Zeolite‐Supported One‐Pot Synthesis of Bis‐azetidinones under Microwave Irradiation

In an attempt to synthesize antibacterial agents effective against gram‐positive and gram‐negative bacteria, the efficient synthesis of novel bis‐azetidinones ( 3a–j ) has been established. Thus, cycloaddition reaction of substituted bis‐imines with chloroacetylchloride under microwave irradiation in the presence of zeolite yielded bis‐azetidinones ( 3a–j ). Structures of the synthesized compounds have been elucidated on the basis of their elemental analysis and spectral data (IR, ¹H‐NMR, ¹³C‐NMR, and mass spectra). The synthesized bis‐azetidinones were screened for their antibacterial activity against five microorganisms: Bacillus subtilis, Proteus vulgaris, Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli. They were found to exhibit good to moderate antibacterial activity.     

Synthesis and in vitro and in vivo antitumor/anticancer activity of novel O-Mannich bases of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-ones

A new series of [4,6 substituted diaryl-1,6-dihydropyrimidin-2-yl-oxymethyl]-amines 5a–o have been synthesized by the Mannich condensation on the respective 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-ones 4, in basic medium using formaldehyde along with three secondary amines, viz., dimethylamine, piperidine and morpholine. The dihydropyrimidinones 4 in turn were synthesized by the cyclocondensation of chalcones 3 with urea. Alternatively, compounds 4 were also prepared directly by one-pot 3-component cyclocondensation reaction starting from acetophenone, benzaldehyde and urea. The structures of all the newly synthesized compounds have been confirmed by their spectral and analytical data. All the O-Mannich bases 5 have been evaluated for their in vitro cytotoxic and antitumor activities, and based on the results, the potent compounds were selected for in vivo activity, as well. Only one compound 5m of the series has been found to be relatively more effective.     

Effect of Protective Measures on Eye Exposure to Solar Ultraviolet Radiation

In this study, ocular biologically effective exposure to solar ultraviolet radiation (UVBE) is investigated with six kinds of sun protective measures (spectacle lenses, sunglasses, cap, bonnet, straw hat and under parasol). Ocular UV exposure measurements were performed on manikins during the summer period in Shenyang city (41.64° N, 123.50° E, 66 m a.s.l.), China. The measurements include the ocular UV exposure of an unprotected eye and the ambient UV as a control concurrently. Based on the relative spectral weighting factors of the International Commission on Non‐Ionizing Radiation Protection (ICNIRP), the ocular biologically effective UV is calculated and compared with the 8‐h exposure limits of ICNIRP (30 J m^?2). The UV index (UVI) of the measurement days is 0–8, and the 8‐h (8:00–16:00 China Standard Time, CST) cumulated UVBE of the unprotected eye is 452.0 J m^?2. The 8‐h cumulated UVBE of the eye with spectacle lenses, sunglasses, cap, bonnet, straw hat and under parasol are 364.2, 69.1, 51.4, 49.0, 56.8 and 110.2 J m^?2, respectively. Importantly, it should be noted that the eye could be exposed to risk despite protective measures. The 8‐h cumulated UVBE of the eye with protection is ca 1.6–15.1 times the exposure limit, respectively. As indicated in the present study, during summer months, high exposure to the sun for more than 30 min without eye protection and more than 1 h with eye protection is not advisable. The protection measures could effectively reduce the UVBE reaching the eye, yet there is still a high degree of risk when compared with the ICNIRP 8‐h exposure limits.     

New Helical Folds in α‐Peptides with Alternating Chirality

In α‐peptides, the 8/10 helix is theoretically predicted to be energetically unstable and has not been experimentally observed so far. Based on our earlier studies on ‘helical induction’ and ‘hybrid helices’, we have adopted the ‘end‐capping’ strategy to induce the 8/10 helix in α‐peptides by using short α/β‐peptides. Thus, α‐peptides containing a regular string of α‐amino acids with alternating chirality were end capped by α/β‐peptides with 11/9‐helical motifs at the termini. Extensive NMR spectroscopy studies of these peptides revealed the presence of a hitherto unknown 8/10‐helical pattern; the H‐bonds in the shorter pseudorings were rather weak. The approach of using short helical motifs to induce new mixed helices in α‐peptides could provide avenues for more versatile design strategies.     

Triply bridged (1,3,5) cyclophanes from cystine and lanthionine linkers—a comparison

The condensation of benzene 1,3,5-tricarbonylchloride with cystine-di-Me [H₂N-CH(COOMe)-CH₂-S-S-CH₂-CH(COOMe)-NH₂] yielded triply bridged (1,3,5) cyclophane 1, which was shown by detailed spectral studies and molecular orbital calculations to have a D₃ symmetry with conformationally identical linkers and a spherical topology. In sharp contrast, the (1,3,5) cyclophane 2 from the rarely studied lanthionine di-Me [H₂N-CH(COOMe)-CH₂-S-CH₂-CH(COOMe)-NH₂], showed only a equatorial twofold symmetry. This work highlights the special properties of the -S-S- bridge in cystine, which makes it an exceptional synthon in nature and organic synthesis.     

Group 4 dimethylsilylenebisamido complexes bearing the 6-[2-(diethylboryl)phenyl]pyrid-2-yl motif: synthesis and use in tandem ring-opening metathesis/vinyl-insertion copolymerization of cyclic olefins with ethylene

Two novel Zr(IV)- and Hf(IV)-based bisamido complexes bearing the 6-[2-(diethylboryl)phenyl]pyrid-2-yl motif, that is, [ZrCl(2){Me(2)Si(DbppN)(2)}(thf)] (9) and [HfCl(2){Me(2)Si(DbppN)(2)}(thf)(2)] (10) (DbppN=6-[2-(diethylboryl)phenyl]pyridine-2-amido) have been prepared. Their reactivities have been compared with that of a model precatalyst that does not bear the aminoborane motif. Upon activation with methylalumoxane, precatalysts 9 and 10 are active in the homopolymerization of ethylene (E) yielding high-density polyethylene (HDPE). In the copolymerization of E with cyclopentene (CPE), for example by the action of 9, the presence of CPE resulted in a dramatic increase in the polymerization activity of E, while CPE incorporation remained close to or at zero. In the vinyl-insertion copolymerization of norborn-2-ene (NBE) with E by the action of 9, statistical cyclic olefin copolymers of these two monomers were obtained. At higher NBE concentrations, however, 9 gave rise to reversible ring-opening metathesis (ROMP)/vinyl-insertion polymerization (VIP) of NBE with E, resulting in the formation of multi-block copolymers of the general formula poly(NBE)(ROMP)-co-poly(NBE)(VIP)-co-poly(E). This particular feature of precatalyst 9, that is, the ability to induce a reversible α-H elimination/α-H addition reaction, is attributed to the unique role of the 6-[2-(diethylboryl)phenyl]pyrid-2-yl ligand. Accordingly, a model precatalyst lacking this ligand does not have the ability to induce α-H elimination/α-H addition reactions. The different (11)B NMR shifts of various diethylborylphenylpyrid-2-ylamines and -amides permit a ranking of the strengths of the B-N bonds in these compounds. This strength of the B-N bond is correlated with the propensity of 9/MAO to produce poly(NBE)(ROMP)-co-poly(NBE)(VIP)-co-poly(E) at different temperatures.     

Low temperature thermoelectric properties of Cu intercalated TiSe2: a charge density wave material

Y₂O₃ nanoparticles and nanorods have been firstly synthesized in bulk Ti-Y films prepared by magnetron sputtering on Si (100) substrates at different temperatures. X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy (EDS) are used to characterize the structure, morphology, and composition of the as-synthesized nanoparticles and nanorods. The mechanical properties of the sputtered films are investigated using nanoindentation techniques. The results indicate that both the nanoparticles and nanorods have a pure cubic Y₂O₃ structure resulting from the reaction of Y atoms with the residual O₂ in the vacuum chamber, and are free from defects and dislocations with uniform diameters of about 30 nm. The Y₂O₃ nanoparticles mainly distribute at the grain boundaries of the Ti matrix and the nanorods have lengths ranging from 250 nm to more than 1 μm with the growth direction parallel to the (002) plane. As the growth temperature elevates, the nanoparticles turn to be coarsening while more and longer nanorods are inclined to form. Compared with the Ti film, the TiY films have a remarkable increase in hardness, but do not exhibit expected increase in elastic modulus. Finally, the growth mechanism is also briefly discussed.