This study presents a high‐precision Cd isotope measurement method for soil and rock reference materials using MC‐ICP‐MS with double spike correction. The effects of molecular interferences (e.g., 109Ag1H+, 94Zr16O+, 94Mo16O+ and 70Zn40Ar+) and isobaric interferences (e.g., Pd, In and Sn) to Cd isotope measurements were quantitatively evaluated. When the measured solution has Ag/Cd ≤ 5, Zn/Cd ≤ 0.02, Mo/Cd ≤ 0.4, Zr/Cd ≤ 0.001, Pd/Cd ≤ 5 × 10−5 and In/Cd ≤ 10−3, the measured Cd isotope data were not significantly affected. The intermediate measurement precision of pure Cd solutions (BAM I012 Cd, Münster Cd and AAS Cd) was better than ± 0.05‰ (2s) for δ114/110Cd. The δ114/110Cd values of soil reference materials (NIST SRM 2709, 2709a, 2710, 2710a, 2711, 2711a and GSS‐1) relative to NIST SRM 3108 were in the range of −0.251 to 0.632‰, the δ114/110Cd values of rock reference materials (BCR‐2, BIR‐1, BHVO‐2, W‐2, AGV‐2, GSP‐2 and COQ‐1) varied from −0.196‰ to 0.098‰, and that of the manganese nodule (NOD‐P‐1) was 0.163 ± 0.040‰ (2s, n = 8). The large variation in Cd isotopes in soils and igneous rocks indicates that they can be more widely used to study magmatic and supergene processes.
In this paper, using a simple method, 17 isostructural polyoxotitanates (POTs) were synthesized, including the pristine [Ti12O16(O(i)Pr)16], the monodefected [Ti11O13(O(i)Pr)18], and the heterometal-doped [Ti11O14(O(i)Pr)17(ML)] (M = Mg, Ca, Zn, Cd, Co, or Ni; L = Cl, Br, I, or NO3). The electronic structures of these POTs were determined by UV-vis spectroscopy and DFT calculations. Upon UV irradiation of the POTs, electron spin resonance showed the formation of Ti(III) under anaerobic conditions and superoxide (O2(•-)) in the presence of O2. The photoactivities of the POTs were then probed with Ti(III) production and short-circuit photocurrent experiments. The photophysical processes were studied using steady-state and transient photoluminescence. The results show that within the very similar structures, the deexcitation processes of the photoexcited POTs can be greatly affected by the dopants, which result in enhanced or decreased photoactivities. Co and Ni doping enhances the absorption of the visible light accompanied by serious loss of UV photoactivities. On the other hand, a Ti vacancy (in [Ti11O13(O(i)Pr)18]) does not reduce the band gap of a POT but improves the UV photoactivities by serving as surface reaction site. The POTs were then used as molecular models of titanium oxide nanoparticles to understand some important issues relevant to doped titanate, i.e., coordination environment of the dopant metal, electronic structure, photoactivities, and photophysical processes. Our present findings suggest that for solar energy harvesting applications of titanium oxides like photocatalysis and solar cells substitution of titanium atoms by transition metal ions (like Co and Ni) to extend the absorption edges may not be an efficient way, while loading of Ti vacancies is very effective.
Volatile components in jujube fruits from Zizyphus jujuba Mill. cv. Dongzao (DZ) and Zizyphus jujuba Mill. cv. Jinsixiaozao (JS) were analyzed under different cold storage periods via headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS). Results identified 53 peaks that corresponded to 47 compounds and were mostly alcohols, aldehydes, esters, and ketones. Differences in the volatile components of jujube fruits were revealed in topographic plots and fingerprints. For DZ, 3-pentanone was the characteristic component of fresh fruits. After storage for 15 days, dipropyl disulfide became the most special substance. Moreover, when stored for 30 and 45 days, the fruits had some same volatile components, like 2-pentyl furan and diallyl sulfide. However, for DZ stored for 60 days, esters were the prominent constituent of the volatile components, simultaneously, some new alcohols appeared. For JS, 2-ethyl furan was the representative of fresh fruits, and 2-butoxyethanol content was the most abundant after 15 and 30 days of storage. Different from that in DZ, the content of ester in JS increased after storage for 45 days. Substances such as amyl acetate dimer, methyl salicylate, and linalool greatly contributed to the jujube flavor during the late storage period. Principal component analysis (PCA) showed that fresh samples and refrigerated fruits were effectively distinguished. Heat map clustering analysis displayed the similarity of volatile components in different samples and was in accordance with PCA results. Hence, the volatile components of jujube fruits can be readily identified via HS-GC-IMS, and jujube fruits can be classified at different periods based on the difference of volatile components.
XynB from Aspergillus niger ATCC1015 (AnXynB) is a mesophilic glycoside hydrolase (GH) family 11 xylanase which holds great potentials in a wide variety of industrial applications. In the present study, the catalytic activity and stability of AnXynB were improved by a combination of computational and experimental approaches. Virtual mutation and molecular dynamics simulations indicated that the introduction of Glu and Asn altered the interaction network at the - 3 subsite. Interestingly, the double mutant S41N/T43E displayed 72% increase in catalytic activity when compared to the wild type (WT). In addition, it also showed a better thermostability than the WT enzyme. Kinetic determination of the T43E and S41N/T43E mutants suggested that the higher xylanase activity is probably due to the increasing binding affinity of enzyme and substrate. Consequently, the enzyme activity and thermostability of AnXynB was both increased by selective site-directed mutagenesis at the - 3 subsite of its active site architecture which provides a good example for a successfully engineered enzyme for potential industrial application. Moreover, the molecular evolution approach adopted in this study led to the design of a library of sequences that captures a meaningful functional diversity in a limited number of protein variants.
The effects of anionic surfactants on the aggregation-induced emission (AIE) feature of cationic M-silole molecules have been studied. The electrostatic binding of M-silole with the surfactants greatly promotes the aggregation of the mixtures. The M-silole/surfactant aggregates at 1:1 charge ratio exhibit the maximum fluorescence intensity. Excess surfactant molecules will distribute the M-silole molecules into different micelles and weaken the fluorescence. The fluorescence intensity of the mixed M-silole/surfactant aggregates can be effectively modulated by choosing different surfactants. The gemini surfactants display a much stronger ability of enhancing fluorescence intensity than do the single-chain surfactants. Especially, the gemini surfactant with benzene rings shows the best performance in enhancing fluorescence of M-silole due to both the strongest aggregation ability and the pi-pi interaction with M-silole.
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