution containing 20 mM SDS, 50% methanol, and 0.02% DS.     

Insertion Reactions of Carbon Disulfide into Mg‐C and Mg‐N Bonds: Syntheses and Structural Determinations of Mg(S2CY)2(THF)n(Y=NEt2, NiPr2, iPr,Ph) and BrMg(S2CZ)(THF)3(Z=Ph,iPr)

The insertion reaction of CS₂ with Mg(NR₂)₂ (R= Et, ⁱPr), MgR′₂ (R′= Et, Ph) and R″MgBr (R″= ⁱPr, Ph) respectively lead solid products, Mg(S₂CNR₂)₂(THF)_n ( 1 : R= Et, n=2; 2 : R= ⁱPr, n=1), Mg(S₂C′R)₂(THF)₂ ( 3 : ′R= Et, 4 : ′R= Ph), BrMg(S₂C″R) (THF)₃ ( 5 : ″R= ⁱPr, 6 : ″R= Ph) in which the inserted carbon disulfides act as terminal chelating ligands. These compounds were characterized with ¹H, ¹³C NMR, IR spectroscopy, mass spectrometry, elemental analyses, and X‐ray crystallography.     

Incompatible reaction evaluation and accident investigation of various acids in chemical industries

This article covers the incompatible properties of nitric acid (HNO₃) with formic acid (CH₂O₂), and more generally with various acids such as sulfuric acid (H₂SO₄), hydrochloric acid (HCl), and acetic acid (C₂H₄O₂). Differential scanning calorimetry (DSC) was employed to determine the thermal hazard such as heat of decomposition (ΔH _d), exothermic onset temperature (T ₀), etc., in various acids. T ₀ of HNO₃ and CH₂O₂ were determined as 50 °C using DSC. Thus it has been observed that HNO₃ mixed with CH₂O₂ should be prohibited during transportation, storage, and use. And more generally, process safety engineers and operator must take care to handle tanker and storage tank of typical acids in the transportation, storage, and manufacturing process. It is clear that there exists a need to follow and enforce in the chemical industries safety data sheets, globally harmonized system of classification and labeling of chemicals of United Nations (UN), education of safety and health, emergency response system, and process safety management. It is the aim of the present study concerning HNO₃ with various acids.     

Ligand‐Functionalization of BPEI‐Coated YVO4:Bi3+,Eu3+ Nanophosphors for Tumor‐Cell‐Targeted Imaging Applications

In this study, surface‐functionalized, branched polyethylenimine (BPEI)‐modified YVO₄:Bi³⁺,Eu³⁺ nanocrystals (NCs) were successfully synthesized by a simple, rapid, solvent‐free hydrothermal method. The BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs with high crystallinity show broad‐band excitation in the λ=250 to 400 nm near‐ultraviolet (NUV) region and exhibit a sharp‐line emission band centered at λ=619 nm under excitation at λ=350 nm. The surface amino groups contributed by the capping agent, BPEI, not only improve the dispersibility and water/buffer stability of the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs, but also provide a capability for specifically targeted biomolecule conjugation. Folic acid (FA) and epidermal growth factor (EGF) were further attached to the BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs and exhibited effective positioning of fluorescent NCs toward the targeted folate receptor overexpressed in HeLa cells or EGFR overexpressed in A431 cells with low cytotoxicity. These results demonstrate that the ligand‐functionalized, BPEI‐coated YVO₄:Bi³⁺, Eu³⁺ NCs show great potential as a new‐generation biological luminescent bioprobe for bioimaging applications. Moreover, the unique luminescence properties of BPEI‐coated YVO₄:Bi³⁺,Eu³⁺ NCs show potential to combine with a UVA photosensitizing drug to produce both detective and therapeutic effects for human skin cancer therapy.     

Influence of cellulose nanofibers on the curing behavior of epoxy/amine systems

Epoxy composites were prepared using diglycidyl ether bisphenol F and water-dilutable diglycidyl ether bisphenol A with curing agents, polyoxypropylenediamine and diethylmethylbenzenediamine, in water or dimethylformamide as a solvent. The influence of cellulose nanofibers and solvents on curing kinetics of epoxy composites was investigated. Curing kinetic parameters were calculated using the model-fitting methods and the isoconversional method. Among these, the Sestak–Berggren equation best fit the experimental data. Results indicated that dimethylformamide decreased the reaction rate, whereas water revealed the opposite pattern. Cellulose nanofibers catalyzed the reaction between bisphenol F resins and the aromatic curing agent.     

K2CO3-Promoted Domino Reactions for Synthesis of Isocoumarins Under Microwave Irradiation

A small library of isocoumarin derivatives has been synthesized via K₂CO₃-catalyzed domino reactions of 2-carboxybenzaldehyde and ω-bromoacetophenones under microwave irradiation (MW). This strategy offers a simple, environmentally acceptable route to synthesize isocoumarin derivatives in moderate to excellent yields. All new compounds were characterized by ¹H NMR, ¹³C NMR, infrared, and high-resolution mass spectroscopic techniques.     

Determination of 129I in cement-solidified radwastes using neutron activation

The purpose of this study is to develop a neutron activation method to determine trace amounts of ¹²⁹I in cement-solidified radwastes. The radwaste samples were alkaline fused using KOH and then ¹²⁹I and iodine carrier were chemically separated by solvent extraction before and after neutron irradiation. Both stable iodine (¹²⁷I) and ¹²⁹I can be activated by neutrons through ¹²⁷I (n, 2n) ¹²⁶I and ¹²⁹I (n, γ) ¹³⁰I reactions; their activated radionuclides were counted together with a high-purity germanium detector. The chemical recovery yields ranged from 30 to 60 %, and it was found that more than 99.9 % of interfering radionuclides can be removed using solvent extraction after neutron irradiation. The minimum detectable amounts can be lowered to less than 1 mBq g^?1, which is superior to low energy γ-ray spectrometry by a factor of >10², on average. The established technique can be applied to re-evaluation of ¹²⁹I content in radwastes that can be re-classified to lower classes, and the cost for designing a final disposal facility can be significantly reduced.     

Synthesis and mesomorphism of 4,4'-bis(omega-hydroxyalkoxy)-alpha-methylstilbenes

A homologous series of 4,4'-bis(omega-hydroxyalkoxy)-alpha-methylstilbenes, denoted HAMS-n, has been synthesized. Here n is the carbon atom length of the peripheral n-alkyl chain; in this work n = 2 to 8 and 11. The composition, microstructure, thermal properties, and mesomorphism of the homologues were determined using elemental analysis, ¹H NMR, FTIR, DSC, wide angle X-ray diffraction, and polarizing optical microscopy with a heating stage. The influence of the length and the even/odd numbers of methylene units of the peripheral chains on the variants of mesomorphism and the stability of mesophases, as well as on their transition temperatures, are discussed. The homologues with n = 8 and 11 were enantiotropic monomorphic, CrG (or CrH). The odd homologues showed monotropic trimorphism on cooling, while the even homologues exhibited enantiotropic trimorphism. A pronounced even/odd effect on the melting temperatures was observed.     

拉曼光谱法定量分析焦磷酸根离子的含量

应用拉曼光谱技术研究了焦磷酸钾、硝酸钾、磷酸二氢钾、乙二胺四乙酸钠等十余种可溶性盐水溶液以及它们的混合物溶液的拉曼光谱特征,考察了共存组分对焦磷酸根拉曼光谱特征峰的影响;建立了基于拉曼光谱技术定量分析溶液中焦磷酸根离子含量的方法。结果表明,以硝酸钾为内标物,保持被测溶液pH 11,焦磷酸根离子拉曼光谱特征峰强度与硝酸根离子拉曼光谱特征峰强度之比值对焦磷酸根浓度呈良好的线性关系,所得线性回归方程为y=1.2110x+0.1515,相关系数R2=0.9996;已经研究过的十余种可溶性盐共存物几乎不干扰焦磷酸根离子的定量分析。     

Zethrene and Dibenzozethrene: Masked Biradical Molecules?

The syntheses, structures, and physical properties of dibenzozethrenes were explored. The results thus obtained were compared with those for zethrenes. Dibenzozethrenes were synthesized by the nickel‐catalyzed cyclodimerization of 9‐ethynyl‐1‐iodoanthracenes. The substituents in zethrene and dibenzozethrene twisted their backbones, and remarkably influenced their properties. Unlike closed‐shell disubstituted derivatives, the parent zethrene and dibenzozethrene are singlet open‐shell biradicals, which were studied by variable‐temperature ¹H NMR, ESR, SQUID and computational methods. Since substituents were observed to affect significantly the biradical properties, the relevant mechanisms were analyzed. The nonlinear optical performance of each of these compounds depends on its π‐conjugation and biradical properties. Dibenzozethrenes have larger two‐photon absorption cross‐sections than zethrenes, as most strongly evidenced by the parent dibenzothrene [σ_max=4323 GM at 530 nm].