Electronic and RAMAN Spectra of an Iron-Dioximato Polymer

Electronic and resonance Raman spectra are reported for the [Fe(Hdmg)₂(clpz)]_n polymer (clpz = 2-chloropyrazine, Hdmg = dimethylglyoximato anion). Excitation at the absorption bands in the visible region led to a selective enhancement of vibrational modes of the Hdmg and clpz ligands, allowing the characterization of the metal-to-macrocycle and metal-to-axial ligand charge-transfer transitions.     

A Six-Coordinate Silicon Dihydride Embedded in a Porphyrin: Enhanced Hydride-Donor Properties and the Catalyst-Free Hydrosilylation of CO2

The catalyst-free hydrosilylation of CO₂ under mild conditions remains limited. Herein, we report the synthesis, characterization, and reactivity of 5,10,15,20-tetraphenylporphyrinato(dihydrido)silicon(IV) ( 1 ) as a six-coordinate silicon dihydride. The Si-H moiety of 1 reacts with polar double bonds and CO₂ in the absence of a catalyst to afford hydrosilylated products. Combining the hydrosilylation with subsequent transformation furnishes formic acid from CO₂. Computational studies indicate that the hydride-donor properties of 1 are exceptionally high for a neutral silicon hydride, and that the direct hydride transfer from silicon to carbon is a pivotal step in the hydrosilylation of CO₂ with 1 .     

Measurements of N2- and O2-broadening and shifting parameters of methane spectral lines in the 5550–6236 cm−1 region

The absorption spectra of mixtures of methane (CH₄) with N₂ and O₂ at different partial pressures of both CH₄ and buffer gases for three temperatures 240, 267, and 296 K have been recorded using the Bruker IFS 125 HR FTIR spectrometer in the 5550–6236 cm^?1 region. The multispectrum fitting procedure has been applied to these spectra to recover the spectral line parameters. The main goal of this procedure was the determination of the N₂- and O₂-broadening and shifting coefficients and the exponents of their temperature dependences. These parameters have been derived for 452 assigned lines with good values of the signal to noise ratio. The rotational dependence of the mean values of these parameters is discussed. The temperature dependence exponents were observed for both N₂ and O₂ buffer gases.     

Complete Assignment of the 1H and 13C NMR Spectra of Carthamin Potassium Salt Isolated from Carthamus tinctorius L.

Carthamin potassium salt isolated from Carthamus tinctorius L. was purified by an improved traditional Japanese method, without using column chromatography. The ¹H and ¹³C nuclear magnetic resonance (NMR) signals of the pure product were fully assigned using one- and two-dimensional NMR spectroscopy, while the high purity of the potassium salt and deprotonation at the 3′ position of carthamin were confirmed by atomic adsorption spectroscopy and nano-electrospray ionization mass spectrometry.     

Terahertz Spectroscopy of the Amidogen Radical, NH2

The rotational spectrum of the NH2 radical in its &Xtilde;2B1 ground vibronic state was investigated between 614 and 1003 GHz. One hundred fifty-nine newly observed lines (188 hyperfine components) of six rotational transitions with 0 相似文献   

Influence of Epoxy Resin Treatment on the Mechanical and Tribological Properties of Hemp-Fiber-Reinforced Plant-Derived Polyamide 1010 Biomass Composites

In this study, we investigated the influence of epoxy resin treatment on the mechanical and tribological properties of hemp fiber (HF)-reinforced plant-derived polyamide 1010 (PA1010) biomass composites. HFs were surface-treated using four types of surface treatment methods: (a) alkaline treatment using sodium chlorite (NaClO₂) solution, (b) surface treatment using epoxy resin (EP) solution after NaClO₂ alkaline treatment, (c) surface treatment using an ureidosilane coupling agent after NaClO₂ alkaline treatment (NaClO₂ + A-1160), and (d) surface treatment using epoxy resin solution after the (c) surface treatment (NaClO₂ + A-1160 + EP). The HF/PA1010 biomass composites were extruded using a twin-screw extruder and injection-molded. Their mechanical properties, such as tensile, bending, and dynamic mechanical properties, and tribological properties were evaluated by the ring-on-plate-type sliding wear test. The strength, modulus, specific wear rate, and limiting pv value of HF/PA1010 biomass composites improved with surface treatment using epoxy resin (NaClO₂ + A-1160 + EP). In particular, the bending modulus of NaClO₂ + A-1160 + EP improved by 48% more than that of NaClO₂, and the specific wear rate of NaClO₂ + A-1160 + EP was one-third that of NaClO₂. This may be attributed to the change in the internal microstructure of the composites, such as the interfacial interaction between HF and PA1010 and fiber dispersion. As a result, the mode of friction and wear mechanism of these biomass composites also changed.     

Variation of characteristics of pentaoxyethylene decyl C10E5 and hexaoxyethylene tetradecyl C14E6 ether micelles with uptake of n-octanol

Wormlike micelles of the surfactant pentaoxyethylene decyl C10E5 and hexaoxyethylene tetradecyl C14E6 ethers were characterized by static (SLS) and dynamic light scattering (DLS) experiments to examine effects of uptake of n-octanol on the micellar characteristics. The SLS results have been successfully analyzed by the light scattering theory for micelle solutions to yield the molar mass Mw(c) as a function of concentration c along with the cross-sectional diameter d of the micelle. The apparent hydrodynamic radius RH,app(c) determined by DLS as a function of c has also been successfully analyzed by a fuzzy cylinder theory which takes into account the hydrodynamic and direct collision interactions among micelles, providing us with the values of the stiffness parameter lambda(-1). It has been found that the micellar length Lw increases with increasing surfactant weight fraction ws and increasing n-octanol content wo in the micelles or with raising temperature T. The values of d and lambda(-1) are found to increase with increasing wo, whereas the spacing s between hydrophilic tails of adjacent surfactant molecules on the micellar surface decreases with increasing wo. Comparison with our previous results for the C10E5 and C14E6 micelles containing n-dodecanol has revealed the salient features in change of the micellar characteristics with uptake of n-alcohols as follows: (i) The Lw values increase more significantly for the C14E6 micelles containing n-dodecanol than those containing n-octanol, whereas Lw of the C10E5 micelles increases by including n-dodecanol and n-octanol without a significant difference for the two alcohols. (ii) The values of d and lambda(-1) of the C10E5 and C14E6 micelles increase with uptake of n-octanol and n-dodecanol into the micelles. They are larger for the C10E5 micelles than for the C14E6 micelles, and their increase with alcohol content is less significant for the C14E6 micelles in comparison with the C10E5 micelles. (iii) The s values of the C10E5 and C14E6 micelles decrease with uptake of n-octanol and n-dodecanol into the micelles. They are somewhat larger in the latter micelles than in the former. (iv) The variation in d, s, and lambda(-1) with uptake of n-alcohol occurs with no difference in the effects for the two alcohols n-octanol and n-dodecanol.     

Titanocene(II)-promoted, one-pot, three-component coupling of thioacetals, alkynyl sulfones, and carbonyl compounds: highly stereoselective formation of tert-homopropargyl alcohols

Titanocene alkylidene complexes, generated by desulfurizative titanation of thioacetals with Cp2Ti[P(OEt)3]2, reacted with alkynyl methyl sulfones to produce organotitanium species, which gave tert-homopropargyl alcohols with high diastereoselectivity on treatment with aromatic and alpha,beta-unsaturated ketones.     

Crab-Eating Monkey Acidic Chitinase (CHIA) Efficiently Degrades Chitin and Chitosan under Acidic and High-Temperature Conditions

Chitooligosaccharides, the degradation products of chitin and chitosan, possess anti-bacterial, anti-tumor, and anti-inflammatory activities. The enzymatic production of chitooligosaccharides may increase the interest in their potential biomedical or agricultural usability in terms of the safety and simplicity of the manufacturing process. Crab-eating monkey acidic chitinase (CHIA) is an enzyme with robust activity in various environments. Here, we report the efficient degradation of chitin and chitosan by monkey CHIA under acidic and high-temperature conditions. Monkey CHIA hydrolyzed α-chitin at 50 °C, producing N-acetyl-d-glucosamine (GlcNAc) dimers more efficiently than at 37 °C. Moreover, the degradation rate increased with a longer incubation time (up to 72 h) without the inactivation of the enzyme. Five substrates (α-chitin, colloidal chitin, P-chitin, block-type, and random-type chitosan substrates) were exposed to monkey CHIS at pH 2.0 or pH 5.0 at 50 °C. P-chitin and random-type chitosan appeared to be the best sources of GlcNAc dimers and broad-scale chitooligosaccharides, respectively. In addition, the pattern of the products from the block-type chitosan was different between pH conditions (pH 2.0 and pH 5.0). Thus, monkey CHIA can degrade chitin and chitosan efficiently without inactivation under high-temperature or low pH conditions. Our results show that certain chitooligosaccharides are enriched by using different substrates under different conditions. Therefore, the reaction conditions can be adjusted to obtain desired oligomers. Crab-eating monkey CHIA can potentially become an efficient tool in producing chitooligosaccharide sets for agricultural and biomedical purposes.