Large‐Area Aminated‐Graphdiyne Thin Films for Direct Methanol Fuel Cells

A two‐dimensional (2D) carbon nanofilm with uniform artificial nanopores is an ideal material to ultimately suppress the fuel permeation in the proton exchange membrane fuel cells. Graphdiyne has great mechanical strength, high dimensional stability, and controllable nanopores, and has good prospects to play this crucial role. It is found that graphdiyne nanofilm with amino groups and natural nanopores can be easily prepared with high integrity. The aminated graphdiyne has good compatibility with the Nafion matrix owing to the acid–base interaction between them. The excellent comprehensive properties of graphdiyne in selectivity, dimensional stability, and integrity effectively improve the power performance and stability of fuel cells at wide temperature. Our results can be developed into a universal method that can easily realize the selective separation of ions and small molecules, and open a new way for the emerging applications in green energy.     

Super‐heptazethrene

The challenging synthesis of a laterally extended heptazethrene molecule, the super‐heptazethrene derivative SHZ‐CF3 , is reported. This molecule was prepared using a strategy involving a multiple selective intramolecular Friedel–Crafts alkylation followed by oxidative dehydrogenation. Compound SHZ‐CF3 exhibits an open‐shell singlet diradical ground state with a much larger diradical character compared with the heptazethrene derivatives. An intermediate dibenzo‐terrylene SHZ‐2H was also obtained during the synthesis. This study provides a new synthetic method to access large‐size quinoidal polycyclic hydrocarbons with unique physical properties.     

Goniodilactone and gomoheptenolactone,two novel cytotoxic styryllactones from the leaves of Goniothalamus cheliensis

Two novel styryllactones,goniodilactone（1） and gonioheptenolactone（2）,were isolated from the leaves of Goniothalamus cheliensis Hu.Their structures were determined on the basis of spectroscopic data as well as X-ray crystallography analysis. Compounds 1 and 2 exhibited significant cytotoxicities in a panel of human cancer cells,including DU-145,PC-3,MCF-7,A-549, KB and KBvin,with GI₅₀S in the range of 1.29-4.56μg/mL.     

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.     

Computational Study of the Substitution Effect on the Mechanism for the Gold(I)‐Catalyzed Ring Expansions of Unactivated Alkynylcyclopropanes

The ring expansion reactions of unactivated alkynylcyclopropanes X‐C≡C‐C₃H₅ → X‐C=C₄H₅ (X = H, F, Cl, Me, OMe, NMe₂, CMe₃) were examined using the density functional theory calculations. All of the structures were completely optimized at the B3LYP/6‐311++G** level of theory. For clarify the effect of the cationic gold(I), we also added AuPH₃⁺ as the catalyst into the system and the structures for Au were calculated at the B3LYP/LANL2DZ level of theory. The main finding of this work is that the singlet‐triplet splitting of X‐C≡C‐C₃H₅ play an important role in determining the kinetic and thermodynamic stability of the unactivated ring expansion reactions. When X‐C≡C‐C₃H₅ with a smaller singlet‐triplet splitting is utilized, the reaction has a smaller activation energy and a larger exothermicity.     

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.     

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.